CHAPTER t

FUNDAMENTALS OF THIN FILMS

1.1 Introduction

Thin film electronic it1d . · . . . .

ustty ts one of the most significant technological drivers of
I
g o b al economy as it it11'f
' tates phenomenal advancements in communication systems as
well as storage and d' I d .
. tsp ay ev1ces. Advantages of thin film technologies make them
attractive for use in s . . . .
evera 1 areas 11ke optical mechanical and decorative coatings,
disinfectant technology d h · ' • · · d
an P otovolta1c technology. As thm films mcreasmgly fin
applications in almost all fields of technology, it becomes important to study about them
with specific focus on fabrication of thin films of newer materials by developing and
implementing novel techniques and procedures. This chapter outlines the basic
properties and some of the important applications of thin films.

A thin film may be defined as a thin layer of material deposited onto a substrate(a
solid support), the thickness of which may be in the range of a few nano metre to a few
micro metre. According to Chopra et al. 1 thin films are formed due to random nucleation
and growth of individually condensing atomic/ionic/molecular species on a substrate.

Based on the thickness, thin films can be classified into three types, viz.(i) ultra thin
films (50-100 A), (ii) thin films (100-1000 A) and (iii) thick films(> 1000 A)2. Even
though, the properties of thin films depend on their thicknel-to som:. extent, it is better
to classify thin films on the basis of the production process rather· than the thickness of
the films. This is because of the fact that thin films of the same material having identical
thickness,but deposited by different methods, more often exhibit different
[Link] other words, the structural, optical, electrical and surface
morphological properties of thin films strongly depend on the deposition techniques
employed and the process parameters involved. By suitably controlling the process
parameters, one can tailor the above mentioned properties of thin films as required by the
application concerned.
The properties of materials which are in thin film form are remarkably different from
their bulk counterparts, mainly because of their large surface to volume ratio.

Introduction to Thin Films 1

 1.2 Adv anta ges of thin film devices over their bulk
coun terp arts
Thin films find applications in various devices like
solar cells, microelectronic
circuits, space science systems, optical devices, com
puter memory devices, military
weapon systems, sensors, opto-electronic devices,
surface acoustic devices and
piezoelectric dev ices. Devices or components mad
e from thin films have several
advantages over their bulk counterpatts. They include

• low cost of production

• high reliability and superior performance
• extreme compactness and light weight
• low power consumption
• large surface area to volume ratio(a prerequisite for man
y applications)
1.3 Thin film growth stages

The process of film growth may be divided into six

stages viz. nucleation stage , island
stage , coalescence stage, channel stage, hole stage and
continuous film stage (Fig . 1.1).

,. .,• i.
~ -,,. , • '
,_, , ••._'
,

•
.;
~,
.
•• ,, .,
".. ..
,

• • . ,•
•
,
~

• , ,
• .

"
Nucle ation stage Island stage Coalescencce stage

Channel stage I toles Countious film stage

Fig. [Link] film growth stages

Intro duct ion to Thin Films

2
Nucleation stage
Thin film formation · I
. tnvo ves the deposition of h . . . .
molecular species, atom by atom ( . t e appropriate atomic, 10111c or
o1 mo 1ecul e by molecu le) and I b I
substrate. The atoms or molecules it . . ayer Y ayer on to the
iipmgmg onto the substrat h
the substrate and interact witl1 ti . ' e move over t e surface of
r.: • d . o 1er spec ies to fo rtll cIusters. rhe assemblages of atoms
r

or mo Iecu Ies JOI me at certain sites on ti1 b .. .r

.· _
. I . e su slt ates are called nuclei. fhese nuclei then
grow up to a ct 1t1ca size by combini ng 'th d
. • _. . . WI new a sorbed species. Thi s first step which
111volves the fo1 mat1on of the critical sized th . d .
. , et mo yna1111cally stable nuclei is known as
the nucleation stage.
Island stage

The critical-sized nuclei then grow both par·all el an d

perpen d'1cu lar to the su bstrate
due to the aITival of new species· These larger nucI · · ·
et or embryos are three d1mens1onal
in nature with their height much less than their lateral dimensions. These larger nuclei
appear as islands onto the substrate with lot of unoccupied space between them and
hence this stage is called island stage.
Coalescence stage

In this stage of thin film growth, the islands are combined with the neighbouring
ones to form larger islands. The phenomenon of formation of larger islands from the
smaller ones is called agglomeration or coalescence. This coalescence stage involves the
transfer of mass between islands by diffusion and hence small islands disappear rapidly.
The time of coalescence is very short, of the order of about O.6 seconds3 •
Channel, hole and continuous film stages
As a consequence of the arrival of more and more species on the substrate, the
coalescence continues, resulting in a network of the deposited areas with channels (void
spaces) in between. These channels last only for a small time, as some secondary nuclei
begin to grow within these void spaces. Further deposition of the material leads to the
diminishing or even vanishing of these voids resulting in an evt ntually continuous film,
even though some pores may be present in some cases. To obtai n a perfectly continuous
film, a minimum thickness is needed which depends upon the nature of the deposited
material, method of deposition and the deposition parameters involved in that particular
deposition technique.

Introduction to Th in Films 3
1.4 Applications of thin films
Thin film coatings are employed in many fields like optics, optoelectronics, and
microelectronics and so on. A broad classification of such applications is illustra
ted in
Fig. 1.i· 5•
Selective solar absorbers
Reflective and antireflective coatings
OpticalCoat_in_g_s----+ L-- Automobile rear view mirrors

Interference filters
Electrical contacts
Memory discs
Electrical insulators
Wave guides
Resistors
Architectural glazings
Capacitors
Electrical, electronic and
opto-electronic devices Varistors

Diodes& transistors
Field effect transistors
Memory discs
Piezo-electric devices
Magnetic devices
~[ Spintronic devices Transparent electrodes

Light emitting diodes

Catalytic coatings
Solar cells

E
Chemical
applications ---1111i• Gas I Liquid sensors

Corrosion resistant and oxidation resistant coatings

Lubrication coatings
Wear and erosion resistant (tribological) coatings
Mechanical applications
Adhesive coatings

Diffusion barriers

watch bezels

Decorative ornament coatings Bands

Eye glass frames

Costume jewellery
Barrier layers
Thermal applications
-[H,t 1tsin ks
1.2Applications of thin films

Introduction to Thin Films 4

 CHAPTER4
THIN FILM DEPOSITION TECHNIQUES
4.1 Introduction
Thin fil m d_eposit!on techniques can be broadl
y classified into phy sica l and chemical
met hods, eac h mvo lvmg a number of techniqu
es, as li sted in Table 4.1.

Tab le 4. 1 Thin film deposition techniqu es

THIN FILM DEPOSITION TECHNIQUES

PHYSlCAL METHODS
Sputtering CH EMI CAL METHODS
Evaporation Gas phase
Glow discharge Vacuum Liquid phase
DC sputtering Che mic al vap or Electro-deposition
evaporation deposition
Radio
frequency Resistive heating Laser chemical Chemical bath
sputtering evaporation vapor evaporation deposition
- Magnetron Electrole ss de position
Flash evaporation Pho to chem ical
sputtering Liquid phase epitaxy
vapor deposition
Ion beam Electron beam Sol-gel spin coating
Plasma enhanced
sputtering evaporation Successive ionic layer
vapor deposition
adsorption and reaction
Pulsed laser Metal organic Spray pyrolysis
deposition chemical vapor technique
A.C. sputtering deposition
Molecular beam
Ultrasonic spray
epitaxy Closed space pyrolysis technique
sublimation
Generally, there are three steps in the deposition
process of thin films
(i) Synthesis of the source material (solid or
liquid).
(ii) Transport of vapors from the source to the
substrate.
(iii) Condensation of vapors followed by nuc
leation and other growth stages of thin
films onto the substrate.
The Fig. 4.1 shows a simple version of sequ
ential steps involved in thin film
depo sition processes.

Introduction to Thin Films

45
 Synthesis of suitable - - - - - - - (Solid or Liquid)
source material

Transport of vapors ____ ___ (Through vncuum.

to the substrat e fluid or plasmn)

Deposition
r- ---
--- (c ondensntion of transported f: )
species onto the substrate sur ace
'------- -
Fig. 4.1 Steps involved in thin film deposition

The selection of a deposition process from a number of available methods depends

on several factors which include:
• Materials to be deposited.
• Purity of the film required, for the application concerned.
• Characteristic features of the films (such as optical, electrical, surface
morphological characteristics) required for the specific application.

• Fabrication cost.
• Availability and cost of the equipments required .
• Rate of deposition .
• Type of substrate and the maximum temperature which the SJj;.trate can
withstand.
• Ecological considerations.
4.2 Physical deposition methods
Physical deposition is a process, by which the atoms/ions/molecules of the source
material is evaporated/ejected by means of an energetic beam of electrons, photons or
positive ions so that the species can be transported to the substrate for condensation and
subsequent formation of the thin film.
Some of the widely used physical deposition methods are described below:
4.2.1 Vacuum evaporation technique
Vacuum evaporation is one of the common physical vapor deposition methods. The
source material to be deposited is evaporated in a high vacuum, by heating it using one
of the following heating sources: direct resistance, eddy current, electron beam, laser

Introduction to Thin Films 46

beam or an arc discharge. The vacuu m aII ows v1 p ·
ubstrate, where they condense to~ . h' . ' or partic 1es to travel directly to the
s 01m at in solid film.
4.2.2 Thermal evaporation
Description and working
The schematic diagram of the ap ar,1t
. t f' P ' us used for thermal evaporati on is shown in Fig
4,2. It cons1s s o a vacuum chamber
b t t 110 Ide.1 t Tl ' vacuum pumps, source holder or crucible,
su s ra e d be c. le source is generally prepared in the form of pellets. Since the
source nee s to e heated up to its melt'mg point, ·
the source holder or crucible should be
made up of a material with high melting point(> 2SOO oc) sue h as tungsten, tanta 1um or
d Th .
molyb enum. e operating temperature should be set at a particular value such that the
· 1·s
vapor pressure of the evaporant is at least of the ord er of 10-2 torr. [Link] con d'1t1on
°
essential in rd er to get useful condensation of the evaporant onto the substrate. As the
source material is th ermally evaporated, this technique [Link] as thermal evaporation.

