Other Semiconductor Materials

• There are a number of alternative semiconductor

materials that have been developed to meet
specific market demands.
• Two classes: inorganic and organic materials
• Applications include: Wireless and high-speed
digital communications, aero- and astro-space
sectors, and consumer markets such as the
automotive industry, display technology, solar
(photovoltaics).
 Inorganic Materials

• Germanium (Ge) vs. Silicon (Si)

• Compound inorganic semiconductors
Compound Semiconductors
• III-V materials
– A major class of
compound
semiconductors formed
from elements in Groups
III and V of the periodic
table.
• Gallium arsenide
(GaAs)
– The most common III-V
material.
Compound Semiconductors (Cont.)
• II-VI materials
– Compound materials
made by combining
Groups IIB and VIA.
• Common II-VI
materials are
cadmium telluride
(CdT) and zinc
sellenide (ZnSe).
Compound Semiconductors (Cont.)
• In addition to III-V and
II-VI materials, intrinsic
semiconductors can
also be combined to
form materials with
desirable electrical
characteristics.
• Silicon germanium
(SiGe) and silicon
carbide (SiC) are
examples of these
compounds.
 150 nm SiC

Due to chemical
SiC inertness

Si

Materials
Dr. Levent Trabzon
 Organic Semiconductors

• Some organic molecules and polymers

behave as semi-conductors.
• Nobel Prize in Chemistry 2000: “for the
discovery and development of conductive
polymers” Link to More Info.
• Usually are aromatic molecules having
extended π-electron systems.
Example Organic Semi-Conductors
Organic Molecules Organic Polymers

Pentacene
Poly(3-hexylthiophene)
P3HT

Poly(phenylene vinylene)
PPV
Copper Phthalocyanine
CuPc

Public Domain: Image Generated by CNEU Staff for free use, 2009.
Altering Semiconductor Materials
Doping
– The introduction of an impurity (dopant) into the crystal
lattice of an inorganic semiconductor to modify its electronic
properties.
– The partial oxidation of or introduction of ions into an organic
semiconductor to modify its electronic properties.
– The degree to which electrical properties are altered
corresponds the relative dopant concentration in the
material.
Dopants display two unique properties:
– Resistivity control
– Creation of electron or hole conduction.
 Impurities vs. Contaminants
Impurity
– From a semiconductor perspective, it is a foreign
substance, such as a dopant, intentionally placed
within a device’s structure to achieve a desired
result.
Contaminant
– A foreign substance that is not intentionally placed
in a device, usually detrimental to normal device
functioning.
 Silicon

“Diamond” structure
Si # density:
8/(5.43Å)3=5´1022cm3

11
 Carrier concentrations of intrinsic (undoped) Si
n=p=ni

ni (cm-3)

Temperature in K

1.12eV >> kT =0.026eV for

T=300K, so ni is very low at room
temperature.
 Doping of silicon
Adding parts/billion to parts/thousand of “dopants” to pure Si can change
resistivity by 8 orders of magnitude !
The key to building
semiconductor
devices and
integrated circuits lies
in the ability to
control the local
doping and hence
local electronic
properties of a
semiconductor
crystal.

1W×m = 100 W×cm

 Doping of silicon

By substituting a Si
atom with a special
impurity atom
(Column V for donor,
Column III for
acceptor), a conduction
electron or hole is
created. Mobile, contribute to
current flow when electric
field is applied.
14
 Energy band description of electrons and
holes contributed by donors and acceptors

EC = bottom of conduction
band At room temperature, the
EV = top of valence band
ED = Donor energy level
dopants of interest are
EA = Acceptor energy level essentially fully ionized.
 Doping of Semiconductors-Cont’d

● Doping for common semiconductor, e.g. silicon (Si) involves adding atoms
with different number of electrons to create unbalanced number of electrons
in the base material (e.g. Si)

● The base material, after doping, with excessive electrons will carry –ve charge.
● The base material, after doping, with deficit in electron will carry +ve charge.

● Doping of silicon can be achieved by “ion implantation” or “diffusion” of

Boron (B) atom for +ve charge or of Arsenide (As) or Phosphorous (P) for
–ve charge.

