THIN FILMS AND THEIR APPLICATIONS

IN MILITARY AND CIVIL SECTORS

 DRDO Monographs/Special Publications Series

Introduction to Camouflage and Deception: JV Ramana Rao (1999)

Solid Propellant Chemistry: K Kishore and K Sridhara (1999)
Environment in Submarines: MVR Koteswara Rao (2001)
An Introduction to Night Vision Technology: R Hradaynath (2002)
Photonics in Warfare: VV Rampal (2002)
Aerodynamic Predictive Methods and their Validation in
Hypersonic Flows: AK Sreekanth (2002)
Modelling Radar ECCM: A System Approach: AK Subramanian (2003)
Microwave Circuits and Components: GP Srivastava (2004)
Inverse Gas Chromatography: AK Sen (2005)
Defence Research & Development Organisation: 1958-1982: RP Shenoy (2005)
Environmental Conservation and Security: AK Datta and Ram Kumar (2006)
Infrared Detectors: Materials and Technology: AK Sreedhar and KSR Koteswara Rao
(2006)
Reminiscences of a Defence Scientist: A Quest for Self-reliance: V Narayana Rao
(2007)
Acousto-optic Devices and their Defence Applications: JC Joshi (2007)
Military Bridging: MR Joshi (2008)
IGMDP: Lt Gen (Retd.) VJ Sundaram, et al. (2008)
Microwave Remote Sensing: OPN Calla (2009)
Defence Against Chemical and Biological Defence: AK Sen (2009)
Proximity Fuzes: Theory and Techniques: VK Arora (2010)
Bioactive Glasses for Implant Applications: V Rajendran and SK Bhandari (2010)
THIN FILMS AND THEIR APPLICATIONS
IN MILITARY AND CIVIL SECTORS

Kamal Nain Chopra

Scientist G (Retd)
Laser Science & Technology Centre
Metcalfe House, Delhi - 110 054

Anil Kumar Maini

Director
Laser Science & Technology Centre
Metcalfe House, Delhi - 110 054

Defence Research and Development Organisation

Ministry of Defence, New Delhi – 110 105
2010
DRDO MONOGRAPHS/SPECIAL PUBLICATIONS SERIES

THIN FILMS AND THEIR APPLICATIONS IN MILITARY AND

CIVIL SECTORS

KAMAL NAIN CHOPRA AND ANIL KUMAR MAINI

Series Editors
Editor-in-Chief Associate Editor-in-Chief Sr. Editor Editor
Dr AL Moorthy Shashi Tyagi Vinod Kumari Sharma Alka Bansal
Asst. Editor Editorial Assistant Printing Marketing
Kavita Narwal Gunjan Bakshi SK Gupta Rajpal Singh

Cataloguing in Publication
Chopra, K.N. and Maini, A.K.
Thin Films and their Applications in Military and Civil Sectors
DRDO Monographs/Special Publications Series.
Includes glossary
1. Thin Films 2. Coatings 3. Defence Applications
I. Title II. Series
621.3.049.772.2
© 2010, Defence Research & Development Organisation, New Delhi 110 105.
ISBN 978-81-86514-32-0

All rights reserved. Except as permitted under the Indian Copyright Act 1957, no part of
this publication may be reproduced, distributed or transmitted, stored in a database or
a retrieval system, in any form or by any means, electronic, mechanical, photocopying,
recording, or otherwise, without the prior written permission of the Publisher.
The views expressed in the book are those of the authors only. The Editors or Publisher
do not assume responsibility for the statements/opinions expressed by the authors.

Designed, produced, and printed by Director, DESIDOC, Metcalfe House, Delhi–110 054.
 Preface

A thin film is a layer of material ranging from fractions of a nanometer to several

micrometers in thickness. Thin films have very interesting properties that are quite
different from those of the bulk materials which they are made of. This is because of the
fact that their properties depend on a number of interrelated parameters, and also on the
technique employed for their fabrication.
Surface quality and material of the substrate, degree of vacuum inside the coating
chamber, flow of the reactive gases in the chamber during the growth process, the rate
of evapouration/sputtering and the purity of the coating material are some of the
important parameters that determine the mechanical, optical and other properties of the
coated components. Some of the problems associated with the fabrication of these
coatings, and the suitable fabrication techniques have been briefly described in the
monograph. Thin films possess a wide range of applications in both civil as well as
military sectors. This includes their use for protection of materials from corrosion,
oxidation, and wear, increasing transmission or reflection in a certain wavelength region,
and also in filters, colour separation, fire-resistance, high temperature superconductors,
silicon devices, anti-fog, and memory devices. Their applications in the military and civil
sectors are also discussed in the monograph. Applications have been classified into
scientific, industrial, consumer, and military applications. The use of thin film catalysts
in nanotechnology such as sensors, miniature fuel cells, printable solar cells, MEMS
and other IC manufacturing industries, has been highlighted. Some novel applications
of thin films in the areas of efficient solar energy conversion, hydrogen conversion and
CO2 conversion to hydrocarbon fuels, bioactive and biocompatible coatings,
nanostructures and nano-material coatings, and coatings useful for protection from a
wide range of high temperature effects are the emerging areas. A brief description of the
future challenges in the fabrication of thin films for such applications in the various
emerging fields has been included in the monograph.
This monograph is intended to provide an overview of the design, development of
thin films and their coatings for various applications. The book comprises of ten
chapters. The first chapter covers types of thin films, thin films design, thin films
fabrication, and thickness control. Chapter two provides an overview of metallic films
and dielectric coatings with a brief on coatings developed at LASTEC. Chapter three
highlights the design parameters, design criteria, and critical issues involving
absorption for withstanding high power densities. In Chapter four, various deposition
techniques such as electron beam deposition, and sputtering are discussed. Chapter
five presents an overview on characterisation tools and equipment. Chapter six provides
detailed scientific applications of thin films like solar cells, Fullerene 60, electronics,
silicide thin films, surgery, nanotechnology, etc. Electronic semiconductor devices and
optical coatings are the main applications benefiting from thin films construction.
Chapter seven provides industrial applications of thin films in chips, solar cells,
biotechnology, photonic crystals, stainless steel, etc. The concept of photonic crystal
structure to optimise the thickness and refractive index of the materials required to make
anti-reflection coatings has been included. Chapter eight is exclusively devoted to
consumer applications including microactuators, artificial jewellery, liquid crystal
displays, cellular phones, artificial retina, and so on. Chapter nine is dedicated to military
applications covering military optics and coating. The concluding chapter gives
summary of the book.

