AN INTRODUCTION TO THIN FILMS

Dr. Jeevan Kumar Padarti

Thisarticle provides a basicknowledgeinthinfilms andwas writtenkeepinginviewofunder graduate and
postgraduate students who arehaving thinfilms intheir curriculum. This lecture notes contains method of
nucleation,types of growth, sputtering process, methods of growthwhich includesvacuum
evaporation,flash evaporation andchemicalvapourdeposition. Methodsfor measurement of thickness of
thinfilmsarealsoincluded.Finally electric and optical properties of these films are illustrated.

1. Introduction:

2. Thin film nucleation and growth:

Thinfilm isabranchthatdealswith very

thinstructurallayers of differentmaterials. In
recent years, thin film
science has been
grownworld
wideintoamajorresearch
area.
Theimportanceofthinfilm
coatingleads
breakthrough inmicro electronics, optics and
nanotechnology/1/. Thin films withthickness
rangingfrom
onetoseveralmicronsarevery
essential for thermal barrier coatings and to
protectmaterialsfrom
thermalandatmospheric
influences/2/.

Athinfilmdoesnotgrowasperfectslabs
of
bulk like materials. When compared with the
bulkmaterial,physical
propertiesofthin
filmson
substratemaystronglydiffer, dependingespecially on
development ofmorphology and structure. Features
like
grainsize,shape,orientationandother
are
determined to a large extent at an early stage of
nucleationandgrowthandcanbeinfluenced
by
depositionconditions/8/.
Theindividual
atomicprocess
which
determinefilm growthinitinitialstageisshownin fig.1.

Thefilm scienceandtechnologyplays an
important role in hightechindustries. Thin film
technologyhasbeendevelopedprimarily
forthe
needoftheintegratedcircuitindustry. Thedemand
fordevelopmentof
smaller
and
smallerdeviceswith
higherspeedespeciallyin
new
generationofintegratedcircuitsrequires
advancedmaterialsand
newprocessing
techniques suitable for future giga scale
integration (GSI) technology. Inthis regard,
physicsandtechnologyofthinfilmscanplay
animportant
roletoachievethisgoal.
The
productionofthinfilmsfordevicepurposes
has
been
developedoverthepast40years.Thin
filmsasatwodimensionalsystem
areofgreat
importance to many real-worldproblems.Their
materialcosts are verysmallascomparedtothe
corresponding bulkmaterialandthey perform the
samefunction when it comes to surface
processes.Thus,knowledge and determination
ofthenature, functionsandnewpropertiesof thin
filmscan be used for the developmentof new
technologies like solar cells/3/, sensors/4/,
optical
applications/5/,
electronic
engineering/6/ferroelectrics/7/etc.

Fig.1
Thesubstrateatomsaregiveninopencirclesand
film
atomsareshownindarkcircles.Condensation
ofnewmaterial fromthegasphasecanbedescribed by
animpinging rate. The numberof particlesper
2
cm persecond is given by
-1/2
r=P (2MKT0)
.. (1).
Where
Pisthevapour
pressure,Mthemolecular
weight,
KBoltzmanConstant
andT0is
the
temperature.
Onceaparticleiscondensedfrom avapour
phase,itmightimmediatelyre-evaporateoritmay
diffusealong the surface. This diffusionprocess
mightleadtoabsorptionparticularlyatspecialsites,
edgesorotherdefectsorthediffusionparticlesmay reevaporate. In all these processes characteristic
activation energy has to be overcome. i.e., the
numberofparticlesbeingable toparticipateina
particularprocess is given by the expression

Introduction to thin films- Dr. Jeevan Kumar P

Edis

KT

V e
(2)
Where
visthe
desorptionrateandEdesisthe
activationenergy
forthe
desorption.
The
corresponding activation energy
for the
absorptionanddiffusiondepends
upontheatomic
details of the particularprocess.

Fig.3
This layer-by-layer growth results
1.Highcrystal quality
2.Filmatomsare more strongly bound to each
otherandfast diffusion.
Island growth:

Fig.2
Besidetheabsorptionofspecialdefectsitesand
surfacediffusion,
nucleationmorethanone
absorption particlemight occur,asmightfurther
film
growthbyadditionofparticlestoanalready
formedisland. Theislands formationisshownin
thefig.2.
Inordertoobtainasmoothfilm
surface
during the growth, sufficient high surface
mobility of the diffusing species and elevated
temperatures areneeded.
In
thermodynamicallyequilibrium,
condensationand re-evaporationsare equaland
hence nonetgrowthis result.Asthereisacrystal
growth,itmust
beclearlyisa
non-equilibrium
process/8/.
Mainlytherearethreetypes
ofthinfilm
growth
phenomenais observed.
1. Layer-by-layergrowth
2. Island growthand
3.layer-plus-island growth
Layer-by-layergrowth:
The layer-by-layer process of growthof
thinfilmisshowninthefigure.3.Inthis
method
theinteraction
betweenthe
substrateandlayer
atomsisstrongerthan betweenneighboring layer
atoms.First a layer of layer atomsis formed on a
substrate substance. Lateran a second layer is
formed on the first layer and completes the
growthonthefirstlayer.Athirdlayerformson
thesecondlayerandsoon.Eachnewlayerstarts
togrow only when the lasthas beencompleted.

IslandgrowthisshowninFig.4.
If
the
interactionbetweenthe neighboringfilm atoms
exceeds the over layer substrate interaction
leadstoislandgrowth. Inthiscaseanisland deports
always near a multilayer conglomerate of
absorptionatoms.
The first few atomiclayers usually
grow as islands of a depositing material
centeredonnucleationsite.Theislandgrows
until they touch each other (percolation
threshold).This
percolationthresholdtypically
occurred
between5to
10nm.Thethinfilm
propertiesaround percolation threshold and
belowpercolationthresholdwillbe very different
frombulk properties.

Fig.4
The film atoms in islands growth are more
stronglyboundtoeachother
thanthesubstrate
withslow diffusion.
Layer-plus-island growth:
The layer-plus-island growth is aninteresting
one and is shown in Fig.5. After formation of
one
orseveralcompletelayers,firstisland
formationcan occurs. A 3D island growsover the
top of the firstfull layer.In thiscase a
latticemismatch between the substrate and the
depositedfilmmay occur. It may not occurin
epitoxialgrowth.