Si Hole Si Extra Electron

Si B Si Si As Si

Si Si

P-type doping N-type doping

 Doping of Semiconductors
● The process “doping” is a key process for producing transistors in
microelectronics industry.
● Semiconducting materials are characterized by their electrical resistivity to be
between electrically conductive and electrically insulators (or dielectric).
● They can be made electrically conductive by proper “doping” processes.
● Three classes of electrically conducting materials are:
Materials Approximate Electrical Classifications
Resistivity, r (W-cm)
Silver (Ag) 10-6 Conductors
Copper (Cu) 10-5.8
Aluminum (A!) 10-5.5
Platinum (Pt) 10-5
Germanium (GE) 101.5 Semiconductors
Silicon (Si) 104.5
Gallium Arsenide (GaAs) 108.0
Gallium Phosphide (GaP) 106.5
Oxide 109 Insulators
Glass 1010.5
Nickel (pure) 1013
Diamond 1014
Quartz (fused) 1018
 Doping of Semiconductors-Cont’d
Doping strength It is determined by the concentration of atom
Dopants. Example for doping of silicon:

Carrier concentration, atoms/cm3

Resistivity of doped Si, Ω-cm

 Diffusion Process

Diffusion process = Introducing a controlled amount of

foreign material into selected regions
of another material.

Diffusion processes may take place in:

Gas – gas (e.g. gas mixing and air pollution)

Liquid – liquid (e.g. spread of drop of ink in a pot of clear water)
Gas – solids (e.g. oxidation of metal)
Liquid – solids (e.g. corrosion of metal in water)

Three major applications of diffusion in microfabrication

- a very important process:

● Doping of semiconducting materials to produce p-n junctions

and the production of piezoresistors.
● Oxidation of semiconducting materials.
● Chemical vapor deposition processes.
 Diffusion Process-Cont’d

Mathematical modelingby Fick’s law:

A diffusion of liquid A into liquid B:

For the case C1>C2:
Liquid A, Concentration, C1 C a , xo - C a , x DC
Ca µ =-
x xo - x Dx
Liquid B
Concentration, C2 Ca = Concentration of A at a distance x away
from the initial contacting surface/m2-s
Xo = position of the initial interface of A and B.
Ca,xo, Cax = respective concentrations of A at xo and x.

x
The above expression may be expressed in a different form o
DC
Ca = - D
Dx
in which D = diffusivity of A into B - a material constant for specific pair of materials
in the process.
The value of D usually increases with temperature →higher e
elevated temperature
 Diffusion Process-Cont’d
Solid-solid diffusion e.g. in doping of silicon with B or As or P
Let J = the atoms (or molecules) of the foreign materials (B
to be diffused into base substrate
¶C material (e.g. Si) can be
J = -D atoms/m2-s
¶x
where D = diffusivity, or diffusion coefficient of the foreign material
in the substrate material, m2/s.
C = concentration of the foreign material in the substrate, atoms/m3.
Diffusivity of Selected Materials
10 10

D , µm / h
1.01
Diffusion Coefficient

0.1
0.1

0.01
0.01

900
900
950
950
1000
1000
1050
1050
1100
1100
1150
1150
1200
1200
1250
1250

Temperature, C
Temperature, C o
 Diffusion Process-Cont’d

Solid Solubility
The theory of “Higher temperature→ Higher diffusion efficiency” does not
always hold for solid-solid diffusion.

The “solubility” diagram below indicates, for example the temperatures at

which maximum diffusion can take place are:

≈ 1220oC for As (-ve Si)

≈ 1350oC for B (+ve si)
≈ 1230oC for P (-ve Si) in doping silicon substrates
Phosphorus Boron Arsenic

Aarsenic
12
(10 atoms/cm )
Solid Solubility
3

10

8 Boron

6
20

4 Phosphrus
2
800 900 1000 1100 1200 1300 1400
o
Temperature ( C)
 Diffusion Process-Cont’d

The Diffusion Equation

This equation is used to predict the concentration of the
foreign material (e.g. B) in the substrate (e.g. Si) at given
depth and time inForeign
a one-dimensional
material diffusion process.
with concentration, Cs
Mask with opening ¶C ( x, t ) 2
¶ C ( x, t )
Hot substrate material =D
¶t ¶ x2
with the following conditions:
Diffused material
with concentration, C(x,t) C(x,0) = 0; C(0, t) =Cs; C(∞,t) = 0
X-direction of diffusion

