Structureandpropertiesoftransparent

conductiveZnOfilmsgrownbypulsedlaser
deposition(PLD)

by
YuHsiu,Lin

Adissertationsubmittedto
theUniversityofBirmingham
forthedegreeof
MasterofResearch

SchoolofMetallurgyandMaterials
UniversityofBirmingham
September2009









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Acknowledgements
I would like to acknowledge sincerely to my supervisor Prof. Abell for his kindness, excellent
explanationsthroughoutmystudy.

IwouldalsoliketoexpressmysinceregratitudetoDrStephenNKukurekaforhisenlighteningideasand
patientguidance.

SpecialthanksaregiventoMrBradshawforhistechnicalsupportduringmyexperiment.

ManythanksaregiventoallstaffinschoolofMetallurgyandMaterialsandespeciallytomycolleagues
ofthesuperconductivitygroupfortheirhelpandsupportduringmyMasterstudies.

Finally,Iwouldliketothankmyfamilyandfriendsfortheinvaluablehelpandendlessencouragement.
.
Abstract
Zinc Oxide (ZnO) has attracted interest due to its potential applications including nonlinear optical
devices, blueviolet emission device, buffer layer for GaNbased devices, visiblerange transparent
electrodes for solar cell and flat panel displays, surface acoustic wave devices, piezoelectric and piezo
optic devices, gas sensors for oxygen, and integrated optical devices such as optical waveguides.
Furthermore, ZnO is nontoxic and inexpensive and has comparable electrical and optical properties to
commerciallyavailableIndiumTinOxide(ITO).

ZnOthinfilmsweregrownonglasssubstratesbythepulsedlaserdeposition(PLD)techniqueusingaKrF
excimer laser with wavelength of 248nm. The influence of ambient oxygen pressure, substrate
temperature, laser fluence, the number of pulses and doping with silicon was investigated. The
structural, optical and electrical properties of ZnO thin films were investigated using Xray diffraction
(XRD),atomicforcemicroscopy(AFM),scanningelectronic microscopy(SEM), spectrophotometersand
resistancemeasurementbythefourpointprobe.

Regarding the influence of oxygen pressure, XRD measurements indicate that the ZnO thin films
depositedattheoxygenpressureof10mTorr(1.3Pa)crystallizewell.AFMresultsshowthatthesurface
roughnessofZnOfilmincreaseswithanincreaseofoxygenpressure.Theelectricalresistivityshoweda
minimumforanoxygenpartialpressureof10mTorr(1.3Pa).

Theeffectof thesubstratetemperaturesintherangeof100 to500 onthepropertiesofZnOthin

films was investigated with the oxygen pressure kept at 10 mTorr. The lowest resistivity was observed
forasubstratetemperatureof200C.

The effect of postgrowth annealing showed that for temperatures < 300 , it is observed that the
resistivity of the ZnO films decreases slightly. As the annealing temperature increases up to 500 , the
resistivity of the ZnO films increases dramatically. Furthermore, The ZnO films show an increase of
transmittance with annealing temperature, which probably indicates that the annealing treatment
improvedthecrystallinity.
ZnO thin films were deposited using a different number of pulses in order to investigate the thickness
dependenceofthestructural,electricalandopticalpropertiesofthefilms.Itwasfoundthatcorrelation
betweenthicknessandresistivityofZnOthinfilmsisnegativeduetothethickerfilmshavingfewerpoint
defectssuchasoxygenvacancies.ThetransmittanceofZnOthinfilmsisdecreasedduetothethickness
effect.
Laserenergydensitywasvariedintherangefrom1.16J/cm
2
to2.73J/cm
2
anditwasobservedthatthe
resistivityofZnOthinfilmsdeclineswithincreasinglaserfluenceupto1.51J/cm
2
.However,athigher
fluences up to 2.27 J/cm
2
, the resistivity dramatically increases, and the relatively low resistivity of the
ZnO thin films of 3.1x10
3
/cm is found at a laser fluence of 1.51J/cm
2
. The optical transmittance
increaseswithincreaseoflaserfluence,from1.16J/cm
2
to2.27J/cm
2
intherangeofwavelengthof350
nm to 450 nm. However, as the laser fluence increases up to 2.73 J/cm
2
, the optical transmittance
significantlydeclines.

Theinfluenceofimpuritydopingwasinvestigatedbyusinga2wt%SiZnOtarget.Itwasobservedthat
thedopedfilmshadlowerresistivitythanpureZnOfilms(from9x10
3
cmto7x10
4
cm).Probably
duetotheincreaseincarrierconcentrationwithdopingtheSiionsenteringintotheZnOlatticecaused
ashiftintheabsorptionedgeandtheaveragetransmittanceincreasedto85%inthevisibleregionafter
dopingwith2wt%silicon.
1

Contents
1 Introduction.................................................................................................................................................7
1.1 Zincoxide.............................................................................................................................................7
1.2 Challengesinthisproject....................................................................................................................8
1.3 Aimsandobjectives.............................................................................................................................8
1.4 Organizationofthethesis...................................................................................................................8
2 LiteratureReview......................................................................................................................................10
2.1 Transparentconductingoxides(TCOs)..............................................................................................10
2.1.1 ZnOstructure.............................................................................................................................10
2.1.2 ElectricalpropertiesofZnO.......................................................................................................11
2.1.3 OpticalpropertiesofZnO..........................................................................................................12
2.1.4 EffectofdopingZnOwithimpurity...........................................................................................13
2.2 Pulsedlaserdeposition(PLD)............................................................................................................14
2.2.1 IntroductiontoPLD...................................................................................................................14
2.2.2 ThegrowthofthinfilmsbyPLD................................................................................................14
2.2.3 TheadvantagesofPLD..............................................................................................................15
2.2.4 ThedisadvantagesofPLD..........................................................................................................16
2.3 OtherZnOthinfilmfabricationmethods..........................................................................................17
2.3.1 RFmagnetronsputtering...........................................................................................................17
2.3.2 Molecularbeamepitaxy............................................................................................................18
2.3.3 Chemicalvapordeposition........................................................................................................18
2.4 ApplicationofZnOthinfilms.............................................................................................................19
3 ExperimentalProcedures..........................................................................................................................21
3.1 PLD.....................................................................................................................................................21
3.2 Conductivitymeasurement...............................................................................................................21
3.3 Transparencymeasurement..............................................................................................................22
2

3.4 Structure............................................................................................................................................23
3.5 SurfaceMorphology..........................................................................................................................24
3.5.1 Scanningelectronmicroscope(SEM)........................................................................................24
3.5.2 Atomicforcemicroscope(AFM)................................................................................................24
3.6 Thicknessmeasurement....................................................................................................................25
4 Resultsanddiscussion...............................................................................................................................26
4.1 Influenceofoxygenpressure............................................................................................................26
4.1.1 Electricalproperties...................................................................................................................26
4.1.2 Opticalproperties......................................................................................................................27
4.1.3 Surfacemorphology..................................................................................................................27
4.1.4 Structuralproperties.................................................................................................................28
4.2 Influenceofsubstratetemperature..................................................................................................28
4.2.1 Electricalproperties...................................................................................................................29
4.2.2 Opticalproperties......................................................................................................................29
4.2.3 Surfacemorphology..................................................................................................................29
4.2.4 Structuralproperties.................................................................................................................30
4.3 Influenceofannealing.......................................................................................................................30
4.3.1 Electricalproperties...................................................................................................................31
4.3.2 Opticalproperties......................................................................................................................31
4.3.3 Surfacemorphology..................................................................................................................31
4.3.4 Structuralproperties.................................................................................................................32
4.4 InfluenceofthenumberofpulsesonZnOfilms...............................................................................32
4.4.1 Structuralproperties.................................................................................................................32
4.4.2 Opticalproperties......................................................................................................................33
4.4.3 Electricalproperties...................................................................................................................33
4.5 InfluenceoflaserfluenceonZnOfilms.............................................................................................33
4.5.1 Structuralproperties.................................................................................................................34
3

4.5.2 Electricalproperties...................................................................................................................34
4.5.3 Opticalproperties......................................................................................................................34
4.6 Influenceofdopingwithsilicon........................................................................................................35
4.6.1 Electricalandopticalproperties................................................................................................35
4.6.2 Structuralproperties.................................................................................................................36
5 Conclusions................................................................................................................................................37
5.1 Conclusions........................................................................................................................................37
6 Futurework...............................................................................................................................................39
7 References.................................................................................................................................................40
Appendix............................................................................................................................................................45
FiguresandtablesfromChapter2................................................................................................................45
FiguresandtablesfromChapter4................................................................................................................61

Figure21StickandballrepresentationofZnOcrystalstructures:(a)cubicrocksalt(B1),(b)cubiczincblend(B3),and(c)
hexagonalwurztie(B4).TheshadedgrayandblackspheresdenoteZnandOatoms,respectively.[79]..........................46
Figure22SchematicrepresentationofawurtziticZnOstructurehavinglatticeconstantainthebaselplaneandcinthe
baseldirection;uparameterisexpressedasthebondlengthorthenearestneighbordistantbdividedbyc(0.375inideal
crystal),andand(109.47
o
inidealcrystal)arethebondangles.[79]..........................................................................46
Figure23(a)Mechanismofphotonabsorptionfornonmetallicmaterialsinwhichanelectronisexcitedacrosstheband
gap,leavingbehindaholeinthevalenceband.Theenergyofthephotonabsorbedis E,whichisnecessarilygreater
thanthebandgapenergyEg.(b)Emissionofaphotonoflightbyadirectelectrontransitionacrossthebandgap.[21]47
Figure24Thespectrumofelectromagneticradiation,includingwavelengthrangesforthevariouscolorsinthevisible
spectrum.[21]..................................................................................................................................................................47
Figure25Therelationbetweenabsorptionandtheenergyband:Metal.......................................................................48
Figure26Therelationbetweenabsorptionandtheenergyband:Semiconductors........................................................48
Figure27TheSchematicdescriptionofaPLDexperimentalsetup[55]..........................................................................49
Figure28SchematicofthePLDprocess[18]...................................................................................................................49
Figure29Filmgrowthmodeslayerbylayer:(a)FrankVanderMerwe,island;(b)VolmerWeber(c),.......................50
Figure210Theprocessofsputter(1)(fromhttp://www.ajaint.com/whatis.htm)..........................................................50
Figure211Theprocessofsputter(2)(fromhttp://www.ajaint.com/whatis.htm)..........................................................51
Figure212Themagnetsputter(fromhttp://www.ajaint.com/whatis.htm)...................................................................51
Figure213TheSchematicdescriptionofMBE................................................................................................................52
Figure214SequenceofgastransportationandreactionprocesscontributingtoCVDfilmgrowth[9]...........................53
Figure215TheSchematicofCVD(fromChiMeiCorporationestablishedChiMeiOptoelectronicsLTD.)........................54
Figure216Thestructureoftransparent thin-film transistor (fromChiMeiCorporationestablishedChiMei
OptoelectronicsLTD.).......................................................................................................................................................54
Figure217ThepictureofthePLDsystemusedinUniversityofBirmingham..................................................................55
Figure218SchematicdiagramofaFourpointProbe....................................................................................................55
Figure219(a)Demonstrationofhowtwowavesthathavethesamewavelength andremaininphaseaftera
scatteringeventafterascattering(b)Demonstrationofhowtwowavesthathavethesamewavelength andbecome
outofthephaseafterascatteringeventafterascattering[21]......................................................................................56
Figure220Diffractionofxraysbyplansofatoms.[21]..................................................................................................57
Figure221TheSchematicdiagramoftransmittance(fromhttp://en.wikipedia.org/wiki/Wiki)....................................57
Figure222ThepictureofSpectrophotometer................................................................................................................58
Figure223ThepictureofSEMJEOL7000.......................................................................................................................58
Figure224TheSchematicdiagramofaSEM(fromProfessorIanJoneslecture)...........................................................59
Figure225ThepictureofFieldemission(fromProfessorIanJoneslecture)..................................................................59
Figure226TheSchematicdiagramofAFM(fromhttp://en.wikipedia.org/wiki/Wiki)...................................................60
Figure227ThepictureofcrosssectionofZnOthinfilmsbySEM...................................................................................60
Figure428ResistivityofZnOfilmsdepositedatvariousambientoxygenpressures(D=55mm,Ts=300 ,Laser
fluence=2.7J/cm
2
)............................................................................................................................................................62
5