Fig.5

Effect of grainsize:
The grain size of the thin film formed on
substratedependson deposition rate and
Temperature/9/.Dependenceofgrainsizeon
variousfactorsis shown inthefigure.6.
Grain size increases with substrate temperature
uptocertaintemperature
andthenbecomes
constant Fig.6 (a).Grain size ismore for the
thicksample thanthinsample. Uptoentertain
temperature,thegrainsizedidnotshow
any
difference on thethicknessof thesample.
Thegrainsizewithdepositrateisshowninfig
.6(b).Grainsizeisconstant
uptocertaindeposit
rate. On further increasing the deposit rate,
grain sizedecreases.

Fig.6
Grainsizeversusannealingtemperature
in
showninthe fig.6(c).Asthetemperature going
ondecreasingthegrainsizealsodecreases.A
graphbetweengrainsizeandthefilm
thickness
atconstanttemperatureisshownin
fig.6(d).On
increasingthe grainsize, the thickness of the
filmincreases.

3. Sputtering process:
Sputteringaphysicalprocesswherebyatoms
inasolidtargetmaterialisejectedintoa
gas
phasedueto
bombardment
ofmaterialby
energeticions. This processiscommonly used for
thin filmdeposition, as showninthe fig.7.
Whenanionstrikesthetargetcluster
ofclosed packed atoms, inthe first collision,
pushestheatom
deeperintothecluster.
Subsequent collisionsbetweentheatoms can

Fig.7
resultin someof theatoms nearthesurfacebeing
ejectedawayfromthe cluster.The numberof atoms
ejectedfromthesurface perincident particle is
called sputter yield. This is an
importantparametertomeasure theefficiency of
thesputteringprocess.
The ionsfor the sputteringprocess are
supplied byplasma that is induced in sputtering
equipment onan ionor electron accelerator.
Mostly organionsare used forthesputtering
process.
3.1. Sputteryield:
It isdefined asthe mean number of
atomsremoved fromthesurfaceofthesolidper
incident ion. It is given by
Sputteringyield,S=(Atoms removed/incident
ions)
Sputteringis called by the interaction of
incidentparticles with the target surface atoms.
The sputter yieldwill influenced by thefallowing
factors
1. Energyif incidentparticle
2.Target material
3. Incident angleof particleand
4.Crystal structure of the target surface.
Sputteryieldcanbemeasured by the
fallowing methods:
1.Weight loss ofthetarget
2. Decreaseof target thickness
3. Collectionof sputteringmaterial etc.

An introduction to thin films- Dr. Jeevan

3.2 Sputteryield- ionenergy:
A graph between sputter yield(S) and ion
energy (E)is shownin the Fig.8.

Plasmaissentbetweentwo plates.One plate is

made with the source called target, and kept
negativepotential.Thetargetismade
withthematerial,ofwhichthethinfilmhas to be
prepared.

S
E0

E
Fig. 8

Thereisnosputteryielduptocertainenergy
andafterthat sputteryieldincreasesand becomes
maximum between 10Kev and
100Kev.Afterthatsputteryield
decreases.E0is
thethresholds energyforthe sputtering.Sputter
yieldismaximum athighenergies.Itdecreases at
very
highenergies(>100Kev)because
the
ionsloosemuchoftheirenergy
farbelowthe
surface.Thesputteringyieldveryless depends on
the temperatureof the target surface.

Fig.9
+
The
plasmapositiveionAr strikesthetarget
bytheforce
ofattractionandknockingthe
atomloose,thetargetatomthenlandonthe
wafer(substrate).Theprocessiscontinued
andmoreand
moreatomsaredepositonthe
substrate to forma thinfilm.
4.Thin

film preparations:

Thinfilmscanbepreparedbydepositing
thematerialsonaninsulatingsubstratewith
0

3.3Advantagesof sputtering:

coating to a thick ness from few

A to

Sputteringiswellemerges ascleaner,more flexible

andcontrollablemeansof
deposition
thanothermeans.Themainadvantages
ofthe
sputtering are:
1.The ability of transferof material fromthe
solid unheated source inthe absenceof
Possibly reactive crucibleor container.
2.Withsuitable precautionsthe source
cathode compositionispreservedinthe
growingfilmand
3. Thistechnique is havinghighadvantageof
depositionofmaterialoversubstratetoform
thin
film.
Asimpleexperimentaltechniqueisshownin
thefigure.Fig.9.
Generallyargongasis
usedforthesputtering
process,andiskeptbetweenthetwoelectrodes,
whichiskeptinavacuumchamber.Whena
highenergyelectronisstrikestheargonatom, it is
+
ionizedforminganAr and anelectron.By using
the high energy field, low pressure plasma is
formedbetween theplates.

100A.Manymethodsforthinfilmthickness
deposits exit. Here depicting some of the
widelyusedmethodsforthepreparationof
thin films.
4.1Vacuumevaporation:
This method is usedto prepare the thin films
of varietyofsubstancesina highevacuated
chamber in which the material is heated by
electricmeansas shown in the figure.10.

Fig.10

Avacuum
pumpisconnectedtoa
chambertobe evacuated. Insidethechamber
maskedwaferissuspendedbyasupporting
standandmaterial tobeevaporatedis kept on
anothersupport.Heatingcoils arearrangedto
heat the material.
Duetoelectricalheating,thematerial
is
radiated in straight lines in all the
directionsfromthesourceanddepositonthe
wafer.Thisprocessiscontinueduntilathin
film of requires size is deposited on the
wafer.Whentheprocessiscompleted,the
vacuumisreleasedandthewaferisremoved,
thisprocessleavesathinuniformfilmonthe
depositionmaterial onall parts of the wafer.
This vacuum evaporated technique is most
suitable for deposition of highly reactive
materialsuchasaluminum,whichisdifficult
toworkwithair.Themethodiscleanand
allowsa bettercontact betweenthelayer of
depositedmaterialandthesubstratesurface.
Inaddition,
because,evaporationtravelsin
straightlines,very preciouspatternis produced.
Kinetic theoryof gas andemission condition:
The deposition condition of thin
filmisbetterunderstoodbythekinetictheory
ofthe
gas/10/.
Whenasolidsubstanceis
meltedorheatedinvacuum,form vapour atoms
ormolecules enclosed in a space and createa
vapourpressure. Atasteadystateof evaporation,
thesemoleculeswill
have
equilibriumvaporpressure.
PV =NKTor
P=(