Vacuum chamber- -
,,- - - - - - - - -Substrate holder
,,:
Substrate - - - ------ ->--- ..i
+ t 'i' ',
I
1
I
I
l
I
'------- - -Deposit ·
I t J
I I I
I I I
I I I
I I I
1 11
◄---------- - -Evaporated species
I 11
Source material - - - ------, Ill
', I IJ
, I I I
'-,III
Resistive heater - - - - - - - - - , n _______ __ _
',4 - =!!!!l!'!l'I........
- -Crucible

Vacuum
pumps

Fig. 4.2 Schematic diagram of Thermal evaporation

A sufficiently high vacuum (with a long mean free path) is needed, so that the
evaporated particles · can travel directly to the substrate without colliding with
themselves.
The rate of deposition onto the substrate surface depends on several factors such as
the evaporation rate, geometry of the source material (point, ring, cylinder, strip, wire
etc.), distance and position of the substrate relative to the source and the con~ensation
coefficient. For a point source, the rate of deposition at any point on a plane substrate is
directly proportional to cos0/r2 (Knudsen's cosine law) where r is the radial distance of

47
Introduction to Thin Films
 . )the substrate from tI,e po int source and 0 is the angle between the radial
1
the pomt (P 01 . . · . of the substrate and the normal to the substrate (h)
vector corresponding to the pomt as
shown in Fig. 4.3.

'
/\ p\
· - Deposit

- --------- Point source

Fig. 4.3 Illustration for rate of deposition

The thickness of the deposit 't' at any point 'P' on the substrate is given by

to
t = ----,-3 (4.1)
(1+ mt?
where f-0 is the thickness of the deposit at the point where the vapor species fall normally
(i.e. at A), h is the normal distance of the point source from the substrate and x is the
distance between A and P.
Depending on the type of heating source, number of source mterials, etc., the
vacuum evaporation [Link] classified into various methods, which include:
• Electron beam evaporation
• Pulsed laser deposition
• Flash evaporation
• Reactive evaporation
• Molecular beam epitaxy
4.2.3 Electron Beam Evaporation (EBE)
Th e depos1t1on
· · process ·m which the source material is made to evaporate bYheatin° . 0
it wi th the use of electron beam evaporators is called electron beam evaporation.
Materials with low vapor pressures are difficult to evaporat.e (1sing resistive heating. h:
such cases, electron beam evaporation can be more useful. This technique is fou nd to,!.
JS
Introduction to Thin Films
 catino trans ·
very promising for fabri
. . . o , parent conducf . .
.
.
films with lower res1st1v1ty and highe r t.tansm1ttanc ing materials like ITO ' Sno 2 and ZnO
e 1-J
Electron beam evaporators utilt'z e ti1e energy 0 f ·
heat the source material. a 6eam of high-energy electrons, to
Description and working
Fig. 4.4 shows the schematic di' ag,.am of a v·1c .
no It . . uum evapo ration system which
employs electron beam heati o· consists of the foll • c

g parts : vacuum chamber,

vacuum pumps, electron gun crucibl e, vacuum gauges sowin bs rate hoId ers, rate [Link],
t
, , u
process controller, etc.

., ., - - Substrate holder

Substrate- - c=:=r========::;=~~
- - - -> _ _ _ _..J
+ ' ' ,_ - --
~.~
I I I -Deposit
I I I
I I
Evaporated - - - ------ ► 1
I
I I
I I
species I
I I I
I I I ..J./ acuum chamber
It 1
,,
I I I

I
Source - -
materials
-Electron beam
evaporator

Vacuum pumps
''- -Crucible

Fig. 4.4 Electron Beam Evaporation setup

Vacuum chamber and vacuum pumping system

ngular box to a more
The vacuum chamber ranges from a simple bell jar or recta
m is generally _based on
complex and sophisticated arrangement. The pumping sy~te
s are employed instead
diffusion pump and recently turbo molecular and cryogenic pump
of diffusion pumps.
Substrate holder and heater
a very simple holding
For stationary flat substrates, the substrate holder has
mum at the point directly
arrangement. In this case, the thickness of the deposit is maxi
move away from it. This
above the source and the thickness decreases gradually as we
gement which moves the
problem can be overcome by connecting a stepper motor arran
evenly on all parts of
substrate during deposition so as to make the vapor flux to reach
the substrate. Hence, a uniform thickness can be obtained.
49
Introduction to Thin Film s
 _ .4 Pulsed laser deposition (PLD)/Laser ablation/Laser induced evaporation
42
Pulsed laser deposition technique was first used by Smith and Turner in l 965
deposit thin films in _a vacuu'.n ch~mber u~ing a puised ~uby laser. This is one of the nio:~
suitable techniques for growmg high quality mate, tals like ZnO, ln20 3 , MgO, Tio C
. . dd .. 2, dO
Al o and Ga-Ge-Te because 1t has a high- spee eposJtton process under a hi gh . '
2 3. 4- 1o Partial
pressure of oxygen .
Principle and working
This technique involves the vaporization of the coating material by irradiatin h
taroet with a laser beam and the condensation of the ablated species onto the sub gt t e
o . . s rate
The wavelength of the laser . to be used 1s selected on the basts of the abso . ·
rpt1on
characteristics of the matenal to be evaporated. Pulsed laser beams are often emplo
in order to get high power density. Pulse width, pulse intensity and repetition rate yed
selected depending on the applications concerned. The pulsed lasers are also used a~e
plasma-assisted reactive evaporation processes. The apparatus for the pulsed 1 ' in
deposition is shown in the Fig. 4.5. The apparatus consists of the following compone~:~r
• substrate holder
• crucible
• evacuated chamber
• vacuum pump
• laser source ..
• laser focusing system

Laser source
,, - - - - - - - Substrate holder
~
_______.+ - - - - - Substrate
"
I
"I
I - Deposit
I I
• , ◄ - - - - - - - - - - Evaporated species
l I
••••• I I
Focusing - l I

system
•••••• I I -Vacuum chamber
...-7 ••. I
... ··•.... ~ , ...... - - - - - - - - Source material
Laser beam - - - ... ····•! ·~ .,,,..,;
___:~r_~
◄ ------- -crucible

Vacuum pumps

Fig. 4.5 Pulsed laser deposition unit

Introduction to Thin Films

Ad-vantages
• High purity films of alloys and
. compounds can be deposited
• The macro pa1t1cle density can b d ·
e ecreased by lowerin th I
• High quality of the d .. . g e aser power Ieve I.
epos1ted films is achiev 'u b h . .
species. c Yt e production of high energy
• Good stoichiometric rehtio 11 b
achieved. c etween source material and the fi Im can be

• Uniform deposition on large ar b . .

. . ea su sttate can be achieved by making the laser
beam to scan a rotatmg target.
Limitations
• As the laser is located outsid th
. e e vacuum chamber, a complex transmitting and
focusmg system is required.
• Wavelength of laser should be compat·b1 · h ·h· · · · s of
1 e w1t t e absorpt10n charactenst1c
the material to be evap~rated.
• Energy conversion efficiency is low - usually around 1 to 2 %11 .
• The size of the deposited film is small as the laser impact spot is small.
Applications
This process has been extensively used for growing semiconductor epitaxial layers,
layers used for band-gap engineering, high critical temperature (Tc) super conducting
films and dielectric films.
4.2.5 Flash evaporation
The schematic diagram of a flash evaporation system is shown in Fig. 4.6. In this
variant of thermal evaporation, only a small amount o( the source material which is in
powder form is fed at a time to the hot boat. Since only a small amount of the source
material is fed at a time, instantaneous evaporation of the entire source material takes
place without leaving any residue in the boat. Generally, the boat is made up of tungsten,
molybdenum or tantalum which is kept at very high temperature requited for the
evaporation of the concerned source material. The source material is fe? to the hot boat
from the reservoir through a chute. The feeding rate and time interval between two
successive feeds are controlled by means of an AC vibrator . .

Introduction to Thin Films 51

 /\C vihrn lnr
r.==========o==::::=:::=:======::=:=,i _Su hstra tc ho Icier
I
I -Suh stratc
I
-!, -1'
I - De pos it
I
I
I
I

I
I f
I f
I f
I f
I f
I
Feed chute - - - - _ ,,. - I lot boat

~= =~ =:::;:,,=~ === ::::: !..J - 1lcalc r

Vacuu m pump s

Fig. 4.6 Exp erim enta l setu p for flash evap orat ion

The main advanta ge of the flash evap orat ion is that

the conden sed deposit onto the
substrate retains the com posi tion of the eva pora
nt with out any deviation in the
prop01tions as all the material fed is evap orat ed at
the sam e time. This method results in
films with con stan t com posi tion .
·
Flash evap orat ion tech niqu e is suit able for coa
ting thin films of materials having
tend ency to dec omp ose or diss ocia te duri ng evap
orat ion. Thi n films of some oxides of
metals and allo ys like Ce0 2, In203, InP and
BaT i03 can be deposited using this
tech niqu e 12- 15 •
4.2. 6 Rea ctiv e eva por atio n pro cess
The prob lem s that aris e in the dire ct ther mal
evap orat ion process, due to the
fragm enta tion of the vap oriz ed com pou nds , are ove
rcom e in reactive evaporation. In this
techniqu e, the mat eria l to be dep osit ed is evap orat
ed in the presence of a reactive gas as
sho wn in Fig. 4.7 and the com pou nd is form ed by
reac tion of the evaporated species with
the mol ecu les of the reac tive gas.
A maj or limi tation of this reac tive eva pora tion tech
niqu e is its lower depo sition rate.
Thi s limi tatio n can be ove rcom e by intr odu cing
plas ma in the process. This variant of
ther mal eva pora tion whi ch invo lves plas ma in
the reac tion kinetics to improve the
dep osit ion rate is kno wn as acti vate d reac tive eva
pora tion (AR E) technique.