The solution of the partial differential equation satisfying th

conditions is: æ x ö
C ( x, t ) = C s erfcçç ÷÷
è 2 Dt ø
where erfc(X) is the complementary error function, erfc(X) = 1-erf(X) in which erf(X)
Is the error function with values available from mathematical handbooks.
 Diffusion Process-Cont’d

The Error functions

X erf(X) X erf(X) X erf(X) X erf(X)
0.0 0.0

0.05 0.0564 0.55 0.5633 1.05 0.8624 1.55 0.9716

0.10 0.1125 0.60 0.6039 1.10 0.8802 1.60 0.9763

0.15 0.1680 0.65 0.6420 1.15 0.8961 1.65 0.9804

0.20 0.2227 0.70 0.6778 1.20 0.9103 1.70 0.9838

0.25 0.2763 0.75 0.7112 1.25 0.9229 1.75 0.9867

0.30 0.3286 0.80 0.7421 1.30 0.9340 1.80 0.9891

0.35 0.3794 0.85 0.7707 1.35 0.9438 1.85 0.9911

0.40 0.4284 0.90 0.7969 1.40 0.9523 1.90 0.9923

0.45 0.4755 0.95 0.8209 1.45 0.9597 1.95 0.9942

0.50 0.5205 1.00 0.8427 1.50 0.9661 2.00 0.9953

Example: erf(1.25) = 0.9229

 Plasma Physics
Plasma
● It is a gas containing high energy ions that carries electronic charges.

● Plasma is used to “knock out” substrate materials at desired localities

- in a “dry etching process”, or is used to carry chemicals in chemical
vapor deposition (CVD) process.

Production of plasma
by high electric voltage: by high energy RF:

Gas to be ionized
Gas to be ionized • Ionization
• Ionization • Dissociation
• Dissociation • Excitation
• Recombination
• Excitation RF
• Recombination Vacuum at 10-3-1 Torr
Vacuum at 10-3-1 Torr
Anode Cathode
Anode Cathode Plasma Potential
Plasma Potential
 Intrinsic and extrinsic silicon

Intrinsic: un-doped, or doping

level lower than ni.
Extrinsic: carrier density
determined/controlled by
doping level.
For semiconductor device, it is
usually extrinsic at room
Approximate definition of doping levels:
temperature.
N-- or P-- : ND or NA < 1014 cm-3 But the semiconductor often
N- or P- : 1014 cm-3 < ND or NA < 1016 cm-3 becomes intrinsic at device
N or P : 1016 cm-3 < ND or NA < 1018 cm-3
fabrication temperatures (e.g.
N+ or P+ : 1018 cm-3 < ND or NA < 1020 cm-3
N++ or P++: ND or NA > 1020 cm-3 oxidation is done at >900oC).
Si # density : 5´1022 cm-3
Intrinsic Si at RT: ni=1.45´ 1010 cm-3
26
 Electron and hole concentrations for
homogeneous semiconductor
n: electron concentration (cm-3)
p : hole concentration (cm-3)
ND: donor concentration (cm-3)
NA: acceptor concentration (cm-3)
Charge neutrality: ND+ + p = NA- + n

At thermal equilibrium, np = ni2

(for intrinsic semiconductor n=p=ni,
so np=ni2. This same relation also
holds for extrinsic case)
Note: Carrier concentrations depend on NET dopant concentration (ND - NA)!
Therefore: p-type doping can be realized on n-type substrate if NA > ND, and vice versa.
27
 Fermi level and carrier concentration

¥ æ E - EF ö 3 3
n = ò F (E )N (E )dE @ N C expç - C ÷ æ 2pm kT ö
* 2 æ 2pm kT ö
* 2
EC
è kT ø N C = 2çç e
2
÷÷ NV = 2çç h
2
÷÷
è h ø è h ø
æ E - EV ö
p = ò [1 - F (E )]N (E )dE @ NV expç - F
EV
÷
-¥
è kT ø
me,h* is density of states effective mass.
For Si at RT, NC = 2.8´1019cm-3, NV =
1.04´1019cm-3
 Carrier drift and carrier mobility
When an electric field is applied to a semiconductor, mobile carriers will be
accelerated by the electrostatic force.
This force superimposes on the random thermal motion of carriers:
E.g. electrons drift in the direction opposite to the E-field.
Average drift velocity = |v| = µE, µ is carrier mobility.