N
)KT
V

N )2
1
2]
V
N P
Fromequation1, = V
KT
N=[(

Substitutinginequation 2,

P
2
1
)
2]
KT
2
l = KT/([P
1
2]
l =[(

KT
2

isnearlybecomes5.Orl=5/P(in

cm.).Hence in high evacuating chambers,

pressureisveryminuteand lis veryhigh.
At equilibrium condition, the vapour
pressure of the gas molecules is alsosaturated,
andthe
numberofmolecules,n,striking
the
surfaceofasubstrateperunit areaperunittime is
givenas

2MKT)
22
As 1/(2K)=3.513x10
n=P/(

(6)

22

n=3.513x10 P/ MT
.(7)
WheremisthemolecularmassandMisthe
grammolarweight.
2
Thecorrespondingmassevaluatedpercm per
sec.isgiven by theequation
-2

WhereNisthetotalnumberofvapouratoms
ormolecules,Vthevolumeofthechamber, T the
absolute temperature and K is the
Boltzmann constant. These molecules or
atomscancolloidwithoneanotherinamean
time andletlistheaveragedistanceof
travelbeforesufferingacollisionwithother.
Then

.(5)

tItisobservedthat,ifthevapourpressureis
loweredthemorewillbethe collision distancel
.IfthevalueofpressurePisverysmall,l
is very
long and even collision may not takes
place(lisgreaterthanthe
dimensionsofthe
container.).If P is very small, the value of

G=5.833x10 P
.. (3)

.(4)

M
2
(in gmcm /sec.)... (8)
T

Similarly,thecorrespondingsaturatedvapour
pressure
P=17.44G

T
M

.(9)

Thevolume of the vapour

V=3638

T
M

. (10)

According to the above equations,it is clear

thattherateofdepositionisproportionaltoP
and

(M/T). It increases with pressure P

andasellas M butdecreases with T.i.e., at high

substrate temperature there will be
decreaseintherateofdeposition.
It is assumedthat thegaseous
molecules incidentonthe substrate will
condense to builda film, but this isnot truein
therealcase.All impingingmoleculesdonot
condense toformthe depositlayers, some are
reflectedback in to thegaseous state ands some

thesurfaceofthecylinderandcanbe
approximately betweenthe point sourceand
surface source
Expression for material deposition:
The amount ofthe material deposition onthe
substratedependsnotonly onthe natureof the
sourcebutalsoonthe inclination of the
waferstream( ) andon thesubstrate
normaldirection.

correction factor has to beinducedandthisis

known as the stickingcoefficient whichhasa
maximumvalue of1,for all the molecules are
assume to condenseon the substrate.
Distribution of deposit:
from
heatersourcewillspreadinallthe
directionsbut
thevelocitydistributiondepends
onthenature
ofthesource,whicharebroadly
classified in tothreegroups.
Point source:
If the
source is tiny sphere
comparingtothedistancefrom
areceiving
substrate is called a point source. The emitting
vapourstreamfromthepointsourcewillbe
having same velocity distribution in all the
directions.
Surfacesource:
Iftheemittedvapour
molecule
velocities are directional, thenthe source is
calledasasurfacesource.The
velocityof
moleculesismaximumalong thesource-normal
directionbutitdecreaseswithincreasing the angle
of inclination of the direction with sourcenormal. The velocity distribution fallows the
cosine law and decreases with
increasingof.If
=0,thesurfacesource
resembles a point source except it is not a
spherical.
Cylindrical source:
Theemission of vapourstreamwill befrom

Substrate

source
Fig.11
Let us now consider the amount of
material(dm)that will emit throughthe solid
angle(dw)ofasourceintheform
ofappoint
surfacesource.Ifm
isthetotalamount
evaporated,thedepositedamount
isdirectly
proportional
tototalmass
ofthe
evaporation(m), solid angle (dw)and the
cosineoftheangleofincidence()tothe
normalbetweenthe sourceand substrate.i.e.,
dm m
dw
Cos
dm mdwCos
dm=(mdwCos)/4
Theaboveequationisvalidforthesurface
source.Ifthesourceisapointsource,=0
and hence,

dm=

mdw
(11)
4

Let dAisthe unitareaof thesubstrateata distancer

fromthesource alongthe vapour direction. In this
case, the amount of the material deposit
alsodependson.

If0
t=

If= 0,

coscos dA (12)

4r 2
If=0,
m
Dm=
cos
dA
2
4r

t=

t=

t0 =

m
2

4r d

cos cos (21)

m 1
2
2
4r d h

(22)

Similarly we can get

Thesubstratereceivesamaximumamountof
deposits.Hence,positionofthesubstratewith
respecttothesourceaswellasthenatureofthe
source, considerably effect the filmthickness.
Considering the point source and surface
source, let isexamining the thicknessofthe
film.
The density d of the filmmaterial,
D=dm/V
.. (17)
Where V is the volume of the film
whichisequaltot dA, wheretisthethickness of the
film.
D= dm/(t dA)or dA= dm/(d.t)
For a point source:

t1 =

m 12
4dh

x 2 23
[1+( ) ]
h

(23)

Dividing equation (23) by equation (22),

x 2 2 3
)]
h
where cos =h/r

t1/ t0 =[1+(

..(24)

Forsurfacesource:wecanwritetheratioas fallows,
t0=

m
dA
2 , substituting for
4r

(25)

dA

Or

..(20)

Nowletusconsiderthethicknessvariationof
depositat different points on horizontalplane
PQRS,whichisatadistanceofhfrom
the
source.Let point A andBareatthedistancesof
h and r from the source respectively. If we
considerapointsourceandlett0 andtarethe
thicknessof thefilmsat two points.
Then,onsubstituting r =hinequation (19)

m
Dm=
.(14)
2cos dA
4r
For = 0,
m
Dm=
.(15)
dA
2
4r
= 0,then
If
=0,and
m
Dm=
.. (16)
dA
2
4r

m dm
,
Dm=
2
4r d.t
t=
m
2
4r d

m
2 cos
4r d

If0,

(13)

For apoint source:

= 0,then

Dm=

(19)

For thesurfacesource:

Hencefor the surface source:

dm=

m
cos
4r2d

t1=

(18)

m 1
2
4d h

and

m
1
2
4d (h + x2)2

(26)

Dividing equation (26) by equation (25) one

canget

boatandlimitedamountof
chargefedata
timetotheboat,there
will
benotimefor
contributiontobuildupthedifferentvapour
pressure.Thismethodofdepositioniscalled
flashevaporation.

t1/t0=(1+
where cos =cos

x
)2
h

..(27)

Thechargeisinapowderformisfedfroma
reservoirtotheheaterboatthroughacute.
The
cute is made vibration which is
connectedtoavibrator. The vibrator is adjusted
such that only small amount of
chargefalls
onthe
boat;
sothatitcan
evaporatecompletelybythetimeof next charge
falls
onit.Bythismethodaconstant
compositionfilmcanbeproduced.

