Handbook of Deposition Technologies For Films and Coatings Science Application2
Handbook of Deposition Technologies For Films and Coatings Science Application2
Handbook of Deposition Technologies For Films and Coatings Science Application2
DEPOSITION TECHNOLOGIES
FOR FILMS AND COATINGS
Science, Technology
and Applications
Second Edition
Edited by
Rointan F. Bunshah
NOYES PUBLICATIONS
np Park Ridge, New Jersey, U.S.A.
Copyright © 1994 by Noyes Publications
No part of this book may be reproduced or
utilized in any form or by any means, elec-
tronic or mechanical, including photocopying,
recording or by any information storage and
retrieval system, without permission in writing
from the Publisher.
Library of Congress Catalog Card Number: 93-30751
ISBN: 0-8155-1337-2
Printed in the United States
10 9 8 7 6 5 4 3 2 1
CIP
DEDICATION
vii
MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES
Editors
Rointan F. Bunshah, University of California, Los Angeles (Series Editor)
Gary E. McGuire, Microelectronics Center of North Carolina (Series Editor)
Stephen M. Rossnagel, IBM Thomas J. Watson Research Center
(Consulting Editor)
v
vi Contents
Series
Related Titles
ADHESIVES TECHNOLOGY HANDBOOK: by Arthur H. Landrock
HANDBOOK OF THERMOSET PLASTICS: edited by Sidney H. Goodman
SURFACE PREPARATION TECHNIQUES FOR ADHESIVE BONDING: by Raymond F.
Wegman
FORMULATING PLASTICS AND ELASTOMERS BY COMPUTER: by Ralph D. Hermansen
HANDBOOK OF ADHESIVE BONDED STRUCTURAL REPAIR: by Raymond F. Wegman and
Thomas R. Tullos
CARBON–CARBON MATERIALS AND COMPOSITES: edited by John D. Buckley and Dan
D. Edie
CODE COMPLIANCE FOR ADVANCED TECHNOLOGY FACILITIES: by William R. Acorn
Contributors
xiii
xiv Contents
Contributors
NOTICE
A decade after the first edition of this volume was published, a second
edition is being brought out partly due to the excellent response to the first
edition and also to update the many improvements in deposition technologies,
the mechanisms and applications.
The entire volume has been extensively revised and contains 50% or
more new material. Five entirely new chapters have been added. The
organization of the book has also been changed in the following respects:
1. Considerably more material has been added in Plasma
Assisted Vapor Deposition Processes.
2. A new chapter on Metallurgical Coating Applications has
been added.
The chapter in the first edition on Polymeric Coating techniques has
been omitted as it deserves a volume by itself. Large topics such as coatings
technology in microelectronics, diamond films, etc., have been treated in
separate volumes in this series.
Although there are some new competing volumes dealing with selected
topics on the materials science of thin films, this volume remains the only
comprehensive treatment of the entire subject of Deposition Technology.
Applications of films and coatings spans the entire gamut of science and
technology. Generic application areas include electronic, magnetic, optical,
mechanical, chemical and decorative applications. New deposition technolo-
gies such as arc evaporation, unbalanced magnetron sputtering, ion beam
assisted deposition, and metal-organic CVD have come on stream for critical
applications. In this post cold war era, many economic solutions to
engineering problems will necessarily involve coatings, e.g., battery materials
for the emerging electric car industry.
ix
x Preface
Contents
The core subjects are the basic technologies for the deposition of films
and coatings. These are the Physical Vapor Deposition (PVD) Processes
consisting of Evaporation, Sputtering, and Ion Plating; Chemical Vapor
Deposition (CVD) and Plasma-Assisted Chemical Vapor Deposition (PACVD);
Electrodeposition and Electroless Plating; Thermal Spraying, Plasma Spray-
ing and Detonation Gun Technologies. Chapters on other subjects common
to the above technologies are included. These are: Adhesion of Coatings,
Cleaning of Substrates, Role of Plasmas in Deposition Processes, Structure
of PVD Deposits, Growth and Structure of PVD Films, Mechanical and
Tribological Properties of PVD Deposits, Elemental and Structural Character-
ization Techniques, and Metallurgical Coatings. A relatively new develop-
ment, Jet Vapor Deposition Process, was added as the last chapter in the
book during the page proof stage because of its novelty.
We hope that this volume will be useful to the multitude of disciplines
represented by the workers in this field and provide a source for future
developments.
xi
xii
Contents
xv
xvi Contents
Deposition Technologies: An
Overview
Rointan F. Bunshah
27
28 Deposition Technologies for Films and Coatings
2.0 INTRODUCTION
Heated
WF6(vapor) + 3H2(gas) ———" W(deposit) + 6HF(gas)
Substrate
the coating. For high energy deposition processes, the depositing particles
react with or penetrate into the substrate surface.
Particulate deposition processes involve molten or solid particles and the
resulting microstructure of the deposit depends on the solidification or
sintering of the particles. Bulk coatings involve the application of large
amounts of coating material to the surface at one time such as in painting.
Surface modification involves ion, thermal, mechanical, or chemical treatments,
which alter the surface composition or properties. All of these techniques are
widely used to form coatings for special applications.
One of the chapters in this volume (Ch. 11) deals with Plasma Spraying
and Detonation Gun Techniques where a high velocity stream of macro-
particles (µm dimensions) impinge on a substrate to form a coating. With the
Deposition Technologies: An Overview 37
Blades and vanes used in the turbine-end of a gas turbine engine are
subject to high stresses in a highly corrosive environment of oxygen-, sulfur-
and chlorine-containing gases. A single or monolithic material such as a high
temperature alloy is incapable of providing both functions. The solution is to
design the bulk alloy for its mechanical properties and provide the corrosion
resistance by means of an overlay coating of an M-Cr-AI-Y alloy where M
stands for Ni, Co, Fe or Ni + Co. The coating is deposited in production by
electron beam evaporation and in the laboratory by sputtering or plasma
spraying. With the potential future use of synthetic fuels, considerable
research will have to be undertaken to modify such coating compositions for
the different corrosive environments as well as against erosion from the
particulate matter in those fuels.
Parts for implants such as heart valves are made of pyrolytic carbon by
CVD techniques. Metal parts are coated with carbon by ion plating in order
to obtain biological compatibility.
18. Film deposition using a high velocity gas jet. Hayashi and
coworkers[9] have developed a process where ultra-fine powders
(~10 nanometer diameter) are carried on a high velocity gas jet
and impinged on a substrate to “write” lines of deposited
materials, e.g., YBCO superconductors. The usage of material
is very high, almost 97% is collected as a deposit. Various
applications are envisioned.
19. Unbalanced magnetron deposition—very useful new development
where some of the electrons are allowed to escape from the
magnetic trap at the sputtering target and from a plasma near
the substrate from which ions can be extracted to bombard the
growing film.
13.0 SUMMARY
Chemical processes
Wetting Process
Spraying Processes
Printing Process also relies on wetting and is a process in which the ink,
conventionally pigment in a solvent, is transferred to and is deposited on a
paper or other substrate, usually to form a pattern; the solvent evaporates to
leave the required print.
Spraying Processes can be considered in two categories;(i) macroscopic
in which the sprayed particle consists of many molecules and is usually grater
than 10 µm in diameter; (ii) macroscopic in which the sprayed particles are
predominantly single molecules or atoms.
Air and Airless Spraying are the first of the macroscopic processes.
When a liquid exceeds a certain critical velocity, it breaks up into small
droplets, i.e., it atomizes. The atomized droplets, by virtue of their velocity
(acquired from a high pressure air or airless source) can be sprayed onto a
substrate.
Flame Spraying is a process in which a fine powder (usually of a metal)
is carried in a gas stream and is passed through an intense combustion flame,
where it becomes molten. The gas stream, expanding rapidly because of the
heating, then sprays the molten powder onto the substrate where it solidifies.
Detonation Coating is a process in which a measured amount of powder
is injected into what is essentially a gun, along with a controlled mixture of
oxygen and acetylene. The mixture is ignited, and the powder particles are
heated and accelerated to high velocities with which they impinge on the
substrate. The process is repeated several times a second.
Arc Plasma Sprayingis a process in which the powder is passed through
an electrical plasma produced by a low voltage, high current electrical
discharge. By this means, even refractory materials can be deposited.
52 Deposition Technologies for Films and Coatings
REFERENCES
1.0 INTRODUCTION
55
56 Deposition Technologies for Films and Coatings
where the subscripts el, ex, ion, a, and oth characterize the particular types
of collisions, namely, elastic or momentum exchange, excitation, ionization,
attachment, and other processes, respectively.
Figure 2.1 shows the cross sections for electrons interacting with Ar
gas. The cross sections are typically a strong function of the energy of the
colliding species. For the case of electrons colliding with gas atoms, the
kinetic energy of the gas atoms is generally much less than that of the
electrons and can be neglected. Consequently, only the electron energy is
shown in Fig. 2.1. The figure shows that at low electron energies the primary
collision process is momentum exchange (σt ≈ σel), while at energies
considerably larger than the ionization potential (15.75 eV for Ar), the primary
process is ionization (σt ≈ σion ).
Plasmas in Deposition Processes 57
Figure 2.1. Collision cross sections for electrons in Ar gas (from Ref. 1).
Figure 2.2. Cross section for the reaction of O+ ions with N2 to produce NO+ + N
(from Ref. 2).
r
Consider a plasma electron in an electric fieldE . Between collisions with
the gas particles, the electron will gain an energy Wf from the electric field that
is equal to the force on the electron eE (where e is the electronic charge) times
the distance that it moves in the electric field. This distance can be
approximated by the mean free path so that, on average, Wf = eEλ. In the
steady state case, this energy gain must be balanced against the energy loss
in an average collision. We neglect inelastic collisions for the moment and
consider collisions with heavy particles in which the electrons lose all of their
momentum, i.e., are deflected by 90o . This permits us to use the momentum
exchange cross section, as defined in the preceding section, for estimating
λ. Application of the conservation of energy and momentum shows that loss
of electron energy in such a collision is[4]
where me and m H are the electron and heavy-particle masses and We and WH
are the initial electron and heavy particle energies before the collision.
Equating ∆W to the energy Wf gained from the electric field, and using Eq.
1 for λ, yields
Figure 2.3. Electron ( Te ) and gas temperatures (Tg ) in an air arc as a function of
pressure (from Ref. 5).
E= ∞
Eq. (5) νk = N (E/2me)1/2 σk(E) Fe (E) dE
E= 0
62 Deposition Technologies for Films and Coatings
where k is the type of collision (e.g., elastic, excitation, ionization, etc). If the
collision cross section σk(E) is assumed to be independent of energy, and the
electrons are assumed to have a Maxwellian velocity distribution at an electron
temperature Te, then Eq. 5 reduces to
Eq. (6) νk = N σk ve
and
with
* From kinetic theory, the average particle energy in one dimension is 1/2 kT. The
average energy in three dimensions is 3/2 kT. Since T and E are so closely related,
it is customary in plasma physics to give temperature in units of eV. To avoid
confusion with the number of dimensions involved, it is not the average energy but
the energy corresponding to kT that is used to denote the temperature.[11] By a 2
eV plasma, we mean that kT = 2 eV, although the actual average energy in three
dimensions is 3/2 kT or 3 eV.
Plasmas in Deposition Processes 63
because these collisions involve long-range coulomb forces and the cross
sections do not cut off as in the hard sphere approximation.
The primary use of Eqs. 9 and 10 is in comparing νee and νei with other
relevant collision frequencies. A plasma for which νee > νeA, where νeA is the
elastic electron/atom collision frequency, is said to be coulomb-dominated.
An approximate condition for coulomb domination is easily derived from Eqs.
6 and 9 (see Ref. 13),
ne σeA [kT(eV)]2
Eq. (12) >> αc = (2.23 x 1013)
N lnΛ
1
(
v12 ≈ 2.5 ×105 )σ N
12 12 T
300
2
Eq. (13)
(m )1
∗ 2
When the collision frequency is sufficiently large that the drift velocity is small
compared to the thermal velocity,
1.6 x 10-12 cm2
Eq. (19) µj =
mj ν V-sec
Table 2.1. Mobilities of Ions in their Own Gas (From Ref. 15)
He+-He 8,000
Ne+-Ne 3,300
Ar+-Ar 1,200
Kr+-Kr 690
H2+-H2 10,000
N2+-H2 2,000
O2+-O2 1,000
CO2 +-CO2 730
When a positive ion collides with a gas molecule or atom, two processes
can occur. First, the ion and molecule can exchange momentum and energy
in a collision in which the particles preserve their identity. Second, an
exchange of charge can occur. For example, fast ions moving through a gas
can engage in collisions in which the ion extracts an electron from a gas atom
with the result that the fast ion becomes a fast neutral atom while the slow atom
becomes a slow positive ion. Charge exchange is particularly important for
ions of low energy passing through their own gas (resonant charge exchange).
Under these conditions, the charge transfer cross section is about one half of
the total cross section[16] and therefore contributes significantly in determining
the mobility.* Charge transfer is very important in high-pressure sputtering and
ion-plating discharges.
Electrical Conductivity and Diffusion Coefficients: The electrical
conductivity σ is just eNµ, so that
where Nj is the particle density in cm-3 and mj is the mass of the current carrier
in grams. The resistivityρ is often used to avoid confusion with σ, which is the
common symbol for both the electrical conductivity and the collision cross
section.
The diffusion coefficient Dj relates the particle flux to the concentration
gradient. Thus, one has
where
kT kT (eV) cm2
Eq. (22) Dj = = (1.6 x 10-12)
mj ν mj ν sec
The orbiting radius is called the gyro, cyclotron, or Larmor radius and is given
by
and
[W⊥(eV)] 1/2
Eq. (26) rg = 3.37 cm
B(gauss)
E⊥ (V/cm)
Eq. (27) ve = 108 cm/sec
B(gauss)
The drift of electrons along a magnetic field line can also be influenced
by gradients in the magnetic field. An example of this behavior is shown in Fig.
2.7.
Electrons moving in such a field tend to conserve the magnetic moment,
µM, defined by[11]
Eq. (28) µM = W⊥ / B
Thus, for a typical glow discharge electron density of 109 cm-3 with an average
energy of 1 eV, Je ≈ 3 mA/cm2.
For heavy particles such as ions, Eq. 31 can be written in the following
useful form:
70 Deposition Technologies for Films and Coatings
where T is the gas temperature (K) and m is the species molecular weight. In
units of current density, Eq. 34 becomes
Thus, for an Ar plasma used in sputtering with an ion density of 109 cm-3 at
300 K, the ion current flux to the wall is 1.6 µA/cm2.
It is clearly seen by comparing Eqs. 33 and 35 that the electrons tend
to flow from a plasma to an adjacent wall at a faster rate than the ions; therefore,
a space charge region in which one species is largely excluded forms adjacent
to such surfaces. The potential variation between the surface and the plasma
is largely confined to this layer, which is called a sheath. Sheaths are typically
several Debye lengths in thickness.
The nature of the sheath will depend upon the current density passing
across it. Except for cases involving very high current densities to anodes, the
space charge region will contain primarily the low-mobility ion species. Such
sheaths are known as positive space charge sheaths. The function of the
sheath is to form a potential barrier, so that the more mobile species, which
is the electrons except in the case of a strong magnetic field, are electrostatically
reflected. Thus, the height of the potential barrier associated with a sheath
adjusts itself so that the flux of electrons to the wall in question just equals the
electron current that is drawn from the wall by the external circuit. If the wall
is electrically isolated, the electron flux is reduced to the point which is equal
to the ion flux.
Figure 2.8 shows that a schematic illustration of a typical glow discharge
plasma which is in contact with wall surfaces that are either cathodes, anodes,
or electrically isolated (floating). The potential Vp is known as the plasma
potential. The potential of a floating surface relative to the plasma potential is
known as the floating potential Vf. For a Maxwellian velocity distribution, the
floating potential is given by[18]
kTe (eV) π me
Eq. (36) Vf = ln
2e 2 m
Generally, the anodes used in glow discharges are large enough that the
current density is less than the thermal current given by Eq. 33. In this case,
there is a positive space charge sheath at the anode, as shown in Fig. 2.8a,
and the sheath potential drop is between zero and V f . The potential
72 Deposition Technologies for Films and Coatings
of a plasma locks into the most positive surface, provided that the surface is
large enough.[19] If the anode area is so small that the current density must
exceed the thermal current, then the anode potential will be above the plasma
potential, as shown in Fig. 2.8b. The local electric field surrounding the anode
will draw sufficient electrons to the anode to complete the external circuit.*
A large potential difference Vs, approximately equal to the entire potential
applied by the power supply, occurs in the cathode sheath as shown
schematically in Fig. 2.9. The sheath thickness ds is taken to be the region
corresponding to Vs over which the electron density is negligible. For the low
pressure case where the ion mean free path is larger than ds, the ion current
density Ji is related to ds and Vs by the Child-Langmuir law. [11] It is useful to
write this relationship as
where µi is the ion mobility in cm 2/V-sec, Vs is the sheath potential drop in kV,
and ds is the sheath thickness in cm. For an Ar plasma at 1 Torr, µi = 1,200
cm2/V-sec from Table 1. Taking V = 1 kV and ds = 1 cm yields Ji = 0.11 mA/
cm 2.
*The potential rise surrounding a small anode cannot become much larger than
the ionization potential of the gas atoms since this potential causes the sheath
electrons to be accelerated. If these electrons gain sufficient energy to produce
ionization, then the electrons liberated by the ionizing collisions can provide the
anode current flow requirement and no additional rise in potential is required.
Plasmas in Deposition Processes 73
In a low pressure plasma, the ions will fall through the entire sheath
potential and bombard the cathode with an energy about equal to eVs. At higher
pressures, where charge exchange is important, the bombarding flux will
consist of both ions and neutrals having energies considerably less than
74 Deposition Technologies for Films and Coatings
The term Da is called the ambipolar diffusion coefficient. Noting that µe >> µi
(see Eq. 19) permits Da to be approximated as:[11]
Plasmas in Deposition Processes 75
where Di is given by Eq. 22. Thus the effect of the ambipolar field is to enhance
the diffusion of ions by a factor of more than two, but the diffusion rate of the
two species together is primarily controlled by the slower species. In the
presence of a sufficiently strong magnetic field perpendicular to the direction
of diffusion, the electron mobility, and thus the electron diffusion coefficient can
be reduced to the point where it is lower than the ion diffusion coefficient and
therefore rate controlling. Under this condition one can write
4.1 Introduction
the rate at which particles are lost by volume recombination and by passage
to the walls of the apparatus. The rate of ionization depends on a relationship
of the form (see Eqs. 6, 8, and 15)
SUBSTRATES (S)
ELECTRODE
Thus, the rate of ionization depends on the type of gas (through the ionization
cross sectionσion), the gas pressure (through the particle density N), and the
electric field strength (through the electron velocity). Wall losses generally
dominate over volume recombination. Accordingly, the occurrence of a
breakdown, and the resulting formation of a sustaining plasma discharge, in
a given apparatus depends on the gas pressure, the electric field strength,
and on the surface-to-volume ratio of the plasma. Figure 2.16 shows the inter-
electrode breakdown voltage as a function of the product of the gas pressure
p and the electrode spacing d for plane parallel electrodes in air[5] and Ar.[24]
Such curves are determined experimentally and are known as Paschen
curves. Relationships of the same general form apply to the conditions under
which a steady-state discharge can be sustained. In such cases d may be
replaced by a characteristic diffusion length for the plasma vessel.[6][17][25]
The rise in voltage at the low pd side in Fig. 2.16 occurs because the
apparatus is small, or the gas density low, such that electrons are lost to the
walls without colliding with gas atoms and producing ionization. The rise in
the required voltage on the right side happens because the electron energy is
becoming too low to produce ionization. This can occur at high pressures,
because electron collisions with gas atoms become so frequent that the
electrons cannot accumulate sufficient energy to overcome the ionization
potential. It can also occur at a given applied voltage in a very large chamber
where local electric fields in the plasma are too weak to deliver sufficient energy
to the electrons between collisions.
Plasmas in Deposition Processes 81
The functional form of the curves in Fig. 2.16 provides a useful guide for
adjusting the operating conditions within a given device in order to produce a
plasma discharge. Conversely, the relation provides guidance for the
prevention of discharges on surfaces such as the back of cathodes. One
simply places a grounded shield over the surface to be protected ensuring that
the spacing d between the shield and the cathode is small enough that the
breakdown voltage is larger than the voltage required to form and sustain
plasma discharge at the operating pressure of interest.
The above considerations are also important in apparatus scaling. A
discharge sustained in a small apparatus must have a high average electron
energy to counteract wall losses. Such a discharge, with the same electron
density but in a larger apparatus size, will be sustained at a lower average
electron energy. This can in turn change the active species that are produced.
Thus, small-bore discharge tubes are sometimes used in lasers to elevate the
average electron energy to a desired value. Typical glow discharge electron
densities are in the range of 108 to 10 12 cm -3 with average electron energies
of 1 to 30 eV. These conditions are shown in Fig. 2.17 and compared with other
forms of discharges.
The negative glow (NG) region of the plasma is where the primary
electrons expend their energy, and its extent corresponds to the range of their
travel from the cathode.[5][15] The electron energy distribution in the NG is
multimodal. It consists of primary electrons, ultimate electrons (primaries that
have transferred their energy), and much larger numbers of low-energy
ionization products. In the classical glow discharge described in most
Plasmas in Deposition Processes 83
4.5 RF Discharges
(a)
(b)
5.1 Introduction
Figure 2.22. Virtual photon model of an electron-atom collision (from Ref. 32).
e− + CF4 → CF4* + e−
Plasmas in Deposition Processes 89
where the symbol * refers to an excited species. There is evidence that all
electronic excitation processes in CF4 produce dissociation. [33] Furthermore,
because of the two-step nature of the excitation-dissociation process, one
bond is broken, and the primary radicals produced are CF3 and F rather than
CF2 and F2.[34] The active F atoms produced in this way play a very important
role in many plasma etching processes.
He 46 24.58 1.87
Ne 37 21.56 1.71
Ar 26 15.76 1.65
Kr 24 14.00 1.71
Xe 22 12.13 1.81
H2 36 15.43 2.33
N2 36 15.59 2.31
NO 29 9.25 3.13
CO 35 14.04 2.49
O2 32 12.15 2.63
CO2 34 13.81 2.46
C2H2 28 11.40 2.45
CH4 29 12.99 2.23
C2H4 28 10.54 2.65
C2H6 27 11.65 2.31
C3H6 27 9.73 2.77
C3H8 26 11.15 2.33
C6H6 27 9.23 2.92
The ionization process can also result in dissociation. Thus, one has
dissociative ionization reactions of the form
e− + O2 → O2 + + 2e −
It has been noted that plasma discharges often contain relatively large
numbers of low energy electrons which have expended their energy in making
inelastic collisions (this is particularly true in regions of low electric field such
as the negative glow). These electrons can attach to electronegative
molecules to form negative ions[23] such as
e− + O2 → O2−
90 Deposition Technologies for Films and Coatings
O2− → O− + O
CH3 + CH3 → C2 H6
A* + Y → Y+ + A + e−
A* + XY → XY+ + A + e−
A* + XY → X + + Y + A + e−
in which no reaction step requires more than 4.76 eV. This explains why NH3
is commonly used in Si3 H4 plasma-assisted CVD deposition. Similarly, the
following reactions show why nitrous oxide N2 O, rather than O2, is often used
as a parent donor molecule for O atoms during plasma CVD deposition of
oxides.
6.1 Introduction
While films in most of the above application areas are deposited by bias
sputter deposition or plasma-assisted CVD, experiments to isolate ion
irradiation effects are often carried out using ion beams. One example is
illustrated in Fig. 2.26 showing experimental and calculated (Monte Carlo
simulations) densities of CeO2 films deposited at ambient temperature by
simultaneous evaporation of Ce and O2+ irradiation from an ion-beam source.
The experiments were carried out as a function of ion energy Ei for an ion-to-
vapor flux ratio of Ji /Jv of unity.[54] The film density initially increased with
increasing Ei due primarily to ion implantation, recoil implantation, and, to a
lesser extent, sputtering of weakly bound species. However, an optimum Ei
for densification was reached as an increasing fraction of the ion energy was
lost deeper in the lattice leaving vacancies which could not be filled by arriving
vapor species. The optimum ion energy, which depends upon the masses of
the collision partners, was ≈200 eV in this case.
It should be noted, as discussed in Ch. 13, that while ion irradiation is
useful for increasing the density and modifying the microstructure of films
deposited at low temperatures, other irradiation-induced effects such as
increased defect densities occur simultaneously. This is shown in Fig. 2.27
from the work of Huang et al.[55] who studied the effects of Ar+ ion
bombardment during the growth of Ag films at room temperature using a dual
ion beam apparatus. They found that the grain size decreased while the
dislocation number density increased with increasing average irradiation
energy per deposited Ag atom. At elevated growth temperatures, however,
Plasmas in Deposition Processes 97
low-energy ion irradiation can have the opposite effect and actually reduce
residual defect densities in as-deposited films. This has been demonstrated
by Hultman et al.[56][57] who used electron microscopy to investigate the
dislocation structure in epitaxial TiN films deposited by bias magnetron
sputtering of Ti in pure N2 at growth temperatures between 550 and 850oC.
Figure 2.26. Experimental and theoretical values of the density D of CeO2 films
deposited at ambient temperature by simultaneous evaporation of Ce and ion-
beam acceleration of O2+ as a function of ion energy Ei for an ion-to-vapor flux ratio
Ji /Jv = 1. The bulk density of CeO2 is 8.1 g/cm3 (from Ref. 54).
probabilities range from purely physical effects such as implantation and recoil
processes to irradiation-assisted chemistry.
Figure 2.27. The average grain size and dislocation number density nd in Ag films
deposited at room temperature as a function of the average energy 〈E〉 per
deposited atom (from Ref. 55).
ACKNOWLEDGEMENTS
REFERENCES
17. Brown, S. C., Basic Data of Plasma Physics, MIT Press, Cambridge,
Mass. (1959)
18. Chen, F. F., in: Plasma Diagnostic Techniques, (R. H. Huddlestone and
S. L. Leonard, eds.), p. 113, Academic Press, New York (1965)
19. Mittleman, M. H., in: Plasma Dynamics, (F. H. Clauser, ed.), p. 54,
Addison-Wesley, New York (1960)
20. Bohm, D., Burhop, E. H. S. and Massey, H. S. W., in:The Characteristics
of Electrical Discharges in Magnetic Fields, (A. Guthrie and R. K.
Wakerling, eds.), p. 13, McGraw-Hill, New York (1949)
21. Glasstone, S., and Louberg, R. H.,Controlled Thermonuclear Reactions,
p. 459, Van Nostrand, New York (1960)
22. Thornton, J. A., J. Vac. Sci. Technol., 15:171 (1978)
23. McTaggart, F. K., Plasma Chemistry in Electrical Discharges, Elsevier,
New York (1967)
24. Ganger, B., Der Elecktrische Durchschlag, Springer-Verlag, Berlin
(1953)
25. Brown, S. C. and MacDonald, A. D., Phys. Rev., 76:1629 (1949)
26. McDaniel, E. S., Collision Phenomena in Ionized Gases, Ch. 13, Wiley,
New York (1964)
27. Williams, D. G., J. Vac. Sci. Technol., 11:374 (1974)
28. Fraser, D. B., in: Thin Film Processes, (J. L. Vossen and W. Kern, eds.),
p. 131, Academic Press, New York (1978)
29. Waits, R. K., Ibid, p. 131
30. Libby, W. F., J. Vac. Sci. Technol., 16:414 (1979)
31. Transfer and Storage of Energy by Molecules,(G. M. Burnett and A. M.
North, eds.), Wiley-Interscience, New York (1969)
32. Christophourou, L. G., Atomic and Molecular Radiation Physics, p. 6,
Wiley-Interscience, New York (1971)
33. Winters, H. F., Coburn, J. W. and Kay, E.,J. Appl. Phys.,48:4973 (1978)
34. Coburn, J. W. and Winters, H. F., J. Vac. Sci. Technol., 16:392 (1979)
35. Muschlitz, E. E., Jr., Science, 159:599 (1968)
Plasmas in Deposition Processes 105
36. Hollahan, J. R. and Rosler, R. S., in: Thin Film Processes, (J. L. Vossen
and W. Kern, eds.), p. 335, Academic Press, New York (1978)
37. Melliar-Smith, C. M. and Mogab, C. J., Ibid, p. 497
38. Yasuda, H. Ibid, p. 361
39. Kern, W. and Ban, V. S., Ibid, p. 257
40. See Ch. 7
41. Chemisorption and Reactions on Metallic films, (J. R. Anderson, ed.),
Academic Press, New York (1971)
42. Coburn, J. W. and Winters, H. F., J. Appl. Phys., 50:3189 (1979)
43. Thomas, S., J. Appl. Phys., 45:161 (1974)
44. Carriere, B. and Lang, B., Surface Science, 64:209 (1977)
45. Holland, L.,Vacuum Deposition of Thin Films, Ch. 3, Chapman and Hall
Ltd., London (1966)
46. Burkstrand, J. M., J. Vac. Sci. Technol., 15:223 (1978)
47. Burkstrand, J. M., Appl. Phys. Lett., 33:387 (1978)
48. Hansen, R. H. and Schonhom, H., Polymer Lett., 4:203 (1966)
49. Bunshah, R. F. and Raghuram, A. C., J. Vac. Sci. Technol., 9:1385
(1972)
50. Davis, W. D. and Vanderslice, T. A., Phys. Rev., 131:219, (1963)
51. Butler, H. S. and Kino, G. S., Phys. Fluids, 6:1346 (1963)
52. Gorczyca, T. B. and Gorowitz, B., in: VLSI Electronics: Microstructure
Science, 8:69, (N. G. Einspruch and D. M. Brown, eds.), Academic
Press, New York (1984)
53. Greene, J. E., Barnett, S. A., Sundgren, J. E. and Rockett, A., in: Ion-
Beam Assisted Film Growth, p. 101, Elsevier, Amsterdam (1988)
54. Muller, K. H., Applied Physics, A40:209 (1986)
55. Huang, T. C., Lim, G., Parmiagiani, F. and Kay, E., J. Vac. Sci. Technol.,
A3:2161 (1985)
56. Hultman, L., Helmersson, U., Barnett, S. A., Sundgren, J. E. and
Greene, J. E, J. Appl. Phys., 61:552 (1987)
106 Deposition Technologies for Films and Coatings
57. Hultman, L., Barnett, S. A., Sundgren, J.-E. and Greene, J. E.,J. Crystal
Growth,92:639 (1988)
58. Winters, H. F., Ramondi, D. L. and Horne, D. E., J. Appl. Phys., 40:2996
(1969)
59. Tarng, M. L. and Wehner, G. K., J. Appl. Phys., 42:2449 (1971)
60. Cuomo, J. J. and Gambino, R. J., J. Vac. Sci. Technol., 12:79 (1975)
61. Zilko, J. L. and Greene, J. E., J. Appl. Phys., 51:1549 (1980)
62. Brett, M. J. and Parsons, R. R., Can. J. Phys., 63:819 (1985)
63. Shimizu, S., Tsukakoshi, T., Komiya, S. and Makita, Y., GaAs and
Related Compounds, Inst. Phys. Conf. Series 79:91 (1985)
64. Harper, J. M. E., Cuomo, J. J. and Hentzell, H. T. G., J. Appl. Phys.,
58:550 (1985)
65. Sundgren, J. E., Johansson, B. O., Rockett, A., Barnett, S. A. and
Greene, J. E., Physics and Chemistry of Hard Coatings, American Inst.
Phys. Series Conf. Proc. 149:95 (1986)
66. Hasan, M. A., Knall, J., Barnett, S. A., Sundgren, J. E., Markert, L. C.,
Rockett, A. and Greene, J. E., J. Appl. Phys. 65:172 (1989)
67. Fons, P., Hirashita, N., Markert, L. C., Kim, Y. W., Greene, J. E., Ni, W.
X., Knall, J., Hansson, G. V. and Sundgren, J. E., Appl. Phys. Letters,
53:1732 (1988)
68. Winters, H. F. and Kay, E., J. Appl. Phys., 38:2928 (1967)
69. Pan, A. and Greene, J. E., Thin Solid Films, 78:25 (1981)
70. Hoffman, D. W. and Thornton, J. A.,J. Vac. Sci. Technol., 20:355 (1982)
71. Hultman, L., Markert, L. C., Sundgren, J. E. and Greene, J. E., Appl.
Phys. Letters, 53:1175 (1988)
72. Ball, D. J., J. Appl. Phys., 143:3047 (1972)
73. Lau, S. S., Mills, R. H. and Muth, D. G., J. Vac. Sci. Technol., 9:1196
(1972)
74. Stirling, D. J., Appl. Phys. Letters, 9:326 (1966)
75. Palmberg, P. W., Todd, C. T., and Rhodin, T. N.,J. Appl. Phys., 39:4650
(1968)
Plasmas in Deposition Processes 107
76. Jordan, M. R. and Stirland, D. J., Thin Solid Films, 8:221 (1971)
77. Lord, D. G. and Prutton, M., Thin Solid Films, 21:341 (1974)
78. Shimaoka, G., J. Cryst. Growth, 31:92 (1975)
79. Ronsille, R., Boch, R., Destefanis, G. L., and Tissot, J. L., Appl. Phys.
Letters, 44:679 (1984)
80. Comfort, J. H., Gaverick, L. M., and Reif, R., J. Appl. Phys., 62:3388
(1987)
81. Gaverick, L. M., Comfort, J. H., Uyeh, T. R., Reif, R., Baiocchi, F. A. and
Luftman, H. S., J. Appl. Phys., 62:3398 (1987)
82. Yu, M. L., Appl. Phys. Letters, 40:986 (1982)
83. Bodo, P. and Sundgren, J. E., J. Vac. Sci. Technol., A2:1498 (1984)
84. Bodo, P. and Sundgren, J. E., Thin Solid Films, 136:147 (1986)
3
Donald M. Mattox
1.0 INTRODUCTION
108
Surface Preparation 109
ation, interface formation, and film growth. These, in turn, affect film
properties such as adhesion, pinhole density, porosity, film microstruc-
ture, morphology and mechanical properties. Often local surface prop-
erties determine film properties such as pinholes which determine the
product yield. Surface treatments that do not influence the product in a
desirable way are unnecessary and expensive.
Surface preparation is an integral part of any film/coating deposition
process. The objective of surface preparation processes is to allow the
fabrication of an acceptable product in the most reproducible and
economical way. In many cases there are allowable trade-offs between
surface preparation and subsequent processing. For example, an
increase in the deposition temperature may decrease the surface clean-
ing requirements. As the technological demands on films and coatings
increase, the need for better and more reproducible surface preparation
techniques also increases.
There is a wide variety of approaches to surface preparation and
each film-substrate couple, deposition process, and function requires
specific techniques and development. Typically, surface preparation
processes are developed empirically and controlled by good processing
specifications.
Process specifications and travelers are the key to obtaining repro-
ducible surface preparation processing, fabrication processes, and thus
product reproducibility. Specifications define the materials, equipment
and procedures that are to be used. Travelers define what has been done
to each individual part or lot. Specifications are the end-product of a
surface preparation development program. Travelers should contain a
response by the operator (e.g., time, meter reading, temperature, etc.).
An important factor in surface preparation is the condition of the
initial surface. A process developed for one surface condition may not
be satisfactory for another surface condition. The initial substrate
material, condition and history (contamination) should be known, and its
condition and properties should be specified where possible.
Monitoring of the surface preparation is often difficult since any
testing of the surface usually contaminates the surface. Generally,
processing relies on following specifications and possibly monitoring and
testing samples from each lot of surfaces.
In addition to the surface preparation process, the handling and
storage of prepared surfaces is an important part of the fabrication process.
If the prepared surfaces are used immediately or if the final step of the
cleaning process is done as part of the deposition process, the problems of
110 Deposition Technologies for Films and Coatings
2.0 CONTAMINATION
2.1 Recontamination
4.4 Fluxing
from the surface and changes the surface pH. Ajax™ cleaner contains
abrasives and care must be taken to eliminate large chunks which can scratch
surfaces. A major problem with soaps is that metal ions such as the calcium
and magnesium which are found in hard water (high content of ionic material)
make the soaps insoluble and leave a residue. Therefore de-ionized water
should be used for detergent cleaning. There is a tendency for people to use
too much soap in a solution giving problems with rinsing and residues,
particularly if the solution is used cold. About 1 tablespoon of detergent per
gallon of water is generally sufficient.
The author has been told that a slurry of carbon black (from burning
acetylene) in de-ionized water mechanically abraded on a glass surface is very
effective in removing absorbed organic contaminants—I have no first hand
experience with this technique.
with high pressure fluid jets (2000 - 3000 psi) is a standard cleaning
procedures.
Spraying may be performed at low pressure (50 psi) or at high pressure
(1000 psi). Spray systems often use copious amounts of material so the liquid
is usually recycled. This means that after the fluid becomes contaminated
above a certain level it must be replaced. With increasing concern about
solvent vapors, many of the newer systems are self-contained with condens-
ers to trap the vapors and allow them to be recycled. Some systems allow the
purification of the solvents by distillation.
Vapor degreasers operate by putting a cold part in hot vapor above a vapor
degreaser “sump”. The solvent condenses on the surface and flows off into the
sump. Cleaning action only occurs during the condensation process, and
when the part reaches a temperature where the solvent doesn’t condense,
cleaning stops and the part should be removed. Parts should never be
immersed in the sump fluid. Fluid in the sump should be changed when it
becomes contaminated. Figure 3.2 shows a schematic of a typical old-style
industrial degreaser for cleaning large parts either by spraying or by vapor
degreasing. This type of system allows the escape of vapors and is becoming
increasingly undesirable.
Figure 3.3. Metal-metal oxide equilibria diagram for hydrogen plus water as a
function of temperature.
After fluid cleaning and rinsing it is important to dry the surface quickly
in order to prevent the liquid film from collecting particles. Drying may be done
by blowing the surface with filtered gas (from a liquid nitrogen tank) or by
displacing the water by a high vapor pressure solvent such as anhydrous
alcohol which dries rapidly. The best technique is an “alcohol vapor dry” where
the cold surface is immersed in the vapor above a heated anhydrous alcohol
sump. The cold surface condenses the alcohol vapor which flows off into the
sump taking water and particulates with it. When the surface becomes hot
condensation ceases and the hot part, when withdrawn, will rapidly dry. Spin
drying tends to leave liquid along the outside edges of the substrate which may
result in contamination of this area. If spin drying is used the part should be
flooded with copious amounts of ultrapure water during spinning.
Anhydrous alcohol, which displaces water and dries quickly, is one of the
best materials with which to wipe and flush surfaces—it leaves the least
residue; however it is not a very good solvent. Alcohol should only be used with
polyethylene gloves. Isopropyl alcohol (IPA) is most commonly used since
it requires no denaturant. Ethyl alcohol is generally more pure but requires the
use of denaturants. Alcohol is denatured to avoid tax and accountability.
Denaturants range from ethyl ether to kerosene (over 200 denaturants
allowed). Low residue denaturants include methanol (5% by vol.) and acetone
(10% by vol.). It is best to use pure (undenatured) alcohol if possible.
Anhydrous alcohols can take up water from the atmosphere and lose their
ability to displace water in the drying operation
Drying and outgassing is especially important for polymers and
porous materials which absorb solvents and water. It is often easier to dry
and outgas prior to placing the materials in a deposition chamber. The
usual technique is to heat the material (to some temperature that doesn’t
degrade it) in a vacuum (vacuum bake) or desiccated environment. A
common mistake is to vacuum bake the material for an insufficient time—often many
Surface Preparation 133
8.0 PLASMAS
Plasmas are gaseous media which contain enough ions and electrons
to be electrically conductive and generally volumetrically neutral. Energy is
introduced into the plasma by the acceleration of electrons in a DC, RF or
microwave field. These electrons then fragment, excite, and ionize particles
by collisions. A processing plasma is one that is used in processing a
material. In a processing plasma, the volume density of the various gaseous
Surface Preparation 135
Figure 3.4. Plasma generation configurations: (a) DC diode, (b) DC diode with
permanent magnets giving a planar magnetron (c) RF plasmas with planar
electrodes immersed in the plasma, electrodes external to a dielectric wall and a
coil immersed in the plasma, (e) electron emitter (thermoelectron) with magnetic
confinement and (e) microwave cavity.
energetic ions and neutrals with a spectrum of energies that bombard the
cathode.
In order to sustain a discharge, the secondary electrons must create
enough ions to compensate for losses. If the anode or ground surface is
brought too close to the cathode, the discharge is extinguished. This effect
can be used to confine the DC discharge to areas of the cathode surface where
bombardment is desired—other areas may have the bombardment prevented
by having a ground shield in closed proximity to the surface. The Paschen
curve gives the relationship between breakdown voltage and the minimum
anode-cathode separation in a gaseous environment. Insulator surfaces
cannot be used as cathodes in a DC diode configuration since charge buildup
on the surface will prevent ion bombardment.
In addition to causing the ejection of secondary electrons, high energy
ions and neutrals which impinge on the target (or other surfaces) cause the
physical ejection of surface atoms (physical sputtering) by momentum
transfer processes. The sputtered particles leave the surface at higher-than-
thermal energies but may be rapidly thermalized by collisions in the gas
phase. The sputtered particles may be scattered back to the target surface;
this effect is more prominent the higher the gas pressure. Some of the
energetic ions that bombard the cathode may be reflected as high energy
neutrals.
The electrical current measured in the DC cathode circuit is the sum of
the charge due to the ion flux to the target and the secondary electron flux away
from the surface. Therefore, the cathode current density and cathode voltage
do not specify the flux and energy of the impinging ions. However these
measurements (along with gas pressure and gas flow) are typically used to
specify the plasma parameters in DC diode plasma processing.
Typically a DC diode discharge plasma is “weakly ionized” with many
more neutral particles than ions (104-107 : 1). It will also have a low electron
temperature and an even lower ion temperature. If molecular gas species are
present in the discharge, many radical species will be formed in the plasma
and they will generally greatly outnumber the ions.
Any surface in contact with the plasma will be subjected to a flux of ions,
neutrals and electrons. A sheath potential will be developed because of the
greater mobility and energy of the electrons as compared to the ions. This wall
potential (typically 3 - 10 volts) will accelerate ions from the plasmas, giving
rise to ion scrubbing of the surface.
In plasma processing, the DC diode configuration has many advantages:
(i) a rather uniform plasma can be generated over large areas; (ii) power
138 Deposition Technologies for Films and Coatings
input (watts/cm2) can be very high;(iii) the power supplies are rather simple,
inexpensive and powerful; (iv) process reproducibility can be attained by
controlling the geometry, gas pressure, and target power (current and
voltage); and(v) sputtering of surfaces may be used as a source of depositing
material. It also has some disadvantages: (i) surface geometries can result
in focusing effects giving non-uniform bombardment; (ii) electron heating of
surfaces can be extensive; and(iii) insulating surfaces cannot be bombarded.
RF Discharge: At high frequencies in a capacitively-coupled discharge,
the electrons oscillate in the changing field thus gaining energy, and by
collision with atoms, create ions and more electrons. Typical RF power
supplies operate at 13.56 MHz (USA industrial frequency) with peak-to-peak
voltages of greater than 1000 volts. The plasma acts as a low density electrical
conductor and the RF field penetrates quite some distance into the plasma.
When the driven RF electrode is a conductor, the surface is bombarded by ions
from the plasma during the half-cycle that the electrode is negative.
If the surface of the RF electrode is an insulator (backed by a conductor),
the metal-insulator-plasma acts as a capacitor and the surface potential that
appears on the insulator surface alternates between a low positive potential
(because the electrons have a high mobility) and a higher negative potential
(because the ions have a relatively low mobility). Ions are extracted from the
RF plasma during the negative portion of the cycle and bombard the insulator
surface. The RF potentials in the plasma can be determined using capacitive
probes. The ion energies bombarding a surface may be determined using a
sampling orifice, a retarding grid and a mass spectrometer.
In capacitively-coupled RF discharges, the plasma potential, hence the
sheath potential at the electrodes, can have a time-varying value of tens to
hundreds of volts. When the electrodes have different effective areas, the
plasma potential can also have a large DC potential with respect to one or more
of the electrodes. These factors affect the distribution of ion energies incident
on the electrode surfaces in an RF discharge. Small area electrodes will attain
higher voltages than large area electrodes and the electrode potentials can be
varied using external capacitance in the circuit.
The amount of energy that is coupled into the RF discharge depends on
the impedance matching (reflected power) and coupling losses to other
surfaces (stray losses). In RF plasma processing, it may be important to
determine just how much energy is actually being coupled into the
plasma.[42] RF power may be coupled to the plasma using metal electrodes
Surface Preparation 139
fields, the plasma (ions and electrons) may be confined and steered into a
processing chamber.
In plasma processing, some of the advantages of the electron emitter
configurations are:(i) the flux of electrons is independent of other plasma and
electrode processes; (ii) very high plasma densities can be attained; iii) the
plasma properties can be controlled by controlling the electron emission; and
(iv) the electron beam can be used as a source for thermally vaporizing
material. Disadvantages are:(i) need for well controlled and long life electron
emitting sources, and(ii) plasma non-uniformity over large areas and complex
surfaces.
Low strength (50 - 500 gauss) magnetic fields may be used to confine the
electrons and increase their path length in any plasma system. There are a
number of ways to establish magnetic fields in plasma chambers including:
(i) internal permanent magnets,(ii) external permanent magnets, (iii) external
electromagnets, and (iv) moving magnets. Permanent magnets have the
advantage that they may be placed in such a way as to position the field lines
in a desirable manner; however, getting a uniform magnetic field over a large
or complex surface is difficult.
Magnetron enhanced plasma configurations have many advantages
including: (i) confining the plasma to a small region, (ii) increased ionization
and plasma density, (iii) may be operated at low pressures where gas phase
collisions are reduced. Disadvantages include:(i) non-uniform magnetic fields
give non-uniform plasma generation; (ii) isolation of the plasma to a small
region of the processing chamber requiring auxiliary plasma sources in some
applications; and (iii) low pressure processing can give rise to a flux of high
energy reflected neutral which may affect the processing in an undesirable
manner.
tunnel and the reactor walls. The etching in a barrel reactor with an etch tunnel
depends on long-lived activated species and the etching is isotropic.
To achieve high reaction rates, one needs high plasma densities and a
large number of reactive species at reasonable power densities. These
characteristics can be increased by increasing the electron-atom collision
probability by:
! Short mean free paths (diode)—“high” pressures (<1 torr)
! Auxiliary electron source (triode)—low pressures (0.01- 0.2
torr)
! Increased path length (magnetron)—very low pressures(<0.01
torr)(Hill)
! Microwave plasma excitation
Flow uniformity is extremely important to etch/cleaning uniformity. Gas
is typically introduced through a series of orifices or in some cases porous
diffusers (though these may clog up easily). Large orifices allow high pressure
regions and electron trapping that give local high density plasma that affect
uniformity.
In high pressure reactors, the electrode spacing is small and plasma
uniformity is difficult to obtain. Various techniques are used to hold the plasma
over the driven electrode. The use of guard rings on the edge of the driven
electrode is the most common technique.
In low pressure plasma reactors, an auxiliary electron (or plasma) source
is used to sustain the plasma and allow the decoupling of the plasma source
and the driven electrode. This allows more process variation to be used.
Electrode spacing is larger but the non-symmetry of the plasma may make
plasma uniformity difficult to achieve, particularly when varying process
parameters. The higher plasma densities may also increase the plasma
sheath potential giving rise to increased radiation damage of the wafer, but it
provides more directional ion bombardment therefore better directional etch-
ing.
In very low pressure reactors, the use of the magnetic fields at high
plasma densities results in a lowered plasma sheath potential so a biased
electrode may be useful.
The reactive etching/cleaning process gives volatile species which may
be deposited in other parts of the system under different conditions and may
have a detrimental effect on the gas handling/pumping system, and may be
a source of particulates in the etching system.[70]
Surface Preparation 147
The more electronegative the element, the higher the chemical bond strength
one would expect. Active bonding sites may become saturated (“poisoned”)
by reacting with molecules in the ambient atmosphere (oxygen, OH, etc.) so
activation of a surface will degrade with time. The activation process may also
permanently change the polymer surface by increasing crosslinking.
Plasma treatment of polymer surfaces with inert gas species may give
surface texturing, and the improved bond strengths are then attributed to
mechanical interlocking.
Mechanical activation of metal surfaces by mechanical brushing just
prior to film deposition is a technique that gives improved adhesion of vacuum
deposited coatings on steel.[79][80]
Plasma deposited polymer films (plasma polymerization) have high
concentrations of dangling bonds and are adherent to many surfaces and may
act as good coupling layers (primer) for subsequent metal deposition if used
before the unsaturated bonds become saturated.