Electron current density: Jn = (-q)nvn = qnµnE, n is free electron concentration.

Hole current density: Jp = (+q)pvp = qpµpE, p is hole concentration.
Total current density: J = Jn + Jp = sE, conductivity s = (1/r) = qnµn + qpµp
r is resistivity. Usually either n or p dominates. E.g. if n >> ni, then p = ni2/n << ni.
For Si at RT, with low doping concentration and small fields, maximum values:
µn = 1500cm2/V×sec; µp = 500cm2/V×sec < µn, so NMOS is faster than PMOS.
29
 P-type Dopants (Cont.)
The atoms will bond covalently (share their valence
electrons). The boron only has 3 e-’s to share and will
leave an opening at one of the bonds.

hole

electron

Si B Si

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 N-type Dopants

The atoms will bond covalently. The phosphorus has 5

valence e-’s and will create an extra electron in the lattice.
Extra electron

Si P Si

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 Silicon Dopant Summary

N-type P-type
Polarity Negative Positive
Conduction Electrons Holes
Element P, As, Sb B
Dopant Terminology Donor Acceptor
Dopant Sources for Silicon
Dopant Source Chemical Name
Arsenic AsH3 Arsine

Phosphorus PH3 Phosphine

Phosphorus
Phosphorus POCl3
Oxychloride
Boron B2H6 Diborane

Boron BF3 Boron trifluoride

Boron BBr3 Boron tribromide

Antimony
Antimony SbCl5
Pentachloride
 Rapid Thermal Anneal - RTA
• This system can be used to
repair crystal damage and to
activate dopants.
• Some systems offer ability to
flow gas during the process.
• Typically used to quickly heat
sample to up to 1200 °C (at
up to 200 °C/sec). Due to
design, process time limited to
“time in minutes.”
• Furnace is appropriate to
longer process times.

34
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 Resistivity Based on
Dopant Concentration in
Silicon
Conductivity vs. Dopant Concentration
for a model organic system

Appl. Phys. Lett. 2004, 84(10), 1707.

 Altering Conduction in
Organic Semi-Conductors
• Some polymers need to be doped.
• Partial oxidation with iodine.
• Stabilizing counter-ions.
• Unintentional doping by exposure to air.
 Materials/Dielectrics

• What is a dielectric?
• Types of dielectrics and their properties
 Dielectrics

Response to an electric field

– When an electric field is impressed on a material it can:
1. Conduct
2. Polarize
3. Both conduct and polarize.
– Dielectrics (insulators) can only polarize.
 Dielectrics
• A highly resistive material with tightly bound valance
electrons.
– A poor conductor of electricity, but does polarize under an
electric field.
• Polarization: Materials distort their charge
distribution (of electrons and ions) to try to reduce
an impressed electric field.
• Dielectric materials are used electrically as
insulators and mechanically as protective layers.
• Dielectrics are characterized according to four
classes of properties:
– Electrical, Optical, Etch, and Mechanical.
 Electrical Properties

• The electrical properties of a dielectric are

characterized by a quantity called the
dielectric constant (k).
– A numerical value representing the effectiveness
of an insulating material in opposing an impressed
electric field. Because of this property, a capacitor
with a voltage across its plates will store more
charge, therefore, the higher the value of k.
• This polarization property quantified by k is key to a
capacitor’s performance.
 Electrical Properties (Cont.)

• Breakdown
– If the impressed field is large enough the material
can become so polarized that electrons break
away and start to conduct an electric current. This
is called dielectric breakdown or breakdown.
 Electrical Properties (Cont.)
• Substances with a low dielectric constant include a
perfect vacuum, dry air, and most pure, dry gases such
as argon and nitrogen.

• Such substrates do not polarize much, so they don’t get

pushed easily to the point of breakdown

• The dielectric constant of air is (kair = 1)

• Materials with moderate dielectric constants include:

distilled water, paper, mica, polyethylene, and glass.
Metal oxides, in general, have high dielectric constants.
 Electrical Properties (Cont.)
• High-k substances, such as aluminum oxide,
make possible the manufacture of high-value
capacitors with small physical volume.