=h/r.

B. Flash evoperation:
Thismethod isgenerally adopted when the
materialhas atendency to decompose or
dissociateduring evaporation.

5.Thinfilmthicknessmeasurements:
Thickness playsanimportant roleinthefilm
properties unlike a bulk material. The film
properties are thickness dependent. The
applicationofthinfilmsin opticaldevices like
interference filters anti-reflection coatings
etc. are highly dependents on film thickness.
Inall thicknessmeasurements, it is
generally assumed that the films are
homogeneous and more or less uniformly
deposited on the substrate, and hence
assumedto havemeanthickness t.
Film
thicknessmeasurement
techniquesare
basedondifferentprinciples
suchasmassdifference,light
absorption
interferenceeffects etc.
5.1 Massmethod:
Thismethoddepends
onincreaseof
massofafilmduetodepositionoffilmand
isshowninthefigure.
Theincreaseinfilm
weightcan be measuredby asuitablemicro
balance.

Fig.12
Inthis
process,a
smallamountof
chargeinpowderform isfedatatimetoa whiter
hotboatmadewithtungstenor molybdenum,sothat
instantaneousevaporation
ofthetotalchargetakesplacewithout remains any
residue. This process is showninthe fig.12.
Becauseof thehigh temperatureofthe

This balance is made up of quartz and

depositsareformedonapanwhich is suspended
from the end of the beam by means of
aquartz fibre.

Theotherendofthebeam
carryinga
counterpoise.Apointeroramirrorisattached
tothebeam
ofthebalance.Withincreasingof
weightduring the deposition, thepointermoves
andits
displacementcanbemeasuredbya
travelingmicroscope.Ifmirrorisfixedin
the
placeof thepointer,with depositionof themass
mirror rotatesand therotation canbe measured

Fig.13
bylampandscalearrangement.Beforedoing
theexperimentthebalanceisstandardizedwith
known weights.
Letm isthemassdeposited duetothe
formation of thin film, V the volume of the film
formed,thendensityofthe materialofthethin film,
d=m/V
..(28)
IfAisthesurfaceareaifthefilmandtisthe thickness,
V=t.A
..(29)
Then density canbe givenbytheexpression
d= m/t.A or
t=m/d.A
..(30)
By knowing the massm,film area A and the
density of the material d,the thickness of the
filmcanbemeasured.

5.2CrystalOscillator Method:
Thismethod
wasinvestigatedbySuerbrey/11/.
Inthis method, thicknessmeasurement depends
on oscillationsof quarts crystal whenexcited,
andthefrequencyoftheoscillationsdepends on
thickness by the equation
F= v/2t
=N/t
..(31)
Wherefisthefrequencyofthecrystalisthe velocity
of the transverse wave normal to
l

plateNthefrequencyconstantdependson
ofthecrystalandtisthethicknessofthethin

nature

film.Forquartzcutat35 20,thevalueofNis
1670mm.kc/s.
On depositingthe material on quartz
substrate,thefrequency
goingonchanges.The
change offrequency
df =-Cft dfilm
.(32)
Wheredfilmisthedensityofthefilmdeposited,Cf
isthesensitivityofthemassdetermination.From
the above equation,
t = df/( Cf dfilm) .(33)
Intheaboveexperiment,thetemperatureofthe
quartzcrystal
canaffect
the
frequencyof
oscillations. Whiledepositingthe film onquartz,
thetemperatureincreases.Toavoidthiseffect,
crystaliscooledbeforetakingthemeasurements.
The sensitivity ofthe thicknessmeasurement by
-8
-2
this methodisabout10 g.cm
5.3 Opticalmethod (photometric method):
There are several thickness measuring
methods which depends on optical properties
such as reflection, transmission, interference etc.
The more commonly usedmethodis photometric
method, bases on transmittanceoflight/12/.
Thismethod depends on changein
transmittance oflightat normalincidence.IfI ois
theintensityincidentlightnormallyonafilmand I is
the intensity of the transmittedlight, then,

I
t
=e
I0

.(34)

Wheretisthethicknessofthefilmand isthe
absorptioncoefficient(Lambertslaw).Thisratio of
I/I0is called transmittance T. Then
T=e t
.(35)
Takinglogarithms both thesides,
logT=-t
..(36)
That is, a transmittance versus filmthickness
graphon asemi-log scalewillbeastraight line.
Hence, if one canmeasure the transmittance,
filmthicknesscanbemeasured.Thismethodcan be
usedforthefilmwhichcan not absorb
the light.
Whenlightfalls onthe thinfilmwhich

is coated ona substrate, bothtransmittance T and

reflectance R will showmaximaand minima,
and
vice
versa.
The
position
of
maximaandminimafor both transmittanceand
reflectancecanberecordedinaspectrograph
as
afunctionofwavelength.Letthemaximum
andtheminimumoccursatwavelengths 1

used,bthedisplacement of thefringe at thestep

anda is the fringewidth.

and 2inthe transmissioncase, then

2 nf t =
t=

1 2
1 2

1 2
2nf(1 2)

or

..(37)

Where nf is the refractive index of thefilm.