Dr KN Chopra
Shri AK Maini

vi
 Acknowledgements

We are thankful to Director, Defence Scientific Information & Documentation

Centre (DESIDOC), New Delhi for sanctioning this monograph project and extending all
the necessary support and guidance throughout the tenure of the project for the
successful completion of the monograph.
We acknowledge with gratitude the support of officers and staff of Thin Films and
Coating Division of LASTEC. We are particularly thankful to Shri SS Tayal, Shri HL Kem,
and Shri OP Grover for extending their support while carrying out the research work at
LASTEC and also for giving valuable comments on the monograph to make it more
useful for the prospective readers.
We are thankful to the referees for their valuable suggestions and technical vetting
of the monograph.
We are grateful to the Director, DESIDOC and his team members including
Ms. Vinod Kumari, Ms. Alka Bansal, and Ms. Kavita Narwal for the support and follow
up in publishing the monograph.

Dr KN Chopra
Shri AK Maini
 Contents

Preface v
Acknowledgements vii
CHAPTER 1: THIN FILMS: TECHNOLOGY AND APPLICATIONS
1.1 Introduction 1
1.2 Types of Thin Films 1
1.3 Thin Films Design 1
1.4 Thin Films Fabrication 6
1.5 Thin Films Thickness Control 8
1.6 Dependance of Thin Films Properties on Various Parameters 9
1.7 Thin Films Applications 10
CHAPTER 2: THIN FILMS: CLASSIFICATION AND TYPES
2.1 Introduction 13
2.2 Types of Thin Films 15
2.3 Metallic Films 25
2.4 Dielectric Coatings 26
2.5 Coatings Developed at LASTEC 27
CHAPTER 3: THIN FILMS: DESIGN METHODOLOGIES
3.1 Design Parameters 31
3.2 Design Criteria 33
3.3 Critical Issues 34
3.4 Absorption for Withstanding High Power Densities 39
CHAPTER 4: THIN FILMS: FABRICATION TECHNIQUES AND
EQUIPMENT
4.1 Thin Films Deposition 41
4.2 Coating Techniques 41
4.3 Deposition Techniques 43
4.4 Critical Issues 47
CHAPTER 5: THIN FILMS CHARACTERISATION
5.1 Important Parameters 51
5.2 Characterisation Tools and EquipmentInduction 51
CHAPTER 6: SCIENTIFIC APPLICATIONS
6.1 Electronics Applications 55
6.2 Medical Applications 59
6.3 Differential Thermal Analysis Measurements 60
6.4 Thin Film Sensors 60
6.5 Thin Films Coatings Applications 61
6.6 Thin Films in Nanotechnology 62
6.7 Optical Applications 63
6.8 Thin Films for Efficient Solar Energy Conversion 64
CHAPTER 7: INDUSTRIAL APPLICATIONS
7.1 Electronics Applications 67
7.2 Thin Films Coatings Applications 70
7.3 Nanotechnology Applications 68
7.4 Medical Applications 74
7.5 Optical Applications 75
7.6 Soil Testing Method 76
7.7 Polyethylene Terephthalate Films (Biaxially Oriented) for Food Packaging 76
7.8 Thin Films for Warming Applications in Agriculture 76
7.9 Thin Films for Information Storage 77
7.10 Thin Films for Electroacoustics 77
7.11 Thin Films in Telecommunications 78
7.12 Ultrananocrystalline Diamond Thin Films 79
CHAPTER 8: CONSUMER APPLICATIONS
8.1 Electronics Applications 83
8.2 Transducers Applications 86
8.3 Thin Films Lithium Batteries 87
8.4 Lead Sulphide Thin Films in Decorative Coatings and Imaging Techniques 87
8.5 Thin Films Amorphous Silicon for Chemical Imaging 88
8.6 Thin Films for Artificial Retina 88
8.7 Thin Film Coatings for Artificial Jewellery 88
CHAPTER 9: MILITARY APPLICATIONS
9.1 Military Optics and Coatings 91
CHAPTER 10: EMERGING TRENDS/CONCLUSIONS
10.1 Future Challenges in Useful Applications of Thin Films 95
10.2 Conclusions 97