62
Intr odu ctio n to Thi n Film s
 Vacuum chamber- - ->
,, , , ,. - -- - Substr ate holder
,.:'
Substrate - - - . ,_ - I
- >l
,
I
A .... l'",

' ,_--
A
I
I I - -Oepo sit
''
I
I I
Reacti ve gas inlet -
- - > I
I
I
I
I

'' <--- -
I
I
-- >-
P-vaporated spec ies
I
Source material - - - - -->- - , I
I
I
I
' ' I

Resisti ve heater - - -- --- ' I '

I
' ~ ' 'I I
------
"""""-
~ ...., .. . ·, . ~" ·· ~:1~,_,. I
- Crucible
I I
[vacuum pumps l
Fig. 4. 7 Reactive evaporation
the high quality
Reactive evaporation technique is very much useful ·in fabricating
thin films of several materials like CdO, Fe2 Q3, Moo 3 and zno16-19_
Single and-multi sour ce evaporation
component film.
Generally, a single source is evaporated to obtain a desired single
component system. In
Sometimes, it is necessary to get a coating which may be a multi
rator and this variant is
those cases, more than one source are placed in the crucible evapo
called multisource evaporation technique.
4.2. 7 Mole cular beam epita xy (MBE)
growth via the
Molecular beam epitaxy (MBE) is a technique for epitaxial
s on the surface of a
interaction of one or several molecular or atomic beams that occur
n of the conventional
heated crystalline substrate. It is technologically an improved versio
tages over the other
thennal evaporation technique. MBE offers additional advan
m (UHV) environment
deposition techniques, particularly in terms of ultra high vacuu
the late 1960s at Bell
that alJows growth of extremely pure epitaxial layers. Invented in
is widely used in the
Telephone Laboratories, by J. R. Arthur and Alfred Y. Cho, MBE
cellular phones and
manufacture of semiconductor devices, including transistors for
materials like ZnO and
WiFi. This technique is very promising one for fabricating some
TiO220, 21 •
source material by
The operating principle behind MBE involves vaporizing the
the substrate to form
heating it to a high temperature and directing the vapor towards
ss by which vapor
epitaxial layer by a process called "effusion". Effusion is a proce
ibrium of the vapor
molecules can escape the vapor container without disturbing the equil
;:.?der suitable conditions.
53
Introduction to Thin Film s
 Consider a container fill ed with gas mol ecul es in equi
librium . If a hole , small
the mean free path of the vapor molecules 1.s mad e m .
the wall of the container mol
er than
. . .
w~th the right velocity compon ents will effu se out of the contamer through' theecule s
hole forming a mol ecular beam (after whic . .
' . . h MB E 1s named). As the hole is suffi c•srna11
small , only a small f-ra ct,on of. the gas molecule s effu iently
ses out of the container and t
. 'bl e exte
equilibrium state is disturbed only to a neg I1g1 he
nt.
An impottant feature of MBE is that it takes plac
e in UHV and hence ·n .
1 -situ
diagnostic techniques like reflected high-energy elec
tron diffraction (RH EED)
energy electron diffraction (LEED) , auger electron spec ' 1ow.
troscopy (AES) and modulated
beam mass spectrometry (MBMS) can be employed
to monitor the growth, durin g the
deposition. Of these, RHEED is the most widely used
technique. The pattern of inten sity
variations of the RHEED signal can provide an asse
ssment of the periodic surface
changes occun-ed during the growth of each monolay
er. Thus, growth can be controlled
precisely at the monolayer level.
Con stru ctio n and wor king of MB E
The MBE apparatus consists of three chambers which
include introduction, analysis
and growth chambers. The block diagram of MB E is show
n in Fig. 4.8.

Sample heating
and rotation
/: ··················· E - gun (RHEED)
l
Beam flow gauge -····-····.......
..J, / .......... ............ Chamber cooled by
/ liquid N2
Load door ··············..
\- Effusion cells

Windows
Shutter
' · ····· ··· ···· ·· ··· ·

···················· ······ Fluorescent scree n

L ........... ..... Sample holder

Fig. 4.8 Block diagram of Molecular Beam Epita xy

(MB E)

54
Intr odu ctio n to Thin Film s
Introduction chamber
In the introduction chamber the sub t.I t
b . _ ' s a es are loaded through the front opening
flange. The su sttates are fixed on a heater bl . .
. . · assem Y using silver paste and they can be
cleaned by degassmg it up to a temperature of soooc A~ I .
. . . , . - ,ter oadtng the substrates, the
chamber is I ap1dly pumped from atmospheric pressure down to ~ I o -9 torr . h h
. wit t e use of
sorption and
. 1011 pumps. The heater assembly hold'ing th e su bstrate 1•s then trans,erre
c: d to
the analysis and/or growth chamber using the transfer rods.
Analysis chamber
This c~amber is equipped with a substrate heater which can heat the substrates up to
gQ0°C. Thts chamber serves the following two purposes:
• cleaning the substrates by ion etching and
• surface characterization of substrates and grown films using X-ray photoelectron
spectroscopy.
The XPS setup is housed in this chamber to determin·e (i) the level of cleanliness of
the substrate and (ii) chemical state and composition of the substrate and grown films.
Growth chamber
The growth chamber is the most important part of the MBE system. In this chamber,
all the controlling elements such as (i) beam sources with their individual shutters, (ii) a
main shutter, (iii) a manipulator with substrate heater and rotor, (iv) pressure control
system, etc., are located. The growth chamber can be evacuated to pressures lower than
10-9 torr by using a combination of turbo-molecular pump and ion pump with a fully
cryoshrouded titanium sublimation pump. A helium closed-loop cryopump is also
mounted for supplementary pumping.
Effusion cells
Effusion cells are also key components of an MBE system. They provide excellent
flux stability and uniformity as well as material purity. The flux of atoms/molecules and
hence the deposition rate can be controlled by controlling the temperature of the
"effusion cell" (evaporation source). Quartz crystal monitor is mounted near the
substrate to monitor the deposition rate. Alternatively deposition rate can also be
monitored by the flux gauge. Each effusion cell includes an oven (filament +
thermocouple) and a fully degassed thick pyrolytic boron nitride (PBN) crucible
surrounded by adequate tantalum shielding for use in the proximity of a cryoshroud. A
Photographic image of MBE setup is shown in Fig. 4.9

Introduction to Thin Films 55

 . . of Molecular Beam Epitaxy (MBE)
. 4 9 Photographic unage
F 1g. .

Advantages . lly less than 3000 nm per hour) which allows th

• Low deposition rate (typ1ca e
fitt ms tO grow epitaxially
. ·t f grown films due to the absence of carrier gases a
· l t hievable pun Y O s
• Htg 1es ac . f ltra high vacuum environment
well as the presence o u
• Low growth temperature
• E cellent interface and surface morphology
x . · b t hetero-J·unctions and complex heterostructures with many
• Abihty to grow a rup
different layers · ·'i-"~
• Scope for in-situ characterization techniques
• Scope for in-~itu deposition of metal seeds
• Precisely controllable thermal evaporation
Disadvantages
• Difficult and costly tq implement and maintain.
• Lack of run-to-run reproducibility
• Difficult to reach su~ciently high temperatures
4.2.8 Sputter deposition process
Principle
Sputtering deposition involves the ejection of atoms/molecules from the target by the
bombardment of highly energetic positive ions and the subsequent condensation of
ejected species onto the substrate. The mechanical knocking out of the atoms is actually
caused by the momentum transfer between the bombarding ions and the atoms of the
target. The number of atoms/molecules ejected per impinging ion is known as the
sputtering yield or sputtering rate. The sputtering yield depends on the nature, energy

Introduction to Thin:Films 56
and angle of incidence of the
6ornbarding ton and
temperature of the target. 1s generally independent of the

4.2.9 DC sputtering
Description and working details
The schematic representation of DC . ·. . .
consists of target (source f .a sputterin
. g unit I
s shown .in F'· 1g. 4. IO . ~rh e unit.
o coattng material)
I amber vacuum pun • · , substr t b h 11
c, ' 1ps, 111g11 0 C voltage source, etc. a e, su strate o ( er, vacuum
The target is mounted opposite to the substrate in a vacuum chamber which is
evacuated to a base pressure wh' h · · . 6
1c IS typically in the range of I 0- to I 0- 10 torr
(1 torr=l mm Hg). ~he chamber is then filled with an inert gas, generally Argon (Ar),
with a pressure rangmg from 1 - 100 m torr, to establish a glow discharge . An inert gas
is used to avoid any chemical reaction takes place at the target and the substrate .
By suitably connecting the terminals of the voltage source, the target is made the
cathode and substrate, the anode. A high DC voltage in the range of 1 kV to 5 kV is
applied between the target and the substrate to create plasma in the space between the
electrodes. The plasma consists of ionized gases, unionized gas molecules and electrons.
The high energy Ar+ ions accelerated towards the target under the influence of the
applied field bombard the target and due to the momentum tra~sfer between the
energetic· ions and the target atoms, the target atoms get dislodged and then they
condense onto the substrate surface to form the thin film. When strike the target, the
energetic positive ions cause the emission of secondary electrons along with the ejection
of target atoms. These secondary electrons are essential for sustaining the glow
discharge.

Inert gas inlet-

Power
supply

Sputtered atoms- - - -

+ _- - -Vacuum chamber

llllTI)S

. 4.10 Schemati·c diagram

F 1g.
. of' DC spu tt en·ng technique
'
57
Introduction to Thin Films
 The phenomenon of the creation of plasma in a gas at a low press Ure due
.· . . .
elect1 tc field mamtamed between the [Link] ts called the. glow discharge and hto an
. ence
t111s DC sputtering is also called as the glow discharge sputtering.
Process parameters
The most crucial process parameters that control the growth and propert·ies of th
films in the sputtering technique are: e

• Target voltage
• Pressure and flow rate of the gas
• Substrate temperature
The target voltage determines the energy of the secondary electrons ejected frorn th
target which are responsible for sustaining the glow discharge inside the chamber. Th:
pressure inside the chamber detennines the mean free path and hence the collision
frequency of the electrons. The substrate temperature generally determines the packing
density and surface properties of the deposited fi1m.
The importan~ features_of the sputtering process are given below:
• The impinging ions are generally non-reactive.
• The sputtered .species are predominantly neutral.
• The sputtering yield depends on the energy and mass of the impinging ions.
• For small oblique angles of incidence, the sputtering yield is proportional to
I/cos 0.
Advantages of sputtering techniqu e
• The most important advantage of the sputtering process is its universality. As the
atoms of the coating material are dislodged from the target, simply by a physical
momentum exchange process, any material can be a coating candidate.
• Films of every element in the periodic table can be prepared by sputtering.
• Alloy films can be coated by employing several different targets simultaneously.
It is also possible to use a single target which is a mosaic of several materials.
• CompositionaIIy multi-layered coatings can be obtained by operating several
different material targets sequentially.
• The microstructure and microchemistry of the films can be tailored to the
requirements by providing ion bombardment on the growing film during the
deposition process by suitably biasing the substrates.