Fromtheaboveequation,thethicknessofthe
filmcanbemeasured.
5.4Interferometry-method:
Film thicknesscanbemeasuredaccurately by
interference fringes usingmultiple beam
interferometers.
A film,thickness of whichisto be
determined,depositedonflat
surface,soasto
leavesharpedgebetweenthe
filmanduncoated
region ofthe substrate. Amicroscopic
Slide can be used as a substrate. This complete
substrate and the filmare coated with silver
coating for a good reflection. It is having a
sharpstepatthefilmedge.Anotherflatglass
slideknownasareferenceplate,coatedwith
Agasinthecaseoffilm
plate,isthenplaced
overthespecimenasshown inthefig.14 (b).A
monochromaticparallel beanoflight isallowed to
fall normally on these plates. The
arrangementforthisisshowninthefigure14
(a),
which is the similar arrangement as that of
thewedgemethodtofindathicknessof the wire.
The reflectedlightisthenobserved throughthe
microscope.Asetofsharpfringes perpendicular
tothe
stepwithequal
displacementswillbe
observedas shown inthe figure 14(b).
Thethicknesscanbemeasured by the equation,
T=

b
2a

(38)

Wheretheis thewavelength of the light

10

Fig.14
Thesharpnessof thefringedepends onthe
reflectivityof the metal coating, airgap etc.The
metal coating on the two plates should besame.
Thin thick ness of the thin filmcan be measured
0

up tothe orderof 30- 20,000A.

6. Chemical Vapour Deposition (CVD):

Chemical vapour depositionis aversatile process
suitableformanufacturingofcoatings,powders,
fibers etc.Thistechnology isnow an essential
factor inthemanufacturingof semiconductors and
other electroniccomponents, optical,
optoelectronic/13/ etc. Chemical vapour
depositionmay bedefinedasa solid ona heated
surfacefroma chemicalreaction in thevapour
phase.It belongstotheclassof vapour-transfer
process whichis atomistic in nature that is the
depositionspecies are the atoms ormolecules or
the combination of these.
The processcanbedefined in general
formas fallows:
Thedeposition of film from gaseous
phase by thermal decomposition or chemical
reactionon substratesurfacesathigh
temperatureisknown aschemical vapour
deposition process orvapourplating
.
This techniqueis used forthe preparing various

inorganicandorganiccompounds.
The
basic
principle
involves
decompositionsofvapour phasespecies and their
subsequent deposition onsubstrates or reactions
amongthe vapourspeciesinaneutral atmosphere.
Sometimesacarriergas alsoused either to control
rate of the reaction or to preventundesired
reactions attheprevailing elevatedtemperatures.
Some of common reactions for formation of
filmsasgiven below:
AB
AB+CD

A+B
AC+BD

2AB2

AB4+A

(AB)n

nA +nB

Fig.16
areusedfortheformationoffilmdepositon the
surface of the wafer (Substrate). The
remaining waste gas is pump out by an
exhaustpump,afterwastetreatment.
6.1.thermal decomposition:

WhereA,B,C,Darethe
differentconstituents
andnis
aninteger.Therector
fortheCVDis
shownas fallows:

Manycompounds
whenheatedtohigh
temperatures
decompose
resultsinthe
formationofsolidaswellas agaseous phase.
When an organic compound such as tetra
ethylene orthosilicate which is inliquidform
isheatedtoatemperature,adielectricfilm
of
SiO2 isformed.
Si(OC2H5)4

SiO2+4C2H4+ 2H2O
(On decomposition)
Sometimesoxygencanalso
beintroducedin
tothereactortocontrolthecharacteristicof
the film.
Siliconorgermaniumwhenheated
0
to700-900 C
atapressureof10Torr,it
decomposeto formSi and Ge films.
SiH4
Si+ 2H2
GeH4
Ge+ 2H2
Silicon film can also be prepared by the
reduction of tetrachloride silicone vapour
withan nalkalimetal hydride inthe presence of
organic solvent tetra ethylene glycol
dimethyl ether
SiCl4+ LiAl5
SiH4+ LiCl + AlCl3
SiH4
Si +2H2
The reaction for the preparation of carbon
filmfor carbon resistors can be prepared by

Fig.15
Inthisreactor,thereshouldbeagasinflowand an
out flow should be provided for waste
products.
Thepressurizedgasshouldbesent
to
deposition chamber through a gas metering
fromgascabinet.Gasmeteringdeviceisused
tocontrolgas flowintothechamber. Gas chamber
contains a substrate at the bottom
whichisprovidedwitha
heater(Fig.16).The
plasmaor the incoming stream linegas
decomposeandtheatomsormoleculeswhich

11

passingbenzene vapours toa temperature of

500- 10000C.
C6H6
C + Gaseousproducts

takesplace asfallows:
0

SiI4+Si(at1100 C)
0
2SiI2(at900 C)

6.2Vapour phasereaction:

SiI4thusformedcan againbeconnectedto SiI2

by recycling. For theformation of thegermanium
0
filmthetwo temperatureregions should be200 C
0
and 300 Conly whichare much lower than the
siliconiodides.

Siliconoxide(SiO2) filmscanbeproducedby the

reaction of SiCl4 vapour with carbon dioxide
inthepresenceofhydrogen.
SiCl4+ CO2+H2

2SiI2
Si+SiI4

SiO2+ C Cl4+ H2

6.5ApplicationsofCVD:
SnO2
filmoftenusedinmetaloxideresistors
canbepreparedfrom SnCl4vapourinpresence of
water and HCl vapour.
SnCl4+2H2O+ HCl

CVDhasapplicationsacrossawiderangeif
industries.
Coatings:
Coatings
for
a variety of
applicationssuchas wear resistance,corrosion
resistance, hightemperature protection,erosion
protection etc.

SnO2+4HCl +HCl

6.3Vapour transportation method:

Inthismethod,vapours
oftworeacting
constituentsare passed oversubstrate keptat high
temperature
region
when the reaction
takesplacetoform
thedesiredfilm.These
techniquesaregenerally used for the preparations
ofverythickfilmsandevenflat shaped crystals of
several mm sizes.

Semiconductorsandrelated
devices:CVDcanbe
used to produce integrated circuits, sensors, and
opto electricdevices.
Dens structure parts:CVD canalsobe usedto
producecomponents that aredifficult oruncommercial
toproduce
usingconventional
fabrication techniques.

FormationofCdSandCdSe bypassingCdand Sor

Sevapourthroughthefurnace
keptathigh
temperaturecanbe achieved.
Cd+S

Optical fibers:For telecommunications.

Composites:thesetechniquesare
usedto
reproduceceramiccompositessuchas
carboncarbon, carbon siliconcarbides siliconcarbidessilicon carbide composites. This process
sometimes calledas chemical vapour infiltration.