Figure429Aplotofelectronconcentrationandresistivityvs.oxygenpressureasresultofHallmeasurements.The
resultsfromsamplesgrownwith1mTorrand200 and300 arealsoplotted.[80]...................................................62
Figure430TransmittancespectraofZnOfilmsonglasssubstrategrownatdifferentambientoxygenpressures.
(D=55mm,Ts=300 ,Laserfluence=2.7J/cm
2
).................................................................................................................63
Figure431AFM3Dimages(22m)ofZnOwithvaryingambientoxygenpressure.(D=55mm,Ts=300 ,Laser
fluence=2.7J/cm
2
)............................................................................................................................................................63
Figure432 RoughnessofZnOfilmsdepositedbyPLD(D=55mm,Ts=300 ,Laserfluence=2.7J/cm
2
)..........................64
Figure433XRDpatternofZnOfilmsdepositedbyPLDwithvaryingoxygenpressures.(D=55mm,Ts=300 ,Laser
fluence=2.7J/cm
2
)............................................................................................................................................................65
Figure434peakintensityofXRDpatternofZnOfilmsdepositedbyPLDwithvaryingoxygenpressures.(D=55mm,
Ts=300 ,Laserfluence=2.7J/cm
2
)..................................................................................................................................66
Figure435VariationintheFWHMof(002)reflectionsofTheZnOfilmsasafunctionofoxygenpressures.(D=55mm,
Ts=300 ,Laserfluence=2.7J/cm
2
)..................................................................................................................................67
Figure436ResistivityofZnOfilmsdepositedatvariousSubstratetemperatures(D=55mm,Po2=10mTorr,Laser
fluence=2.7J/cm
2
)............................................................................................................................................................68
Figure437TheelectricalpropertiesofZnOthinfilmsdepositedatvarioustemperatures[14]........................................68
Figure438OpticaltransmittancespectraoftheZnOthinfilmsgrownatvarioussubstratetemperature.(D=55mm,
Po2=10mTorr,Laserfluence=2.7J/cm
2
)............................................................................................................................69
Figure439AFMimageofZnOthinfilmsdepositedatvarioussubstratetemperatures..................................................70
Figure440RoughnessofZnOthinfilmsdepositedatvarioustemperatures...................................................................70
Figure441FWHMof(002)XRdpeaksfromZnOthinfilmsdepositedatvarioustemperatures......................................71
Figure442XRDpatternsofZnOthinfilmsdepositedatvarioussubstratetemperatures................................................71
Figure443Peakintensityof(002)diffractionpeakfortheZnOfilmsdepositedatvarioustemperatures.......................72
Figure444ResistivityofZnOfilmsdepositedatvariousannealingtemperatures(D=55mm,Po2=10mTorr,Ts=200 ,
Laserfluence=2.7J/cm
2
)..................................................................................................................................................73
Figure445theopticaltransmittancespectrumofZnOthinfilmsdepositedonglasssubstrateforasdeposited,and
postgrowthannealedatvariousannealingtemperatures.(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)74
Figure446Peakintensityof(002)diffractionpeakfortheZnOfilmsdepositedatvariousannealingtemperatures
(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)..........................................................................................75
Figure447AFMimageofZnOthinfilmsdepositedatvariousannealingtemperatures.(D=55mm,Po2=10mTorr,
Ts=200 ,Laserfluence=2.7J/cm
2
)..................................................................................................................................76
Figure448TheSEMimageofZnOthinfilm:(a)asgrow,and(b)annealingat500 for2hinoxygen(D=55mm,
Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)...........................................................................................................77
Figure449RoughnessofZnOthinfilmdepositedatvariousannealingtemperatures.(D=55mm,Po2=10mTorr,Ts=200 ,
Laserfluence=2.7J/cm
2
)..................................................................................................................................................78
Figure450TheXRDpatternofZnOthinfilmsdepositedatvariousannealingtemperatures..(D=55mm,Po2=10mTorr,
Ts=200 ,Laserfluence=2.7J/cm
2
)..................................................................................................................................79
Figure451XraydiffractionspectraofZnOthinfilmdepositedatthevariousnumberoflaserpulses.(D=55mm,Po2=
6

10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)...................................................................................................................80
Figure452Peakintensityof(002)diffractionpeakfortheZnOfilmsdepositedatthevariousnumberoflaserpulses.
(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)..........................................................................................81
Figure453theopticaltransmittancespectrumofZnOthinfilmsdepositedonglasssubstratewiththevariousnumber
oflaserpulses.(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)..................................................................82
Figure454TheresistivityofZnOthinfilmsdepositedatthevariousnumberoflaserpulses..........................................83
Figure455XraydiffractionspectraofZnOthinfilmdepositedatvariouslaserfluence.(D=55mm,Po2=10mTorr,
Ts=200 )........................................................................................................................................................................84
Figure456Peakintensityof(002)diffractionpeakfortheZnOfilmsdepositedatvariouslaserfluence(D=55mm,
Po2=10mTorr,Ts=200 ).................................................................................................................................................85
Figure457ResistivityofZnOthinfilmsdepositedatvariouslaserfluence.....................................................................86
Figure458theopticaltransmittancespectrumofZnOthinfilmsdepositedonglasssubstrateswiththevariouslaser
fluence(D=55mm,Po2=10mTorr,Ts=200 ,thenumberoflaserpulse=5000)...............................................................87
Figure459Resistivity,andcarrierconcentrationasafunctionofSiZnOthinfilms(D=55mm,Po2=5mTorr,Ts=200 ,the
numberoflaserpulse=5000)...........................................................................................................................................88
Figure460AbsorptionspectraofpureZnOthinfilmand2wt%SidopedZnO................................................................89
Figure461XraydiffractionspectraofZnOthinfilmandSiZnOthinfilm(D=55mm,Po2=5mTorr&10mTorr,Ts=200 ,
Laserfluence=2.7J/cm
2
)..................................................................................................................................................90

1 Introduction
1.1 Zincoxide
Much of the academic literature on transparent conductive oxides (TCO) films by pulsed
laserdeposition(PLD)isfocussedonIndiumTinOxide(ITO)thinfilms.Howeverinrecent
years, due to the wide application of ITO materials, the cost of ITO materials is rising,
which is forcing many scientists to search for new kind of materials to replace ITO. Of
these new kinds of materials, ZnO thin films have attracted the most attention, because
unlike the more commonly used ITO, ZnO is a nontoxic and inexpensive material due to
abundant ZnO resources. We can find obvious evidence in the fact that more than 1500
papers have been published on ZnO thin films growth and properties of ZnO in this
decade.
Zincoxide(ZnO)isan ntypesemiconductorhavingabandgapof3.3eVatroom
temperature, large exciton binding energy (60 meV) and optical transparency [1, 2]. The
propertiesofZnOwithadirectbandgapandhighexcitonbindingenergyaremuchhigher
than those of other widely used widebandgap materials, for example, ZnSe (20 meV)
andGaN(21meV).Moreover,theZnOthinfilmscanbedepositedatalowertemperature
than ZnSe and GaN. Therefore, its widebandgap properties enable ZnO to become a
potentialmaterialforshortwavelengthoptoelectronicdevices,suchasUVlasers,blueto
UV lightemitting diodes and UV detectors [3, 4], which can be applied to high density
datastoragesystems,solidstatelighting,securecommunicationsandbiodetection.
The growth method of ZnO thin films has been considered by major techniques, such as
magnetron sputtering [5, 6], chemical vapour deposition (CVD) [710], metalloorganic
vapour phase epitaxy (MOVPE) [11], solgel processing [12], spray pyrolysis [13] and
pulsedlaserdeposition(PLD)[14].Ofthesemethods,thePLDtechniqueisconsideredasa
veryeffectivemethodtogrowthhighqualityfilmswithcomplexcomposition.Additionally,
thin films deposited by PLD can result in better crystal structure at lower temperature
thanbyothertechniques,whichiscausedbythehigherenergyoftheablatedparticlesin
thelaserproducedplasmaplume[15].Moreover,therearestillotheradvantagesofusing
the PLD technique making it so effective. For example, deposition processes in
controllable oxygen ambient pressure result in high controllability of thin film chemical
elementcompositionandgraingrowthprocesses.Thus,inthisproject,ZnOthinfilmsare
depositedonglasssubstratesbyPLD,andtheinfluenceoffilmgrowthconditions,suchas
substrate temperature, ambient oxygen pressure, laser fluence and the number of laser
pulsesonthestructural,opticalandelectricalpropertiesofZnOthinfilmswasstudied.
8

1.2 Challengesinthisproject
AhighqualityZnOthinfilmcanbedepositedbyPLDundercertainprocessconditions,but,itis
wellknownthatdifferentprocessmachinesordifferentZnOtargetswouldmaketheconditions
alittledifferent,sometimestotallydifferent.Therefore,forunderstandinganewmaterial(ZnO)
and new equipment (PLD), firstly we should systematically arrange a series of experiments to
findouttherelativeoptimizedPLDconditions.

For investigating the influence of different parameters of PLD on ZnO thin films, in each
experimentwecanonlyvaryoneparameterandkeeptheotherparametersatthesamelevel.
If there is any change in the the parameters of PLD, the experiment should be done all over
again.

To commercialize ZnO is each researchers purpose, but the electrical properties of ZnO are
always a weakness compared with ITO. Therefore, in this project we dope the pure ZnO with
2%wt silicon in order to grow a low resistivity and high transmission thin film. Therefore, for
achieving the optimized properties of thin film by using new targets, we should rearrange a
seriesofexperimentstooptimizethePLDparameters.

1.3 Aimsandobjectives
I. TooptimizethepulsedlaserdepositionofZnOthinfilmswithrespecttoconductivity
andopticaltransparencybyvaryingoxygenpressure,laserenergydensityand
substratetemperature.
II. Toinvestigatetheinfluenceofoxygenpressure,substratetemperatureandlaser
fluenceandannealingtreatmentonZnOthinfilms
III. Tooptimizethepulsedlaserdepositionof2%wtSiZnOthinfilmswithrespectto
conductivityandopticaltransparencybyvaryingoxygenpressures,substrate
temperatures.
1.4 Organizationofthethesis
Chapter 2 gives background theory of ZnO and pulsed laser deposition technique. A
literaturereviewofZnOdepositionbyPLDandothermethodsisgiven.

Chapter3explainstheZnOdepositionanditscharacterization.

Chapter4containsdetaileddepositionresultsfortheZnOthinfilmsbyPLD.Theeffectof
the oxygen pressure, substrate temperatures, laser fluence, the number of laser pulses,
and doping with Si on the conductivity and optical properties of the ZnO thin films is
discussed. The surface morphology and roughness of the thin films and their crystal
structurearealsoinvestigated.

Chapter5concludesthethesis.Themainfindingsoftheprojectaresummarized.

Chapter6Furtherworkwhichneedstobedoneisgiven.

10

2 LiteratureReview
2.1 Transparentconductingoxides(TCOs)
Transparent conducting oxide (TCO) films have been used extensively in the
optoelectronicsindustry,suchastheLCDindustry,duetotheirhighelectricalconductivity,
high optical transmittance in the visible region, and high reflectance in the infrared (IR)
region.AfterBadeker[16]reportedthefirstresearchaboutTCO,TCOfilmshavestartedto
be widely utilized as an essential part of many optoelectronic applications such as, solar
collectors,gassensorsandliquidcrystaldisplays.
Overtheselastfewdecades,alargenumberofTCOmaterialshavebeeninvestigatedsuch
as In
2
O
3,
SnO
2
, ZnO and CdO as well as their doped oxides; most effort has been
concentrated on creating thin films to improve the electrical conductivity and optical
transparencyofthefilms.Additionally,itiswellknownthatmostoftheTCOmaterialsare
ntype semiconductors. So, there has also been some effort on developing ptype TCO
films,suchasNdopedZnO[17].
OfalltheTCOfilms,ITOthinfilmsarethemostwidelyusedinspecificapplications,such
as flat panel displays, solar cells and LEDs, but due to the cost issue impuritydoped ZnO
filmsalsobegantoattractmuchattentionbecausetheyarenontoxicandinexpensiveand
havecomparableelectricalandopticalpropertiestoITO[18].

2.1.1 ZnOstructure
ZnO belongs to the group of IIVI binary compound semiconductors which crystallize in
either a cubic zincblende or hexagonal wurtzite structure where each anion is
surroundedbyfourcationsatthecornersofatetrahedron,andviceversa.Thebondingof
thistetrahedralcoordinationischaracteristicofsp
3
covalentbonding,butthesematerials
also have substantial ionic character. Therefore, as shown in Figure 21, the crystal
structures of ZnO are wurtzite (B4), zinc blende (B3), and rocksalt (B1). Under ambient
conditions, the thermodynamically stable phase is wurtzite, while the zincblende ZnO
structure is only revealed by growth on cubic substrates; moreover, the rocksalt (NaCl)
structureprobablygrowsatrelatively highpressure. Therefore,thestructure ofZnOthin
filmsdepositedbyPLDbelongstothewurtzitestructure.
The wurtzite structure has a hexagonal unit cell with two lattice parameters, a and c, in
the ratio of c/a= =1.633. The schematic structure is shown in Figure 22, and this
11

structure has two interpenetrating hexagonalclosepacked (hcp) sublattices. Each

sublatticeconsistsofonetypeofatomrepresentedwithrespecttoeachotheralongthe
threefoldcaxisbytheamountofu=3/8=0.375(inanidealwurtzitestructure)infractional
coordinates.