Activation of ionically bonded solids may be by exposure to radiation
which creates point defects which may act as bonding sites. Electrons and
photon radiation of insulator and semiconductor surfaces prior to film deposi-
tion have been used to enhance the adhesion of the film,[81] probably by
changing the nucleation behavior.
Sensitization of a surface means adding a small amount of material to
the surface to act as nucleation sites for adatom nucleation. This may be less
than a monolayer of material. In electroplating, the addition of nucleating
agents (Sn - stannate, Zn - zincate) to the surface of difficult-to-plate metals
such as Ti, Al, Zr, and U[82] allows the deposition of adherent metal coatings
(example, zincate process for Al, ASTM -B-253). In electroplating, the
sensitization process often involves simultaneous etching and displacement
plating.
150 Deposition Technologies for Films and Coatings
Various materials are used to sensitize polymer surfaces for bonding and
electroplating (Teflon™—napthelenides or alkali metals, Nylon™— iodine). In
plasma processing, polymer sensitization is the addition (chemisorption) of a
surface species which acts as a coupling agent to react with the depositing
atoms. One sensitization technique is plasma activation with the addition of
a coupling agent (usually oxygen) to the active site; this coupling agent in turn
reacts with other organics (amine epoxy treated with oxygen plasma then
coated with urethane) or with depositing metal atoms.
Oxygen plasma treatment of polymer surfaces has been shown to form
an oxygen complex with the carbon in the plastic.[83]-[85] The deposition of
copper allows the copper to react with the oxygen giving improved adhe-
sion.[86]
Some silicon surfaces have been preserved by coating with a metal such
as Ga,[97] In[98] or I[99] onto the clean surface and then evaporating the species
from the surface as an in situ technique.
13.0 SAFETY
REFERENCES
11. Sowell, R. R., Cuthrell, R. E., Bland, R. D., and Mattox, D. M., J. Vac.
Sci. Technol., 11:474 (1974)
12. Vig, J. R., J. Vac. Sci. Technol., A3:1027 (1985)
13. Grunze, M., Strasser, G., and Elshazly, O., J. Vac. Sci. Technol.,
A4:2396 (1986)
14. Holland, L., Vacuum, 26:97 (1976)
15. Bouwman, R., van Mechelen, J. B., and Holscher, A. A., J. Vac. Sci.
Technol., 5:91 (1978)
16. Newhouse, R. D., Microelectronic Manuf. Test, 9:1 (1986)
17. Meeks, R. F.,Contamination Control Training Manual, General Electric
report 74ND-3 (GEPP-121) available from NTIS
18. Malczewski, M. L., Borkman, J. D., and Vardian, G. T., Solid State
Technol., 29(4):151 (1986)
19. Goldsmith, S. H. and Grundelman, G. P., Solid State Technol., 28:219
(1985)
20. Grant, R. D., Mat & Design, 9:22 (1988)
21. Balcar, G. and Woelfel, M., Met Finish, 83(12):13 (1985)
22. Bibliography on Chemical Cleaning of Metals, Vol. 1 (#52135), Vol. 2
(#52129), available from NACE (National Association of Corrosion
Engineers), PO Box 218340, Houston, TX 77218
23. Cherepnin, N. V., Treatment of Materials for Use in High Vacuum,
Ordentlich, Isreal (1976)
24. Sundahl, R. C., J. Vac. Sci. Technol., 9:181 (1972)
25. Manko, H. H., Solders and Soldering, Ch. 2, McGraw-Hill (1981)
26. Brazing Manual, Ch. 4, American Welding Society (1975)
27. Jackson, L. C., Adhesives Age, p. 23 (Dec.1974)
28. Physical Principles of Ultrasonic Cleaning, Vol. 1, (L. D. Rozenberg,
ed.), Plenum Press (1973)
29. Cieslak, W. R., Proc. ASM Third Conf. on Electronic Packaging:
Materials and Processes & Corrosion in Microelectronics, Minneapolis,
MN (April 28-30, 1987)
30. Fredrick, J. R., Ultrasonic Engineering, Wiley (1965)
31. Walker, R., Treatise on Clean Surface Technology, (K. L., Mittal, ed.),
1(3) Plenum Press (1987)
32. Walker, R., TSF 119, 223, 84
33. Holland, L., The Properties of Glass Surfaces, Ch. 6, Wiley (1964)
154 Deposition Technologies for Films and Coatings
34. Norstrom, H., Ostling, M., Buchta, R., and Petersson, C. S., J.
Electrochem. Soc., 132:2285 (1985)
35. Saito, J., Ishikawa, T., Nakamura, T., Konagai, M., and Takahashi, K.,
Jpn. J. Appl. Phys., 25:1216 (1986)
36. Ishikawa, Y., Ikeda, N., Kenmochi, M., and Ichinokawa, T., Surf. Sci.,
159:256 (1985)
37. Olefjord, I., Brox, B., and Jelvestam, J., J. Electrochem. Soc., 132:2854
(1985)
38. Faust, C. L., Metal Finish, 82:29 (1984)
39. Shigolev, P. V., Electrolytic and Chemical Polishing of Metals, Freund
Pub. (1974) from the Russian
40. Smith, F. J., R & D Mag, 30, 54 (1988)
41. Holland, L., The Properties of Glass Surfaces, Ch. 5, Wiley (1964)
42. Horwitz , C. M., J. Vac. Sci. Technol., A1:1795 (1983)
43. Dahimene, M. and Asmussen, J., J. Vac. Sci. Technol., B4:126 (1986)
44. Goebel, D. M., Hirooka, Y., and Sketchy, T. A., Rev. Sci. Instrum.,
56:1717 (1985)
45. McDaniel, E. W., Collision Phenomona in Ionized Gases, Wiley (1964)
46. Hollahan, J. R., and Bell, A. T., Techniques and Applications of Plasma
Chemistry, J. Wiley (1972)
47. McTaggert, F. K., Plasma Chemistry in Electrical Discharges, Elsevier
(1967)
48. Kushner, M. J., J. Appl. Phys., 53:2923 (1982)
49. Thornton, J. A., J. Vac. Sci. Technol., 15:188 (1978)
50. Berg, R. S. and Kominiak, G. J., J. Vac. Sci. Technol., 13:403 (1976)
51. Kowalski, Z. W., J. Mat. Sci. Lett., 6:69 (1987)
52. Betz, G., Surf. Sci., 92:283 (1980)
53. Malherbe, J. B., Hofmann, S., and Sanz, J. M., Appl. Surf. Sci., 27:355
(1986)
54. Mathews, A. and Gethin, D. T., Thin Solid Films, 117:261 (1987)
55. Achard, B., Gruzza, B., and Pariset, C., Surf. Sci., 160:L519 (1985)
56. Fonash, S. J., Solid State Technol, 28(4):201 (1985)
57. Sawin, H. H., Solid State Technol, 28(4):211 (1985)
58. Kominiak, G. J. and Mattox, D. M., Thin Solid Films, 40:141 (1977)
Surface Preparation 155
59. Baker, W. A., and Mossman, A. L., The Matheson Gas Data Book,
Matheson Co.
60. Webber, J.,Microelectronic Manufacturing and Testing, p. 40 (Jan 1985)
61. Boyd, H. and DeBord, D., Microelectronic Manufacturing and Testing,
8:1 (April 1985)
62. Choe, D. H. G., Knapp, C., and Jacob, A.,Solid State Technol, 28(3):65
(1985)
63. Nordstrom, H., Buchta, R., Runovc, F., and Klund, P. W., Vacuum
32:737 (1982)
64. Oehrlein, G. S., Clabes, J. G., and Spirto, P., J. Electrochem. Soc.,
133:1002 (1986)
65. Pang, S. W., J. Electrochem. Soc., 133:784 (1986)
66. Geis, M. W., Lincoln, G. A., Efremow, N., and Piacentini, W. J., J. Vac.
Sci. Technol., 19:1390 (1981)
67. Winters, H. F., Coburn, J. W., and Chuang, T. J., J. Vac. Sci. Technol.,
B1:469 (1983)
68. Poulsen, R. G., J. Vac. Sci. Technol., 14:266 (1977)
69. Broydo, S., Solid State Technol, 26(4):159 (1983)
70. Poll, H. U., Meichsner, J., and Steinrucken, A., Thin Solid Films, 112:
369 (1984)
71. Kelber, J. A.,Plasma Treatment of Polymers for Improved Adhesion To
be published in Vol 119 of MRS Proceedings (D. M., Mattox, J. E. E.,
Baglin, R. Gottschall, and C. D. Batich, eds.)
72. Bodo, P. and Sundgren, J.-E., Thin Solid Films, 136:147 (1986)
73. Wheeler, D. R. and Pepper, S. V., J. Vac. Sci. Technol., 20:442 (1982)
74. Suzuki, K., Christie, A. B., and Howson, R. P., Vacuum, 36:323 (1986)
75. Bodo, P. and Sundgren, J.-E., J. Appl. Phys., 60:1161 (1986)
76. Schonhorn, H., Ryan, F. W., and Hansen, R. H., J. Adhesion, 2:93
(1970)
77. Sowell, R. R., DeLollis, N. J., Gregory, H. J., and Montoya, O., Recent
Advances in Adhesion, (Lieng-Huang Lee, ed.), pp. 77–89, Gordon &
Breach (1973)
78. Ouellette, R. P., Barbier, M. M., and Cheremisinoff, P. N., Low-
temperature Plasma Technology Applications, Technomic Publishing
79. Schiller, S., Foerster, H., Hoetzsch, G., and Reschke, J., Thin Solid
Films, 72:351 (1980)
156 Deposition Technologies for Films and Coatings
80. Schiller, S., Foerster, H., Hoetzsch, G., and Reschke, J., Thin Solid
Films, 83:7 (1981)
81. Gazecki, J., Sai-Halasz, G. A., Alliman, R. G., Kellock, A., Nyberg, G.
L., Williams, J. S., Appl. Surf. Sci., 22/23:1034 (1985)
82. Dini, J. W. and Johnson, H. R., ASTM Spec. Pub. 830, (R. T. Webster
and C. S. Young, eds.), p.113-123 (1984)
83. Burkstrand, J. M., J. Vac. Sci. Technol., 16:363 (1979)
84. Burkstrand, J. M., J. Vac. Sci. Technol., 15:223 (1978)
85. Burkstrand, J. M., Appl. Phys. Lett., 33:387 (1978)
86. Hosokawa, T. and Hosokawa, N., J. Vac. Sci. Technol., 16:348 (1979)
87. Sharp, D. J. and Panitz, J. K. G., Surf. Sci., 118:429 (1982)
88. Sproul, W. D. and Richman, M. H.,J. Vac. Sci. Technol., 12:842 (1975)
89. Mattox, D. M., Thin Solid Films, 18:173 (1973)
90. Osaka, T., Nagata, H., Nakajima, E., and Koiwa, I., J. Electrochem.
Soc., 133:2345 (1986)
91. Elmore, G. V. and Hershberger, R. F., J. Electrochem. Soc., 121:107
(1974)
92. Berg, R. S. and Kominiak, G. J., J. Vac. Sci. Technol., 13:403 (1976)
93. Campbell, P. and Green, M. A., J. Appl. Phys., 62:243 (1987)
94. Liberman, R. and Klein, D. L., J. Electrochem. Soc., 113:957 (1966)
95. Ingrey, S., Lau, W. M., McIntyre, N. S., J. Vac. Sci. Technol., A4:984
(1986)
96. McClintock, J. A., Wilson, R. A., and Byer, N. E., J. Vac. Sci. Technol.,
20:241 (1982)
97. Wright, S. and Kroemer, H., Appl. Phys. Lett., 36:210 (1980)
98. Yang, H. T. and Berry, W. S., J. Vac. Sci. Technol., B(2):206 (1984)
99. Liberman, R. and Klein, D. L., J. Electrochem. Soc., 113:957 (1966)
4
Rointan F. Bunshah
157
158 Deposition Technologies for Films and Coatings
electron beam heated sources. For zinc and aluminum, deposition rates
as high as 25 µm per second have been reported using electron beam
evaporation sources.
The thickness limits for thin and thick films are somewhat arbitrary. A
thickness of 10,000 Å (1 µm) is often accepted as the boundary between thin
and thick films. A recent viewpoint is that a film can be considered thin or thick
depending on whether it exhibits surface-like or bulk-like properties.
Historically the first evaporated thin films were probably prepared by
Faraday[1] in 1857 when he exploded metal wires in a vacuum. The
deposition of thin metal films in vacuum by Joule heating was discovered in
1887 by Nahrwold[2] and was used by Kundt[3] in 1888 to measure refractive
indices of such films. In the ensuing period, the work was primarily of
academic interest concerned with optical phenomena associated with thin
layers of metals, researches into kinetics and diffusion of gases, and gas-
metal reactions.[4][5] The application of these technologies on an industrial
scale had to await the development of vacuum techniques and therefore
dates to the post World War II era, i.e., 1946 and onwards. This proceeded
at an exponential pace in thin films and is covered in an excellent review by
Glang[6] on evaporated films and in other chapters of the Handbook of Thin
Film Technology[7] as well as in the classic text by Holland.[8] A more recent
reference on the Science and Technology of Surface Coatings[9] includes
material on PVD techniques as well as the other techniques for surface
coatings. The work on mechanical properties of thin films has been reported
in several review articles.[10]-[15]
The work on the production of full-density coatings or self-supported
shapes by high deposition rate PVD processes started around 1961
independently at two places in the U.S.A. Bunshah and Juntz at the
Lawrence Livermore Laboratories of the University of California produced
very high purity beryllium foil,[16]-[21] titanium sheets,[22] and studied the
variation of impurity content, microstructure and mechanical properties with
deposition conditions, thus demonstrating that the microstructure and
properties of PVD deposits can be varied and controlled. At about the same
time, Smith and Hunt were working at Temescal Metallurgical Corporation in
Berkeley on the deposition of a number of metals, alloys and compounds and
reported their findings in 1964.[23][24] The development of evaporation
processes in the U.S.S.R is described in the Appendix kindly supplied to the
author by Dr. A. V. Demchishin of the Paton Electric Welding Institute, Kiev.
In the years between 1962 and 1969, there was considerable effort on
the part of various steel companies to produce Al and Zn coatings on steel
using HRPVD techniques on a production scale.[25][26] In 1969, Airco
Evaporation 159
2.0 SCOPE
3.1 Preamble
bombarded by high-energy gas ions which sputter off the material present
on the surface. This results in a constant cleaning of the substrate (i.e., a
removal of surface impurities by sputtering) which is desirable for producing
better adhesion and lower impurity content. This ion bombardment also
causes a modification in the microstructure and residual stresses in the
deposit. On the other hand, it produces the undesirable effects of decreasing
the deposition rates since some of the deposit is sputtered off, as well as
causing a considerable (and often undesired for microelectronic applications)
heating of the substrate by the intense gas ion bombardment. The latter
problem can be alleviated by using the supported discharge ion-plating
process[31a,b] where the substrate is no longer at the high negative potential;
the electrons necessary for supporting the discharge come from an auxiliary
heating tungsten filament. The high gas pressure during deposition causes
a reasonably uniform deposition of all surfaces due to gas-scattering as
discussed above.
In the sputtering process, illustrated schematically in Fig. 4.3, positive
gas ions (usually argon ions) produced in a glow discharge (gas pressure:
20 to 150 mTorr) bombard the target material (also called the cathode)
dislodging groups of atoms which then pass into the vapor phase and deposit
onto the substrate. Alternate geometries of importance in various processing
applications are shown in Fig. 4.4. For example, hollow cathode sputtering
would be the ideal geometry for coating the outer surface of a wire.
Sputtering is an inefficient way to induce a solid-to-vapor transition. Typical
yields (atoms sputtered per incident ion) for a 50 eV argon ion incident on a
metal surface are unity. Thus the phase change energy cost is from 3 to 10
times larger than evaporation.[32] Thornton[32] has provided an excellent
review on sputtering as applied to deposition technology. The reader is also
referred to the proceedings of a special conference on "Sputtering and Ion-
Plating."[33]
The deposition rates for the various processes are indicated in Table
4.1. The deposition rates of the evaporation and ion-plating processes are
much higher than those of the sputtering process. Recently, Schiller and
Jasch,[228] reported on large scale industrial applications of deposition of Al
on strip steel continuously at a deposition rate of 20 µ/min. It should be noted
that sputter deposition rates at the high side (approximately 10,000 Å/min)
with diode sputtering can only be obtained for target materials of high thermal
conductivity like copper, since heat extraction from the target is the limiting
parameter. For most materials, it is much lower, i.e., 50 to 1,000 Å/min. With
magnetron sputtering, much higher deposition rates are obtained (see Ch.
5 in this volume).
164 Deposition Technologies for Films and Coatings
dNi
Eq. (1) = (2πmkT )−½ p
A e dt
dN e
Eq. (1a) = ( 2 πmkT ) −½(p* − p ) cm2 sec −1
A e dt
dN e
Eq. (2) = α ν ( 2 πmkT ) −½(p* − p )
A e dt
dMr ( σ, θ) Me
Eq. (3) = cos φ cos θ
dA r πr 2
Figure 4.5. Surface element dA r receiving deposit from a small-area source dAe.
(From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used with
permission of McGraw-Hill Book Company.)
dMr M
Eq. (4) = e cos φ
dAr πr 2
For a uniform deposit thickness, the point source must be located at the center
of the spherical receiving surface such that r is a constant and cosθ = 1.
In high rate evaporation conditions, e.g., using a high power electron
beam heated source, the thickness distribution is steeper than with a point
or small area source discussed above. This has been attributed by some
Evaporation 169
combination with high vacuum gages (such as the hot cathode ionization
gage and/or capacitance manometer). A partial pressure gage is highly
desirable particularly for ultra-clean applications as well as for leak hunting.
Evaporation Sources: These are discussed separately in Sec. 6).
Substrate Holders and Heaters: Substrate holders may be very
simple for stationary flat substrates or can incorporate quite complex motions
as illustrated by planetary or rotating devices. The reason for this is to ensure
deposition thickness uniformity and control over a large number of small
parts such as lenses or silicon wafers. Substrate heating can be accomplished
by radiant heaters with refractory wires or quartz lamps acting as the heat
source. Occasionally, substrates are directly heated by a scanning or diffuse
electron beam.
Deposition Rate Monitors: These are discussed in Sec. 8.
The simplest vapor sources are resistance heated wires and metal
foilsof various types shown in Fig. 4.9.
Figure 4.9. Wire and metal-foil sources. (A) Hairpin source. (B) Wire helix. (C) Wire
basket. (D) Dimpled foil. (E) Dimpled foil with alumina coating (F) Canoe type.
(From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used with
permission of McGraw-Hill Book Co.)
Since the electrical resistance of the source is small, low voltage power
supplies, 1 to 3 kW, are recommended. The current in the source may range
from 20 to 500 amps. In some cases, the evaporant is electroplated onto the
wire source.
The principal use of wire baskets is for the evaporation of pellets or
chips of dielectric materials which either sublime or do not wet the wire on
melting. In such cases, if wetting occurs, the turns of the baskets are shorted
and the temperature of the source drops.
The rate of evaporation from such sources may vary considerably due
to localized conditions of temperature variation, wetting, hot spots, etc.
Therefore, for a given thickness of film, the procedure is to load the source
with a fixed weight of evaporant and evaporate to completion or use a rate
monitor and/or thickness monitor to obtain the desired evaporation rate and
thickness.
Si which reach a vapor pressure of 10-2 torr before melting. Hence, they can
sublime and produce a sufficiently high vapor density. The contact area
between the evaporant and the source crucible is held to a minimum. Figure
4.10 shows such a source designed by Roberts and Via.
Figure 4.10. Chromium sublimation source after Roberts and Via. The electric
current flows through the tantalum cylinder (heavy lines). (From Handbook of Thin
Film Technology. © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book
Co.)
Figure 4.11. Optically dense SiO sources. (A) The Drumheller source. (B)
Compartmentalized source. (After Vergara, Greenhouse and Nicholas.) (From
Handbook of Thin film Technology. © 1970, McGraw-Hill. Used with permission of
McGraw-Hill Book Co.)
Figure 4.12. Oxide crucible with wire-coil heater. (From Handbook of Thin Film
Technology. C 1970, McGraw-Hill. Used with permissionof McGraw-HillBookCo.)
180 Deposition Technologies for Films and Coatings
Figure 4.13. DaSilva crucible source. (From Handbook of Thin Film Technology.
© 1970, McGraw-Hill. Used with permission of McGraw-Hill Book Co.)
Electron beam heated sources have two major benefits. One is a very
high power density and hence a wide range of control over evaporation rates
from very low to very high. Two, the evaporant is contained in a water-cooled
copper hearth thus eliminating the problem of crucible contamination.
The evaporation rate for pure metals like Al, Au, Ag, which are good
thermal conductors, from water-cooled copper crucibles decreases due to
heat loss to the crucible walls. In such cases, crucible liners of carbon and
other refractory materials are used.
Any gun system must consist of at least two elements—a cathode and
anode. In addition, it is necessary to contain these in a vacuum chamber in
order to produce and control the flow of electrons, since they are easily
182 Deposition Technologies for Films and Coatings
Figure 4.16. Simple electron beam guns. (a) Work-accelerated gun. (b) Self-
accelerated gun.
Evaporation 183
Electron beam guns may be further subdivided into two types depending
on the source of electrons: (i) thermionic gun and (ii) plasma gun.
Thermionic Gun: In thermionic guns, the source of electrons is a
heated wire or disc of a high temperature metal or alloy, usually tungsten or
tantalum. Such guns have the limitation of a minimum operating gas
pressure of about 1 x 10-3 torr. Higher pressures cause scattering of the
electron beam as well as a pronounced shortening of the cathode life (if it is
a wire or filament) due to erosion by ion bombardment. Figure 4.17 shows
examples of thermionic electron beam heated work-accelerated sources.
The close cathode gun shown in Fig. 4.17A is not a desirable configuration
since molten droplet ejection from the pool impinging on the cathode will
terminate the life of the cathode due to low melting alloy formation. Thus
cathodes are hidden from direct line-of-sight of the molten pool and the
electron beam is bent by electrostatic fields (Figs. 4.17B and 4.17C) or
magnetic field (Figs. 4.18 and 4.19) generated by electromagnets. The latter
is a preferred arrangement since variation of the X and Y components of the
magnetic field can be used to scan the position of the beam on the molten
pool surface.
Figure 4.18. Bent-beam electron gun with water-cooled evaporant support. (With
permission of Temescal Metallurgical Co., Berkeley, CA). (From Handbook of Thin
Film Technology. © 1970, McGraw-Hill. Used with permission of McGraw-Hill Book
Co.)
Figures 4.17, 4.18 and 4.19 show linear cathodes (i.e., wires or rods)
and are referred to as transverse linear cathode guns. Figure 4.20 shows a
disc cathode which is characteristic of a high power Pierce type electron
beam gun. Low power Pierce type guns may have a hair pin filament or awire
loop as the cathode. In either case the beam geometry of the Pierce gun is
different than that of the transverse linear cathode guns. In some instances,
the electron emitter assembly is located at a distance from the crucible in a
separately pumped chamber to keep the pressure below 1 x 10 -3 torr, with
a small orifice between the emitter chamber and the crucible chamber for the
passage of electrons.
Figure 4.22. Schematic of the hot hollow cathode electron beam gun.
Evaporation 189
This technique with many names was first used by Smith and Turner[64]
in 1965 to deposit thin films in a vacuum chamber using a pulsed ruby laser.
Systematic studies in the 1970’s were performed to provide a better
understanding of the physics of laser-solid interactions and the related
issues of deposition mechanisms and film quality. More recently the process
has been extensively used for growing highly crystalline dielectric films,[65]
compound semiconductor epitaxial layers, layers for band-gap
engineering,[66][67] and very extensively for high T c superconducting
films.[68][69] The reader is referred to an excellent review by Cheung and
Sankur.[70]
Evaporation 193
Figure 4.25. Ionization rate monitor designs and arrangements. (A) After Schwarz.
(B) After Giedd and Perkins. (C) After Perkins. (D) After Dufour and Zega. (From
Handbook of Thin Film Technology. © 1970, McGraw-Hill, Used with permission
of McGraw-Hill Book Co.)
Figure 4.27. (A) Schematic drawing and (B) circuit diagram of a microbalance
constructed from a micro-ammeter movement. (Hayes and Roberts.) (From
Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used with permission
of McGraw-Hill Book Co.)
Figure 4.29. Oscillator crystal holders for deposition monitoring. (A) After Behrndt
and Love. (B) After Pulker. (From Handbook of Thin Film Technology. © 1970,
McGraw-Hill. Used with permission of McGraw-Hill Book Co.)
Figure 4.30. Schematic of an RF sputtering system (after Davidse and Maissel) with
optical-thickness monitor. (From Handbook of Thin Film Technology. © 1970,
McGraw-Hill. Used with permission of McGraw-Hill Book Co.)
Evaporation 199
Evaporation
203
204 Deposition Technologies for Films and Coatings
Table 4.6. (Cont'd)
Evaporation 205
Figure 4.34. Flash-evaporation mechanisms. (A) Belt feeder. (Harris and Siegel.)
(B) Worm-drive feeder with mechanical vibrator. (Himes, Stout, and Thun, Braun
and Lood.) (C) Disk feeder (Beam and Takahashi.) (D) Disk magazine feeder.
(Marshall, Atlas, and Putner.) (E) Mechanically vibrated trough and cylinder source.
(Richards.) (F) Electromagnetically vibrated powder dispenser. (Campbell and
Hendry.) (From Handbook of Thin Film Technology. © 1970, McGraw-Hill. Used
with permission of McGraw-Hill Book Co.)
Table 4.7. Flash Evaporation of Materials
Evaporation
207
208 Deposition Technologies for Films and Coatings
Table 4.7. (Cont'd)
Evaporation 209
Reactants Products
Ti (metal atoms) TiC (deposit)
C2 H2 (gas) H2 (gas)
Reaction
Interface
a pulsed laser beamwherethe pulse rate and pulse width can be appropriately
adjusted to control the rate of material generation and fragmentation.
Moreover, in many cases, the energy of the laser beam can also be used as
source for plasma excitation.
Both of these approaches have been explored. A process developed
by Bunshah et. al.[98] for the synthesis of cubic boron nitride involves boric
acid as an reactant, which can be easily evaporated from a resistance-
heated tungsten boat. In addition to the ease of evaporation, this process
also excludes the toxicity problems associated with fine boron particles
which can be produced during e-beam evaporation of boron. A similar
approach can be extended to evaporation of carbon using a low melting point
carbon compound such as adamantine. It is likely that many new materials
hitherto difficult to synthesize may possibly be deposited using this routine.
Moreover, this novel approach may contribute to further development in
reactive MBE processes and other vapor deposition processes involving
organometallic compound reactants.
The use of pulsed laser beams in an ARE type of process has been
demonstrated in recent literature on high Tc superconducting films. Films
with high Tc (90 K) and high critical current density (0.7 x l06 A·cm-2 at 77 K)
have been produced.[99] It is claimed that pulsing of the laser beam avoids
fractionation of the compound and hence good control of film stoichiometry
is achieved. It is also suggested that the photon energy is sufficient to
activate the reactive gas/metal species thereby increasing their reactivity,
leading to increase in oxygen concentration in the deposited films.
New Plasma Excitation Modes and Geometries. As discussed
earlier, the attributes of the ARE processes are due to the possibility of
controlling the plasma parameters independently of the deposition process.
However, improvement in excitation and confinement of the plasma, as well
as control and optimization of plasma parameters in the ARE processes, are
likely to enhance the process capabilities. Recent developments include (i)
the use of inductively coupled RF with parallel plate RF geometries, and (ii)
the use of multiple filaments and anodes with magnetic confinement. These
enhancements have led to substantial improvements in film properties as
well as process control. Examples are high rate deposition of a-Si-H
films,[100] transparent conducting films on polymeric substrates(101) and TiSx
and MoSx[102][103] films with variable x values.
Two additional modes of ionization are being explored. Currently an
auxiliary RF excitation source similar to that reported by Oeschner[104] is
being developed for use in ARE. It is believed that the high electron density
222 Deposition Technologies for Films and Coatings
Ti + C → TiC Ti + CH → TiC + H
Ti + CH2 → TiC + 2H Ti + CH3 → TiC + 3H
the order ofa few hundred angstroms width between the tapered crystallites.
It also contains a high dislocation density and has a high level of residual
stress. Such a structure has also been called “Botryoidal” and corresponds
to Zone 1 in Figs. 4.39 and 4.40.
As the substrate temperature increases, the surface mobility increases
and the structural morphology first transforms to that of Zone T, i.e., tightly
packed fibrous grains with weak grain boundaries, and then to a full density
columnar morphology corresponding to Zone 2 (Fig. 4.40).
The size of the columnar grains increases as the condensation
temperature increases. Finally, at still higher temperatures, the structure
shows an equiaxed grain morphology, Zone 3. For pure metals and single
phase alloys, T1 is the transition temperature between Zone 1 and Zone 2
and T2 is the transition temperature between Zone 2 and Zone 3. According
to Movchan and Demchishin’s original model,[75] T1 is 0.3 Tm for metals, and
0.22 - 0.26 Tm for oxides, whereas T2 is 0.45 - 0.4 (Tm is the melting point in
°K).
Thornton’s modification shows that the transition temperatures may
vary significantly from those stated above and, in general, shift to higher
temperatures as the gas pressure in the synthesis process increases.
It should be emphasized that:
1. The transition from one zone to the next is not abrupt but
smooth. Hence the transition temperatures should not be
considered as absolute, but as guidelines.
2. All zones are not found in all deposits. For example, Zone T is
not prominent in pure metals, but becomes more pronounced
in complex alloys, compounds, or in deposits produced at
higher gas pressures. Zone 3 is not seen very often in
materials with high melting points.
The reader is referred to a more extensive description given by Greene
in this book in Ch. 13, which includes a discussion of the effects of substrate
surface roughness and pressures.
Most thick deposits exhibit a strong preferred orientation (fiber texture)
at low deposition temperatures and tend towards a more random orientation
with increasing deposition temperature. Figure 4.41 shows the evolution of
a large-grained columnar morphology in a Be deposit from a much larger
number of fine grains which were originally nucleated on the substrate. As
growth proceeds, only those grains with a preferred growth direction survive,
presumably due to considerations of the minimization of surface energy.
Evaporation 229
10.2 Texture
Residual stresses in deposits are of two types. The first kind arises
from the imperfections built in during growth (the so-called growth stresses).
An increase in deposition temperature produces a marked decrease in the
magnitude of this stress.[127][137] The other source of residual stress is due
to the mismatch in the coefficient of thermal expansion between the substrate
and the deposit. Its magnitude and size depend on the values of the thermal
expansion coefficients as well as the thickness and size of the substrate and
deposit. The influence of a negative bias on the substrate produces a
compressive stress in the deposit, which reaches a maximum value at -200
to -300 V DC bias and then decreases.[133]
High residual stresses can cause plastic deformation (buckling or
bending), cracking in the deposit or the substrate, or cracking at the
substrate-deposit interface. The latter can be minimized by grading the
interface, i.e., producing the change in material over a finite distance instead
of producing it abruptly at a sharp interface. A graded interface can be
produced by gradually changing the deposition conditions or by interdiffusion,
which is enhanced by higher substrate temperature or increased kinetic
energy of the vapor species.
10.4 Defects
Figure 4.47. Flake defects in (a) and (b) produced by accelerated coating
deposition on foreign particles. Glass bead peening incorporates flake into the
coating (c) or knocks it out and forms a pit (d) (Boone et al.). (Courtesy of Amer. Inst.
of Physics.)
Long term creep rates have been measured and for gold they vary
from 10-7 to 10-4 min-1 depending on load, dimensions and the amount of
prestrain.[148] The estimates of the relative elastic and plastic extension at
fracture vary from completely elastic to an almost even mixture of elastic and
plastic deformation.
Fracture in ductile gold single crystal films[154] results from a localized
plastic deformation with resultant thinning of the film and a rise in stress level.
Eventually the smaller cracks formed in this manner join to cause fracture.
The dislocations—necessary for the deformation—are not the grown-in
dislocations but those which nucleate and multiply in discontinuous regions.
Most observations show no necking prior to fracture. The maximum stress
appears to correspond to that needed to propagate cracks from flaws
existing in the specimen. In polycrystalline nickel, the fracture is the “clean-
cleavage” type.[149]
Mechanical Properties of Thick Condensates and Bulk Deposits:
Table 4.11 lists the mechanical properties of thick deposits of metals, alloys,
refractory compounds, and laminated structures. In many cases, the
mechanical test data are quite extensive showing yield strength, ultimate
tensile strength, hardness, and ductility as a function of grain size, deposition
temperature, and test temperature. One of the features of the data is that the
properties of thick deposits of metals and alloys are very similar to those of
wrought materials which are produced by the conventional processes of
melting, casting, mechanical working, and heat treatment.
We consider each type of material separately since the behavior of
metals and alloys is vastly different from that of refractory compounds.
The early work in this area was that of Bunshah,[17][18] Bunshah and
Juntz, and Smith[23] who deposited thick films of Be, Ti, and Cu, respectively,
[22]
Evaporation
245
246 Deposition Technologies for Films and Coatings
Table 4.11. (Cont'd)
Table 4.11. (Cont'd)
Evaporation
247
248 Deposition Technologies for Films and Coatings
Table 4.11. (Cont'd)
Evaporation 249
σys = σo + kd-½
where σys is the yield strength, d is the grain diameter, and σo and k are
constants. Figure 4.51 shows an example of this relationship for Ni-20Cr
alloy.
250 Deposition Technologies for Films and Coatings
Figure 4.51. Yield stress vs. inverse square root of average diameter for Ni-20Cr
alloy at 25°C. ∆ - wrought; O - deposited; # - Wilcox et al.; $ - Webster. (J. Vac.
Sci. Technol., Vol. 12, No. 2:662 (1975), Refs. 12 and 13).
For all these metals and alloys, the yield strength, ductility and
hardness values correspond to those of the same materials produced by
casting, mechanical working, and recrystallization. The variation of yield-
strength and hardness with grain size, i.e., Hall-Petch type relationships,
were also very similar between the deposited and wrought materials, small
variations being ascribable to differences in grain morphology and preferred
orientations. The Ni-20Cr alloy showed good strength at 1000°C and also
obeyed the Hall-Petch relationship.
The Hall-Petch relationship is also obeyed by thick films of Cu and Ag
to grain-sizes as small as 0.05 µm as shown by Nenioto, Jumbou and
Suto.[194] Thus, these thick deposits behave as true engineering materials.
Chambers and Bower[195] studied the mechanical properties of 18-8
stainless steel, gold, and magnesium, and showed that their tensile properties
were very similar to their wrought counterparts.
Smith, Kennedy, and Boericke[122a] studied the (α + β) type Ti-6Al-4V
alloy. They showed that the tensile properties are very similar to the wrought
material except for a much smaller value in percent elongation due to
Evaporation 251
which confirms the model proposed by Mott[225] who suggested that the ideal
creep-resistant material is one with a fine grain size in which the grain
boundaries are filled with some substance, say a refractory oxide, to inhibit
the motion of grain boundaries.
Perhaps the most interesting result from Movchan’s work[196][197][226]
is that the dispersed phase alloys show a maximum in room temperature
ductility in the W-ZrO2 system at 1 vol.% ZrO2, in the Fe-Al2 O3 system at 0
3 vol.% Al2O3, and in the Fe-NbC system at 0.1 vol.% NbC. The yield
strength and tensile strength do not show such a maximum but monotonically
increase with volume fraction of the oxide phase. The significance of this
observation lies in the possibility of increasing the ductility of MCrAlY
coatings which, in turn, would result in increased resistance to spalling,
thermal shock and fracture, thus improving the performance of the coating.
One might speculate on reasons for this effect including strain-relaxation
sites at particle matrix interface, or at grain boundaries due to the greatly
increased grain boundary area, favorable changes in residual stress
distribution in the coating possibly due to changes in elastic modulus or
strength, increased toughness or crack propagation resistance conferred by
the dispersed phase particles, change in crystallographic texture, etc.
Movchan, Badilenko, and Demchishin[227] have recently presented a
very detailed treatment on the regulation of microstructure and mechanical
properties of thick vacuum condensates with the help of dispersed phases.
They give a detailed theoretical model of(i) the influence of dispersed phases
on grain size; (ii) the size and shape of dispersed particles as affected by
deposition parameters; (iii) strength and ductility of two phase condensates
as influenced by the grain size, particle size, mean free path, nature of the
particle (deformable vs. nondeformable) and particle-matrix adhesion
energies; (iv) steady-state creep behavior. The model is then confirmed
by the experimental results. As a good illustration of one of these points,
Fig. 4.5 shows the difference in strength and ductility vs. volume fraction
of second phase when the latter is deformable or nondeformable. For
both types of particles, there is a ductility maximum at a particular Dg / l
ratio, but the strength behavior is diametrically opposite showing a monotonic
increase for a nondeformable particle and a minimum for the deformable
particle. Dg is the grain size in the plane perpendicular to the vapor flux
direction and λ is the interparticle spacing. This model forms an excellent
basis for design of experiments to study the effect of dispersed phases on
the structure and properties of MCrAlY alloys.
Evaporation 253
superplasticity is developed.
Laminate Composites. Laminate composites are attractive and
preferable over fibrous composites because of their uniform properties in the
plane of the sheet. In comparison to mechanical methods of producing
laminate composites, e.g., bonding of sheets or foil, physical vapor deposition
techniques are very suited to the production of such composites, particularly
if each lamellae is to be very thin (0.01 to 1 µm thickness) in order to improve
the strength and toughness of the composite.
From theoretical considerations, it may be expected that the mechanical
properties of microlaminate composites would follow an adaptation of the
well known Hall-Petch relationship.[192][193] (Yield strength or hardness =αd-
½ where d is a characteristic microstructural parameter such as grain
stress of such brittle coatings is the Hertzian fracture test which measures
the fracture stress and the surface energy at the fracture surface.[198] Colen
and Bunshah[182] used this test to measure the fracture behavior of Y 2O3
deposits of various grain sizes.
Figure 4.52 shows the variation in microhardness with deposition
temperature for Al2O3 and ZrO2 from the work of Movchan and Demchishin,(75)
showing that the behavior of these oxide deposits is quite different in one
respect from that of metals (Fig. 4.47). The hardness falls when the structure
changes from tapered crystallites (Zone 1) to columnar grains (Zone 2) as
with metals. However, unlike metals, the hardness increases markedly as
the deposition temperature rises from 0.3 Tm to 0.5 Tm. The authors attribute
this to a more “perfect” material produced at the higher deposition temperature
due tovolume processes of sintering. A similar hardness curve was obtained
for Y2 O3 deposits. [182]
Figure 4.53 from the work of Raghuram and Bunshah[127] also shows
a very marked increase in microhardness of TiC deposits on going from 0.15
Tm (500°C) to 0.3 Tm (1000°C). The hardness increases for the oxides and
TiC with increasing deposition temperature. Both sets of results may be
explained by the following concept. Since the strength of ceramics is very
adversely effected by growth defects and at the higher deposition temperature,
the occurrence of these defects is markedly reduced, the hardness (or
strength) increased very significantly. However, it should be noted that
the absolute value of the hardness of the oxides is much lower than that of
the carbides. Thus thepossibility of a different explanation for the “similar”
256 Deposition Technologies for Films and Coatings
behavior of these materials, i.e., the hardness increase with the deposition
temperature needs to be investigated.
The hardness data on sputtered TiC and TiN coatings are quite similar
to those produced by evaporation techniques.[186]
Impurities in the deposit can be classified into two types, metallic and
nonmetallic. Knowing the composition of the evaporant, the experimental
conditions (temperature and time), certain thermodynamic data (vapor
pressure and activities in solution), the composition of the vacuum environment
during the experiment, and the types of melt-crucible reactions, if any, it is
possible to estimate the impurity content of the distillate. The amount of
impurity transfer to the vapor phase and hence in the deposit (assuming a
sticking coefficient of unity) depends directly on the partial pressures of the
impurity and the basis metal. For metallic impurities, one assumes that each
impurity behaves independently of the other and, using Rayleigh’s equation,
the metallic impurity content of the distillate may be estimated. Experimental
verification has been demonstrated by Bunshah for beryllium.[20]
The amount of nonmetallic impurity (C, O2, N 2, and H2) is estimated
as follows: for example, for oxygen,
Evaporation 257
∑ υG
ppm (atomic) O2 =
υM
APPENDIX
A. V. Demchishin
E. O. Paton Electric Welding Institute
Kiev, Ukraine, U.S.S.R
REFERENCES
42. Smith, H. R. and Hunt, C. D’A., Trans. Vac. Met. Conf., p. 227, Am.
Vac. Soc. (1965)
43. Hayashi, C. and Oku, Y., Trans. Vac. Met Conf., p. 257, Am. Vac. Soc.
(1966)
44. Cocca, M. A. and Stauffer, L. H., Trans. Vac. Met. Conf., p. 203, Am.
Vac. Soc. (1963)
45. Morley, J. R., ibid, p. 186
46. Berghaus, B., German Patent No. 683,414 (1939)
47. Sabalev, L. P., et al., US. Patent 3,783,231 (Jan. 1, 1974); 3,793,179
(Feb. 19, 1974)
48. Dorodnov, A. M., Soviet Phys. Tech. Phys., 23:1058 (1978)
49. Osipov, V. A., et al., Soviet Rev. Sci. Inst., 21:1651 (1978)
50. Wroe, H., Br. J. Appl. Phys., 9:488-491 (1958)
51. Gilmour, A. S., Jr., Lockwood, D. L., Proc. IEEE, 60:No. 8:977-991
(1972)
52. Snaper, A. A., “Arc Deposition and Apparatus,” US. Patent No.
3,625,848 (1971)
53. Snaper, A. A., “Arc Deposition and Apparatus,” US. Patent No.
3,836,451 (1974)
54. Sablev, L. P., “Apparatus for Vacuum Evaporation of Metals under the
Action of an Electric Arc,” US. Patent No. 3,783,231 (1974)
55. Sablev, L. P., “Apparatus for Metal Evaporation Coating,” US. Patent
No. 3,793,179 (1974)
56. Sanders, D. M., Handbook of Plasma Processing Technology, (S.
Rosnagel, J. J. Cuomo, and W. D. Westwood, eds.), p. 419, Noyes
Publications (1990)
57. Martin, P. J., et al., Thin Solid Films, 153:91 (1987)
58. Martin, P. J., Netterfield, R. P., and Kinder, T. J., Thin Solid Films, 193/
194:77 (1990)
59. Vasin, A. I., Dorodnov, A. M., et al., Sov. Tech. Phys, Lett., (Engl.
Trans. of Pis’ma Zh. T Fiz.), 5: No. 23-24, (1979)
60. Ehrich, H., Hasse, B., et al., Proc. 8th Intl. Conf. Discharge Appl., 591-
592, 596, Essen Univ. (1985)
264 Deposition Technologies for Films and Coatings
61. Dorodnov, A. M., Kunetsov, A. N., et al., Sov. Tech. Phys. Lett., Engl.
Trans. of Pis’ma Zh. T Fiz., 5: No. 418-419 (1979)
62. Ehrich, H., J. Vac. Sci. Technol., A6: 134-138 (1988)
63. Meassick, S., Chan, C., and Allen, R., “Thin Film Deposition Techniques
using the Anodic Arc,” to be published
64. Smith, H. M. and Turner, A. F., Appl. Opt., 4:147 (1965)
65. Sankur, H., DeNatale, J., Gunning, W., and Nelson, J. G., J. Vac. Sci.
Technol., A5:2869 (1987)
66. Cheung, J. T. and Madden, J., J. Vac. Sci. Technol., B5:705 (1987)
67. Cheung, J. T., Chen, J. S., and Otsuka, N., Proc. IRIS IR Detector
Specialty Meeting, Seattle, WA (Aug. 1987); This work was followed
by several other similar investigations presented at the 34th Nat’l.
Symp. of Am. Vac. Soc., Anaheim, CA (Nov. 1987)
68. Dijkkamp, D., Venkatesan, T., Wu, X. D., Shaheen, S. A., Jisrawi, N.,
Min-Lee, Y. H., Mclean, W. L., and Croft, M., Appl. Phys. Lett., 51:619
(1987)
69. Wu, X. D., Dijkkamp, D., Olgale, S. B., Ina, A., Chase, E. W., Miceli, P.
F., Chang, C. C., Tarascon, J. M., and Venkatesan, T., Appl. Phys.