• These materials are generally not able to

withstand electrostatic fields as intense as
low-k substances (such as air).
 Optical Properties
• Index of refraction
– The angular change in a light ray’s path as it
passes through the interface between two media
(based on a change in velocity).
• This dielectric property can be used to:
– Measure film thickness.
– Measure material purity levels.
Index of Refraction

Air
n=1.0
SiO2
q n=1.46

SiO2
n=1.46
Air
q n=1.0

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 Mechanical Properties
• Refers to the mechanical strength of the
dielectric material:
– Resistance to flaking or cracking.
– Dielectric integrity.
• The structure of the dielectric material plays a
large role in mechanical strength.
 Outline

• What is a dielectric?
• Types of dielectrics and their properties
 Dielectric Material
There are several materials that are commonly
used as dielectric materials:
– Silicon dioxide (SiO2).
– Silicon nitride (Si3N4).
– Spin-on glass (SOG).
– Polyimide (a plastic material).
 Silicon Dioxide
• Due to silicon’s ability to easily form a stable
oxide, silicon dioxide is the most common
dielectric.
• SiO2 is grown by exposing a silicon
substrate’s surface to oxygen at an elevated
temperature in an oxidation furnace.
– Si (solid) + O2 (gas) ® SiO2(solid)
 Si-Oxide

High compressive stress on the surface

 Oxidation – Cont’d
Principle of thermal oxidation:
It is a combined continuous physical diffusion and chemical reactions
Oxidizing species: O2 or steam
Oxidizing species: O2 or steam

SiO2 layer

Silicon substrate
(1) At the inception of oxidation (2) Formation of oxide layer by chemical reaction

Oxidizing species: O2 or steam

Growing
SiO2 layer
Instantaneous
SiO2/Si boundary
(3) Growth of oxide layer with diffusion
and chemical reactions
 Oxidation – Cont’d
Rate of thermal oxidations:

Because of the extreme complexity of thermal oxidation, analytical methods

for predicting the rate of this process is impossible. The following quasi-
empirical formulas are used for the thickness of SiO2 layer (x):
B (8.9)
For small time, t: x = (t + t )
A
For larger time, t: x = B(t + t ) (8.10)
æ d 2 + 2D d ö
in which ç o o÷ (8.11)
ç k ÷ N1
t=è ø
s

2D N o
D = diffusivity of oxide in silicon, e.g. D = 4.4x10-16 cm2/sec at 900oC.
do = initial oxide layer (~ 200 in dry oxidation, = 0 for wet oxidation)
ks = surface reaction rate constant.
No = concentration of oxygen molecules in the carrier gas.
= 5.2x1016 molecules/cm3 in dry O2 at 1000oC and 1 atm.
= 3000x1016 molecules/cm3 in water vapor at the same temperature and pressure.
N1 = number of oxidizing species in the oxide.
= 2.2x1022 SiO2 molecules/cm3 with dry O2,
= 4.4x1022 SiO2 molecules/cm3 in water vapor.
 Oxidation
SiO2 is an important element Major application
of SiO2 layers or films are:

(1) To be used as thermal insulation media

(2) To be used as dielectric layers for electrical insulation

● SiO2 can be produced over the surface of silicon substrates either by:
(1) Chemical vapor deposition (CVD), or
(2) Growing SiO2 with dry O2 in the air, or wet steam by the following
two chemical reactions at high temperature:
Si (solid) + O2 (gas) ® SiO2 (solid)
Si (solid) + 2H2O (steam) ® SiO2 (solid) + 2H2 (gas)

Resistance heater Controlled

air chamber
O2 or H2 O +
carrier gas Fused quartz cassette to vent
Wafers

Fused quartz
Resistance heater
tubular furnace
 Oxidation – Cont’d
Rate of thermal oxidations – Cont’d
Determination of constant A and B in Eqs. (8.9) and (8.10):
For small time, t in Eq. (8.9):

æBö (8.12)
!og ç ÷ = aT '+b
è Aø
For larger time, t in Eq. (8.10):
(8.13)
!n( B ) = aT '+b
where T’ = 1000/T, with temperature T in Kelvin, K. Constant a and b are from the Table:

Constants Coefficient (a) Coefficient (b) Conditions

Linear rate -10.4422 6.96426 Dry O2, Ea = 2 eV, (100) silicon
constant -10.1257 6.93576 Dry O2, Ea = 2 eV, (111) silicon
Eq. (8-12) -9.905525 7.82039 H2O vapor, Ea = 2.05 eV, (110) silicon
-9.92655 7.948585 H2O vapor, Ea = 2.05 eV, (111) silicon

Parabolic rate -14.40273 6.74356 Dry O2, Ea = 1.24 eV, 760 Torr vacuum
constant -10.615 7.1040 H2O vapor, Ea = 0.71 eV, 760 Torr
Eq. (8-13) vacuum
 Example 8.3
Estimate the thickness of the SiO2 layer over the (111) plane of a “clean”
silicon wafer, resulting from both “dry” and “wet” oxidation at 950oC for
one and half hours.
Solution:
Since oxidation take place on a new “clean” silicon wafer, we can use the
condition that ‫ = ح‬0. Thus, we may use:
B
x= t for small time, and x = Bt for larger time.
A
The constants, A and B in the above expressions are selected from Table 8.4
as follows:
a b Conditions

Eq. (8-12) -10.1257 6.9357 Dry O2

Eq. (8-12) -9.9266 7.9486 Wet steam
Eq. (8-13) -14.4027 6.7436 Dry O2
Eq. (8-13) -10.6150 7.1040 Wet steam
Example 8.3 – Cont’d

Since we have T’ = 1000/(950+273) = 0.8177, we obtained the constants

B/A and B from Eqs. (8.12) and (8.13) as:

Dry oxidation Wet oxidation

B/A (µm/hr) 0.04532 0.6786
B (µm/hr) 0.006516 0.2068

The rates of oxidation in two conditions after 1.5 hours are thus obtained
from the two equations available as:

Dry oxidation (µm) Wet oxidation (µm)

B for small time 0.068 1.018
x= t
A
x = Bt for larger time 0.0989 0.5572

We observe that wet oxidation results in much fast rates in oxidation

than dry oxidation.
SiO2 thickness by observations - A quick way to tell!

● Both SiO2 and Si3N4 layers have distinct color from the silicon
substrates in which these layers grow.
● In the case of SiO2 layers, they are essentially transparent but with
distinct light refraction index from that of the silicon substrate.
● Consequently, when the surface is shone by the rays of white light
one can view the surface exhibiting different colors corresponding
to the layer’s thickness.
● The color of the surface of a SiO2 layer is the result of the interference
of the reflected light rays.
● However, the same color may repeat with different layer thickness,
as shown below:

SiO2 layer 0.050 0.075 0.275 0.310 0.50 0.375 0.390

thickness 0.465 0.493
(µm)

Color Tan Brown Red Blue Green to Green Yellow

violet Yellow yellow
green
 Oxidation

• Not like deposition but

a new material is
formed
• @R.T. 2nm oxide
formed
• The process
temperature is very
high around 900 oC
Wet and Dry Oxide Growth
 SiO2 Properties

• Index of refraction These properties depend

on the stoichiometry (x and
n = 1.46
y) of the SiyOx. Ideally, the
• Dielectric constant ratio of silicon dioxide is 1:2
(x/y). Changing the ratio of
k = 3.9 Si to O changes the n and
k values.

Dielectric breakdown voltage for SiO2 that is contaminant/defect free:

Millions of Volts!
Example: Modifying the Index of
Refraction
• If there is more oxygen present in the dielectric,
SiOx nSiOx is closer to 1.

– If there is more silicon present in the dielectric, SiOx

nSiOx is closer to 2.

– For example, in reference to the standard

(nSiO2 = 1.46), if nSiOx = 1.5 the oxide is more silicon-
rich and if nSiOx = 1.4 then it is more oxygen-rich.
 High k Dielectric Materials

• Ta2O5, k = 22-30
• TiO2, k = 20-85
• Nb2O5, k = 11
• HfO2, k = 17
• Y2O3, k =15
 Low k Dielectric Materials

• FSG, (Fluorinated Silicate Glass) k= 3.4-4.1

• HSQ, (Hydrogen Silsesquioxane) k = 2.9
• Nanoporous silica, k = 2.6-2.9
• Fluorinated polyimide, k = 2.6-2.9
• PTFE,Teflon® (polytetrafluoroethylene) k = 1.9
• DVS-BCB, (Benzocyclobutene) k = 2.65
• Aromatic hydrocarbon, k = 2.65
 Silicon Nitride

As an alternative to SiO2, silicon nitride is:

– Physically harder, used for top layer
protection of devices.
– A better barrier against moisture, sodium,
and oxygen diffusion.
– More resistant to dielectric breakdown.
 Silicon Nitride (Cont.)

