Table Of ContentSilicon Nanocrystals
Edited by
Lorenzo Pavesi and
Rasit Turan
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Silicon Nanocrystals
Fundamentals, Synthesis and Applications
Edited by
Lorenzo Pavesi and Rasit Turan
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V
Contents
List of Contributors XVII
1 Introduction 1
L.PavesiandR.Turan
References 4
2 ElectronicandOpticalPropertiesofSiliconNanocrystals 5
CeyhunBulutayandStefanoOssicini
2.1 Introduction 5
2.2 ElectronicStructureandOpticalPropertiesforSmallNanocrystals:
AbInitioCalculation 7
2.2.1 HydrogenatedSiliconNanocrystals 9
2.2.2 OxidizedSiliconNanocrystals 11
2.2.3 DopedSiliconNanocrystals 14
2.2.3.1 Single-DopedSiliconNanocrystals 14
2.2.3.2 CodopedSiliconNanocrystals 15
2.2.4 SiliconNanocrystalsEmbeddedinaSiO Matrix 18
2
2.3 ElectronicStructureandOpticalPropertiesforLargeNanocrystals:
AtomisticSemiempiricalPseuodopotentialCalculations 22
2.3.1 EffectiveOpticalGap 24
2.3.2 RadiativeLifetime 25
2.3.3 LinearOpticalAbsorption 26
2.3.3.1 InterbandAbsorption 28
2.3.3.2 IntrabandAbsorption 29
2.3.3.3 ExcitedStateAbsorption 30
2.3.4 Third-OrderNonlinearOpticalProperties 30
2.3.5 Quantum-ConfinedStarkEffectinSiNanocrystals 35
References 38
SiliconNanocrystals:Fundamentals,SynthesisandApplications.EditedbyLorenzoPavesiandRasitTuran
Copyright(cid:1)2010WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32160-5
VI Contents
3 OpticalPropertiesofIntrinsicandShallowImpurity-Doped
SiliconNanocrystals 43
MinoruFujii
3.1 Introduction 43
3.2 PLPropertiesofIntrinsicSiliconNanocrystals 45
3.2.1 FundamentalProperties 45
3.2.2 EffectofSizeandShapeDistributiononthePLBandwidth 48
3.2.3 ResonantQuenchingofPLBandDuetoEnergyTransfer 48
3.2.4 PLQuantumEfficiencyofIntrinsicSiNanocrystals 51
3.3 ShallowImpurity-DopedSiNanocrystals 53
3.3.1 PreparationofImpurity-DopedSiNanocrystals 53
3.3.2 PLfromB-DopedSiNanocrystals 54
3.3.3 PLfromP-DopedSiNanocrystals 55
3.3.4 ElectronSpinResonanceStudiesofShallowImpurity-Doped
SiNanocrystals 55
3.3.5 LocationofDopantAtoms 57
3.4 PandBCodopedSiNanocrystals 58
3.4.1 PLPropertiesofPandBCodopedSiNanocrystals 59
3.4.2 PLLifetimeofPandBCodopedSiNanocrystals 62
3.4.3 CodopedButNotCompensatedSiNanocrystals 63
3.5 Summary 63
References 64
4 ElectricalTransportMechanismsinEnsembles
ofSiliconNanocystallites 69
I.Balberg
4.1 Introduction 69
4.2 Background 71
4.2.1 BasicConceptsAssociatedwithTransportandQuantumDots 71
4.2.2 PreviousStudiesofTransportinSystemsofSi 75
4.3 ExperimentalDetails 78
4.4 ExperimentalResultsandTheirInterpretation 81
4.4.1 TheLow-xRegime 84
4.4.2 TheLow-xtoIntermediatexTransitionRegime 86
4.4.3 TheIntermediate-xRegime 87
4.4.4 ThePercolationThresholdRegime 89
4.4.5 TheHigh-xRegime 92
4.5 DiscussionandOverview 96
References 101
5 ThermalPropertiesandHeatTransportinSilicon-Based
Nanostructures 105
Han-YunChangandLeonidTsybeskov
5.1 Introduction 105
5.2 ThermalConductivityinBulkSolidsandNanostructures 107
Contents VII
5.2.1 KineticTheory:ThermalPropertiesandHeatFlow 107
5.2.2 LatticeThermalConductivity 108
5.2.3 ElectronicThermalConductivity 112