Introduction to Thin Films 58

 • Gases like 0 2, N2 H2s et
' ' c. can be introduced .
achieve reactive sputtering. mto the chamber in order to

• Thin films with high purity and ') ·r , .

I c, ect surfa ce fini sh can be obtai ned
• The substrate temperature cac n bc suitab. ' ·
ly varied . , ·, 1 f I
•
the ,·equ · over ct w1ue range o va ues
dependmg on trements.
Limitations
• High initial cost.
• Requirement of high vacuum.
• DC sputtering method cannot be use d 1or
c .
coat111g non-conducting materials as it
would lead to accumulation of cI1arge at the target surface. This difficulty can be
overcome by employing RF voltage.
Applications
cting
Sputter deposition technique can be used in the fabrication of transparent condu
capacitors,
electrodes, reflective and anti reflective coatings, thin ·film resistors and
sed memory
luminescent films for display devices, piezo-electric layers, optically addres
devices, etc.
nism,
Depending on the various factors involved in the sputtering deposition mecha
elaborated
this method can be classified into different types. Some of the varients are
below viz. reactive sputtering, RF sputtering and magnetron sputtering.
4.2.10 Reactive sputtering
any
In the normal sputtering processes, only inert gases are used, to avoid
oxygen or
unintentional chemical reactions in the preparation of thin films. But, when
the target
nitrogen is used, the ionized species formed from these gases can react with
such as
material to form oxide or nitride films. For example, nitride and oxide films22 26
ring - .
Zr02, ZnO, SiO 2-TiO2 , AIN, SnO2 etc., can be prepared· using reactive sputte
Advantages
ut the use
• Reactive sputtering can be used to deposit insulating compounds witho
of RF potential.
other
• Thin films of nitrides and borides which cannot be easily fabricated by
and
techniques can be made by the reactive sputtering technique using nitrogen
born-hydride.
4.2.11 RF sputtering
When a
RF sputtering method is widely used to deposit non-conducting materials.
electrodes as
high frequency ac field (100 kHz to a few MHz) is applied bet\\.:een the
59
Introduction to Thin Films
 shown in Fig. 4.11 , there will be a sustained glow discharge due to the ioni .
. zat, 011
gases by the oscillating electrons, unlike in the case of de sputtering where the io . . of
[Link],on
takes place due to the secondary electrons.
This technique is particularly useful for the deposition of material s like MgB 2, Ceo
2
ITO and Zn0 27 -30 . '

Substrate
Vacuum
pumps
Power
supply
Target

Sputtered
atoms
~----

Fig. 4.11 RF sputtering deposition unit

4.2.12 Magnetron sputtering

In this arrangement, a transverse magnetic field is applied perpendicular to the
electric field in order to increase the fonization efficiency of electrons. The presence of
electric and magnetic fields causes the electrons to travel in a helical path which leads to
an increase in the path length of the electrons. Therefore, the probability of interaction of
the electrons with the gas increases resulting in higher ionization. Usua1ly, the applied
magnetic field is only in the range of a few hundred gauss and hence it affects only the
plasma electrons but not the positive ions. Several oxides and borides thin films like
LiCo02, Ti02, MnO, and ZrB2 canbe fabricated using this technique 31 -34 _
Advantage
• Deposition rate in magnetron sputtering is relatively high compared with that of
non-magneton sputtering process.
4.3 Chemical deposition methods
Thin film deposition methods that use chemically vaporized solids, evaporating
liquids and gases are cJassified as chemical deposition techniques.

Introduction to Thin Films 60

4.3.1 Chem ica l Vapor Deposition (CVD)

principle

In this process, a thin so lid fi lm is deposited by mea ns of a chemical reaction of the

gaseous reactants, occurring on the surface of th e hot substrate or in the vicinity of the
substrate surface. The chemical reaction that takes place can be represented by the
equation
(4 .2)
where AB(g) is a gaseous reactant (compound), A (s) is a resultant solid material and B eg) is
a gaseous reaction product. A typical example for this thermal decom position process is
(4 .3)

Description and working

The CVD unit generally consists of five main components viz. (i) the reaction gas
distribution system, (ii) chamber in which the reaction takes place, (iii) the exhaust and
reactant recycle system, (iv) vacuum pumps with pressure controller and (v) substrate
heating and monitoring system.
The schematic diagram of a CVD system is shown in Fig. 4.12. The chamber is a
horizontal quartz tube through which the reaction gas mixture is allowed to pass after
pressure regulation. The substrates are mounted inside the chamber in such a manner that
the reactant gas passes over the coating surface. The substrates are kept at elevated
temperatures, generally in the range of 300°C to 900°C, by means of lamp heating,
resistive heating or inductive heating. When the reactant gases react, thermal
decomposition takes place resulting in the deposition of thin films onto the substrate.
The rate of deposition mainly depends on the substrate temperature and pressure inside
the reactor. If the reactants are in the gaseous state at room temperature, they are
admitted into the chamber from the gas bottles using the flow control valves. ln the case
of reactants which are in liquid or solid states at room temperature, their vapors are fed
into the reaction chamber by heating them above the boiling or sublimation points,
respectively.