CdS

Cd+Se
CdSe
In this technique, their will be three
temperaturezones,twoforvaporization of two
constituent elements and bringthem together to
reactat a thirdzonetoformdirectproduct.

Powder production: This technique is used to

produce thenovel powders.

6.4 Disproportionalmethod:

Thesetechniquesarealsousedincatalystsand
nanomechines.

Thisdependsonthedifferenceinthestability
ofpolyvalent
metalcompounds
attwo
temperatures.
BothSiI2and GeI2arestable atlower
temperatures
whereasSiI2andGeI2at
comparatively high temperatures. By preparing
0
SiI2
vapourathightemperatures(1100 C)and
passingthemthroughatube
keptatlower
0
temperature(900 C),areaction cycle will

7. Electrical properties of thin films:

In the case of thinmetallic films, its resistively
hasbeenfound to bemuch highertothat of
correspondingbulk material,and it decreases with
increasing film thickness and attains a valueafter
approaching the bulk and then becomes constant
as shown inthe fig.17.

12

An introduction to thin films Dr. Jeevan

filmfromwhichtheelectronsscatteringinall
thedirections.Thereare threeregions of scattering
1)between0and 1,theelectrons will not able to
travel
their mean free
path (mfp)l`b
,andhencetheystrikethesurface.In

region(2)between 1 and2,theelectronswill travel

l band in region (3)

between2and,theelectronsonceagainhit
surface asmfp is less thanl b.
their full mfp

Conductivityagainstthicknesst

Fig.17

Theratiooftheconductivityofthefilmf to
the bulkl bis givenas fallows:

f lf
=
b l b

Thin films are classified as continuous and

discontinuous media. If the thin film is
continuous with out any break or gap in
betweentheadjacent
regionsandhassome
crystallinestructurethat
of
bulkmaterial,is
calledcontinuous
film,if
not,itiscalled
discontinuous film.
7.1.Conductionin continuous metallic film:
Ifthethicknessofthefilmisattheorderofthe
meanfreepathofelectron,thentheconduction
electrons willbemorefrequentlyscatteredby two
surface
boundaries.
Consequently,
its
conductivitydecreases.Thisdecrease
of
conductivityduetoreductionofthematerial size is
calledsize effect.

Filmsurface

Fig.18
Theconductivityofthinfilm

=
If

f dependson

thethicknessofthefilmt.Thescatteringof
electronscanbe explained asfallows:
Let us consider anarbitrarypoint withinthe

3t
1t
l
+
log b
4l b 2l b
t

t
= k, then one can write the equationas
lb

f3kk1
= + log
b 4 2 k

. (39)

Accordingto Sondheimer, the relation between

conductivity of filmandbulkis givenas,fort
lb and k 1,

f3k1
[log ]
b
k
For thickfilms,tl b,and k 1,
f

3 1
= b = [1+ ]
b f
8k
3 3l
fb
=1+ = 1+
b
8k
8t
=
4

Filmsurface

the

(40)

On expanding inpower seriesandneglecting

thehigher orderterms,

f 3
b

=t[1 l]
8

(41)

An introduction to thin films- Dr. Jeevan

It is observedthatbis always greater thanf . Let P

is the fraction of electrons is secularly scattered
from two surfaces and the rest are
diffusedwithcompletelossoftheirenergy.Then,
onecan write

b
f

3
=1+ (1p)
8k

cs
Na
Rb

f.d

.. (42)

From theequation(42),itcanbeobservedthat, when

p=1,b =f ,thatistheconductivityof thefilm
isindependentofthethickness, and same asthatof
thebulk..
If p 1, or nearly equal tozero,

1
3
1+
8k
1
f =b
.(43)
3lb
1+
8t
Thevaluesoff decreaseswithdecreasingthe

f =b

thickness. A graph between

f
b

against k is

showninthefigure.19,fordifferentvaluesofp.
These experimental curves show a reasonable
agreement with predicted values.

P=1

d
Fig.20
A graph betweenf.t
versus where t is the
Theslopeofthegraphgivesgivesthevalue
off .
7.2. Temperature coefficient of resistivity:
Thetemperaturecoefficientofresistivitycan
bedefinedastheratioofthechangeofthe
resistivelyperunitriseofthetemperatureto
its initial resistivity.

d bis
If b istheresistivelyofthebulk,
the change in resistivity in dT rise of
temperature, then
Temperaturecoefficientofresistanceofthe bulk
(TCR) b=

P=0

1 db
=b
b dT

(44)
Similarly, the temperature coefficient of
resistancefor thefilmcan bewrittenas

1 dt
(TCR) f =
=
t dT

(45)

Dividingtheequation(45)bytheequation
(44)

k
Fig.19
Thicknessofthefilm,fordifferentelementsis
shownin thefigure.20.

f
df dT
= b. .
b f
dT db

Forasmallriseoftemperature,thechangein
bulk resistivity and the change in film
resistivity is almost equal and hence,

An introduction to thin films Dr. Jeevan

f
b

b f
=
f b

8. Optical behavior of thin films:

(46)

ThisratioofTCRofafilmtoitsbulkisproportional
totheratio of their conductivities.
7.3.Conductivity and activation energy
Athinfilm
generallyexhibitsa
highresistivity.
Conductioncanbetakesplaceinhighelectricfields
fortheelectrons
to
overcomethepotentialbarrier
betweenthe islands.
The variation of resistance withtemperaturecan be
represented as

R=AT
eKT
0
Where

..(46)

A0,theconstantsforaparticularmetalfilm

and Eis theactivationenergyfortheconduction.

The resistance of such a film decreases with
temperature.Inthehighfields,theresistanceofthe
filmlinearly dependent onthe field.
Thevalueofconductivity versus1/T,whereTis the
temperature inKelvin for the thin filmscoated on
Pyrexsubstrateatdifferentthicknessisshowninthe
figure.21.