…but Si3N4 has some disadvantages:

– It is difficult to etch.
– As a rule of thumb, it will crack or flake
above 200 nm thickness, due to
mechanical stresses in the film.
– Mechanical stresses come from bonds in
the material.
 Silicon Nitride (Cont.)

• Si3N4 cannot be grown, it must be deposited

on a surface by reactive process gases:
3SiH4(gas) + 4NH3(gas) ® Si3N4 + 12H2
• Si3N4 can also be deposited by sputtering.
 Si3N4 Properties

• Index of refraction
n = 2.0

• Dielectric Constant
k = 7.5 (can vary according to stoichiometry)

• These properties can be altered similarly to

SiO2.
 Spin-on Glasses

• Spin-on glasses (SOG) are an alternative to

conventional dielectric layers.
• As their name implies, they are spun on like
photoresist.
• They are used for two reasons:
– As an actual dielectric film.
– As a dopant source.
• Detailed information about SOG can be found
online at www.filmtronics.com.
 Spin-on Glass (Cont.)

• Advantages
– Fills voids (equalizes the focal plane, improving
depth of focus in optical applications).
– Low temperature process
– Low cost
– Little hardware is required.
• Disadvantages
– Poor etch qualities, due to an amorphous
structure.
– Undesirable diffusion of dopants.
 SOG as a Void Filler

Apply SOG
Substrate Substrate
Before After
(thin features can collapse) (voids are filled/DOF improved)

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 Types of SOG
Silsesquioxane polymer films
– SiO structure with 10 to 15 percent organic
component.
– Dielectric constants of 2.6 to 3.0 upon final cure at
425 °C.
– Can be spun to a thickness greater than 10,000 Å.
– Used for planarizing, direct on metal processes and
passivation coatings.
 Types of SOG (Cont.)

Siloxane polymer films

– SiO backbone with up to 20 percent organic
component
– Dielectric constants of 2.9 to 3.5 upon final cure of
425 °C
– Films can be spun to a thickness of 5,500 Å
– Used for a variety of planarization processes
 Types of SOG (Cont.)

Inorganic/organic hybrids
Used for intermetal dielectric layers with low
dielectric constants below 2.3

Organic polymer films

– Experimental films with low dielectric constants
and thicknesses.
– Used for global planarization as a sacrificial layer.
 Types of SOG (Cont.)

Phosphosilicate films
– Films contain either 2% or 4% phosphorous
forming an SiO-P2O5 glass layer.
– Dielectric constants of 3.9 to 4.4 upon final cure of
425 °C.
– Films can be spun to a thickness of 1,600 Å.
– Used for planarizing polysilicon or metal lines.
 Types of SOG (Cont.)

Silicate films
– SiO polymer that converts to a silicate glass upon
final cure.
– Dielectric constants of 4.1 to 7 depending on the
cure method.
– Uses: dry or wet etch layer, polysilicon
planarization, CVD/SOG/CVD planarization,
optical coatings.
 Polyimide

• Polyimides are low k organic polymers

– Used mainly as an inter-dielectric between two
layers of conducting metal.
• Polyimides offer the dielectric strength of
deposited SiO2 with the ease of a spin-on
application.
• Polyimides possess excellent planarization
capabilities.
Polyimide Molecule
(an organic polymer)

Public Domain: Image Generated by CNEU Staff for free use, 2009.
 Block Copolymers

• Used for self-assembly.

• Used for pattern transfer.
 Copolymers
What happens when two different
= Monomer A + = Monomer B starting materials (monomers) are
used to make one polymer
molecule?

Homopolymer of A

Homopolymer of B

Random Copolymer of A & B

Alternating Copolymer of A & B

Block Copolymer of A & B

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 Block Copolymers
Covalent bond between A & B

Block of A Block of B
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• If A and B do not like each other, they behave like oil and water.
• Phase separation: A only wants to be with A and B only wants to be with B.
• But, the A block is covalently (permanently) attached to the B block.
• Blocks can phase separate, but cannot move very far away from each other.
• The length of each polymer molecule depends on how many repeat units it contains.
• However, the length of many useful block copolymers is in the nanometer range.