Introduction to Thin Films 61

 ..
··------ Reactor
I
>
Substrates
Flow meter ' -~ -- -Substrate holder
~~~-

Flow control
valve~
--- ,) t t t __ .__.___ 1-:lcc trical hea ter
Vacuum
Pump s
and
press ure
Other reactor~--------.,- control
and dopants «------- Gas bottle

Fig. 4.12 Chemical Vapor Deposition system

Imp orta nt var ian ts of CVD

• Atmospheric pressure chemical vapor deposition
(APCVD)
• Low pressure chemical vapor deposition (LP
CVD)
• Plasma enhanced chemical vapor deposition
(PECVD)
• Hot wire chemical vapor deposition (HWCV
- D)
The choice of the CVD system for the preparat
ion of thin films depends on several
factors which include (i) the reactant materials
used, (ii) purity of the coating requ ired,
(iii) type , size and shape of the substrate and (iv)
cost allowed.
4.3.2 Atmospheric Pressure Chemical Vap
or Dep osition (APCVD)
This method is suitable for coating dielectric
thin films and polycrystalline layers.
The reactors based on APCVD result in less unif
ormity of the deposited thin films and
cause comparatively higher wastage of the reac
tant materials. TiN, V2O5 and ZnO thjn
films can be produced by atmospheric pressure
chemical vapor deposition (APCVD)35- 37_
4.3.3 Low Pressure Chemical Vapor Deposit
ion (LPCVD)
The LPCVD system operates at reduced pressure
s, approximately in the rang~e ,~f
0.25-2.0 torr. LPCVD is very much useful for
fabricating thin films like ZnO, Si, etc-' 3,-' ·
4.3.4 Plasma Enhanced Chemical Vapor Dep
osition (PECVD)
In this variant, plasma is used as a tool for prov
iding energy to the reacting gases.
The reactor is usually cylindrical in shape, whi
ch is made up of stainless steel. Two
parallel plates are mounted as shown in the Fig.
4.13 which act as electrodes. Sub st rates
are arranged at the bottom electrode and an
RF signal is applied between the two
electrodes to create a glow disc harge in betw
een them. The plasma causes the
dissociation of gases and then the rad icals are dep
osited onto the substrate s to form th e
required thin film s.

Introduction to Thi n Film s

62
Adsorption
In the first step, the cations present in th e precurso r so lution.
d bd
•face of the substrate. Thus, the He lmholtz 1, ·t .·, 1 are a sor e on the
slit .. . . e ec t 1c <. ouble layer is formed h. h .
osed of pos1t1vely charged tnner layer , _..st. of the cations and w 1c· 1s
cof11 P . . · consi ing
.
·aed outer layer cons1stmg of cou nter io11s of ti1e cations. negatively
cIHllo
Rinsing (I)
In this step, the excess adsorbed ions arc rinsed away.

Reaction
· • precurso r
In this step, reaction takes . place between adsorbed cat·ions an d anionic
.
resulting a so ltd layer of the desired material on the substrate.
Rinsing (II)
In this step, the unreacted species and the reaction by-products are removed.
Improved SILAR technique
In the case of CdS film deposition, in order to achieve good stoichiometry, a fresh
anionic solution was used after a particular number of cycles of immersion by the
authors' team and found that it resulted expected output. This variant i~ named as
improved SILAR technique and this improved version of SILAR has been successfully
employed for the deposition of indium doped CdS films also 72.
4.3.9 Spray pyrolysis technique
Spray pyrolysis is one of the widely used chemical deposition techniques for the
fabrication of thin films. In this technique, the precursor solution sprayed onto a hot
substrate decomposes pyrolytically to yield thin films. The st~rting solution is generally
an aqueous solution of soluble salts which contain the atoms of the compound to be
deposited. The substrate is maintained at a high temperature, usually in the range of 300-
500 °C, which facilitates the pyrolytic decomposition of the sprayed droplets reaching
the surface of the substrate and the evaporation of the unwanted by-products and the
excess solvent.
Deposition parameters
The deposition parameters that determ ine the characteristics of the obtained films are
as follows:
• concentration of precursor solution
• type of solvent
• substrate temperature (Ts)

lntrod · 71
uction to Thin Films
 • type of substrate
• nozzle to substrate distance (NSD)
• dimension of the nozzle
• spray rate
• deposition time
• time interval between two successive sprays
• nature and percentage of dopant etc.
spray technique
Experimental arrangement for conventional
k diagram of the con vention al spray pyro lysis setup is .shown . in Fig.4_ 21 · The
A bloc I . . r,
. system are spray gun, so utio.n reservoir, earner gas cont aine
mam components of the
expenmental setup F'and a photogra ph'IC
substrate heater and holder, enclosure, etc.. The h .
. p are s own m 1g. 4.22 and 4_ 23 ,
image of the conventional spray pyrolysis setu
respectively.
Solution reservoir

Solution filter
Compressed carrier gas
(Oxygen, Nitrogen or air)

Spray nozzle Solution flow

motion control control
Dust filter moisture / oil Exhaust
vapor separator
.AI
I

Gas pressure control

and gas flow meter

·- - - - - - - - - • Spray nozzle

Temperature controller
- - - Deposit
- - - Substrate

Heater supply - - - Thermally insulated

chamber
,
,,
Substrate heater ___ , ' '

p
Fig. 4.21 Block diagram of spray pyrolysis setu

Introduction to Thin Films

-
72
spraY gun
The spray gun is a co-axial assembl f .
. ·1 . . y o two thick walled I
· 1ner one is a cap, lai y tube. The inlet of ti . g ass tubes, of which he
• 1e capill ary tub · '
11
tube is c e ,s conne cted to the soluti on
servoir and that of the outer . onnected to the co , . .
re _ . rnpressed a,r container. The
,tlet of the cap, llary tube 1s fused with ti .
ot , le tip (nozzle) of th
facilitates the Ventury effect to take place at th e nozzle The atom e outer tube such that it
izat' f h
solution into a spray of fine dropl ets is cause d b
11
·. ~ ion
gas
°to
t e precursor
th h
. ya owing the earne r
rate can be varied b I . pass roug
the outer cylmder. The spray Y regu atmg the flow of the carrier a
· . g s.
The spray gun is fitted above the substrates such th t th . I of the
. . a e ang e betwe en the axis
gun and the substtate surface 1s 45°.
Solution reservoir and carrier gas container
d hose outlet 1s.
'th.·
The solution reservoir is a burette or a beaker fitted
.
stan w Wt ~
le tube. The height
connected to the [Link] ~be of the spray gun by means of a flexib
ing process and
of the precursor solution m the burette plays a vital role in the spray
following adverse
therefore it should be adjusted to an optimum level to avoid the
effects:
the optimum
• in intennittent spray process, if the solution height is more than
g the spray
level, it will cause the fall of liquid drops on the substrates durin
interval. .
tion of air
• if the height is less than the op~imum level, it may cause the forma 73
bubbles in the capillary tube which would disturb the-atomization
•

r and the other is

One end of the carrier gas container is connected to air compresso
gauges and a control
connected to the outer tube of the gun through an air filter, pressure
oil contaminants and
valve (regulator) as shown in the Fig. 4.22. The air filter filters the
case of Sn02 films)
dust particles, if any, in the carrier gas. The carrier gas may (as in the
ding on the case
or may not (as for CdS films) be involved in the pyrolytic reaction depen
as it may be.

73
lntrod . ·
uction to Thin Film s
 i _~ - - - - Solution reservoir
Exhaust
r - - - Pressure gm,gc
I
,J, r - - ·Control valve
Thcrmocm1ple
Tcmpcraturc
'
' - ,Compressed gas
controller
\
I
Disp lay 1
panel
--- -- Substrate

Fig. 4.22 Spray pyrolysis setup

Substrate heater and holder
An electrical he'fiter is generaJly fabricated ·with the use of Kanthol coils, the
temperature of which can go up to a maximum of 700 °C. A high quality stainless steel
plate is placed on the heater, which can acts as the substrate holder. A temperature
controller., comprising a chromel-a]umel thermocouple and a digital display is employed
to monitor and maintain the temperature of the substrate to an accuracy of± 5 °C.
Enclosure
The entire spray system is completely housed in a glass walled reaction chamber.
There is an exhaust system at the top of the chamber which facilitates the removal of
volatile by-products of the pyrolytic reaction. To minimize the heat lost to the
surroundings, proper thermal insulation is provided in the chamber.

Fig. 4.23. Photographic image of conventional spray pyrolysis setup

Introduction to Thin Films 74

 aoes of spray pyrolysis technique
AdV}lll t t, • •

Spray pyrolysis technique has several advantages over other meth

ods.
, It is a simple and inexpensive method

• It has the abi Iity to prncluce uniform , strongly adherent,

pin-hole free large area
coatings.
• There is no need for vacuum in this process.
• The amount of doping can be easily controlled.
, This technique has the ability to deposit multi-component alloy
s.
, By appropriately changing the process parameters, films with
a wide range of
characteristics suitable for different applications can be prepared.
Applications
This method is used to deposit solar cell layers, reflective and
anti-reflective coatings,
transparent conducting layers, multi-component alloy coatings
and magnetic layers of
materials such as Zn 0, Ce02,-CdO, CuS, ln203, InS, La Th0
2 7 , MgFe20 4 , Ni 0 , Ti 0 2 ,
74-84
WO 3, etC •
An inexpensive spray pyrolysis technique using perfume atom
V Spray pyrolysis technique can be further simplified by repla
izer
cing the spray gun
assembly, solution reservoir, compressor, compressed gas conta
iner, etc. by a simple
perfume atomizer (generally used in cosmetics). A block diagr
am of simplified spray
technique is shown in Fig. 4.24

Substrate
Spray nozzle
Thermocouple

Temperatur[Link]t::====::::::-.....
controller ...• ~ - n:- -P-er-n-1111-e---,
~~~~~"C'C'I
atomizer

Heater
supply
Substrate
holder

Substrate
heater

Fig. 4.24 Block diagram of simplified spray pyrolysis setup.

Introduction to Thin Films 75

 1 ti··
11 11 s simplified spray technique, the precur sor solut ·ion ·13 sprayed ma nual! ,
l b . - . , I
10 t su strates ustng the perfume atomi ze r in stea d of convent'.onc~ s~ray ~un.
Y onto
Sawada
al. 85 introduced this spray procedure for growing good quality ind ium
tin86 oxide (IT •t
ft !ms at relatively low temperatures (325 - J40°C ). Fukano an . 0 t h'
dM O)
·o iro have further
- d ti I· •
Pl ove 1at t 11s techmque can be success u Y usc<l for pro<luc111 g low-cost
1· 11 a 1
· ' nc go 0d
quality fluorine doped tin oxide (FTO) film s.
. . r th e conve nt ion al spray method
Ad vanta ges of simplified spray techmqu e ove
.. - t' al spray techn ique, thi s simplified ,
1n ·add1t1on to the advantages of convc n 10n, . . spray
I ti •
que usmg perfume atomizer offers sevcra O , et 'advantages. Bes ides being low in
.
the perfume atomizer avoids the nee d of a spt
·ay gun and a separate so lution rese cost, .
. . · .
nts which are low in cost but hi gh • · rvo1r.
Tl11s technique requires only s1111ple equipm e ' .
• • .c
throuohput which are the prerequ1s1tes ,or , e
ti comm ercial produ ction of economic s 11n
° ' • I'fi d ray technique is show n in Fig. 4.25 oar
cells 86 . The experimental setup of s1mp I te sp
·

Chrome ! - Alumel
th(:nnocouole

Substrates

Temperature controller

Fig. 4.25Simplified spray pyrolysis setup with perfume atomi zer

Atomization is based on hydraulic pressure and hence there is no need

for the
compressor and the carrie r gas. Carrier gas used in conventional spray metho
d tends to
dry the sprayed microparticl es of the solution before they arrive at the
substrate surface .
This leads to an insufficient wettability between the microparticles and the
previously
deposited layers, which results in film s with low packin g density as we ll as large
number
of pinholes. But the perfume atomi zer increases the wettability betwe
en sprayed
Introduction to Thin Films 76
 of
. . article s and the previously deposited layers and thereby enhances the quality
n11c1DP . . • • ed
~, s The intermittent sptaymg process enables the substrate to attain the requir
the f1 n1 . . . ..
the sta,t of the spray. Perfume atomi zer facilitates fine
.
,pera. wre befote . next
11 ts which
te . tion of the precur sor solut,on and avoid s deposition of large drople '
w1111za
a kes place in conventional spray pyroly sis depositions. For the depos ition of TCO
often ta . . .
ers using conve ntiona l spray pyroly sis tech111 que, generally the substrate temperature
laY . kept at 400 oc 01. mote . . fied spray [Link] usmg
· th'ts s1mpl1
. s1-9o. But 111 . perfume
(Ts) IS •
. er a comparatively lesser Ts (about 360 °C) can be employed.
atotlllZ ,
tory to
This simplified technique has been successfully employed in the authors' labora
fabricate the following thin film materials:
• Fluorine doped tin oxide films,
• Fluorine doped zinc oxide films,
• Antimony doped tin oxide films,
• Doubly doped (antimony + fluorine) tin oxide films,
• SnOrZnO films,
• Aluminium doped zinc oxide films and
of these
• Doubly doped (Mg+F, Sn+F) ZnO films. The analyses of the properties
of
films proved that the qualities of the films are very much comparable with that
9 101
their conventional spray counterparts ~- .
a team
Employing this simplified spray pyrolysis technique using perfume atomizer,
(TFTs)
of Gennan researchers have recently fabricated thin film transistors
successful Iy102 .
4.3.10 Sol- gel spin coating technique
ely
Spin coating is a simple technique for rapid deposition of thin films onto relativ
103 several
flat substrates. This method was first introduced by Emslie et al. and
10 one of the
simplifications were made by Meyerhofer et al. 4. The sol-gel process is
BiFeO3,
most practical solution-deposition methods of preparing oxide thin films like
In203, TiO2, ZrO 2, and Zno -iw_In this process, the substrate to be covere
105 d is fixed on
the coating
a rotatable stage (often using vacuum to clamp the substrate in place) and
solution · ct· rated
is ispensed onto the surface of the substrate. Then the substrate is accele
· um rotatio
up to its final , optim ·
· d time.
· n speed for a desire · · g causes
· of spmnm
The action

lntrod . 77
Uction to Thin Films
5.4 Structura l properties
Th e study on the stru ctural properties
of thin film s is very important , as the
act ually determines mo st of the oth structure
er properties of thin films. The cry
stal structures,
l8ttice pa rameters, crystallite [Link], deg
ree of cry stallinity and defects in the
th in fi lms can be studied usi ng X-r crystalline
ay diffractometry . In thi s section ,
the work ing
principl e. descriptio n and other exp
erimental details of X-ray diffra ctro
metry are
elaborated.
5.4 .1 X-R ay Diffractometry (XRD)
X-ray diffractometry (XRD) is a pow
erful tool use d for the stru_ctura_!_stud
materi als . It is an impo11ant technique ies of re
suitable for the characterization of
since it provid es a broad range of inf thin films
ormation such as ~omposition, crystal '
lattice constants , crystallite size, cr)'stal structure
defects, etc., of the films. '
Pri nci ple of X-ray powder diffra
ction
When a beam of ~-ray is incident on
a crystal, it is diffracted by the electro
of the atoms of the [Link] as shown in n clouds
the Fig. 5.6.