Lett., 51:861 (1987)
70. Cheung, J. T. and Sankur, H., Solid State and Materials Sciences,
15:63 (1988)
71. Greer, J. A., J. Vac. Sci. Technol., 10(4):1821 (1992)
72. Nimmagadda, R., Raghuram, A. C., and Bunshah, R. F., J. Vac. Sci.
Tech., 9 (1972)
73. Santala, T. and Adams, M., J. Vac. Sci. Tech., 7:s22 (1970).
74. Shevakin, Y. F., Kharitonova, L. D., and Ostrovskaya, L. M.,Thin Solid
Films, 62:337 (1979)
75. Movchan, B. A. and Demchishin, A. V., Fizika Metall, 28:653 (1969)
76. Auwarter, M., US. Patent 2,920,002 (1960)
77. Bunshah, R. F. and Raghuram, A. C., J. Vac. Sci. Technol., 9:1385
(1972)
78. Hoffman, D. and Liebowitz, D., J. Vac. Sci Technol, 9:326 (1972)
Evaporation 265
119. Sherman, M., Bunshah, R. F., and Beale, H. A., J. Vac. Sci. Technol.,
11:1128 (1974)
120. Kennedy, K., Trans. of the Vacuum Metallurgy Conf., p.195, Am. Vac.
Soc. (1968)
121. Mah, G. and Nordin, C. W., Proc. of the 16th Ann. Conf., p. 103, Soc.
of Vac. Coaters, Chicago (1973)
122. Paton, B. A., Movchan, B. A., and Demchishin, A. V., Proc. 4th Int'l.
Conf. on Vacuum Metallurgy, p. 251, Iron and Steel Inst. of Japan
(1973)
122a. Smith, H. R., Jr., Kennedy, K., and Boericke, F. S., J. Vac. Sci. Tech.,
7:S48 (1970)
123. Chambers, D. L. and Bower, W. K.,J. Vac. Sci. Technol.,7:S63 (1970)
124. Agarwal, N., Kane, N., and Bunshah, R. F., Nat’l. Vac. Symp., New
York (1973)
125. Neirynck, M., Samaey, W., and Van Poucke, L., J. Vac. Sci. Technol.,
11:647 (1974)
126. Movchan, B. A., Demchishin, A. V., and Kooluck, L. V., J. Vac. Sci.
Technol., 11:640 (1974)
127. Raghuram, A. C. and Bunshah, R. F., J. Vac. Sci. Technol., 9:1389
(1972)
128. Bunshah, R. F. and Juntz, R. S., J. Vac. Sci. Technol., 9:404 (1972)
129. Mattox, D. M. and Kominiak, G. J., J. Vac. Sci. Technol., 9:528 (1972)
130. Morley, J. and Smith, H. R., J. Vac. Sci Technol., 9:1377 (1972)
131. Mah, G., McLeod, P. S., and Williams, D. G., J. Vac. Sci. Technol.,
11:663 (1974)
132. Stowell, W. R. and Chambers, D.,J. Vac. Sci. Technol.,11:653 (1974)
133. Bland, R. D., Kominiak, G. J., and Mattox, D. M., J. Vac. Sci. Technol.,
11:671 (1974)
134. Bunshah, R. F., unpublished research.
135. Turk, C. F. and Marcus, H. L., Trans. AIME, 242:2251 (1968)
136. Beale, H. A. and Bunshah, R. F., unpublished research
268 Deposition Technologies for Films and Coatings
160. Palatnik, L. S., Ill’inski, A. I., Federov, G. V., and D’yachenko, V. S.,
Izvestra VUZ, Fizika (Soviet Physica Journal) 1:122 (1966)
161. Grunes, R. L., D’Antonio, C., and Kies, F. K., J. Appl. Phys., 36:2735
(1965)
162. Ya Fuks, M., Belozerov, V. V., and Boyko, Y. F., Fizika Metall.,33:571
(1372)
163. Kinosita, K., Maki, K., Nakamizo, K., and Takenchi, K., Jpn. J. Appl.
Phys., 6:42 (1967)
164. Ya Fuks, M., Velozero V. V., and Boyko, Y. F., Fizika Metall., 33:571
(1972)
165. Doljack, F. A. and Hoffman, R. W., Thin Solid Films, 12:71 (1972)
166. Ya Fuks, M., Palatnik, L. S., Belozerov, V. V., Zolotnitsky, Y. V., and
Roschchenko, S. T., Fizika Metall., 36:316 (1973)
167. Pines, B. Y. and Tan, N. S., Fizika Metall., 19:899 (1965)
168. Aleksanyan, I. T., Fizika Metall., 25:947 (1968)
169. Hoffman, R. W., Thin Solid Films, 34:185 (1976)
170. Palatnik, L. S., Federov, G. V., Prokhavulov, A. I., and Federenko, A.
I., Fizika Metall., 20:574 (1965)
171. Palatnik, L. S., Ya Fuks, M., Boiko, B. T., and Pugacheu, A. T., Soviet
Phys. Dokl., English Translation, 8:713 (1964)
172. Oding, A. and Aleksanyass, I. T., Soviet Phys. Dokl., 8:818 (1964)
173. Bunshah, R. F., Vacuum, 27(4):353 (1977)
174. Yamamoto, H. and Kamoshita, G., Trans. Jpn. Inst. Metals, 12:12
(1971)
175. Palatnik, L. S., Ya Fuks, M., Ill’inski A. I., and Alaverdova, O. G., Fizika
Metall., 22:744 (1966)
176. Henning, C. A. O., Boswell F. W., and Corbett, J. M., Acta Met.,23:177
(1975)
177. Ziling, K. K., Pkrovskiy, L. D., and Pohelkin, V. Y., Fizika Metall.,
29:1112 (1970)
178. Palatnik, L. S., Ill’inski A. I., and Ravlik, A. G., Fizika Metall., 19:310
(1965)
179. Henning, C. A. O., Boswell, F. W., and Corbett, J. M.,Acta Met.,23:187
(1975)
270 Deposition Technologies for Films and Coatings
180. Palatnik, L. S., Ill’inski, A. I., Ravhk, A. G., Nechitayls, A. A., and Lyakh,
G. Y., Fizika Metall., 27:1114 (1969)
181. Bunshah, R. F. and Schramm, R. J., Thin Solid Films, 41 (1977) in
press
182. Colen, M. and Bunshah, R. F., J. Vac. Sci. Tech., 13:536 (1976)
183. Furuuchi, S., Sakata, H., and Aiwaka, K., Japan J. Appl. Phys.,
13:1905 (1974)
184. Grossklaus, W. and Bunshah, R. F., J. Vac. Sci. Technol., 12:811
(1975)
185. Wasa, K., Nagai, T., and Hayakowa, S., Thin Solid Films, 31:235
(1976)
186. Mah, G., Norden, C. W., and Fuller, J. F.,J. Vac. Sci. Technol., 11:371
(1974)
187. Henning, C. A. O., Boswell, F. W., and Corbett, J. M.,Acta Met.,23:193
(1975)
188. Palatnik, L. S., Ill’inski, A. I., and Sapelkin, N. P.,Soviet Phys. Solid St.,
8:2016 (1967)
189. Solonovich, I. I. and Startsev, V. I., Problemy Prochn., 1:28 (1973)
190. Palatnik, L. S., Ill’inski, A. I., Biletchanko, N. M., and Sinel’nikova, R.
I., Fiz. Metall., 32:199 (1971)
191. Bunshah, R. F., Gupta, Y. D., and Raghuram, A. C., unpublished data
192. Hall, E. O., Proc. Phys. Soc, Lond., B64:747 (1951)
193. Petch, N. J., J. Iron Steel Inst., 174:25 (1951)
194. Nenioto, M., Jumbou, R., and Suto, H.,Trans. Jpn. Inst. Metals,12:113
(1971)
195. Chambers, D. L. and Bower, W. K.,J. Vac. Sci. Technol.,7:S62 (1970)
196. Movchan, B. A., Demchishin, A. V., and Badilienko, G. F., Thin Solid
Films, 40:237 (1977)
197. Movchan, B. A., Demchishin, A. V., and Kooluck, L. D., Thin Solid
Films, 44:285 (1977)
198. Frank, F. C. and Lawn, B. R., Proc. R. Soc. Lond., 229A:291 (1967)
199. Boone, D. H. and Sullivan, C. P., STP, 520:401, Am. Soc. for Testing
and Materials (1973)
Evaporation 271
244. Palatnik, L. S., Ill’inski, A. I., and Sapelin, N. P., Soviet Physics Solid
State, 8(8):2016 (1967)
245. Palatnik, L. S., Ill’inski, A. I., Biletchenko, N. M., and Sinel’nikova, R.
I., Fiz. Met. Metalloved., 32(6):1312 (1971)
246. Solonovich, I. I. and Startsev, V. I., Problemy Prochnosti, 1:28-30
(1973)
247. Hordon, M. J. and Wright M. A., in Metal-Matrix Composites, Symp. of
the Metallurgical Soc. AIME,DMIC Memorandum 243, pp.10-12 (May
1969)
248. Springer, R. W. and Catlett, D. S., Thin Solid Films, 54:197 (1978)
249. Lehoczky, S. L., J. App. Phys., 49:5479 (1978)
Books
Berry, R. W., Hall, P. M., Harris, M. T., Thin Film Technology, D. Van
Nostrand Co. (1968)
Bhushan, B. and Gupta, B. K., Handbook of Tribology, McGraw-Hill (1992)
Chopra, K. L., Thin Film Phenomena, McGraw Hill Book Co., (1969)
Handbook of Thin Film Technology, (L. I. Maissel, and R. Glang, eds.)
McGraw Hill Book Co. (1970)
Holland, L., Chapman and Hall, Vacuum Deposition of Thin Films, (1968);
The Bible
Ohring, M., Materials Science of Thin Films, Academic Press, (1992)
Physics of Thin Films, Vols. 1-6, Academic Press (1963-1971)
Science and Technology of Surface Coatings, (B. N. Chapman and J. C.
Anderson, eds.) Academic Press (1974)
Techniques of Metals Research, Vol. 1, part 3, (R. F. Bunshah, ed.) John
Wiley & Sons (1968)
Thin Films, Am. Soc. for Metals (1964)
The Use of Thin Films in Physical Investigation, (J. C. Andrews, ed.)
Academic Press (1966)
274 Deposition Technologies for Films and Coatings
Journals
1.0 INTRODUCTION
275
276 Deposition Technologies for Films and Coatings
play a decisive role, as discussed in Ch. 13, in determining film nucleation and
growth kinetics, microstructure evolution, dopant incorporation probabilities,
and hence the physical properties of as-deposited layers. The controlled use
of ion bombardment effects allows a considerable enhancement in the ability
to tailor film properties.
Sputter deposition is inherently a vacuum coating process. In operation,
the source of coating material, termed the “target,” is mounted opposite the
substrates in a vacuum chamber which is then evacuated to a base pressure
which typically ranges from 10-6 to 10-10 Torr*, depending upon the process.
The most common method of providing the ion bombardment necessary for
sputtering is to backfill the evacuated chamber, using a continuous flow of a
gas such as Ar, to a pressure of from 1 to 100 mTorr, and establish a glow
discharge. A negative potential, typically between 0.5 and 5 kV, is applied to
the target in order to initiate positive-ion bombardment while the counterelectrode
(the substrate) is grounded. A sputtering apparatus in which the target and
substrate are opposing parallel plates, shown schematically in Fig. 5.1, is
termed a diode system. The discharge in such a device is commonly operated
in the abnormal negative-glow mode.[2]
The most striking characteristic of the sputtering process is its universal-
ity. Since the coating material is passed into the vapor phase by a physical
momentum-exchange process, rather than a chemical or thermal process,
virtually any material is a coating candidate. DC discharge methods are
generally used for sputtering metals, while an RF potential must be applied to
the target when sputtering nonconducting materials. In some applications,
rather than immersing the target in a plasma, it is more convenient to use a
separate ion-beam source consisting of a self-contained discharge with ion-
acceleration optics.
Sputter-deposition technology includes many variations of the basic
process described above. For example, coatings may be formed by:
1. Employing a target which is a mosaic of several materials.
2. Employing several different targets simultaneously to obtain an
alloy film.
3. Employing several targets sequentially to create a composi-
tionally layered coating.
*The pressure unit of Torr (1 Torr = 1 mm Hg) is a carryover from the time when pressure was
measured with a Hg manometer. Most commercial pressure gauges are still calibrated in Torr
or microns (1 µm Hg = 1 mTorr). Therefore, Torr will be used in this chapter although both
Torr and Pa (SI units) are given in some of the figures. 1 Torr = 133 Pa = 1.33 mbar = 1.316
x 10-3 atm.
Sputter Deposition Processes 277
Figure 5.2. Planar-diode sputtering system of the type used for research end small
production runs. The system can be used for both DC and RF sputtering. (Photo
courtesy of CVD Products, Inc., Rochester, NY)
pressure causes the transport of coating material from the target to the
substrate to be primarily diffusive rather than ballistic and sputtered material
is lost to the walls of the container by scattering. This, coupled with the low
current density, leads to deposition rates which are generally less than 75 nm/
min (4.5 µm/h).
Triode devices, in which additional electrons are injected into the
discharge by thermionic emission from a third electrode, can be used to
produce intense sputtering discharges at low pressures. The deposition rates
that can be achieved with triode devices are also higher than with planar
diodes. For example, high-rate triode sputtering has been used to fabricate
a free-standing 1.3 kg deposit of a Cu-alloy in the form of a cylinder 15 cm in
diameter.[3] However, the complexity of triode designs for obtaining uniform
deposition has, in general, limited their use to special applications.
The recent development of a class of sputtering sources with magnetic
plasma confinement, called magnetrons, has greatly enhanced the capabili-
ties of the sputtering process. There are many forms of magnetrons. They vary
from small ring sources—often referred to as Sputter-gunsTM (Sloan Technol-
ogy, Santa Barbara, CA) and S-gunsTM (Varian Associates, Palo Alto, CA)—
to long rectangular planar magnetrons and cylindrical magnetrons with post
or hollow cathodes. Magnetrons can be used for both DC and RF sputtering
but are particularly effective for DC sputtering, where deposition rates can be
more than an order of magnitude larger than those obtained with planar diodes.
Planar and cylindrical magnetrons can be scaled to large sizes to provide
uniform deposition over very large areas (many m2). In addition, well-designed
magnetrons virtually eliminate substrate heating caused by electron bombard-
ment.
Figure 5.3. Multi-source sputtering system designed for wafer processing. Wafer
batches are passed into and out of the coating chamber through vacuum interlocks.
(Photo courtesy GCA Corporation, Vacuum Industries Division, Somerville, MA)
Sputter Deposition Processes 281
Planar diodes are still widely used, particularly for depositing materials
requiring RF power. However, recent trends find magnetrons replacing planar
diodes for many DC, and some RF, applications. In addition, the magnetrons
have opened up new applications because of their large-area capability and
reduced substrate heating. For example, large in-line systems with vacuum
interlocks use planar magnetron sources to coat 2 m x 3.5 m architectural
glass plates at three-shift production volumes of about 106 m2/yr.[4] Sputtering
is being investigated as a means for depositing selective absorber coatings for
solar heating and for manufacturing photovoltaic cells for direct solar-to-
electrical energy conversion. Because of the reduced substrate heating,
magnetrons are used on a production basis to deposit chromium decorative
coatings on automobile grilles and other exterior trim. Figure 5.4 shows an
automated load-lock sputtering system designed for metallizing plastic
automotive parts.
Almost any vacuum chamber capable of evacuation into the 10-6 Torr
range can be used for sputtering. Provisions are usually required for throttling
the pumping system so that the desired working gas pressure can be
sustained with the pumps in operation. Small planar and gun-type magnetrons
are particularly easy to install. Some forms of cylindrical magnetrons require
special chamber geometries. Chambers used in large production runs
generally include substrate-loading interlocks so that the target surface is not
exposed to the atmosphere between deposition cycles. Examples are shown
in Figs. 5.3 and 5.4.
Sputter Deposition Processes 283
Several review papers written over the last twenty years permit the
interested reader to follow the developments in sputtering technology. An
extensive review of the basic process was published by G. K. Wehner, one of
the most prominent of the early workers, in 1955.[7] Film properties obtained
in early experiments were discussed by E. Kay in a 1962 review.[8] Sputter
deposition processes were reviewed by L. Maissel[9] and Kay[10] in 1966. The
Handbook of Thin Films , published in 1970, contains reviews by Wehner
and Anderson [11] and by Maissel. [12] A review article by Thornton
284 Deposition Technologies for Films and Coatings
Figure 5.6. Variation of the sputtering yield of several materials as a function of Ar+
ion energy at normal angle of incidence. Data from R. V. Stuart and G. K. Wehner,
J. Appl. Phys. 33, 2351 (1962); D. Rosenberg and G. K. Wehner, J. Appl. Phys. 33,
1842 (1962); and R. Behrisch, Ergeb. Exakt. Naturw. 35, 295 (1964).
Sputter Deposition Processes 287
Table 5.1. Sputtering Yields for Various Materials under Argon Ion
Bombardment. Ion energy in eV. Data from Ref. 36.
Note that for typical ion acceleration energies, the sputtering yields of
most metals are near unity and within an order of magnitude of one another.
This is in contrast to evaporation where the rates for different materials at a
given temperature can differ by several orders of magnitude. In addition, the
evaporation rate for a given material varies exponentially with temperature
while the sputtering yield is essentially independent of temperature.
The general dependence of the sputtering yield on the ion angle of
incidence is indicated in Fig. 5.7.[30] In glow-discharge sputtering devices,
the ions generally approach the target in a direction normal to the target
288 Deposition Technologies for Films and Coatings
Figure 5.7. Schematic diagram showing variation of the sputtering yield with ion
angle of incidence for a constant ion energy.
JSMA
Eq. (1) R = 6.23 (nm/min)
δ
Sputter Deposition Processes 289
where J is the ion current density in mA/cm2, S is the sputtering yield in atoms/
ion, MA is the atomic weight in grams, andδ is the density of the target material
in g/cm3.
The reader should be cautious about using Eq. 1 in attempting to predict
absolute sputtering rates, especially in planar diode systems where the
average energy of ions striking the target may be considerably less than Ei =
eVT (VT is the applied target potential), due primarily to inelastic charge
exchange collisions[31] between accelerated ions and neutral sputtering gas
species. S(Ei ) data, on the other hand, are usually obtained from ion beam
experiments carried out in low pressure (long mean-free path) environments
where the ion energy is given by the accelerating energy. The apparent lower
yield in the glow discharge sputtering case (due to the lower average ion
energy) is, however, partially offset by the flux of energetic charge-exchanged
neutrals which are incident at the target.
4 Mi Mt
Eq. (2) ε =
(Mi + Mt)2
of the kinetic energy of the incident particle is transferred to the target particle.
An expression for the yield, which can be written in the form shown in Eq.
3 below, has been derived by assuming perpendicular ion incidence onto a
target consisting of a random array of atoms (a good approximation for a small-
grain polycrystalline material) with a planar surface.[32]-[34]
E
Eq. (3) S = (constant) ε α(Mt/M i)
U
When the ion mass is lower than that of the target atom, it may be
reflected backward in a single collision with a kinetic energy that is still a
significant fraction of its initial energy. For a 180o reflection, this fraction is
(Mi - M t)2
Eq. (4) f =
(Mi + Mt)
Sputter Deposition Processes 291
If Mi > Mt, reflection requires more than one collision and the reflection
coefficient is low.[35]
Since the ions have a high probability of being neutralized prior to impact,
they are reflected as energetic neutrals which are therefore not influenced by
the electric field over the target surface.[36] The flux of reflected species
contributes to substrate heating,[37] particularly in devices operating at low
pressures where the reflected neutralized ions may reach the substrates with
little loss of kinetic energy by gas-phase collisions. Consequently, the
reflected species bombard, and can become entrapped in, the growing
film.[38]-[41]
The energy flux which leaves the cathode via backscattering can be
estimated using the sputtering efficiency[42]-[44] which is defined as the
fraction γ of the bombarding ion energy incident on the target surface, Ein,
which leaves the surface in the backward direction, Eout, in the form of
sputtered atoms or backscattered ions.
Figure 5.9. Sputtering efficiency versus target-to-ion mass ratio. The solid curve
is from the theoretical work of Sigmund (Ref. 42). The experimental data is from
substrate heating experiments with cylindrical-post magnetrons (Ref. 37).
target, the sputtered flux will, in general, be rich in one of the constituents. The
composition of this altered surface layer continues to change until the product
of the partial sputtering yield times the surface concentration for each species
is proportional to its concentration in the target. The process is indicated
schematically in Fig. 5.10. Once a steady-state altered layer is formed, the
composition of the sputtered flux is equal to the bulk target composition.
The thickness and composition of the altered layer will depend on the
target material and sputtering conditions. Typical altered-layer thicknesses
are 3 - 10 nm for single-phase alloys[49][51] and up to several µm for multiphase
alloys.[52] A change in sputtering conditions will in general require an
adjustment of the altered layer. It is important to note that the partial sputtering
yield of a constituent in an alloy or compound will not be the same as for that
constituent by itself because of the difference in binding energies and the
different atomic masses involved in the collision sequence within the alloy or
compound. In an alloy for which the constituent species have similar binding
energies, the low mass species can be expected to have higher partial
sputtering yields. If the masses are similar, the weakly-bound species will
have higher partial sputtering yields.[34][47]-[48] Thus, in the sputtering of most
oxides, the altered layer becomes deficient in the flow-mass oxygen compo-
nent.[47]
294 Deposition Technologies for Films and Coatings
The most complete data on the dependence of the sputtering yield on the
ion species are those collected by Almen and Bruce, shown in Fig. 5.12.[68]
Although the ion energies were considerably above those generally used for
sputter coating technology, they do illustrate trends. Sputtering yields
increase with the mass of the ions and, for a given row in the periodic table,
the rare-gas ions have the highest yields. Of particular interest is the fact
that yields vary much more with ion species (factor of 100 or more) than
296 Deposition Technologies for Films and Coatings
they do with target atom species (factor of 10).[11] This is believed to result
from the bombarding ions forming alloys or compounds with high binding
energies on the surface of the target. Note that the yields for the three target
materials examined in Fig. 5.12 are particularly low for reactive species such
as Be, C, Mg, Si, Ti, and Zr.
Figure 5.12. Sputtering yields for various ions impacting at normal incidence on
Ag, Cu, and Ta surfaces at high energies (45 keV). Data from Ref. 68.
monolayer coverage and no trimer ions from samples with less than two
monolayers. The sputtering yield of monomer, dimer, and trimer ions all
saturated at a coverage of ≈3 monolayers.
In the case of compounds, most of the information available on molecular
sputtering is for alkali halides and oxides where clusters can account for a
significant percent of the total sputtered flux. Coburn et al.[86] showed that the
relative fraction MO/(M + O) of sputtered species from MxOy metal oxide
targets increased with increasing M-O bond energy. Rare gas matrix isolation
spectroscopy was used by Gruen et al.[87][88] to identify Al2 O and AlO
molecular species sputtered from Al2 O3 targets under Ar + bombardment and
TiO and ZrO species from metal targets sputtered with 2 keV O2 + ions.[89]
The only published work on compound semiconductors is for GaAs.
Using 140 eV Ar+ bombardment, comparable to the average impact energy in
many glow discharge deposition experiments, Comas and Cooper[90] found
from post-ionized mass spectroscopy measurements that molecular species
(GaAs, Ga2, As2) amounted to less than 1% of the total sputtered flux.
However, for 6 keV Ar+ ion sputtering, Szymonski and Bhattacharya[91]
observed that at room temperature, sputtered GaAs and As2 molecules
accounted for ~14% and 11% (data uncorrected for the variation in the detector
efficiency as a function of mass), respectively, of the flux. The fraction of
sputtered GaAs molecules was found to increase rapidly for target tempera-
tures above 250oC. This latter effect was explained as being due to enhanced
sputtering from collisional spikes.
E
Eq. (6) ∆N/∆E ∝
(E + U)3
where ∆N/∆E is the differential flux of sputtered particles with energy E and
U is the surface binding energy. In practice, the high-energy tails of
experimentally determined sputtered-atom energy distributions for rare-gas
bombardment energies from≈1 to 10 keV generally follow a E-2 dependence
in agreement with Eq. (6).
Figure 5.14. Average energies (top) and velocities (bottom) of sputtered atoms
ejected by 1.2 keV Kr+ ion bombardment. Data from Ref. 11.
cosine (more emission at large angles) while at higher energies (≈3 keV) it is
over cosine.[10] Under oblique-incidence bombardment, the target atoms are
sputtered in the forward direction from smooth surfaces. However, the
roughness of most practical targets causes the emission to be random. This
is particularly true for polycrystalline targets, where the difference in yield for
different crystallographic directions can lead to an increase in surface
roughness as sputtering proceeds. Thus, a cosine distribution is often a
reasonable approximation for estimating deposition profiles.[11]
The planar diode shown schematically in Fig. 5.15 is the simplest and
probably the most widely used sputtering configuration. Cathode diameters
are typically 10 to 30 cm and the cathode-to-anode spacing≈5 to 10 cm. Such
systems are operated with both DC and RF power supplies. In DC diodes, the
cathode serves a dual capacity. It is the target or source of coating material
as well as the cathode electrode for sustaining the glow discharge and is
generally water-cooled. Often the target consists of a disc of the material to
be sputtered which is attached with solder or conducting epoxy to a backing
plate which serves as part of the cathode-cooling channel. A low-pressure
glow discharge of a type known as an abnormal negative glow[97] is maintained
between the cathode and an adjacent anode which may also serve as the
substrate mounting table, as shown in Fig. 5.15.
302 Deposition Technologies for Films and Coatings
Figure 5.16. Schematic illustration of the charge-exchange process that affects ion
transport across the cathode dark space.
Figure 5.17. Maximum distance from the target at which sputtered Al and Ta
atoms of different initial energies are thermalized in Ar at various pressures.
Data from Ref. 109.
Planar diodes are widely used despite substrate heating and low
deposition rates. The reason is their simplicity and the relative ease with which
planar targets can be fabricated from a wide range of materials. Sputter
cleaning of the substrate and bias sputtering are easily accomplished by
adding an auxiliary anode and applying a negative bias to the substrate holder.
3.3 Magnetrons
The magnetron configuration shown in Fig. 5.20 has been termed the
“cylindrical-post magnetron.”[113]-[115] It provides the simplest geometry for
explaining the principles of magnetron operation.[113]-[118] The cathode
consists of a cylindrical barrel with end plates, all composed of the material
to be sputtered. It is mounted in a chamber with a uniform magnetic field B̄
directed parallel to the cathode axis. The magnetic field is of such strength
308 Deposition Technologies for Films and Coatings
(a few hundred gauss or less) that it affects the plasma electrons but not the
ions. Figure 5.21 shows a typical chamber configuration for cylindrical
magnetrons. A set of solenoidal field coils is positioned surrounding the
cylindrical vacuum wall, which is constructed of a nonmagnetic material. A
magnetic steel shell surrounds the coils and makes contact with the chamber
top and bottom plates which are also fabricated from a magnetic material such
as low-carbon steel. Thus, a low reluctance return path is provided for the
solenoidal flux, as indicated in the figure, with the consequence that the coil
system efficiently provides a uniform magnetic field within the chamber.
Figure 5.21. Chamber and magnetic field coil configuration used for cylindrical-
post magnetron sputtering sources.
potential and on the fourth side by the magnetic field. Anode rings are
located adjacent to the end plates on one or both ends of the cathode.
Therefore, electrons emitted from the cathode must migrate radially across
the cavity in order to reach the anode. Electron collisions of the type required
to sustain a plasma discharge play an essential role in allowing this migration
to occur. Thus, in contrast to the conventional discharge, the electrons are
forced to make the required collisions, and an effective sputtering discharge
is maintained in the cavity.
The electron motion can be understood as follows.[119][120] When an
electron is in a uniform magnetic field, its motion perpendicular to the field
lines can be pictured as an orbit around a field line, as shown in Fig. 5.22a.
Its motion along the field is unimpeded, so that if it has a component of
velocity along the field line its net motion is a spiral as shown in Fig. 5.22b.
Such electrons can be considered to be trapped on magnetic field lines and
can advance to adjacent field lines by making a collision, as indicated
schematically in Fig. 5.22c. An electron will also undergo a drift motion
across the magnetic field if an electric field E is present. However, this
motion, known as ĒxB̄ drift, is not in the direction of the electric field but in
a direction perpendicular to both the electric and the magnetic fields. ĒxB̄
drift has the cycloidal form shown in Fig. 5.22d if the initial electron energy
is small compared to that gained from the electric field, and the more circular
motion shown in Fig. 5.22e if the initial electron energy is large compared
to the electric-field-induced variations during the course of an orbit.
Referring back to Fig. 5.20, a radial electric field also exists in the
annular cavity. The field will be strong in the sheath region adjacent to the
cathode but relatively weak at larger radii. Electrons emitted from the
cathode will therefore undergo motions of the type shown in Fig. 5.22d and
will become trapped in orbits revolving around the cathode. They will be
able to advance radially only by making collisions or by the action of plasma
oscillations which produce azimuthal electric fields and radial drifts.[113][114]
Since the electrons leave the cathode sheath with energies of several
hundred eV, electron collisions with gas atoms have a high probability of
resulting in ionization. The ĒxB̄ drift motions of the primary electrons and
the products of ionization collisions produce an intense azimuthal current
sheet of trapped electrons adjacent to the cathode. Because of the free axial
movement of the electrons along the field lines, the sheet tends to be uniform
along the cathode length. Large numbers of ions are produced which give
rise to uniform sputter-erosion and high sputtering rates along the cathode
barrel.
310 Deposition Technologies for Films and Coatings
3.4 RF Sputtering
Figure 5.33. Schematic drawing of a planar RF diode sputtering device. From Ref.
13.
occurs via the relatively small ion and electron current components that are in
phase with the voltage. Thus, in the equivalent circuit approximation, the
power transfer to produce sputtering occurs as the ion currents pass through
the sheath resistances. Efficient power transfer requires that the RF power
supply operate into a resistive load. Therefore a matching network is used to
introduce inductance, and often capacitance, into the circuit in such a way
that, in combination with the load, they form a resonant circuit.[171] When the
variable matching network components are tuned to resonance, high circulat-
ing currents flow within the resonant circuit. However, the power supply sees
only the resistive component of the load, the current passing from the power
supply to the resonant circuit is in phase with the load and represents the
power passing to the load. Many commercial sputtering sources monitor the
reflected power from the load as an index of how effectively the matching
network is adjusted. The reflected power should be minimized.[32][141][172]
The ion current, and thus the sputtering rate at a given electrode, is
determined by the average difference in potential between the electrode and
the plasma. Thus it is useful to consider the plasma potential as a zero-point
reference voltage in examining the performance of RF sputtering systems.
The electrical character of RF sputtering systems can be classified in
general as being either balanced or single-ended. In a balanced system, both
electrodes are configured as identical sputtering targets and their potentials
are 180o out of phase. The average sputtering voltage is about equal to half
the peak-to-peak applied RF potential. The link center trap is placed at ground
potential to stabilize the system and the chamber walls and substrates are
connected to the center tap ground, as shown in Fig. 5.36. Since this point
is at zero potential relative to the RF voltage, no RF current will flow to these
elements. Furthermore, because of the capacitance in series with each of the
electrodes, there is no DC current path from the plasma to the wall and
substrates and then back through the electrodes into the plasma.[173] Thus
a charge will develop on the capacitors such that the substrates float at a
potential slightly negative with respect to the plasma, just like a floating
electrode in a DC plasma.
In an unbalanced RF system, the electrode on which the substrates
are placed is made considerably larger than the target electrode.[142] This
makes the sheath capacitance large, and the RF voltage drop across the
substrate electrode small, as shown schematically in Fig. 5.37. The
chamber and one side of the link are generally grounded (Fig. 5.35). Again,
the capacitance in both electrode circuits prevents a DC current flow to the
chamber, and a negative bias develops relative to the plasma potential. A
Sputter Deposition Processes 325
potential relative to the plasma potential will exist on the substrates and
chamber wall unless the substrate electrode area is large enough to reduce
this potential to essentially zero and to move the RF balance point to the
grounded end of the link. It is important that these voltage drops be small so
that sputtering from uncontrolled surfaces does not introduce contamination
into the coatings. An impedance may be added to the substrate electrode
circuit so that the potential of this electrode relative to the plasma can be
controlled for purposes of bias sputtering.[173]
The above discussion has been presented in the context of planar diode
sputtering systems. Magnetron sputtering sources can also be used for RF
sputtering. Cylindrical-post,[114][116] cylindrical-hollow,[114][174] planar, [127]
and gun-type[129] magnetrons have all been successfully operated with RF
power. However, some problems are encountered. Magnetron sputtering
technology is basically a DC concept. The cathodes are shaped such that,
in concert with the magnetic field, they form electron traps with specific
symmetry. Anodes are placed to collect electrons which diffuse out of the trap.
326 Deposition Technologies for Films and Coatings
Early ion sources were of the duoplasmatron type, where an ion beam
was extracted through an aperture from a low pressure arc.[176] Hollow-
cathode ion sources were also used.[177] These devices were limited for
practical deposition because of the small ion-beam sizes (≈1 cm). The
recent adaptation of ion thruster technology has provided distributed ion
sources with ion beams of relatively large diameter (≈10 - 30 cm). [175]
328 Deposition Technologies for Films and Coatings
Although these devices cannot compete as deposition sources with the very
large substrate areas that are provided by magnetrons, they are attractive for
ion beam etching and for special deposition applications and research studies.
Sources designed for etching have provided 500 eV, 1 mA/cm2, ion beams that
are 30 cm in diameter with a uniformity of ±5% over 20 cm.[178] Reviews of the
fundamentals of ion beam deposition are provided in Ref. 21 and 179.
growth is a subject of study unto itself and recent reviews may be found in Refs.
22 - 25. Ion irradiation has been shown to strongly affect film nucleation and
growth kinetics, adhesion, film microstructure and chemistry, and hence film
properties. Mechanisms by which ion/surface interactions modify film
nucleation, growth, microstructure evolution, and film properties are dis-
cussed in Ch. 13 while reviews on adhesion[204][205] andion-induced changes
in film chemistry (including trapping, secondary implantation, and prefer-
ential sputtering) [24][206] have been published recently.
As shown schematically in Fig. 5.43, the value and sign of Bext has a
strong effect on the plasma density near the substrate, and hence on the ion
flux, Ji, incident at the substrate, with only a minor effect on the target-atom
flux. For a Ti target sputtered in pure Ar at 20 mTorr with a target-substrate
separation of 6.5 cm, changing Bext from -50 G (opposing the field of the outer
PM pole) to +600 G (reinforcing the field of the outer PM pole) varied the ion-
to-Ti flux ratio Ji/JTi incident at the substrate by a factor of sixty from 0.1 to 6
with the bias held constant at any desired negative value between ~ -15 V
(limited by the difference between the floating Vf and plasma Vp potentials) and
the highest values examined, -100 V. For reactive sputter deposition in N2
(where the primary ion is N2+) under the same conditions, Ji/JTi varied by a
factor of fifty from 0.7 to 35. Vp was negative with Bext set to positive values
and ranged form ~ 0 (Bext = 0 G) to -13 V (Bext > +200 G) in Ar and 0 to -20
V in N2. Using an N2+ ion energy of 20 eV (10 eV per N) to bombard the growing
film, Adibi et al.[210] showed that by varying Ji/JTi from 1 to ≥ 5.2, the
microstructure of metastable NaCl-structure Ti0.5Al0.5N alloys deposited at
250°C could be controllably altered from a porous columnar structure with a
complete (111) texture to a dense completely (002)-oriented structure with no
residual ion-induced defects observable by high-resolution plan-view and
cross-sectional transmission electron microscopy.
ACKNOWLEDGEMENTS
Figure 5.43. Schematic diagram illustrating the effect on the plasma during
sputter deposition of superimposing an external magnetic field B ext which (a)
opposes and (b) reinforces the field of the outer permanent magnet in the
planar magnetron target.
Sputter Deposition Processes 337
REFERENCES
23. Greene, J. E., Motooka, T., Sundgren, J. E., Lubben, D., Gorbatkin, S.
and Barnett, S. A., J. Nucl. Instr. Methods, B27:226 (1987)
24. Greene, J. E., Sol. St. Technol., 30:115 (April, 1987)
25. Greene, J. E., Barnett, S. A., Sundgren, J. E. and Rockett, A., in Ion-
Assisted Film Growth, (T. Itoh, ed.), p. 101, Elsevier, Amsterdam
26. Harrison, D. E., Kelly, P. W., Garrison, B. J. and Winograd, N., Surf.
Sci., 76:311 (1978)
27. Hagstrum, H. D., Phys. Rev., 104:317 (1956)
28. Hagstrum, H. D., Phys. Rev., 123:758 (1961)
29. McCracken, G. M., Rep. Prog. Phys., 38:241 (1975)
30. Navinsek, B., Progress in Surface Sci., 7:49 (1976)
31. Davis, W. D. and Vanderslice, T. A., Phys. Rev., 131:219 (1963)
32. Sigmund, P., Phys. Rev., 184:383 (1969)
33. Townsens, P. D., Kelly, J. C. and Hartley, N. E. W., Ion Implantation,
Sputtering and Their Applications, p. 111, Academic Press, New York
(1976)
34. Sigmund, P., J. Vac. Sci. Technol., 17:396 (1980)
35. Eckstein, W. and Biersack, J. P., Z. Phys., B63:471 (1986)
36. Vossen, J. L., J. Vac. Sci. Technol., 8:S12 (1971)
37. Thornton, J. A., Thin Solid Films, 54:23 (1978)
38. Winters, H. F. and Kay, E., J. Appl. Phys., 38:3928 (1967)
39. Brodie, I., Lamont, L. T. Jr. and Jepson, R. L., Phys. Rev. Lett., 21:1124
(1968)
40. Lee, W. W. and Oblas, D., J. Vac. Sci. Technol., 7:129 (1970)
41. Lee, W. W. Y. and Oblas, D., J. Appl. Phys., 46:1728 (1975)
42. Sigmund, P., Can. J. Phys., 46:731 (1968)
43. Anderson, H. H., Rad. Effects, 3:51 (1970)
44. Oechsner, E. and Gesang, W. R., Phys. Lett., 37A:235 (1971)
45. Kornelsen, E. V., Can. J. Phys., 42:364 (1964)
46. Blank, P. and Wittmaack, K., J. Appl. Phys., 50:1519 (1979)
47. Coburn, J. W., Thin Solid Films, 64:371 (1979)
48. Anderson, H. H., in Symp. on the Physics of Ionized Gases 1980, (B.
Cobic, ed.) Boris Kidric Aust. Nucl. Sciences, Belgrad, Yugoslavia
(1981)
49. Eltoukhy, A. H. and Greene, J. E., J. Appl. Phys., 51:4444 (1980)
Sputter Deposition Processes 339
126. Heisig, U., Goedicke, K. and Schiller, S., Proceedings 7th Intl. Symp.
Electron and Ion Beam Science and Technology, Washington, DC, p.
129, Electrochemical Society, Princeton, NJ (1976)
127. Waits, R. K., J. Vac. Sci. Technol., 15:179 (1978)
128. Waits, R. K., in Thin Film Processes, (J. L. Vossen and W. Kern, eds.)
p. 131, Academic Press, New York (1978)
129. Fraser, D. B., in Thin Film Processes (J. L. Vossen and W. Kern, eds.)
p. 115, Academic Press, New York (1978)
130. Aronson, A. and Weinig, S., Vacuum, 27:151 (1977)
131. Van Vorous, T., Optical Spectra, p. 30 (November, 1977)
132. Smith, H. R. Jr., Proceedings 20th Annual Tech. Conf., Society of
Vacuum Coaters, p. 1, Atlanta, GA (1977)
133. Corbani, J. F., U.S. Patent 3,878,085 (1975)
134. Clarke, P. J., U.S. Patent 3,616,450 (1971); U.S. Patent 3,711,398
(1973)
135. McLeod, P. S., U.S. Patent 3,956,093 (1976)
136. Rainey, R. M., U.S. Patent 4,100,055 (1978)
137. Chapin, J. S., U.S. Patent 4,166,018 (1979)
138. Vossen, J. L., J. Vac. Sci. Technol., 8:S12 (1971)
139. Davidse, P. D., Vacuum, 17:139 (1967)
140. Probyn, B. S., Vacuum, 18:253 (1968)
141. Jackson, G. N., Thin Solid Films, 5:209 (1970)
142. Koenig, H. R. and Maissel, L. I., IBM J. Res. Develop., 14:168 (1970)
143. Brodsky, M. H., Title, R. S., Weiser, K. and Pettit, G. D., Phys. Rev. B,
1:2632 (1970)
144. Messier, R., Takamori, T. and Roy, R., J. Vac. Sci. Technol., 13:1060
(1976)
145. Barnett, S. A., Bajor, G. and Greene, J. E., J. Appl. Letters, 37:735
(1980)
146. Eltoukhy, A. H. and Greene, J. E., J. Appl. Phys., 50:6390 (1979)
147. Hovel, H. J. and Cuomo, J. J., Appl. Phys. Lett., 20:71 (1972)
148. Shuskus, A. J., Reeder, T. M. and Paradis, E. L., Appl. Phys. Lett.,
24:151 (1974)
149. Glew, R. W., Thin Solid Films, 46:59 (1977)
150. Corsi, C., J. Appl. Phys., 45:3467 (1974)
Sputter Deposition Processes 343
151. Wasa, K., Nagai, T. and Hayakawa, S.,Thin Solid Films, 31:235 (1976)
152. Takei, W. J., Formigoni, N. P. and Francombe, M. H., J. Vac. Sci.
Technol., 7:442 (1970)
153. Wickersham, C. E. and Greene, J. E., Phys. Status Solidi (a) 47:329
(1978)
154. Morrison, D. T. and Robertson, T., Thin Solid Films, 15:87 (1973)
155. Hickmott, T. W., J. Appl. Phys., 45:1050 (1974)
156. Salma, C. A. T., J. Electrochem. Soc., 117:913 (1970)
157. Pratt, I. H., Solid State Technol., 12:49 (1969)
158. Young, P. L., Fehler, F. P. and Whitman, A. J., J. Vac. Sci. Technol.,
14:176 (1977)
159. Goldstein, R. M. and Wigginton, S. C., Thin Solid Films, 3:R41 (1969)
160. Wu, L. C. and Greene, J. E., J. Appl. Phys., 50:4966 (1979)
161. Greene, J .E., Wickersham, C. E., Zilko, J. L., Welsh, L. B. and Szofran,
F. R., J. Vac. Sci. Technol., 12:72 (1976)
162. Takao, T., Wasa, K. and Hayakawa, S.,J. Electrochem. Soc., 123:1719
(1976)
163. Westwood, W. D. and Bennewitz, C. D., J. Appl. Phys., 45:2313 (1974)
164. Titchmarsh, J. G. and Toombs, P. A. B., J. Vac. Sci. Technol., 7:103
(1970)
165. Paradis, E. L. and Shuskus, A. J., Thin Solid Films, 38:131 (1976)
166. Lakshmanan, T. K., J. Electrochem. Soc., 110:548 (1963)
167. Shimomoto, Y., Matsumaru, H. and Nishimura, T., Jpn. J. Appl. Phys.,
Suppl. 2, Pt. 1:701 (1974)
168. Robertson, T. and Morrison, D. T., Thin Solid Films, 27:19 (1975)
169. Biederman, H., Ojha, S. M. and Holland, L., Thin Solid Films, 41:329
(1977)
170. Butler, H. S. and Kino, G. S., Phys. of Fluids, 6:1346 (1963)
171. Terman, F. E.,Electronics and Radio Engineering,p. 458, McGraw Hill,
New York (1955)
172. Logan, J. S., Mazza, N. M. and Davidse, P. D., J. Vac. Sci. Technol.,
6:120 (1969)
173. Coburn, J. W. and Kay, E., J. Appl. Phys., 43:4965 (1972)
174. Thornton, J. A. and Chin, J., Ceramic Bulletin, 56:504 (1977)
175. Kaufman, H. R., J. Vac. Sci. Technol., 15:272 (1978)
344 Deposition Technologies for Films and Coatings
176. Chopra, K. L. and Randlett, M. R., Rev. Sci. Instr., 38:1147 (1967)
177. Reader, P. D., White, D. P. and Isaacson, G. C., 14th Symp. Elect. Ion
Photon Beam Tech., Palo Alto, CA (May 1977)
178. Robinson, R. S., J. Vac. Sci. Technol., 15:277 (1978)
179. Harper, J. M. E., inThin Film Processes (J. L. Vossen and W. Kern, eds.)
pp. 175-206, Academic Press, New York, (1978)
180. Johansson, B. O., Sundgren, J. E., Greene, J. E., Rockett, A. and
Barnett, S. A., J. Vac. Sci. Technol., B3:303 (1985)
181. Thornton, J. A., Cornog, D. G. and Anderson, W. W., J. Vac. Sci.
Technol., 18:199 (1981)
182. Kusano, E., Theil, J. A. and Thornton, J. A., J. Vac. Sci. Technol.,
A6:1663 (1988)
183. Vossen, J. L., in Physics of Thin Films, (G. Haas, M. H. Francombe,
and R. W. Hoffman, eds.) 9:1, Academic Press, NY (1977)
184. Harra, D. J. and Haywood, W. H.,Supplemento al Nuovo Cimento, 5:56
(1967)
185. Heller, J., Thin Solid Films, 17:163 (1973)
186. Maniv, S. and Westwood, W. D., J. Appl. Phys., 51:718 (1980)
187. Holland, E. and Campbell, D. S., J. Mater. Sci., 3:544 (1968)
188. Harvey, J. and Corkhill, J., Thin Solid Films, 6:277 (1970)
189. Stirling, A. J. and Westwood, W. D., Thin Solid Films, 30:19 (1975)
190. Abe, T. and Yamashina, T., Thin Solid Films, 30:19 (1975)
191. Shinoki, F. and Itoh, A., J. Appl. Phys., 46:3381 (1975)
192. Donaghey, L. F. and Geraghty, K. G., Thin Solid Films, 38:271 (1976)
193. Berg, S., Blom, H. O., Larsson, T. and Nender, C.,J. Vac. Sci. Technol.,
A5:202 (1987)
194. Berg, S., Larsson, T., Nender, C. and Blom, H. O.,J. Appl. Phys., 63:887
(1988)
195. Larsson, T., Blom, H. O., Nender, C. and Berg, S.,J. Vac. Sci. Technol.,
A6:1832 (1988)
196. Schiller, S., Heisig, U., Goedicke, K., Schade, K., Teshner,G. and
Henneberger, J., Thin Solid Films, 64:455 (1979)
197. Schiller, S., Heisig, U., Steinfelder, K. and Strümpfel, J., Thin Solid
Films, 63:369 (1979)
198. Este, G. and Westwood, W. D., J. Vac. Sci. Technol., A2:1238 (1984)
Sputter Deposition Processes 345
199. Natarajan, B. R., Eltoukhy, A. H., Greene, J. E. and Barr,T. L., Thin Solid
Films, 69:217 (1980)
200. Sproul, W. D., Thin Solid Films, 107:141 (1983)
201. Sproul, W. D., Thin Solid Films, 118:279 (1984)
202. Sproul, W. D. and Tomashek, J. E., U.S. Patent 4,428,811
203. Sproul, W. D., U.S. Patent 4,428,812
204. Baglin, J. E. E., Matrl. Sci. Engr., B1:1 (1988)
205. Mattox, D. M., Baglin, J. E. E., Gottschall, R. E. and Batich, C. D.,
Adhesion in Solids, Vol. 119, MRS Symposium Proceedings (1989)
206. Greene, J. E., Barnett, S. A., Sundgren, J. E. and Rockett, A., inPlasma-
Surface Interactions and Processing of Materials, (O. Auciello, A.
Grass-Marti, and D. L. Flamm, eds.), p. 281, NATO Advanced Study
Institute, Klewer, Boston (1990)
207. Window, B. and Savvides, N., J. Vac. Technol., A4:196 (1986)
208. Window, B. and Savvides, N., J. Vac. Technol., A4:453 (1986)
209. Petrov I., Adibi, F., Greene, J. E., Sproul, W. D., and Münz, W.-D., J.
Vac. Sci. Technol., A10:3283 (1992)
210. Adibi, F., Petrov, I., Greene, J. E., Hultman, L., and Sundgren, J.-E., J.
Appl. Phys., 73:8580 (1993)
6
Ion Plating
Donald M. Mattox
1.0 INTRODUCTION
346
Ion Plating 347
Figure 6.1. An ion plating configuration using a DC diode discharge and a thermal
vaporization source.[1]
Early work on the ion plating process was concerned with thedeposition
of atoms originating from thermal evaporation/sublimation, sputtered sur-
faces (sputter ion plating), or from chemical vapor species in the gas
(chemical ion plating).[4] Bombardment was by ions extracted from a plasma
by applying a negative potential to the surface to be coated which was
immersed in the plasma. The plasma could be of an inert gas species,
contain reactive species, or contain gaseous chemical compound species.
In the latter cases, the chemical species could be activated in the plasma to
either become more reactive with depositing species (for example, nitrogen
to form the nitrides) or could be decomposed to deposit a coating from the
constituents of the gaseous chemical compound (e.g., Ti from TiCl4).[14] The
latter process might be considered an early form ofplasma enhanced CVD[15]
with ion bombardment in addition to the plasma activation.
348 Deposition Technologies for Films and Coatings
Most recently, the termion plating has been applied to processes where
the surface to be coated is in contact with a plasma and the term ion assisted
deposition (IAD) or ion beam enhanced deposition (IBED) is used where the
substrate is bombarded by an ion beam in a vacuum environment during
deposition.[16]-[18] There are several other modifying terms which are some-
times used with ion plating such as: sputter ion plating and chemical ion
plating which specify the origin of the depositing species (sputtered material
or chemical vapor precursor gases respectively),vacuum ion plating which is
done in a vacuum environment,[19] and reactive ion plating,[20] used for the
deposition of films of compound materials.
Initially the film property of most interest was the adhesion of the film to
the substrate and the ability to have an in situ substrate surface cleaning
process, as well as to introduce thermal energy directly into the surface region
without having to heat the bulk of the material. In the early 70’s a number of
studies were made on the modification of film microstructure,[21][22] stress,[23]
composition[24] and properties[25][26] by the concurrent bombardment during
deposition, and the excellent coverage obtained by gas scattering and
sputtering-redeposition during ion plating. Bombardment during reactive
deposition was shown to improve the stoichiometry of the deposited film
material.
In the latter part of the 70’s and the early 80’s, sources of low energy (100
to 10,000 eV) ion beams of gaseous species became more generally available
and bombardment could be done in a vacuum environment. This led to studies
of bombardment effects under more controlled conditions. Studies included
both those of a physical nature such as the effect of bombardment on film
stress,[27] and those of a chemical nature (reactive deposition).[28][29] Re-
cently it has been shown that bombardment during vacuum deposition greatly
improves the properties of vacuum deposited optical coatings[16] by increasing
the index of refraction (density) and the environmental stability.
Recently ion implantation accelerators have been used to give high
energy (50 to 100 keV) particle bombardment of surfaces to give recoil
implantation of previously deposited material or “mixing” of the interfacial
region between a film and the substrate. [30][31] This high energy bombard-
ment may be concurrent with the atomistic film deposition or may be used
as a post-deposition treatment. The development of ion sources for fusion
reactor applications has lead to large area, high current, ion sources that
allow higher fluxes and larger areas of bombarding particles. [32][33] Also
during the early and mid 80’s, equipment and techniques were further
Ion Plating 349
Plasmas are gaseous media which contain enough ions and electrons
to be electrically conductive (e.g., fifty). Energy is introduced into the plasma
by the acceleration of electrons in a DC, RF, or microwave electric field. These
energetic electrons then fragment, excite, and ionize atoms and molecules by
collisions. A processing plasma is a plasma that is used in materials
processing.[51]-[53] In many, if not most, cases of film deposition the
processing plasma is a weakly ionized plasma such that there are many more
neutral particles than ions in the gas phase and there is a large number of
radical species compared to ions when a molecular gas is used. In a
processing system, the local plasma densities and plasma properties may
vary significantly due to electrode configurations, presence of fixturing, and
other geometrical factors.
Typical properties of a weakly ionized plasma are:
Ratio of neutrals to ions 107 - 104:1
(100 times as many radicals as ions when using a molecular gas)
Gas pressure 10-3 - 10-1 torr
Electron temperature 1 - 10 eV
Ion temperature 0.025 - 0.035 eV
Figure 6.2. Plasma generation configurations: (a) DC diode; (b) DC diode with
permanent magnets giving a planar magnetron; (c) RF plasmas with planar
electrodes immersed in the plasma, electrodes external to a dielectric wall and a
coil immersed in the plasma; (d) electron emitter (thermoelectron) with magnetic
confinement; and (e) microwave cavity.
accelerated across the cathode fall region to impinge on the cathode (target).