2.1.2 ElectricalpropertiesofZnO
Theelectricalresistivity()ofZnOfilmsisdeterminedbythecarrierconcentration(N)and
carriermobility(),whichisalsopresentedas=1/(Ne)whereeistheelectroncharge.
Itisknownthateisaconstant,so,forobtaininglowresistivity,thecarrierconcentration
(N) and carrier mobility () should be simultaneously maximized, and most research
papershavesuggestedthatthemethodofachievingmaximumcarrierconcentrationisby
oxygenvacanciesanddoping.
Oxygen vacancies can be created by controlling the substrate temperature or ambient
oxygenpressure.Theliterature[18]indicatesIfanoxygenvacancyiscreatedinaperfect
crystal,twoelectronsarecreatedinthecrystalandcontributedasionizeddonors.But,if
there is too much oxygen created in the thin films, suboxides will form, causing the
resistivitytorise.
In addition to the oxygen vacancies, doping also can change the electrical conduction of
TCOs. As hostcations aresubstitutedbyelementswith avalencehigherthan that ofthe
host,theextraelectronscanbecomeconductionelectrons.Toavoidthechargeneutrality,
substitutionofahighervalenceelementcreatesextraelectrons.
Itiswellknownthatpurezincoxidefilmsusuallyhaveacharacteristichighresistivitydue
to their low carrier concentration. Therefore, in order to decrease resistivity, we can
increase either the carrier concentration or the carrier mobility in zinc oxide thin films.
Theformerisprobablyobtainedbyoxygenand/orzincnonstoichiometry,ordopingwith
an impurity. However, Hu et al. [19] pronounced that nonstoichiometric films have
excellentelectricalandopticalproperties,buttheybecomeveryunstableastheambient
temperature becomes higher. On the other hand, for obtaining stable low resistivity ZnO
thinfilms,dopedZnOthinfilmisprobablyagoodapproach.
In conclusion, the majority of research for achieving low resistivity ZnO thin films is
focused on increasing the free carrier concentration in thin films through use of dopants
and oxygen vacancies. But, Johson et al. [20] in 1947 stated that increasing the carrier
densityviadopingoroxygenvacanciesisselflimitingbecausetheincreaseofthenumber
of free carriers decreases the mobility of carriers due to carriercarrier scattering.
Therefore, there is a tradeoff relation between the carrier density and the carrier
mobilityforobtaininglowresistivity.
12

2.1.3 OpticalpropertiesofZnO
When light proceeds from one medium into another,several phenomena occur. Some of
the light radiation may be transmitted through the medium, some will be absorbed, and
some will be reflected at the interface on the surface. Moreover, the intensity I
O
of the
beamincidentonthesurfaceofthethinfilmsmustequalthesumoftheintensitiesofthe
transmitted, absorbed, and reflected beams, which can be written as I
O
=I
T
+I
A
+I
R
. An
alternate form of the above equation is T+A+R=1, where T, A, R, respectively, are the
transmissivity(I
T
/I
O
),absorptivity(I
A
/I
O
),andreflectivity(I
R
/I
O
).Thus,materialsthatare
capable of transmitting light with relatively little absorption and reflection are
transparent.
The optical phenomena that occur within solid materials, such as ZnO thin films, involve
interactions between the electromagnetic radiation and atoms, ions and electrons. Of
these interactions, electronic polarization and electron energy transitions are the most
important. Nevertheless, absorption by electronic polarization is only explained for the
lightfrequenciesinthevicinityoftherelaxationfrequencyoftheconstituentatoms[21].
Thus,fornonmetallicmaterialslikeZnOfilmsatshortwavelength( <400nm),absorption
phenomenacanbeexplainedbythefundamentalenergygap[18],whichdependsonthe
electron energy band structure of the materials; band structures for semiconductors like
ZnOthinfilmsareanimportantproperty.
As demonstrated in Figure 23, absorption of a photon of light probably occurs by the
promotion or excitation of an electron from the nearly filled valence band, across the
band gap, and into an empty state within the conduction band; a free electron in the
conductionbandandaholeinthevalencebandarecreated.Furthermore,theenergyof
excitation E is related to the absorbed photon frequency based on the electron
transitions equation: E=h . Thus, absorption phenomena can take place only if the
photonenergyisgreaterthanthebandgapE
g,
thatisrepresentedas:h >E
g
.
Based on the above theory in which the absorption occurs by h > E
g
, we extend our
discussion to metallic materials. As shown in Figure 25, since metallic materials lack a
band gap, every photon has enough energy to excite the electron into a higher energy
unoccupied state. In contrast, for semiconductors like ZnO thin films, the absorption
phenomenon occurs when the energy of the photon in some range of wavelength is
greaterthanE
g
whilethetransparencyphenomenonoccursasthatofphotonundersome
range of wavelength is smaller than E
g
. Hence, that is the reason why the ZnO thin films
are only transparent in the visible range; visible light lies within a very narrow region of
thespectrumwithwavelengthsragingbetween400nmto700nm[22](showninFigure
13

24).
Thetransmittanceandreflectancedatacanbeusedtocalculateabsorptioncoefficientsof
thefilmsatdifferentwavelengths.Theabsorptioncoefficient, ,isgivenbytherelation:
=
1
t
ln
(1-R)
2
1
[23]
wheretisthefilmthickness,TisthetransmittanceandRisthereflectance.Additionally,
theabsorptioncoefficientdataalsocanbetransferredtoanotherequationrelativetothe
bandgap(E
g
),whichcanberepresentedasthefollowing:
ob: = (b: - E
g
)
1
2

where isthephotonenergy[24].
2.1.4 EffectofdopingZnOwithimpurity
Recently, doped zinc oxide thin films have been widely studied for their application as
conducting electrode materials in flatpanel displays or solar devices. Unlike the more
commonly used indium tin oxide (ITO), zinc oxide is a nontoxic and inexpensive material.
Furthermore, it is a IIVI ntype semiconductor with band gap of approximately 3.3 eV at
room temperature anda hexagonal wurtzitestructure [25].Pure zinc oxide films are highly
transparent in the visible range (light wavelength of 400700 nm) and have high electrical
conductivity. However, nonstoichiometric or impurity (Group III elements or Group IV
elements) doped zinc oxide films have electrical conductivities as well as high optical
transparent. Nonstoichiometric zinc oxide films have unstable electrical properties at high
temperature because the sheet resistance of ZnO thin films increases under either oxygen
chemisorption and desorption [26] or heat treatment in vacuum or in ambient oxygen
pressure at 300
o
C~400
o
C [27]. Turning to impurity doped ZnO thin films, unlike
nonstoichiometric ZnO thin films, impurity doped ZnO thin films possess stable electrical
and optical properties. Among the zinc oxide films doped with group II elements such as
barium, aluminum, gallium and indium, aluminumdoped zinc oxide (AZO) thin films show
thelowestelectricalresistivity[28].Aluminumdopedzincoxide(AZO)hasalowresistivityof
2410
4
cm [2830], which is quite similar to that of ITO films, which is about 1210
4

cm[3133],andAZOalsoshowsgoodopticaltransmissioninthevisibleandnearinfrared(IR)
regions. Thus,AZO filmshave beenused astransparent conducting electrodesinsolarcells
[19,34].InadditiontodopingwithGroupIIIelements,dopingZnOwithGroupIVelements
such as [35, 36] Ge, Sn, Ti, Si is also a good way to obtain low resistivity transparent
materialsinordertoreplaceITObecauseGe,Ti,ZrcouldsubstituteontheZnatomsite.For
example,SncanserveasadoublyionizeddonorwiththeincorporationofSnO
2
asasolute
in ZnO and, consequently, provide a high electron carrier concentration. It is, therefore,
14

expected that the Sn doped ZnO (SZO) will have a higher electrical conductivity and better
fieldemissionpropertiescomparedwithundopedZnO[36].

2.2 Pulsedlaserdeposition(PLD)
2.2.1 IntroductiontoPLD
Pulsed laser deposition (PLD) is a physical vapour deposition process, which involves a
deposition process in a vacuum system. Functionally, it shares some process
characteristics in common with molecular beam deposition and some with sputter
deposition.AsshownschematicallyinFigure27,apulsedlaserisdirectedontoatarget
ofthematerial,suchaspureZnOtarget,toperformadepositionprocess.Eachlaser
pulseablatesasmallamountofthematerialcreatingaplasmaplume.Then,theablated
materialisejectedfromthetargetinahighlyforwarddirectedplume.Theablatedspecies
condenseonthesubstrateplacedoppositetothetarget(Figure28).
2.2.2 ThegrowthofthinfilmsbyPLD
Duringvapourphaseepitaxialgrowthonaflatsubstrate,nucleationandgrowthofislands
play important roles. Nucleation leads to the formation of surface steps and growth of
islands causes the lateral movement of these steps. Since they occur far from
thermodynamic equilibrium both of them are determined by kinetics that also further
affectsthefinalsurfacemorphology.
For a thermodynamically stable system, the thermodynamic approach to crystal growth
can be used to describe crystal growth close to equilibrium. Local fluctuations from
equilibriumlead to nucleation, which gives rise to a phase transition from the gas to the
solidphase.Markovetal.[37]statedthatthegasphaseisaprerequisitefortheformation
ofthesenucleiwhereastheformationprobabilityisdeterminedbytheactivationenergy,
andnucleiwillbeformeduntilacriticaldensityisreached.Then,thenucleiwillgrowand
crystallizationproceeds.
Bauer[38]furtherusedthethermodynamicapproachtodeterminegrowthmodesofthin
films,andstatedthatthebalancebetweenthefreeenergiesofthethinfilmsurface(
F
),
substrate surface (
S
), and the interface between film and substrate (
I
) is used to
determine the film morphology. So, based on this concept, there are three types of film
modes, shown schematically in Figure 29. In layerbylayer growth (Figure 29(a)
FrankvanMerwegrowthmode),thetotalsurfaceenergy(
F
+
I
)ofthewettedsubstrate
15

is lower than the surface energy of the bare substrate

s
. Strong bonding between film
and substrate reduces
I
such that
F
+
I
<
s.
On the contrary, if there is no bonding
betweenfilmandsubstrate,threedimensional(3D)islandsareformed.Thefilmdoesnot
wetthesubstratebecausethiswouldleadtoanincreaseofthetotalsurfaceenergy,and
thisgrowth mode is called theVolmerWeber growth mode (SeeFigure29(b)). Turning to
the third type of growth mode, heteroepitaxial growth, is called the StranskiKrastanov
growth mode (Figure 29(c)). During this type of growth mode, the lattice mismatch
betweensubstrateandfilmgivesrisetobiaxialstrain,causinganelasticenergythatgrows
with increasing layer thickness. Moreover, misfit dislocations at the substratefilm
interface will be created if the layer thickness is over a critical thickness, where it is
thermodynamically favorable to introduce dislocations due to the increase of the elastic
energy,relievedbythedislocations,intheinterfacialenergy.
2.2.3 TheadvantagesofPLD
Many techniques such as magnetron sputtering[5, 6], chemical vapour deposition
(CVD)[8],metallorganicvapourphaseepitaxy(MOVPE)[11],solgel[12],spraypyrolysis[13],
and pulsed laser deposition (PLD) have been used to deposit ZnO films. Among these
techniques,thePLDtechniquehasbeenprovedtobeaveryeffectivemethodtodeposit
highqualityfilms.Thatisbecauseofthefollowingreasons:
FilmsgrownbyPLDcanberealizedatlowtemperature
The most import characteristics in PLD is the ability to implement stoichiometric
transfer of ablated material from targets to substrate for many materials. This comes
from the nonequilibrium nature of the ablation process itself due to absorption of
high laser density by a small volume of material. However, if the laser fluence is too
low, the laser pulse simply heats the target. In this case, the evaporative flux from a
target would be determined by the vapour pressures of the constituents. In contrast,
as the laser fluence is increased, the ablation threshold is reached where the laser
energyablationishigherthanthatneededforevaporation.Consequently,absorption
by the ablated species occurs, resulting in the formation of plasma at the target
surface. Therefore, with appropriate choice of ablation wavelength and absorbing
target,highenergydensitiesareabsorbedbyasmallvolumeofmaterial,resultingin
vapourizationthatisnotdependentonthetargettemperature.[15]
Highcontrollabilityofcompositionofthinfilmsandgrowthprocesswithcontrollable
gaspartialpressure,suchasambientoxygenpressure.
The purpose of ambient gas introduced into PLD chamber can be explained by two
reasons. First, the formation of thin film materials often requires a reactive species,
suchasmolecularoxygenforoxides,asacomponentoftheflux.Interactionofablated
16