e
X-ray diffraction becomes possible due
to the fact that crystalline solids act
dimensi onal gratings for X-rays , since as three
the wavelength of X-rays is compar
interplanar spacings of crystal lattice able with the
. X-ray diffraction occurs in crystallin
to the con structive interference that tak e samples due
es place after coordinated reflection
planes. The interaction of incident X-r at the lattice
ays with crystalline sample produces
interference when the cond itions sat constructive
isfy Bragg 's law (2d sin0=nl) . By
sca nning the
specimen through a range of 20 ang
les , the diffracted X- rays for all pos
d"irect,on
· s Of · sible diffrac ti~n
·
the lattice are obtamed. The diffracte
d X-rays are processed and counte d tor
Int rod uction to Th in Fil m s
100
 . ·on of diffraction peaks to d-spacings. Typically the identi ftcation of the
, conve1st . .·
the . is achieved by compattng the" observed X-ray d1ffrac .' . .
t1on profile with the
111 8
terial • cerence pattern
· · avai·1abl e .tn JCPD · Committee
·
dard ie 11 S (Joint on Powder Diffraction
stall ·ds) data.
s1andat .
ntation details
1115
trun1c
X-ray diffractometer system consists of three basic components: i) X-ray source ,
1
At le holder and iii) X-ray detector. Monochromatic X-rays required for diffraction
··)
11 satnP .
_ obtained after filtenng the X-rays generated by the X-ray
tube using foils or crystal
ate hromators. The most common target used in the X-ray tube for X-ray diffraction
monoc .
. er and the wavelength of the CuKa radiation is 1.5418 A. The monochromatic X-
1s copp '
e collimated and directed onto the sample placed in the sample holder. By suitable
rays ar
ents the sample is made to rotate in the path of the collimated X-ray beam
at1'angel11 '
through an angle 0 while the detector rotates through an angle 20 and the detecto
r
collects the diffracted X-rays as shown in Fig. 5.7. The apparatus used to rotate the
sample and maintain the angle is called goniometer ..For typical powder samples, data
is
collected at 20 from ~5° to 100°. Fig. 5.8 shows the photographic image of the X-ray
diffractometer.

Receiving slit
------- ...,I....
I '
, I
I
'
\
, ; Diverging slit ' ,1 ''
I
I ., ...._. ~--- Detector
X-ray source- - - ., #<:::...,., \

, I \
\
I
I
I l
I
Sample --\- ---- - -• f===== :;=~ 20 I
\ I
\ ..., ' I
\
\
\
''
' ... ..,
I
I
I

'' I

,, ,,
I
''
' ... ,,. ,,.

Fig.-5.7 Principle of X-ray diffractometer

lntrod •
uction to Thin Films
 Fig. 5.8 Photographic image of X-ray diffractometer

Chemical analysis by X-ray diffraction

The X-ray diffraction pattern of a substance is characteristic of that substa
nce and
forms a sort of finger print. Therefore, the pattern can be used to identify
the substance,
whether it is present in the pure state or as one constituent of a mixture
of substances.
Both quantitative and qualitative analyses are possible. Qualitative analys
is for a
substance is achieved by the identification of the diffraction pattern of that
substance.
Quantitative analysis is also possible, because the intensities of diffraction
lines depend
on the proportion of that constituent in the specimen.
Using the diffraction analysis, we can find the presence of a substance,
as that
substance actually exists in the sample and not in terms of its constituent
elements. For
example, if a specimen contains a compound AxBy, we can find the presen
ce of AxByas
such, using the diffraction analysis, whereas ordinary chemical analysis
would show
only the presence of elements A and B. Moreover, if the sample contains
both AxByand
AxB2y, both of these compounds can be identified using the diffra
ction analysis.
Therefore, diffraction analysis is useful for finding the phases in which the
compounds
are present in a specimen.
 JCPDS cards
'f]Vl all d . ,
,-s rhe chemical analysts ol a substa nce c~n- be carried out using a method called
It 111 ethod. In I936, Ilana wait class1fl ed the diffraction data of some
1-tanawa . substances2• I n th cse r:11 Ics, the d.1rr.1ract1 ·011 patterns are arranged as groups1000in
·fferent ~ .
di . 0 values of ' d' for the strongest line in the pattern .
dccreas111o . . . . . . .
, several tec~rn tcal soc1et1es, 111clu.d111g the American Society for Testing and
111 1941
~ terials (ASTM) published the fil e cards. Stnce 1969, this activity has been carried out
~
8
Joint Committee on Powder Diffraction Standards (JCPDS)3. The substances
b)' tile . . . . .
d d at·e elements, mgantc compounds, tnorgantc compounds mmerals and organo
inclu e , '
111eat Il
ic compounds.
The typical cards of ZnO and SnO2 from the JCPDS file are shown in Fig. 5.9
and Fig. 5.10, respectively.
1t provides
• serial number of the card,
• wavelength of the X-ray used,
• chemical formula and name of the compound,
• crystal structure,
• lattice constants and
• space group.
The 'd' spacings associated with all the observed diffraction lines along with the relative
intensities and the corresponding Miller indices (hkl) are also available in the card.
In addition to that, the details of the diffraction method (radiation, camera diameter,
method of measuring intensity, etc.) used for obtaining the pattern and a reference to the
original experimental work are given in the file.
By matching the 'd' spacings dl, d2 and d3 corresponding to the first three strongest
lines (having highest relative intensities) of the unknown specimen with the standard
data files, one can identify the element or compound present in the specimen.
To illustrate the identification procedure, an example is given below. The Fig. 5.1 1
represents the XRD pattern and diffraction profile of an unknown sample. As •d'
spacings of the first three strongest lines found to be matched well with the data of the
card no· 41 14 .
· - 45, the specimen 1.s .1dentrfied
.
as SnO2.
. _The X-ray diffraction pattern of SnO 2 film with indexed diffraction peaks is shown
tn Fig. 5. 12.

lntrod .
Uction to Th in
. F'l
i ms 103
 Fig. s. to JCPDS file of Sn02
l V ! l V !
[Link]
«:O

,0 ro
R:eticn[_"2lh;t~ (O:J+e'" (~)

Pos. Height FWHM Left d-spacing Rel. Int.

[ 2Th.]
0
[cts] [ 2Th.]
0
[A] [%]
26.6114 280.46 0.1332 3.34699 100.00
34.1025 26. 12 0.1626 2.64002 9.23
37.9902 147. 15 0.2873 2.3 6662 52.53
51.7434 187.37 0.11 24 1.76532 66.82
54.7236 18.10 0.3020 1.67617 6.36
61 .8723 38.60 0.2911 -1.49847 13 .64
65.8636 173.44 0.1845 1.41694 61.86
78.6632 30.56 0.2103 1.21534 10.89

Fig. 5.11 XRD data of an unknown thin film material

400
..,;
::: (110)
0

~
~ 300
::.. (211)
.f;
s (200) (301)
0
2.-
t
~
200

.5 ( to I )
100 (.31 0 )

0
JO 20 30 ·10 50 hO 70 so

20 (degree)

Fig. 5.12 Indexed XRD pattern or thin film identified as Sn02

Introduction to Thin Films -
106
 • 1applications
Get1CI a .
' x ~raY diffractomctry ts the most widely d .
, 1 • • use techn,q Fi . .
unknown crysta lI me materi als. ue or the 1dent1fication of
It is used for the structura l investigations f ,
.
, .- . . o crystal Iine materials.
Unit cell d1mens1ons such as lattice constant d
, ' s, an the volume 0 f th .
be determined. e unit ce ll can
, It can be used to find the purity of the sample.
. ations in the field of thin film research
[Link] IIC • •
In polycrystallme thm fi lms, the orientation of · b
• . grains can e found using this
techmque.
, lt is used to determine the lattice mismatch between the depos1·ted fil1m an d the
substrate.
• Stress and strain produced in the films can be estimated using this technique.
• Crystallite size of the thin film samples can be calculated from the broadening of
the X-ray diffraction peaks.
, Dislocation density and the quality of the ·film can be estimated using this
technique.
• Thickness, roughness and density of the films can be determined using glancing
incidence X-ray reflectivity measurements.
Advantages
• It is a fast and powerful technique.
• Identification of an unknown material can be made in less than 20 minutes.
• Generally, it provides unambiguous mineral determination.
• It does not need any special sample preparation processing.
• Interpretation of X-ray diffraction profile is relatively straight forwa rd ·
. . l · l <lino structural profiles for
• This technique provides multiple resu ts inc u o
elemental identification and crystal lattice detai ls, etc.
• It is a non-destructive technique.
Limitations .
. . .. d for comparing d-spacmg.
• Standard reference fil e of materials 1s requu e
• F . - · · 2¾ of the sample.
or mixed materials, detection 11m1t 1s ~ 0

107
Introd .
Uction to Thin Films
 5.5 Opt ical prop ertie s
lt is well known th at preci se knowled ge or th e opti
cal propertie s like tran srnitta
absorbance, rellectance and optical cons tants is of - nee
paramount important for design in :
optoelectronic and optical devices. ~h? to lu min ~sce
nce (PL) characteri sti cs are verg
much use ful for inve stigating the intrinsic and extrin
sic properties of the semi cond uctin~
thin films 4 . In additio n, PL studies can provide va luab
le information on the detectiori~o~
~fs cts and the i:eco1J1binatio n process in semiconduct
ing fi lms 5 • As the aforesaid optical
properties are studied using the UV-v is-NIR doub
le beam spectrophotometry and
spectrofluorometry, in this section, the working
prin cipl e, descripti on and other
experimental details of these two techniqu es are elab
orated.
5.5.1 UV- vis- NIR dou ble beam spec trop hom etry
UV-vis-NIR doub le beam spectrophotometry is
an absorption , transmi ssion or
reflection spectroscopy, which is used to study the
optical characteristics of materials by
means of the absorption or reflection of the visible
or adjacent (near UV and near IR)
ranges of light. The _molecules of the material
to be analyzed undergo electro_nic
transiti~n due to the abso rption of these electromagne
tic radiations.
The block diagram of UV-vis-NIR double beam spec
trophotometer is shown in Fig.
5.13. The instrume nt consists of the following main
parts: a __!ight source, !ocusing
system, sample and reference holders, a monochr
omator, a detector with an amplifier
and readout system.