The cathode fall region, which surrounds the cathode, is where most of the
potential drop in a DC discharge is to be found.[54] The plasma region is located
between the edge of the cathode fall region and the anode where there is little
potential drop. In the DC discharge, energetic particles (ions and neutrals)
impinging on the cathode (target) cause the ejection of secondary
electrons which then accelerate across the cathode fall region, collide with
gas species, and create ions which sustain the discharge process. The
secondary electron emission coefficient of a surface depends on the
chemical nature and morphology of the surface. Oxides typically have a
higher electron emission coefficient than metals, and rough surfaces have
a lower secondary emission coefficient than smooth surfaces. The
secondary electrons can be accelerated to high energies and impinge on the
Ion Plating 353
anode or other surfaces in the system. This can give rise to extensive heating
of surfaces (substrates) in the system. The DC discharge requires a relatively
high gas pressure to sustain the discharge (>10 microns argon).
In the cathode fall region, some of the ions may be neutralized by charge
exchange processes which give rise to energetic neutral particles[55][56] which
are not affected by the applied electric field. The cross-section for charge
exchange is much larger than that for physical collision. The charge exchange
process is dependent on the gas pressure, and at low pressures the
accelerated ions will arrive at the cathode with the full cathode fall energy since
the collision probability is low. Because of these charge exchange processes
there is, at the cathode, a flux of energetic particles consisting of ions and
neutrals with a broad spectrum of energies.
In order to sustain a DC discharge, the secondary electrons must create
enough ions to compensate for losses by recombination. If the anode or
ground surface is brought too close to the cathode the discharge is extin-
guished. This effect can be used to confine the DC discharge to areas of the
cathode surface where bombardment is desired—other areas may have the
bombardment prevented by having a ground shield in closed proximity to the
surface. The Paschen curve gives the relationship between breakdown voltage
and the minimum anode-cathode separation in a gaseous environment.
Typically argon gas pressure of about 10 microns is used to sustain the DC
diode discharge. At this pressure the width of the cathode dark space is about
1 cm. Insulator surfaces cannot be used as cathodes in a DC diode
configuration since charge buildup on the surface prevents ion bombardment.
Electrically insulating films deposited in a DC discharge will build-up a surface
charge which will cause arcing through the film.
In addition to causing the ejection of secondary electrons, high energy
ions and neutrals which impinge on the target (or other surfaces) cause the
physical ejection of surface atoms (physical sputtering) by momentum
transfer processes. The sputtered particles leave the surface at higher than
thermal energies but may be rapidly thermalized by collisions in the gas
phase.[57][58] The sputtered particles may be scattered back to the target
surface—this effect is more prominent the higher the gas pressure. Some of
the energetic ions that bombard the cathode may be reflected as high energy
neutrals.[40]
354 Deposition Technologies for Films and Coatings
System geometry
Substrate: Power input (voltage and current)
Plasma uniformity
Applied potential
Pre-sputtering time
Deposition rate/uniformity
Plasma: Gas pressure
Gas purity
Deposition source geometry
3.2 RF Discharge
area electrodes will attain higher voltages than large area electrodes, and
the electrode potentials can be varied using an external capacitance in the
circuit.
The amount of energy that is coupled into the RF discharge depends
on the impedance matching (reflected power) and coupling losses to other
surfaces (stray losses). In RF plasma processing, it may be important to
determine just how much energy is actually being coupled into the
plasma.[66]-[69] RF power may be coupled to the plasma using metal
electrodes external to a dielectric wall [70] or the RF plasmas may be
excited using immersed electrodes (see Ref. 71, for example). Very high
plasma densities and ionization efficiencies can be attained in RF driven
plasmas and the discharge may be established at lower pressures than
the DC diode discharge.[72]
In plasma processing, the RF discharge has the advantage that
insulating surfaces or insulating films on conductive surfaces can be
bombarded by applying an RF potential. Disadvantages are: (a) high
power inputs (heating) to insulating materials cause cracking, (b) elec-
trode geometries can cause problems with coupling to the RF power, (c)
there are many sources of RF power loss in systems, (d) plasma
uniformity is difficult to obtain over complex surfaces, and (e) the bias
conditions on surfaces in the RF plasma are variable and often difficult to
control.
Permanent magnets have the advantage that they may be placed in such a
manner as to position the field lines in a desirable manner. However, getting
a uniform magnetic field over a large or complex surface is difficult with any
magnetic field configuration.
Magnetron enhanced plasma configurations have many advantages
including: (a) confining the plasma to a small region, (b) increased ionization
and plasma density, and (c) may be operated at low pressures where gas
phase collisions are reduced. Disadvantages include: (a) non-uniform
magnetic fields give non-uniform plasma densities,(b) isolation of the plasma
to a small region of the processing chamber requiring auxiliary plasma sources
near the substrates in some applications, and(c) low pressure processing can
give rise to a flux of high energy reflected neutrals which may affect bombarded
surfaces and growing films, and affect their properties in an undesirable
manner.[43]
function of the mass of the incident particle and the mass of the target atoms.
The sputtering process only begins after a threshold energy is reached where
there is enough momentum transfer to give ejection (> 20 eV).
The sputtering yield is a function of crystallographic orientation of the
surface material, giving differing yields for differing planes and allowing the
delineation of crystallographic structure of a surface by sputter etching. The
sputtering yield is also a function of the incident particle energy, increasing
from some threshold value to some maximum above which most of the energy
is deposited too far below the surface to affect the collision cascade where it
intersects the surface and the sputtering yield decreases. There have been
some reports of an equilibrium time for the sputtering yield to stabilize,
possibly due to saturation of the surface with bombarding gas.
For surfaces bombarded at normal incidence, the ejected particles will
come off with a cosine distribution at low bombarding energies,[111] and an
over-cosine distribution as the energies become higher,[112] and with some
dependence on mass when sputtering alloys or isotopic mixtures.[113] This
angular dependence may change with texturing of the sputtered surface. If the
bombarding flux is off-normal, the ejected flux will be skewed in a forward
direction. (The ejection from a single crystal surface will depend on the
orientation of the crystal planes). The energy of the ejected particles will
depend on the bombarding angle with oblique bombardment giving higher
energy ejected particles.
The sputtering yield is also a function of the angle of incidence of the
impinging particle. For this off-normal bombardment, the sputtering yield, as
a function of incident particle bombardment angle, initially increases to a
maximum then decreases rapidly above some angle as the bombarding
particles are reflected from the surface. The maximum generally occurs at
about 70 degrees off-normal but this varies with the relative masses of the
particles. This property may be used to give forward sputtering of materials
where the impingement angle on the target (inclined plane with ion beams,
edges of cylinders) is high. This angular dependence of sputtering also results
in the formation of cones on a sputtered surface. The taper of the cones is
determined by the angle-of-incidence dependence of the sputtering yield.
For a single component surface, the material will be removed from the
surface with the bulk composition. If the surface is an alloy or compound,
preferential sputtering may occur with some surface species being removed
more easily than others (may actually extend several monolayers into the
366 Deposition Technologies for Films and Coatings
give a long term change in the sputtering yield (2 - 3X) from the surface since
the surface morphology changes (changing angle of incidence and redeposition
processes).[120] Texturing is used to generate optical “trapping” surfaces,[121]
to treat surfaces for medical implants to improve bone growth[122] and
adhesion, and to reduce secondary electron emission from surfaces.
If the surface species is a “foreign” atom the process of removal may be
termeddesorption and may be calledion-induced desorption or cleaning.[123]
It has been shown that the process of recoil implantation is an important
parameter in the desorption (sputter cleaning) of monolayers of chemisorbed
species from a surface.
Surfaces may be etched byreactive plasma etching where a chemically
active species (Cl, F) is formed in a plasma and reacts with the surface to form
a volatile species. Typically a volatile chemical species is formed on the
surface and volatilization removes the surface species. The process is
somewhat difficult to control since the plasma composition and the flux of
impinging particles from the plasma may vary. If the particles are accelerated
to the surface, chemical reaction is enhanced and the process becomes
reactive ion etching or reactive plasma cleaning.[124]
The desorption of weakly bound surface species is important to plasma
cleaning and may be used to reduce the incorporated contaminants in
deposited films.[6][125] The desorption may also be useful in desorbing
unreacted species in reactive deposition processes giving rise to more
stoichiometric and chemically stable deposits.
In ion-assisted chemical etching,[126] a molecular beam of the
chemically reactive species and a beam of inert gas ions simultaneously
bombard the surface to be etched. Using this technique, very high etching
resolution can be obtained at high etch rates.[127]
The bombardment-assisted chemical processes that occur on
surfaces are very poorly understood.[109][128]-[130] On one hand the
increased chemical activity may be due to the increased “temperature”
due to momentum transfer from the bombarding ions. On the other hand,
secondary electrons from the bombardment of the surface may play an
important role. In some cases, surface changes due to the bombardment
may provide sites for chemical reactions. The etching process is sensitive
to the amount of adsorbed reactive gases.
368 Deposition Technologies for Films and Coatings
The combination of high defect densities and heat allow rapid diffusion
(similar to radiation enhanced diffusion[144]) and the generation of analtered layer
whose composition may differ from the bulk (alloys and compounds).
The implantation of the bombarding species and the recoil implantation
of the surface species results in the compaction(peening) of the near-surface
region and the formation of a compressive stress in that region. The
implantation process also incorporate bombarding (and surface species -
recoil implantation) species into the near surface region often in amounts
that are above the normal solubility limits. Both the peening action and the
incorporation can affect the stress in this region film.
formed this way since the resulting films have higher index of refraction (more
dense) and are more environmentally stable than are vacuum deposited
films.[16] The adhesion of optical films may also be improved by the concurrent
bombardment.[147] By bombarding the growing film with reactive ions,
compounds of materials such as TiN can be formed.[148]
High energy electron beam evaporation may also be done in a plasma
environment as long as the hot filament is not exposed to the plasma. This
may be done by differentially pumping the chamber below the electron beam
evaporator where the electron emitting filament is located.[1]
6.2 Sputtering
Vacuum arc vaporization sources can also provide film-ions in vacuum ion
plating. Arc evaporation (vacuum arc) occurs when a high current, low voltage
arc passes between electrodes in a vacuum. The arc is confined to spots which
have a very high energy density (1011 W m-2). The vaporized material may be
deposited as a film, often with a bias applied to the substrates. Arc vaporization
is an old method of vaporizing carbon to form thin carbon films. By using a reactive
gas atmosphere, compounds may be deposited. In arc evaporation, a large
fraction (0.5) of the vaporized material is ionized.[151]-[153] The potential
distribution in the arc gives a “hump” near the cathode allowing ions on the anode
side of the hump to be accelerated to a high potential (80 eV).[48] Problems with
this deposition technique include stabilization of the arc and the formation of
globules of the ejected material. Arc steering over the cathode surface and
plasma deflection have been applied to reducing theglobule problem. The ions
372 Deposition Technologies for Films and Coatings
Figure 6.4. Configurations for using an ion beam in a vacuum system to allow
concurrent bombardment of a depositing film.
formed in the vacuum arc may be accelerated to a biased substrate, and thus
constitutes a source of bombardment and deposition in the ion plating
process.
The vacuum arc melting process[154] utilizes a vacuum arc to melt
materials and the melting equipment may also be used as a source of ions
(from the molten anode) for deposition.
Ion Plating 373
The nature and type of interfacial region that is formed during film
deposition is important to adhesion and the functionality of the film-substrate
couple. Interfacial regions may be classed as: (a) mechanical, (b) abrupt, (c)
compound,(d) diffusion,(e) pseudo-diffusion or combinations thereof.[36] The
type of interfacial region formed during deposition depends on the film/
substrate materials, chemical interactions, energy available, nucleation
behavior, contamination, and surface morphology. Particle bombardment
prior to and during film deposition affects many of these factors. Of particular
interest is the ability to clean a surface, influence nucleation, and to provide
energy to the surface region to enhance diffusion and chemical reactions.
effect of adsorbed surface species may also be important. The following are
some of the film properties that can be modified by controlled concurrent
bombardment during deposition.
RF sputter deposited chromium films at zero bias and a -500 volt bias during
deposition. Note that the bombardment completely disrupted the columnar
microstructure. Bombardment-related effects may also improve the sur-
face coverage and decrease the pinhole porosity in a deposited film. This
increased film density is reflected in film properties such as: better corrosion
resistance, lower chemical etch rate, higher hardness, lower electrical resistivity
(metals), and the increased index of refraction (optical coatings). However,
it has been found that if the bombarding species is too energetic and
the substrate temperature is low, high gas incorporation gives rise to
Ion Plating 377
voids (e.g., Ref. 179). Some investigators have used the parameter
resputtering rate (deposition rate with and without an applied bias) as the
parameter for disruption of the columnar morphology; however this parameter
does not take into consideration the backscattering from the gas phase which
will be greater with higher gas pressure, and so must be used with caution.
ment will heat, densify, and consolidate the deposited material into a high
quality film over the whole surface. On a more microscopic scale, sputtering
and redeposition of the depositing film material will lead to better coverage on
micron and submicron sized features,[24][179][196]-[199] and reduce pinhole
formation. On the atomic scale, the increased surface mobility, increased
nucleation density, and erosion/redeposition of the depositing adatoms will
disrupt the columnar microstructure and eliminate the porosity along the
columns. In total, the use of gas scattering, along with concurrent bombard-
ment, increases the surface covering ability and decreases the microscopic
porosity of the deposited film material as long as gas incorporation does not
generate voids.
Many other properties of the film material may be changed and improved
by bombardment during deposition. They include: (a) electrical resistivity of
metal films,(b) hardness of hard-coatings,(c) chemical etch rate,(d) corrosion
resistance,(e) pinhole density,(f) index of refraction of dielectric coatings, (g)
color of TiN films, etc.
Generally the equipment used for ion plating is the same as that used
for sputter deposition except that now the substrate is the sputtering target and
another vaporization source has been added. Figure 6.8 shows some of the
possible configurations.
Figure 6.8. Some configurations for bombarding a surface from a plasma by using
accelerated or reflected high energy particles: (a) diode, (b) grid to allow bombard-
ment of complex surfaces or insulators, (c) thermoelectron sustained plasma with
magnetic enhancement/confinement, (d) e-beam evaporation with a differentially
pumped vacuum chamber, (e) utilizing reflected high energy neutrals and sputter-
ing, (f) magnetron sputtering source, and (g) moving magnetron plasma to allow
uniform bombardment of substrate surface.
Ion Plating 383
tions often used in ion plating systems, the insulators of electrical feed-
throughs must be carefully shielded from deposition or else they will become
shorted. These conditions may also lead to gas-phase nucleation of particles
which will deposit on the system walls (called “black sooty crap”, BSC, by the
operators). This material has a very low density and if the material is
pyrophoric (Ti, Zr etc.) the BSC may ignite if disturbed in air. In such a case
system cleanup should be done wet.
Power supplies must be capable of withstanding electrical arcs in the
deposition chamber and their attendant electrical transients. Substrate
potentials may be DC or RF and with or without magnetron enhancement. In
some configurations (beam, grounded cathode) the substrate may be at
ground potential. Very high voltage (to 1-00 keV) pulsing of substrates
immersed in plasmas is being studied as a way to modify surfaces by ion
bombardment.[199] This technique could be used in ion plating to allow periodic
bombardment of the depositing film material and might be termed pulsed ion
plating.
The ion plating process is very complex and monitoring what goes on
is usually done in a comparative manner rather than an absolute manner. This
means careful control of process variables.
10.1 Plasma
Typically the plasma is monitored by the gas pressure, gas flow through
the system, and power input. Calibrated flow meters are useful for process
control. The species in the plasma may be monitored by the optical emission
from the plasma, and this analysis may be correlated to the composition and
properties of the resulting film.[201] In some cases, mass spectrometry may
be used to determine gas species but if a plasma is used in the process, the
mass spectrometer must be differentially pumped and the calibration is
confused by the initial presence of ionized species.
10.3 Specifications
Problem areas which exist with ion plating arise because of:
“Activated” reactive contaminants in the plasma
Redeposition of sputtered contaminates
Plasma uniformity
High field regions
Points
Focusing fields
High plasma density region
Trapped secondary electrons
High secondary emission
Unwanted shielding of substrate areas
Wasted power
Unshielded leads/areas
Substrate heating
Coating (shorting) high voltage insulators
Non-uniform availability of reactive species (reactive depo-
sition)
Electrical contact points are not coated
Gas incorporation
These problem areas can generally be avoided by design of the fixturing
and other “tricks” such as:
Rotating fixturing
Use of grids to smooth out electric fields
Periodic plating (on-off) mode to reduce substrate heating
Heating of substrate to outgas material as it deposits
A major problem area in using plasmas for thin film deposition is that of
obtaining a uniform plasma density over a surface so that uniform bombard-
ment and reactive gas availability can be attained. Plasma non-uniformity can
arise from a number of sources including: (a) geometrical arrangement of
power input electrodes and substrate fixturing,(b) substrate geometry,(c) the
presence of surfaces that allow recombination and loss of species in the
nearby plasma, and (d) in the case of reactive deposition, reactive surfaces
that deplete the supply of reactive gas at the growing film surface.
Ion Plating 387
Figure 6.9. Example of using an auxiliary plasma near the substrate to allow ions
to be extracted and bombard the growing film.
388 Deposition Technologies for Films and Coatings
Figure 6.10. Ion plating “barrel plating” configuration using a rotating cage to
contain the parts.[200]
Ion Plating 389
12.0 APPLICATIONS
There are many applications of the ion plating process some of which
are:
! Obtaining good adhesion: Ag on steel for mirrors, soft metals
on surfaces for space lubrication, Ag on Be for diffusion
bonding, Cu and Au on Ta and Mo for subsequent brazing,
Cu-on-ceramic metallization.
! Metallization: Al, Ag, Au on plastics and semiconductors.
! Good surface coverage on complex surfaces: TiN on tool
bits, molds and jewelry items; semiconductor metallization.
! Good reaction and stoichiometry: TiN on tool bits, molds
(hardness, wear); jewelry items.
! Corrosion protection: Al on U, steel and Ti (galvanic); C and
Ta on biological implants.
! Abrasion resistance: MgF2 coatings on plastics.
! Deposition of diffusion barriers: HfN and TiN on semiconduc-
tor devices.
13.0 SUMMARY
Like any deposition technique the ion plating process has its advan-
tages and disadvantages.
Advantages:
! Excellent surface covering ability(throwing power) under the
proper conditions.
! Ability to have in situ cleaning of the substrate surface.
390 Deposition Technologies for Films and Coatings
REFERENCES
45. Romesser, T. E., Vanek, V., Tang, J., Dixon, D., Bayless, J., Musetto,
M., Strawitch, C., and Higgins, L., A Large Area Plasma Source, IEEE
International Conference of Plasma Science, 83CH1847-3, US DOE
Contract No. DE-ACO3-77ET33006 (1983)
46. Letokhov, V. S., Sov. At Energy, (Translation) 62(4):297 (1987)
47. Cuomo, J. J., Gambino, R. J., Harper, J. M. E., Kuptsis, J. D., and
Webber, J. C., J. Vac. Sci. Tech., 15:281 (1978)
48. Boxman, R. L. and Goldsmith, S., Surf. Coat. Tech., 33:153 (1987)
49. Melngailis, J., J. Vac. Sci. Tech., B5:469 (1987)
50. Chapman, B., Glow Discharge Processes, J. Wiley (1980)
51. Thornton, J. A., Thin Solid Films, 107:3 (1983)
52. Mattox, D. M., Plasma-Surface Interactions and Processing of Mate-
rials, (O. Auciello, A. Gras-Marti, J. A. Valles-Abarca, and D. Flamm,
eds.), 176:377, NATO ASI Series, Kluwer Academic Publishers (1988)
53. Mattox, D. M., Plasma-surface Engineering, (E. Broszeit, W. D. Munz,
H. Oechsner, K.-T. Rie, and G. K. Wolf, eds.), 1:15,
Informationsgesellschaft, Verlag (1988)
54. Gras-Marti, A., Abril, I. and Valles-Abarca, J. A., Thin Solid Films,
124:59 (1985)
55. Davis, W. D. and Vanderslice, J. A., Phys. Rev., 131:219 (1963)
56. Savlnier, J. P., Fzguerra, J., and Guille, J., Vacuum, 33:279 (983)
57. Somekh, R. R., J. Vac. Sci. Tech., A2:1285 (1984)
58. Bessaudou, A. and Weissmantel, C.,Thin Solid Films, 149:225 (1987)
59. Logan, J. S., Mazza, N. M., and Davidse, P. D., J. Vac. Sci. Tech.,
6:120 (1969)
60. Yatsuzuka, M., Morishita, K., Satoh, K., and Nobuhara, S., Jpn. J.
Appl. Phys., 24:1724 (1985)
61. Kohler, K., Coburn, J. W., Horne, D. E., Kay, E., and Keller, J. H., J.
Appl. Phys., 57:59 (1985)
62. Thompson, B. E., Allen, K. D., Richards, A. D., and Sawin, H. H., J.
Appl. Phys., 59:1890 (1986)
63. Coburn, J. W., Ann. Rev. Mat. Sci., 13:91 (1983)
64. Kaufman, H. R. and Rossnagel, S. M., J. Vac. Sci. Tech., A6:2572
(1988)
65. Kushner, M. J., J. Appl. Phys., 58:4024 (1985)
394 Deposition Technologies for Films and Coatings
89. Zanner, F. J. and Bertram, L. A., IEEE Trans. on Plasma Science, Vol
PS-11:223 (1983)
90. Boelens, S. and Veltrop, H., Surf. Coat. Tech., 33:63 (1987)
91. McDaniel, E. W.,Collision Phenomena in Ionized Gases, Wiley (1964)
92. Hollahan, J. R. and Bell, A. T.,Techniques and Applications of Plasma
Chemistry, J. Wiley (1972)
93. McTaggert, F. K.,Plasma Chemistry in Electrical Discharges, Elsevier
(1967)
94. Kushner, M. J., J. Appl. Phys., 53:2923 (1982)
95. Veprek, S., Thin Solid Films, 130:135 (1985)
96. Thornton, J. A., J. Vac. Sci. Tech., 15:188 (1978)
97. Coburn, J. W. and Chen, M., J. Appl. Phys., 51:3134 (1980)
98. Dreyfus, R. W., Jasinski, J. M., Walkup, R. E., and Selwyn, G. S., Pure
Appl. Chem., 57:1265 (1985)
99. Wormhoudt, J., Stanton, A. C., Richards, A. D., and Sawin, H. H., J.
Appl. Phys., 61:142 (1987)
100. Murakami, A. T., Namura, T., and Itatani, R.,Jpn. J. Appl. Phys., 24:512
(1985)
101. Plas, F., Guille, J., and Machet, J., Vide, Suppl., 196:45 (1979)
102. Hoffman, D. W. and Badgley, J. S.,J. Vac. Sci. Tech., A6:1691 (1988);
Theoretical treatment to be published - private communication with D.
W. Hoffman
103. Hoffman, D. W. and Thornton, J. A., J. Vac. Sci. Tech., 20:355 (1982)
104. Hoffman, D. W. and Thornton, J. A., J. Vac. Sci. Tech., 16:134 (1979)
105. Thornton, J. A. and Hoffman, D. W., J. Vac. Sci. Tech., A3:576 (1985)
106. Mathews, A. and Gethin, D. T., Thin Solid Films, 117:261 (1987)
107. Roth, J., Sputtering by Particle Bombardment ll, (R. Behrisch, ed.), p.
91, Springer-Verlag (1983)
108. Itoh, N. and Hasebe, Y., J. Nucl. Mat., 139:77 (1986)
109. Winters, H. F., Coburn, J. W., and Chuang, T. J., J. Vac. Sci. Tech.,
B1:469 (1983)
110. Topics in Applied Physics, Vol. 47 (1981); Vol. 52, (R. Behrisch, ed.),
Springer-Verlag (1983)
111. Szymonsaki, M., Huang, W., and Onsgaard, J., Nucl. Instrum. Met.
Phys. Res., B14:263 (1986)
396 Deposition Technologies for Films and Coatings
112. Matsuda, Y., Yamamura, Y., Ueda, Y., Uchino, K., Muraoka, K.,
Maeda, M., and Akazaki, M., Jpn. J. Appl. Phys., 25:8 (1986)
113. Wehner, G. K., J. Vac. Sci. Tech., A1:487 (1983)
114. Betz, G., Surf. Sci., 92:283 (1980)
115. Baritzky, B. and Taglauer, E., Surf. Sci., 162:996 (1985)
116. Cuomo, J. J. and Gambino, R. J., J. Vac. Sci. Tech., 12:79 (1975)
117. Mundy, J. N. and Rothman, S. J., J. Vac. Sci. Tech., A1:74 (1983)
118. Navinsek, G., Prog. Surf Sci., 7:49 (1976)
119. Wehner, G. K., J. Vac. Sci. Tech., A3:1821 (1985)
120. Panitz, J. K. and Sharp, D. J., J. Vac. Sci. Tech., 17:282 (1980)
121. Berg, R. S. and Kominiak, G. J., J. Vac. Sci. Tech., 13:403 (1976)
122. Kowalski, Z. W., J. Mat. Sci., 20:15211 (985 )
123. Winters, H. F. and Sigmund, P. S., J. Appl. Phys., 45:4760 (1974)
124. Kominiak, G. J. and Mattox, D. M., Thin Solid Films, 40:141 (1977)
125. Jacobs, M. H., in Surface Modification and Coatings, (R. D. Sisson, Jr.
ed.), p. 291, ASM Conference Proceedings (1986)
126. Geis, M. W., Lincoln, G. A., Efremow, N., and Piacentini, W. J., J. Vac.
Sci. Tech., 19:1390 (1981)
127. Tsou, L. Y., J. Electrochem. Soc., 132:2010 (1985)
128. Lincoln, G. A., Geis, M. W., Pang, S., and Efremow, N., J. Vac. Sci.
Tech., B1:1043 (1983)
129. Winters, H. F., Nucl. Instrum. Met. Phys. Res., B27:243 (1987)
130. Harper, J. M. E., Cuomo, J. J., and Henzell, H. T. G., Appl. Phys. Lett.,
36:456 (1980); also Appl. Phys. Lett., 37:540 (1980)
131. Ashok, S., Krautle, H., Beneking, H., and Mogro-Campero, A., Thin
Solid Films, 126:251 (1985)
132. Winters, H. F., J. Appl. Phys., 38:3928 (1967)
133. Kornelsen, E. V., Rad. Effects, 13:227 (1972)
134. Kornelsen, E. V. and Van Gorkum, A. A., Rad. Effects, 42:93, 112
(1979)
135. Mattox, D. M. and Kominiak, G. J., J. Vac. Sci. Tech., 11:52 (1974)
136. Mattox, D. M. and Kominiak, G. J., J. Vac. Sci. Tech., 8:194 (1971)
137. Cuomo, J. J. and Gambino, R. J., J. Vac. Sci. Tech., 14:152 (1977)
138. Chleck, D., Maehl, R., Cucchiara, O. and Carnevale, E., Int. J. Appl.
Radiation and Isotopes, 14:581 (1963)
Ion Plating 397
139. Cheleck, D. and Maehl, R.,Int. J. Appl. Radiation and Isotopes, 14:593
(1963)
140. Chleck, D. and Cucchiara, O., Int. J. Appl. Radiation and Isotopes,
14:599 (1963)
141. Carden, J. E., Isotopes and Radiation Tech., 3(3):206 (1964)
142. Carden, J. E., Isotopes and Radiation Tech., 3(4):318 (1964)
143. Sharp, D. J. and Panitz, J. K., Surf. Sci., 118:429 (1982)
144. Corbett, J. W., Surf. Sci., 90:205 (1979)
145. Miyoshi, K., Spalvins, T., and Buckley, D. H.,Thin Solid Films, 127:115
(1985)
146. Mah, G., Mcleod, P. S., and Williams, D. G., J. Vac. Sci. Tech., 11:663
(1974)
147. Gibson, V. J. and Kennemore, C. M., III,Thin Solid Films, 124:27 (1985)
148. Satou, M., Andoh, Y., Ogata, K., Suzuki, Y., Matsuda, K., and
Fujimoto, F., Jpn. J. Appl. Phys., 24:656 (1985)
149. Jacobs, M. H., Surf. Coat. Tech., 29:221 (1986)
150. Cuomo, J. J., Ion Plating and Implantation: Applications to Materials,
(R. F. Hochman, ed.) ASM Conference Proceedings (1986)
151. Kimblin, C. W., J. Appl. Phys., 45:5235 (1974)
152. Daalder, J. E., J. Phys. D, Appl. Phys., 9:2379 (1976)
153. Daalder, J. E., Physica., 104:91 (1981)
154. Zanner, F. J. and Bertram, L. A., IEEE Trans. on Plasma Sci., Vol. PS-
11:223 (1983)
155. Mori, T. and Namba, Y., J. Vac. Sci. Tech., A1:23 (1983)
156. Bubenzer, A., Dischler, B., and Nyaiesh, A., Thin Solid Films, 91:81
(1982)
157. Weissmantel, C., Thin Films from Free Atoms and Particles, (K. J.
Klabunde, ed.) p. 153, Academic Press (1985)
158. Shanfield, S. and Wolfson, R., J. Vac. Sci. Tech., A1:323 (1983)
159. Harper, J. M. E., Cuomo, J. J., and Henzell, H. T. G., J. Appl. Phys.,
58:550 (1985)
160. Mattox, D. M., J. Vac. Sci. Tech., A7(3):1105 (1989)
161. Shawki, G. S. A., El-Sherbiny, M. G., and Salem, F. B., Thin Solid
Films, 75:29 (1981)
398 Deposition Technologies for Films and Coatings
162. Hibbs, M. K., Johansson, B. O., Sundgren, J. E., and Helmersson, U.,
Thin Solid Films, 122:115 (1984)
163. Miranda, R. and Rojo, J. M., Vacuum, 34:1069 (1984)
164. Rossnagel, S. M., Surf. Sci., 123:89 (1982)
165. Chopra, K. L., J. Appl. Phys., 37:2249 (1969)
166. Bovey, P. E., Vacuum, 19:497 (1969)
167. Mattox, D. M., J. Appl. Phys., 37:3613 (1966)
168. Muller, K. H., J. Vac. Sci. Tech., A4:184 (1986)
169. Narusawa, T., Shimizu, S., and Komiya, S.,J. Vac. Sci. Tech., 16:366
(1979)
170. Harper, J. M. E., Cuomo, J. J., Gambino, R. J., and Kaufman, H. R.,Ion
Bombardment Modification of Surfaces Fundamentals and Applica-
tions, (O. Aucello and R. Kelly, eds.), Ch. 4, Elsevier (1984)
171. Mattox, D. M. and Cuthrell, R. E., MRS Symposium Proceedings,
Adhesion in Solids, (D. M. Mattox, J. E. E. Baglin, R. E. Gottschall, and
C. D. Batich, eds.), 119:141 (1988)
172. Oh, R. S., Cannon, R. M., and Richie, R. O., J. Cer. Soc., 70:C352
(1987)
173. Thornton, J. A., Thin Solid Films, 40:335 (1977)
174. Thornton, J. A., Ann. Rev. Mat. Sci., 7:239 (1977)
175. Thornton, J. A., J. Vac. Sci. Tech., A4:3059 (1986)
176. Messier, R., Giri, A. P., and Roy, R. A., J. Vac. Sci. Tech., A2:500
(1984)
177. Meissier, R. and Yehoda, J. E., J. Appl. Phys., 58:3739 (1985)
178. Patten, J. W., Thin Solid Films, 63:1211(979 )
179. Panitz, J. K. G., Draper, B. L., and Curlee, R. M., Thin Solid Films,
166:45, (1988)
180. Klokholm, E. and Berry, B. S., J. Electrochem. Soc., 115:823 (1968)
181. Blachman, A. G.. J. Vac. Sci. Tech., 10:299 (1973)
182. Thornton, J. A., Tabcock, J., and Hoffman, D. W., Thin Solid Films,
64:111 (1979)
183. Thornton, J. A. and Hoffman, D. W., J. Vac. Sci. Tech., 18:203 (1981)
184. Thornton, J. A. and Hoffman, D. W., J. Vac. Sci. Tech., A3:576 (1985)
185. Brighton, D. R. and Hubler, G. K., Nucl. Instrum. Method Phys. Res.,
B28:527 (1987)
Ion Plating 399
Jan-Otto Carlsson
1.0 INTRODUCTION
400
Chemical Vapor Deposition 401
In CVD, gaseous reactants are admitted into a reactor (see Fig. 7.1).
Near or on a heated substrate surface, a chemical reaction of the following type
occurs:
Because of the gas flows as well as the temperature used in CVD, five
important reaction zones are developed during the CVD process (see Fig. 7.2).
The properties of CVD materials are affected by the interacting processes
occurring in these reaction zones. In a CVD process, a main gas flow (the
reaction gas mixture) passes over the substrate/coating surface. For fluid
dynamical reasons, a more or less stagnant boundary layer occurs in the vapor
adjacent to the substrate/coating. During the deposition process, the
gaseous reactants and the gaseous reaction products are transported across
this boundary layer. In reaction zone 1 (see Fig. 7.2) as well as in the main
gas stream, homogeneous reactions in the vapor may occur. These reactions
may lead to an undesirable homogeneous nucleation resulting in a flaky and
non-adherent coating. In some cases however, these reactions, when not
accompanied by homogeneous nucleation, are favorable to the CVD process
(for instance CVD of Al2 O3,[1] of B13C2,[2] and of Si,[3] respectively). The
heterogeneous reactions occur in the phase boundary vapor/coating (zone 2).
These reactions determine, in many systems, the deposition rate and the
properties of the coating.
Relatively high temperatures may be used during CVD. This means that
various solid state reactions (phase transformations, precipitation, recrystal-
lization, grain growth, for example) may occur during the process (the zones
3 - 5). In zone 4, which is a diffusion zone, various intermediate phases may
be formed. The reactions in this zone are important for the adhesion of the
coating to the substrate.
402 Deposition Technologies for Films and Coatings
Coupled reactions are often used in CVD. For instance, CVD of Al2O3
from AlCl3, CO2 and H2 can be described in an overall reaction:
Chemical Vapor Deposition 405
3.2 Thermodynamics
G = ∑ n iµ i
i
406 Deposition Technologies for Films and Coatings
µi = µi0 + RTlnai
ai = pi = (ni /n)P
where n is the number of moles in the gas phase, and P the total pressure.
For pure condensed substances, the activities are equal to unity.
Eriksson[8] developed a computer program (SOLGAS) based on the
minimization of the free energy. This program became a prototype for many
other equilibrium calculation programs. From the basic equations given
above, dimensionless quantity G/RT was defined (see eq. below) and used
in the calculations.
g s
m 0
g µ n ig n 0
s µ
∑ ∑
G
= ni + ln P + ln + ni
RT i =1 RT i n i =0 RT i
The superscripts g and s refer to the gas phase and the solid phase, respectively.
The value of µ0/RT for a specific substance is calculated from
µ0
=
(
G 0 − H 298
0
+
)
∆H f0,298
RT RT RT
By minimizing the quantity G/RT (or G) and using mass balance equations
as subsidiary conditions, the equilibrium composition of a system can be
calculated.
The input data in the calculations are the number of moles of the
different reactants, the total pressure, the substrate temperature, the different
substances, and their thermochemical data. From the calculations, various
quantities like the partial pressures of the vapor species, the amounts of the
different substances available for CVD, i.e., the yield, thermodynamic
functions (supersaturation, reaction enthalpies, driving force of different
processes, etc.), are obtained.
Chemical Vapor Deposition 407
Figure 7.4. Calculated CVD phase diagram for the W - Si system. Reactants WF6,
SiH4, and H2, total pressure 0.1 Torr, H2/WF6 = 39.[9]
3.3 Adhesion
The volatile reaction product HX formed reacts with the substrate S according
to the reaction
The solid substance SX formed may result in poor adhesion. The reaction
above can be predicted from thermodyamics.
economy, etc. In the following, some general comments on the design of CVD
systems are given.
A CVD system is advantageously constructed in three modules:
1. The reaction gas dispensing system.
2. The reactor, including components for defining the gas flows.
3. The exhaust system containing a total pressure controller,
vacuum pump, scrubber and/or reactant recycle system.
The process selected and the size, shape, and number of substrates
define the type of reactor and its geometry. Two main reactor types can be
distinguished:
1. In the hot wall reactor (see Fig. 7.7), the reactor tube is
surrounded by a tube furnace. This means that the
substrates and the wall of the reactor have the same
temperature. In addition to the film growth occurring on the
substrates, film growth might thus take place on theinside of
the reactor walls. With thicker films on the reactor walls,
414 Deposition Technologies for Films and Coatings
2. In the cold wall reactor (Fig. 7.8), the walls of the reactor are
cold and usually no depositionoccurs on the walls, eliminating
the risk of particles breaking loose from the walls. Furthermore,
a low wall-temperature reduces the risk of contaminating
vapor/wall reactions. In the cold wall reactor, the homogenous
reactions in the vapor are suppressed and the importance of
the surface reactions is increased. The steep temperature
gradients near the substrate surface may introduce severe
natural convection resulting in a non-uniform film thickness
and microstructure. However, with the higher flexibility of the
cold wall reactor, high cleanliness, high deposition rates
(yielding high wafer throughput), high cooling rates combined
with the needs of thickness uniformity, automatic wafer
handling and use of increasing wafer diameter, there is
tendency to more frequently use cold wall reactors in the
microelectronics.
Chemical Vapor Deposition 415
Figure 7.9. Examples of some CVD reactors. (a) and (b) RF heated cold wall
reactors, (c) vertical hot wall reactor, (d) barrel reactor.
be chosen with respect to its compatibility with the specific gaseous species.
The polymerization of the oil can easily be followed by measuring its viscosity
at different times. Mechanical pumps also produce back-diffusion of oil
molecules into the system. The back-diffusion can be stopped in a trap
(zeolite trap, liquid nitrogen cold trap) just before the pump. With the current
trend of using lower pressures to create abrupt interfaces and superlattices,
diffusion (to pump hydrogen) and turbo pumps are also utilized. Finally,
external oil filtering systems reduce the wear of the mechanical pumps in
processes where solid particles are formed and transported in the vapor to the
pump.
In a CVD process, more or less toxic, explosive, and corrosive gases
are used/formed. To remove them before exhaust, scrubbers are used. The
scrubber type is appropriate to the CVD process used. Halides can easily be
neutralized in a water scrubber. Carbon monoxide and hydrogen can be burnt
in a flame. Arsine can be removed by simply heating the reactor gas in a
furnace especially arranged for this purpose (i.e., with a high efficiency for
stripping arsenic from the gas stream).
Recycling is frequently used to improve process economy. It becomes
necessary in large scale processes, where expensive reactants are utilized
and the conversion efficiency of the reactants is low. The technique of
recycling varies from process to process. A simple recycling can be achieved
in some processes by selective condensation. It can easily be applied in
systems where the component to be recycled has the highest boiling point.
In the production of boron fibers for instance—where hydrogen and boron
trichloride are used—the unconverted boron trichloride is condensed in the exit
stream from the reactor, while the hydrogen and the hydrogen chloride (formed
in the process) are not condensed.
The rate and arrangements of the gas flows in a CVD reactor influence
the deposition conditions considerably. In the following, some fundamentals
418 Deposition Technologies for Films and Coatings
of gas flow dynamics are given. For further details the reader is recommended
textbooks in chemical engineering or other books treating transport pro-
cesses.
In a gas, different states exist. In the molecular state, the mean free
path of the molecules is much longer than the dimensions of the vessel. In
the viscous state, the mean free path is much shorter than the vessel
dimensions. The viscous state can be divided into two flow regimes. The
laminar flow regime, where the flowing gas layers are parallel, is appropriate
to low gas velocities. At higher velocities, the flow becomes turbulent. The
limit between the laminar and the turbulent flow is defined by the value of
Reynold’s number, Re:
ρ • V •D
Re =
η
Figure 7.10. Forces at a heated substrate surface. The value, g, the gravitational
force, dT/dx the temperature gradient.
In many CVD processe,s the laminar flow region is normally used. High
flow rates (turbulence) usually decrease the conversion efficiency of the
reactants to the coating and very large gas volumes have to be handled. The
flow situation around the object to be coated can be visualized in smoke
experiments where the smoke is generated inside the reactor from, for
instance, titanium tetrachloride and water.
Figure 7.12. Gas flow pattern in a cold wall reactor, where the forced and buoyance-
driven convection (a) interact, and (b) counteract, substrate temperature 900 K, Re
= 50.[34]
Figure 7.13. Gas flow pattern in a cold wall reactor with a geometry different from
that in Fig. 12.[35]
Figure 7.14. Gas flow pattern in a hot wall reactor with a temperature gradient of
6 K cm-1, linear gas flow velocity of 2 cm s-1, and channel height 5 cm, deposition
system Ga-AsCl3, H2.[32]
δ = a(ηX/ρν)1/2
424 Deposition Technologies for Films and Coatings
Figure 7.16. Temperature profile in helium. Linear gas flow velocity: 24.9 cm s-1.[28]
Figure 7.17. Concentration profiles of SiCl4 and HCl in the CVD of silicon from SiCl4
and Hc. Transport distance along the susceptor: 12.5 cm, linear gas flow velocity:
24.9 cm s-1, - - - 1000°C, —— 1140°C. [28]
426 Deposition Technologies for Films and Coatings
the susceptor, the partial pressure of SiCl4 was reduced to about 50% of the
initial value. Sedgwick et al.[29] measured temperature and concentration
profiles in an air-cooled horizontal cold wall reactor using Raman scattering.
They observed a steep temperature gradient near the susceptor. The
temperature profile developed was dependent on the position along the
susceptor.
Figure 7.18. Partial pressure profile of SiCl 4 as a function of the transport distance
along the susceptor at a height of 7 mm above the susceptor.[28]
Giling also pointed out the importance of entrance effects, i.e., that it will
take some distance (the entrance length) from the susceptor edge for full
velocity and temperature profiles to develop. According to Schlichting[36] the
entrance length for the development of the full velocity profile is given by the
equation
X = 0.04hRe
where h is the height of the channel and Re is the Reynolds number. Hwang
and Cheng[40] predicted that the thermal entrance length was seven times
longer than the flow entrance length. Giling confirmed this for H2 in his
measurements.
Coltrin et al.[41] have developed a mathematical model of silicon CVD
from silane in a cold wall reactor. The model includes gas phase chemistry
as well as fluid mechanics, and predicts temperature, velocity, and concen-
tration profiles for many vapor species. Figure 7.19 depicts the temperature
contour in a typical calculation. The thickness of the boundary layer is in the
centimeter range and increases with increasing gas transport distance along
the susceptor.
Figure 7.19. Calculated temperature contours for silicon CVD from silane (0.6 Torr)
and helium as a carrier gas (600 Torr). Temperature: 1018 K, gas flow velocity: 15.3
cm s-1.[41]
428 Deposition Technologies for Films and Coatings
Since the mass transport in the vapor or the surface kinetics usually
controls the deposition rate, the following discussions are limited to just these
two cases. Surface kinetics control is normally desirable and means a
maximum in throwing power or step coverage. Figure 7.21 shows conditions
of complete mass transport control, complete surface kinetics control and
mixed control. In the surface kinetics control, a fast diffusion in the vapor is
combined with a slow surface reaction. For a mass transport control, the
surface kinetics is fast while the mass transport in the vapor is slow.
JD = D Pb − Ps
R• T δ
km (
JM = Ps − Peq)
RT
km • δ
Pb + • Peq
Ps = D
km • δ + 1
D
Km is thus given by
Pb − Peq
JM = 1
RT δ + 1
D km
Pb - P eq is the driving force of the process and δ/D and 1/km are reaction
resistances. If δ/D >> 1/km the process is controlled by the mass transport
in the vapor, while surface reaction control is achieved at 1/km << δ.
432 Deposition Technologies for Films and Coatings
1
η • x 2
δ = a
ρ •υ
M• p
ρ=
R•T
where M = molecular weight and p = total pressure;
m
η = ηo T
To
υ = υo T
To
δ = const • T
m/ 2
p1/ 2
1.75
Pi T
D = Di ,o • •
P To
Chemical Vapor Deposition 433
where Di,o is the reference value of the diffusion coefficient andPi is the partial
pressure of species i. The reaction resistance is then
δ = const • P1/ 2
D . −m/ 2
T175
E
− a
km = A • e RT
Figure 7.22. Schematic Arrhenius plots for endothermic and exothermic pro-
cesses.
Chemical Vapor Deposition 435
Figure 7.23. Regions of mass transport and surface kinetics control at different
total pressures (P1<P 2<P3).
Figure 7.24. Influence of gas flow velocity on the control of a CVD process.
436 Deposition Technologies for Films and Coatings
SiH2Cl2(b) → SiH2Cl2(g)
where (b) and (g) refer to the bulk gas and the gas near the
substrate surface, respectively.
Chemical Vapor Deposition 437
SiH2Cl2(g) + * → SiH2Cl2*
SiCl2(g) + * → SiCl 2*
l/2 H2(g) + * → H*
4. Surface reactions:
Si* → Si(st)
Si(st) → Si(cryst)
SiCl2* → SiCl2(st)
In CVD of silicon from SiH2Cl2, the last reaction given was the
rate-determining.
438 Deposition Technologies for Films and Coatings
7.0 NUCLEATION
Figure 7.27. The Terrace, Ledge, and Kink (TLK) model of a surface.
during a relatively long period of time, is achieved (see Fig. 7.28).[48] The
saturation value is obtained at a stage when the nuclei are so dense that a
supersaturation high enough for nucleation can not be built up between the
nuclei, i.e., when the mean diffusion distance is longer than half the mean
nucleus distance. Subsequently the nuclei grow laterally and the nucleus
density is constant until coalescence occurs. The saturation nucleus
density, Ns, is strongly dependent on the experimental conditions. Figure
7.29 shows the influence of temperature on Ns for different silanes at siliconCVD.
Chemical Vapor Deposition 441
(a)
(b)
Figure 7.30. The surface of a tungsten filament (a), and preferentially nucleated
boron on ridges of the filament (b).[52]
over the mask. The process is then called ELO (Epitaxial Lateral Over-
growth). For a review of the ELO process, the reader is referred to Ref. 64.
A key point in the SEG is the suppression of the nucleation on the mask
(usually silicon oxide or silicon nitride). As mentioned in Sec. 7, the incubation
time for nucleation varies with the substrate material and the deposition
conditions. In an ideal case, this incubation time is longer than the deposition
time required to prepare the desired structures. However, by using an
alternating growth and etching process, SEG can be attained even for
conditions of short incubation times for nucleation.[65] The growth conditions
are then prevailing for about the incubation time. After the growth cycle, the
process is switched over to etching with, for instance, HCl. A minor etch is
also obtained of the monocrystalline silicon in the SiO2 openings.
The GaAs SEG/ELO is nearly as old as the silicon SEG/ELO. Tausch
and Lapierre reported in 1965 on a GaAs ELO process based on a chloride
vapor transport system.[66] With the development of the purification tech-
niques of metal-organic compounds like trimethyl gallium (TMG) and triethyl
gallium (TEG), CVD as well as MBE, based on the use of these compounds
together with AsH3, are highly attractive for GaAs SEG. MBE and elemental
sources yields monocrystalline growth in etched openings as well as
polycrystalline GaAs on the mask (microstructure-selective deposition).[70]
GaAs SEG has received much attention during the last few years as a
technique for achieving monolithic integration of electronic and optoelectronic
devices.
Growth of GaAs from AsH3 and TMG by MBE or CVD is usually
considered to be a non-equilibrium process. The perfection of the crystals
grown, their morphology, and the correlation between the growth rate and
thermodynamic parameters indicates that near-equilibrium conditions exist at
the interface between the vapor and the solid. Hence thermodynamics can be
utilized to analyze selective growth as well heterogeneous nucleation condi-
tions in GaAs CVD.
According to nucleation theory, a certain supersaturation is needed for
heterogeneous nucleation on the mask. From experimental selectivity data,
the maximum supersaturation for maintaining selectivity can be calculated.
The supersaturation is favorably expressed in terms of chemical potentials.
The influence of temperature on the chemical potential of GaAs (expressed
in elemental chemical potentials of Ga and As2 ) at equilibrium with solid
GaAs is shown in Fig. 7.32. Growth will occur if the chemical potential of
GaAs for the homogeneous equilibrium in the vapor is higher than that for the
heterogeneous equilibrium.
448 Deposition Technologies for Films and Coatings
Figure 7.32. Chemical potential of GaAs for the heterogeneous equilibrium (full
line), and for two homogeneous equilibria at different total pressures (dashed
lines). H2/AsH3/TMG = 500/10/1.[68]
Figure 7.33. Selective growth regime for GaAs. Precursors: Ga(CH3)3, AsH 3.[69]
The deposition occurs on all substrate surfaces exposed to the vapor, since
both the source material (WF6) and the reducing agent (H2) are gases.
