Graphene: Synthesis, Properties, and Phenomena

426 Pages·2013·8.986 MB·English

by  C. N. R. Rao, Ajay K. Sood

Editedby
C.N.R.Rao andA.K.Sood
Graphene
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Edited by C. N. R. Rao and A. K. Sood
Graphene
Synthesis, Properties, and Phenomena
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V
Contents
Preface XIII
ListofContributors XV
1 Synthesis,Characterization,andSelectedPropertiesofGraphene 1
C.N.R.Rao,UrmimalaMaitra,andH.S.S.RamakrishnaMatte
1.1 Introduction 1
1.2 SynthesisofSingle-LayerandFew-LayeredGraphenes 4
1.2.1 MechanicalExfoliation 5
1.2.2 ChemicalExfoliation 5
1.2.3 ChemicalVaporDeposition 8
1.2.4 ArcDischarge 8
1.2.5 ReductionofGraphiteOxide 10
1.3 SynthesisofGrapheneNanoribbons 12
1.4 SelectedProperties 15
1.4.1 MagneticProperties 15
1.4.2 ElectricalProperties 19
1.4.2.1 Supercapacitors 22
1.4.2.2 PhotovoltaicsandPhotodetectors 24
1.4.2.3 FieldEmissionandBlueLightEmission 25
1.4.3 MolecularChargeTransfer 25
1.4.4 DecorationwithMetalandOxideNanoparticles 28
1.4.5 SurfaceAreaandGasAdsorption 30
1.4.6 MechanicalProperties 32
1.4.7 QuenchingofFluorescenceofAromatics 34
1.4.8 ChemicalStorageofHydrogenandHalogens 36
1.5 InorganicGrapheneAnalogs 39
References 40
2 UnderstandingGrapheneviaRamanScattering 49
A.K.SoodandBiswanathChakraborty
2.1 Introduction 49
2.2 AtomicStructureandElectronicStructureofGraphene 49
2.3 PhononsandRamanModesinGraphene 51
VI Contents
2.4 LayerDependenceofRamanSpectra 57
2.4.1 G-Band 57
2.4.2 2D-Band 57
2.4.3 D-Band 59
2.4.4 CombinationModesintheRange1650–2300cm−1 59
2.4.5 Low-FrequencyModes 61
2.5 PhononRenormalizationDuetoElectronandHoleDopingof
Graphene 61
2.5.1 OpticalPhononMixinginDopedBi-andMultilayer
Graphene 66
2.5.2 ChargeInhomogeneityandp–nJunctionintheFETChannelProbed
byRamanSpectroscopy 68
2.6 RamanSpectroscopyofGrapheneEdgesandGraphene
Nanoribbons 70
2.6.1 EffectoftheEdgeOrientationontheG-Band 70
2.6.2 EffectoftheEdgeOrientationontheD-Band 72
2.6.3 RamanSpectroscopyofGrapheneNanoribbons 73
2.7 EffectofDisorderontheRamanSpectrumofGraphene 74
2.8 RamanSpectroscopyofGrapheneunderStrain 77
2.9 TemperatureandPressureDependenceofRamanModesin
GrapheneasNanometrologicalTools 83
2.10 Tip-EnhancedRamanSpectroscopyofGrapheneLayers 85
2.11 Conclusions 86
Acknowledgments 87
References 87
3 PhysicsofQuantaandQuantumFieldsinGraphene 91
GanapathyBaskaran
3.1 Introduction 91
3.2 DiracTheoryin3+1Dimensions:AReview 93
3.3 BandStructureofGraphene:MasslessChiralDiracElectronsin2+1
Dimensions 95
3.3.1 PhaseVorticesofBlochStatesink-Space 99
3.4 Anomaly – ABriefIntroduction 100
3.4.1 AnomalousCommutatorin(1+1)Dimensions 101
3.4.2 AxialAnomalyin(1+1),(3+1)Dimensions 102