species with the background gas often produces molecular species in the ablation
plume, and these species can cause phase formation. Secondly, the background gas
can also be used to reduce the kinetic energies of the ablated species, which can
moderate the plume energies to much than less 1eV [39]. Consequently, interaction
withambientgasslowstheablationplumeexpansion.
ThecomplexmaterialfilmscanbedepositedbyPLD
PLD can provide stoichiometric transfer of material from the target, generation of
energetic species, hyperthermal reaction between the ablated cations and the
backgroupgasintheablationplasma.Moreover,itsbackgrouppressurecandecrease
up to ultrahigh vacuum. So, films could be deposited by PLD from single,
stoichiometrictargetsofmaterialsormultipletargetsforeachelement.
UniformthinfilmscanbeproducedbyPLD
The thickness distribution of the thin films is determined by the highly
forwarddirectednatureoftheablationplumewhichisquitenonuniform,andthatis
because the distribution of material deposited from the ablation plume is symmetric
withthetargetsurfacenormalandcanberepresentedasacos
n
()distribution,where
ncan vary from430.However, ,using fasterscanningoftheablation beamoverthe
target and rotating the substrate, PLD can produce uniform coverage over large
areas[18].
The biggest advantage is that it is versatile. A very wide range of materials, including
oxides, metals, semiconductors and even polymers, can be grown by PLD. All that is
required is a target of the desired composition. It is unlike Molecular Beam Epitaxy
(MBE)andChemicalVapourDeposition(CVD),whereadifferentsourceofprecursors
isrequiredforeachelementofthecompound.[9]
Ithastheabilitytomaintaintargetcompositioninthedepositedthinfilms.Becauseof
theveryshortdurationandhighenergyofthelaserpulse,thetargetmaterialplumes
instantlytowardthesubstrate:everycomponentofthephasehasasimilardeposition
rate.Thismakesoptimizationofthedepositionprocessmucheasier[18].
Theenergyassociatedwiththehighioniccontentinlaserablationplumes(typicallyof
the order of 10% and rising with increasing incident laser power density) and high
particle velocities (of the order of 106 cm s
1
) appear to aid crystal growth and lower
thesubstratetemperaturerequiredforepitaxy.
Other advantages are that PLD is clean, low cost relative to CVD, and capable of
producingmultilayerssimplybyswitchingbetweenseveraldifferenttargets[40].
2.2.4 ThedisadvantagesofPLD
AlthoughPLDhasbeensuccessfullyappliedtomanyresearchareas,itstillhassome
17

disadvantages,thatinclude:[41]
Theablationplumecrosssectionisgenerallysmall(intheorderofcm
2
)duetoa
limitedlaserspotsize.This,inturn,limitsthesamplesizethatcanbepreparedby
PLD.Inaddition,thisalsocreatesdifficultyincontrollingthicknessuniformity
acrossthesample:thisproblemcanbeovercome,tosomeextent,byscanningthe
laserbeamonalargersizetarget.
Theplumeofablatedmaterialishighlyforwarddirected,whichcausespoor
conformalstepcoverage.Italsomakesthicknessmonitoringdifficult.
Finally,thereisanintrinsicsplashingassociatedwithlaserablationitself,which
producesdropletsorbigparticlesofthetargetmaterialonthesubstratesurface.
Fromanindustrialperspective,thisisparticularlyseriousasitwillresultindevice
failure.
2.3 OtherZnOthinfilmfabricationmethods
2.3.1 RFmagnetronsputtering
Sputteringisatechniqueusedtodepositthinfilmsofamaterialontoasubstrate.First,it
will create gaseous plasma and then accelerating the ions from this plasma on to the
target.Thetargetmaterialiserodedbythearrivingionsviaenergytransferandmolecules.
(SeeFigure210)Whenthesenaturalparticlesareejectedtheywilltravelinastraightline
unless they come into contact with something, such as other material particles. At this
moment, the substrate placed in the path of these ejected particles will be coated by a
thinfilmofthesourcematerial(SeeFigure211).
Although sputtering is proven to be a useful technique in the deposition of thin films, it
has two major problems the deposition rate is slow and the electron bombardment of
the substrate is extensive, causing overheating and structural damage. So, the
development of magnetron sputtering deals with both of these issues simultaneously. It
usesmagnetsbehindthecathodetotrapthefreeelectronsinamagneticfieldabovethe
targetsurface (See Figure 212 ). These electrons are not free to bombard the substrate,
but in traditional sputtering they do. The trapped electrons form curved circuitous paths
in the magnetic field, enhancing their probability of ionizing a neutral gas molecule by
severalordersofmagnitude.Thisincreaseinavailableionssignificantlyincreasestherate
atwhichtargetmaterialiserodedandsubsequentlydepositedontothesubstrate.
In early ZnO research, RF magnetron sputtering was one of the most used growth
techniques. Due to its low cost and low operation temperature [10], magnetron
sputtering was a preferred method, when compared to sol gel and chemicalvapour
18

deposition[7]. The growth usually took place in the chamber ambient with O
2
/Ar+ O
2

ratiosrangingfrom0to1atapressureof10
3
10
2
Torr(0.13Pa1.3Pa),O
2
wasusedasthe
reactivegasandAractingasthesputteringenhancinggas.
2.3.2 Molecularbeamepitaxy
Molecular beam epitaxy (MBE) was developed in the early 1970s as a means of growing
highpurity epitaxial layers of compound semiconductors [42]. MBE can produce
highqualitylayerswithaveryabruptinterfaceandgoodcontrolofthickness,dopingand
composition due to the high degree of control possible with MBE. So, MBE is a valuable
toolinthedevelopmentofsophisticatedelectronicandoptoelectronicdevices.
Molecular beam epitaxy implements deposition in high vacuum or ultra high vacuum
(10
8
Pa). The most important characteristic of MBE is the slow deposition rate (probably
lessthan1000nmperhour),whichallowsthefilmstogrowepitaxially.
InMBE,themolecularbeamsaretypicallyfromthermallyevaporatedelementalsources,
and the gaseous elements then condense on thesubstrates. This means that evaporated
atomsdonotinteractwitheachotherorthevacuumchambergasesuntiltheyreachthe
substrate due to the long mean free paths of the atoms. During deposition, RHEED
(Reflection High Energy Electron Diffraction) is used to monitor the growth of the crystal
layers(seeFigure213).Thecomputercontrolsshuttersinfrontofeachsource,allowing
precisecontrolofthethicknessofeachlayer,downtoasinglelayerofatoms.
For ZnO thin films deposited by molecularbeam expitaxy (MBE), Zn metal and O
2
are
usually used as the source material. High purity Zn metal is evaporated from an effusion
cell, where the cell temperature can be varied to examine the effect of Zn flux on the
growthrateandmaterialproperties.Theoxygenradicalbeam,whichcanbegeneratedby
ECR or a RF plasma source, is directed on the film surface to obtain high oxidation
efficiency. When the oxygen plasma is used, the chamber pressure is around 10
5
Torr
duringdeposition.
2.3.3 Chemicalvapordeposition
Chemical vapour deposition (CVD) is the process of chemically reacting a volatile
compoundofamaterialtobedeposited,withothergases,toproduceanonvolatilesolid
that deposits atomistically on a suitably placed substrate. It differs from physical vapour
deposition (PVD), which relies on material transfer from condensedphase evaporant or
sputtertargetsources.BecauseCVDprocessesdonotrequirevacuumorunusuallevelsof
power,theywerepractisedcommerciallypriortoPVD[7].
19

ThefundamentalsequentialstepsthatoccurineveryCVDprocessaresketchedinFigure
214andinclude:
1. Convective and diffusive transport of reactants from the gas inlets to the reaction zone
2. Chemical reactions in the gas phase to produce new reactive species and by-products.
3. Transport of the initial reactants and their products to the substrate surface
4. Adsorption (chemical and physical) and diffusion of these species on the substrate surface.
5. Heterogeneous reactions catalyzed by the surface leading to film formation
6. Desorption of the volatile by-products of surface reactions
7. Convective and diffusive transport
In the CVD method, ZnO deposition occurs as a result of chemical reactions of the
vapourphaseprecursoronthesubstrate(showninFigure215),whicharedeliveredinto
the growth zone by the carrier gas, which is hydrogen (H
2
). The reactions occur in a
reactorinwhichanecessarytemperatureprofileiscreatedinthegasflowdirection.The
typical pressure is 133Pa and the flow rate is about 40ml/min. Targets made from Zn
powder are placed in the evaporation zone where the temperature is about 770
o
C. The
following chemical reaction between the Zn target and H
2
carrier gas takes place in the
evaporationzone:
ZnO+H
2
Zn+H
2
O
Onthesubstrate,wherethetemperaturewaskeptintherangeof590610
o
C,thereverse
reactionoccurs:
Zn+H
2
OZnO+H
2
TheZnOfilmsgrownbythismethodshowquitehighcrystal,electricalandluminescence
properties[43].

2.4 ApplicationofZnOthinfilms

HavingthepropertyofwidebandgapcausesZnOtonotonlybeamaterialtransparentin
the visible and near UVvisible regions, but also be electrical conductive (ntype).
Moreover, the cost of ZnO compared to ITO is relatively lower. ZnO has been used
therefore for transparent conducting electrodes instead of expensive ITO for flatpanel
display and solar cells [44]. In addition to pure ZnO thin films, doping with various
elements (Al, Ga, In) is an efficient way to increase the electrical conductivity [45, 46].
AmongthesedopedZnOthinfilms,Aldopedzincoxde(AZO)thinfilmshavebeenusedas
ananodecontactfororganiclightemittingdiodes(OLED).
As shown in Figure 216, ITO has been used as an active channel layer in a transparent
thinfilm transistor (TFT) that can be operated in the presence of visible light in a LCD
20

display for a while. Butdue to the improvement of ZnO optical and electrical properties,
ZnOthinfilmsalsohavebeenusedasanactivechannellayerinaTFT[47].
AnotherinterestingpointofZnOthinfilmapplicationistogrow(0001)orientedZnOthin
filmsbyPLDonanamorphoussubstrate.SuchtexturedfilmonaGaAssubstratehasacted
as an alignment layer for the growth of caxisoriented GaN films [48]. Although the
textured ZnO films do not exhibit outstanding crystalline quality, very strong emission
features associated with exciton transitions were observed, which further lead ZnO thin
films on GaAs to become a plausible system for shortwavelength visible or UVlight
emittingdiodes(LEDs).

21

3 ExperimentalProcedures
3.1 PLD
ZnO thin films were deposited on glass substrates in a vacuum chamber using a 248um
KrFexcimerlaser(LambdaPhysicsLPX300).Thelaseremits25nspulseswitharepetition
rate of 10Hz. High purity O
2
gas was introduced through independent mass flow
controllersandtheprocesspressurewaskeptintherangefrom5mTorrto10mTorr.The
PLDsystemusedinthisprojectisshowninFigure217.
The ZnO target was brought from PIKEM Ltd.[49] It has a diameter of 25 mm. It is
composedof99.999%highpureZnO.TheSidopedZnOtargetwasbroughtfromPIKEM
Ltd[49].Ithasadiameterof25mm.Itiscomposedof98wt%ZnOand2wt%silicon.
Thelaser beamwithatypicalenergy of 350mJwas generated outsidethechamber.The
optical instruments, such as lenses, mirrors and apertures, whose objective was to steer
and focus thelaserbeamwith anincident angleof45
o
toward thetargetwitharotating
speedof10rpm,throughavacuumwindow,wereplacedbeforetheportofthedeposition
chamber. A10Hz frequency of pulseswassupplied for depositing of ZnO films, whilethe
powerdensityofthelaserbeamatthetargetsurfacewasabout2.7J/cm
2
.
The glass substrates used in the depositions are borosilicate Corning 1737 brought from
Corning technologies Ltd [50]. The size of the as received substrate is 75 mmx50 mm. It
was cut by a diamond knife into 10x10 mm pieces. The substrates were glued on to the
heaterwithsilverpaintfromAgarscientificLtd[51]toensureagoodthermalcontact.The
silver paint is composed of very fine silver flakes suspended in methyl isobutylketone.
Before deposition, the substrates were cleaned by using acetone for 10 min and ethanol
for10minwithultrasonicagitation.Then,theywererinsedwithdistilledwateranddried
by compressed air. Finally glass substrates were clamped on to the heater, which can
adjustthesubstratestemperaturetoaroundatemperatureof200
o
C.
ForobtainingtheoptimizedpropertiesofZnOthinfilms,severalparameterslistedinTable
41,Table42andTable43,andthefollowingchapterinvestigatesallparameters.
3.2 Conductivitymeasurement
The average electrical resistance of the ZnO thin films was calculated by the fourpoint
probemethod,bymeasuringatninedifferentpositionsbutinsymmetricalplacesoneach
film, and using an EXCEL program to analyse all values. As shown in Figure 218, the
4pointprobesystemconsistsoffourequallyspacedtungstentipswithfiniteradius.Each
22

tipissupportedbyaspringtominimizesampledamagewhenthesamplesaremeasured.
Ahighimpedancecurrentsourceisusedtosupplycurrentthroughtheoutertwoprobes;
a voltmeter measures the voltage across the inner two probes (see Figure 218) to
determinethesampleresistance.
Inreference[52],forbulksampleswherethesamplethicknesst>>s,theprobespacing,
we assume a spherical protrusion of current emanating from the outer probe tips. The
differentialresistanceis:
R = p(
Jx
A
)

Thenintegrationbetweentheinnerprobestips(wherethevoltageismeasured)gives:
R=
2
2
2 x
dx
S
S

=
x
1
2

|
s
s
2
=

2 2
1
s

where s is probe spacing.Additionally, the superposition of current at the outer two tips
canbeR=V/2I.Therefore,wefurthermodifytheexpressionforbulkresistivity:
p = 2ns _
I
I
]

Ifthethinfilmsareverythin(thicknesst<<s),weobtaincurrentringsinsteadofspheres.
So,wecanputtheexpressionfortheareaA=2 xtintotheresistanceequation.