Mechanical Chop per Refe rence

I I
I I
I I
Mech anica l Chop per 'f
"
Optical
source \
Detector

Sample~ Plotter

Samp le Co mpnrlment

Fig. 5.13 Bloc k diagram or UV -vi s-N IR doub le bea m spec trophotometer

Introduction to Thin F'iL ,ns 108

 1he light source is ge1~erally a tungsten filament (wavelength range 300-250 nm) or a
1
18
n- an,p. The d_etector I generally
r I11 a photomultiplier
. tube. A scanning monochromator ,
,eno
r,1iers the
light such that on .Y •g ray of. smgle. wavelength
. . enters the detector at a time.
.
1• a double beam specti ophotomete1, the light is split up mto two beams, one of them for
'
I1e s~111P
le and the other is used as the reference.

t The sp ecti·ophotometer
. . measures the percentage of transmittance 1/1 o, where I is the
1 . 0 flight ti·ansmltled through the sample and l0 is the intensity of light incident on the
·ntensit)' ....., · · t .d I . 1 . b b .
e surface. TlllS mstrumen prov, es 11e optica transmittance and a sor ance 111
sanipl
Percentage as a function of wavelength. Information regarding optical transmittance is
. I e: f I. . II d . .d
. 1 in evaluating the opttca per1ormance o t 1111 films especia y con uct1ve ox, e
essentiaA typical · and absorpt1on · spectra of · · th"m filI mare ·
transmission a tm oxide given ·111 p·1g.
5films.
14 an d F·g
t • 5. 15 ' respectively. Fig. 5.16 shows the photographic image of a double beam
· . NIR spectrophotometer
uv-vis-
100 -.-------------,

/ ----~~
/ '·'---
80 · /~--/~/ ----

r/
~ 60 i
~
t:
-~
I
I'

j 40 - I/
. I
i
I
20 .. i
I
:
0 I

400 600 800 1000

\V,weleuglhl1un)

. spectrum of a t·m oxide thin film sample

Fig. 5.14 Transmission

0.7 . - - - - - - - - - - - - - - - I
06 -

\V,i,•dt.•nt,lhlum )

Fig. 5.15 Absorption spectrum of a tin oxide thin film sample

109
Introduction to Thin Films
 'h))fl)thn1i11fonum11·u1mH
•·J~

Fig. 5.16 Photographic image of UV-vis-NIR double beam spectrophotometer

Advantages
• It is a simple and non-destructive method.
• There is no need for any special sample preparation procedure.

Calculation of band gap using transmission spectrum

When photon is incident on a semiconducting material, electronic transitions
between the valance and the conduction bands take place which can be direct or indirect.
The transition probability is related by the following equation:
A
a= hv (hv - E9 )P (5.1 I)
where A is a constant related to the effective masses associated with the bands and p has
discrete values like .!. , ~, 2 or more depending on whether the transition is direct or
2 2
indirect and allowed or forbidden. In the direct and allowed cases the index p =
2
½, whereas for the direct but forbidden cases it is ~. Thus, a linear graph when a is
drawn against hv, will suggest a direct but allowed transition.
A t
a = hv (hv - Eg)z
or
AZ
a 2 =-(hv
(hv) 2
-E)
g

or
(ahv) 2 = A 2 (hv - Eg) (5.1 2)
GeneralJy , a plot drawn for (ahv)2 against hv (called Tauc 's plot) is used to find th e
band gap of direct or indirect type.

Introduct ion to Thin Films 110

 Fig. 5.50 Photographic image of RBS
s.s.S Fourier Transform Infrared (FTIR) spectroscopy
Fourier transfonn infrared (FTIR) spectro scopy is a technique used to analyze the
chemical composition of polymers, paints, coatings, adhesives, lubricants
.
semiconductor materials, coolants, gases, biological samples and minerals. This'
technique works on the fact that bonds and groups of bonds vibrate at characteristic
frequencies. A molecule that is exposed to infrared rays absorbs infrared energy at
frequencies which are characteristic of that molecule. During FTIR analysis, a spot on
the specimen is subjected to a modulated IR beam. The IR transmittance and reflectance
of the sample at different frequencies is translated into an IR absorpt ion plot consisting
of reverse peaks. The resulting FTIR spectral pattern is then analyzed and matched with
known signatures of identified materials in the FTIR library. When the library of FT1R
spectral patterns' does not provide an acceptable match, individual peaks in the FT1R plot
may be used to obtain partial information about the specimen.
The schematic diagram of a FTIR spectrophotometer is shown in the Fig. S.51. A
parallel beam of radiation is directed from the source to the interferometer, consisting of
a beam splitter B and two mirrors Ml and M2. The beam splitter is a plate of suitable
transparent material coated so as to reflect 50 % of the radiation falling on it. Thus half
of the radiatio n goes to Ml and half to M2 and the refl ected beams return from both
these mirrors then recombined to a single beam at the beam splitter. lf a monochromatic
radiation is emitted by the source, the recombined beam leav ing B shows conS tructive or
destructive interference depending on the path difference. As the mirror MZ is moved
~moothly towards or away from B, a detector records radiation which is alternating in
intensity.

lntrod · 139
uction to Thin Films
 Moving Mirror (M2)

lknm Output dc1ta

co ll ec tor dev ice
Fixed Mirrn~(M,) B)~
itt-cr_(_
S1~ .- ...__--S~ntn1---pl_c_

r Detector

@ Light source

Fig. 5.51 Principle of FTlR spectroscopy

The production of spectrum is a two stage process. Firstly, without the sample, the
mirror M2 is moved smoothly over a period of time through a distance of about 1 cm. At
that time, the detector signal, the interferogram, is collected into the multichannel
computer which carries out the Fourier transformation of the stored data to produce the
background spectrum. Secondly, with the sample in the sample holder, an interferogram
is recorded in exactly the same way, F:mrier transformed and then ratioed against the
background spectrum and plotted as a transmittance spectrum. Alternatively, the spectral
data of the sample and background spectra may each be calculated in terms of
absorbance and the latter is simply subtracted from the former to get the final result 12 • A
typical photographic image of the FTIR instrument and the FTIR spectrum of ZnO
material are shown in Fig. 5.52 and Fig. 5.53, respectively.

Fig. 5.52 Photographic image of FTIR instrument

Introduction to Thin Films 140

 l()fl 1 - - - - - - --

Rt1

lf.1(1(1
r--.......
5f)(I 1500 21 [Link] 2Sfl0
If)fl1l \:;nn -1nnn
\\:a,·e numh er (c rn ')

Fig. 5.53 FTIR spectrum of ZnO material

Advantages .
er oxygen nor nitrogen
, FTIR spectroscopy does not require a vacuum, since neith
absorbs infrared rays.
of materials in any form
, FTIR spectroscopy can be used to analyze a wide range
ders, fibers and other
i.e. bulk or thin film forms, liquids, solids, pastes, pow
fonns.
or molecular structure of
, It provides information about the chemical · bonding
materials, whether organic or inorganic.
tities of materials, in either
, This technique can be applied even to very small quan
solid or liquid or gaseous form.
5.8.6 Raman Spectroscopy
tional, rotational and other
Raman spectroscopy is a technique used to study ·vibra
scattering or Raman scattering
low-frequency modes in a system • It relies on .inelastic
13

le, near infrared or near

of monochromatic light, usually from a laser in the visib
or other excitations in the
ultraviolet range. The laser light interacts with phonons
system, resulting in the energy of the laser photons being
shifted up or down. The shift in
energy gives information about the phonon modes in the
system.
omatic light and the light
In this technique, the sample is illuminated with a monochr
eter. At the molecular level,
scattered by the sample is examined using a spectrom
Photons can interact with matter by absorption or scatt
ering proc ess. Raman scatt ering
b tI
occurs wh en the system exchanges energy with the photon and the system su sequ en Y
d
the initial state. The lrequen~y
s:Ys to vibrational energy levels above or below that of
tween the incid ent and scattered photon 15
corresponding to the energy diffe rence-be
~
lritrod . 141
Uction to mi. .
11
v·z s
iin rim
 Solution growth technique is subdivided . . .
into two ma_1or categories viz.
• Low temperature so luti on growth
• High temperature so luti on growth
7.4.1 Low temperature solution growth
In this technique, crysta lline solid s
. _. . ' , are grown from low temperature aqueous
so lutions. In thi s p1ocess, th e crystallization m h • ,1 • •
. , cc a111sm uepends on interactions between
molecules/tons of the so lute and the so lvent , concentration .
· o f t he solution, temperature
and pressure.
Low temperature solution growth is subdivided into
• Slow cooling method
• Slow evaporation method and
• Temperature gradient method
7.4.2 Slow cooling method
Slow cooling is the best way to grow crystals by solution technique. The principle of
this technique is that a saturated solution results in a solid deposit on lowering the
temperature as the solubility decreases with temperature.
This slow cooling process is based on dissolving the desired solute in a solvent
system to give a near saturated solution at a suitable temperature and then letting the
system cool to a lower temperature. A large cooling-rate changes the solubility beyond
the metastable zone width and multinucleation occurs at the expense of the seed crystal.
A balance between the temperature lowering and the growth rate has to be maintained.
The experimental setup for slow cooling method is shown in Fig. 7.1. This technique is
found to be very prom1smg for the growth of crystals like PrVO-i,
14
Pb(Sc112Nb112)0_58 Tio.4 2 0 3, Bb W06 and KGd(P03)4 with good quality .