List of Acronyms 99
Physical Quantity and Units 102
Glossary 103
Index 107
x
 Chapter 1

Thin Films: Technology and Applications

1.1 INTRODUCTION
The main purpose of depositing thin film optical coatings on an optical surface is to
so modify it to provide environmental protection and/or improve optical performance.
Thin films are thin material layers ranging in thickness from fractions of a nanometer to
several micrometers. Electronic semiconductor devices and optical coatings are the
main applications benefitting from thin films construction.
Some work is being done with ferromagnetic thin films as well for use as
computer memory. Ceramic thin films are also in wide use. The relatively high
hardness and inertness of ceramic materials make this type of thin films coatings of
interest for protection of substrate materials against corrosion, oxidation, and wear.
In particular, the use of such coatings on cutting tools may extend their life by
several orders of magnitude.

1.2 TYPES OF THIN FILMS

1.2.1 Classification of Thin Films Coatings

Thin films are classified in many ways, mainly, according to the materials used for
the coatings, the damage threshold, the strength, and the characteristics, etc. There are
metallic coatings, and dielectric coatings. The metallic coatings always have lot of
absorption and have only limited applications. The dielectric coatings have practically
negligible level of absorption, and hence, are very useful for various applications in
optics, e.g., laser systems and imaging instruments. Higher laser damage threshold
coatings are useful for high power lasers. The coatings with higher mechanical strength
and higher abrasion resistance are used for mechanical tools for increasing their life.

1.3 THIN FILMS DESIGN

1.3.1 Designing of Dielectric Coatings

The designing of dielectric mirrors is a very interesting and specialised topic, and
some important work is done by Willy1, Dobrowolski2,3,et al. and Tikhonravov4. A
dielectric coating consists of two or more thin layers of different transparent optical
 Thin Films and their Applications in Military and Civil Sectors

materials. The design is done by considering the Fresnel reflection coefficient from a
single interface between two materials and is carried out by keeping in mind the function
to be performed by the coated component, e.g., high reflection, anti-reflection (AR),
polarisation, chromatic dispersion, beam splitting or filtering, etc. Other parameters to
be considered are the operational wavelength range and the desired angle of incidence.
It is interesting to note that even if the value of the reflection coefficient is small for
a particular interface because of small difference of refractive indices of the materials of
the layers surrounding it, it is still possible to obtain a very high overall reflectivity of
the component because of the contributions of the reflection from other interfaces,
based on constructive interference in a certain wavelength range.
The well known laser mirrors have all the optical layer thicknesses equal to a quarter
of thickness of the desired wavelength. The design becomes more complicated if the
desired effect is to be obtained in a broader region of wavelengths. For AR coatings,
design is based on the destructive interference. It is also possible to design coatings for
other specific functions like beam splitting, polarisation, a combination of beam splitting
and polarisation, edge filters (like short wave pass filters, long wave pass filters, and
band pass filters), a combination of desired reflection properties in different wavelength
ranges (like AR at certain wavelengths and high reflection at other wavelengths or vice
versa), and chromatic dispersion, i.e., dichroic mirrors.
The design of dielectric coatings is a complete topic in itself, and has to be learnt by
the optical design engineer. Here the subject is being introduced and its physics is
discussed. It is to be understood that the complexity of the design depends upon the
nature and the number of functions to be performed by the coated component. The more
complicated the functions, and more the number of functions, the more complex is the
design. In some cases, the number of layers is small (3 to ~21), and in some cases, it can
be very high indeed (in the vicinity of 100). The design also depends on the difference
of the values of refractive indices of the materials of the layers. Resonator mirrors in
lasers are mostly dielectric-coated mirrors, as these are free from absorption associated
with the metallic coatings, and leading to very high reflection (99.99 per cent or higher).
However, these do not give shining lustre like appearance as is the case for metallic
mirrors. Instead, they appear transparent, since they have high reflection at a particular
wavelength, and also because the materials have negligible absorption.
The reflection properties of a multilayer (ML) mirror can be calculated by matrix
method, in which each layer is associated with 2 × 2 matrix, and the matrix of the design
is obtained by multiplying together the matrices of all the layers. The resultant matrix
can be used to calculate the complex amplitudes of the reflected and the transmitted
waves, along with the field distribution in the multilayer structure. The frequency
dependence of these coefficients results in achieving chromatic dispersion, i.e.,
designing of dichroic mirrors. It is to be noted that nowadays, many numerical
optimisation software based on the matrix method are commercially available. Some
refined softwares like Monte Carlo method are also available for efficient optimisation of
the designs.
(a) Anti-reflection Coatings
The AR coatings (optical thin film coatings for reducing reflections from surfaces)
are one of the most important coated components. These AR coatings are dielectric thin
film coatings applied to an optical surface to reduce the optical reflectivity of that