However, if the reducing agent was replaced by a solid reducing agent (like
elemental silicon), the deposition should only occur on those substrate
regions having a reducing agent. So if a wafer exposes areas of elemental
silicon and silicon dioxide to WF6, tungsten deposition takes place only on the
silicon areas and not on the adjacent silicon dioxide areas. Silicon in silicon
dioxide can not act as a reducing agent, since this silicon has its maximum
oxidation number. This is the basis of the initial stage of selective tungsten
CVD.
The selective tungsten deposition may proceed according to the
scheme described above as long as elemental silicon is exposed to the vapor.
After a while, however, the tungsten deposited onto elemental silicon will
separate silicon from the vapor: hence a self-limiting growth process has been
obtained. The mechanism of self-limitation is under discussion and might be
also be due to a polymerization reaction involving lower tungsten fluorides.[74]
The polymer formed may also separate silicon from the vapor, hence inhibiting
the growth process. For growth of thicker tungsten layers, a reducing agent,
H2 , has to be added to the reaction gas. If the WF6 concentration is low and
the H2 concentration is high, i.e., conditions of low supersaturation are
prevailing, deposition of tungsten will occur where tungsten already has been
deposited (on elemental silicon) and not on the silicon dioxide. For deposition
on the silicon dioxide, resulting in a loss of selectivity, tungsten nucleation
must take place. The nucleation step requires a much higher supersaturation
than growth. Hence a deposition window, ranging from the supersaturation
corresponding to equilibrium conditions up to the supersaturation value
needed for heterogeneous tungsten nucleation on silicon dioxide, exists.
Finally, the selective deposition of tungsten to substrate areas where tungsten
already has been deposited, is favored by the dissociation of hydrogen
molecules on these areas.[75]
Chemical Vapor Deposition 451
The chemical reactions in the first step are usually extremely fast and
a thermodynamically controlled CVD process is obtained. In the second
process step, the deposition process was operated at a low supersaturation
to avoid nucleation on the mask material (SiO2 ). The growth conditions in the
second step are close to those existing in the area-selective epitaxy
discussed above and can be analyzed from thermodynamics. Thermodynam-
ics has been used as a guide for prediction of trends in selectivity and substrate
etching when the deposition conditions are changed. It has also been used
for identification of plausible (and often undesired) side reactions as well as of
gaseous selectivity modifiers, improving selectivity.[9]
Adsorption-Induced Selective Growth. As discussed above, the
heterogeneous nucleation on one of the substrate materials must be
suppressed during a relatively long time in an ideal selective growth
system. The incubation time for nucleation is influenced by many factors:
temperature, substrate reactivity, adsorption, etc. Adsorbed molecules
may reduce the rate of surface reactions and, in extremes, inhibit the
nucleation completely. A concept of strongly adsorbed molecules to one
of the substrate materials was used to achieve area-selective growth of
boron carbide on a patterned substrate exposing areas of titanium and
molybdenum to the vapor.[77] Boron trichloride, ethylene, and hydrogen
were used as reactants and the deposition temperature was 1400 K. The
ethylene molecules (or fragments of them) were preferentially and strongly
adsorbed on molybdenum and no nucleation of boron carbide was
observed. On titanium, however, fast nucleation kinetics was obtained.
The deposition was located only to those substrate areas having titanium.
The boron carbide was amorphous and contained about 21 at% carbon.
This illustrates that adsorbed molecules may act as masks and can be
used to inhibit the deposition on desired substrate areas.
11.0 OUTLOOK
CVD offers many advantages in thin film deposition. With the use of new
precursors, the deposition temperature can usually be lowered considerably.
By lowering the total pressure, extremely sharp interfaces with respect to
chemical composition and topography can be obtained. The atmospheric
pressure CVD is attractive in many applications with its high deposition rates
and hence short process times. Since CVD processes are based on
interfacial chemistry, they are sensitive to contamination and load-lock
systems must be used to keep the contamination level low. The selective
deposition opens fascinating prospects for the future, not only for microelec-
tronic applications but also for materials science in general, and for engineer-
ing of interfaces and artificial materials.
456 Deposition Technologies for Films and Coatings
REFERENCES
22. Boman, M. and Carlsson, J. O., in Proc. of the 9th Int'l. Conf. on CVD,
(M. Robinsson, C. H. J. van den Brekel, G. W. Cullen, J. M. Blocher,
Jr., and P. Rai-Choudhury, eds.), p. 150, The Electrochemical Society,
Pennington, NJ (1984)
23. Spear, K. E., ibid., p. 81 (1984)
24. Carlsson, J. O., J. Vac. Sci. Technol., A6:1656 (1988)
25. Powell, C. F., Oxley, J. H., and Blocher, J. M., Jr., Vapor Deposition,
John Wiley & Sons, Inc., New York (1966)
26. Yee, K. K., Int. Met. Reviews, 1:19 (1978)
27. Perry, A. J., Beguin, C., and Hintermann, H. E., in Proc. of the 3rd
European Conf. on CVD, (H. E. Hintermann, ed.), p. 131 (1980)
28. Ban, V. S. and Gilbert, S. L., J. Cryst. Growth, 31:284 (1975)
29. Sedgwick, T. O., Smith, J. E., Ghez, Rh., and Cowher, M. E., J. Cryst.
Growth, 31:264 (1975)
30. J. Nishizawa, and M., Saito,in Proc. of the 8th Int'l. Conf. on CVD, (J.
M. Blocher, Jr., G. E. Vuillard, and G. Wahl, eds.), p. 113, The
Electrochemical Society, Pennington, NJ (1981)
31. Bird, R. B., Stewart, W. E., and Lightfoot, E. N., Transport Phenomena,
John Wiley & Sons, Inc., New York (1960)
32. Westphal, G., J. Cryst. Growth, 65:105 (1983)
33. Jensen, K. F., Proc. of the 9th Int. Conf. on CVD, (M. Robinsson, C. H.
J. van den Brekel, G. W. Cullen, J. M. Blocher, Jr., and P. Rai-
Choudhury, eds.), p. 3, The Electrochemical Society, Pennington, NJ
(1984)
34. Wahl, G., Thin Solid Films, 40:13 (1977)
35. Wahl, G. and Hoffman, R., Rev. Int. Hautes Temp. Refract., 17:7 (1980)
36. Schlichting, H., Boundary Layer Theory, 6th ed., McGraw-Hill, New
York (1968)
37. Eversteijn, F. C., Severin, P. J. W., van den Brekel, C. H. J., and Peek,
H. L., J. Electrochem. Soc., 117:925 (1970)
38. Talbot, L., Cheng, R. K., Schefer, R. W., and Willis, D. R., J. Fluid
Mech., 101:737 (1980)
39. Giling, L. J., J. Electrochem. Soc., 129:634 (1982)
40. Hwang, G. J. and Cheng, K. C., J. Heat Transfer, Trans ASME, 95:72
(1973)
458 Deposition Technologies for Films and Coatings
41. Coltrin, M. E., Kee, R. J., and Miller, J. A., Proc. of the 9th Int'l. Conf.
on CVD, (M. Robinsson, C. H. J. van den Brekel, G. W. Cullen, J. M.
Blocher, Jr., and P. Rai-Choudhury, eds.), p. 31, The Electrochemical
Society, Pennington, NJ (1984)
42. Rosenberger, F.,Fundamentals of Crystal Growth, Springer, New York
(1979)
43. Carlsson, J. O., J. Less-Common Metals, 70:97 (1980)
44. Claassen, W. A. P. and Bloem, J., J. Electrochem. Soc., 50, 807,
(1980)
45. Venables, J. A. and Price, C. R., Epitaxial Growth, (J. W. Matthews,
ed.), p. 381, Academic Press, New York (1975)
46. Chernov, A. A., J. Cryst Growth, 42:55 (1977)
47. Carlsson, J. O., Proc. of the 3rd European CVD Conference, (H. E.
Hintermann, ed.), p. 10 (1980)
48. Venables, J. A., Phil. Mag., 27:698 (1973)
49. Claassen, W. A. P. and Bloem, J., J. Electrochem. Soc., 127:1836
(1980)
50. Hirth, J. P. and Pound, G. H.,Condensation and Evaporation, MacMillan,
New York (1963)
51. Walton, D., J. Chem. Phys., 37:2182 (1962)
52. Vega-Boggio, J., Vingsbo, O., and Carlsson, J. O., J. Mater. Sci.,
12:1750 (1977)
53. van den Brekel, C. H. J. and Jansen, A. K., J. Cryst. Growth, 43:364
(1978)
54. Blocher, Jr., J. M., J. Vac. Sci. Technol, 11:680 (1974)
55. Eherlich, D. J. and Tsao, J. Y., ibid., B1:969 (1983)
56. Chin, B. H. and Ehrlich, G., Appl. Phys. Lett., 15:253 (1981)
57. Matsui, S. and Mori, K., J. Vac. Sci. Technol., B4:299 (1986)
58. Kunz, R. R., Allen, T. E., and Mayer, T. M., ibid., B5:1427 (1987)
59. Melngailis, J., ibid., B5:469 (1987)
60. Kato, T., Morimoto, H., Saitoh, K., and Nakata, H., ibid., B3:50 (1985)
61. Higashi, G. S., Blonder, G. E., and Fleming, C. G.,“Photon, beam, and
plasma stimulated chemical processes at surfaces”, (V. M. Donelly, I.
P. Herman, and M. Hirose, eds.), 75:117, Materials Research Society,
Pittsburgh, PA (1987)
62. Joyce, B. D. and Baldrey, J. A., Nature, 195:485 (1962)
Chemical Vapor Deposition 459
63. Borland, J. O., Proc. of the 10th Int'l. Conf. on CVD, (G. W. Cullen and
J. M. Blocher, Jr., eds.), p. 307, The Electrochem. Soc., Pennington,
NJ (1987)
64. Jastrzebski, L., J. Cryst. Growth, 63:493 (1983)
65. Jastrzebski, L., Corboy, J. F., McGinn, J., Pagliaro, R., Jr., J.
Electrochem Soc., 130:1571 (1983)
66. Tausch, F. W. Jr. and Lapierre, A. G., III, ibid., 112:706 (1965)
67. Furumura, Y., Mieno, F., Nishizawa, T., Maeda, M., ibid., 133:379
(1986)
68. Carlsson, J. O., Proc. of 13th Nordic Semiconductor Meeting, (M.
Östling, ed.), p. 298, The Royal Institute of Technology, Stockholm
(1988)
69. Carlsson, J. O., Unpublished
70. Green, M. L., Borland, J. O., Proc. of the 10th Int'l. Conf. on CVD, (G.
W. Cullen and J. M. Blocher, Jr., eds.), p. 603, The Electrochem. Soc.,
Pennington, NJ (1987)
71. Lami, P. and Pauleau, Y., J. Electrochem. Soc., 135:980 (1988)
72. Pauleau, Y., Lami., P., Tissier, A., Panyel, R., and Oberlin, J. C., Thin
Solid Films, 143:259 (1986)
73. Green, M. L., Ali, Y. S., Boone, T., Davidsson, B. A., Feldman, L. C.,
and Nakahara, S., J. Electrochem. Soc., 134:2285 (1987)
74. Lifshitz, N., Appl. Phys. Lett., 51:967 (1987)
75. McConica, C. M. and Krisnamani, K., J. Electrochem. Soc., 133:2542
(1986)
76. Levy, R. A., Greene, M. L., Gallagher, P. K., and Ali, Y. S., J.
Electrochem. Soc., 133:1905 (1986)
77. Jansson, U. and Carlsson, J. O.,J. Vac. Sci. Technol., A6:1733 (1988)
78. Jansson, U., Carlsson, J. O., Markert, L. M., and Greene, J. E.,
Submitted to J. Vac. Sci. Technol., A7(6):3172 (1989)
79. Jansson, U., Carlsson, J. O., Markert, L. M., and Greene, J. E.,J. Vac.
Sci. Technol., A9(2):266 (1991)
8
Arthur Sherman
1.0 INTRODUCTION
460
Plasmas in Deposition Processes 461
next to the cathode where few collisions occur and charge neutrality is not
obeyed. In this region, ions are accelerated toward the cold cathode, and upon
striking emit secondary electrons. These secondary electrons sustain the
discharge. An alternative would be to use a hot cathode which serves as a
thermionic emitter. The sheath includes the Aston, Crookes and Faraday dark
spaces as well as the cathode and negative glows. This region has a net
positive charge because of the excess of ions there. The positive column
shows no net space charge, so this is the true plasma. It’s electrical resistivity
is low, so only a weak electrical field is necessary to establish a current flow.
Ions and electrons recombine to neutral atoms in this region, either by gas
phase recombination or diffusion to the tube walls. They are regenerated by
electron impact ionization.
A potential difference is established between the positive column and the
tube wall, because the highly mobile electrons tend to flow rapidly out to any
surface, while the heavy ions remain immobile. This creates a negative
potential on the wall which hinders further electron outflows. A sheath forms
next to the wall which has a deficit of electrons and therefore a positive net
charge. The ions in the plasma see the negative wall potential, however, and
are attracted to the wall. This ion diffusion to the walls is referred to as
ambipolar diffusion.
When the glow discharge of Fig. 8.1 is operated under AC conditions
(below 10 kHz), two dark spaces are observed. We have essentially created
DC discharges of alternating polarity, since there is time between cycles for
the discharge to extinguish at low frequencies. Depending on geometry and
gas, the starting of an AC discharge depends on frequency and pressure.[5]
Finally, when an AC discharge is set up with a blocking capacitor between the
power supply and one of the electrodes, that electrode has a negative self-bias.
This causes ions to accelerate toward this electrode at high energies, and
plasma etching for ICs uses this phenomena to create anisotropic etches.[6]
Figure 8.2 provides an excellent explanation of why a negative self-bias
forms.[7] In the figure on the left, a conducting probe is placed in a plasma
where a positive voltage causes a large current flow. A negative voltage
produces only a small current because the ions cannot move readily. This
produces a zero self-bias. When the probe is attached to a capacitor, the
figure on the right shows what happens. The average applied voltage must be
negative to satisfy the condition of no average current flow. Therefore, a
negative bias forms.
Plasmas in Deposition Processes 463
Next, we can evaluate the situation that occurs when one electrode is
larger or smaller than the other, as shown in Fig. 8.3. If it is assumed that the
ion current density to all internal surfaces is the same, then a relationship
between V1/V2 and A 1/A2 can be derived.[8]
4
V1 A2
=
V2 A1
Eq. (1)
Some experimental work has been done to examine the validity of Eq. (1).[9]
Here peak-to-peak and AC bias voltages were measured in a 13.56-MHz glow
discharge. Results showed that voltage ratios depended on the electrode area
ratios as well as the electrode material, the gas, the pressure and the peak-
to-peak voltages. Some of these results are shown in Fig. 8.4 for argon in a
stainless steel chamber operated at 50 mTorr with a peak-to-peak voltage of
600 V.
Under these conditions, V1/V2 = (A1/A2)n is a fair representation of the
data, but n≅ 4 for only 0.6 < A1 /A2 < 1.0 Smaller ratios give n ≅ 1. From these
results, we conclude that the DC bias that will appear on the electrode carrying
wafers will depend on the electrode configuration. It can also be a function of
the frequency used, as discussed next.
Plasmas in Deposition Processes 465
Figure 8.4. Voltage ratio versus area ratio for argon plasma.[9]
466 Deposition Technologies for Films and Coatings
Figure 8.5. Cl2 plasma beam maximum ion energy. Circles = 27 MHz; triangles
= 100 kHz; solid = Cl2*; open = Cl*.[10] (Reprinted by permission of the publisher,
The Electrochemical Society, Inc.)
Plasmas in Deposition Processes 467
One explanation of why the lower frequency produces more intense ion
bombardment is that the sheath potential is higher. Then, since the electrons
are lighter, they diffuse out of the plasma first and the electrode assumes a
negative bias. For higher frequencies, however, there is less time for electrons
to diffuse out between cycles, so there is less need for a strong negative bias
to form. A weaker negative bias means lower energy ions at the electrode
surface.
Alternately, we recognize that the plasma potential varies with time.[12]
When an ion can cross the entire sheath before a reversal of the applied field,
it sees the maximum sheath potential. For higher frequencies, the ion does
not make it all the way across before the applied field reverses, so it sees only
the average sheath potential or 1/3 the maximum.
There are three well-known methods of creating plasmas for thin film
deposition. In one, a pair of electrodes are placed in a low pressure gas, and
either an AC or a DC voltage applied to create a glow discharge. If the film being
deposited is a nonconductor, only AC will work, so it is generally used. A
second approach uses a coil wound around a nonconducting tube containing
the gas. Then an AC field excites strong fields inside the tube and a discharge
can be created. Finally, a pair of electrodes can be placed, one on each side
of a dielectric tube filled with gas, and again an AC voltage applied. This also
produces a strong field inside the tube, and a discharge can be created.
468 Deposition Technologies for Films and Coatings
In the present section, we review some of the films that can be deposited
by PECVD, with particular emphasis on those that are commercially important
for fabrication of integrated circuits. Therefore, we concentrate on silicon
nitride and silicon dioxide films. Amorphous silicon films are also deposited
by PECVD, but they are used commercially in the manufacture of solar cells
(not in the IC industry). Many other films can be deposited by PECVD,
including conducting films, and these are reviewed briefly. More details are
available elsewhere.[1]
PECVD of silicon nitride has generally been done using SiH4 as the silicon-
bearing reactant and some combination of NH3, N2 and H2 with one of several
inert gases as diluents. The reactors used are all capacitively coupled and run
at RF frequencies. For a particular reactor configuration, some of the parameters
governing the film are:(i) operating pressure,(ii) operating temperature,(iii)
discharge frequency, and (iv) reactant gas mixture.
Plasmas in Deposition Processes 473
Table 8.1. Physical and chemical properties of CVD and PECVD silicon
nitride films.[19]
Figure 8.11. Stress in silicon nitride films as functions of pressure, frequency and
temperature.[20] (Reprinted by permission of the publisher, The Electrochemical
Society, Inc.)
As circuit parameters have become more extreme with the advent of VLSI
and ULSI circuits, the demands on PECVD silicon nitride films have increased.
An excellent review of problems in passivation, such as its influence on
aluminum voiding, electromigration, hillock formation, hot carriers, etc. has
been published recently.[22]
One way to deal with these new requirements is to use a PECVD
reactor operated with dual frequency, such as the one shown in Fig. 8.6.[14]
The use of this feature allows considerably more flexibility in film deposition
476 Deposition Technologies for Films and Coatings
Figure 8.12. Hydrogen % versus deposition temperature for films deposited with
SiH4 + NH3, SiH4 + N2 and SiH4 + NH3 + N2 (one point).[21]
Plasmas in Deposition Processes 477
Figure 8.14. Si-H and N-H content of PECVD silicon nitride as a function of percent
of low frequency power.[14]
478 Deposition Technologies for Films and Coatings
PECVD oxide can be grown from a number of reactants. Most work has
been done with SiH4 plus any one of a number of oxidizers such as O 2, CO2,
N2 O. Because of the potential for gas phase nucleation, O2 is generally
avoided; the most commonly studied system is SiH4 + N2 O.[17] More
recently, there has been considerable interest in the use of TEOS
(tetraethoxysilane) plus O2, because of the improved step coverage possible
with this system.[23]
To illustrate the process, we can review the SiH4 + N2O PECVD process
carried out in a cold-wall parallel-plate reactor (Fig. 8.8) at 57 kHz, 400 mTorr
and 300°C. Typical results are listed in Table 8.2, where they are compared
to similar results for PECVD silicon nitride. Observe that although the power
level used for oxide is one-third that for nitride, the deposition rate is twice as
high. Probably, the most significant finding is that there can be nitrogen as
well as hydrogen in this film. In fact, adjusting the film stoichiometry and
creating only nitrides is one of the most useful features of such a system.
For example, we can adjust the dielectric constant over a range of 3:1
by changing the gas phase ratio of N2O to silane, as shown in Fig. 8.15. These
experiments were carried out again in a parallel-plate cold-wallreactor at 600
mTorr and 350°C at a high frequency, 13.56 MHz.[24] Increasing the silicon
content of the film appears to increase the dielectric constant.
Figure 8.16. SEM cross section micrographs of plasma oxide deposited from (a)
silane and (b) TEOS for an aspect ratio of 0.74 (aspect ratio = metal height/metal
space)[23]
The process conditions for the PECVD TEOS films are shown in Table
8.3, and the film properties are reported in Table 8.4. It is interesting to note
that these depositions were done at 13.56 MHz in a cold-wall reactor.[23] Also,
in spite of the film deposited from TEOS, there is very little carbon contamination
of the film.
Plasmas in Deposition Processes 481
The silicon nitride and oxide films just discussed are the only PECVD
films currently being used commercially in integrated circuit manufacture.
There are, however, many materials that can be deposited by this technique.
These include other dielectrics, semiconductors (polysilicon, epi-silicon) as
well as conductors. The latter may eventually be of commercial significance,
so it is of value to summarize some of the more interesting studies that have
been done. Table 8.5 lists some of the more interesting PECVD conducting
films.
482 Deposition Technologies for Films and Coatings
REFERENCES
29. Hieber, K., Stoltz, M., and Wieczorek, C.,Proceedings of 9th International
Conf. on Chem. Vapor Dep., (McD. Robinson, G. W. Cullen, eds.), 84-
6:205, Electrochemical Society, Pennington, NJ, (1984). This figure was
originally presented at the Spring 1984 Meeting of the Electrochemical
Society, Inc. held in Cincinnati, OH.
30. Rosler, R. S., and Engle, G. M., J. Vac. Sci. and Technol., 82(4):733
(1984)
31. Ito, T., Sugii, T. and Nakamura, T., Digest of Papers of 1982 Symp. on
VLSI Technol., IEEE, New York (1982)
32. Jang, D. H., and Chun, J. S., J. Vac. Sci Technol., A7(1):31 (1989)
33. Hilton, M. R. et al., Thin Solid Films, 139:247 (1986)
9
Rointan F. Bunshah
1.0 INTRODUCTION
485
486 Deposition Technologies for Films and Coatings
The objective of any deposition process is to end up with a film with the
desired composition, structure and properties. In plasma-assisted reactive
process, there are some key issues.
E =x
RA = N
∫ (E/ 2me ) 12 n e σ (E )f (E )dE
E =0
The most commonly used plasma assisted techniques for the deposition
of compounds can be classified under the following two categories.
1. Plasma-assisted chemical vapor deposition (PACVD) pro-
cesses.
2. Plasma-assisted physical vapor deposition (PAPVD) pro-
cesses such as(a) reactive sputtering (RS), using DC or RF
magnetron geometries and ion beams,and (b) activated
reactive evaporation (ARE).
Although they have been treated in other chapters, a summary is given
here for each process with relevance to the main theme of the chapter.
Figure 9.3. Schematic of the activated reactive evaporation system: (a) using an
electron beam evaporation source, and (b) using a resistance-heated evaporation
source.
Plasma-Assisted Vapor Deposition Processes 499
Most of the above limitations are due to the interdependency of the three
reactions, i.e., plasma-source, plasma-volume, and plasma-substrate reac-
tions. For an ideal plasma-assisted process, one should be able to control
each of the above reactions independently of each other.
In view of the above, attempts have been made to develop hybrid
processes by combining various features of the plasma-assisted deposition
techniques to extend the processing capabilities and to overcome the
limitations of the individual techniques. Many modifications of the PACVD
have been developed and have been discussed by Deshpandey and Bunshah.[17]
In view of the facts discussed in the previous section, attempts have been
made to develop hybrid processes by combining different plasma-assisted
deposition techniques to extend the processing capabilities and to overcome
the limitations of the individual techniques. The general thrust is directed
towards:
1. Separation of the various parts of the process so as to exert
independent control over each part and avoid complications
due to overlap between the parts.
2. Use substrate/film bombardment with different species of
controlled energy as contrasted to a spectrum of energies.
A representative list of such hybrid techniques together with their
advantages in processing is given in Table 9.3 and illustrated in Fig. 9.4
9.0 CONCLUSIONS
REFERENCES
Morton Schwartz
1.0 INTRODUCTION
506
Deposition from Aqueous Solutions 507
The stability of the gold cyanide complex ion is such that it exists in mildly
acidic gold plating solutions.
It should be noted that the complex ions described above and other
types are anionic and would migrate to the anode during electrolysis. Yet,
deposition still takes place at the cathode, indicating that mechanisms other
than simple electron reactions are involved in the cathode film. These
complex anions approach the cathode by convection and/or diffusion where
specific adsorption effects can occur in the double layer as discussed by
Wagner, citing Frumkin and Florianovich.[6] The influence of simple cations
present in the film are also involved in the reduction process.
Faraday’s Laws of electrolysis (1833) are basic to electrodeposition.
* Most acidic plating solutions fall into this category, involving the simple ions.
510 Deposition Technologies for Films and Coatings
They relate the current flow, time, and the equivalent weight of the metal with
the weight of deposit and may be stated as follows:
1. The amount of chemical change at an electrode is directly
proportional to the quantity of electricity passing through the
solution.
2. The amounts of different substances liberated at an electrode
by a given quantity of electricity are proportional to their
chemical equivalent weights.
Faraday’s Laws may be expressed quantitatively:
I · t Eq
Eq. (4) W = ____________
F
t2
I dt
t1
** The Faraday can be derived from the fact that 1 gram-atomic weight of an element
contains 6.023 x 1023 atoms (Avogadro’s Number, N). If the charge on the ion is A,
then Z x N electrons are required to deposit 1 gram-atomic weight, and Z x N/A =
6.023 electrons are required to deposit (or dissolve) 1 equivalent weight of an
element. Since the charge on an electron is 1.602 x 10-19 coulombs, 6.023 x 1023
electrons x 1.602 x 10-19 coulombs = 96,496 coulombs.)
Deposition from Aqueous Solutions 511
I · t Eq
____________
Eq. (5) F =
W
Rearranging Eq. (4) to
WF
_________
Eq. (6) It =
Eq
permits the determination of the charge passing through a circuit by the
known deposition or dissolution of an element, usually silver. Devices which
utilize this application of Faraday’s Laws are known as coulometers.
Coulometers are used to determine the efficiency of a deposition process.
They are also employed as either timers or integrators possessing
“electrochemical memory” and producing sharp potential “end-points,” i.e.,
significant changes in electrode potentials which activate electronic circuits.
Figure 10.2 schematically illustrates such a device—an electrochemical cell
called an E-cell as part of an electronic circuit.
Table 10.1 indicates typical cathode current efficiencies for some common
deposits from various electrolytes. With knowledge of the actual efficiency,
predicted (average) thickness of deposit can be obtained, limited by the
control of the current distribution.
Ag CN 100
Au Acid
Neutral 50 - 100
CN
Cd CN 85 - 95
Cr CrO3 /H2SO4 10 - 15
CrO3 /SO4-F 18 - 25
Fe Acid 90 - 98
In Acid or CN 30 - 50
Ni Acid 93 - 98
Pb Acid 95 - 100
Rh Acid 10 - 50
Sn Acid 90 - 95
Alkaline 70 - 95
Zn Acid ~95
CN 50 - 80
___________________________________________________
Deposition from Aqueous Solutions 513
Eq. (8) E = IR
where E = volts, I = amps, and R = ohms. This law regulates both the current
flow and its paths in an electrodeposition cell. A commercial electroplating
installation and operation involves a multiplicity of series and parallel
electrical circuits with only the total current and applied voltage controlled.
The current distribution on each individual part or portion of a part (and
resulting deposit thickness and properties) depends on the electrode potentials
and resistances involved in the “mini-circuits” as well as the geometry and
spacing of parts. Since the resistances of the solid, metallic conductors in
the circuit are several orders of magnitude lower than the electrolytic
(solution) resistances, they can usually be neglected. The potentials within
the electrolyte and, more importantly, the electrode-electrolyte interfaces,
are fundamental controlling factors and are not as straight-forward as
suggested by Ohm’s Law.
When a metal is immersed in a solution containing its ions, an equilibrium
condition is set up between the tendency for the metal to go into solution and
the tendency for the metallic ions in solution to deposit on the metal: M0 ← →
Mn+ + ne-. However, before this equilibrium is established (i.e., the exchange
currents or current densities are equal |i+| = |i-| = i0 ), one of the reactions may
be faster than the other, resulting in a “charge separation.” If the reaction
proceeding to the right is faster than to the left, the metal surface would be
negatively charged. If the deposition reaction (to the left) is faster, then the
surface would be positively charged. This resulting potential between the
metal and the solution (at unit activity) is called the single or standard
electrode potential. Since this is a half-cell reaction, a reference electrode,
the saturated hydrogen electrode (SHE) is used to complete the circuit and
is given the arbitrary value of zero potential. In many instances other
reference electrodes such as the calomel electrode are substituted with
appropriate corrections. Potential measurements made in this manner (or
values derived thermodynamically) result in a series known as the
Electromotive Force (EMF) Series.
This origin of the electrode potential was first formulated by W. Nernst
(1889). The magnitude of the potential difference between the metal and its
ionic solution is given by the Nernst equation:
514 Deposition Technologies for Films and Coatings
RT ax (products)
Eq. (9) E = Eo + _____ ln ______________
nF ay (reactants)*
* Since the metal (solid) is the reactant in a plating cell, its activity is considered =
1 for all practical purposes and can be neglected. Also, as a practical approximation,
the concentration in moles/L can be substituted for activities.
** 0.059 = 2.303 x 8.316 x 298.1 / 96,496.
*** When complex ion reactions are involved:
Eq. (11) Mn+ + qX p- →
← [MXq]n-pq
RT RT a nM− pq
q
Eq. (12) E= Eo - nF ln Kf + nF ln q
a p−
X
Kf is the stability constant of the complex ion. Since Kf will be quite large for very
stable complexes, the potential can shift substantially negatively.
Deposition from Aqueous Solutions 515
The practical significance is that a copper cyanide strike provides the best
undercoat on a zinc surface since the potentials are essentially the same.
Attempts to use an acid copper (Cu2+ ) (Eo = +0.34 volts) solution would
provide a potential difference of 1.1 volts, resulting in an immersion or
displacement deposit with poor adhesion. The closeness of the electrode
potentials for the [Zn(CN)4]= and [Cu(CN)3 ]= complexes also permits these
metals to be deposited simultaneously as a brass alloy deposit from cyanide
solutions.
For electrodeposition reactions to occur, an additional potential is
required to overcome the equilibrium conditions discussed above, i.e., to
provide a non-equilibrium, irreversible condition. Referring to Fig. 10.1, the
total plating voltage is the sum of three components. E2 represents the
potential required to overcome the resistance of the electrolyte and obeys
Ohm’s Law; it would be the only potential required if only the single electrode
potentials were involved in the electrodeposition process. E1 and E3 are the
potentials at the electrodes required to sustain the electrolysis process when
the current is flowing and exceed the single electrode potentials. The
additional voltage is called polarization which usually increases as the
current increases. The electrical energy is converted to heat according to
Joules Law:
thereby consuming them and/or converting them into other compounds which
may be detrimental to the electrodeposition process. In some pro-
cesses, such as anodizing of aluminum or where insoluble anodes are
involved such as in chromium plating, anode polarization is desirable.
Cathodic concentration polarization may result in the evolution of
hydrogen as the competing reaction. The pH of the cathode film increases
and hydrates or hydroxides may precipitate and be occluded in the deposit.
The co-deposition of hydrogen may result in brittleness of the deposit and,
by migration and diffusion into the substrate, result in hydrogen embrittlement.
The latter step is usually the slower, rate-determining step, and a higher
potential is required to discharge the gas.
The factors influencing hydrogen or oxygen overvoltage include:
a. Electrolyte composition
b. Type of metal electrode
c. Nature of electrode surface
d. Current density
e. Temperature
518 Deposition Technologies for Films and Coatings
Type of Electrolyte
Simple “Free” Ions
Complex Ions
Supporting Ions
Polarization
Conductivity
Cathode Efficiency-
Current Density Curves
Geometry of Plating System
Other Factors
Substrate Composition and Structure
Surface Preparation and Pre-treatment
Cell,[11] and Wagner number are reviewed and analyzed by Ibl.[12] Shawki et
al[13] devised a method for measuring throwing power into recesses and holes
using cathodes with varying tube diameters and determining plate thickness
along the depth of the tubes.
The concept of microthrowing power is discussed later.
3.0 ELECTRODEPOSITION
ogy and properties of the final deposit. The presence of other inorganic ions
and organic additives in the double layer or adsorbed on to the surface can
greatly modify the electrocrystallization and growth process (Fig. 10.5).
Figure 10.5. (a) The distribution of ions and dipoles in the electrical double-layer.
(1) Cations, (2) anions, (3) specifically adsorbed anions, (4) adsorbed additives, (5)
adsorbed water dipoles, (6) electrons. (b) The potential as a function of distance in
the double-layer [corresponding to (a)] measured from the metal surface.[16]
522 Deposition Technologies for Films and Coatings
Figure 10.7. Relation of Nernst diffusion layer (δN) to actual diffusion layer (δ).
The limiting current (or current density) (see Fig. 10.4) can be defined*
as:
* Electroplaters consider the limiting current density as the maximum current density
which will still produce acceptable deposits. This value is generally lower than
calculated values using Eqs. 18 and 19.
Deposition from Aqueous Solutions 525
rather the ratio of actual plating current density to the limiting current
density,i/iL . He determined that when the ratio exceeded 0.6, rough deposits
generally resulted, with the concentration overpotential, ηC, becoming
appreciable. The limiting current density is higher as agitation is increased,
especially in the turbulent regime.
3.2 Parameters
Basic Electrolyte
Composition Controlled Plating
Variables
Impurities
pH
C.D.
Temperature
Agitation
Additives Composition and Time
Structure of
Leveling Deposit
Brightening Current
Anti-pitting Characteristics
Grain refining Thickness
Stress relieving DC-% ripple
PR
IC
Superimposed AC
Asymmetrical AC
Pulsed
Density Hardness
Coefficient of thermal Ductility
expansion Tensile Strength
Electrical resistance Stress
Modulus of elasticity
Corrosion resistance
Magnetic properties
The time interval (on + off) is the reciprocal of the frequency, the on time being
the product of the time interval and duty cycle.
The average current density is calculated as the peak current density
times the duty cycle. The average current density in pulse plating cannot
Deposition from Aqueous Solutions 533
Eq. 21 Cu2+ + e- → Cu 1+
where Eq. 21 is faster than Eq. 22 during the first interval of the pulse. Thus,
the cuprous ion (Cu1+) accumulates and during the relaxation (off) period
disproportionates:
Eq. 23 2Cu1+ ←
→ Cu2+ + Cu0
The throwing power of copper, as measured with the Haring Cell, was
somewhat reduced by pulse plating while that of gold from a citrate-
phosphate solution was improved; however, the improvement diminished
rapidly with increasing peak current densities. Using a rotating disc
electrode, they found a slight improvement in the microthrowing power of the
gold solution due to pulsing; however, the current densities and especially
the agitation used had more significant effects.
Reid[51] found that pulsed plating in cobalt-hardened gold deposits
virtually eliminated polymer formation under low C.D. (~5 mA/cm2 ) and high
off-to-on ratios (100 ms/10 ms). Other effects in the properties noted were:
1. Improved ductility without any significant decrease in hard-
ness.
−even in the presence of polymer−
2. Increased density− −from 17.1
gm/cm3 for DC plating (1 mA/cm 2) to 19.2 gm/cm3.
534 Deposition Technologies for Films and Coatings
Some of the effects and advantages attributed to pulse plating and other
modulated current wave forms are very similar to those for ultrasonic
agitation. Both attempt to reduce the adverse polarization effects by
decreasing the Nernst diffusion layer thickness while increasing mass
transfer of the reacting species, permitting the use of higher current densi-
ties. In many instances, pulse plating has an effect similar to organic addition
agents, especially as related to grain size.
A more recent approach to modification of plating processes and
resulting deposits involving the simultaneous application of laser energy was
first reported by von Gutfeld et al.[60] The impingement of a laser beam on
the cathode surface resulted in increased plating rates by as much as a factor
of 1000. The mechanisms responsible for this deposition rate increase were
investigated by Puippe et al.[61] The absorption of laser energy resulted in
localized increase in temperature at the cathode/solution interface which
produced vigorous agitation (microstirring), a shift in the rest potential (open
circuit potential), and an increase in both the charge transfer and mass
transfer rates.
Gutfeld and Romankiw[62] described the application of laser-enhanced
plating to gold patterning, i.e., the selective deposition on spots and patterns
or tracks with the ability to “write directly” without the use of masks as well as
potential use in repair of electronic circuitry. Bocking[63] described plating
equipment and set-up combining laser-enhanced plating with high speed jet
selective plating with plating rates as high as 16 ∝m/s. Pure gold was
deposited on both metallic and metallized ceramic substrates without the
need for any masking. Gutfeld et al.[64] developed a method for selective
pattern plating by applying a dielectric coating and utilizing a laser (Nd-YAG
laser) to produce the desired pattern leaving a clean surface which could then
be plated by conventional means. Gelchinski et al.[65] found that laser-
enhanced jet plating of gold increased deposit smoothness and decreased
nodularity and voids with increasing laser power density; hardness of the
deposits was in the range characteristic of soft gold.
Kuiken et al.[66] indicated that laser-enhanced plating was not very
effective on good heat-conducting substrates since only a limited tempera-
ture rise results. They suggested depositing an undercoat of a relatively poor
heat-conducting material such as a nickel-phosphorus alloy (which is almost
1/20 that of nickel), significantly improving the effectiveness of laser-
enhanced plating and reducing the need for high laser power densities.
536 Deposition Technologies for Films and Coatings
The lower pH’s and free cyanide are used for sensitive metals such as
aluminum or zinc alloys; the higher pH is used for steels. The cleaning or
activating ability is increased with increasing pH, free cyanide, C.D. and
temperature. The deposit thickness is approximately 0.25 - 0.50 ∝m (0.01
- 0.02 mils); thicker deposits—1.25 - 2.5 ∝m (0.05 - 0.1 mils)—are applied
at slightly higher temperatures.
The second most common strike is the Woods nickel strike or its
modifications. This strike is effective (and preferred) on high nickel or
chromium containing alloys. A typical formulation is:
Nickel Chloride, NiCl2· 6H2 O 240 g/L (32 oz/gal)
Hydrochloric Acid (Conc.): 125 ml/L (16 fl. oz/gal)
Temperature RT (20 - 30oC)
C.D. 5 - 20 A/dm2 (50 - 200 A/ft2)
Time 0.5 - 3 minutes
Silver or gold strikes are used prior to plating thicker deposits of these
metals. Either a gold strike or the strike of the particular precious metal is
used prior to plating the specific metal. These are generally formulated
similar to the plating solution except that they contain approximately one-
tenth the metal ion concentration. The strikes may be applied directly to the
substrate or, more commonly, on the copper or nickel strikes discussed. The
use of these strikes minimizes the possible contamination of precious metal
plating solutions.
Unusual strikes are sometimes employed in special procedures. For
example, a chromium strike appears to be most effective for plating on
molybdenum alloys or an acid copper or electroless nickel strike on titanium
alloys followed by a thermal diffusion treatment to obtain adhesion of
subsequent deposits.
Properly designed preparation cycles and the establishment of a stable
receptive surface are prime requisites for good quality deposits. However,
the condition and integrity (or lack of it) of the surface prior to plating also
affect the quality of the deposit; this is becoming more evident as quality and
functional requirements of electrodeposits are increased.
Some plating processes require post-plating treatments. To improve
the corrosion resistance of zinc or cadmium deposits or the tarnish resis-
tance of silver, chromate conversion coatings are applied by chemical or
electrochemical treatments; these gel-like films also improve adhesion of
paint films.
Since most preparation and plating processes generate hydrogen
which can be occluded and can migrate into the substrate, possibly causing
Deposition from Aqueous Solutions 539
High temp. oxidation Cr, Rh, Pd, Pt, Air and space craft
resistance Au, Ni Electronic devices
Diffusion Barrier
Figure 10.11. Binary alloys which have been electrodeposited form aqueous
solution: % indicates alloys reported up to 1960, $ indicates alloys electrodeposited
for the first time between 1961 and 1964, and & indicates alloys reported since
1964.[73]
544 Deposition Technologies for Films and Coatings
(a)
(b)
(c)
Figure 10.12. Diffused Co-W/Cr/Co-W composite coatings. (a) H.T. in air, 1680°F,
10 hrs (500x) (unetched), (b) H.T. in carburizing atmosphere, 1680°F, 10 hrs (500x)
(unetched), (c) H.T. in atmosphere, 1680°F, 10 hrs (500x) (etchant: hot Murakami).
Deposition from Aqueous Solutions 547
TiO 2 (0.01 - 0.03 ∝m) although Al 2O3, BaSO4, Pb3 O4 and W additions were
also studied,[97] indicating the possibility of specificity with respect to the
dispersoid. Greco and Baldauf[98] found 2 - 15% of Al2O3 to be the effective
range for dispersion-hardening of Ni deposits from a sulfamate bath. The
increase in hardness appeared to be linear to the square root of the volume
fraction of the dispersoid with Al2 O3 showing a higher slope than TiO2 . The
deposits contained three times (v/o) more TiO2 than Al2O3 at the same
solution concentrations and plating conditions; the particle size averaged
0.074 ∝m Al 2O3 (0.013 - 0.339 ∝m range) and 0.2 ∝m TiO2 (0.037 - 0.313
∝m range).
Table 10.6 indicates the variations in mechanical properties of particle-
dispersed nickel alloys due to the dispersoid material and the plating solution
composition.
Electrophoresis is the term used to describe the migration, by virtue of
the electric charge on their surfaces, of colloidal or near-colloidal particles in
a suspending medium when a potential is applied. This migration is
analogous to ionic migration through a solution. The electrical double layer
of charges discussed above is involved. The process has been applied to
the deposition of a variety of materials including metal powders, oxides,
cermets and other particles to metal substrates. Usually the particles ranging
in size between 0.5 and 45 ∝m are suspended in a non-conducting (or poorly
conducting) medium and a high potential (50 - 1000 V) is applied to the
electrodes. High rates of deposition are obtained and coating thicknesses
can be varied by controlling voltage, electrode spacing, suspension concen-
tration and time. The coating is air dried and baked to remove the solvent
medium. The coating is nonadherent and must be processed further by
compression and/or sintering or by subsequent electrodeposition to bond it
to the substrate. Electrophoretic deposition has been applied to produce Ni,
Ni-Cr, Ni-Cr-Fe coatings to base metals as well as inclusion of such
dispersoids as molybdenum disulfide or silicon carbide.[99] Ortner[100]
applied electrophoretic deposition of TaC-Fe-Ni coatings onto graphite,
sintered at 2300oC (4170oF) for the protection of rocket nozzle inserts and
oxidation resistant coatings for refractory alloys.
A mechanical method of applying a coating involves peening soft
metals (Cd, Zn) and alloys onto a substrate with glass beads in an aqueous
medium in a tumbling operation. The equipment is similar to a cement mixer.
“Alloys” of Cd-Sn deposited in this manner exceeded two thousand hours in
salt fog corrosion tests.
Table 10.6. Mechanical Property Data for Nickel-Particle Composites[122]
catalytic
Eq. (24) M+n + ne- (supplied by R.A.) → Mo (+reaction products)
surface
Figure 10.15. Wear of electroless Ni in Taber Wear Test. Adapted from Ma and
Gawne.[126]
556 Deposition Technologies for Films and Coatings
6.2 Electroforming
Permanent Carbon steel Availability, low cost Attacked by some plating solutions,
such as acid copper and hot ferrous
chloride.
Zinc and zinc base Can be die-cast Acid stripping solution more likely to
alloys attack electroform than caustic solution
used for dissolving aluminum.
Plastics Moldable. Low cost. Fairly Cannot be used in hot plating baths.
close tolerances. May swell in some baths. Requires
conductive coating.
Fusible Low melting alloys Can be cast at low cost. Difficult to remove from electroform
(Pb-Sn-Bi types) completely.
6.3 Anodizing
Figure 10.18. Influence of carbon on tensile strength: full curve, all data[134]
Figure 10.20. Fracture surface of part with sulfur content varying from 88 to 210 ppm
(x 1000).[135]
The anodic films are classified according to the solvent action of the
electrolyte. The films produced in sulfuric or chromic acids are porous type
films. Phosphoric acid has even greater solvent action, resulting in
oxides with a greater degree of porosity; these coatings are used for
adhesive bonding and for plating on aluminum processes to provide
deposit adhesion by mechanical locking in the enlarged pores. On
the other hand, less aggressive mild electrolytes such as tartaric acid,
ammonium tartrate, boric acid, borate compounds, citric acid, etc., have little or
no ability to attack the anodic oxide. These films are essentially non-porous and
thin (approximately 0.5 ∝m = 20 ∝in) and are considered barrier type coatings.
Due to their unique electrical characteristics, the barrier type films are used for
such applications as electrical capacitors; they arealso applied as protective
Deposition from Aqueous Solutions 563
Rack
Clean
Etch Brightening
Mechanical
Alkaline Chemical
Cold Rinse
Acid Electrochemical
Special Sealing
Dye
Dichromate — 5 w/o
Cold Rinse Hot Rinse Seal or
Silicate
or
Dye Sealing Other
Ni or Co acetate (98 - 100 oC, 208 - 212 oF)
(4 - 12 g/l)
Dry
Hot Rinse Unrack Hot Rinse
Alloy 4% Cu 5% Cu ? ?
Limitations 7% Si
7 - 9% Cu+Si
__________________________________________________________________________________________________________________
Limiting
Film Corrosion Adhesion/
Condition Thickness Hardness* Resistance Porosity Dye Absorption
_________________________________________________________________________________________________________
Temperature
increased ' ' " ( (
Current
Density ( ( " ' '
increased
Anodizing
time ' ' ( ' (
increased
Acid
concentration ' ' " ( (
increased
Use of less
aggressive ( ( " ' '
electrolyte
Alloy
homogeneity ( ( ' ' '
increased
Temperature, oC 18 - 24 20 90 - 95
Voltage 20 - 25 30 - 110 35 - 40
____________
Yellow 0.15 5 - 12
Violet to 0.3 13 - 22
Blue-Violet
____________________________________________________________________________________________________________
570 Deposition Technologies for Films and Coatings
* L. Kadison, U.S. Patent 3,668,130 (June 6, 1972), (assigned Crown City Plating
Company).
Deposition from Aqueous Solutions 571
The adhesion of the deposits is also related to the activation of the surface.
The most widely used system is the stannous chloride (SnCl2)/palladium
chloride (PdCl2) 1- or 2-step treatment based on the redox reaction:
The 2-step activation involves first adsorption of SnCl2 on the etched surface,
followed by the redox reaction in a solution of PdCl2. The 1-step or mixed
catalyst system includes both components and is considered either a complexed
chloride of Sn and Pd or a colloidal mixture. There is considerable controversy
regarding the nature of the system.[158]
Perrins[156] determined that the adhesion of electroless nickel and elec-
troless copper (on polypropylene co-polymers) was dependent on the amount
of palladium deposited. Low palladium gave high copper adhesion and low
nickel adhesion. High palladium initially gave low adhesion to both which
improved, peaking, with 3 - 5 week aging. Accelerated aging at 70oC for 1.5
hours gave a 70% improvement over control values. (Improved adhesion by
heating is also found with other plastics.) An oxidation mechanism at the
deposit/polymer interface is suggested as being responsible for increased
adhesion.
Selective plating of plastics[159] can be accomplished by applying an
organic stop-off which remains on the surface as a finish coat. Deposition is
prevented on the stop-off film by use of a chromating treatment after etching.
The printed circuit board (PCB), also called printed wiring board, has made
rapid advances since its development in the late 1930’s. It is a pre-determined
electrical conducting design or path, on a non-conductive base, whose primary
function is to carry an electronic impulse or signal. The non-conductive base
or board can be made of a wide variety of materials including wood, masonite,
or resins such as epoxy, epoxy-glass, phenolics (flame-retardant or paper-
reinforced), polybutadienes, polyimides, and ceramics. Presently, the most
popular materials seem to be phenolics, epoxies (and glass), and polyimides.
The types of PC boards fabricated today include:
1. Print-and-Etch*
2. Plate-and-Etch
3. Plated-Through-Hole (PTH)
a. Panel Plate
b. Pattern Plate
4. Multi-Layered (MLB)*
5. Additive Circuits
6. Integrated Circuits
7. Flexible Circuits
The pre-plating preparation steps involve alkaline cleaning, acid etching as do
other plating cycles. Additional steps such as abrasive cleaning or honing to remove
smeared polymer in the drilled holes and “etch-back” (of polymer) to expose the
intermediate layers of copper in MLB’s (Fig. 10.22) are required. Also required for
through-hole plating is the SnCl2/PdCl2 activation treatment discussed above. After
activation, electroless copper is deposited over the exposed outer circuits and
through the hole. This is followed by electrodeposited copper.