R=]
p
2nxt
2s
s
dx
x
=
p
2nt
ln (x)|
s
2s
=
p
2nt
ln2
Thus,forR=V/2I,thesheetresistivityforathinsheetis:
p =
nt
ln2
_
I
I
]

Since the equation for resistivity of thin films is obtained, we can use 4point probe to
measure the resistance of thin films, and then using this equation to calculate the
resistivity.

3.3 Transparencymeasurement
In optics theory[21], the transmittance is the fraction of incident light at specific
wavelength that passes through a sample, and we will measure the same sample two to
threetimes,thenuseanEXCELprogramtodrawatransparencyspectrumtoanalyzethe
23

optical property. As shown in Figure 221, the transmittance (T) can be expressed as the
followingequation:
T=
I
I
0

whereI
o
istheintensityoftheincidentlightandIistheintensityofthelightcomingoutof
the sample. Therefore, based on the above theory, we can use the model 6130 double
beam spectrophotometer (brought from Jenway company [53]) to measure the
transmittance of all our samples. The transmittance was measured as a function of
wavelength (300 1000 nm), and a typical result is shown in Figure 430. Furthermore,
transmittanceisrelatedtoabsorbanceAas:
A=lnT=ln(
I
I
0
)
3.4 Structure
ThecrystalstructureoftheZnOfilmswasinvestigatedbyXraydiffraction(XRD)analysis
using a Siemens goniometer with a Cu K radiation source. Cullity [54] stated that
diffraction occurs when a wave interacts with a series of regularly spaced obstacles that
arecapableofscatteringthewaveandhavespacingsthatarecomparableinmagnitudeto
thewavelength.Moreover,thediffractionisaconsequenceofspecificphaserelationships
that are established between two or more waves that have been scattered by the
obstacles.
AsshowninFigure219,inthebeginning,theyallhavethesamewavelength( )andboth
waves suffer the scattering event. If this path length difference is an integral number of
wavelengths, as noted in Figure 219 (a), these scattered waves are still in phase. It is
calledamutualreinforcementofoneanother.However,inFigure219(b),wherethepath
length difference after scattering is some integral number of half wavelengths, the
scatteredwavesareoutofphase.Therefore,Braggusedthisphenomenontodiscoverthe
Bragglaw(n =2dsin )toexaminematerialstructure.
In practice, we can measure the angle ( ) by the angle between the arms of the
diffractometer when they move. As the arm moves at constant angular velocity, a
recorderautomaticallyplotsthediffractedbeamintensityasfunctionof2 ;2 istermed
the diffraction angle, which is measured experimentally. Figure 433 shows a diffraction
pattern for ZnO thin films. The highintensity peaks result when the Bragg diffraction
conditionissatisfiedbysomesetofcrystallographicplanes.
24

3.5 SurfaceMorphology
ThesurfacemorphologyofZnOthinfilmswasinvestigatedbyscanningelectron
microscopy(SEM)(seeFigure223)andatomicforcemicroscopy(AFM)incontactmode.
3.5.1 Scanningelectronmicroscope(SEM)
AsshowninFigure220,thescanningelectronmicroscopegeneratesabeamofelectrons,
which come from a filament (see Figure 225 ). The filament is a loop of tungsten which
functionsasacathode.Avoltageisappliedtotheloop(inthisresearch,weuse10kVA),
making it to heat up. The anode, which is positive with regard to the filament, forms
powerful attractive forces for electrons. This makes the electrons accelerate toward the
anode.Someacceleraterightbytheanodeanddownthecolumntothesample.
Thebeamiscollimatedbyanelectromagneticcondenserlenses,focusedbyanobjectlens,
and scanned across the surface of the sample by electromagnetic deflection coils. The
primary imaging method is done by collecting secondary elements that are released by
thesample.Thesecondaryelectronsaredetectedbyascintillationmaterialthatproduces
flashesoflightfromtheelectrons.Thelightflashesarethendetectedandamplifiedbya
photomultiplier tube. By correlating the sample scan position with resulting signal, an
image can be formatted, which is similar to what would be seen through an optical
microscope.
3.5.2 Atomicforcemicroscope(AFM)
AsshowninFigure226,theAFMconsistofamicroscalecantileverwithasharptipatits
end which is used to scan the sample surface. The cantilever is typically silicon or silicon
nitridewithatipradiusofcurvatureontheorderofnanometers.AlthoughAFMhastwo
types of measurement, that is contact mode and tapping mode, we only used contact
modetomeasureallsamples.
In contact mode measurement, the tip automatically approaches extremely near surface
of sample, and forces between the tip and the sample and lead to a deflection of the
cantileverareVanderWaalsforces.Typically,thedeflectionismeasuredusingalaserspot
reflectedfromthetopofthecantileverintoanarrayofphotodiodes.
Then,thesinglecollectorwillreceiveallthedifferenceofsamplesurface.ThePCmonitor
will show the morphology of sample. The AFM software also can calculate the range of
therootmeansquare(RMS)ofsamplesurfaceroughness,whichisastatisticalmeasureof
themagnitudeofavaryingquantity.
25

3.6 Thicknessmeasurement
Because all the samples were extremely thin, that is around 250~300nm, the only
practical way to measure the thickness of the films was to use the SEM to image
crosssections of the films and then use the SEM software to calculate the thickness of
thin films automatically. (See Figure 227) Normally, each sample was measured two to
threetimes,thentheEXCELprogramwasusedtocompareallsamples.

26

4 Resultsanddiscussion
4.1 Influenceofoxygenpressure
Theoxygenpressurewasalwaysconsideredtobeoneofthemostimportantparameters
ofthePLDgrowthprocess.Itsensitivelyaffectstheepitaxialquality,surfacemorphology
and optoelectronic properties[55]. Moreover, oxygen pressure is also used to control
densities of vacancies of oxygen and defects that influence film conductivity; too
numerous oxygen vacancies will act as defects without donating electrons and will
decrease the conductivity by decreasing the conduction electrons. Consequently, a
certain degree of ambient oxygen pressure in the film growth was required with the
purpose of conductivity improvement. In this section, for investigating the influence of
oxygen pressure on ZnO thin films, we only varied the oxygen pressure and kept other
parametersthesame.ThedetailedinformationisshowninTable41.
4.1.1 Electricalproperties
Figure428indicatesthevariationofelectricalpropertiesasafunctionofambientoxygen
pressureforZnOfilmsdepositedonglasssubstrates.Theresistivityincreasesslowlywith
increasing oxygen pressure to 10 mTorr (1.3 Pa) and then dramatically increases with a
furtherincreaseinP
O2
upto50mTorr(6.7Pa).Itcanbeclearlyobservedthattheresistivity
of the ZnO film is very sensitive to the ambient oxygen pressure, and a low range of
resistivity can be obtained in a small range of oxygen pressures between 10mTorr(1.3Pa)
and20mTorr(2.6Pa)..
The ambient oxygen pressure affects accordingly the electrical properties of the ZnO
films,[56, 57] which results fromstoichiometry effects,and this argument can beseen in
Figure 429. As the oxygen pressure increases, the electron concentration tends to
decreasewhiletheresistivityofthefilmincreases,beingassociatedwithadecreaseinthe
density of oxygen vacancies as shallow donors; this also is a sign that the ZnO film
approachesanimprovedstoichiometrywithanincreasedoxygensupply.
Additionally,ZhengandKwok[58]alsodeclaredthatthesensitivitytotheambientoxygen
pressure can be explained by a characteristic of PLD. They observed that at low oxygen
pressures, the density of various species is not uniform on the surface of the substrate
duetothedifferentvelocityforeachspecies.Thisalsocreatesdefectcentersinthefilm,
which increase the film resistivity. Nevertheless, if the oxygen pressure is too high, the
velocity of various species in the lasergenerated plume will be slowed down because of
27

thecollisionswithoxygenmolecules,andthenthesurfaceactivationofthespecieswillbe
decreased.Therefore,thehighoxygenpressureleadstolowmobilityofspecies,andthis
lowmobilityofspeciesfurthercausesthelowcrystalquality.
In conclusion, the ambient oxygen pressure is sensitively relative to the electrical
resistivityofZnOfilmsbecauseofmobilityofspeciesandstoichiometryeffects.Thus,for
achievinghighconductivityZnOfilm,thesupplyoftheambientoxygenpressurewouldbe
ataround10mTorr.
4.1.2 Opticalproperties
Figure430showsthetransmittancespectrafromwavelengthsof300nmto1000nmfor
ZnO films on glass substrates at different ambient oxygen pressures. The observed
transmittances are improved with raising ambient oxygen pressures, and average
transmittance taken across the wavelength of 91 % can be achieved at the ambient
oxygen pressure of 50 mTorr. This result also indicates that the transmittance is very
sensitivetotheambientoxygenpressure,andJinetal.[56]declaredthatoneimportant
qualityoftheUVemissionmaybethestoichiometryoftheZnOwhichusuallyhasalotof
oxygen vacancies in its lattice. It is thus expected that the ZnO film grown at higher
oxygen pressure of 50 mTorr probably has more improved stoichiometry with fewer
oxygenvacancies.
4.1.3 Surfacemorphology
Figure 431showsfiveAFM images oftheZnOfilmsgrownonglasssubstratesby PLD at
an ambient oxygen pressure of 10 mTorr to 50 mTorr. It is clear that the particle size
increases with an increase in the ambient oxygen pressure. Moreover, Figure 432 also
indicates that the roughness of ZnO films deposited in D=55mm, laser fluence=2.7J/cm
2

andTs=300 increaseswithanincreaseintheambientoxygenpressure.
This increase in surface roughness with increasing oxygen pressure may be attributed to
an enhanced particulate formation in the laser induced plume, which is a typical
characteristic of highpressure laser ablation [59]. On the other hand, if a laser ablation
experimentisdoneinvacuum,therearenocollisionsbetweentheejectedspeciesbefore
they reach the substrate. At this moment, particulates are predominantly formed from
solidified liquid droplets that are expelled from the target by the recoil pressure. As a
result,wecanobservethatthevapourspeciesaregrownasauniformbackgroundfilm.
However,iftheambientoxygenpressureincreases,thevapourspecieswouldfaceenough
collisionsso that nucleation andgrowthofthesevapourspecies toform particulates can
occur before they arrive at the substrate. Then, the formation of particulates shifts from
28