2
 Thin Films: Technology and Applications

surface at a certain wavelength or in a certain wavelength range. The AR coatings are

used for reducing reflection and contrast degradation in the images due to multiple
reflections. The AR coatings, designed by optimisation, can reduce the reflection to
~ 0.1 per cent per surface for a given wavelength and a given angle of incidence. In case
of the requirement of such coatings for a wide wavelength range and a wide range of
incidence angles, the achievable reduction is much less.
The AR coatings are employed for laser crystals and nonlinear crystals, e.g., lithium
triborate crystals. These are also usefully employed on the open ends of the optical
fibres. While designing the AR coatings, damage threshold of the coatings has to be
considered for certain applications like Q-switched lasers, which depends on the
refractive indices of the material combination wrt that of the substrate, and also the
fabrication technique. For achieving very high damage thresholds, dual ion-beam
sputtering technique is used. Generally, these are based on the principle that the
reflected waves from different optical interfaces largely cancel each other by destructive
interference. A single-layer AR coating designed for normal incidence consists of a
single quarter wave layer of a material with the value of refractive index (n) equal or close
to the geometric mean of the refractive indices of the two adjacent media. Such an
arrangement results in two reflections of equal magnitude arising at the two interfaces,
and these cancel each other by destructive interference, as these are out of phase.
However, the problem in designing such coatings is that it is not always possible to
find a coating material with suitable refractive index, especially in cases where the bulk
medium has a relatively low refractive index, e.g., in case of glass with n = 1.5, the
material required should have n ~ 1.24, if the coated component is to be used in air
(n = 1). Such a dielectric material suitable for coating is not available, and so generally
MgF2 with n = 1.38 is used which reduces the value of reflection from a single surface
from ~ 4 per cent to ~ 1.33 per cent. Another limitation of this coating is that it works only
at a single wavelength or in a limited wavelength range around it. The wideband AR
coatings can be obtained from gradient index coatings, in which case the composition of
a layer material is gradually varied. Theoretically, it is possible to suppress the reflection
over a wide spectral and angular ring by a smooth index transition between two optical
materials over a range of a few wavelengths. However, the difficulty arises because for
the surfaces next to air, all materials have value of refractive index quite different from
that of air (n = 1). Still good broadband AR coatings in a wide angular range without
using materials with a very small refractive index, can be obtained by integrating gradient
index layers into a ML coating.
(b) Designing of Anti-reflection Coatings for Photonic Crystals
The field of designing the AR coatings for photonic crystals (PhCs) is emerging,
and because of its great importance, an introduction of the topic is given here. The PhCs
are materials with periodic variation in dielectric constant. These are man-made materials,
and have many interesting properties like negative refraction, with a period of the
wavelength of the electromagnetic radiation for which these are to be used. These are
designed with a particular band gap, which means that it does not allow that band of
frequencies to propagate through these. The PhCs are attractive optical materials
capable of controlling and manipulating flow of photons, i.e., flow of light. The PhCs are
periodic dielectric or metal-dielectric structures that can modify the propagation of
electromagnetic waves in the same way the periodic potential in a semiconductor crystal

3
 Thin Films and their Applications in Military and Civil Sectors

modifies the electron motion by defining allowed and forbidden electronic energy
bands. Thus, PhCs can be considered as the artificial structures with the optical
equivalent of the energy gap in a semiconductor. Using high speed photons in place of
relatively slow electrons as the carriers of information, the speed and bandwidth of
advanced communication systems is expected to increase dramatically, and thus,
revolutionising the telecommunications industry. During the data movement on silicon
chips, electrons pass through electronic gates, and being charged interact with each
other, thus generating excessive heat and limiting their movement.
The PhCs use uncharged photons for data flow and are thus free from this problem.
It is to be noted that negative refraction has been observed in periodically
inhomogeneous substances. This has been demonstrated in photonic crystals, both
theoretically as well as experimentally. Negative refraction of acoustic waves has also
drawn the attention of the researchers. The experimental confirmation of negative
refraction has helped the electromagnetic research community to identify many
observable and exploitable effects. When photons pass through a block of transparent
dielectric material, these encounter regions of high refractive index (dielectric)–
separated by regions of low refractive index (the air holes).
This contrast in refractive index acts like a periodic potential experienced by
electrons traveling through a silicon crystal. In case of a large contrast in refractive
index between the two regions, most of the light is confined in either of the two regions,
thus resulting in the formation of allowed energy regions separated by a forbidden
region, i.e., photon band gap. The effect can be more pronounced in the presence of
defects which are nothing but irregularities introduced by changing the size of a hollow
ball or the chemical microstructure of the PhC. This is because the defects act like
efficient guides routing light through desired paths at a speed much higher than that of
electrons in a chip.
The PhCs have applications in waveguides, Bragg reflectors, supercollimators, and
superprisms. Choi5, et al. have studied improved transmittance in one-dimensional
metallic PhCs5. They have theoretically considered the effect of absorption losses in
metal layers, and have shown that the transmittance of a one-dimensional metallic PhC
can be increased up to 67 per cent. The starting structure for their study consisted of a
stack of five alternate layers of Ag (layer thickness 30 nm) and four layers of GaN (layer
thickness 64 nm), and also one layer each of GaN of 32 nm (i.e., half thick) on top and
bottom of the stack. The total thickness of Ag layers chosen in this PhC was 150 nm, so
that it is several times longer than the skin depth of Ag.
An interesting observation made by them is that the stack without the two GaN
layers produces strong oscillations in the transmittance spectrum, with the peak value
of only 30 per cent. The addition of one GaN layer to the structure results in
smoothening of the overall increase of transmittance, but with the same peak value. It is
only in the case of having the two additional layers, that one can achieve the smoother
transmittance spectrum with more than twice the transmittance.
Recently, Alejo-Molina6, et al. have studied the metallo-dielectric photonic crystal
(MDPhC) in relation to the substratum DPhC, by carrying out the analytical and
numerical analysis of metallic insets embedded in a DPhC. The complex MDPhC
dispersion relation curves and the transmission coefficient at different propagation
regimens through the finite stack have been described. It has been observed that in a