5.3 MeasurementsofThermalConductivityinNanostructures 114
5.3.1 The3oMethod 115
5.3.2 In-PlaneThermalConductivityMeasurements 117
5.3.3 Pump-ProbeandOtherOpticalMeasurements 119
5.3.4 RamanScatteringandThermalConductivity 120
5.4 ThermalPropertiesofSi-BasedNanostructures 122
5.4.1 Two-andOne-DimensionalSiNanostructures:Si-on-Insulator
andSiNanowires 122
5.4.2 EpitaxiallyGrownSi/SiGeNanostructures:Superlattices
andClusterMultilayers 125
5.4.3 ElectrochemicallyEtchedSi(PorousSi) 131
5.4.4 NanocrystallineSi/SiO Multilayers 134
2
5.5 Conclusions 143
References 145
6 SurfacePassivationandFunctionalizationofSiNanocrystals 155
JonathanVeinot
6.1 Introduction 155
6.2 FunctionalizingFreestandingParticles 156
6.3 InSituSurfaceChemistryTailoring 156
6.4 Aerosol-BasedFunctionalization 158
6.5 Solution-BasedPostsyntheticModification 158
6.6 Hydrosilylation 161
6.7 SubstitutionalApproachestoSurfaceFunctionalization 167
6.8 BuildingonanOxideLayer 168
6.9 HowManySurfaceGroupsareontheParticle? 169
6.10 InfluenceofSurfaceChemistry 171
6.11 FutureOutlookandtheRoleofSurfaceChemistry 171
References 172
7 Si-ncinAstrophysics 173
IngridMann 173
7.1 Introduction 173
7.2 LateStellarEvolution 174
7.3 InterstellarMediumandDustEvolution 177
7.4 EarlyStellarEvolutionandPlanetarySystemFormation 181
7.5 DustintheSolarSystem 183
7.6 ExtendedRedEmissionandSiNanoparticlesasaPotentialCarrier 184
7.7 FormationofSiNanoparticlesunderNonequilibrium
Conditions 189
7.8 Conclusions 191
References 192
VIII Contents
8 Size-ControlledSiNanocrystalsusingtheSiO/SiO
2
SuperlatticeApproach:Crystallization,Defects,and
OpticalProperties 195
MargitZacharias
8.1 Introduction 195
8.2 SizeControlofSiNanocrystalsbytheSiO/SiO
2
SuperlatticeApproach 196
8.3 CrystallizationBehavior 200
8.4 DefectsandtheirSignaturesinESR 206
8.5 OpticalProperties 215
8.6 ApplicationsofSiNCsandConcludingRemarks 219
References 220
9 TheSynthesisofSiliconNanocrystalsby
IonImplantation 223
RobertElliman
9.1 Introduction 223
9.2 IonImplantation 224
9.3 SpatialDistribution 226
9.3.1 IonRangeDistributions 226
9.3.2 MultipleEnergyImplants 229
9.3.3 High-FluenceEffects 230
9.3.4 LateralPatterning 231
9.4 SizeDistribution 231
9.4.1 AnnealingTemperatureandTime 232
9.4.1.1 NucleationandGrowthofNanocrystals 232
9.4.2 SpinodalDecomposition 235
9.4.3 EffectofSurfacesandInterfaces 236
9.4.4 HotImplants 236
9.4.5 AnnealingAmbient 237
9.5 IrradiationEffects 237
9.5.1 RadiationDamage 238
9.5.2 Ion-BeamMixing 239
9.5.3 Irradiation-InducedPrecipitation 240
9.6 NovelStructuresandApplications 241
9.6.1 AlloyingandDoping 241
9.6.2 ChoiceofSubstrateMaterial 241
9.6.3 Light-EmittingDiodes 242
9.6.4 WaveguidesandAll-OpticalAmplifiers 242
9.6.5 NonvolatileMemory 243
9.6.6 MicrodiskResonatorsandLasers 243
9.6.7 PhotonicCrystalStructures 243
9.7 Summary 244
References 244
Contents IX
10 StructuralandOpticalPropertiesofSiliconNanocrystalsSynthesized
byPlasmaEnhancedChemicalVaporDeposition 247
FabioIacona,GiorgiaFranzò,AlessiaIrrera,SimonaBoninelli,
andFrancescoPriolo
10.1 Introduction 247
10.2 Synthesis,Structure,andThermalEvolutionofSiO Films 249
x
10.3 ADeeperInsightintotheThermalEvolutionofSiOxFilms 253