liquiddropletstovapourspecies.Fromthetimewhenthegrowthmechanismchangesto
diffusion, the resident time of particulate in the vapour control decides the size of the
particulate. Consequently, it can be observed that with increasing residence time the
particulatesarebecominglarger.
4.1.4 Structuralproperties
Figure 433 shows the XRD patterns of ZnO films grown on glass substrates at various
oxygenpressures.ItisclearlyobservedthatZnOfilmsintheoxygenpressureregimeof5
mTorr to 50 mTorr are completely caxis oriented in the films normal direction without
anytraceofdifferentlyalignedplanes.Yooetal.[44]indicatedthatZnOfilmsusuallygrow
with caxis preferred orientation under typical growth conditions, which is attributed to
thelowestsurfaceenergyofthe(002)basalplaneinZnO,leadingtoapreferredgrowthin
the(002)direction.
It can be seen from Figure 434 that the peak intensity values of the (002) diffraction
orientation are quite similar for the ZnO films grown in an oxygen pressure regime of 5
mTorr to 20 mTorr. However, for the ZnO films grown in the regime of 30 mTorr to 50
mTorr, the intensity of (002) diffraction orientations is extremely low, indicating that the
ZnOfilmgrowninhigheroxygenpressureshasaverylowcrystallinequality.
AsshowninFigure435,thefullwidthathalfmaximum(FWHM)ofthe(002)XRDpeaks
oftheZnOfilmsstaysquitelowforallthefilmsdepositedintheoxygenpressureregime
of 5 mTorr to 20 mTorr, but rapidly increases as the oxygen pressure increases up to 30
mTorr. It is well known that the smaller the FWHM, the higher the film crystallinity.
Therefore, the result of the FWHM is consistent with that of peak intensity values (002),
againsupportingtheresultthattheZnOfilmsdepositedaboveacertainoxygenpressure
showadeterioratingcrystallinequality.
4.2 Influenceofsubstratetemperature
From section 4.1, it can be concluded that for obtaining higher conductive ZnO film, the
relativelyoptimizedoxygenpressurewouldbe10mTorrbasedonFigure428.So,asTable
42 shows, using the PLD technique, ZnO films of 10 mTorr oxygen pressure were grown
for various substrate temperatures on to glass substrates and their electrical properties,
opticalproperties,morphologicalandcrystalpropertieswereexamined.
Intheliterature[60],thedependenceofthefilmsqualityonthegrowthtemperaturecan
beattributedprimarilytothemobilityoftheatomsduringthedepositionandthegrowth.
At low substrate temperature, vapour species with a low surface energy are arriving on
thesubstratesurface,andtheselowmobilityspeciesintheabsenceofathermaldiffusion
29

process further hinder the crystallization of the films. However, at the high substrate
temperature,thespecieshaveenoughmobilitytoarrangetheatomsatsuitablepositions
inthecrystallinecell.Additionally,theincreaseofthegrowthtemperaturemakesdiffused
oxygen and zinc atoms increase on the surface, which can lead to a decrease of the
oxygen and zinc vacancies. As a result, the density of the defects is reduced and higher
crystallinityfilmsaregrown.
4.2.1 Electricalproperties
As shown in Figure 436, the resistivity decreases from 8.6310
2
to 9.0110
3
with a
substrate temperature increase from 100 to 200 but if the substrate temperature is
increased from 200 to 500 , the resistivity increases from 9.0110
3
to 4.2610
1
. This
resultispartiallysimilartotheresearchfromKangetal.[14](asshowninFigure437)but
theresultisnotsimilartoFigure437between100 and200 .So,itisbelievedthatas
thesubstratetemperatureisincreased,thenumberofoxygenatomsabsorbedonthethin
film will increase, causing a decrease of the defect density. As a result, the carrier
concentration declines. Therefore, this result further indicates that when the substrate
temperature is increased from 100 to 500 , the ZnO films become closer to the
stoichiometriccomposition.
4.2.2 Opticalproperties
Figure 438 shows the transmittance spectra of ZnO films grown at the substrate
temperatures of 100 , 200 , 300 , 400 and 500 at a fixed oxygen pressure of 10
mTorr.Fromthesetransmittancespectra,itcanbeobservedthatthereisaslightrelation
between the substrate temperature and the transmittance. At a substrate temperature
lower than 100 , Zn and O
2
molecules could not have enough energy to form
stoichiometric ZnO thin films,so we can see the transmittance spectrum of the ZnO film
grown at a temperature of 100 is worse than others. However, the relative higher
transmittanceof theZnOfilmdeposited atsubstrate temperature of 400 indicatesthe
stoichiometry of the ZnO films has been improved when the substrate temperature
increases up to 400 . But, on increasing the substrate temperature above 400 , the
transmittance of the ZnO film surprisingly decreases. Bae et al.[61] indicated that ZnO
filmsgrownat400 aremorestoichiometricthanotherfilmsdepositedabove400 .
4.2.3 Surfacemorphology
Figure 439 shows the AFM images of the surface morphologies of the ZnO thin films
30

deposited at various substrate temperatures. In the case of the thin films deposited at
100 ,smallgrainswereobserved.However,asthesubstratetemperatureisincreasedup
to500 ,thesurfacemorphologyisobservedtoconsistoflargerandmoreuniformgrains.
Moreover, the surface roughness is increased from 1 nm to 19 nm with increasing
substrate temperature up to 500 (shown in Figure 440). This increase of the surface
roughness may be due to the increase of the grain size. This result is also observed in
Figure441,whichistheFWHMofthe(200)XRDpeaksfromZnOthinfilmsdepositedat
various temperatures. It is well know that smaller FHWM value we observe, the larger
grainsizeweobtain.
The growth of grains along the substrate surface is controlled by the substrate
temperature which is relative to the surface diffusion ability of atoms[59]; at a substrate
temperatureof100 ,thegrowthofgrainsalongthesubstrateislimited.Asaresult,the
grainsizeissmall.Asthesubstratetemperatureincreasesupto200 ,thegrowthofgrain
size is enhanced, the films also become relatively compact. However, compared with the
grain size of films grown at substrate temperature of 100 , that of the films grown at
substratetemperatureof200 isrelativelylarger,whichisattributedtograinrefinement
byrecrystallizationoftheZnOfilmsattheappropriatetemperature(200 )[62].Whenthe
substrate temperature increases up to 500 , the high temperature can provide more
energy for mobility of particles on the surface. Consequently, the grain size of ZnO thin
filmsislargerat500Cthanatlowertemperatures.
4.2.4 Structuralproperties
Figure 442 indicates the XRD pattern for the ZnO films deposited at various substrate
temperatures. As shown in Figure 442, only the (002) diffraction peaks were observed.
ThisindicatedthattheZnOfilmshaveacaxispreferredorientationperpendiculartothe
substratesurface,andthisresultcanbeexplainedbythefactthat,inthecaseoftheZnO
filmshavingawurtzitehexagonalcrystalstructure,the(002)planehasthelowestsurface
energydensity[63].Moreover,Figure443furtherindicates,theZnOthinfilmdeposited
at100 showsarelativelylow(002)diffractionpeak.Thisisattributedtothelowatomic
mobility, which limits the crystal growth during the crystallization process. However, as
the substrate temperature increases up to 500 , there is enough thermal energy to
supplytoatomsonthesubstrate,whichincreasesthesurfacemobility.Asaresult,itleads
toanincreasedpeakintensityinthe(002)planeorientation(showninFigure443).
4.3 Influenceofannealing
From section 4.1 and 4.2, we can obviously see that the relatively optimized deposition
31

parameters are D=55mm, Po2=10mTorr, Ts=200 . In this section, we examine the effect
of postgrowth annealing (for 2 hours) of ZnO thin films on the structural as well as
electricalpropertiesinordertofindanewwaytoimprovethevariouspropertiesofZnO
thinfilms.ThedetailedparametersareshowninTable43.
4.3.1 Electricalproperties
Figure444showstheresistivityoftheZnOfilmsasafunctionofannealingtemperature.
For annealing temperature < 300 , it is observed that the resistivity of the ZnO films
decreases slightly. As the annealing temperature increases up to 500 , the resistivity of
the ZnO films increases dramatically. This result is similar to the result of Kang et al. [64]
and Stamataki etal.[65],sowe probably couldattributethisphenomenon tothe decline
ofthecarrierconcentrationastheannealingtemperatureincreases.Additionally,Kanget
al.[64]andStamatakietal.[65]believethatthisisbecausethenumberofZninterstitials
decreases probably due to Zn evaporation by increasing annealing temperature, or the
oxygenvacancies,whichcontributethefreecarriers,declinedbyoxygendiffusionintothe
filmwithannealingtreatment.
4.3.2 Opticalproperties
Figure 445 shows the optical transmittance in the wavelength range of 3001000 nm of
the asdeposited and postgrowth annealed ZnO films deposited on glass substrates as a
functionofannealingtemperature.TheZnOfilmsshowaslightincreaseoftransmittance
withannealingtemperature,whichprobablyindicatesthattheannealingtreatmentcould
slightlyimprovethecrystallinity(seeFigure446).ThisalsofurtherconfirmstheRusopet
al. research[66] that higher transmittance in the visible region indicates that the films
havefewerdefectsandbettercrystallinity.However,thedifferenceoftransmittancewith
differentannealingtemperatureisnotsignificant,soweneedtodomoreexperimentsto
confirmthisresult,eventakingaccountofexperimentalerrors.
4.3.3 Surfacemorphology
Figure 447 shows the AFM images of asgrown and annealed samples at various
temperatures for 2h in oxygen, and Figure 448 illustrates the SEM images of asgrown
and annealed samples for 2h at 500 in oxygen. It is clearly observed that the
morphologywasimprovedbyannealingat500 andtheneedlelikeshapewasobserved
inFigure448bannealedsample.Furthermore,thisresultalsocanbeobservedinFigure
449 which shows the roughness of ZnO films deposited at various annealing
32

temperatures. Therefore, we probably can deduce that the quality of ZnO thin films was
improvedbytherecrystallizationofZnOthinfilmbysupplyingsufficientthermalenergy.
4.3.4 Structuralproperties
Figure 451 shows XRD patterns of ZnO films deposited by PLD on glass substrates at
200 with ambient oxygen (asdeposited), and ZnO films postgrowth annealed at
variousannealingtemperatures.Itisclearlyobservedthata(002)texturedfilmisformed
in an effective equilibrium state which gives enough surface mobility to impinge atoms.
Evenaftertheannealingtreatment,thepeakofdiffraction(002)isstilltheonlyobserved
peak. Moreover, as shown in Figure 446, the peak intensity of ZnO thin films with
annealing treatment is relatively higher than that of the asdeposited thin film. So, we
probablycanconcludethatthepostannealingtreatmentofthefilmshasapositiveeffect
on the crystallization. Sun et al.[67] explained that high temperature could enhance the
diffuseactivationenergyofthesurface,asaresulttheZnandOatomsoccupythecorrect
siteinthecrystallatticeandgrainswiththelowersurfaceenergywillbecomelargerata
hightemperature.
4.4 InfluenceofthenumberofpulsesonZnOfilms
Table 45 shows that ZnO thin films were deposited on glass substrates with various
thicknesses using the pulsedlaser deposition (PLD) technique in order to investigate the
thickness dependence of the structural, electrical and optical properties of the films. The
thickness of thin films is controlled by changing the number of pulses, and the structural,
electrical and optical properties were characterized with XRD, resistance and transmittance
measurement.
4.4.1 Structuralproperties
Figure 451 shows the XRD spectra of ZnO thin films deposited at the various number of
laser pulses. Only (002) ZnO peaks were observed in the range 34
o
35
o
, and it also further
indicatedthatZnOthinfilmsdepositedonglasssubstrateswithvariousthicknessesarestill
stronglycaxisoriented.Additionally,asshowninFigure452,thecrystalqualityoftheZnO
films is enhanced with an increase in the number of laser pulses, from 5000 to 15000.
However,whenthenumberoflaserpulsesincreasesupto20000,thecrystalqualityofZnO
filmsstartstodegrade.
33

4.4.2 Opticalproperties
Thetransmittancespectraasafunctionofwavelengthintherange300800nmforthree
samplesareshowninFigure453.Theaveragetransmittanceinthevisibleregionforthe
number of pulses of 5000, 15000 and 20000 is 79 %, 65 % and 64 % respectively. With
increaseofthickness,thetransmittanceofZnOthinfilmsIdecreasesduetothethickness
effect. That the increase in thickness affects the optical properties can be explained by
the LambertBeer Law [59], which can be expressed: I/I
o
=exp(t), where I is the light
intensityatadistancetintomedium; istheabsorptioncoefficientofthematerial;Iois
the incoming light intensity. Therefore, when the number of laser pulses or thickness of
ZnO,increases,thetransmittanceaccordinglydecreases.
4.4.3 Electricalproperties
Figure 454 shows the resistivity of ZnO thin films deposited at the various number of
laser pulses. The observed resistivity decreased significantly with increasing thickness
from315nmto895nm,butleveledoffasthethicknessincreasedover895nm.E.SShim
etal..[2]IndicatedthatthecorrelationbetweenthicknessandresistivityofZnOthinfilms
is negative due to the thicker films having fewer point defects like oxygen vacancies.
Moreover, the conductivity of ZnO thin films can probably be attributed to oxygen
vacancies and Zn interstitials which are donor type point defects. Therefore, the
enhancementofthedefectsleadstotheriseofcarrierconcentration.Onthecontrary,the
decreaseofdefectswithincreaseofthethicknessofZnOthinfilmscausesthedeclineof
carrierconcentration,ortheincreaseofresistivity.