4
 Thin Films: Technology and Applications

DPhC6, the band gap argument corresponds to undefined complex solutions of a real
dispersion relation, but in a MDPhC, it corresponds to a definite complex solution which
is a function of the metal thickness; and analytic continuation of the dispersion curve
on the imaginary K plane.
As it is clear that in these applications, light has to be coupled into the PhC, and so
insertion losses take place, especially at the frequencies near band gaps, and this
provides noise. The coupling losses can be controlled by long mode matching
structures or by short AR coatings. This concept is comparatively new, and not much is
known about the coupling losses, and so designing of efficient PhC AR coatings is
done by trial and error method, which involves a lot of numerical simulation. However, in
case, the impedances of the PhCs used in the design are known, these trials become
simple and can be calculated easily.
Impedance is an intrinsic property of the substance, and if its value for two adjacent
materials is known, the reflection and transmission coefficients at their interfaces can be
easily calculated. It is difficult to extend the concept of impedance to PhCs, as the bulk
PhCs scatter light in multiple directions, and it is difficult to distinguish the interface
reflections from the internal scattering. So, various ad hoc impedance definitions have
been proposed in the literature, but they are all scalar and not very useful for efficient
design of AR coatings for PhCs.
For a good AR coating design, the impedance should satisfy two criteria, viz., it
should be uniquely defined for each PhC at any wavelength, incident angle, and
polarisation, and also should be sufficient to find the reflection and transmission
between the two PhCs. Lawrence7, et al. have designed and discussed AR coatings for
two-dimensional PhCs using a rigorous impedance definition. In the latest treatment of
this type of design, at each wavelength, the field inside each PhC is considered as a
superposition of propagating and evanescent Bloch modes and their quasiperiodic
eigenmodes, since PhC's Bloch mode travels through the PhC's interior without
reflection. Each PhC is considered as a stack of gratings, and its Bloch modes are
represented as a superposition of propagating and evanescent plane wave solutions to
the grating equation.
Since the Bloch modes are infinite in number, the calculations are made manageable
by projecting the field onto a truncated but sufficiently complete set of propagating and
slowly evanescent Bloch modes by a least square approximation that satisfies the two
criteria in a balanced manner and is economical. The set is divided into N forward
travelling/decaying modes and N backward modes, and thus the interface reflection and
transmission coefficients become M × M matrices mapping between the truncated Bloch
sets. It should be noted that a larger value of N leads to better accuracy, but the accuracy
is good for M approximately equal to the number of propagating plane wave solutions to
the grating equation.
The impedance is defined by calculating the reflection at an interface between
uniform dielectrics, and is generalised to work with Bloch modes. The Bloch modes are
mapped in each PhC to plane-wave field amplitudes and are used to compare fields
across the interface and to find the reflection. The matrix that maps forward Bloch modes
to plane-wave field strength coefficients, are found numerically via the transfer matrix,
for the E and M field components. The columns of E and M are taken from the sums and
differences of forward and backward plane-wave expansions of Bloch modes. It should

5
 Thin Films and their Applications in Military and Civil Sectors

be noted here that the accuracy of the AR coating design depends upon the accuracy of
finding the impedances. The AR coating consists of one or more thin layers coated on
the substrate, i.e., bulk medium. The refractive indices and the thicknesses of the layer
materials have to be so chosen that all the interface reflections cancel. Since a PhC's
width cannot be varied continuously, two layers are required in general for designing a
perfect AR coating. The net reflection is easily derived from the interface reflections and
the phase changes across the layers, and is made to approach zero.