10.4 Room-TemperaturePLPropertiesofSi-ncs 258
10.5 ExcitationandDe-ExcitationPropertiesofSi-ncs 260
10.6 CorrelationbetweenStructuralandOpticalPropertiesofSi-ncs 264
10.7 Er-DopedSiNanoclusters 267
10.8 Summary 271
References 272
11 FormationofSi-ncbyReactiveMagnetronSputtering 275
F.Gourbilleau,C.Ternon,C.Dufour,X.Portier,andR.Rizk
11.1 Introduction 275
11.2 Experimental 276
11.3 Results 276
11.3.1 SingleLayer 277
11.3.2 CompositeLayer 279
11.3.3 Multilayer 283
11.3.3.1 EffectoftheSublayerThickness 284
11.3.3.2 EffectoftheAnnealingTemperature 287
11.4 Conclusion 292
References 292
12 SiandSiCNanocrystalsbyPyrolysisofSol–Gel-DerivedPrecursors 297
AylinKarakuscuandGianDomenicoSoraru
12.1 TheSol–GelandPDCProcesses 298
12.2 Sinc/SiO GlassesandFilms 300
2
12.3 (Si-ncþSiC-nc)/SiO GlassesandFilms 302
2
12.4 OpticalpropertiesofMulticomponentSi-C-O-NCeramics 305
References 306
13 NonthermalPlasmaSynthesisofSiliconNanocrystals 309
LorenzoMangoliniandUweKortshagen
13.1 Introduction 309
13.2 BasicsofNanocrystalFormationinPlasmas 310
13.2.1 NanoparticleNucleationinNonthermalPlasmas 310
13.2.2 NanoparticleCharging 312
13.2.3 NanoparticleHeatinginPlasmas 314
13.3 SiliconNanocrystalSynthesisinNonthermalPlasmas 317
13.3.1 ExperimentalApparatus 318
13.3.2 NanocrystalCharacterization 320
X Contents
13.3.2.1 TEMCharacterization 320
13.3.2.2 ParticleSizeDistribution 320
13.3.2.3 NanocrystalSurfaceConditions 322
13.3.2.4 OpticalPropertiesofSurface-OxidizedSiliconNanocrystals 326
13.4 SurfaceFunctionalizationofSiliconNanocrystals 327
13.4.1 Liquid-PhaseFunctionalization 327
13.4.2 Liquid-PhaseHydrosilylationProcedure 328
13.4.3 PlasmaGraftingofSiliconNanocrystals 330
13.5 OpticalPropertiesofPlasma-SynthesizedandSurface-Functionalized
SiliconNanocrystals 337
13.6 SummaryandConclusions 341
References 342
14 SiliconNanocrystalsinPorousSiliconandApplications 349
BernardGelloz
14.1 Introduction 349
14.2 PreparationofPorousSiLayers 350
14.2.1 PorousSiPreparedbyAnodization 350
14.2.1.1 ConditionsLeadingtoPorousSiFormation 350
14.2.1.2 PorousSiFormationMechanism 351
14.2.1.2.1 ElectrochemicalEtchingofSi 351
14.2.1.2.2 PoreInitiationandPropagationinMicroporousSi 352
14.2.1.3 EffectofAnodizationConditions 352
14.2.1.4 LocalFormationandPatterningofPorousSi 354
14.2.1.5 AnodizationCells 355
14.2.2 FormationofPorousSiWithoutExternalPowerSupply 355
14.2.2.1 GalvanicEtching 355
14.2.2.2 ElectrolessEtching 356
14.2.3 DryingofPorousSi 357
14.3 StructuralPropertiesofAs-FormedandModifiedPorousSi 358
14.3.1 As-FormedPorousSi 358
14.3.2 OxidationofPorousSi 359
14.3.3 StabilizationofthePorousSiSurface 359
14.4 PhysicalPropertiesandApplicationsofPorousSi 360
14.4.1 ElectricalProperties 360
14.4.1.1 ElectricalConductionandTransport 360
14.4.1.2 Electro-OpticMemory 361
14.4.1.3 SensingBasedonChangeofConductivity 361
14.4.1.4 Photodetection 362
14.4.1.5 BallisticTransportandApplications 362
14.4.1.5.1 BallisticElectronEmission 362
14.4.1.5.2 ApplicationasFlatPanelDisplays 364
14.4.1.5.3 BallisticElectronEmissioninGasandLiquids 364
14.4.2 Photonics 365
14.4.2.1 RefractiveIndexandAbsorptionCoefficient 365