Decreasingd

Optical
propertiesoffilmshave
beenstudied
extensively because of their applications in
variousopticalandelectro-opticaldeviancesand
ithasbeen foundthatthereis oftenaconsiderable
deviationofopticalparametersfrom
thatofbulk
material.
8.1.Reflection,transmission,
absorptionand
energy gap:
Whenabeamoflightpassesthroughathinfilm,
it
ispartiallyreflected,
transmittedandabsorbed.
LetR,AandTarethereflected,absorbedand
transmittedlightand
incident light, then

I0 =R+A+T

.. (47)

Reflectancecanbedefinesastheintensityoflight
reflected tothe intensity of incident light.
If Ir istheintensityofthereflectedlight,the
reflectance
R=

Ir
I0

(48)

Absorbance can be defined as the ratio of

intensity of the light absorbed to the incident
light.If I istheintensityoflightabsorbed,the
a

absorbance,

I
A= a
I0

Log

I0 istheintensity0fthe

.. (49)

Transmittancecan be definesasthe ratioof intensity

oflight transmittedtothe intensity of incident light.
IfIt istheintensityoflighttransmitted,then,the

1/T
Fig.21

the transmittance,

I
T= t
I0

.. (50)

Addingtheequations48, 49and 50,

Itisinterestingto
notethattheactivationenergy
also
dependsonthefilm
thickness.Onincreasingthefilm
thickness, the activation energy
decreases
continuously, and becomes constant after certain
thickness. Beyondthat, the activation energy and
conductivity behaves like a bulkmaterial.

R+A+T=(Ir +Ia +It)/I0=1 .(51)

Forperfectlynon-absorbingmaterial,Ia =0and
hence, R + T=1.

Whenamonochromaticbeam oflightincident ona

medium ata normalincidence,therelationbetween R,n
andKare givenas
2

R=

(n1) +k
(n+1)2 +k2

.. (52)

Theresultingabsorptionspectrum
is
however,iscontinuous
ofintenseabsorptionat
shorter wavelength.
A plot between energy versus wave
vector k isshown inthefigure.23.

And
2 t

T=

(1R) e
(53)
2t
1R
isthecoefficientofabsorption,tisthe

Where
thicknessofthefilmthroughwhichthelightpasses
and k is the extinctionconstant.
Anabsorptionspectrum
ofathinfilmmaterialis
showninthe
fig.22.Theabsorptionoflightbythe
filmmay takesplacebroadly by twoprocesses:

direct
indirect

E Eg

k
Fig.23

log

h
Fig.22
1. Byraisingtheelectronsfromvalenceband
totheconduction band and
2. By exciting the lattice vibrations of the
materialbyphotonenergy,
orbyboth
processes.
The lattice provides the information of bond
length, effective charges and lattice vibrational
frequencies. Electronic bond structure can be
studied by process1.
Opticalmethodsprovide very simpleway of
findingthe bandgapcomparingto electrical methods.
Evenintheabsenceofanythermalenergyat
0Konlypossibleabsorptionthattcantakesplace is
whentheincidentradiationhassufficientenergyto
excite valence electrons across forbidden energy
band gapin to theconduction band.

Thetransitionissaidto
be direct
whenthe
conduction band minimum and the valence
bandmaximum
occursatthesamewavelength.
The absorption edge
may occur
at
h=EgwhereEg,theminimumwidthofthe
forbiddenenergy
band
ofthematerial.Ifthe
minimum
oftheconductionbandandthe
maximumofthevalencebanddonotcoincide,
the transition is saidto be indirect.
Thus the
electronic
transitions
betweenthevalenceandconductionbands
can
beadirectorindirect.Thetransitionprobably
related withabsorptioncoefficient as

=A(hEg)

..(54)

Where p is called transition probability. A

graphforlogand loghis shown in fig.24.
Allthegraphsarestraightlinesandtheslopeof the
graph gives the value of p. The p has
discretevalueslike,1,3/1,2..
Letusnowconsiderthecaseofmetals
wheretheabsorptionisprimarilyduetofree
charge carriers leadingto theinterband

An introduction to thin films Dr. Jeevan

transitions involving nochangeof energy. Then
the absorptioncoefficientisgiven as
2
4
Ne
=
ncm *(1+22)

.. (55)

Wherenis therefractive index,c thevelocity of

light,Nfreechargeconcentration, relaxation
*

time andm is the reducedmass. If

2 2

1, then

2
4
Ne
=
* 2 2
ncm

Refractionand transmission by single film:

Let us consider a thin film PQ, RS on their
boundaries,letalightisincidentatAwithan
angleof0.Apartofthelightisreflectedand the rest is
transmitted through the film and
emerges out from other side of the film of
thicknessd 1 .Let 1 istheangleofrefraction.
TherayatCcanalsobereflectedintothesame
medium and suffers number of reflections as
shownin thefig.25.

4 Ne2
=
* 2
ncm
2c

As=

On substituting andsimplification,

Ne 2 2
3
c m*n

.. (56)

whereis thewavelength of the lightused.A

2

graph between and is shown inthe fig.24.

Fig.25

Fig.24

Combinationof
parallelreflected
beams
representedby
1,2,3,4thetransmittedbeamof
lightrayscam berepresentedby1,2,3,4. These
raysmayleadto constructive or destructive
interference depending on optical pathlength
traveledbythe rays, beforetheircombination. Let
DBis perpendiculartoAB,thenthepath difference
ofthetworays
= (AC+CD)-AM
=2n1d1cos 1

It shows that and is linearlydependent.

Thisgenerally happensin visibleandinfrared
region .Thelinearity generally observed for
metals andsemimetallic substances.

.. (57)
idthethicknessofthemedium(thin

d1
film)andn1 is the refractive index. The pointD
Where

AndMwillbeinthesamephase.Thenthe optical
pathdifference,

= 2n1d1cos 1

(58)

Whereis thewavelength of the lightused.

Nowifweconsiderallthereflected
rays1,2,3, there will be a constant phase
difference 1 betweenthesuccessiveraysdue
toextraopticalpathtraversedbythemediumin
thefilm.Andis given by

1 =

2
n1d1cos 1

r= a1r1+a 2r2 +........