1.4 THIN FILMS FABRICATION

1.4.1 Interdependent Steps in the Deposition of Coatings

The deposition of coatings is really a complex process in which many parameters
(refractive index, temperature of the substrate, degree of vacuum, rate of deposition,
etc.) are interdependent. For example, the choice of coating material depends on the
design requirements that include many properties like optical, mechanical, chemical, and
electrical, and also energy density. In addition, the preparation and form of the coating
material are selected according to the deposition process to be employed and also its
parameters, which are responsible for the microstructure of the deposited layer, and
thus determines its optical and mechanical properties.
The mechanical and chemical durability of thin films depend on many structural
factors including packing density (PD) and surface morphology, which are affected
mainly by the deposition technique. Higher packing densities (approaching unity) and
excellent surface morphology are obtained employing the technique using higher energy
for the fabrication of the coatings, e.g., dual ion-beam sputtering produces coatings
with unit PD (and hence a higher refractive index of the material), low scattering, and
high damage threshold. The ion-beam sputtering technique (IBST) results in a higher
refractive index of the layer at all the wavelengths (400 nm–800 nm) than that obtained in
case of the layer coated by conventional technique (e.g., electron beam deposition).
The refractive index of TiO2 increases from ~2.1 (in case of conventional coatings)
to ~2.3 (in case of the coatings done by IBST). It has to be noted that it is also a function
of wavelength. Thus, it should be appreciated that while designing of the ML stacks of
thin films, these factors have to be taken care of. For a thin films component to be
fabricated for a broadband wavelength region, the central wavelength is considered for
using the refractive index in the thin films design. Also, the PD expected to be achieved
by the process has to be taken in the design, which is never an easy preposition, as it is
also dependent on the process control parameters in addition to the choice of the
coating technique. Thus, the coating designing is a complex and tedious job requiring a
lot of designing skills and understanding of the effect of process parameters which have
to be optimised for achieving the value of the refractive index taken in the optical thin
films design. The effect of the use of the coating technique on the refractive index of the
coated layer is shown in Fig. 1.1.
The desired values of the refractive index and the transmission of the films
depend upon the layer composition. The oxide coatings, e.g., Ta2O5, have a tendency
to dissociate into the lower oxides or even to metal, and hence, their deposition has to
be carried in the presence of oxygen (generally activated oxygen species) to
compensate for the oxygen loss or for reaction so as to get films of the correct

6
 Thin Films: Technology and Applications

2.5

IBST
REFRACTIVE INDEX (n)

2.0
CONVENTIONAL

1.6

400 500 600 700 800

WAVELENGTH (mm)

Figure 1.1. Ion-beam sputtering technique produces coatings of higher refractive index
than those by conventional techniques (e.g. electron beam deposition).

stoichiometry (i.e., desired oxygen state). The problem is not so acute in case of other
oxides like CeO2 and Ta2O5. On the other hand, the films of fluoride compounds like
MgF2 and CeF2 have to be grown in high vacuum for high purity and low absorption.
Thus, it is clear that in the case of fabrication of ML stack of different types of
materials without any cross-contamination, the process parameters involved are
interrelated, and hence, the development of a particular coating for any specific
application is really a complicated process.
The mechanical properties of the coatings, namely, adhesion, hardness, and
abrasion resistance depend on the microstructure of the coatings and the nature of
chemical bonds, besides matching the stress coefficients and the thermal coefficients.
The stress in a thin film layer is generated either within the layer or at the interface
with the other layer or the substrate surface. In case of the stress originating at the
interface, the difference in the thermal coefficients has to be minimum, which also results
in minimising the structural mismatch due to the differences in the mutual chemical
bonding. Thus, it is necessary to choose the coating materials with compatible thermal
coefficients and stresses, especially when the coated samples are to be used in large
variations of temperature. It is very important to note that the temperature and the stress
are inter-related.
Many coating materials, especially oxides and fluorides, are coated on substrates
heated to temperatures in the vicinity of 200 °C–300 °C for achieving the efficient
mechanical and optical properties, and hence, the relative stress of the layers is affected.
The stress can be either compressive or tensile in case of metals, while it is, in general,
tensile for metals. A very interesting case is that of TiO2/SiO2 ML stack, which produces
a low stress in it in a good temperature region, as TiO2 has tensile stress, and SiO2 has
compressive stress. To some extent, the stress can be controlled by the deposition
process, e.g., the sputtering is a very versatile process for controlling the sign of stress
by varying power and pressure at low substrate temperature, while electron beam

7
 Thin Films and their Applications in Military and Civil Sectors

deposition has very little control on it.

It is worthwhile to note that the achievement of the required stress in the coatings
is really a complex process, as it is affected by a number of parameters including water/
impurity absorption at the interface, the layer thickness (which actually affects the
morphology of the films) and the incidence angle of the condensing atoms, e.g., the
coatings of ZrO2, MgF2, and ZnS.
Interestingly, stress in case of SiO2 films is compressive, which can be changed to
tensile by adding a partial pressure of water during film growth which reduces the
tensile stress as the impurity atoms/ions are larger in size than the film atoms. Finally, the
higher incidence angle results in the films of higher tensile stress, and thus of lower
volume density.
In addition to the above discussed factors, the rate of deposition also plays a very
important part in determining the degree of the entry of the included impurity atoms/
molecules (e.g., the water from the walls and the mechanical components of the coating
chamber, or the plasma gas composition in a sputtering chamber) from the residual
atmosphere in the coating chamber. For most of the ML stacks, the materials having
maximum refractive index ratio are used because they give optimum performance. For
high refractive index coatings, many materials like TiO2, Ta2O5, CeO2 are available.
However, only two good materials, viz., MgF2 (n=1.38) and SiO (n=1.45) are available for
low index coatings.
Thin films of PD close to unity are fabricated by the techniques having high
energetics, e.g., sputtering, ion-assisted deposition (for supplementing energy by using
ion gun), and using materials having strong chemical bonds. They are structurally
strong, besides having high wear resistance, and are very stable as they are nearly free
from any absorption/desorption of water and other air pollutants. Some specially
processed material are also used for achieving the required properties. Dense films can
also be prepared by doping the coating materials which stop the grains from increasing
in size, and hence, give amorphous and small grain structures having better cohesion
and adhesion properties. It is thus clear that the process parameters like the substrate
temperature, the rate of deposition and degree of vacuum, etc., are very important for the
quality of the coatings, and are generally the confidential proprietary information of the
thin films engineers.