Stages involved in the experimental process include:

• Dissolving the sample at some elevated temperature and then insulating the
container (eg. with cotton wool, metal foi I, and/or a large thermal buffer)
• Letting the sample cool slowly to ambient temperature.
• Finally, placing the insulated container into a lab fridge or freezer to get the final
product.

165
Introduction to Thin Films
 . lly the crystallization takes, pl ace when th .
F,na . .
. turated. The high temperature crystal h c so lution becomes criticall y
sLIPe1sa growt can he divided . t .
.. in o two maior type<;
,,,z. ' .
, Growth irom smgle component systems
, Growth from multi component systems
This method is most suitable for growing Ph(Fe211 W , , .
13-16 in)O,, CuS, L 1Bi)s and Cr2AIC
crystals ·
7,.5 Melt growth
In this process of crystal growth, crystallization occurs by c:us·1on an d reso 1·d·fi .
• 1 1 1 1cat1on 1

the material to be crystallized. During the process , the melt crys . t . .

of . . a11 1zes on coo 1mg
below its ~eez~ng pomt. There are several techniques based on this melt growth
pnn. ciple wh1ch mclude:
, Bridgman technique
, Vemeuil technique
, Czochralski technique
, Heat exchanger technique
7.5.1 Bridgman technique
In this technique, the material which is to be grown as crystal is taken in a vertical
18
cylindrical container with a point bottom as shown in Fig. 7.4 •

··· ··· ·······

.............
...... ...... .
, ........... .

, ..... _ .... .
...... .. - ... . ······· ... ..
...... ,,,.....
.....
..... ··:·····
···-.... - - ....... _...... ---·--···· l'vldt
............ .
.... ...... ···.. -....
_
... ..
..... ··:····· ...... ·······
······· ......
····· ····· :·····
..... - .... ...... ·······
..... ··· - .... . -- - -- ::·_.. :· .. ~:: ·_ - -. - Crystal
Thermometer ---------- ·.:;·:·.:-.-.: ·.:".'. .······ ...... ..
...........
······ ......
....... ..... ..
-:.'..:-:;,';.:::!:}· l ll:ali11g roil
.............
....... ......
-·······..
..·····... ····· =
'."~'" '~ -'& ~~
F1.g. 7.4 Bridgman technique
169
Introduction to Thin Films
 The material is made to melt using a furna ce and the container is lowered slowly
using a pulley arrangement as illustrated in the Fig. 7.4. As the container moves slowly
from the hot zone to the cold zo ne, crysta lli za ti on ta kes place beginning from the tip.
The movement rate may be in the ran ge of 0.1-200 mm/hour. Thi s technique has been
employed to grow single crystals of Gai\ s and Pb [Link] 17 ·
Advantages
• It is a simpl e method
• Higher growth rate
• Less contamination
Disadvantages
• As the melt is kept for a long time in the container, there is a possibility for
increasing impurity pick-up.
• Due to the compression at the sharp end of the container and consequent
development of stresses, dislocations may occur in the crystal.
• It is not suitable for materials which decompose before melting.
7 .5.2 Czochralsk.i method
The Czochralski process is a method of crystal growth used to obtain single crystals
of semiconductors, metals and salts. The process is named after Jan Czochralski, who
discovered the method in 1918 while investigating the crystallization rates of metals.
Fig. 7.5 shows the experimental setup of Czochralski method.

c:+><-················· Counter clockwise rotation

<- -· --- ----- ----- - -- - -- ------- - --- --- Seed crystal
Single --- ---- ------------..
crvsta.l .
. ·, --------------- Graphite susceptor
Fused silica -----·-- _Q__ ~X,/, 0
crys1al 0 t--_ ________._ _,___ _<~ ·
0
( ,,.. -- 0
- ---- - ---- Boron tnox1
. 'd e cap
0 0
. _ __ _ _ __
<-_ _--_-J · ,, __ -- -- --- - ---- - - - Liquid melt
R. F. Coils --- ---- -0 0

<:P<------- ···---- --- ----- Clockwise rotation

Fig. 7.5 Czochralski method

Introduction to Thin Films

170
 n,aterial to be grown as crystal is melted .in a [Link] wh . h .
fhC . , ic is usually made of
ing a suitable induction or resistance h 1 he te
rtZ us . . . eater .
adiusted such that 1t 1s sltghtly above th e melting . ~perature of the melt is
q113 po, t Th
·tab1y ~ it just tou h h n · en a seed crystal,
stll d on a rod, is lowered so that c es t e surfa of th . I ,fhe seed
ce
ounte e me t.
111 , rod is pulled slowly upwards and rot ated at the same ti me B ·
rYsta1s of pulling <l . · . Y preci sely
c lling the temperature gradients, rate an spee d of rotation, ,t is poss ible
contrO . I . . .
tract a large , smg e-crystal, cylin drical ingo t from th
to ex . e me 1t. More over by suitabl
h .. ' Y
lling the pull rate and rotation rate it .is possible t0 81•, or t e doping profile in the
t
contrO . .
in an inert at h
crysta ·
l This proc ess 1s normally perfo . rmed mosp ere, such as argon, and in
It 1s the most frequently us ed tec hnique . .
·oert chamber,. such .as quartz.. . to grow h1gh-
an 1 · Iy emp Ioye d to grow
rature melt mg oxid es. This Czochralsk1 method is to be main
tentpe 19
crysta ls like Y3Als012, Ga1-xlnxSb, Zn2Te30 8 and Ge -2J_
Advantages
cylindrical ingots, or
, The most important application may be the growth of large
bowls of single crystal silicon. .
itions can be suitably
• It is a versatile technique i.e. as the thermal cond
etc., it is possible to
manipulated by means [Link] shields, shape of crucible,
grow a range of crystals with different properties.
process. Therefore, it is
• The crystal can be viewed directly during the growth
growing crystal.
possible to regrow the crystal if any flaw has developed in a
n.
• Using this technique, dislocation free crystals can be grow
Limitations
ined in a silica (quartz)
• When silicon is grown by this method, the melt is conta
ble dissolve into the
crucible. Therefore, during growth, the walls of the cruci
rities with a typical
melt and Czochralski silicon therefore contains oxygen impu
18 3
concentration of I 0 cm- •
due to the geometry,
• The hydrodynamics of Czochralski melts is rather complex
re distributi on.
the rotation of the crystal and the crucible, and the temperatu
7·53 Verneuil technique
melting temperature
This technique is particularly useful for crystallizing high
stone crystals base d on
rnaterials and has been widely used to grow synth etic gem
st Vern euil, the French
~ ndum (A)i03). This technique was developed by Prof. Augu
sctentist in 189). This technique is also called as flam e fusion. In this techniq~1e, ~he
of a tine powder (with size
SOurce material to be crystallized is taken in a box in the form
...,,
171
[Link] to [Link]
D'[
ms
 I orowth
1,6 Ge "
(lnition .
1s one of the attractive method t' . .
J)C
oe. I·tyIriethod s or
feasibility and versatility. The gel is a high!
crystal I1zat1on b
. ~ ecause of its
•
j111phCI , . . • • . y vi scous two component system
s .15 semi-sohd 111 nature and 1s nch in liquid h • fi
~,i,ich aving me pores. These fine pores
' the free passage of electrolyte s and sustain nucleation ~rh . .
~now . . . · e materials, which
.
ose befoie meltmg, can be •grown usmg this method · Crys ta1s wit• h d'1mens1ons
decot11 P • of
ral mm can be grown m .
a period of 3 to 4 weeks. Crystals grown by th·1s tec hnique
seY e •
.
igh degree of perfection and have only a small amount of de-"1ects as th'1s tee hn1que
have 11
requires only room temperature for the crystal growth process.
The gels are of different types which include silica gel, agar gel, carbohydrate
palymer gelatin .g~l, clay gel, p~ly-acrylamide and soft soaps. The silica gel made out of
sodium meta s1hcate (SMS) 1s often used due to its easy availability and better
performance in growing many crystal compounds. This method is used to grow various
36 39
types of crystals like hydroxyapatite, a and y-glycine, lysozyme and diglycine nitrate -
7.6.1 Chemical reaction method
The chemical reaction method is one of the widely used methods to grow a farge
variety of crystals. This method is particularly suitable for the growth of materials which
are insoluble in water and decompose before melting.
In this method, the crystals grow inside the gel. The gel medium allows the free
diffusion of the ions in a controlled manner which enables the process of crystallization.
This irreversible reaction can be represented as
AX+ BY--+ AY + BX (7.1)

where AX and BY are two water soluble compounds which on reaction give rise to AY,
the insoluble substance and BX, the waste product which is soluble in water. Nucleation
takes place when the concentration of the reaction products exceeds super saturation
limit. If the size of the nucleus exceeds the critical value, it grows further into a crystal.
The gel medium limits the number of nuclei and the rate of growth either by controlling
th e diffusion of the reacting ions or by governing the reaction velocity on the surface of
th0
lhe growing crystal. Both inorganic and organic crystals can be grown using this me d.
Rare earth molybdate and sulphates also been grown by this method. The experimental
arrangement for this method is as illustrated in Fig. 7.8.

lntrod • · 175
uction to Thin Films
 <- ----- [3 y

Fig. 7 .8 Gel method for crystal growth

7.6.2 Chemical reduction method

This method is suitable for growing metallic crystals from gel media. Crystals like
copper, nickel, lead selenium, gold, cobalt etc., can be grown by this method. The
metallic complexes are usually taken along with the meta silicate solution and is reduced
by the diffusion of a proper reducing agent into the gel. The slow diffusion of the
reducing agent may result in the formation of the metallic crystals.
Advantages of gel method
• This method is extremely simple and inexpensive.
• This technique yields defect less crystals.
• The gel medium prevents the convection currents considerably and remams
chemically inert.
• The gel is transparent m nature and hence the crystals can be observed
practically in all stages of growth.
• All nuclei are spatially separated, minimizing precipitation.
• The growth procedure is suitabl e for mass production of crystals.
• By suitably changing the growth conditions, the crystals with different sizes and
morphologies can be obtained.

Introduction to Thin Films 176