Rothschild and Schwartz[160] and Smith[161] describe fabrication and plating
operations. A trouble-shooting chart[162] and manual[163] identify possible sources
of trouble and their rectification or suggested cures.
Rothschild and Kilgore[164] discuss the problems of plate distribution(throwing
power, T.P.) in MLB’s and relate T.P. to the ratio of surface to minimum hole thickness
(S/H) and the ratio of total board thickness (hole length) to hole diameter (B/D). They
also discuss fabrication and plating steps, the choice of deposits (Au, Sn-Pb, Sn-Ni),
solderability and diffusion and/or migration problems.
Copper plating is used for through-hole plating. Acid sulfate and acid fluoborate
plating solutions possessing high throwing power have been developed. These are
low-metal ion, high acid concentration formulations (to promote desirable polariza-
tion at high current density surfaces) with grain refiners to eliminate columnar
structures which may develop cleavage planes at corners, resulting in cracking. The
pyrophosphate copper solution is the other type of solution employed. (Cyanide
copper formulations damage the board due to the high alkalinity and cyanide
content.) Which solution is the preferred plating solution is a moot question and
invokes considerable controversy among the “practitioners of the art.” However, the
“high throw” bright acid copper sulfate solutions are the most widely used; they are
easier to control and are more economical.
A high-throw Sn-Pb, solder plate, has also been developed for through-
hole plating.[165]
Other electrodeposited coatings used on PCB’s include: Sn-Pb, Sn-Ni,
Sn, Ni, Au with various functions as etch resists and to provide solderability,
corrosion resistance, wear resistance, or low contact resistance.
Also, the brightness and smoothness of the deposit increase as grain size
decreases.
Grain size can vary widely from 100 to 50,000 angstroms; the grain size
of fine-grained or banded deposits is usually between 100 and 1000 angstroms.
Read[168] observed that frequently the grain size of electrodeposits is much
larger than indicated by etched specimens (the metallographic procedures
usually used) and that x-ray techniques are more reliable, especially for
measuring larger grain sizes. As indicated previously, certain deposits,
especially alloys, show no grain structure, i.e., are amorphous.
Some metals (notably Cu, Ni, Co, and Au) can be deposited in all four types
of grain structures depending on the solution composition and plating condi-
tions. This is shown in Figure 10.24 for copper deposits. Typical properties of
these structures are given in Table 10.11.
Zentner, Brenner, and Jennings[169] (AESF Research Project No. 9)
studied the structure-property relationships of nickel electrodeposits to plating
solution composition and operating variables. The effect of current density, pH,
temperature, and chloride content on deposit structure are shown in Figs. 10.25
- 10.28. The trends appear to be:
1. Grain structure changed from fine-grain to coarse-grain as tem-
perature increased.
2. Significant structural changes occurred at both low and high
current densities. Typical columnar structure is obtained between
2 and 25 A/dm2 (20 - 250 A/ft2) in Watts-type solutions. The
structural changes at low C.D. may be explained by the increased
sulfur and carbon contents of the deposit as shown in Table 10.13.
Thus, low C.D. produced a banded structure similar to bright nickel
deposits.
3. There is essentially no structural change in Watts-type deposits in
the pH range 1 - 5. At pH’s above 5 there is a distinct change from
columnar to fibrous or fine-grained which is probably due to
inclusion of basic material (Ni(OH)2?).
4. Deposits from Watts solutions produced the coarsest, columnar
deposits. Increasing the chloride content of the solution results in
finer-grained deposits. All-sulfate (no chloride) solution showed a
somewhat finer columnar structure than a Watts deposit, with
some evidence of a banded structure.
A good correlation was found to exist between structure and properties as
shown in Fig. 10.29. Typical values of the mechanical properties of nickel deposited
from various engineering electroplating solutions are given in Table 10.12.
578 Deposition Technologies for Films and Coatings
Figure 10.25. Effect of temperature of the plating solution on the structure of nickel
deposited at 5 A/dm2 (46 A/ft2). Cross section x 250. Etchant: glacial acetic and nitric
acid.[169]
Deposition from Aqueous Solutions 581
Figure 10.26. Effect of current density on the structure of nickel deposited from the
SIIICI solution at 55oC (131oF), and a pH of 3.0. Cross section x 250. Etchant: glacial
acetic and nitric acid.[169]
Deposition from Aqueous Solutions 583
Figure 10.27. Effect of the pH of the plating bath on the structure of nickel deposited
from the SIIICI solution at 5 A/dm2 (46 A/ft2)and 55oC (131oF). Cross section x 250.
Etchant: glacial acetic and nitric acid.[169]
Deposition from Aqueous Solutions 585
Figure 10.28. Effect of increasing chloride content of the solution on the structure
of nickel deposited at 55oC (131oF), 5 A/dm 2 (46 A/ft2)and a pH of 3.0. Cross section
x 250. Etchant: glacial acetic and nitric acid.[169]
586
Deposition Technologies for Films and Coatings
Table 10.11. Comparison of Structure and Properties of Copper Deposited at 4 A/dm 2 in Several Different Copper
Solutions.[122] (From The Properties of Electrodeposited Metals & Alloys by W.H. Safranek, published by AESFS, 1986.
Reprinted with permission.)
Table 10.12. Nickel Solutions for Heavy Plating[22]
Figure 10.29. Range and trend of physical properties of nickel deposited from 5
different types of solutions, each point is the average of the properties of 5 or more
deposits obtained under various conditions of plating.[169]
1 equals a, b, c, d, e, f, OB, and OBT solutions. Bright nickel.
2 equals SICIII, C, Ac, C (-4N) solutions. Chloride nickel.
3 equals SICI solution.
4 equals S and oS solutions.
5 equals SIIICI, oSIIICI, S IIICI (-1N), NH4, Na and F solutions. Watts nickel.
Deposition from Aqueous Solutions 589
* The higher the stress (in tension) of the deposit, the greater the reduction in fatigue
strength.
Deposition from Aqueous Solutions 591
* Hardness values should be reported with designated loads, e.g., VHN100, or KHN25,
where 100 and 25 (as subscripts) represent the load in grams. Loads less than 25
grams are subject to serious errors and are undesirable due to poor reproducibility.
592 Deposition Technologies for Films and Coatings
atoms are farther apart than they should be in a normal lattice spacing, they
tend to pull closer together, exerting a compressive stress on the substrate.
Stress measurements are subject to variations in testing procedures
and conditions and are generally not reproducible. A particular stress
measuring instrument or technique is useful in controlling a plating solution
and its operating conditions as well as in predicting the quality of the deposit
within parameters experimentally established and observed. Weil[172]
reviewed the various methods used to measure internal stress of electrode-
posits and discussed the reasons for possible variances between measured
values and those actually present in plated parts. He also made a compre-
hensive analysis of the various types of stresses encountered in electrode-
posits.[173] The various mechanical methods and calculations (formulas)
used to measure macrostress were examined critically (microstresses can
be measured only from broadening of x-ray diffraction lines). It contained an
extensive review of the literature dealing with stress, including the various
theories proposed on the origin of stresses in electrodeposits.
Stress Corrosion. The tensile strength and ductility and internal
stress of the deposit are interrelated in determining the degree of resistance
to stress corrosion cracking when deformation may be involved or antici-
pated.
Magnetic Properties. Magnetic properties of deposits are usually
restricted to ferromagnetism and characterized by B-H hysteresis loops,
where H is the applied field and B the induced magnetic flux density.
Magnetic materials are classified as soft or hard, depending on the value of
the coercive force, Hc, which is the magnitude of H when B = O, i.e. the force
required to cause random orientation to the domains.
If Hc is small, the magnetic material is considered “soft”. These are
generally materials which are mechanically soft, i.e., they have a low yield
strength. Permalloy (80 Ni, 20 Fe) is such an alloy. If Hc is large, usually>200
oe, the material is considered a hard magnetic material, useful in fast
switching computer memory components. Alloys of Co with P and other
constituents are usually of this type.
The saturation flux density (BS) is a physical property determined by the
chemical composition of the material. The remanent flux density or retentiv-
ity (BR) and Hc are structure-sensitive properties. The composition, micro-
structure (grain size and orientation and defects), stress, thickness and
impurities of the deposit affect these properties. Romankiw and Thomp-
son[174] reviewed the magnetic properties and applications of plated mag-
netic films as well as methods of measurements.
594 Deposition Technologies for Films and Coatings
(a)
(b)
8.0 SUMMARY
Number Title
B 177-68 (73) Rec. Practice for Chromium Plating on Steel for Engineer-
ing Use
* Book of ASTM Standards, Vol. 2.05, Sec. 2, revised annually. Also approved by
the American National Standards Institute.
598 Deposition Technologies for Films and Coatings
* See C. Levy, Proc. AES, 43, 219 (1956) for activation for Cr plating and W. W.
Sellers and C. B. Sanborn, Ibid., 44, 36 (1957) for Ni and Ni alloys prior to Ni plating
for detailed formulations.
** Modern Electroplating, 3rd ed., Ch. 27, 618, (F. Lowenheim, ed.), John Wiley &
Sons (1974)
*** Plating, 54 (No. 9), 1035 (Sept., 1967)
Deposition from Aqueous Solutions 599
1. Nickel-Phosphorus
(See reference below) (a) (a) (a) (b)
2. Nickel-Boron (c)
pH 5.5
Temp. oC 77
3. Cobalt-Phosphorus (d)
pH 8.5
Temp. oC 92
600 Deposition Technologies for Films and Coatings
4. Copper (e)
Temp. oC 25
5. Palladium (f)
Temp. oC 80
Temp. oC 75 75 85
7. Silver (h)
Sodium silver cyanide 1.83 g/L
Sodium cyanide 1.0
Sodium hydroxide 0.75
Dimethylamine borane 2.0
(thiourea 0.25)
Temp. o C 55 - 65
Deposition from Aqueous Solutions 601
8. Platinum (i)
Sodium platinate 10 g/L
(Na2 Pt(OH)6)
Ethylamine 10
Hydrazine (as sulfate) as required for reduction
Sodium hydroxide as required for pH 10
Temp. oC 30
Note: (1) Some of the above formulations are protected by U.S. Patents.
Their listing here does not imply any right to infringe.
(2) See Ref. 175 for additional solution formulations.
602 Deposition Technologies for Films and Coatings
1. Corrosion resistance of coatings are as high (if not higher) than Type
II coatings.
4. Under conditions used for wrought alloys, casting alloys tend to use
excessive current and “burning” may occur. In such cases, conditions
might require changes to 30 - 35 volts at 90oF with compensating
increase in time to obtain adequate coating thickness.
6. Wrought and cast alloys with high alloy content (such as 7075) tend to
develop thinner coatings and may behave erratically or poorer in salt
spray tests.
1. Thicker coatings are obtained with the purer or higher conducting alloys
containing magnesium or zinc:
Purer alloys EC, 1100, 3003
Al-Mg alloys 5005, 5050, 5052, 5252
Al-Mg-Si alloys 6061, 6063
Al-Zn alloys 7075
5. The color of the Hard Anodize Coating reflects the alloying constituents.
Deposition from Aqueous Solutions 605
REFERENCES
1. Dini, J. W., Plat. and Surf. Fin., 72(7):48 (July 1985); 1st Int’l SAMPE
Metals Conf., 1:91 (August 1987)
2. Lindsay, J. H. and LaSala, J., Plat. and Surf. Fin., 72(2):54 (1985)
3. Lee, R. A., Proc. 29th Ann. Conf., IPC, Boston (1986)
4. Poskanzer, A. M., Plat. and Surf. Fin., 74(3):20 (1987)
5. Best, T. G. et al., Int’l Conf. on Met. Ctgs, AVS (April 1985)
6. Wagner, C., J. Electrochem. Soc., 101(4):181 (1954); Frumkin, A. N.
and FLorianovich, G. M., Doklady Akad, Nauk SSSR, 86:907 (1951)
7. Schaefer, R. A. and Pochapsky, H., Proc. American Electroplaters’
Soc., 38:155 (1951)
8. Rothschild, B. F., Plat. and Surf. Fin., 66(5):70 (May 1979)
9. Foulke, D. G. and Johnson, D. C., Proc. American Electroplaters’ Soc.,
50:107 (1963)
10. Hull, R. O., Proc. American Electroplaters’ Soc., 27 (1939)
11. Blum, W., Trans. Electrochem. Soc., 44:313 (1923)
12. Ibl, N.,Electrodics:Transport, (E. Yeager et al., ed.), 4:6, Plenum Press
(1983)
13. Shawki, S., Hanna, F. and Hamid, Z. A., Metal Finishing, 85(12):59
(December 1987)
14. Electrode Processes, Discussions of The Faraday Society, No. 1:1947,
Butterworths (1961)
15. Schaefer, R. A. and King, W., Plating, 39:487,627,769 (1952) (Ameri-
can Electroplaters’ Soc., Res. Proj. No. 8)
16. Conway, B. E. and Bockris, J. O’M., Plating, 46(4):371 (April 1959)
17. Damjanovic, A., Plating, 52(10):1017 (October 1965)
18. Vetter, K. J., Electrochemical Kinetics, p. 282 ff., Academic Press
(1967)
19. Fischer, H., Plating, 56(11):1229 (November 1969)
20. Fischer, H., Electrodep. and Surf. Treatment, 1:239 (January 1973)
21. Nageswar, S., Electrodep. and Surf. Treatment, 3:417 (Sept/Nov
1975)
22. Modern Electroplating, 3rd edition, (F. A. Lowenheim, ed.), p. 17ff,
(Sponsored by the Electrochemical Society) John Wiley & Sons (1973)
606 Deposition Technologies for Films and Coatings
42. Puippe, J. C., Ibl, N., Angerer, H. and Schenk, H. J., Oberfläche-
Surface, 20(4):77 (1979)
43. Proc. Pulse Plating Symposia., American Electroplaters and Surf. Fin.
Soc., (a) Boston, MA (April 19 - 20, 1979) (b) Rosemont, IL (October
6 - 7, 1981)
44. Theory and Practice of Pulse Plating, (J. C. Puippe, F. Leamon, eds.),
published by American Electroplaters and Surf. Fin. Soc., Orlando, FL
(1986)
45. Cheh, H. Y., J. Electrochem. Soc., 118:551 (1971)
46. Ibl, N., Surf. Technol., 10:81 (1980)
47. Osero, N., Theory and Practice of Pulse Plating, (J. C. Puippe, F.
Leamon, eds.), Ch. 13, published by American Electroplaters and Surf.
Fin. Soc., Orlando, FL (1986)
48. Avila, A. J. and Brown, M. J., Plating, 57(11):1105 (1970)
49. Cheh, H. Y., Linford, H. B. and Wan, C. C.,Plat. and Surf. Fin., 64(5):66
(1977); Chey, H. Y., Andricacos, P. C. and Linford, H. B., ibid. 64(7):42
(1977); Chey, H. Y., Andricacos, P. C. and Linford, H. B., ibid. 64(9):44
(1977)
50. Mattson, E. and Bockris, J. O’M.,Trans. Faraday Soc., 55:1586 (1959)
51. Reid, F. H., Metalloberfläche, 30(10):453 (1976)
52. Raub, C. J. and Knödler, A., Gold Bulletin, 10(2):38 (April 1977)
53. Knödler, A., Theory and Practice of Pulse Plating, (J. C. Puippe, F.
Leamon, eds.), Ch. 9, published by American Electroplaters and Surf.
Fin. Soc., Orlando, FL (1986)
54. Hosokawa, K., Angerer, H., Puippe, J. C. and Ibl, N., Plat. and Surf.
Fin., 67(10):52 (October 1980)
55. Puippe, J. C. and Ibl, N., Plat. and Surf. Fin., 67(6):68 (June 1980)
56. Dossenbach, O., Theory and Practice of Pulse Plating, (J. C. Puippe,
F. Leamon, eds.), Ch. 6, published by American Electroplaters and
Surf. Fin. Soc., Orlando, FL (1986)
57. Avila, A. J., Theory and Practice of Pulse Plating, (J. C. Puippe, F.
Leamon, eds.), Ch. 11, published by American Electroplaters and Surf.
Fin. Soc., Orlando, FL (1986)
58. Ibl, N., Surf. Technol., 10:81 (1980)
59. Puippe, J. C. and Ibl, N., J. Appl. Electrochem., 10:775 (1980)
608 Deposition Technologies for Films and Coatings
60. von Gutfeld, R. J., Tynan, E. E., Melcher, R. L. and Blum, S. E., Appl.
Phys. Lett., 35:651 (1979)
61. Puippe, J. C., Acosta, R. E. and von Gutfeld, R. J., J. Electrochem.
Soc., 128(12):2539 (1981)
62. von Gutfeld, R. J. and Romankiw, L. T., Gold Bull., 15(4):120 (October
1982)
63. Bocking, C., Trans. Inst. of Metal Finish., 66:50 (1988)
64. von Gutfeld, R. J., Gelchinski, M. H. and Romankiw, L. T.,J. Electrochem.
Soc., 130(9):1840 (1983)
65. Gelchinski, M. H., Romankiw, L. T., Vigliotti, D. R. and von Gutfeld, R.
J., J. Electrochem. Soc., 132(11):2575 (1985)
66. Kuiken, H. K., Mikkers, F. E. P. and Wierenga, P. E., J. Electrochem.
Soc., 130(3):554 (1983)
67. Zahavi, S., Tamir, S. and Halliwell, M. J., Plat. and Surf. Fin., 73(2):56
(February 1986)
68. Holt, M. L., Modern Electroplating, 3rd edition, (F. A. Lowenheim, ed.),
pp. 461-485, John Wiley & Sons (1973)
69. Spencer, L. F., Metal Finishing, 69(10):69 (October 1971)
70. Brenner, A., Electrodeposition of Alloys, Principles and Practice,
Academic Press (1963)
71. Electrodeposition of Alloys (V. A. Averkin, ed.), (1961), Translated from
Russian by the Israel Program for Scientific Translations (1964) OTS
64-11015, U.S. Dept of Commerce
72. Brenner, A., Plating, 52(12):1249 (1965)
73. Krohn, A. and Bohn, C. W., Electrodep. and Surf. Treatment, 1(3):199
(January 1973); Plating, 58(3):237 (March 1971)
74. Sadana, Y. N., Metal Finishing, 82,83,84 (1984 - 1986)
75. Brenner, A., Burkhead, P. S. and Seigmiller, E., J. Res. Nat’l. Bureau
of Standards, 39:351 (1947)
76. Clark, W. E., and Holt, M. L., J. Electrochem. Soc., 94:244 (1948)
77. Hoar, T. P. and Brickley, I. A., Trans. Inst. of Metal Finish., 32:186
(1955)
78. Frantsevich, T. F. and Zayats, A. I.,Zhur. Priklad Khim., 31:234 (1958);
English translation, p. 224, Ukrain. Khim Zhur. 24:585 (1958)
79. Machu, W. and El Ghandour, Werkstoffe u. Korrosion, 11(7):420 and
11(8):481 (1960)
80. Machu, W. and Fathi, M., U.S. Patent 3,093,556 (June 11, 1963)
Deposition from Aqueous Solutions 609
123. Okinaka, Y.,Gold Plating Technology, (F. H. Reid and W. Goldie, eds.),
Ch. 11, Electrochemical Publications, Ltd. (1974)
124. Saubestre, E. B., Proc. American Electroplaters’ Soc., 46:264 (1959)
125. Saubestre, E. B., Plating, 59(6):563 (June 1972)
126. Ma and Gawne,Trans. Inst. of Metal Finish., 65, (part 2) (August 1985)
127. Hadley J. S. and Harland, L. E.,Metal Finishing, 85(12):51 (December
1987)
128. Parker, K., The Properties of Electrodeposited Metals and Alloys, A
Handbook, 2nd edition, 23:497, and 24:531, published by The Ameri-
can Electroplaters’ and Surface Finishers’ Soc. (1968)
129. “Recommended Practice for Processing of Mandrels for Electroform-
ing,” ASTM Standard B431-65, Also see, Plating, 51(11):1075 (No-
vember 1964)
130. DiBari, G. A., 64th Metal Finish. Guidebook and Directory, p. 435,
Metals & Plastics Publ., Inc. (1978)
131. Spencer, L. F., Metal Finishing, 57(5):48 (May 1959)
132. Spiro, P.,Electroforming, 2nd edition, International Publ. Services, NY
(1971)
133. Braddock, D. M. and Harris, S. J., Electrodep. and Surf. Treatment,
2(2):123 (1973/74)
134. Dini, J. W. and Johnson, H. R., Surf. Technol., 4(3):217 (May 1976)
135. Dini, J. W., Johnson, H. R. and Saxton, H. J., Electrodep. and Surf.
Treatment, 2(2):165 (1973/74)
136. Withers, J. C. and Abrams, E. F., Plating, 55(6):605 (June 1968)
137. Wallace, W. A. and Greco, V. P., Plating, 57(4):342 (April 1970)
138. Greco, V. P., Wallace, W. A., and Cesaro, J. N. L., Plating, 56(3):262
(March 1969)
139. Wernick, S. and Pinner, R., The Surface Treatment and Finishing of
Aluminum, 3rd edition, 1 vol. (1964); 4th edition, 2 vols. (1972) Robert
Draper, Ltd.
140. Wernick, S., Metal Finishing, 53(6):92 (1955)
141. Sweet, A. W., Plating, 44(11):1191 (November 1957)
142. Keller, F., Hunter, M. S. and Robinson, D. L., J. Electrochem. Soc.,
100(9):411 (1953)
143. Spooner, R. C., Paper No. AN-10, Aluminum Finishing Seminar,
Detroit, Michigan, sponsored by Aluminum Assoc. (1968)
144. Wernick, S., Plat. and Surf. Fin., 75(6):51 (1988)
612 Deposition Technologies for Films and Coatings
145. Short, E. P. and Morita, A., Plat. and Surf. Fin., 75(6):102 (1988)
146. George, D. J. and Powers, J. H., Plating, 56(11):1240 (1969)
147. Wernick, S. and Pinner, R., Metal Finishing, 53(11):(1955)
148. Coulston, E. L., Paper No. AN-6, Aluminum Finishing Seminar, Detroit,
Michigan, sponsored by Aluminum Association (1968)
149. Tin and Its Uses, 133, Tin Research Institute (1982)
150. Woods, J. L., U.S. Patent 3,857,766 (December 31, 1974); Newman,
F. S., Hartman, J. T., and Dedona, F. A., U.S. Patent 3,983,014
(September 28, 1976); Knodo, M. and Shizouka, T. (Japan) U.S.
Patent 3,996,125 (December 7, 1976)
151. Konno, H., Theory and Practice of Pulse Plating, (J. C. Puippe, F.
Leamon, eds.), 12:209, published by American Electroplaters and
Surf. Fin. Soc., Orlando, FL (1986)
152. Metals Handbook, 9th edition, 5:632, ASM (1982)
153. Geduld, H., Metal Finishing, 65(4):62 (April 1967)
154. Saubestre, E. B., Durney, L. J., and Washburn, E. B., Metal Finishing,
62(11):52 (1964)
155. Saubestre, E. B., Trans. Inst. of Metal Finish., 47:228 (1969)
156. Perrins, L. E., Trans. Inst. of Metal Finish., 50:38 (1972)
157. Courduvelis, C. L., “Applications of Plasmas in the Electroplating of
Plastics,” paper presented at 65th Annual Technical Conf., American
Electroplaters’ Soc. (1978), pre-print, American Electroplaters’ Soc.,
Orlando, FL
158. Shipley, C. R., U.S. Patent 3,011,920; Matijevic, E.,Plating, 63(11):1051
(1974); Cohen, R. L.. and West, K. W., J. Electrochem. Soc.,120(4):502
(1973); Plating, 63(5):52 (May 1974), (colloid hypothesis); Zeblinsky,
R. J., U.S. Patent 3,672,938; Rantell, A. and Holtzman, A., Trans. Inst.
of Metal Finish., 51,62 (1973) and Plating, 63(11):1052, 1054 (1974)
(complex hypothesis)
159. Martin, J. J., Plating, 58(9):888 (1971)
160. Rothschild, B. F. and Schwartz, M., “Plating and Finishing of Printed
Circuit Boards,” American Electroplaters’ Soc., Illustrated Lecture
#41, American Electroplaters’ Soc.
161. Smith, C. M., Plating, 56(4) (April, 1969)
162. Rothschild, B. F., Farmer, M. E. and Brewer, T. W.,Plating, 49(12):1269
(December 1962)
163. Jawitz, M. W., Insulation/Circuits, p. 5 (April 1976)
Deposition from Aqueous Solutions 613
Supplementary References–Journals
Electrochim. Acta
Electronic Packaging and Production*, Milton S. Kiner, Publ., 222 W. Adams,
Chicago, IL 60606
614 Deposition Technologies for Films and Coatings
Supplementary References–Books
1.0 INTRODUCTION
* The detonation gun process was developed by Union Carbide Corporation[1] and detonation
gun coatings are currently available in the United States, Japan, Singapore, and Western
Europe through Praxair Surface Technologies, Inc. (formerly Union Carbide Corp.). Plasma
spray and HVOF coatings (also developed by Union Carbide[2]) are available from a number
of coatings service organizations and the equipment is available from several sources for
in-house use.
617
618 Deposition Technologies for Films and Coatings
The essential elements of a plasma torch are shown in Fig. 11.1. The
anode is usually copper and the cathode tungsten. A gas, usually argon or
nitrogen or a mixture of these with hydrogen or helium, flows around the
cathode and through the anode which serves as a constricting nozzle. A direct
current arc, usually initiated with a high frequency discharge, is maintained
between the electrodes. The current and voltage vary with the anode/cathode
design, gas flow, and gas composition. The power varies from about 5 to 120
kilowatts depending on the type of torch and the operating parameters. In one
variant of a coating torch, a partially transferred arc is used; i.e., part of the arc
goes to the anode and part to the substrate being coated. This causes
substantial heating of the substrate and is used only in special situations.
Fully transferred arc surfacing torches will not be discussed here, since their
use constitutes a form of welding rather than coating.
The gas plasma generated by the arc consists of free electrons, ionized
atoms, and some neutral atoms and undissociated diatomic molecules if
nitrogen or hydrogen are used. The specific anode/cathode configuration, gas
density, mass flow rate, and electrical power determine the plasma tempera-
ture and velocity. Plasma gas velocities with most conventional torches are
subsonic, but supersonic velocities can be generated by using converging-
diverging nozzles with critical exit angles. The temperature of the core of the
plasma may exceed 30,000°C (50,000°F). A schematic of a typical distribu-
tion of temperature in the plasma is shown in Fig. 11.2. The enthalpy of the
plasma and efficiency of heat transfer to the powder particles can be increased
substantially with the inclusion of diatomic gases, such as hydrogen or
nitrogen, Fig. 11.3.
Advanced Thermal Spray Deposition Techniques 619
As a result, powder entry is usually in the diverging portion of the nozzle or just
beyond the exit as shown in Fig. 11.1. Attempts[3][4] have also been made to
adjust the point and angle of entry of the powder into the plasma stream for the
melting point of the powder. The goal in some cases was to heat the powder
close to, but not over, the melting point. In one high velocity torch design,[5]
in which shock diamonds are generated, the powder is introduced a short
distance beyond the exit in a region of rarefaction in the plasma stream.
In another plasma torch design,[6][7] a cylindrical extension is placed on
the nozzle encompassing the entry for the powder. Additional inert gas is also
introduced. The result is a cooler, but more uniform and higher velocity gas
effluent with higher powder velocities.
The most important parameters relative to the powder particles at
impact on the substrate are their temperature, velocity, and extent of reaction
with the gaseous environment. The velocity of the powder, as previously
mentioned, is a function of the mass flow rate of the plasma, the density, mass
and shape of the powder, and the distance the powder travels in the plasma.
With most of the conventional commercial torches available up to the mid 70’s,
velocities varied from about 400 to 1000 ft/s. Higher velocity torches have since
become available[3]-[5][8] with powder velocities claimed [9] to be in excess of
1800 ft/s (measured by a rotating mirror), but velocities measured with a more
sophisticated technique (Doppler laser) for similar torches were reported to be
1200 ft/s.[10]
It has often been stated that any material that can be melted without
decomposition can be used as a plasma coating. There appear, however, to
be two schools of thought on whether or not the powder should be molten on
impact. Certainly the combination of particle plasticity or fluidity and velocity
must be high enough to allow the particle to flow into a thin, lenticular shape
that molds itself to the topology of the substrate or previously-deposited
material. The extent to which this is achieved determines the density and
strength of the coating. With a relatively low-velocity torch, reasonably high
densities can only be achieved if the particles are substantially molten. As
noted previously, the intent of at least some high velocity torch designs is to
achieve highly plastic, but not molten, particles. Excess fluidity (superheat-
ing) can lead to undue shattering and bounce of the particles, resulting in a poor
microstructure and low deposition efficiency.
Care should be exercised in developing the coating parameters to not
heat the powder to an excessive temperature for other reasons as well. The
most obvious hazard is vaporization of all or part of the powder. This is most
likely when,(a) the difference between the melting and boiling point of a single-
622 Deposition Technologies for Films and Coatings
those cases where the gas is not thermodynamically inert. The use of
hydrogen to reduce the amount of oxidation during spraying may be somewhat
effective, but the effect may be due as much to shielding (by reacting with
oxygen from the air inspirated into the plasma stream) as to actual reduction
of oxide formed on metallic powder. On the other hand, oxide powders or oxide
films on metallic powders may be decomposed in the plasma spray; e.g.,
zirconia coatings sprayed with an argon plasma are slightly oxygen deficient,
and the amount of oxygen in copper can be lowered simply by thermal
decomposition of its oxide.
Usually of greater concern than reaction with the plasma gas is the
extent of reaction of the powder with oxygen or nitrogen from the air inspirated
into the plasma stream after it exits the nozzle. This effect is strongly a
function of the type of torch used, as illustrated in Fig. 11.4. None of these
coatings were shielded from the atmosphere, yet the differences in extent of
oxidation is dramatic. Nitration of some materials may also occur, but has not
been extensively studied.
If coatings with even less oxide than that shown in Fig. 11.4 are desired,
several means of shielding the plasma stream are available. One of the best,
and certainly the most adaptable to production, is a patented inert gas shroud
that surrounds the effluent with argon.[12] A comparison of the results obtained
with this shield compared to those obtained with the same torch that produced
the relatively clean microstructure of Fig. 11.4 is shown in Table 11.1. Note that
the oxygen contents of molybdenum, copper, and nickel are all lower in the
coating than in the starting powder when using the inert gas shroud, while that
of titanium, a very reactive metal, is only slightly higher. Alternative methods
of excluding air include spraying in a low partial pressure of inert gas in a
vacuum chamber[13][14] or in an enclosure filled with argon. An extreme
example used for coating large parts is an entire room or cubicle filled with
argon in which the operators wear life support suits.[15]
Both argon-shrouded and low pressure, inert-gas-chamber spray coat-
ing methods are used in the commercial production of the very reactive
“MCrAlY” coatings on gas turbine components (described more fully in Sec.
4.8). Some of the relative advantages and disadvantages of the two methods
are listed in Table 11.2 and the process steps used with both are shown in
Table 11.3.
624 Deposition Technologies for Films and Coatings
Figure 11.4. Microstructures of aluminum bronze coatings made with three types
of standard plasma spray torches illustrating varying degrees of oxidation during
deposition. As-polished.
Advanced Thermal Spray Deposition Techniques 625
Table 11.2. Advantages and Disadvantages of Inert Gas Shroud and Low
Pressure Inert Gas Plasma Deposition
so most materials can be melted. The distance that the powder is entrained
in the high velocity gun is longer than in a plasma device which accounts, in
part, for the much higher particle velocity. After the powder has exited the
barrel, a pulse of nitrogen purges the barrel. The cycle is repeated about four
to eight times a second.
higher powder particle velocities, to about 1000 m/s or more. Thus the kinetic
energy of the particles are about double those of the standard detonation gun
particle energies. This yields coatings with higher densities, better bonding,
and improved mechanical and other properties.
stand-off which is too long may allow the powder particle velocities to diminish
and their temperature to drop too far. The actual powder temperature and
velocity distributions are strongly a function of the design of the high velocity
combustion spray device as well as the operating parameters, morphology,
and composition.
3.1 Powder
Most of the powder used for advanced thermal spray deposition falls
between 5 and 60 microns in size. To achieve uniform heating and acceleration
of a single component powder, it is advisable to have the size distribution as
narrow as possible. The additional cost of sizing is, at least partially, recovered
in higher deposition efficiency and better coating quality. The specific powder
size range to be used is a function of the torch or detonation gun design and
the heating characteristics of the powder discussed earlier. Generally
speaking, fine powders are accelerated and heated more rapidly, but they
also tend to lose momentum more rapidly when spraying at longer distances
(greater stand-offs). They generally result in denser, but more highly stressed
coatings. Finer powders also tend to create more torch operating problems
and have higher oxide contamination levels.
Good quality control of powder is essential, not only during manufac-
ture, but during storage and handling. Powder specifications and quality
control should include, as a minimum, chemical analysis (including interstitials
for metallic powders), shape characterization, size distribution, and flowability.
A wide variety of equipment is available for analyses, and selection of a
specific technique or type of test will vary with the type of powder. It is obvious
that the powder should be kept clean and dry; too little attention paid to this
will result in dispensing problems, torch clogging, and lumps in the coating.
3.3 Masking
3.4 Coating
of gases to be used and their flow rates, the torch or gun design (e.g., anode
design), the power level to be used, and for some plasma torches, the point
of powder entry. All of these vary with the specific torch or gun model used.
The torch or gun manufacturer should be able to provide specific instructions,
or at least detailed guidelines.
It is always advisable to coat a quality control specimen to verify the
coating deposition rate and coating microstructure before coating any parts.
Metallographic examination of this specimen should include, as a minimum,
general phase content, the amount of oxidation occurring during deposition,
apparent porosity, and microhardness. It is also advisable to check the grit
inclusion level and/or amount of substrate surface contamination, but this is
only meaningful if the quality control specimen is made of the same material,
is in the same heat-treat condition, and has undergone the same surface
preparation as the parts to be coated. Metallographic examination is only
meaningful if well-standardized mounting and polishing techniques have been
developed as well as appropriate visual and numerical standards based on
significant statistical analyses.
It should be noted that the microstructure, hardness, etc. of the coating
on a special quality control specimen may not (in fact, usually will not) be the
same as on the part because of differences in angle of deposition, relative part/
torch surface velocity, cooling, mass of the part, etc. This should not be of
concern relative to quality, since the objective of examining the quality control
specimen is to ensure that the torch or detonation gun is producing the right
coating (process control). With the process in control, a coating with
consistent properties will be applied to the part (assuming all the deposition
parameters then remain constant while coating the parts). Whether or not the
properties of coating produced meet the objectives of using it is a separate
issue.
One of the major advantages of plasma and detonation gun coatings is
that they may be applied to substrates without significantly heating them
above room temperature. As a result, a part can be fabricated and fully heat-
treated without changing the substrate microstructure or strength. This also
avoids any possibility of distortion or volumetric change during any post-
coating heat-treatment that is common to many other coating methods. It is,
however, advisable to warm the surface slightly, usually with a pass of the torch
without powder flowing, to remove most adsorbed gases from the surface
before applying the coating. The surface temperature usually does not exceed
125 to 150°C during this warming pass. During coating deposition, a
substantial amount of heat is transmitted to the part through the plasma gas
Advanced Thermal Spray Deposition Techniques 635
and the molten powder. To ensure uniform coating thickness and minimize
residual stress within the coating, it is necessary to carefully control the areal
rate of deposition. This can only be accomplished satisfactorily by using
automated part and torch handling equipment with the selection of appropriate
surface speed, overlap pattern and deposition rate. Cooling air or CO2 jets may
be used as well. Under normal circumstances, the part temperature does not
exceed about 150°C during coating.
3.5 Finishing
returns the oxide to stoichiometry and its normal color without any other
noticeable changes in the coating other than, perhaps, its electronic charac-
teristics.
The surface topography of as-deposited coatings is quite complex. Not
only do molten or highly plastic drops flow and conform to the rough surface
(grit-blasted substrate or previously-deposited coating), but some particles
rupture with subdroplets “skittering” along the surface for some distance
before sticking. An excessive amount of this behavior leads to higher
porosity, poor intracoating fracture strength, higher roughness, and lower
deposition efficiency. An occasional microcrack can be observed in some
coatings, particularly cermet and oxide coatings, due to residual stresses
developed within an individual particle during freezing. While usually
undesirable, they may not be significantly detrimental to performance
(e.g., wear resistance) if they are limited in number and do not propagate
from one particle to another. For some thermal barrier applications, they
are intentionally induced during deposition to increase thermal shock
resistance (in part, by lowering the in-plane elastic modulus).
4.2 Microstructure
Both plasma and detonation gun coatings consist of many layers of thin
lamellar particles, the result of the impact of molten or semimolten powder
particles as illustrated in Fig. 11.7. The major microstructural difference
between the two types of coatings is that detonation gun coatings have a
higher density. The impacting particles may split with some small droplets
branching out or separating from the central particle. Thus, the average splat
volume may be smaller than the average starting powder size, and the total
surface area much larger in the coating. Typically, a splat may be a few
microns thick and 10 to 50 microns in diameter.
The cooling rate of the impacting particles has been estimated[22] to be
10 to 106 C/s for oxides and 106 to 108 C/s for metals. It is evident, however,
4
that rates may vary significantly with the substrate material and thickness of
the coating. As a result of the rapid cooling, some coatings have been found
to have no crystallographic structure by x-ray[23] or neutron diffraction, [24] or
low temperature heat capacity measurements.[25] Others may have a thin
amorphous layer next to the substrate followed by crystalline layers.[22]
Many coatings form columnar grains within the splat in one or two layers
perpendicular to the surface of the substrate, Fig. 11.8.
638 Deposition Technologies for Films and Coatings
metallurgical bond is formed.[37] Similar results are reported for the so-called
exothermically reacting nickel aluminide coatings.[38] Interdiffusion and/or a
more nebulous “surface reaction” may depend in part on added surface energy
in the substrate due to grit blasting, as evidenced by recrystallization of the
surface.[39]
The bond strength of ceramic coatings is generally attributed to
interlocking, but some degree of spinel formation or similar reaction has been
reported for Al2O3 on steel[23] and Al2 O3/TiO2 on aluminum.[33]
Oxide cementation was cited as important in bonding metals or cermets
to metals[4l][42] in earlier work, but is not considered desirable in modern
practice. In general, oxides on the surface of the substrate or oxidation
occurring during spraying[43] decreases bond strength.
Most of the factors that affect the bond strength of “conventional” plasma
deposited coatings also apply to detonation gun coatings and some HVOF
and “high velocity” plasma coatings, but the situation may be somewhat more
complex. Because of the unusually high velocity of the particles, some,
particularly carbide or oxide, particles are actually driven into the surface of
most metallic substrates. As previously noted, some substrates require no
grit blasting to achieve adequate bonding, since the coating itself roughens the
interface. This embedding/roughening process creates atomically clean
interfaces between the coating and substrate over most of the coating area,
which facilitates chemical bonding and can be likened to the explosive bonding
of sheets of metal. This undoubtedly plays a role in forming the unusually high
bond strengths of such coatings.
A more theoretical approach to the impact of thermal spray particles
on a substrate was undertaken by Houben.[44] His thermodynamic and
mechanical considerations provide, perhaps, some insight into the conver-
sion of the kinetic energy, predicting that coarse grains at high velocity may
explode on impact, the temporary inversion of liquid into an amorphous solid.
He also provides a method to calculate the shock, nonequilibrium, and final
temperature of the material. Only a qualitative discussion of the lateral
spreading or flow of the material is given along with illustration of the flow of
both wetting and nonwetting material. Wetting almost always leads to
cracking of the adhering material, while nonwetting leads to a weak interface.
to the temperature of the part and is usually tensile. The magnitude of the
residual stress is a function of torch parameters, deposition rate, the relative
torch to part surface speed, the thermal properties of both the coating and the
substrate, and the amount of auxiliary cooling used. The use of finer powders
frequently leads to higher residual stresses, but this can generally be
controlled by adjusting the coating parameters. If the part temperature is
allowed to rise above room temperature, there will be a secondary change in
the state of stress of the coating as both the part and the coating cool to room
temperature. Residual stress frequently increases linearly with coating
thickness above some minimal initial thickness.[45]-[47] The rate of increase,
however, is a function of the parameters of deposition already listed and the
coating material.
While the residual stress in most thermal spray coatings is tensile, the
stress in some detonation gun and perhaps a few HVOF coatings is
moderately compressive. This is thought to be due to the relatively high kinetic
energies carried by the impacting powder particles, particularly some of the
cermets. With the extraordinary velocities and kinetic energies of the powder
particles in Super D-Gun deposition, very high compressive stresses can be
developed if it is desirable.
Residual stress may have a significant effect on bond strength, as
already noted, and must be considered when the coating is placed in service,
since it may detract from its inherent mechanical strength. For example,
coatings are frequently in tension as a result of the residual stress, and this
stress must be subtracted from the allowable fracture stress calculated from
mechanical property tests of free-standing specimens. Residual stress is,
however, reproducible and can be controlled with adequate knowledge of the
stress and adequate control of the coating parameters.
4.5 Density
Powder Size
Coarse Medium Fine
Coating Property (10 - 105) (10 - 74) (10 - 44)
less than ideal on part or all of the coated area. Nonetheless, a good deal of
data has been compiled on a wide range of coatings to serve as very useful
guidelines to equipment designers and other users. For purposes of
illustration in subsequent discussion and to provide a general feeling of
comparison with other types of materials, the mechanical properties of a few
specific coatings are listed in Table 11.7. The moduli of elasticity and rupture
and strain-to-failure were measured on free-standing rings of coatings 1 inch
in diameter, 0.5 inch wide and 0.010 inch thick.
The mechanical (as well as other) properties of advanced thermal spray
coatings are anisotropic because of their splat structure and directional
solidification. This anisotropy is probably more pronounced for cermets and
metallic coatings with somewhat oxidized splat boundaries than it is for either
pure ceramic or pure metallic coatings. An example of this anisotropy is given
in Table 11.8.[53] Although most coatings are used with loading normal to the
surface, measurement of mechanical properties normal to the surface is
particularly difficult because of the limited thickness of most coatings and is
seldom done. Properties parallel to the surface are also important, however,
particularly if the substrate expands or contracts thermally or under mechani-
cal loading.
The most frequently quoted mechanical property is hardness. The
hardness of the higher-velocity coatings is generally higher than that of
conventional plasma coatings of the same composition as shown in Table
11.3. This is primarily due to their higher density and greater cohesive
strength. For a plasma coating with a given composition, the hardness
usually increases with an increase in density. Thus, for example, hardness
generally increases with the use of a finer powder, as already shown in Table
11.4. Hardness may be reduced for a given material if the coating is applied
in an inert atmosphere as compared to spraying in air, as has been noted for
WC-Co,[43] for Mo,[54] and for Ti, Nb, and Zr.[55] Although it may increase the
hardness of the coating, excessive oxidation will weaken its internal cohesive
strength and may be detrimental to the coating’s performance.
Hardness is used not only as a guideline for wear resistance, but for the
strength of the coating. In both cases it may be quite misleading. The
measurements of hardness are usually made on metallographic cross-
sections of the surface, even though loading is usually perpendicular to the
surface, and the hardness in the two directions may be different due to the
anisotropic microstructure of the coatings. Hardness measurements made
on test specimens may differ from those on actual parts due to differences
in angle of deposition and stand-off and, in some cases, residual stress.
Table 11.7. Properties of D-Gun and Plasma Coatings
Parallel Perpendicular
to Surface to Surface
cobalt coatings. Also note that, as expected, increasing the cobalt content
increases the strain-to-fracture (either measured directly or calculated from
the ratio of modulus of rupture to the elastic modulus).
An example of the use of this kind of test data is as follows:
A plasma chromium oxide coating was specified on
the interior surface of an aluminum hydraulic cylinder in an
aircraft landing gear, because of its earlier success on another
landing gear and cyclic pressure bench testing on prototype
cylinders without pistons. Even though visual examination of
the bench tested cylinders revealed no irregularities, the
coating failed when the complete assembly was placed in
service. The cylinder expansion under pressure clearly ex-
ceeded the strain-to-failure of the coating and it cracked. The
additional stress of the piston caused spalling. Re-examina-
tion of the bench-tested cylinder revealed microscopic cracks.
The designer had not adequately taken into account the
difference in elastic moduli between the coating and the
substrate and the limited strain-to-failure of the coating. Evalu-
ation of data from ring tests indicated both aluminum bronze
and nickel coatings had adequate strain-to-failure. Subse-
quent tests verified this as well as the fact that they had
sufficient wear resistance.
It is obvious, of course, that all the coating process variables and the
resulting microstructures strongly affect the mechanical properties of the
coating. For example, tungsten coatings made with fine powder have a higher
modulus of rupture than those made with coarse powder when both are
protected from oxidation by spraying in an inert atmosphere,[51] as shown in
Table 11.6. Referring to Tables 11.5 and 11.6, it is apparent also that oxidation
during deposition can seriously weaken a coating. In a study of the effect of
oxidation on aluminum bronze, it was found that even minor oxidation during
deposition was detrimental to compressional strength, both parallel and
perpendicular to the surface, Table 11.9.[53] Additions of discrete oxide
particles, on the other hand, not only strengthened the coatings, but added
wear resistance (discussed in Sec. 4.7).
Before leaving the subject of mechanical properties, it might be well to
mention that the properties of the substrate cannot be ignored in considering
a coating application. One of the first considerations is that the substrate must
be able to support the coating without yielding beyond the coating’s strain-to-
failure as shown in the following:
652
Deposition Technologies for Films and Coatings
Table 11.9. Mechanical Properties of Plasma-Deposited Aluminum Bronze (Cu-IOAl)
Compressional Properties
Alumina Vol.% Hardnessa Perpendicular to Surface Parallel to Surface
Type of Deposition Addition Al2 O3 HV 300 E (10 6 psi)b YS (106 psi)b E(10 6 psi) b YS (103 psi)b
The major use of advanced thermal spray coatings today is for wear
resistance, particularly for adhesive and abrasive wear resistance. Their use
in erosive situations is growing steadily as well, particularly for detonation gun
coatings. No attempt will be made here to tabulate the wear resistance of
coatings or, conversely, to recommend specific coatings for the various types
of wear. To do so, it would be necessary to assume that all coatings of a
given composition are the same (while, in fact, they are a function of the
specific coating device and operating parameters used), and to assume that
all wear situations can be fit into a relatively few, well defined categories
(which is definitely not the case). The situation is far from hopeless, however,
and experienced coatings service engineers or equipment manufacturers
654 Deposition Technologies for Films and Coatings
I. Wear System
A. Adhesive or Abrasive
1. Type of relative motion—unidirectional, oscillating, impact
2. Surface speed—velocity and frequency, if cyclic
3. Load or impact energy
4. Abrasive particles or wear debris—trapped or removed, size, shape,
and composition
5. Conformability requirements
6. Embeddability requirements
B. Erosive
1. Gas, liquid, or solid particle erosive material
2. Media—gas or liquid
3. Gas or particle velocity and angle of impingement
4. Particle size, shape, mass, and composition
II. Environment
A. Temperature—maximum, minimum, and rate of change
B. Media—gas or liquid
C. Contaminants
D. Corrosive characteristics—chemical, galvanic
E. Lubricant
III. Mating Material
A. Composition
B. Heat-treatment condition
C. Hardness
D. Surface roughness and topology
IV. Substrate Material
A. Composition
B. Heat-treatment condition
C. Dimensional changes after coating
1. During assembly due to press fit, shrink fit, etc.
2. In service due to thermal expansion/contraction or mechanical loading
V. Coating Requirements
A. Cost limitations
B. Required life, time or maximum wear
C. Compositional limitations
D. Thickness limitations
E. Coefficient of friction requirement
F. Surface finish
G. Geometric constraints
H. Overspray limitations
Advanced Thermal Spray Deposition Techniques 655
LFW-1
450 lb/load in
Dry Rubbing Hydraulic Fluid
Wear Rate vs. Steel for
(10-6 in/1000 5409 rev.
Material ft. of sliding) (10-6 cm3 )
Figure 11.10. Alpha block-on-ring wear test of aluminum bronze, wrought (Al-Cu)
and plasma-sprayed (PD Al-Cu), and beryllium copper, wrought (Be-Cu) and
plasma-sprayed (PD Be-Cu) vs. SAE 4640 steel (Rc 60) in hydraulic fluid at 65 ft/
min for 1950 ft.