1.5 THIN FILMS THICKNESS CONTROL

The thin films thickness is controlled by optical techniques and the crystal monitor
technique. The optical technique is usually applicable for interference coatings, and
only for the visible region. In interference coating, the optical film thicknesses are
generally of quarter wave thickness, and in some cases of half wave thickness. The
quarter wave thickness is complete at the point of inflexion on the transmission or the
transmission value. The half wave thickness of a coating material is achieved by
undergoing two points of inflexion, and the layer of this thickness is usually referred to
as 'absentee layer', as this has no effect on the transmission/reflection value.
However, there is a great challenge in the film thickness monitoring as the growth
temperature is usually significantly different from the operating temperature of the
coating, and the temperature dependence of the refractive index is not easily known. In

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 Thin Films: Technology and Applications

case of non-interference coatings, the solution is provided by the crystal monitor, in

which case the difference of the crystal frequencies between two crystals (one standard,
and the other which is exposed to the source of deposition while the coating is going
on) is measured. However, this method is only suitable for optical coatings, as the
crystal gets saturated at very high thicknesses which are invariably encountered in case
of infrared (IR) coatings.
To overcome these shortcomings, a thin films in situ film thickness monitor based
on optical technique and useful for IR regions has been devised at LASTEC, Delhi. The
system uses two laser sources, one He-Ne laser for alignment, and the other CO2 laser
for monitoring the film thickness. The system can be used in both, the transmission
mode as well as the reflection mode, as shown Fig. 1.2. The two laser beams are made
collinear for monitoring. The IR detector module measures the reflectivity/transmissivity
value while the coating is in progress. This system is particularly useful in making
output couplers, as the output is measured in situ and the operation can be stopped
after achieving the required output. This in situ monitor, as fitted in the box coater of the
Balzers vacuum coating unit, is shown in Fig. 1.2.
IR DETECTOR
MODULE
6 GLASS
WINDOW
He-Ne LASER 5
DETECTOR
4

3 SUBSTRATE
SUBSTRATE HEATER
HOLDER QUARTZ
CRYSTAL

E-BEAM VACUUM
EVAPORATOR CHAMBER
2

1-2-3-4-5 ZnSe
1
WINDOWS CO2 LASER
SILVER
MIRROR He-Ne LASER
(0.6328 nm)

Figure 1.2. Balzers vacuum coating unit fitted with in situ film thickness monitor, designed
and developed at LASTEC.

1.6 DEPENDANCE OF THIN FILMS PROPERTIES ON VARIOUS PARAMETERS

Many text books on the subject are available which give a very good account of
their structures, properties, fabrication techniques, and applications in various
fields 1-25.The field of ‘Thin Films Coatings’ is more of an art than science. The physics
of the subject is complicated. The properties of the thin films depend on the deposition

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 Thin Films and their Applications in Military and Civil Sectors

conditions and the cleaning of the substrate to be coated, especially in case of the
optical thin films. The properties of the optical coatings depend on the refractive index
of the coatings materials, which is strongly dependent on the various factors like rate of
evapouration, degree of vacuum, temperature of the substrate being coated, and the
coating technique which determines the packing density of the coating. The packing
density of the coatings is large (approaching unity in the case of the technique
employing the adatoms carrying high energy ~ 1000 eV e.g. in case of ion-beam
sputtering technique which gives the value of refractive index close to that of the bulk
material). The optical coatings fabricated by such techniques are stable and of high
damage threshold resistance, and are particularly suitable for high power laser
applications. Lower than unity packing density coatings results in very slow absorption
of moisture and other chemicals by them, which change the refractive index of the layers
thus changing the performance of the coatings.
The thin film technologies are also being developed as a means of substantially
reducing the cost of photovoltaic (PV) systems. The rationale is thin film modules are
expected to be cheaper to manufacture owing to their reduced material costs, energy
costs, handling costs and capital costs. However, the thin films have to be developed
using new semiconductor materials, including amorphous silicon, copper-indium
diselenide, cadmium-telluride, and film crystalline silicon. In all the cases, these
technologies face major technical and financial hurdles.

