"Physics of Thin Films": Chapter1. Introduction

"Physics of Thin Films"
Chapter1. Introduction
1.1. General
Each material surface is exposed to various environmental influences. The
surface of a solid body is subjected to corrosion and wear and interacts with light
and electromagnetic fields. From the technological point of view the miniaturization
of mechanic, electronic, optical and optoelectronic components permanently
increases the surface to volume ratio of the involved materials. In modern material
science specific surface properties therefore gain increasing importance.
Nonetheless, the desired mechanical, optical chemical or electronic properties

are often opposed to the bulk properties which may be high mechanical stability,
easy manufacturing or low material cost.
Because of this fact a multitude if High Tech components are composite materials
which mean that the surface properties significantly differ from the bulk properties.
An example may be a mechanical part which has to exhibit high hardness (i. e. low
wear under tribological load) as well as high fracture toughness (i. e. high resistance
against crack propagation). One material alone may not fulfill these demands.
The solution of the problem can be a composite material consisting of a

surface zone (coating) with high surface hardness and a tough bulk core.
Other machine components as e. g. high temperature blades of gas turbines have to
exhibit high temperature and corrosion resistance as well as high mechanical
stability. Also in this case one property such as corrosion resistance can be provided
by a modified surface or a coating while mechanical stability is given by the base
material.
Another large filed of examples is constituted by thin film systems which act as
laser mirrors, anti-reflex coatings and other optically active surface modifications.
In the optical industry they are deposited on substrates which guarantee mechanical
stability and other specific properties.
Thin films can also be found in optoelectronic, electronic and magnetic

components which can only be manufactured because of the special physical
properties of thin films which may deviate significantly from those of the bulk
material. A prominent example foe this case are hard disk read heads based on the
Giant Magnetoresistance effect (GMR) which only operate due to the special
properties of a combination of magnetic and insulating thin films.
1.2. History
In the following a brief history of thin film technology is given for the sake
of completeness:
~1650: Observation and interpretation of interference patterns (e. g. oil on
water) by R.Boyle, R.Hooke, I. Newton.
~1850: Development of first deposition techniques (M.Faraday; .Grove;

T.A.Edison) and of methods of thickness determination (Arago, Fizeau;
Wernicke; Wiener) Commercial introduction of electrochemistry
(Galvanic) for gold plating of uniform-accessories.
~1940: Industrial manufacturing of coatings for optical, electronical and

mechanical applications (mostly military).
~1965: Thin film technology develops to an integral part of the mass

manufacturing processes in semiconductor and optical industry.
~1990: Thin films of High Tc-Superconductors.
~1995: Thin film processing allows for the tailoring of microstructures of

atomic and mesoscopic dimensions („Quantum-Dots "by PVD, „Cu-
technology "by electrochemistry applied to integrated circuits).
~2000: Manufacturing of nano crystalline materials with defined

composition and structure for applications as protective coatings and in
tribology. Deposition of highly ordered two and three dimensional objects
with sizes in the nm range.
~2004: Upscaling of complex reactive coating processes for industrial

applications (coatings on glass, thermal management). Combinatorial
investigation of turnery and quaternary material systems.
~2006: Investigation of organic coatings leads to the emergence of organic

electronics (OLED, printable circuits).
~2010: Preparation and characterization of the prototype two dimensional

(2d) materials, Graphene. Introduction of reliable solid state touch screens
to communication media (Smartphone).
~2015: Generation of heterostructure made from 2d materials. Approaches

to manufacture flexible electronic devices consisting of ultrathin materials.
1.3. Definition of Terms
In the beginning the following definitions may be useful:
Substrate:
Base material on of a film; (there may be, however, also free standing
films).
Film, Coating:
Solid (or liquid) body which exhibits a significantly lower geometrical
extension in one dimension then in the remaining two spatial dimensions.
The properties of the film or coating have to differ significantly from the
bulk.
Distinction: "Thin" Film - "Thick" Film:
The limit between "thin" and "thick" films cannot generally be defined,
although literature sometimes gives an arbitrary value of 1 μm.
Basically, a film can be considered as:
"thin" when its properties are significantly different from the bulk.
This can be due to:
1. the increasing surface to volume ratio at decreasing film thickness,
and
2. the microscopic structure which is dependent on the deposition

parameters
ad 1.: a low film thickness can cause the following effects : optical
interferences, increase of the electrical resistivity and decrease of the
temperature coefficient of electrical resistivity, increase of the critical
magnetic induction and of the critical temperature in superconductivity,
tunneling of Cooper pairs . The film thicknesses which lead to the
appearance of these thin film effects can be quite different.
An Indium-Oxide film (In2O3), e. g., which can be used as temperature
barrier coating due to its high transmission in the visible region and its
high reflectivity in the infrared region (this is caused by optical
interference effects) has to be approx. 300 nm thick.
For optical applications this film can be considered as thin. If the same
material would serve as insulator in a Josephson junction, 300 nm would
be much too thick to allow Cooper pairs to tunnel through the oxide.
For this application the In2O3 film should have a thickness of only 2 nm.
In other words: for one given application a film can be considered as
"thin" while for another one the film can still be considered as "thick".
ad 2.: as a consequence of a microstructure which is different from the bulk (e.
g. in respect to grain or crystallite size) the following effects may be observed:
increase of corrosion resistance, increase of hardness, increase of the magnetic
saturation induction, increase of the critical temperature of superconductivity,
increase of the optical absorption.
Structures like this are often metastable and can not only be achieved by thin
film deposition methods, but also by many different methods of surface
modification as there are electron beam, laser surface melting or ion
implantation. In the latter case the "thin film" is a modified surface zone with
properties significantly different from the bulk.
Also in this case thicknesses range from few nm to several μm, and no definite
distinction between "thin" and "thick" coatings may be justified.
Surface and Interface:

In general, each border between well discernible phases is termed as
"Interface". This can be the interface between a substrate and a film or between
a coating and the environment, but also e. g. a grain boundary between two
single crystalline grains in a solid.
The term "Surface" is a sub quantity of the term "Interface" and designates the
border between a solid or a liquid and gas or vacuum.
Film Deposition and Film Formation:

The deposition process of a film can be divided into three basic phases:
1. Preparation of the film forming particles (atoms, molecules, cluster)
2. Transport of the particles from the source to the substrate
3. Adsorption of the particles on the substrate and film growth
These phases can - depending on the specific deposition process and/or on the
choice of the deposition parameters - be considered as either independent or as
influencing one another.
The former is desirable since it allows controlling the basic steps
independently and therefore yields a high flexibility in the deposition process.
1.4. Applications of Thin Film Technology:
a. Engineering/Processing
... Tribological Applications: Protective coatings to reduce wear, corrosion
and erosion, low friction coatings.
... Hard coatings for cutting tools
... Surface passivation
... Protection against high temperature corrosion
... Self-supporting coatings of refractory metals for rocket nozzles,
crucibles, pipes
... Decorative coatings
... Catalyzing coatings
b. Optics
... Ant reflex coatings ("Multicoated Optics")
... Highly reflecting coatings (laser mirrors)
... Interference filters
... Beam splitter and thin film polarizers
... Integrated optic
c. Optoelectronics
... Photodetectors
... Image transmission
... Optical memories
... LCD/TFT
d. Electronics
... Passive thin film elements (Resistors, Condensers, Interconnects)
... Active thin film elements (Transistors, Diodes)
... Integrierted Circuits (VLSI, Very Large Scale Integrated Circuit)
... CCD (Charge Coupled Device)
e. Cryotechnics
... Superconducting thin films, switches, memories
... SQUIDS (Superconducting Quantum Interference Devices)
f. New Materials
... Super hard carbon ("Diamond")
... Amorphous silicon
... Metastable phases: Metallic glasses
... Ultrafine powders (diameter < 10nm)
... Spheroidization of high melting point materials (diameter 1-500μm)
... High purity semiconductors (GaAs)
g. (Alternative) Energies
... Solar collectors and solar cells
... Thermal management of architectural glasses and foils
... Thermal insulation (metal coated foils)
h. Magnetic Applications
... Audio, video and computer memories
... Magnetic read/write heads
i. Sensors
... Data acquisition in aggressive environments and media
... Telemetry
... Biological Sensors
j. Biomedicine
... Biocompatible implant coatings
... Neurological sensors
... Claddings for depot Pharmacia
1.5. Deposition Methods – Overview
Classification of Thin-Film Deposition Technologies
* Physical Vapor Deposition
a. Evaporative Methods:
• Vacuum Evaporation
Conventional vacuum evaporation Molecular-beam epitaxy (MBE)
(Thermal)
Electron-beam evaporation Pulsed laser evaporation
b. Glow –Discharge Processes:

• Sputtering • Plasma Processes
Diode sputtering Plasma-enhanced CVD
Reactive sputtering Plasma oxidation
Bias sputtering (ion plating) Plasma anodization
Magnetron sputtering Plasma polymerization
Ion beam deposition Plasma nitridation
Ion beam sputter deposition Plasma reduction
Reactive ion plating Microwave ECR plasma CVD
Cluster beam deposition (CBD) Cathodic arc deposition
Gas-Phase Chemical Processes

* Chemical Vapor Deposition (CVD) • Thermal Forming Processes
CVD epitaxy Thermal oxidation
Atmospheric-pressure CVD (APCVD) Thermal nitridation
Low-pressure CVD (LPCVD) Thermal polymerization
Metalorganic CVD (MOCVD)
Photo-enhanced CVD (PHCVD)
Laser-induced CVD (LICVD)
Electron-enhanced CVD Ion implantation
Liquid-Phase Chemical Techniques

• Electro Processes • Mechanical Techniques
Electroplating Spray pyrolysis
Electroless plating Spray-on techniques
Electrolytic anodization Spin-on techniques
Chemical reduction plating
Chemical displacement plating
Electrophoretic deposition Liquid phase epitaxy

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"Physics of Thin Films"

Nonetheless, the desired mechanical, optical chemical or electronic properties

The solution of the problem can be a composite material consisting of a

Thin films can also be found in optoelectronic, electronic and magnetic

~1850: Development of first deposition techniques (M.Faraday; .Grove;

~1940: Industrial manufacturing of coatings for optical, electronical and

~1965: Thin film technology develops to an integral part of the mass

~1990: Thin films of High Tc-Superconductors.

~1995: Thin film processing allows for the tailoring of microstructures of

~2000: Manufacturing of nano crystalline materials with defined

~2004: Upscaling of complex reactive coating processes for industrial

~2006: Investigation of organic coatings leads to the emergence of organic

~2010: Preparation and characterization of the prototype two dimensional

~2015: Generation of heterostructure made from 2d materials. Approaches

2. the microscopic structure which is dependent on the deposition

Surface and Interface:

Film Deposition and Film Formation:

Classification of Thin-Film Deposition Technologies

* Physical Vapor Deposition

b. Glow –Discharge Processes:

Gas-Phase Chemical Processes

Liquid-Phase Chemical Techniques

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