Phase separation of the blocks creates patterns on the nano-scale.

 Block Copolymer Phases
Increasing Length of A ® ¬ Increasing Length of B

20:80 30:70 50:50 70:30 80:20

Spheres of A Cyl of A Lamellae Cyl of B Spheres of B

Patterns result from the

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Generated by CNEU Staff for minimization of surface
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area (unfavorable
interactions) between two
incompatible materials.
 Images of Block Copolymers
30:70 A to B 50:50 A to B
Cylinders of A in a matrix of B Lamellae

100 nm

70:30 A to B
Cylinders of B in a matrix of A
Increasing size of A block

Decreasing size of B block

Overall size (A + B) remains constant

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 Nano-Pattern Development and
Transfer Using Block Copolymers
Self-Organized Block Copolymer Film Chemically modify only one block

Material to be Patterned

Substrate

Use difference between

blocks to selectively remove
Transfer pattern to underlying layer only one component

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Images of Nano-Structured Polyimide
Top View Side View

100 nm 100 nm

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 Common Polymers
• Polyethylene (PE)
• Polydimethylsiloxane (PDMS)
• Poly(ethylene glycol) (PEG)
 Polymeric Materials

• Polyethylene (PE)
– Ultra High Molecular Weight Polyethylene
(UHMWPE) – most common PE used.
– Thermoplastic – can be reheated and reformed.
– Inexpensive
– Very high impact strength.
– Often used in prosthetic devices.
 Polymeric Materials

• Polyethylene (PE) limitations

– High thermal expansion.
– Subject to stress cracking.
– Difficult to bond.
– Flammable
– Poor temperature capability.
– Wear Particles can cause failure of the UHMWPE.
 Polymeric Materials

• Polyethylene (PE)
– Coated with PEG - poly(ethylene glycol), proves to
be a biocompatible material.
– Will not produce an immune response.
– Will not act as an antigen.
– Will not cause protein rejection.

Alcantar, NA. Adyil, ES. Israelachvili, JN.

Polyethylene glycol-coated biocompatible
surfaces. J Biomed Mater Res. 2000 Sep
5;51(3):343-51.
 Biotechnology Materials

• Polydimethylsiloxane (PDMS)
– Inexpensive material
– Hydrophobic material
– Easily modified to a hydrophilic material.
– Often used in protein, microfluidic, and cell
culturing applications.
– Commonly used to make contact lenses.
 Polymeric Materials

• Polydimethylsiloxane (PDMS)
– Optical transparency.
– Chemical and biologically inert.
– Nontoxic
– Permeable to gases.
– Sealable with other materials such as glass and
polymers.
 Modification of PDMS

• O2 plasma treatment of PDMS

– Can be used for bonding materials.
– Changes the hydrophobicity of the material.
Water
Water

14°
100°
PDMS PDMS
Oxygen Plasma treatment

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 O2 plasma treatment of PDMS

PT – plasma treatment
PEG - poly(ethylene glycol): applied to PDMS after plasma
treatment to create a permanent hydrophilic surface
Vikash Sharma, Marshal Dhayal Govind, S.M.
Shivaprasad and S.C. Jain. Surface characterization of
plasma-treated and PEG-grafted PDMS for micro fluidic
applications. Science Direct Volume 81, Issue 9, 25
May 2007, Pages 1094-1100.
 Polymeric Materials

• Polydimethylsiloxane (PDMS) limitations

– Cure time depends on temperature
– Shrinkage after curing (rule of thumb = 1%, but
can vary depending on PDMS materials).
– PDMS residues are persistent and hard to remove
from working environments.
 Polymers Comparison
$ Advantages Disadvantages
PDMS Inexpensive Flexible Reduced
Easily modified biocompatibility
for desired as material ages
mechanical,
optical, and
chemical
properties
Polyethylene Inexpensive to Rigid Material absorbs
(linear) Moderate Able to modify oxygen after
material density modification.
Becomes less
hydrophilic.
Polyethylene Inexpensive Flexible Difficult to
(branched) Able to modify control the
material density polymerization
Biocompatible reaction