Figure 11.11. Alpha block-on-ring wear test of aluminum bronze with Al2O3 addition
(block) vs. SAE 4640 steel (Rc 60) in hydraulic fluid at 65 ft/min for 1950 ft under a
180 lb load. (#) Wrought alloy; (∆) standard plasma; (◊) oxidizing plasma; ($, *)
alumina additions to plasma; (U,X) plasma pure alumina.
658 Deposition Technologies for Films and Coatings
Coefficient
Materials Rating Wear** of Friction
* Rotating member
** Total system wear, 10-6 in/1000 ft.
surface treatment. For example: Some gas turbine blades and vanes,
depending on the type of fuel and operating environments, are subject to hot
corrosion. The best solution to this problem at the present time is an MCrAlY
(where M is Ni, Co, and/or Fe) type of coating. (Other elements may also be
present; e.g., Pt, Hf, or Si.) These coatings were first applied commercially
by physical vapor deposition, an expensive method with some elemental
limitations. Plasma deposition offers significant economic advantages and
has no elemental limitations. To be effective, however, the coatings must be
deposited without oxidation and then sealed to prevent rapid internal
oxidation of the coating and oxidation of the substrate. Methods have been
developed to achieve this using inert gas shrouding during deposition and
post-coating heat-treatment and peening to effectively sinter the coating.
Alternative methods using deposition in a low pressure, inert gas chamber
followed by peening and heat-treatment have also been developed. Since
the substrates are superalloys, the coating heat-treatment can be combined
with or precede the alloy heat-treatment and not interfere with the structural
properties of the component.
Detonation gun coatings, because of their high density, often do not
need to be sealed with a high temperature sintering to prevent internal
oxidation or oxidation of the substrate. For example:
For many years detonation gun coatings of chromium
carbide-nickel chromium have been used on the shroud
edges and lacing wire of gas turbine engines to prevent
fretting and impact wear. More recently a new family of cobalt
based alloys with oxide additions has been developed[52] to
provide better performance for more advanced engines.
These coatings do not require heat-treatment to prevent
internal oxidation, although heat-treatment is used to further
improve the already superior bond strength in particularly
severe impact situations.
5.0 SUMMARY
REFERENCES
49. Tucker, R. C., Jr., Linde Division, Union Carbide Corp., private
communication
50. Yenni, D. M., Linde Division, Union Carbide Corp., private
communication
51. Mash, D. R. and Brown, I. M., Met. Eng. Quarterly 18 (1964)
52. Wolfla, T. A. and Tucker, R. C., Jr., “High Temperature Wear Resistant
Coatings,” presented at Int'l Conf. on Metallurgical Coatings, San
Francisco, CA (3-7 April, 1978)
53. Tucker, R. C., Jr. and Bishop, T. N., “The Utilization of Plasma and
Detonation Gun Coatings in Design,” presented to AIME Symp. on
Interaction of Design and Materials II (1973)
54. Elyutin, V. P., et al., Svar. Proizvod, 6:72 (1969)
55. Muller, K. N., “Structure and Properties of Arc-Sprayed Titanium
Coatings,” presented at the 7th Int’l Metal Spraying Conf. (1973)
56. Tucker, R. C., Jr., and P. W. Traub, “Wear Behavior of Wrought and
Plasma-Deposited Aluminum Bronze and Beryllium Copper,” presented
to the Metallurgical Soc. of AIME (1971)
57. Tucker, R. C., Jr., “Wear Characteristics of Modified Plasma-Deposited
Aluminum Bronze,” presented to the Am. Soc. for Testing and Materials
Symp. on Erosion, Wear and Interfaces with Corrosion (1973)
58. Taylor, T. A., Overs, M. P., Gill, B. J., and Tucker, R. C., Jr.,J. Vac. Sci.
Technol. A3:2526-2531 (Nov/Dec 1985)
59. Tucker, R. C., Jr., Taylor, T. A., Weatherly, M. H., “Plasma Deposited
MCrAlY Airfoil and Zirconia/MCrAlY Thermal Barrier Coatings,” presented
at the Third Conf. on Gas Turbine Materials in a Marine Environment,
Bath, England (20-23 September 1976)
Non-Elemental Characterization of
Films and Coatings
Donald M. Mattox
1.0 INTRODUCTION
669
670 Deposition Technologies for Films and Coatings
Films are thin coatings, and in some instances the film properties are
influenced by the substrate properties. In this chapter, a film is defined as a
coating with a thickness less than 1 micron (103 nanometers or 40 micro-
inches).
Films and coatings may be fabricated in a variety of compositional,
morphological, and microstructural configurations. These include:
1. Monolithic—one composition throughout
2. Alloyed or mixed and not reacted
3. Compound
4. Graded composition
5. Layered structures—few to many, alternating
6. Composite (dispersed phases)
7. Dispersed impurities—possibly to greater than solubility
limits
8. Special configuration, e.g., fine line metallization
9. On surfaces with properties that influence the film properties,
e.g., roughness, hardness
Films, coatings, and modified surfaces are often unique materials with
properties that differ from those normally encountered in the same materials
prepared in other ways, and these unique characteristics should be consid-
ered when making property, stability/degradation or compositional measure-
ments. In many instances, these unique properties are derived from the
fabrication techniques and parameters as well as the limited size and
thicknesses that are encountered in film structures. Unique conditions,
characteristics, and properties of films and coatings include:
1. Substrate influence on properties
2. Presence of the interface and interfacial (interphase)material
3. Graded composition and properties with thickness
4. Dispersed impurities
5. Non-stoichiometric compositions
6. Unique microstructures (bulk, surface), e.g., columnar
morphology
7. High surface/volume ratio
8. Local property variations, e.g., pinholes, nodules
9. Non-equilibrium conditions (defects, stress, crystallographic
phase, structures, composition, impurities, etc.)
Non-Elemental Characterization of Films and Coatings 671
2.0 CHARACTERIZATION
(i.e., position equivalency). It may be helpful to identify each sample and its
position in the fixture for future reference—variations in properties may be
position dependent for reasons such as: angle-of-incidence of the depositing
flux, plasma density variations, heating variations, presence of nearby virtual
leaks, etc.
After the samples have been removed from the fixturing they may be
subjected to further testing. Simple and easy tests may be used to determine
functionality and relative comparison. These simple tests include: (i) adhe-
sion,(ii) residual stress,(iii) reflectivity,(iv) electrical resistivity,(v) thickness,
(vi) optical transmission of films on optically transparent substrates for
thickness or pinholes, (vii) some types of elemental composition, (viii)
chemical etch rate, and(ix) oblique lighting to see bumps on smooth surfaces.
Often these simple tests can give the first indication of problems in processing
or functionality. In many cases one characterization technique will give results
that depend on several properties of the material. For example: a chemical
etch rate test will depend on film density, pinholes, surface area, thickness,
and chemical composition.
After the films have been exposed to the ambient, do they change with
time? Changes may be evident in color, adhesion, chemical composition of
the surface, wetting angle, or bondability.
After the simple and easy tests, the films may be subjected to more
complex and comprehensive tests which generally take a much longer time
and require special techniques and configurations.
In many cases, the functionality of the system must be determined in
context of the intended use of the film. The best test is the operational life-
test where the film is used as it would be in service and samples are tested
periodically to determine any degradation. Since this means a long test
period, it is often desirable to used accelerated life-tests where the degrada-
tion mechanisms are accelerated by increasing the temperature (corrosion,
diffusion processes), chemical concentration (corrosion), cyclic rate (fatigue
failures), etc. A comparison between the accelerated tests and the opera-
tional tests gives an acceleration factor. A major concern in accelerated life
tests is to be sure the right degradation mechanisms are being accelerated.
Most often, both types of tests (operational and accelerated) are run, and in
addition, control samples (archival or shelf samples) are kept in pristine
condition so that operational or accelerated aged samples can be compared
to the original materials. All of this assumes that the samples were
reproducible when fabricated.
Non-Elemental Characterization of Films and Coatings 675
Figure 12.1. Types of interfaces and problems that can be associated with each
type of interace.
For reactive film deposition processes, two general cases exist. In the
first case, there is a condensible species and a gaseous reactive species
(e.g., Ti + N). In the second case, both species are condensible and reactive
under the proper conditions but may only form a mixture under other conditions
(e.g., Ti + C). In reactive film deposition processes, the rate and degree of
reaction is dependent on the chemical reactivity of the reactive species, the
temperature, the extent of the reaction, and the availability of the reactive
species to the depositing species which, in turn, may be very dependent on
system geometry and relative surface areas.[21]
When a reactive species is present, concurrent energetic particle
bombardment enhances chemical reactions. The nature of this enhance-
ment is poorly understood since heating, physical collisions, molecular
fragmentation, intermediate species, and the presence of energetic electrons
(secondary electrons) may each play a role in the chemistry of the reaction.
The existence of bombardment-enhanced chemical reactions iswell estab-
lished in etching studies where the reaction products are volatile[22][23] and
bombardment effects are found in reactive film deposition processes where the
reaction products are non-volatile (reactive deposition).[24]
In the condensation of atoms, there is developed a residual lattice strain
which is usually evident as a residual tensile stress in the film. Where there
is concurrent bombardment during deposition, this strain may be compressive
in nature due to theatomic peening (stuffing) of atoms into the lattice by recoil
implantation. These growth stresses are very important to some film
properties such as adhesion and stability.[14][25][26]
It should be realized that very few surfaces are chemically and physically
homogeneous. Inhomogeneity in the substrate surface leads to variations in
film nucleation, growth, and properties. Processing which leads to greater
surface and growth homogeneity will lead to greater film homogeneity.
Substrate morphology, surface chemistry, and physical properties may
have a important affect on film growth and thus on the subsequent film
properties. Substrate specification and characterization are important parts
of process development and production reproducibility. Specifications for the
in-coming substrate material and the surface preparation must be included as
part of the process development.
Post-deposition processing may be used to change the film or interface
properties. Such processing includes: (i) burnishing or shot peening (soft
metal films), (ii) rapid thermal processing,[27] (iii) annealing, (iv) ion beam
mixing.[28]
Non-Elemental Characterization of Films and Coatings 681
5.1 Adhesion
paths and can act as stress concentrators to initiate and propagate the
fracture. Another important factor in fracture propagation is the presence of
stress and stress gradients in the material. These stresses may enhance
fracture propagation (tensile stress) or retard fracture propagation (compres-
sive stress), to some degree. The stress may be intrinsic to the system—
arising from the deposition process, or may be extrinsic—arising from applied
stresses. In either case, the nature of the stresses which appear at the
interface depend on the properties of the materials involved.
Localized regions of high intrinsic stress may be found in films due to
growth discontinuities or defects such as pinholes[42] or nodules, or near
features such as edges. These stressed areas may lead to localized adhesion
failure under applied stress.
The fracture path is determined by the properties of the film and substrate
materials, the presence and distribution of flaws, stress distribution, and the
presence of features which may blunt or change the fracture propagation
direction. Conceptually, the energy needed to propagate the fracture and
create the new surfaces can be measured and this fracture energy would be
a good measure of the adhesion of the system.[43][44] Energy may be
absorbed by:(i) plastic deformation (slip, atom motion),(ii) elastic
deformation (heat),(iii)generation of free surfaces.
The fracture of a brittle material is often accompanied by acoustic
emission which results from the release of energy. This acoustic emission has
both an energy and a frequency spectrum.[46] In one method of the detection
of adhesion failure by acoustic emission, the coated surface is scratched by
a rounded diamond point and the load on the point is increased while
monitoring the acoustic emission using a piezoelectric accelerometer. This
mode of detection is often more sensitive than the normally-used optical
detection techniques
The fracture of an insulator interface is often accompanied by the
emission of electrons, photons and/or ions (fractoemission). This
fractoemission is probably due to microdischarges resulting from charge
separation during fracture.[46]
Adhesion is determined by the nature of the stresses that appear at the
interface and the fracture energy needed to propagate a fracture. Good
adhesion is promoted by: high fracture toughness of the materials, low
concentration of flaws, non-planar defects, presence of fracture blunting
features, interfacial roughness that necessitates the change of direction of a
propagating fracture, low stresses and stress gradients, and the absence of
operational degradation mechanisms.
Non-Elemental Characterization of Films and Coatings 685
Poor adhesion may be attributable to: low degree of chemical bonding (as
evidenced by a low nucleation density), poor interfacial contact , low fracture
toughness (brittle materials, flaws, stresses), high residual film stresses, and
operational degradation mechanisms. Poor adhesion may be localized,
giving local failure on stress (pinholes, nodules, spallation).
Loss of adhesion may also occur due to non-mechanical stresses such
as: corrosion or solution of interfacial material, generation of flaws, diffusion to
or away from the interface of species which can influence adhesion, precipi-
tation of diffusing species (e.g., H, He) at the interface, or static fatigue
processes that propagate existing flaws in brittle materials. These degrada-
tion processes are often time, temperature, and environment dependent.
An example of the loss of adhesion due to corrosion effects is the
degradation of some Ti-Au metallizations in an HCl environment.[47] This
electrochemical degradation may be eliminated by the addition of a thin
intermediate layer of palladium between the titanium and the gold.
An example of the loss of adhesion due to diffusion is the diffusion of
chromium from the interface of an oxide-Cr-Au metallization through the gold
to the surface on heating to >200°C in air. At the surface, the chromium
oxidizes and creates a non-bondable surface and the loss of chromium at the
interface results in loss of adhesion. This out-diffusion of the interfacial
material is dependent on the composition of the gaseous ambient, and a non-
oxidizing ambient reduces the diffusion.[48] The addition of a small amount of
oxygen in the chromium and/or the gold during deposition reduces the
chromium diffusion rate and gives a more thermally stable metallization.[49]
The adhesion of the Ti-Au metallization can be degraded by the diffusion of Ti
to the surface and by chlorine impurities in the film material (chemically-
induced segregation).[50]
The diffusion of hydrogen through a film to an interface where it
precipitates has been used by the electroplating community as an adhesion
test.[51] Gases incorporated into a surface or film during surface preparation
or film deposition may diffuse to the interface on heating, giving a loss of
adhesion.
Diffusion of water vapor through a polymer film to the interface can lead
to the degradation of metal-polymer adhesion.[53] Interfacial mixing can
improve the moisture degradation properties of polymer-metal film
systems.[53]
686 Deposition Technologies for Films and Coatings
Contacting techniques:
• Surface profilometer (stylus technique). Measures the
height of a step from the substrate surface to the film surface.
Step is formed by masking during deposition or by masking
and etching. Stylus scans length of several centimeters with
a resolution of <0.2 mictrons and measures height of greater
than 100 Å.[79] Sensitivity is dependent on surface rough-
ness, flatness, and abruptness of the step. Commercial
units are available that scan over a surface and present the
surface topography on a screen.
Non-contacting techniques:
• Michelson interferometry - Measures the height of a step
using a split beam of light. The differing optical path lengths
give constructive and destructive interference patterns. By
knowing the wavelength of the light and the number of fringes,
the step height can be calculated. Measures step heights of
300 - 20,000 Å ± 150 - 300 Å.[80][81]
• X-ray fluorescence (XRF) - Measures the mass per unit area
of a material. By assuming the density (or calibrating the
instrument) the measurement can be presented as a
thickness. Measures thicknesses from 100 nm to 40
microns, depending on the material.[82]
• X-ray absorption - Measured by x-ray attenuation. Thickness
by knowing the absorption coefficient or by calibration.
Measures thicknesses from 0.1 to >1000 µm ±5%.
• Ellipsometry - Measures dielectric film thickness by the
rotation of polarization axis as the beam passes through the
film. Thickness is determined by knowing the index of
refraction of the dielectric or calibration.[83]
• Beta backscatter - Energetic electrons from a radioactive
source are backscattered from the film and underliying
substrate. Thickness is measured by calibration. Thickness
range depends on the electron source and the scattering
properties of the material. For example, using a C14 source,
1.25 to 1.9 microns of gold can be measured; using a Ru106
source, 15 to 38 microns gold can be measured ± 5%. [83]
• Other techniques
- Scanning Tunneling Microscopy (STM) (step height)
- Atomic Force Microscopy (AFM) (step height)
- Photon Tunneling Microscopy (PTM) (step height)
- Magnetic eddy current techniques
- Multiple beam interferometry (step height, 10 - 10,000 Å)
Non-Elemental Characterization of Films and Coatings 691
t f E s t s
2
t E y
σf= − s + 6 f f
Eq. (1) ( 6 ρ) t f tf t s tf
692 Deposition Technologies for Films and Coatings
where Tf and Ts are the thicknesses of the film and substrate, Ef and Es are the
elastic moduli of the film and substrate material,ρ is the radius of curvature and
the term yf /tf is the relative position in the film for which the stress is calculated
and is measured from the midplane of the film (yf = 0) and is positive toward
the film-substrate interface where the film stress is maximum.
Figure 12.3 shows a sample calculation.
Figure 12.3. Sample stress calculation for a molybdenum film on a thin glass
substrate.
Figure 12.4. Large area Michelson interferometer with associated illumination and
data treatment system.[98] The setup shown is for measuring the mechanical
properties of a coated substrate by four-point loading of the sample.
Film lattice strain (stress) may also be measured by x-ray diffraction and
lattice parameter measurements.[99] However, this technique may not give the
same value of stress as measured by the deflection techniques since it does
not sum over all the stresses (those associated with the grain boundaries for
instance) and is influenced by other factors such as grain size and film
morphology. Strain in the surface lattice (few atom layers) can be measured
by LEED techniques.[100]
Non-Elemental Characterization of Films and Coatings 695
R = ρL/A
where ρ is the resistivity, L the length, and A the area. For a thin film, the
resistivity may be a strong function of the film properties such as morphology,
composition, etc.[113]
The film resistivity is often given as the sheet resistivity (sheetρ) in ohms
per square since the resistance of any square is the same no matter what the
size of the square, as long as the thickness is uniform and other properties are
the same:
The sheet resistance is measured using a four-point probe technique
where the current[1] is injected through two probes and the voltage drop (V)
between two other probes is measured.[114][115] This technique avoids contact
resistance problems.[116][117]
For a linear probe arrangement, the resistivity is given by:
Rs = 4.532 V/I
5.8 Electromigration
5.9 Density
5.10 Porosity
The porosity in a deposit may consist of:(i) open porosity where the pores
are interconnected, (ii) closed porosity where the pores are isolated and not
interconnected, and(iii) through-porosity where the pore extends through the
deposit from the surface to the interface. Typically, a deposit will contain both
open and closed porosity to some extent. A material with closed porosity will
show a decrease in density while a material with open porosity will not (as
measured by many of the techniques described under density measure-
ments). Voids is another term used for isolated pores, whilemicrovoids is the
term used for very small voids down to clusters of lattice vacancies (few
angstroms in diameter).
Voids in the bulk of the material form by the growth processes or by
agglomeration of defects during or after deposition. Voids in the bulk affect
density of the material, the deformation and fracture properties of the material,
and the thermal and acoustic transmission of the material.
Closed voids in materials are typically measured and studied by: (i)
density measurements or (ii) transmission electron microscopy (TEM).
In TEM, the sample is thinned and the voids are observed directly by
using the underfocus-overfocus technique. Voids as small as 7Å in diameter
may be resolved using this technique.
Non-Elemental Characterization of Films and Coatings 699
Figure 12.5. SEM photograph of corrosion products emerging from a pore in a gold
coating on Kovar®. Corrosion was performed in a moist UV/O3 atmosphere.
6.0 SUMMARY
This discussion has given the reader an indication of the factors in film
deposition technologies and film growth that affect the properties of the
resulting material. Some simple characterization techniques have been
discussed but there are many more to be found in the literature. The need for
reproducible samples and characterization specifications has been strongly
emphasized.
702 Deposition Technologies for Films and Coatings
REFERENCES
23. Winters, H. F., Coburn, J. W., and Chuang, T. J.,J. Vac. Sci. Technol.,
B1:469 (1983)
24. Harper, J. M. E., Cuomo, J. J., and Henzell, H. T. G., Appl. Phys. Lett.,
36:456 (1980); also Appl. Phys. Lett., 37:540 (1980)
25. Hoffman, R. W., Thin Solid Films, 89:155 (1982)
26. Pulker, H. K., Thin Solid Films, 89:191 (1982)
27. Singh, R., J. Appl. Phys., 63(8):R59 (1988)
28. Wie, C. R., Yang, J. Y., Tombrell, T. A., Grant, R. W., and Housley, R.
M., Vacuum, 38:157 (1988)
29. Metals Handbook, 9th. ed., Vol. 10, (R. Wahn, ed.), American Society
for Metals, Metals Park, OH 44073 (1986)
30. Good, R. J., J. Adhesion, 8:1 (1976)
32. Pulker, H. K., Perry, A. J., and Berger, R., Surf. Technol., 14:25 (1981)
33. Kinloch, A. J., [polymer] J. Mat. Sci., 15:2141 (1980)
34. Adhesion Aspects of Polymeric Coatings, (K. L. Mittal, ed.), Plenum
(1981)
35. Mattox, D. M., J. Vac. Sci. Technol., 10:47 (1973)
36. Baglin, J. E. E., Ion Beam Modification of Insulators, (P. Mazzolsdi,
and G. Arnold, eds.), Ch. 15, Elsevier (1987)
37. Benjamin, P. and Weaver, C., Proc. Royal Soc., 261A:516 (1961)
38. Laugier, M., Thin Solid Films, 75:L19 (1981)
39. Kominiak, G. J. and Mattox, D. M., J. Electrochem. Soc., 120:1535
(1973)
40. Hershkovitz, M., Blech, I. A., and Komem, Y.,Thin Solid Films, 130:87
(1985)
41. Kikuchi, A., Baba, S., and Kinbara, A.,Thin Solid Films, 124:343 (1985)
42. Zito, R. R., Thin Solid Films, 87:87 (1982)
43. Bascom, W. D., Becher, P. F., Bitner, J. L., and Murday, J. S.,
Adhesion Measurement of Thin Film, Thick Film and Bulk Coatings, (K.
L. Mittal, ed.), ASTM STP 640, pp. 63-82 (1977)
44. Oh, T. S., Cannon, R. M., and Richie, R. O.,J. Am. Cer. Soc., 70:C352
(1987)
45. Hintermann, H. E., J. Vac. Sci. Technol., B2:816 (1984)
46. K’Singam, L. A., Dickenson, J. T., and Jensen, L. C., J. Am. Cer. Soc.,
68:510 (1985)
47. Speight J.D . and Bill, M. J. Thin Solid Films, 15:325 (1973)
48. Ray, S. K. and Lewis, R. K., Thin Solid Films, 131:197 (1985)
49. Mattox, D. M., unpublished results
50. Krzyzanowski, S., Sylwestrowicz, W. D.,J. Mat. Sci. Lett., 1:35 (1982)
704 Deposition Technologies for Films and Coatings
110. Bourcier, R. J., Nelson, G. C., Hayes, A. K., and Romig, A. D., Jr, J.
Vac. Sci. Technol., A4:2943 (1986)
111. Schmale, D. T., Bourcier, R. J., Martinez, E., Sandia Laboratory Report
SAND86-0509 (April 1986), available from NTIS
112. Cook, S. and Latham, R. V., Surf. Coat. Technol., 27:379 (1986)
113. Angadi, M. A., J. Mat. Sci., 20:761 (1985)
114. Valdes, L. B., Proc. IEEE (IRE), 42:420 (1954)
115. Keenan, W. A., Johnson, W. H., and Smith, A. K., Solid State Technol,
28(6):143 (1985)
116. Cohen, S. S., Thin Solid Films, 104:361 (1983)
117. Cohen, S. S., Gildenblat, G., Ghezzo, M., and Brown, D. M., J.
Electrochem. Soc., 129:1335 (1982)
118. Albers, J. and Berkowitz, H. L.,J. Electrochem. Soc., 132:2453 (1985)
119. Albers, J. and Berkowitz, H. L., J. Electrochem. Soc., 131:392 (1984)
120. Esqueda, P., Octavio, M., and Callarotti, R. C.,Thin Solid Films, 89:33
(1982)
121. Teal, V., Vaidya, S., and Fraiser, D. B.,Thin Solid Films, 136:21 (1986)
122. Felton, L. E., Schwartz, J. A., Pasco, R. W., and Norbury, D. A., J.
Appl. Phys., 58:723 (1985)
123. Antilla, A., Koskinen, J., Bister, M., and Hirvonen, J., Thin Solid Films,
136:29 (1986)
124. Pratten, N. A., J. Mat. Sci., 16:1737 (1981)
125. Young, D. M. and Cromwell, A. D., The Physical Absorption of Gases,
Butterworth Pub. (1962)
126. Rootare, H. M.,Advanced Experimental Techniques in Powder Metallurgy,
(J. S. Horschorn and K. H. Roll, eds.), 5:225, Plenum (1970)
127. Tvarusko, A. and Hinterman, H. E., Surf. Technol., 9:209 (1979)
128. Kern, W., RCA Rev, 34:655 (1973)
129. Kern, W. and Comizzoli, R. B., J. Vac. Sci. Technol., 14:32 (1977)
130. Kern, W., Solid State Technol., 17:78 (1974)
131. Kern, W., Solid State Technol., 17:35 (1974)
132. Morrissey, R. J., J. Electrochem. Soc., 119:446 (1972)
133. Martin, S. J., Frye, G. C., Ricco, A. J., and Zipperian, T. E.,Proc. IEEE,
(1987); Ultrasonics Symposium, p. 563, (1987)
134. Pliskin, W. A., Physical Measurement and Analysis of Thin Films, (E.
M. Murt and W. G. Guldner, eds.), Ch. 8, Plenum Press (1969)
135. Adachi, S., Susa, N., J. Electrochem. Soc., 132:2980 (1985)
13
Joseph E. Greene
1.0 INTRODUCTION
707
708 Deposition Technologies for Films and Coatings
however, the supersaturation ratio S = P/P e must be larger than one since
small particles such as nuclei have a larger vapor pressure than that of bulk
material due to their high surface-to-volume ratio.
A large surface-to-volume ratio also leads directly to the requirement
that clusters must be greater than a certain minimum critical size in order for
growth to occur. This is easiest to understand in the case of homogeneous
nucleation such as the formation of an embryonic ice particle in water cooled
below its freezing point Tm. At temperatures less than Tm, solidification
lowers the volume free energy ∆Gv of the system and is, hence, favorable.
However, the formation of the solid particle increases the total Gibbs free
energy ∆G since it introduces new interfacial surface area. The difference
between the decrease in ∆Gv and the increase in the free energy Γ results
in a free energy activation barrier for nucleation. That is, the incipient clusters
must reach a critical size before the volume term overcomes the surface term
and stable nuclei are formed.
Most theoretical treatments of heterogeneous three-dimensional
nucleation from the vapor phase are an extension of homogeneous nucle-
ation theory using the capillarity, or droplet model.[7]-[9] More sophisticated
treatments are also available.[5][10][11] However, the capillarity model has
the virtue of being simple while still retaining all the essential physical
features observed in experiments. In any case, all models, even the more
sophisticated ones, suffer from several shortcomings. For example, macro-
scopic thermodynamic values, which are not strictly appropriate for small
clusters, are used for surface energies, free energies of formation, contact
angles, etc. In addition, convenient geometries, e.g., a spherical cap, are
used to represent nuclei which are often anisotropic or crystallographic in
shape.[6] Thus, for clarity of discussion, the capillarity model will be used in
this chapter.
Assume that a cluster of mean dimension r forms on a solid surface.
The cluster has a surface area a1r2 exposed to the vapor phase, a contact
area a2r2 with the substrate, and a volume a3 r3 where the ai terms are
constants of geometry. The total free energy of the cluster with respect to
dissociation into the vapor phase is
Γc-v is the positive free energy associated with the formation of a new surface
between the condensate and the vapor phase; Γs-c, which may be either
positive or negative, is the surface free energy between the substrate and the
712 Deposition Technologies for Films and Coatings
condensate; and the term a2 r2 Γs-v accounts for the disappearance of free
substrate area.
The problem can be simplified if we consider an isotropic geometry
such as a spherical cluster. Equation 1 then becomes
Eq. (3) r * = − 2Γ
∆Gv
where, for simplicity of notation, Γ is used to represent Γc- v. The free energy
barrier is then obtained by substituting Eq. 3 into Eq. 2 to give
16πΓ 3
Eq. (4) ∆G ∗ =
3(∆ Gv )
2
where V and S are the system volume and entropy, respectively. Substitut-
ing the ideal gas law PV = kT at constant temperature,
kT P kT
Eq. (7) ∆Gv = ln = ln(S)
Ω Pe Ω
2ΩΓ
Eq. (8) r* = −
kT ln(S)
Nucleation, Film Growth, and Microstructural Evolution 713
Figure 13.4. Schematic diagram showing free energy vs. the radius r of a
spherical nuclei.
dn1 n
= R − 1 − 2 J1 − ∑ Ji
Eq. (9a) dt τd i ≥1
dn 1
Eq. (9b) = J i −1 − J i (i ≥ 2)
dt
714 Deposition Technologies for Films and Coatings
Figure 13.5. Schematic illustration of sequential steps during nucleation and the
early stages of film growth. (From Ref. 8.)
Figure 13.6, taken from the work of Donohoe and Robins,[14] is a plot
of the number density of evaporated Au nuclei on NaCl(100) as deter-
mined by replication TEM studies carried out as a function of deposition
time.[15] The experiments were performed in ultrahigh vacuum using a
deposition rate of 0.1 nm/min onto vacuum-cleaved substrates maintained
at 250oC. The number density n reached a maximum of≈1.5 x 1011 cm-2 after
depositing an equivalent thickness of ≈1 nm. A series of electron micro-
graphs which provided some of the data for Fig. 13.6 are shown in Fig. 13.7.
Both n and the average island size are increasing in the sequence Figs. 13.7a
(0.5 min of deposition) through 13.7d (8 min of deposition) with a significant
amount of coalescence clearly observable in Fig. 13.7d.
A series of micrographs illustrating the nature of the morphological
changes which occur during coalescence are shown in Fig. 13.8 from the
work of Pashley et al.[15] on the growth of Au on MoS2 at 400oC. The clusters
labeled A and B in Fig. 13.8a, observed at time t, have well-defined
crystallographic shapes. As the islands touch in Fig. 13.8b, taken 1 to 2 s
later, there is a very rapid mass transport between them. The driving force
for coalescence is a reduction in surface energy causing the islands to
become taller and more rounded. Their total projected area on the substrate
716 Deposition Technologies for Films and Coatings
−2 a1Γc − v + a 2 Γs − c − a 2 Γs − v
Eq. (10) r* =
3 a 3 ∆Gv
Figure 13.10a. Average grain size <d> vs. film thickness t for InSb layers deposited
by evaporation onto cleaved mica substrates at ambient temperature and then
annealed at 465oC. (From Ref. 16.)
Figure 13.10b. Average grain size <d> normalized to the film thickness t plotted as
a function of the growth temperature Ts and the deposition rate R of InSb layers
deposited on CaF2(111) substrates by rf sputtering. (From Ref. 17.)
Nucleation, Film Growth, and Microstructural Evolution 721
Eq. (11) 2
(
a2 r Γs −v < a2 r Γs −c + a1r Γc −v
2 2
)
In other words, the net surface free energy associated with the formation of
a cluster is positive. This led directly to the establishment of a free-energy
barrier (or, equivalently, a critical cluster size) to be overcome in order for
embryonic clusters to grow and, in turn, required that the supersaturation
necessary to obtain film growth be greater than unity. The assumption
represented by Eq. 11 is generally a good one. However, there are cases,
such as, for example, the growth of material A on a clean single-crystal
surface of A in ultra-high vacuum (UHV), where Eq. 11 does not hold and no
nucleation barrier exists. Instead, growth occurs in a quasi layer-by-layer
fashion with the motion of steps, which may be as small as one monolayer,
across the surface. In the presence of such steps, often insured by the use
of substrates with vicinal surfaces, growth can proceed with supersatura-
tions approaching unity. Even in the absence of an initially high step density,
steps can be created under conditions of high supersaturation.
A more general description of the requirement for a film/substrate
system to exhibit two-dimensional nucleation is that the desorption energy
of film atoms condensed on the substrate be equal to or larger than the
desorption energy of film atoms condensed on other film atoms. That is,
where Ed,s and Ed,f are the desorption energies for film adatoms on sub-
strate and film surfaces respectively. One obvious way to fulfill this
requirement is to grow a film on a substrate of the same material, e.g., Si on
Si or GaAs on GaAs, under very clean conditions. In the case of Si, it was
shown by Joyce et. al.[21] that small traces of carbon, near the detection limit
of Auger spectroscopy (≈ 0.01 monolayer), resulted in island formation
during film growth on Si(111)7x7 surfaces. Reflection high-energy electron
diffraction (RHEED) analysis showed that the carbon was in the form of β-
SiC particles.[22] Removing the carbon by flash heating the sample to ≥
1200o C,[21] sputter cleaning and annealing,[23] or depositing a thick buffer
layer over the contaminated surface[24] resulted in two-dimensional nucle-
ation and growth of Si films by molecular beam epitaxy (MBE),[24] chemical
vapor deposition (CVD),[23] and sputter deposition. [25]
RHEED has long been used as an in situ diagnostic technique for
investigating surface reconstruction and roughness during film growth.
However, more recently, it has been applied to in situ nucleation studies (see,
for example, Refs. 26 - 28). In one mode of operation, the time variation of
Nucleation, Film Growth, and Microstructural Evolution 723
Figure 13.12. RHEED intensity oscillations during GaAs MBE growth on a vicinal
(100) GaAs substrate at 600oC. The deposition flux was varied such that the time
to deposit one bilayer was: (a) 150 s, (b) 40 s, (c) 16 s, and (d) 5 s. (From Ref. 27.)
724 Deposition Technologies for Films and Coatings
Figure 13.13. RHEED intensity data showing differences in the recovery time for
the intensity of a specular beam after shuttering the group-III effusion cells during
the MBE growth of GaAs and (Ga,Al)As on GaAs(100). (From Ref. 31.)
dimensional growth. The escape depth for Si Auger electrons through the
In overlayer was obtained by fitting data from the first In monolayer (ML).
nected column and void boundaries following air-exposure of the film can
result in large, and time-dependent, changes in measured stress values.
where Q is the activation energy for surface diffusion and Φ is the energy of
a single bond. Boltzmann statistics were used to simulate fluctuations in
adatom vibrational energy. Müller found that above a critical temperature
range the porous columnar microstructure changes to a configuration of
maximum packing density. That is, the hopping rate of adatoms to shadowed
regions becomes large enough to exceed the rate of void incorporation.
Figure 13.21 shows calculated results for a two-dimensional Ni lattice (Φ =
- 0.74 eV) deposited at a rate of 1 nm s-1 with a vapor impingement angle α
= 45o . The lower three atom layers in the figure correspond to the substrate.
The typical open columnar structure characterizing low adatom mobility
growth was obtained at Ts = 350 K. Increasing the deposition temperature
to 420 K resulted in a film with much higher density, although still columnar.
At Ts = 450 K, a fully dense film with local defects was obtained.
Müller’s simulations also predict that the temperature range over which
the transition occurs from a film with a columnar microstructure to one that
is densely packed increases slowly with increasing deposition rate. Figure
13.22 shows results for a Ni film deposited at α = 45o in which R was
increased from 0.01 to 100 mn s-1 . The four orders of magnitude increase
in deposition rate raised the “transition” temperature from 340 to 525 K since
higher adatom migration rates were required to overcome the larger void
incorporation at higher deposition rates.
Nucleation, Film Growth, and Microstructural Evolution
Figure 13.21. Computer-simulated two-dimensional microstructures of Ni films deposited with an incident flux angle α = 45o,
deposition rate R = 1 nm/s, and growth temperatures Ts of (a) 350 K, (b) 420 K, and (c) 450 K. The deposition time, t, is shown.
735
(From Ref. 58.)
736 Deposition Technologies for Films and Coatings
Figure 13.23. Structure-zone diagram for thick high-rate evaporated films. T1 and
T2 are the growth transition temperatures between zone-1/zone-2 and zone-2/zone-
3 microstructures, respectively, as described in the text. (From Ref. 65.)
pressure to values such that the mean-fee path for elastic collisions between
sputtered (or evaporated) species and the fill gas becomes of the order of the
source-substrate distance increases the oblique component of the deposi-
tion flux resulting in a more open zone-1 type structure. In addition,
decreasing the pressure during sputter deposition results in increased
energetic-particle bombardment, and hence densification, of the growing
film as discussed below in Sec. 5. Finally, it has been proposed that
increasing the inert gas pressure during deposition leads to a decrease in
adatom mobilities.[53] While this is undoubtedly true, it is probably not a major
effect since the surface residence time of physisorbed inert gas species is
very short, and hence the steady-state coverage is quite low.
Thornton also added an additional region, labeled zone T in Fig. 13.24,
to his SZD which consisted of a “dense array of poorly defined fibrous grains”
which represented the transition between zones 1 and 2. He defined the
zone T structure as the limiting form of the zone 1 structure at zero Ts/Tm.[67]
That is, the zone T “fibers” formed the internal structure of the zone 1
crystallites. Examples of fracture cross-sections of metal coatings exhibiting
zones 1, T, and 2 structures are shown in Fig. 13.25. The coatings were
deposited using cylindrical hollow-magnetron sputtering at the Ts/Tm values
indicated and examined by scanning electron microscopy (SEM).
Grovenor et al.[75] have further modified earlier SZDs based upon the
results of their plan-view transmission electron microscopy (TEM) examina-
tions of evaporated metal films with thicknesses of either 100 nm (Ni, Pt, Au,
Cu, Al, Pb, Ti, Co, W, and Cr) or 9 - 14 µm (Ni and Ni-Al alloys thinned from
both sides and examined at a thickness of ≈ 5-7 µm from the substrate).
These researchers observed that the tapered columns in the zone-1 struc-
ture are not single grains but are composed of bundles of small grains (with
sizes of order of tens of nm depending upon film thickness) which are
relatively equiaxed. Their zone 1 corresponded to Ts/Tm < 0.1 while zone T,
in which the small-grained substructure consisted of a bimodel distribution
of sizes, extended to Ts/Tm = 0.3.
Substructure was also observed in sputter-deposited amorphous Ge
films by Messier et al.[73] using a combination of SEM, TEM, and field-ion
microscopy. The microstructure of the a-Ge films consisted of columns
which were observed to be composed of smaller columns spanning several
different size scales, in a fractal-like behavior,[76] ranging from ≈ 2 nm to 300
nm. Messier further extended earlier SZDs by adding a film thickness axis
to underscore the evolutionary nature of film microstructure as the dominant
features move through different observable size scales.
740
Deposition Technologies for Films and Coatings
Figure 13.25. Scanning electron microscopy cross-sections of metal coatings deposited by cylindrical magnetron sputtering in Ar
illustrating (a) zone-1 microstructure, (b) zone-T microstructure, and (c) zone-2 microstructure. (From Ref. 53).
Nucleation, Film Growth, and Microstructural Evolution 741
Low-energy (often < 100 eV) ion and fast-neutral irradiation during
vapor-phase film growth has been shown to be useful for controllably altering
the microstructure of as-deposited layers. In PVD, ion irradiation during film
growth is commonly used in glow-discharge bias sputter deposition (see Ch.
5). In addition, low-energy ion bombardment is also an important technique
for modifying the properties of films deposited by primary-ion deposition
(PID) and ion-assisted molecular-beam epitaxy (MBE) as well as by CVD
techniques such as plasma-assisted chemical vapor deposition (PA-CVD).
Examples of applications in which low-energy ion/surface interac-
tions are used to modify film microstructure include: densification and
increased oxidation resistance in optical films; minimization or elimination
of columnar microstructure in microelectronic metallization layers; altering
the state of stress, average grain size, and preferred orientation; increased
film/substrate adhesion; enhanced conformal coverage; controlling mag-
netic anisotropy in recording layers; and low-temperature epitaxy. Although
the focus of this chapter is on microstructural effects, it is important to be
aware that ion irradiation is also used to controllably alter film microchem-
istry through collisionally-induced dissociative chemisorption,[81] preferen-
tial resputtering,[82]-[86] and selective deposition on patterned substrates.[87]-
[89] Ion irradiation has been used to promote the growth of unique new
One of the first studies of the role of incident energetic species during
3-D nucleation was carried out by Chapman and Campbell[99] who used very
high energy, 40 - 50 keV, Ar and Xe ion-beam sputtering to deposit Au onto
746 Deposition Technologies for Films and Coatings
when growth conditions leading to high nucleation rates are combined with,
for example, self-ion bombardment under conditions in which there is a high
incident ion-to-vapor flux ratio.
Hasan et al.[105] have recently carried out experiments using both
thermal In and partially-ionized In+ beams (ion-to-neutral ratio = 0.35) to
deposit In islands on amorphous Si3 N4 substrates in an ultra-high vacuum
(UHV) MBE system. The low-energy ion beams were provided using the
UHV metal-ion source described in Ref. 106. The deposition temperature
was ≈ 30oC (Ts/Tm = 0.7 where Tm is the In melting point in K), the thermal
In flux was 3 x 1013 cm-2 s-1, and the total flux was 4.6 x 1013 cm-2s-1. A series
of depositions were carried out with nominal film thicknesses t of 1.5 and 10
nm (the loss of material by sputtering was accounted for in determining t) with
acceleration energies EIn of 0 (i.e., thermal), 150, 200, and 300 eV. Typical
transmission electron microscopy (TEM) images of the resulting layers are
shown in Fig. 13.28. For a given film thickness, ion irradiation clearly resulted
in larger average island sizes. In fact, from island size distribution histograms
obtained using lower-magnification, larger-area, micrographs, <d> for films
with t = 10 nm increased from 6.5 to 8 to 13 to 50 nm with increasing EIn.
Another striking feature was the decrease in secondary nucleation at higher
acceleration energies until at 300 eV essentially no islands were observed
with <d> ≤ 11 nm. (The minimum island size resolution was ≈ 1 nm). The
histograms showed that the island size distributions were more uniform at
higher EIn values.
Increases in <d> and decreases in the secondary nucleation rate were
explained, as discussed above, as being due primarily to the loss of small
clusters (incipient islands) by ion-bombardment-induced processes. The
suppression of secondary nucleation in these experiments led, in turn, to
significant differences in island growth kinetics. In the accelerated-beam
case, island growth continued to be dominated by random surface-diffusion
processes even for 10-nm-thick overlayers. However, in the thermal-beam
deposits, coalescence of small islands had a much stronger influence on
island growth resulting in the observed differences in island-size distribuions.
Ion irradiation can also directly enhance adatom diffusivities during
deposition through the initiation of shallow collision cascades and the
excitation of surface phonons. However, the excess energy of incident
accelerated ions, as well as the excess energy gained by adatoms involved
in individual collision cascades, is lost to the lattice, i.e., the atoms become
thermalized, within several vibrational periods. Thus this mechanism, while
it may be important in contributing to bombardment-induced decreases in the
748 Deposition Technologies for Films and Coatings
protective films, the application of ion irradiation to densify and increase the
internal strength of the layers as well as to increase film/substrate adhesion
is already a prerequisite to commercial success. However, ion irradiation
during growth can also be disadvantageous for certain applications due to,
for example, the generation of very high compressive stress levels in the
films which can lead to spalling.
During growth at low substrate temperatures (Ts/Tm less than ~ 0.3) for
which, as discussed in Sec. 4, the films are generally underdense with a
columnar (zone 1) microstructure, many experiments involving both electri-
cally conductive[117]-[121] and insulating films[122][123] have shown that the
number density of voids and pores decreases dramatically with increasing
ion energy and/or ion flux. Mattox and Kominiak[117] were among the first to
demonstrate this effect. They found, in the case of sputter-deposited Ta
films, that the microstructure changed from a pronounced columnar mor-
phology to a more equiaxed structure and that the film density increased from
≈ 14.5 to 16.3 g cm-3 (bulk density = 16.6 g cm-3) as the negative substrate
bias was increased from 0 to 500 V (see Fig. 13.30).
Figure 13.30. The density, as a function of negative substrate bias Vs, of 6-µm-thick
Ta films deposited at 300oC by DC sputter deposition in Ar. (From Ref. 117.)
Nucleation, Film Growth, and Microstructural Evolution 753
Figure 13.32. Experimental and theoretical values of the density of CeO2 films
deposited at ambient temperature by simultaneous evaporation of Ce and ion-beam
acceleration of O2+ as a function of the ion energy Ei for an ion-to-vapor flux ratio Ji/
Jv of 1. The bulk density of CeO2 is 8.1 g/cm3. (From Ref. 125.)
While ion irradiation is useful for increasing the density and modifying
the morphology of films deposited at low temperatures, other irradiation-
induced effects occur simultaneously. For example, as the ion energy and
ion flux are increased, atomic displacements produced in the collision
cascades result in an increasing number of residual interstitials and vacan-
cies. These point defects can, in turn, lead to an increased density of
extended defects such as dislocation loops.
Huang et al.[126] have studied the effect of Ar+ ion bombardment during
the growth of Ag films at room temperature using a UHV dual-ion-beam
apparatus. They found that the void density decreased with increasing
ion energy in agreement with the results presented in the previous
paragraphs. However, they also showed that the use of average
irradiation energy densities <E> ranging from thermal (obtained by
evaporation) to 190 eV per deposited metal atom yielded a decrease in
the grain size from 42 to 14.5 nm while the dislocation number density nd
756 Deposition Technologies for Films and Coatings
increased from 0.7 x 1011 to 13.2 x 1011 cm-2 (see Fig. 13.34). In addition,
the degree of (111) preferred orientation decreased while the plane stress
reversed from 0.6 x 108 N m-2 tensile to - 4.5x108 N m-2 compressive for <E>
larger than 42 eV. Increased defect concentrations and reduced grain sizes
have also been observed in a number of other polycrystalline thin film
systems grown under low-energy ion irradiation.[121][127]-[130]
Figure 13.34. The average grain size and dislocation number density nd in Ag films
deposited at room temperature as a function of the average energy <E> per
deposited atom. (Plotted from data given in Ref. 126.)
Ion irradiation in the above experiments played at least two major roles.
For the lower biases, the primary effect was to enhance adatom mobilities
thereby accelerating the rate at which defects (both growth-related and ion-
irradiation-induced) were annealed out during deposition. At higher bias
voltages (Vs > V s*), the increased projected range of the impinging ions
resulted in a larger fraction of the irradiation-induced defects being trapped
in the growing film. Eventually, nd became high enough that renucleation
occurred during growth and polycrystalline films were obtained.