1.6.1 Material Selection of the Deposited Layers

The thin films coatings engineer is provided with the application of the coating,
the spectral transmission and reflection, the mechanical strength and durability values
(e.g., hardness, abrasion resistance, resistance to moisture and other pollutants
present in the atmosphere) and also their evaluation by MIL or ISO standards, and
sometimes laser damage threshold value and its testing. The spectral transmission
depends on the values of the absorption coefficient (k) of the coated layers. For
general applications, k must be ~ 0.001, but for low- and high-power applications, it
should be more than and less than this value respectively. The TiO2, SiO2, and Ta2O5
are some of the most commonly used materials, because of the versatility of their
excellent properties, vis-a-vis, their absorption, hardness, and compatibility with the
material of the substrate and the various coating techniques. The SiO2 and TiO2 are
found very useful for applications in wide-band AR coatings, laser mirrors, and
interference filters to be used in the visible region.
However, it has high band gap absorption in the ultraviolet (UV) region (below
~ 475 nm), and hence, is not useful, especially for ML designs. It has water band
absorption above 900 nm, and so is not very useful for laser coatings in this region.
Ta2O5 is free from these shortcomings and is very suitable for such demanding
applications in the range of 400 nm to ~ 2000 nm. The laser mirrors, and the filters (VIS-
NIR and WDM) in the IR region (around 1500 nm) are fabricated using SiO2 and Ta2O5.
The TiO2 and SiO2 can be deposited by both electron beam deposition (EBD) and
sputtering, but Ta2O5 can be deposited well only with sputtering.
In some cases, coatings of mixed materials with the required refractive indices and
other properties are also used. These are prepared by co-evapouration or co-sputtering
of materials with high and low refractive indices, in which the material properties are

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 Thin Films: Technology and Applications

controlled by continuous monitoring of coating and sputtering rates of the constituents

of the mixed materials and gas composition.

1.7 THIN FILMS APPLICATIONS

Thin films have great importance and significance for a large variety of industrial
applications. Some of the important applications are wear- and corrosion-resistant
coatings, which are capable of extending the lifetime of a large number of critical
products. In addition, optical and electrically active, as well as magnetic thin films can be
usefully employed in sensors, actuators, solar cells, thin film electroacoustic devices,
porous nanocomposite films, etc.
Thin film technology is available for tailoring coating materials for specific
applications, e.g., properties varying from hard diamond to soft polymer films. The thin
film technology for tribological applications capable of producing superhard and tough
coatings, and also self-lubricating coatings are available. Smart windows based on
electrocromic-controlled transparency have already been studied. A lot of work has
also been reported on the magnetic properties of thin films, including the synthesis of
piezoelectric and ferroelectric thin films, and also the design and fabrication of devices.
The thin films techniques for investigations of magnetic properties and hydrogen
uptake have also been developed. Some of the investigations in this direction are
magnetic MLs, superlattices, and films of metals and/or oxides.
The research is going on with the aim to study which physical properties are
affected by shrinking the materials in one or more directions, and also to see how these
properties can be tailored for sensor applications and information storage. It is really
interesting to note that the hydrogen uptake in certain metals changes the properties
substantially, and this can be used for continuous, reversible modification of some
properties like electric resistance. Also, hydrogen absorbing thin films serve as model
systems for investigating novel hydrogen storage materials.
Researchers have succeeded in developing techniques for extremely well
controlled (atomic layer by layer) growth of thin films, and are currently active in
computer modelling for predicting physical and chemical properties of new thin films
materials. Thus, it is clear that the thin films are useful for optics (laser mirrors and
transmission increasing coatings), electronics (layers of insulators, semiconductors,
and conductors on ICs), packaging (Al foils), purification of metals like copper by
electroplating, and so on.

REFERENCES
1. Willey, Ronald R. Practical design and production of optical thin films. Willey
Optical, Consultants. CRC Press, Marcel Dekker Incorporated, Charlevoix,
Michigan, 2002.
2. Dobrowolski, J.A. & Lowe, D.G. Optical thin film synthesis program based on the
use of Fourier transforms. Applied Optics, 1978, 17(19), 3039.
3. Dobrowolski, J.A. & Kemp, R.A. Refinement of optical multilayer systems with
different optimisation procedures. Applied Optics, 1990, 29(19), 2876.
4. Tikhonravov, A.V.; Trubetskov, M.K. & DeBell, G.W. Application of the needle
optimisation technique to the design of optical coatings. Applied Optics, 1996,
35(28), 5493.
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 Thin Films and their Applications in Military and Civil Sectors

5. Choi, Young-Kyoung; Ha, Young-Ki; Kim, Jae-Eun; Park, Hae Yong & Kim, Kihong.
Improved transmittance in one-dimensional metallic photonic crystals. Physics B:
Cond. Matt., 2003, 338, 132-35.
6. Alejo-Molina, A.; Sánchez-Mondragón, J.J.; May-Arrioja, D.A.; Romero, D.;
Escobedo-Alatorre, J. & Zamudio-Lara, A. Complex dispersion relation of 1D
dielectric photonic crystal with thin metallic layers. Microelectronic, 2009, 40,
459-61.
7. Lawrence, Felix J.; Botten, Lindsay C.; Dossou, Kokou B. & Sterke, C. Martjin de.
Antirefection coatings for two-dimensional photonic crystals using a rigorous
impedance definition. Appl. Phys. Lett., 2008, 93, 121114/1-3.

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