4.5 InfluenceoflaserfluenceonZnOfilms
To investigate the influence of laser energy density on the process parameters of ZnO
films,aseriesofdepositionswereperformedasfollows:atafixedoxygenpressureof10
mTorrandafixedsubstratetemperatureof200 ;laserenergydensitywasvariedinthe
rangefrom1.16J/cm
2
to2.73J/cm
2
;thetargetsubstratedistancewaskeptat55mmand
theglasssubstrateswereusedforallsamples.ThedetailedinformationisshowninTable
44.
34

Afterdeposition,thecrystalstructureofthefilmwasinvestigatedbyXraydiffraction(XRD)
andtheresistivitymeasuredbyfourpointprobe.Themorphologyofthefilmwasstudied
usingaJEOLscanningelectronmicroscope(SEM).
4.5.1 Structuralproperties
TheXRDspectraofZnOfilmsdepositedatvariouslaserfluencesisshowninFigure455.It
can be observed that all films are caxis oriented, exhibiting only (002) XRD diffraction.
Thepeakintensityofthe(002)diffractionofZnOfilmsdepositedatvariouslaserfluences,
increaseswithincreaseoflaserfluence,from1.16J/cm
2
to2.27J/cm
2
.However,whenthe
laser fluence increased up to 2.73 j/cm
2
, the intensity of the (002) diffraction decreases
dramatically (shown in Figure 456). The low laser fluence is related to the low kinetic
energy of the species and it also leads to island growth.[55] Conversely, too high a laser
fluencecausesadegradationofthecrystallinityofZnOfilmsthroughthebombardmentof
thegrowingfilmbyenergeticspecies.
4.5.2 Electricalproperties
Figure 457 shows that the resistivity of ZnO thin films declines with increasing laser
fluence up to 1.51 J/cm
2
. However, at higher fluences up to 2.27 J/cm
2
, the resistivity
dramaticallyincreases.TherelativelylowresistivityoftheZnOthinfilmsof3.1x10
3
cm
isfoundatthelaserfluenceof1.51J/cm
2
.Fromtheparticleenergypointofview,withthe
increase of kinetic energy from raising the laser fluence, the ejected species cause some
structural damage to the growing film reducing the mobility of free carriers. Thus, this is
thereasonwhytheincreasinglaserfluenceincreasestheresistivityofZnOthinfilm[55].
4.5.3 Opticalproperties
Figure 458 shows the optical transmittance spectrum of ZnO thin films which are
deposited on glass substrates with the various laser fluences. It can be seen that the
optical transmittance increases with increase of laser fluence, from 1.16J/cm
2
to 2.27
J/cm
2
in the range of wavelength of 350 nm to 450 nm. However, as the laser fluence
increases up to 2.73 J/cm
2
, the optical transmittance significantly declines. If the thin
film is deposited under too much laser fluence, it causes a degradation of optical
propertiesofZnOfilmsduetothebombardmentofthegrowingfilmbyenergeticspecies
[55].
35

4.6 Influenceofdopingwithsilicon
Accordingtopreviousresearch[6870],itiswellknownthatpurezincoxidefilmsusually
exhibithighresistivityduetolowcarrierconcentration.Theelectricalresistivity()ofZnO
films depends on the carrier concentration (N) and carrier mobility () as follows:
1 ( N e), where e is the electron charge. Since e is a constant, to achieve lower
resistivityofZnOfilms,we shouldincreaseeither thecarrierconcentrationorthe carrier
mobility in ZnO films. For the purpose of increasing the carrier concentration, it can be
achievedthroughoxygenorzincnonstoichiometryanddopingwithanimpurity.
Therefore,inthissection,forstudyingtheinfluenceofdopingwithanimpurity,weuseda
newtargetwhichis2wt%SidopedZnOtodepositnewfilmstoinvestigatetheeffecton
electricalproperties,opticalpropertiesandstructuralproperties.
4.6.1 Electricalandopticalproperties
Figure 459 shows the difference of resistivity and carrier concentration between pure
ZnO thin film and 2 wt% Sidoped ZnO thin film. The former is deposited under the
relatively optimized parameters based on the result of sections 4.1 and 4.2 while 2 wt%
Sidoped ZnO thin films are deposited under substrate temperature of 200 , oxygen
pressureof5mTorrandlaserfluenceof2.7J/cm
2
.Consequently,asshowninFigure459,
it is evidently observed that the carrier concentration increases with content of SiO
2
,
which also causes a decrease in the resistivity. This phenomenon could be explained by
the amount of silicon which was introduced into the film; it is ionized to Si
+4
, normally
replacing Zn
+2
, with two electrons produced for each zinc atom replacement. Therefore,
the resistivity of thin films should decrease significantly due to increase of the carrier
concentration,from9x10
3
cmto7x10
4
cm.
Figure460showsopticalabsorptionspectraofapureZnOthinfilmanda2wt%Sidoped
ZnO film measured at room temperature. The pure ZnO thin film shows a sharp
absorption edge at 3.25eV (Figure 460) while that of the 2wt% Sidoped ZnO thin film
shiftstothehigherenergyof3.5eV.Moreover,theabsorptionedgeofthe2wt%Sidoped
ZnO thin film is less sharp than that of the pure ZnO thin film due to silicon states
extending into the band gap (Figure 460). The shifted absorption edge and the
developmentofstateswithinthegapareindicationsthattheSiionshaveenteredintothe
ZnO lattice. This characteristic has also been observed in Mndoped ZnO thin films
fabricated by pulsed laser deposition [71]. But, that of Sidoped ZnO fabricated by PLD
presents another story [72]. As the Si was incorporated, the band gap shifted to lower
energy. Therefore, from the above discussion, it can be seen that different doped
36

materials have different characteristics. However, Yoo et al. [72] also suggested that the
reasonforthisphenomenonisstillunderdispute.
4.6.2 Structuralproperties
ThecrystallinestructureofthepureZnOthinfilmandtheSiZnO(2wt%silicon)thinfilm
was investigated by XRay diffraction. Figure 461 shows the xray diffraction patterns for
theundopedZnOthinfilm,anditshowsadiscretepatternwithevidenceofonlythe(002)
peak,whilethexraydiffractionpatternfortheSiZnO(2wt%silicon)revealedanotvery
sharpdiffraction peakat(002) orientation. ThisprobablyindicatesthattodopeZnOthin
films with silicon deteriorates the crystallinity of films due to the formation of stress by
thedifferenceinionicsizebetweenzincandthedopant[45].However,inboththinfilms
onlydiffractionpeakswith(002)orientationcanbeobservedandthisresultindicatesthat
the SiZnO (2 wt% silicon) thin film and the pure ZnO thin film were strongly orientated
withthecaxisperpendiculartotheglasssubstrateplane.

37

5 Conclusions
5.1 Conclusions
The main PLD growth parameters, i.e. the oxygen pressure, the substrate temperatures,
the laser fluence and the number of pulses were varied one by one. The effect of each
parameter on the physical and structural properties were investigated and explained.
Furthermore,thephysicalpropertiesoftheZnOthinfilmswerealsooptimized.

Initially, for obtaining the optimized oxygen pressures all parameters were kept at the
same level except oxygen pressure. As a result, we found that the ambient oxygen
pressureissensitiverelativetotheelectricalresistivityofZnOfilmsbecauseofmobilityof
species and stoichiometry effects. As the oxygen pressure increases, the electron
concentration tends to decrease while the resistivity of the film increases, being
associatedwithadecreaseinthedensityofoxygenvacanciesasshallowdonors;thisalso
is a sign that the ZnO film approaches an improved stoichiometry with an increase in
oxygen supply. Thus, for achieving low resistivity of ZnO films, the supply of the ambient
oxygen pressure would be at around 10 mTorr, and the relative lower resistivity is
1.89x10
2
cm.Butahightransmittanceof91%canbeachievedattheambientoxygen
pressure of50 mTorr. This result indicates thatone important quality of the UV emission
may be the stoichiometry of the ZnO which usually has many oxygen vacancies in its
lattice.ItisthusexpectedthattheZnOfilmgrownathigheroxygenpressureof50mTorr
probablyhasmoreimprovedstoichiometrywithfeweroxygenvacancies.
From the above discussion, it can be concluded that for obtaining a more highly
conductive ZnO film, a relatively optimized oxygen pressure would be 10 mTorr. So, as
Table 42 shows, using the PLD technique, ZnO films of 10 mTorr oxygen pressure were
grown for various substrate temperatures on to glass substrates and the effect of the
substrate temperatures were investigated. The resistivity decreases from 8 10
2
to
910
3
cm

with substrate temperature increase from 100 to 200

but on increasing
the substrate temperature from 200 to 500 , the resistivity increases from 910
3
to
410
1
cm, It is believed that as the substrate temperature increases, the number of
oxygen atoms absorbed on the thin film will increase, causing a decrease of the defect
density.SotheoptimizedsubstratetemperatureforobtaininglowerresistivityofZnOthin
films wouldbe at substrate temperatureof200
o
C, whichis9x10
-3
cm and the average
transmittance is 80 % in the visible region.
After discussing the effect of oxygen pressures and the substrate temperatures, we
38

obtained the relatively optimized deposition parameters as Po2=10mTorr, Ts=200 .

However, for further improving the electrical properties, we examined the effect of
postgrowthannealing(for2hours)ofZnOthinfilmsonthestructuralaswellaselectrical
properties.Forannealingtemperature<300 ,itisobservedthattheresistivityoftheZnO
filmsdecreasesslightly.So,theresistivityimprovesto7x10
3
cm and transmittance still
remains at the same level. Furthermore, it can be observed that the postannealing
treatmentofthefilmshasapositiveeffectonthecrystallization.
ForachievinghighconductivityZnOthinfilms,weturnedtostudythenextparameter,the
value of laser fluence. The result shows that the resistivity of ZnO thin films decreasess
with increasing laser fluence up to 1.51J/cm
2
. However, at higher fluences up to
2.27J/cm
2
, the resistivity dramatically increases. The relatively low resistivity of the ZnO
thin films of 3x10
3
cm is found at the laser fluence of 1.51J/cm
2
, and the average
transmittance is 82 % in the visible region..
Finally, summarizing all the results, we can conclude that the optimized parameters are:
oxygen pressure of 10 mTorr, substrate temperature of 200
o
C and laser fluence of 1.51
J/cm
2
, and we can obtain the relative lower resistivity of 3x10
3
cm and the
transmittance is 85 % at light wavelength of 625 nm. But, this result compared to ITO
thin films (resistivity=1x10
4
cm) is still not enough to replace the ITO in flat-panel
display and solar energy applications. Therefore, thin films were deposited from a 2
wt% Si - ZnO target, and then the physical properties were investigated. As a result,itis
evidently observed that the carrier concentration increases with content of SiO
2
, which
also causes the decrease of the resistivity. This phenomenon could be explained by the
amount of silicon which was introduced into film, it is ionized to Si
+4
, normally replacing
Zn
+2
, with two electrons produced for each zinc atom replaced. Therefore, the resistivity
of thin films should decrease significantly from 3x10
3
cm to 610
4
cm due to the
increase of the carrier concentration,. Furthermore, the introduced 2 wt% silicon causes
theabsorptionedgeofthe2wt%SidopedZnOthinfilmtobelesssharpthanthatofthe
pure ZnO thin film and the sharp absorption edge of pure ZnO thin films of 3.25eV was
shiftedtothatofthe2wt%SidopedZnOthinfilmof3.5eVduetosiliconstatesextending
intothebandgap.Ontheotherhand,theaveragetransmittanceincreasesto85%inthe
visibleregionduetodopingwith2wt%silicon.