= a1 r1
Where a1r1,a 2r2.Aretheamplitudesof
the reflectedwaves1, 2,3..
The total reflectance or the reflectivity is
given by the equation,

R=r =

fieldwithreferenceto zeromagneticfieldscan
defineas magneto-resistance.
The magneto-resistanceof amaterial
canbedefinedasthechangein resistively due
tothe applied magnetic field totheresistively
at zero field.
If H and0 are theresistivities
of a substanceat fieldH and field zero, then
The magneto resistance

The summation of the amplitudes of the

reflected rays

2
21 2 1 2 1

The length of the sample will reduce causing

increasingof its resistance. The change inthe
electricalresistanceduetoapplied magnetic

r+r+2rrcos2
1+r1 r22 2 +2r1r2cos2 1

..(59)

Similarly, the transmittance T is given by

2 2
ntt
T =t =
2 2
n01+2rrcos2
+r1 r 1
12
2 11 2

.(60)

9. Magneto resistance:
The application of magnetic field alters the
electricalresistance ofa thin film.Thischange in
the resistanceof materialdue to the applicationof
themagnetic
fieldprovides
informationregardingthe
shapeoftheFermi
surfaceof the thinfilm.
When electrons are moving in a
substance, and a magnetic field is applied
perpendiculartothecurrentdirection,aHall
field will be built up to counterbalance the
Lorentzforce.Alltheseelectronswillnothave
samevelocity.AsaresulttheHallEffectcan
compensate the Lorentz force and the net
current inthe directionis zero. Fast electrons
whichdeviateone way orother undergo more
collisions. As theresult theirmeanfree along

H 0
=
0
0

(61)

As the resistivity is the reciprocal of

conductivity and let Hand arethe
0
conductivities at field H andzero respectively,
Magnetoresistance
=

(62)

Whenmagnetic fieldissmall, the magneto

resistance isproportional tothe squareof the
field,and hence,

2
=AH
0

..(63)

Where is isknown as coefficientof magneto

resistivity. Forhigher fields, the magneto
resistancefallows thequadratic law
2

AH
=
0 1+CH

..(64)

Wherec= andis the electron mobility. If

H=0,equation (64)convertstoequation (63)
In the caseof transverse magnetic
field, the coefficientof magneto resistance

A=(

0 2
)
2ne

. (65)

Where nis thenumberof electronsper unit

volumeand eis the chargeofthe electron.
Substituting the value ofA in equation (63)

0 2 2
=( )H
0
2ne

..(66)

Kohler showedthat the magneto resistance

depends on temperature, magnetic field and
even
onsamplepurityand
geometrical
consideration.Accordingto him,

H
=f ( )
0
0

..(67)

F is a function depending on geometrical

consideration and field direction. The

H
is
0

dependenceofmagnetoresistanceon
shown in the
temperatures.

figure

.26.at

different

Wilson-Summerfieldtheorygivestherelation
between resistivity inthe magnetic field H as

H =0 (1+0.2732H2)Or
H
2 2
.(68)
=(1+0.273 H )
0
It indicates that, the magneto resistance is a
strong function of mobility. Higher the
. This

parameterdependsongeometryofthesample.
Forarectangularsample,

H
0

variesonlength

tobreadthratio(l/b).Forasmallervalueof
(l/b),

H
0

.(69)

where istheresistivityofthematerial.IfW
isthewidthandtisthethicknessofthethin film, then
we can write,

Fig.26

H
0

Sheetresistanceisthemeasureofresistanceof thin
films that hasuniformthickness.
For a rectangular three dimensional
conductor, the resistance of a conductor is
directlyproportionaltoitslengthandinversely
proportional to the areaofcross section.
IfListhelengthandAistheareaof
crosssection,resistance

L
or
A
L
R=
A

H
0
(1)78K (2)195K (3)219K

mobility, higher the ratio of

10. Sheet Resistance:

2
1

less than, the magnetoresistance is

independent of its dimensions (Reverse in the
caseof
HallEffect).Themagnetoresistanceof
thinfilmdecreaseswithdecreasingofparticle
size/14/

isalarger one.Ifthe(l/b)value is

LWt
R=
L
R=
tW
L
R=R s
.(70)
W
Rsiscalledsheetresistanceandcanbe
Where
L
definesasresistivityperunitthickness.As
W
isadimensionallessquantity,theunitofsheet
resistance must be ohm. To differentiate from
resistance,theunitofsheetresistance is considered
as ohm/square. If L=W, for a
square,R= R s forasquarelamina,thesheet
resistance is equal to the resistance of the
lamina.
Measurement:
Sheetresistancecanbemeasuredbyfour-point
probemethod.Ageometricalcorrectionfactor
(CF) is usually required to convert the

factoraccountsaccordingtothesamplesize, shape
andspacing.
The sheet resistance measured by the fourprobemethod

V
R s= x(CF)
I

..(71)

Where Visthe measured DC voltage across the

voltageprobe
andIistheDCcurrentpassing
throughthetwocurrentprobes.Thevalueof
CFforsamplesof various sizesandshapes can
befound inthe referencebooks.
Thesheetresistanceofathinfilm
with
differentdopingconcentrationsis
showninthe
fig.27.

Fig.27
Onincreasingthedoping
concentration,the
sheetresistancedecreases continuously.The value
of sheet resistance is less for
n-type
dopingthanp-typedopingforthe
samedoping
concentration.

Applications:
It is usually usedtoevaluatethe out come of
semiconductor doping,metal deposition and
resistivepasteprinting.Thisapplicationcanalso
be used in screen printing and hybrid micro
circuits.

References:
1.J.A.Venables, Rep.Prog.Phys.47 (1984)399
2.C.Ratsch,
J.A.Venables.Jour.Vac.Science&Tech.A21
(2003) S96
3.J.Poortmansand V. Arkipov,thin filmsolar
cells, John Wiley & sonspublications(2006)
4.Joachim.P et al Sensors4(2004)156
5.Mereno, etal.Opticsletters30 (2005)914
6. H.Okimura. 17(1980)5359
7.Rezamoazzami, IEEE tras. Elct. dev.
39 (1992) 2044
8.Thinfilmprocesses: ElsevierPublishing,1991
9.M.YamaguchinandTNagotoma Jpn.Jour.
Phys. 37(1998)5166
10.Hand book of thinfilmdeposition processes
and techniques. Krishna sheshan, William
AndrewPublishing,2002.
11.G.Sauerbrey,ZeitschriftfrPhysik,155
(1959) 206-222
12. B. A. Nikitinet.al. Measurement techniques,
30 (1987)196
13.Hideki Matsumura et.al, Thin Solid Films,
501(2006) 58.
14.B. P. ZoteV,Russian physics journal,
18(1975)69