ACKNOWLEDGEMENTS
REFERENCES
19. Jacobs, M. H., Pashley, D. W., and Stowell, M. J., Phil. Mag. 13:129
(1966)
20. Barna, P. B., Proc. IX Internet. Vac. Congr., p. 382, Madrid (1983)
21. Joyce, B. A., Neave, J. H., and Watts, B. E., Surf. Sci. 15:1 (1969)
22. Henderson, R. C., Polito, W. J., and Simpson, J., Appl. Phys. Letters
16:15 (1970)
23. Henderson, R. C. and Helm, R. F., Surf. Sci. 30:310 (1972)
24. Abbink, H. C., Broudy, R. M., and McCarthy, G. P., J. Appl. Phys.
39:4673 (1968)
25. Aleksandrov, L. N. and Lovyagin, R. N., Thin Solid Films 20:1 (1974)
26. Van Hove, J. M., Pukite, P. R., and Cohen, P. I., J. Vac. Sci. Technol.
B3:563 (1985)
27. Van Hove, J. M. and Cohen, P. I., J. Cryst. Growth 81:67 (1987)
28. Reflection High-Energy Electron Diffraction and Reflection Electron
Imaging of Surfaces, NATO AISI Series B: Physics, (P. K. Larson and
P. J. Dobson, eds.) Vol. 188, Plenum Press, New York (1988)
29. Rockett, A., J. Vac. Sci. Technol. B6:763 (1988)
30. Rockett, A., SPIE Proceedings, 944:63 (1988)
31. Shtrikman, H., Heiblum, H., Seo, K., Galbi, D. E., and Osterling, L., J.
Vac. Sci. Technol. B6:670 (1988)
32. Price, G. L. and Venables, J. A., Surf. Sci. 49:264 (1975)
33. Wagner, R. S. and Voorhoeve, R. J. H., J. Appl. Phys. 42:3948 (1971)
34. Voorhoeve, R. H. J. and Wagner, R. S., Met. Trans. 2:3421 (1971)
35. Henrion, J. and Rhead, G. E., Surf. Sci. 29:20 (1972)
36. Delamare, F. and Rhead, G. E., Surf. Sci. 35:172 (1973)
37. Yagi, Y., Takayanagi, K., Kobayashi, K., and Honjo, G., J. Cryst.
Growth 9:84 (1971); Honjo, G. and Yagi, K., in Current Topics in
Materials Science (E. Kaldis, ed.) Vol. 6, North Holland Publishing Co.,
Amsterdam (1980)
38. Eltoukhy, A. H. and Greene, J. E., J. Appl. Phys. 50:505 (1979)
39. Matthews, J. W. and Blakeslee, A. E., J. Cryst. Growth 27:118 (1974)
40. Bean, J. C., Sheng, T. T., Feldman, L. C., Fiory, A. T., and Lynch, R.
T., Appl. Phys. Letters 44:102 (1984)
40a. People, R. and Bean, J. C., Appl. Phys. Letters 47:322 (1985) and
49:229 (1986)
40b. Tsao, J. Y., Dodson, B. W., Picraux, S. T., and Cornelison, D. M.,
Phys. Rev. Letters, 59:2455 (1987)
762 Deposition Technologies for Films and Coatings
41. Horng, C. T. and Vook, R. W., J. Vac. Sci. Technol. 11:140 (1974)
42. Soria, F. and Poppa, H., J. Vac. Sci. Technol. 17:449 (1980).
43. Hopkins, B. J. and Watts, G. D., J. Phys. C: Solid State 7:4259 (1974)
44. Steinhage, P. W. and Mayer, M., Thin Solid Films 28:131 (1975)
45. Van Loenen, E. J., Iwami, M., Tromp, R. M., and van der Veen, J. F.,
Surf. Sci. 137:1 (1984)
46. Honzay, F., Guille, C., Moison, J. M., Henoc, P., and Barthe, F., J.
Cryst. Growth, 81:67 (1987)
47. Stranski, I. N. and Krastanov, L., Acad. Wiss. Math-Nat. KIIIb 146:797
(1938)
48. Venables, J. A., in Current Topics in Materials Science (E. Kaldis and
H. J. Scheel, eds.) Vol. 2, p. 165, North Holland, Amsterdam (1977)
49. Price, G. L., Surf. Sci. 46:697 (1974)
50. Knall, J., Barnett, S. A. and Sundgren, J. E., Surf. Sci., in press
51. Rich, D. H., Samsavar, A., Miller, T., Lin, H. F., Chiang, T. C.,
Sundgren, J. E., and Greene, J. E.,Phys. Rev. Letters, 58:579 (1987)
52. Ehrlich, G. and Stolt, K., Ann. Rev. Phys. Chem. 31:603 (1980)
53. Thornton, J. A., J. Vac. Sci. Technol. 11:666 (1974)
54. Dirks, A. G. and Leamy, H. J., Thin Solid Films 47:219 (1977)
55. Leamy, H. J., Gilmer, G. H., and Dirks, A. G., in Current Topics in
Materials Science (E. Kaldis, ed.) 6:309 North Holland Publishing Co.,
Amsterdam (1980)
56. Henderson, D., Brodsky, M. H., and Chauderi, P., Appl. Phys. Letters,
25:641 (1975)
57. Kim, S. and Henderson, D. J., Thin Solid Films, 47:155 (1977)
58. Müller, K. H., J. Appl. Physics, 58:2573 (1985)
59. Holmwood, R. A. and Glang, R., J. Electrochem. Soc. 112:831 (1965)
60. Klokholm, E. and Berry, B. S., J. Electrochem. Soc. 115:823 (1968)
61. Huang, T. C., Lim, G., Parmiagiani, F., and Kay, E., J. Vac. Sci.
Technol. A3:2161 (1985)
62. Müller, K. H., J. Appl. Phys. 62:1796 (1987)
63. Srolovitz, D. J., J. Vac. Sci. Technol. A4:2925 (1986)
64. Srolovitz, D. J., Mazor, A., and Bukiet, B. G., J. Vac. Sci. Technol.
A6:2371 (1988)
65. Movchan, B. A. and Demchisin, A. V., Phys. Met. Metallogr. 28:83
(1969)
Nucleation, Film Growth, and Microstructural Evolution 763
66. Hentzell, H. T. G., Grovenor, C. R. M., and Smith, D. A., J. Vac. Sci.
Technol. A2:218 (1984)
67. Thornton, J. A., Ann. Rev. Mater. Sci. 7:239 (1977)
68. Guenther, K. H., Thin Solid Films, 77:239 (1981)
69. Guenther, K. H., Appl. Optics, 20:1034 (1981)
70. Messier, R., Krishnaswamy, S. V., Gilbert, L. R., and Swab, P., J. Appl.
Phys. 51:1611 (1980)
71. Swab, P., Krishnaswamy, S. V., and Messier, R., J. Vac. Sci. Technol.
17:362 (1980)
72. Ross, R. C. and Messier, R., J. Appl. Phys. 52:5329 (1981)
73. Messier, R., Giri, A. P., and Roy, R. A., J. Vac. Sci. Technol. A2:500
(1984)
74. Thornton, J. A., J. Vac. Sci. Technol. 12:830 (1975)
75. Grovenor, C. R. M., Hentzell, H. T. G., and Smith, D. A., Acta. Metall.
32:773 (1984)
76. Messier, R., J. Vac. Sci. Technol. A4:490 (1986)
77. Thornton, J. A., J. Vac. Sci. Technol. A4:3059 (1986)
78. Venables, J. A. and Price, G. L., in Epitaxial Growth, Part B, (J. W.
Matthews, ed.) p. 381, Academic Press, New York (1975)
79. Leamy, H. J. and Dirks, A. G., J. Appl. Phys. 49:3430 (1978)
80. Helmersson, U., Sundgren, J. E., and Greene, J. E., J. Vac. Sci.
Technol. A4:500 (1986)
81. See, for example, Winters, H. F., J. Chem. Phys. 44:1472 (1966)
82. Winters, H. F., Ramondi, D. L., and Horne, D. E., J. Appl. Phys.
40:2996 (1969)
83. Tarng, M. L. and Wehner, G. K., J. Appl. Phys. 42:2449 (1971)
84. Cuomo, J. J. and Gambino, R. J., J. Vac. Sci. Technol. 12:79 (1975)
85. Harper, J. M. E. and Gambino, R. J., J. Vac. Sci. Technol. A4:448
(1986)
86. Zilko, J. L. and Greene, J. E., J. Appl. Phys. 51:1549 (1980)
87. Berg, S., Nender, C., and Gelin, B., J. Vac. Sci. Technol. A4:448
(1986)
88. Nender, C., Berg, S., Gelin, B., and Stridh, B., J. Vac. Sci. Technol.
A5:1703 (1987)
89. Kondo, N. and Kawashima, M., GaAs and Related Compounds 1985,
Inst. Phys. Conf. Series 79, p. 97 (1985)
764 Deposition Technologies for Films and Coatings
111. Herbots, N., Noggle, T. S., Appleton, B. R., and Zhur, R. A., J. Vac.
Sci. Technol., in press
112. Yagi, K., Tamura, S., and Tokuyama, T., Jpn. J. Appl. Phys. 16:245
(1977)
113. Tokuyama, T., Yagi, K., Miyaki, K., Tamura, M., Natsuaki, N., and
Tachi, S., Nucl. Instr. Meth. 182/183:241 (1981)
114. Müller, K. H., Phys. Rev. 35:7906 (1987)
115. Müller, K. H., Surf. Sci. Lett. 184:L375 (1987)
116. Tsao, J. Y., Chason, E., Horn, K. M., Brice, D. K., and Picraux, S. T.,
Nucl. Instr. Meth., in press
117. Mattox, D. M. and Kominiak, G. J., J. Vac. Sci. Technol. 9:528 (1972)
118. Mizzoguchi, T. and Cargill, G. S., III, J. Appl. Phys. 50:3570 (1979)
119. Mnz, W. D. and Hofmann, D., Metalloberflche, 37:279 (1983)
120. Parmiagiani, F., Kay, E., Huang, T. C., Perrin, J., Jurich, M., and
Swalin, J. D., Phys. Rev. B33:879 (1986)
121. Hakanssan, G., Sundgren, J. E., McIntyre, D., Greene, J. E., and Mnz,
W. D., Thin Solid Films, 153:55 (1987)
122. Martin, P. J., Netterfield, R. P., and Sainty, W. G.,J. Appl. Phys. 55:235
(1984)
123. Netterfield, R. P., Sainty, W. G., Martin, P. J., and Sie,S. H., Appl. Opt.
24:2267 (1985)
124. Müller, K. H., J. Appl. Phys. 58:2803 (1986)
125. Müller, K. H., Appl. Phys. A40:209 (1986)
126. Huang, T. C., Lim, G., Parmiagiani, F., and Kay, E., J. Vac. Sci.
Technol. A3:2161 (1985)
127. Igasaki, Y. and Mitsuhashi, H., Thin Solid Films 70:17 (1980)
128. Poitevin, J. M., Lemperiere, G., and Tardy, J., Thin Solid Films 97:69
(1982)
129. Johansson, B. O., Sundgren, J. E., and Helmersson, U.,J. Appl. Phys.
58:3112 (1985)
130. Kay, E., Parmigiani, F., and Parrish, W., J. Vac. Sci. Technol. A5:44
(1987)
131. Hultman, L., Helmersson, U., Barnett, S. A., Sundgren, J. E., and
Greene, J. E., J. Appl. Phys. 61:552 (1987)
132. Hultman, L., Barnett, S. A., Sundgren, J. E., and Greene, J. E., J.
Cryst. Growth 92:639 (1988)
766 Deposition Technologies for Films and Coatings
14
Metallurgical Applications
Rointan F. Bunshah
1.0 INTRODUCTION
Corrosion and wear are often referred to as the twin demons of materials
degradation. The loss of material annually due to these causes is a significant
fraction of their total production each year. Often, materials degradation
results from both corrosion and wear phenomena acting simultaneously, e.g.,
corrosive wear, corrosion erosion, etc. The following sections discuss each
of these phenomena and the role of coatings in decreasing the resultant
materials degradation.
2.0 CORROSION
766
Metallurgical Applications 767
H+ → ½H2 - e-
Cu++ → Cu - 2e-
Fe+3 → Fe ++ - e-
Zn → Zn++ + 2e-
Al → Al +3 + 3e-
Fe++ → Fe+3 + e-
These represent oxidation in the chemical sense. For metals, it is at the anode
that corrosion usually occurs.
Metallurgical Applications 769
In galvanic cells, the cathode is the positive pole and the anode is the
negative pole.
There are three main types of cells that take part in corrosion reactions.
Dissimilar Electrode Cells. These are illustrated by the dry cell
discussed earlier. A metal containing electrically conducting impurities on the
surface as a separate phase, or a copper pipe connected to an iron pipe, or
a bronze propeller in contact with the steel hull of a ship are examples of this
type of corrosion cell. These cells also include cold-worked metal in contact
with the same metal annealed, or grain boundary metal in contact with grains,
or a single metal crystal of definite orientation in contact with another crystal
of differing orientation
Concentration Cells. These are cells having two identical electrodes
each in contact with a solution of differing composition. There are two kinds
of such cells. The first is called a salt concentration cell. For example, if one
copper electrode is exposed to a concentrated copper sulfate solution, and
another to a dilute copper sulfate solution, on short-circulating such a cell,
copper dissolves from the electrode in contact with the dilute solution (anode)
and plates out on the other electrode (cathode). Both reactions tend to bring
the solutions to the came concentration.
The second kind of concentration cell, which in practice is the more
important, is called a differential aeration cell. This may include two iron
electrodes in dilute NaCl solution, the electrolyte around one electrode being
thoroughly aerated (cathode), and the other deaerated (anode), brought about,
for example, by bubbling through nitrogen. The difference in oxygen concen-
tration produces a potential difference, and causes current to flow. This type
of cell accounts for pronounced damage at crevices such as are formed at the
interface of two coupled pipes, or at threaded connections, because O2
concentration is lower within the crevice or at the threads than elsewhere. It
also accounts for pitting damage under rust or at the water line (water-air
interface). Less oxygen reaches the metal that is covered by rust or other
insoluble reaction products than at other portions where the permeable coating
is thinner or absent.
Differential aeration cells also usually initiate pits in the stainless steels,
aluminum, nickel, and other so-called passive metals when they are exposed
to aqueous environments, such as water.
Differential Temperature Cells. Components of these cells are
electrodes of the same metal, each of which is at a different temperature,
immersed in an electrolyte of the same initial composition. Less is known
about the practical importance and fundamental theory of differential
770 Deposition Technologies for Films and Coatings
temperature cells than for the cells previously described. They occur in heat
exchangers, boilers, immersion heaters, and similar equipment.
In CuSO4 solution the copper electrode at the higher temperature is
cathode and the copper electrode at the lower temperature is anode. On short-
circuiting the cell, copper deposits on the hot electrode and dissolves from the
cold electrode. Lead acts similarly, but for silver the polarity is reversed.
For iron immersed in dilute aerated NaCl solutions, the hot electrode is
anodic to colder metal of the same composition, but after a matter of hours,
depending on aeration, stirring rate, and whether the two metals are short-
circuited or not, the polarity may reverse.
In practice, cells responsible for corrosion may be a combination of these
three types.
7.1 Preamble
777
778 Deposition Technologies for Films and Coatings
caused by particles in the gas stream can occur. The severest problem is in
rotating parts such as the turbine airfoil where a combination of high
temperature strength and oxidation resistance is desired. In spite of extensive
superalloy development (i.e., Co, Ni, or Fe base material) over a 20 year span,
a single alloy composition which has the requisite strength (produced by γ’
precipitation strengthening) and which develops a sufficiently dense protective
oxide by thermal growth has not been developed. Fortunately, coating
technology has enabled the development of a composite material where the
high temperature strength results from the base superalloy composition and
the corrosion resistance is provided by the coating which is enriched in the
oxide forming elements such as Al, Cr or Si.
Figure 14.1. Plot of parabolic rate constant vs. 1/T for various metals forming CoO,
NiO, SiO2 and Al2O3 layers showing the diffusional stability of Al2O3 forming system.
Metallurgical Applications 779
This type of wear occurs when solid particles impact against a target
material at speed. It is measured as a weight of material removed (Ε) by a
unit weight of impacting particles. When considering the performance of
target materials of different densities, it is more appropriate to use volumetric
erosion εν which is ε/ρ), ρ being the density.
The important parameters are the size, morphology, hardness, and
angle of impingement of the particles, and the hardness of the impacted
surface.
Brittle erosion can occur by micro-fracture with little or no deformation.
Ductile erosion can occur by: (i) cutting action, (ii) extrusion and
fragmentation
Special circumstances lead to the following additional types of wear.
Metallurgical Applications 783
10.1 Friction
Friction Coefficient
Low Moderate
Humidity Humidity Deposition
Material Pair (0.5 - 20%) (~50%) Methodology Reference
METAL/METAL
1. SS-Type 304/SS Type 410 0.67 - - 1
2. Titanium/SS Type 410 0.75 - - 1
METAL/CERAMIC
1. Tool Steel/SiC - 0.23 CVD 2
2. Tool Steel/TiC - 0.25 CVD 2
3. Tool Steel/TiN - 0.49 CVD 2
4. SS Type 304/TiC 0.42 - ARE (PVD) 1
5. SS Type 304/TiN 0.75 - ARE (PVD) 1
6. Ti/TiN 0.45 - ARE (PVD) 1
7. Steel/BN, TiN 0.1 - 12 - - 4
CERAMIC/CERAMIC
1. TiC/TiN - 0.05 - 0.2 ARE (PVD) 3
2. TiC/TiN 0.18 - CVD 2
3. TiC/TiC 0.32 - CVD 2
4. TiN/TiN - 0.19 CVD 2
5. TiN/TiN - 0.65 ARE (PVD) 3
6. TiN/Ti2N + TiN - 0.1 - 0.3 ARE (PVD) 3
7. Al2O3/TiC - 0.19 CVD -
References:
1. Suri, A. K., Nimmagadda, R., and Bunshah, R. F., Thin Solid Films, 64:191 (1979)
2. Hintermann, H. E., Thin Solid Films, 84:215 (1981)
3. Jamal, R., Nimmagadda, R., and Bunshah, R. F., Thin Solid Films, 73:245 (1980)
4. Dimigen, H. and Hübsch, H., ICMC '83
Metallurgical Applications 785
10.2 Lubrication
10.3 Wear
The most prominent application of hard coatings for wear is in the life
improvement of cutting tools. The CVD process for deposition of hard coatings
was developed in the late 1940's and commercially applied to improve cutting
tool life nearly 20 years later. One of the problems that had to be overcome
to make CVD processing commercially feasible was the need to reharden and
temper the high-speed steel substrate after the CVD process was carried out
at temperatures ranging from 1000 to 1100°C (1830 to 2010°F). This spurred
the development of a low-temperature high-rate deposition process for hard
coatings. Such a process (the ARE process) was developed by Bunshah and
Raghuram in 1971 (Ref. 25). The application of TiC and TiN coatings onto M42
high-speed steel tools by Bunshah and Shabaik (Ref. 26) in 1975 was the first
demonstration of large increases in cutting-tool life. Bhusan and Gupta[24]
have compiled a table that summarizes tool wear-life improvement. Table 14.4
is an adaptation of Bhusan’s original table.
HSS (M42) cutting TiC 5-8 ARE Three to eight times Bunshah et al.
tool (1975,1977)
Cemented carbide TiN, TiC 5 IP, CVD IP comparable to Kobayashi and Doi
cutting tool CVD (1978)
HSS (M-10) drill TiC, TiN 2 ARE Twenty times Nimmagadda et al.
(1981)
HSS (M-10) drill TiN 1-2 MS Fifty times Sproul and Rothstein
(1985)
Cemented carbide (Ti, Al)N, TiN/TiC - CVD Three times better Knotek et al. (1987)
cutting tool with (Ti, Al)N
HSS (M-10) drill (Ti, Al)N, TiN - IP Three times better Knotek et al. (1987)
with (Ti, Al)N
Cemented carbide TiN, HfN, ZrN 8 - 18 CVD, IP Hardness of IP, MS, Quinto et al. (187)
cutting tool ARE Coatings at
Room Temperature
Superior to CVD
Metallurgical Applications 787
REFERENCES
17. van Leaven, L., Alias, M. N., and Bronon, R.,Corrosion Behavior of Ion
Plated and Ion Implanted Films, - to be published
18. Walters, R. P., Surface and Coatings Technology, 39/40:655 (1989)
19. Yoshioka, T., Ukegawa, H., Kawai, H., Fujita, N., and Iragashi, T., paper
presented at the International Conference on Metallurgical Coatings,
San Diego (1988)
20. Goward, G. W., J. of Metals, 22:31 (1970)
21. Stephan, M., Dietrich, W., Feurstein, A., and Hoffmann, O. H.,
Metallurgy, 5:2 (1981)
22. Radhaknshna, M. C., Doerr, H. J., Deshpandey, C. V., and Bunshah,
R. F., Surface and Coatings Technology, 36:143 (1988)
23. Radhaknshna, M. C., Doerr, H. J., Deshpandey, C. V., and Bunshah,
R. F., Surface and Coatings Technology, 39/40,153 (1989)
24. Goward, G. W., J. of Metals, 22:31 (1970)
25. Stephan, M., Dietrich, W., Feuerstein, A., and Hoffmann, O. H, Metall,
5:2 (1981)
26. Radhakrishna, M. C., Doerr, H. J., Deshpandey, C. V., and Bunshah,
R. F., Surface and Coatings Technology, 36:143 (1988)
27. Radhakrishna, M. C., Doerr, H. J., Deshpandey, C. V., and Bunshah,
R. F., Surface and Coatings Technology, 39/40:153 (1989)
28. Spalvins, T., Thin Solid Films, 53:285 (1978)
29. Bhusan, B. and Gupta, B. V., Handbook of Tribology, McGraw-Hill,
(1991)
30. Bunshah, R. F. and Raghuram, A. C.,J. Vac. Sci. Tech., 9:1385 (1972)
31. Bunshah, R. F. and Shabaik, A. H.,Research and Development, 26:46
(1975)
15
Gary E. McGuire
1.0 INTRODUCTION
789
790 Deposition Technologies for Films and Coatings
where EK is the energy of the ionized core level, E L1 is the energy of the level
from which the electron originates to fill the initial core hole,E L2,3 is the energy
level from which the Auger electron is emitted and Ø is the work function.
Except for the lighter elements, multiple characteristic Auger transitions occur
due to the various core electrons that undergo electron stimulated emission
and the multiple combinations of outer energy levels available for de-excitation
and Auger emission. The characteristic AE is usually described by the three
energy levels involved in its emission as in Eq. 1.
Figure 15.1. Energy level diagram describing the process for the emission of Auger
and photoelectrons.
Characterization of Thin Films and Coatings 791
Figure 15.3. Plot of electron inelastic mean free path versus energy which
illustrates the basis for the surface sensitivity of the electron spectroscopies.
(Reprinted with the permission of the publisher, John Wiley & Sons, Ltd.)
Figure 15.5. AES depth profile of a sample of multiple 50 nm layers of Ni and Cr.
(Reprinted with the permission of the publisher, John Wiley & Sons, Ltd.)
AES may be utilized on a wide variety of materials but, due to the use
of an electron beam for excitation, it suffers limitations. The electron beam,
and ion beam used for sputtering, may induce sample decomposition. This
problem is accentuated by the high current densities that occur with small
probe diameters. Insulating materials may be difficult to evaluate due to
sample charging effects. The imbalance of currents from the primary beam,
the secondary electrons, and the sample result in a surface potential which
distorts the Auger electron energy.
Eq. (2) BE = hv - KE + Ø
Figure 15.7. Schematic diagram of an XPS system utilizing a bent quartz crystal x-
ray monochromator in conjunction with an electrostatic lens and spherical sector
analyzer.
Characterization of Thin Films and Coatings 799
The spectra are usually plotted in the N(E) versus BE format. Each
element exhibits a unique set of photoelectron (PE) transitions corresponding
to its atomic energy levels. The PE transition energies are a function of atomic
number so that the energy levels of adjacent elements in the Periodic Table
are shifted in binding energy.[12] The spectral features are Gaussian-like,
sitting on a low background. In addition to elemental identification, the
strongest attribute of XPS is its ability to distinguish different oxidation states.
Figure 15.8 shows the XPS spectrum of a bare Si wafer. The two peaks
associated with the Si2p transition are from elemental Si and SiO2 of the 20
- 30 Å of native oxide. So, in addition to illustrating the chemically-shifted
peaks, this figure also illustrates the surface sensitivity of XPS. The surface
sensitivity, as in AES, is controlled by the inelastic mean free path of the
electron as illustrated in Fig. 15.3, rather than the path length of the x-rays
used for excitation.
Figure 15.8. XPS spectrum of a Si surface showing two Si2p peaks, one associated
with elemental Si and the other associated with the SiO2 of the native oxide.
800 Deposition Technologies for Films and Coatings
XPS, like AES, can be combined with ion sputtering in order to generate
in-depth profiles. Since the area of analysis for XPS is larger than for AES, the
ion beam must be defocused or rastered over a larger area in order to obtain
an analysis area of uniform depth. As a result, the sputter rate is much slower
which, especially when coupled with the longer data acquisition times of XPS,
results in longer times to generate concentration versus depth profiles. By
monitoring the chemically shifted peaks it is possible to generate chemical
oxidation state versus depth profiles. This is extremely valuable for multicom-
ponent systems. For example, Table 15.3 lists the oxide formed during the
thermal oxidation of various compound semiconductors. Typically one of the
components of the system will oxidize more readily; based on the heats of
formation, the predominant oxide may be predicted. Frequently the other
component is concentrated at the interface or lost due to evaporation. The
composition of the oxide, especially as a function of depth, has been found to
be strongly dependent on the method and conditions of formation.
Since the photoelectron spectra of many elements exhibit only small
chemical shifts for a series of compounds, it is frequently necessary to
examine the other features of the spectrum. One of these features which
frequently exhibits useful chemical information, even when the photoelectron
transitions do not, is the corresponding Auger transition. Since Auger
emission is a multi-step process in which two electrons are emitted—the
Auger and photoelectron—the electron shells surrounding the atom have more
802 Deposition Technologies for Films and Coatings
time to undergo relaxation. This results in larger chemical shifts for the Auger
transition as compared to the corresponding photoelectron transition. Table
15.4 compares the binding energies of photoelectron and Auger transitions for
a series of metals and their oxides.[12] In all cases, the Auger transition
exhibits a factor of two larger chemical shift over that of the photoelectron
transition. However, Auger spectra are more complex and exhibit broader line
widths which limits the use of the chemical shift information they contain. In
addition, Auger transitions are not always excited due to the limited energy
range of the typical Al or Mg x-ray source.
The detection limit for XPS is approximately 0.5% atomic or 5 x 1018
atoms/cm3 with a sensitivity variation of 102. There are several data sets
available which provide relative sensitivity factors based on peak area.[15]
The x-rays used for excitation do less damage to the surface than the
electron beams used for AES. Sample charging is minor since only the
photoemission and sample return currents must be balanced.
809
bombardment of high purity silicon.
810 Deposition Technologies for Films and Coatings
Figure 15.14. Depth profile of the isotopic distribution of oxygen in an anodic oxide
grown on GaAs (001). Curve (A) is for GaAs (001) anodized in H2O18 then H2O16.
curve (B) is for anodization first in H2O16 then H2O18. (Reprinted with the permission
of the Electrochem. Soc.)
where
2
M cos ∅ + M 2 − M 2 sin 2 ∅
1 2 1
K =
M1 + M2
cantly larger than other surface analysis equipment. The analysis of the
backscattered ions may be achieved through the use of an electrostatic
analyzer or a solid state detector. The solid state detector, the preferred
detection system, is positioned in front of the target at an angle of approxi-
mately 30° from the incoming primary beam. A thin mylar sheet is placed in
front of the detector to attenuate low energy secondary ions and secondary
electrons.
The spectra are plots of scattered ion intensity versus energy. An RBS
spectrum is the sum of a family of scattering curves from each atomic mass
in the target. As shown in Fig. 15.18, KEo represents inelastic scattering from
the front surface of the target.[24] At a depth X, the primary ion loses additional
energy through electron scattering, both going into and escaping from the
solid. Since Rutherford scattering occurs at all depths, a curve is generated
which is the sum of all these events. Each atomic mass in the target generates
a separate curve based on its scattering cross-section.[25]
Figure 15.18. A plot of the Rutherford backscattering yield versus the energy of the
backscattered ion with an accompanying illustration showing the scattering
location in the sampled depth. (Reprinted with the permission of the publisher,
Acad. Press.)
Characterization of Thin Films and Coatings 817
Figure 15.19. RBS spectra of the phases of nickel silicide formed following the
deposition and annealing of nickel on silicon. (Reprinted with the permission of the
publisher, Akademie-Verlag.)
818 Deposition Technologies for Films and Coatings
Figure 15.20. RBS spectra for Si (100) in the random and < 110 > aligned direction
before and after 80 keV 30Si+ implant and subsequent anneal at 550° and 850°C.
(Reprinted with the permission of the Electrochem. Soc.)
Characterization of Thin Films and Coatings 819
The same equipment used to do RBS can be used for nuclear reaction
analysis (NRA).[24] Instead of Rutherford scattering, the primary ion must
penetrate the nucleus of the target atom and induce a nuclear reaction as
depicted in Fig. 15.21. The nuclear reaction cross-section as a function of
incident energy must be known in order to select an energy which will result
in adequate yield. The energies required for NRA are frequently higher than
those used for RBS. Table 15.5 lists some nuclear reactions that are used for
thin film analysis. NRA compliments RBS in that many of the useful nuclear
reactions are for low atomic number elements for which RBS has low
sensitivity. Since the nuclear reaction cross-sections are well known, NRA,
like RBS, is quantitative without the use of standards. This is especially
beneficial for elements like H which are difficult to detect and quantify by other
analytical techniques. NRA is also used to calibrate other surface analysis
techniques like SIMS. For example, Fig. 15.22 shows the data from NRA and
SIMS analysis of B implanted into Si at 10 keV. NRA is not as sensitive as
SIMS but it is less matrix dependent and as a result can be used to calibrate
the higher concentration portion of the profile.
Figure 15.22. Depth profile analysis of boron implanted into silicon at 10 keV using
NRA (circle) and SIMS (solid line). (Printed with the permission of M. L. Swanson
and N. R. Parikh.)
822 Deposition Technologies for Films and Coatings
Figure 15.23. Diagram illustrating the interaction of the primary electron beam with
a solid surface in the production of secondary and backscattered electrons, x-rays,
and other secondary radiation.
824 Deposition Technologies for Films and Coatings
Figure 15.24. Plot of the average intensity of secondary electrons from metals as
a function of energy.
Figure 15.25. Schematic diagram of a scintillator tube used for the detection of
secondary electrons.
Characterization of Thin Films and Coatings 825
Figure 15.26. Plot of the electron backscattering coefficient versus atomic number.
preamplifier. The useful energy range for EDS systems is from 1.0 to 220
keV which limits the analysis to elements with Z > 9. EDS detectors with thin
protective layers or no protective layer, when used in ultra-high vacuum
systems, permit analysis of the lighter elements down to B. The analysis
depth is dependent on the path length of the x-rays, not the primary electron
beam. As a result, EDS signals may originate from depths of 0.5 µm or more.
used with EDX requires liquid nitrogen cooling to keep the Li from diffusing
and rapidly degrading the detector’s performance.[30]
A schematic diagram of a wavelength-dispersive detector is shown in
Fig. 15.28. The electron beam excited x-rays interact with a crystal which
disperses the x-rays. As the crystal is rotated, the different wavelength x-rays
enter the detector. A variety of crystals are used in order to optimize the energy
resolution and collection efficiency of the broad range of x-ray energies for
elements Z≥ 6. A spectrum of x-ray intensity versus wavelength is generated
from which the characteristic x-ray lines may be identified. The detector may
also be operated at a fixed wavelength, so that the detector output represents
an intensity map of the sample surface for one characteristic x-ray when the
electron beam is rastered. The most commonly used detector for the WDX
spectrometer is a gas flow proportional counter. When an x-ray enters the tube
through a thin window and is absorbed, it causes a photoionization-induced
cascade which gives rise to a charge pulse.
Figure 15.28. Diagram illustrating the detection of electron beam excited x-rays with
a wavelength dispersive detector.
For bulk samples more than a few micrometers thick, spatial resolution
for elemental analysis does not improve for beam diameters much less than
one micrometer since the volume of x-ray production is determined by electron
beam scattering.
It is possible to obtain images of magnetic domains in an SEM.
Ferromagnetic materials are composed of small subgrain-sized regions
828 Deposition Technologies for Films and Coatings
Figure 15.31. Plane view TEM micrograph of the growth of polycrystalline CoSi2 on
the open Si regions between patterned SiO2 lines. Upon high temperature
annealing, the CoSi2 tends to agglomerate toward the center of the open region and
away from the silicide/oxide boundary.
832 Deposition Technologies for Films and Coatings
Figure 15.32. Diagram of the electron scattering that occurs from single crystalline,
polycrystalline, and randomly oriented films. (Reprinted with the permission of the
publisher, Marcel Dekker, Inc., Ref. 36.)
4.1 Ellipsometry
where N1 and N2 are the indices of refraction (complex numbers) of air (or
medium of the incident beam) and the substrate, respectively and Ø1 and Ø 2
are the angles of incidence and angle of refraction, respectively. For
dielectrics, Eq. 4 consists of only real numbers.
Ellipsometry invariably involves the reflection of light from a surface.
When a light beam is reflected at an interface, the reflection coefficient is
defined as the ratio of the amplitude of the reflected wave to the amplitude
of the incident wave for a single interface (Fresnel reflection coefficient).
Characterization of Thin Films and Coatings 835
Figure 15.34. Schematic of the planar structure assumed for ellipsometric analysis
showing a collimated monochromatic beam of light interacting with a surface at the
air/medium interface. The electric vectors of the plane polarized light are defined
as p waves (in the plane of incidence) and s waves (perpendicular to the plane of
incidence). (After Woollam et al.)[37]
Reflection coefficients are defined in terms of the electric vectors of the plane
polarized light; p waves in the plane of incidence and s waves perpendicular
to the plane of incidence. The Fresnel reflection coefficients are given by[38]
N2 cos ∅1 − N1 cos ∅2
Eq. (5a)
p
r12 =
N2 cos ∅1 + N1 cos ∅2
and
s = N1 cos ∅1 − N2 cos ∅2
Eq. (5b) r12
N1 cos ∅1 + N2 cos ∅2
rp
Eq. (6) s = tanΨexp ( j∆ )
r
whereΨ (Psi) and∆ (Delta) are the parameters determined by the ellipsometer
from which one of the parameters of interest, the index of refraction, can be
determined. Delta denotes the difference between the phase angle between
the parallel and perpendicular component of the incoming wave, δ1, and the
outgoing wave, δ2, respectively. Psi is the angle whose tangent is the ratio
of the magnitudes of the total reflection coefficients.
There are a variety of ellipsometer configurations; these include null
ellipsometers, modulation ellipsometers, and rotating element ellipsometers.
A typical null instrument, for example, is shown in Fig. 15.35. When the
analyzer is rotated about the light beam, a sinusoidally varying intensity will
be detected. When the polarizer is properly oriented so that the ellipticity is
just canceled by the reflection, the light being detected will be linearly
polarized and the signal intensity will be at its maximum and minimum. The
proper orientation is found by adjusting alternately the polarizer and the
analyzer until the true extinction is found.
Figure 15.36. Plot of the TiO 2 film thickness for a thermally oxidized TiN x measured
by ellipsometry versus that measured using AES. (Reprinted with permission of
the publisher, the Amer. Inst. of Phys.)
the sensitivity is proportional to the optical path length. Since C and O are
not electrically active in Si, no significant gain in sensitivity for these
impurities is obtained by lowering the sample temperature. Thinner speci-
mens may be used with a proportionate drop in sensitivity. Quantitative
analysis is based upon the measured IR absorption at a characteristic
wavelength compared to standards or a known absorption coefficient. Since
impurities such as O and C can occupy different sites in the Si lattice, they
exhibit several IR absorption bands. The frequencies of these bands have
been used to determine the presence of interstitial and precipitated O and the
intensities provide a measure of the concentration.[44]
One unique aspect of FTIR is the capability for measuring epitaxial layer
thicknesses of Si. This is a challenge for most techniques since the film and
substrate are the same material. Epitaxial Si layers are typically lightly doped
and will transmit in the IR range of 2 - 50 micrometers. The substrate is heavily
doped and will reflect the IR radiation. Depending on the difference in doping
levels between the epitaxial Si and the substrate, multiple internal reflections
will occur before the radiation reaches the detector. At each reflection, the IR
will undergo a phase shift which will be different for the epi-air interface and the
epi-substrate interface. The resulting spectrum will show interference fringes
with a period which is related to the epitaxial film thickness.[45]
840 Deposition Technologies for Films and Coatings
5.0 CONCLUSION
A wide variety of analytical techniques are available for the analysis of thin
films. The ones described in this chapter represent some of the most widely
used; however, there are many others that provide unique capabilities not
described here. This chapter is intended as a brief overview so references are
included which provide more detailed information about the analytical tools
described here, as well as other related techniques.
Characterization of Thin Films and Coatings 845
REFERENCES
1.0 INTRODUCTION
848
Jet Vapor Deposition 849
The most important elements in a JVD system are the jet source and
substrate motion mechanism; these are mounted in a low pressure deposition
chamber in which a fast flow of gas is sustained by a mechanical pump.[4][5]
The jet source is based on a nozzle, made of metal or glass, having
an exit diameter Dn from several mm to 2 cm. Helium or other inert gas
is supplied to the nozzle and exits from it as a jet. Ordinarily the nozzle
pressure P n is several torr, and the downstream pressure P d is a torr or
less, but the range may be wide: in a few applications both pressures can
be ten times higher. When the ratio Pn /P d > 2, the flow is “critical”, and
the jet emerges at its maximum velocity, the speed of sound; for He at
298°K, the exit velocity is ~105 cm/sec. The structure and operating
parameters of a generalized jet source are shown in Fig. 16.1.
The jet can convey any atomic, molecular or cluster vapor to a
substrate for condensation as a film. The vapor source is placed in the nozzle
within several nozzle-diameters of the exit, a region in which the He carrier
velocity is nearing the speed of sound. Vaporization can be effected by any
convenient technique, such as thermal evaporation, glow discharge
sputtering, microwave or DC discharge reaction, and laser ablation.
An atom of gold, for example, injected upstream into the He flow will be swiftly
850 Deposition Technologies for Films and Coatings
Figure 16.1. A generalized "jet in low vacuum" JVD source showing representative
operating conditions. Both jet velocity and density change at the Mach disc, but the
jet remains nearly cylindrical. At the substrate the jet transforms sharply to a thin,
radially flowing wall jet, but deposition remains localized. Flow is sonic at the nozle
exit, subsonic after the Mach disc.
Jet Vapor Deposition 851
In order to deposit uniform films over larger areas, either the substrate,
nozzle, jet, or some combination of them must be moved.[4][5] Although Jet
Process Corporation has implemented all these possibilities, this chapter will
consider only substrate motion. This is accomplished as in Fig. 16.2;
substrates are mounted on a “carousel” which can both spin rapidly around and
translate slowly along its axis; the carousel motion is computer controlled, and
various motions can be programmed. The jet is aimed radially at the carousel.
If the carousel is only spinning, a band of deposition appears around it; if the
carousel is also vertically “scanned” at constant speed, the band is broadened
to cover the entire carousel surface, and that of any substrate on it. The deposit
thickness is uniform because all areas are exposed for equal times to a
constant jet flux.
Figure 16.2. Different motions of the carousel yield different deposition patterns.
The combination of spin and oscillation produces uniform coverage over large
areas.
852 Deposition Technologies for Films and Coatings
3.0 DISCUSSION
x2 ≈ 2Dτ ≈ 2DL/v
relative importanceof diffusion and inertia in the wall jet region. However, we
have measured the deposit profile of gold atoms injected along the jet axis and
find it to be Gaussian with a half-width less than the jet radius.[12] We have
also shown by microbalance measurements that 95% of the wire vaporized in
the nozzle is deposited on the substrate.[12] Accordingly, jet collimation and
localized deposition give JVD the “line of sight” characteristics of high vacuum
vaporization. The efficiency is far higher, however: all vaporized material goes
in one direction rather than many; it is confined to the jet, and most of it
deposits in the impact zone.
The independence of the jets is an invaluable feature of JVD. Not only
are the jets spatially distinct, but the operation of one does not alter the
upstream nozzle conditions of any other. As long as Pn/Pd exceeds ~2, Pn
remains constant despite changes in Pd . The jets all emerge at the speed of
sound, and neither “information” nor mass can propagate upstream. An
example of the benefits: we vaporize many metals in a “glow discharge sputter
jet” and oxidize the growing metal film with O2 or O atoms injected down-
stream. The metal sputtering target in the nozzle is shielded from the oxidants
downstream by the sonic gas flow out of the nozzle; a comparable process in
high vacuum PVD is difficult to carry out. Controlled deposition of
multicomponents is a direct consequence of jet independence.
The wide range of workable jet pressures in JVD is useful in syntheses
involving metal atoms: we have used JVD to deposit single atoms or clusters.
At the lower range (several torr), only single metal atoms deposit. Cluster
formation must be initiated by three body collisions involving two metal atoms
and a helium atom. While we cannot rule out contributions of heterogeneous
processes in the nozzle,[13] three body collisions are highly improbable in the
jet: the metal atom and He concentrations are too low, and the transit times
from nozzle to substrate are too short. The time for a metal atom to undergo
a three body collision, using a typical three body recombination rate con-
stant,[14] is
where (M) and (He) are gas phase concentrations (#/cm3) and Pm, PHe the
pressures in torr. For Pm = 0.01 torr and PHe = 1 torr, τ3B ≈ 10 seconds; this
is much longer than the transit time from nozzle to substrate. Only at much
higher pressures of several tens of torr does cluster growth becomes dominant
in the jet.
856 Deposition Technologies for Films and Coatings
In the case of PZT we have dz/dt = 5000 A°/hr, H = 10 cm, D = 1 cm, and δ
= 3A°; the required rotation frequency is f ≈ 5 Hz. Micromixing is assured by
this easily attained frequency.
Micromixing is indispensible in JVD. It enables reaction of many
components to yield complex materials, results in better film uniformity, and
can reduce required substrate temperatures as well as annealing times after
deposition. It assures that transport limitations in the growing solid are as
absent as they are in the high speed jet. Micromixing and multiple jet, moving
substrate synthesis are exploited in a number of JVD applications described
later.
Common to many JVD applications is an environmentally sound
strategy: volatilization of the elemental metal, deposition of metal atoms from
one or more jets, and conversion of the growing film to oxide or nitride, layer
by layer, with a flux of O or N. Since most JVD metal sources are based on
techniques such as glow discharge sputtering or direct vaporization, capable
of depositing nearly every metal in the Periodic Table at high rate, no toxic
metal precursors or harmful exhausts need ever be involved.
The “jet in low vacuum” strategy also has a decisive manufacturing
advantage: it is economical to implement. Even relatively small, inexpensive
mechanical pumps will maintain critical flow conditions, providing high speed
collimated jets in a small footprint, flexible apparatus. The batch process
turnaround times in a JVD chamber are matters of minutes, negligible in
comparison with non-load locked high vacuum systems. The carrier gas flows
represent only a small material cost, and in the range of several torr, even
<<1% entrained condensible vapor corresponds to an economically high
deposition rate.
Jet Vapor Deposition 857
Figure 16.4. Wirefeed jet vapor source. The wire feed rate is computer controlled;
this allows the deposition rate to be determined and varied. For some metals, the
tungsten filament must have a protective sheath to avoid alloying.
858 Deposition Technologies for Films and Coatings
Lead zirconate titanate (PZT) is a candidate for thin film memories. PZT
can store charge at high density, and retain it in zero applied field; films of
several thousand angstroms can switch states within the 5 volt range of
computer power supplies. JVD is one of several processes (sol-gel, vacuum
sputtering) now competing for this future market. In addition, PZT thin films
are potentially useful for pyroelectric infrared detectors.
Jet Vapor Deposition 859
JVD employs four jet sources to supply Pb, Ti, Zr and oxygen to Pt-
coated, heated Si wafers mounted on the spinning carousel, as seen in Fig.
16.3. The Pt barrier layer is also deposited by JVD. These jet sources build
up a one micron film of PZT in less than one hour,[6] to give high quality PZT
films at high rate. The ferroelectric perovskite phase appeared on deposition;
after annealing, the film was entirely 100 oriented perovskite. Key parameters
for effective PZT memory cells, and the value measured for JVD PZT films, are
listed below:
remanent polarization 6 - 20 microcoulombs/cm2
coercive field 60 kilovolts/cm2
switching endurance > 1011 cycles
dielectric constant > 1300
These values equal or exceed those obtained with more conventional meth-
ods.
5.0 SUMMARY
Jet Process Corporation. The range of applications is already wide and the
technique is maturing rapidly.
REFERENCES
Index
864
Index 865
B Brush painting 51
Buffered hydrofluoric acid. See HF
Backfill using Ar 276 Bulk
Backscattering 291 deposits 159
Backscattering yield 822 effect of bombardment 369
Bacteriological contamination 119
Ballistic aggrega- C
tion 708, 732, 733, 741
Band-to-band recombination 841 c-BN
Banded structures 576 synthesizing of 224
Bearings Capacitive coupling 319
corrosion resistance 775 Capillarity model 711
Behavioral properties Capture cross-section 714
characterization of 672 Carbides
Bernoulli's principle 854 hydrogen ion bombardment of 368
Beta backscatter 690 Carbon
Bias evaporation of 220
sputtering 332 Carburizing 49, 403
substrate 236 Carousel 851, 858
Biased activated reactive evaporation motion 856
(BARE) 52 rotation frequency 856
Bimetallic layer process 829 Carrier gas 411
Binding energy 298 Cascade
of emitted photoelectrons 797 photoionization-induced 827
Biomedical Cathode
uses of coatings 44 current efficiency (CCE) 533
Blow-off 120 dark space 353
Bombardment fall region 352
by energetic species 141 hollow 83, 370
concurrent 373 poisoning 330
during deposition 679 Cathodic arc 190
effects 360, 364, 373, 374 Cathodic coatings 770
sources of 360 Cd
Bombardment enhanced-chemical on W 725
etching 363 Cells
Bombardment-enhanced chemical corrosion 769
etching 678 Ceramic host–organic guest 860
Bond strength 148, 643, 644 Channeling
Boron of ions 818
evaporation of 220 Characterization
Bound excitons 842 of thin films and coatings 789
Boundary layer Charge exchange 65, 353
gas stream 423 Charge separation 513
mass transport across 428 Charge-induced migration 810
thickness of 432 Chelating agents 123
Breakdown strength 859, 861 Chemical
Brightness 526 cause of adhesion loss 410
Brittle erosion 782 etch rate measurement 701
Index 867
Hard coating I
tool wear-life improvement by 786
Hardness 591 Impact erosion 782
of higher velocity coatings 648 Impact mobility 749
of metal and alloy deposits 244 Impurities
values for various deposits 539 in deposits 256
varies with deposition tempera- in plating solutions 529
ture 255 In 747
Hardness testing 695 Induction heated sources 180
Haring-Blum %TP 518 Inelastic collisions 60
Harmonic electrical spraying 52 Inelastic mean free path 791, 799
Heat treatment Inert coatings 770
of Ni3P or Ni3B 554 Inert gas
Heating entrapped 291
sources 370 shroud 623
the substrate 415 Inhibitive coatings 770
Hertz-Knudsen equation 167 Injection rate
Heteroepitaxial films reactive-gas 330
are often pseudomorphic 725 Integrated electronics 849
High temperature Interface
protective metallic coatings 779 characterization of 679
High temperature corrosion 42 during CVD is unstable 443
History formation 350, 678
of evaporated thin films 158 trap density 859
Hollow-cathode ion sources 327 types 678
Homogeneous nucleation 409 Interfacial regions
Homogeneous reaction control 429 classified 374
Host-guest 848, 860 Intergranular corrosion 767
Hot hollow cathode Intermetallic compounds 409
discharge beam 187 deposition of 205
electron beam gun 188 Interphase 678
Hot wall reactor 413 Ion
Hot-cathode triode bombardment 93
sputtering systems 305 bombardment during deposi-
Hot-wall tion 750
PECVD reactors 468 carburizing 49
Humidity current 324
in clean room 116 current monitor 194
Hybrid processes 501 hollow-cathode source 327
Hydriding 409 implantation 53
Hydrogen implantation accelerators 348
charge 368 irradiation 97, 333, 743
overvoltage 517 irradiation effects 744, 759
reduction cleaning 130 mixing 683
Hydrophilic wetting method 51 mobility 72
Hydrosonic nitriding 49
agitation 529 replenishment 522
cleaning 128
876 Deposition Technologies for Films and Coatings
Ni and Cr Optics
depth profile of 794 nonlinear 849
Ni on Si Orbiting frequency 66
interactions 817 Organic impurities 530
Ni-Cr-Fe Orientation
electrophoretic deposition of 548 crystallographic 380
Nickel Oscillations
composite electroless 557 plasma 75
containing P or B 551 Outgassing
deposition of 230 after fluid cleaning 132
electrodeposits 577 Overlay coating
Nitridation definition of 669
of UHV cleaned surfaces 151 Overlay coatings 31
Nitriding 49, 403 Overvoltage 515
NixPy compounds 551 Oxidation
Noble metals 860 cleaning 128
Non-destructive evaluation high temperature 776
(NDE) 675 Oxidation states
Novel coatings 848 ability to distinguish 800
Nozzle Oxide films 410
pressure 849 Oxygen plasma cleaning 144
Nuclear fuels 44
Nuclear reaction analysis (NRA) 819 P
Nucleation 438, 707, 710
3-D 710 PACVD 495
activation barrier 711 Palladium
control 429 adhesion dependent on 571
density 374, 677 Partial pressure
heterogeneous 452, 711 affects growth of films 494
kinetics 743 Particle impingement rate moni-
kinetics model 713 tor 194
secondary 716 Particles
two-dimensional 722, 724, 725 lenticular 617, 621
Nucleation sites Particulate
preferential 744 contamination 114
Nuclei size 716 deposition processes 36
Number density origin of 111
of Au nuclei on NaCl 715 removal 120
of ion-irradiation-induced 744 Parting
surface site 710 corrosion 767
Parylene 861
O Paschen
curves 80
Optical emission 304 relation 77, 83
Optical monitors 196 Passivation 859
Optically functional of clean surfaces 151
applications 41 PAVD
film growth by 493
880 Deposition Technologies for Films and Coatings
X
X-ray
analysis in STEM 834
emission 825
source 797
X-ray fluorescence (XRF) 690
XPS 797
detection limit for 802
Y
YBCO
film deposition 193, 194
Yield
secondary ion 806, 811
Z
Zinc
coatings 773
complexed with cyanide 514
Zirconia
as a thermal barrier 780
Zn deposition
conditions 774
Zone T 226
Zones
defined 737
Zone T 739