39

6 Futurework
In order to obtain the optimized parameters of ZnO thin films, the influence of oxygen
pressure, substrate temperature, the numbers of pulses, annealing treatment and laser
fluencehavebeenstudied.However,theinfluenceofthenumberofpulsesonresistivityis
not very clear, and further work is needed to use 1000 pulses, 2000 pulses, and 3000
pulses and up to 5000 pulses. Also the laser energy as the pulses increase up to 5000
pulses should be measured because the laser energy may decrease with rise of laser
pulses.
In section 4.6, although the Sidoped ZnO has been investigated, and the resistivity also
improved, the resistivity of ITO is still lower than the optimized 2wt% Sidoped ZnO thin
film(ITO:1~210
4
cmvs.2wt%SiZnO:710
4
cm).Inordertoattainthehighpotential
offered by ZnO, both highquality n and ptype ZnO are indispensable. However, ZnO is
easily doped to ntype, while ptype is difficult [73]. Thus, the future work can be
categorizedintotwoprojects:
A. ntypedoping
GroupIIIelements,suchasAl,GaandIn,andGroupIVelements(Ge,TiandZr)
as substitutional elements for Zn and GroupVII elements Cl and I as
substitutional elements for O can used as ntype dopants [74]. Doping with Al,
Ga and In has been attempted by many groups, resulting in highquality
conductiventypeZnOfilms.Forexample,Ataevetal.reportedresistivityaslow
as 110
4
cm for Gadoped ZnO films grown by chemicalvapour deposition,
whichisquiteclosetotheelectricalpropertiesofITO.WhilegroupIVandgroup
VII elements have been widely investigated, and that is a future potential
project.
B. ptypedoping
ForobtainingptypeZnO,knownacceptorsinZnOincludegroupIelementsuch
as lithium (Li)[75, 76], Na and K, copper (Cu) [77], silver (Ag)[78], Zn vacancies,
and groupV elements such as N, P, and As. However, among those acceptors,
only GroupV elements are believed as the most promising dopants for ptype
ZnO[77].Ontheotherhand,ptypedopingstillneedsexploring.

40

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45

Appendix
FiguresandtablesfromChapter2






















46

Figure21StickandballrepresentationofZnOcrystalstructures:(a)cubicrocksalt(B1),(b)cubiczincblend(B3),and(c)
hexagonalwurztie(B4).TheshadedgrayandblackspheresdenoteZnandOatoms,respectively.[79]

Figure22SchematicrepresentationofawurtziticZnOstructurehavinglatticeconstantainthebaselplaneandcinthe
basel direction; u parameter is expressed as the bond length or the nearestneighbor distant b divided by c (0.375 in
idealcrystal),andand(109.47
o
inidealcrystal)arethebondangles.[79]


47

Figure23(a)Mechanismofphotonabsorptionfornonmetallicmaterialsinwhichanelectronisexcitedacrossthe
bandgap,leavingbehindaholeinthevalenceband.Theenergyofthephotonabsorbedis E,whichisnecessarily
greaterthanthebandgapenergyEg.(b)Emissionofaphotonoflightbyadirectelectrontransitionacrossthebandgap.
[21]

Figure24Thespectrumofelectromagneticradiation,includingwavelengthrangesforthevariouscolorsinthevisible
48

spectrum.[21]

Figure25Therelationbetweenabsorptionandtheenergyband:Metal

Figure26Therelationbetweenabsorptionandtheenergyband:Semiconductors




49

Figure27TheSchematicdescriptionofaPLDexperimentalsetup[55]

Figure28SchematicofthePLDprocess[18]


50

Figure29Filmgrowthmodeslayerbylayer:(a)FrankVanderMerwe,island;(b)VolmerWeber(c),
StranskiKrastanov,(d)andstepflow.[18]

Figure210Theprocessofsputter(1)(fromhttp://www.ajaint.com/whatis.htm)




51

Figure211Theprocessofsputter(2)(fromhttp://www.ajaint.com/whatis.htm)

Figure212Themagnetsputter(fromhttp://www.ajaint.com/whatis.htm)
52

Figure213TheSchematicdescriptionofMBE
(fromhttp://projects.ece.utexas.edu/ece/mrc/groups/street_mbe/mbechapter.html)
53

Figure214SequenceofgastransportationandreactionprocesscontributingtoCVDfilmgrowth[9]

54

Figure215TheSchematicofCVD(fromChiMeiCorporationestablishedChiMeiOptoelectronicsLTD.)

Figure216Thestructureoftransparent thin-film transistor (fromChiMeiCorporationestablishedChiMeiOptoelectronics

LTD.)
55

Figure217ThepictureofthePLDsystemusedinUniversityofBirmingham

Figure218SchematicdiagramofaFourpointProbe

56

Figure 219 (a) Demonstration of how two waves that have the same wavelength and remain in phase after a
scatteringeventafterascattering(b)Demonstrationofhowtwowavesthathavethesamewavelength andbecome
outofthephaseafterascatteringeventafterascattering[21]

57

Figure220Diffractionofxraysbyplansofatoms.[21]

Figure221TheSchematicdiagramoftransmittance(fromhttp://en.wikipedia.org/wiki/Wiki)

58

Figure222ThepictureofSpectrophotometer

Figure223ThepictureofSEMJEOL7000




59

Figure224TheSchematicdiagramofaSEM(fromProfessorIanJoneslecture)

Figure225ThepictureofFieldemission(fromProfessorIanJoneslecture)



60

Figure226TheSchematicdiagramofAFM(fromhttp://en.wikipedia.org/wiki/Wiki)

Figure227ThepictureofcrosssectionofZnOthinfilmsbySEM
61

FiguresandtablesfromChapter4

62

Figure 428 Resistivity of ZnO films deposited at various ambient oxygen pressures (D=55mm, Ts=300 , Laser
fluence=2.7J/cm
2
)

Figure 429 A plot of electron concentration and resistivity vs. oxygen pressure as result of Hall measurements. The
resultsfromsamplesgrownwith1mTorrand200 and300 arealsoplotted.[80]
63

Figure 430 Transmittance spectra of ZnO films on glass substrate grown at different ambient oxygen pressures.
(D=55mm,Ts=300 ,Laserfluence=2.7J/cm
2
)

Figure 431 AFM 3D images (22m) of ZnO with varying ambient oxygen pressure. (D=55mm, Ts=300 , Laser
fluence=2.7J/cm
2
)

64

Figure432 RoughnessofZnOfilmsdepositedbyPLD(D=55mm,Ts=300 ,Laserfluence=2.7J/cm

2
)
65

Figure 433 XRD pattern of ZnO films deposited by PLD with varying oxygen pressures. (D=55mm, Ts=300 , Laser
fluence=2.7J/cm
2
)
66

Figure 434 peak intensity of XRD pattern of ZnO films deposited by PLD with varying oxygen pressures. (D=55mm,
Ts=300 ,Laserfluence=2.7J/cm
2
)
67

Figure 435 Variation in the FWHM of (002) reflections of The ZnO films as a function of oxygen pressures. (D=55mm,
Ts=300 ,Laserfluence=2.7J/cm
2
)
68

Figure 436 Resistivity of ZnO films deposited at various Substrate temperatures (D=55mm, Po2=10mTorr, Laser
fluence=2.7J/cm
2
)

Figure437TheelectricalpropertiesofZnOthinfilmsdepositedatvarioustemperatures[14]

69

Figure 438 Optical transmittance spectra of the ZnO thin films grown at various substrate temperature. (D=55mm,
Po2=10mTorr,Laserfluence=2.7J/cm
2
)

70

Figure439AFMimageofZnOthinfilmsdepositedatvarioussubstratetemperatures

Figure440RoughnessofZnOthinfilmsdepositedatvarioustemperatures

71

Figure441FWHMof(002)XRdpeaksfromZnOthinfilmsdepositedatvarioustemperatures

Figure442XRDpatternsofZnOthinfilmsdepositedatvarioussubstratetemperatures

72

Figure443Peakintensityof(002)diffractionpeakfortheZnOfilmsdepositedatvarioustemperatures.
73

Figure 444 Resistivity of ZnO films deposited at various annealing temperatures (D=55mm, Po2=10mTorr, Ts=200 ,
Laserfluence=2.7J/cm
2
)

74

Figure 445 the optical transmittance spectrum of ZnO thin films deposited on glass substrate for asdeposited, and
postgrowthannealedatvariousannealingtemperatures.(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)

75

Figure 446 Peak intensity of (002) diffraction peak for the ZnO films deposited at various annealing temperatures
(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)

76

Figure 447 AFM image of ZnO thin films deposited at various annealing temperatures. (D=55mm, Po2=10mTorr,
Ts=200 ,Laserfluence=2.7J/cm
2
)

77

(a)

(b)
Figure 448 The SEM image of ZnO thin film: (a) as grow, and (b) annealing at 500 for 2h in oxygen (D=55mm,
Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)

78

Figure 449 Roughness of ZnO thin film deposited at various annealing temperatures. (D=55mm, Po2=10mTorr,
Ts=200 ,Laserfluence=2.7J/cm
2
)

79

Figure450TheXRDpatternofZnOthinfilmsdepositedatvariousannealingtemperatures..(D=55mm,Po2=10mTorr,
Ts=200 ,Laserfluence=2.7J/cm
2
)

80

Figure451Xraydiffraction spectraofZnOthinfilmdepositedatthevariousnumber of laserpulses.(D=55mm,Po2=

10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)

81

Figure 452 Peak intensity of (002) diffraction peak for the ZnO films deposited at the various number of laser pulses.
(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)

82

Figure453theopticaltransmittancespectrumofZnOthinfilmsdepositedonglasssubstratewiththevariousnumber
oflaserpulses.(D=55mm,Po2=10mTorr,Ts=200 ,Laserfluence=2.7J/cm
2
)

83

Figure454TheresistivityofZnOthinfilmsdepositedatthevariousnumberoflaserpulses

84

Figure455XraydiffractionspectraofZnOthinfilmdepositedatvariouslaserfluence.(D=55mm,Po2=10mTorr,
Ts=200 )

85

Figure456Peakintensityof(002)diffractionpeakfortheZnOfilmsdepositedatvariouslaserfluence(D=55mm,
Po2=10mTorr,Ts=200 )

86

Figure457ResistivityofZnOthinfilmsdepositedatvariouslaserfluence

87

Figure 458 the optical transmittance spectrum of ZnO thin films deposited on glass substrates with the various laser
fluence(D=55mm,Po2=10mTorr,Ts=200 ,thenumberoflaserpulse=5000)

88

Figure459Resistivity,andcarrierconcentrationasafunctionofSiZnOthinfilms(D=55mm,Po2=5mTorr,Ts=200 ,the
numberoflaserpulse=5000)
Carrierconcentration
Restitvity
89

Figure460AbsorptionspectraofpureZnOthinfilmand2wt%SidopedZnO

90

Figure461XraydiffractionspectraofZnOthinfilmandSiZnOthinfilm(D=55mm,Po2=5mTorr&10mTorr,Ts=200 ,
Laserfluence=2.7J/cm
2
)

91

Substrate Target
Distance
(mm)
PO2
(mTorr)
Ts()
Laser energy
(mJ)
Resistivity
(-cm)
Transmittance
Glass ZnO 55
10
300 350 1.89E-02 71.6
Glass ZnO 55
20
300 350 5.70E-02 90.5
Glass ZnO 55
30
300 350 4.49E+00 84.3
Glass ZnO 55
40
300 350 7.43E-01 77.5
Glass ZnO 55
50
300 350 8.73E-01 77.5
Table41 Summarizing the electrical and optical properties of ZnO films on glass substrates at a temperature
of 300 with varying oxygen pressure

Substrate Target
Distance
(mm)
PO2
(mTorr)
Ts()
Laser energy
(mJ)
Resistivity
(-cm)
Transmittance
Glass ZnO 55 10 100 350 8.63E-02 79.6
Glass ZnO 55 10 200 350 9.01E-03 86.9
Glass ZnO 55 10 300 350 1.89E-02 71.6
Glass ZnO 55 10 400 350 1.37E-02 78.1
Glass ZnO 55 10 500 350 4.26E-01 80.3
Table 42 Summarizing the electrical and optical properties of ZnO films on glass substrates at the oxygen
pressure of 10mTorr with varying substrate temperature.

Substrate Target
Annealing
for 2h
D (mm)
PO2
(mTorr)
Ts( )
Laser energy
(mJ)
Resistivity
(-cm)
Glass ZnO none 55 10 200 350 0.009014043
Glass ZnO 300 55 10 200 350 0.007925144
Glass ZnO 400 55 10 200 350 0.01790256
Glass ZnO 500 55 10 200 350 0.022995634
Table 43 Summarizing the electrical and optical properties of ZnO films on glass substrates under optimized
conditions with varying annealing temperature

92

Substrate Target Distance(mm) PO2(mTorr) Ts()

Laser
energy(mJ)
laser fluence
Glass ZnO 55 10 200 127.2 1.16
Glass ZnO 55 10 200 166.3 1.51
Glass ZnO 55 10 200 250 2.27
Glass ZnO 55 10 200 300 2.73
Table44Summarizing the growth parameters of ZnO films on glass substrates with varying laser fluence

Pulse Target Distance(mm) PO2(mTorr) Ts()

Laser
energy(mJ)
thickness(nm)
5000 ZnO 55 10 200 350 315
10000 ZnO 55 10 200 350 895.5
15000 ZnO 55 10 200 350 1542.6
20000 ZnO 55 10 200 350 1854
Table45Summarizingthegrowthparameters ofZnOfilmsonglasssubstrateswithvariousthickness