3.5 Grapheneand2+1-DimensionalParityAnomaly 105
3.6 Zitterbewegung 107
3.7 KleinParadox 110
3.8 Relativistic-TypeEffectsandVacuumCollapseinGraphenein
CrossedElectricandMagneticFields 111
3.9 PredictionofSpin-1QuantafromResonatingValenceBond
Correlations 116
3.10 MajoranaZeroModefromTwo-ChannelKondoEffectin
Graphene 120
Contents VII
3.11 LatticeDeformationasGaugeFields 125
3.12 Summary 127
Acknowledgment 127
References 127
4 MagnetismofNanographene 131
ToshiakiEnoki
4.1 Introduction 131
4.2 TheoreticalBackgroundofMagnetisminNanographeneand
GrapheneEdges 134
4.3 ExperimentalApproachtoMagnetismofNanographene 139
4.3.1 MagneticStructureofEdge-StateSpinsinNanographene 139
4.3.2 Magnetismofσ-DanglingBondDefectsinGraphene 143
4.4 MagneticPhenomenaArisingintheInteractionwithGuestMolecules
inNanographene-BasedNanoporousCarbon 146
4.4.1 MagneticSwitchingPhenomenon 146
4.4.2 HeliumSensor 152
4.5 Summary 154
Acknowledgment 155
References 155
5 PhysicsofElectricalNoiseinGraphene 159
VidyaKochat,SrijitGoswami,AtindraNathPal,andArindamGhosh
5.1 Introduction 159
5.1.1 Single-LayerGraphene 159
5.1.1.1 EffectiveTight-BindingHamiltonian:SublatticeandValley
Symmetry 161
5.1.1.2 ValleyandSublatticePseudospin 161
5.1.1.3 Chirality 162
5.1.1.4 BerryPhaseandAbsenceofBackscattering 162
5.1.2 BilayerGraphene 163
5.1.2.1 BiasedBilayerGraphene 164
5.1.3 MultilayerGraphene 165
5.1.4 DisorderandScatteringMechanisminGraphene 166
5.1.4.1 CoulombImpurityScattering 167
5.1.4.2 PhononScattering 169
5.1.4.3 Electron–HolePuddlesatLowDensity 169
5.2 FlickerNoiseor‘‘1/f’’NoiseinElectricalConductivityof
Graphene 169
5.2.1 MicroscopicOriginof1/fNoiseinGraphene 173
5.2.2 EffectofBandgaponLow-FrequencyNoiseinBilayerGraphene 175
5.2.3 ShotNoiseinGraphene 178
5.3 NoiseinQuantumTransportinGrapheneatLowTemperature 179
5.3.1 QuantumTransportinMesoscopicGraphene 179
5.3.2 UniversalConductanceFluctuationsinGraphene 184
VIII Contents
5.4 Quantum-ConfinedGraphene 188
5.4.1 1DGraphene–Nanoribbons(GNRs) 188
5.5 ConclusionsandOutlook 193
References 193
6 SuspendedGrapheneDevicesforNanoelectromechanicsandforthe
StudyofQuantumHallEffect 197
VibhorSinghandMandarM.Deshmukh
6.1 Introduction 197
6.2 QuantumHallEffectinGraphene 198
6.3 FabricationofSuspendedGrapheneDevices 200
6.4 NanoelectromechanicsUsingSuspendedGrapheneDevices 201
6.5 UsingSuspendedGrapheneNEMSDevicestoMeasureThermal
ExpansionofGraphene 203
6.6 High-MobilitySuspendedGrapheneDevicestoStudyQuantumHall
Effect 206
Acknowledgments 208
References 208
7 ElectronicandMagneticPropertiesofPatternedNanoribbons:
ADetailedComputationalStudy 211
BiplabSanyal
7.1 Introduction 211
7.2 ExperimentalResults 212
7.3 TheoryofGNRs 214
7.3.1 Tight-BindingMethod 214
7.3.2 FirstPrinciplesStudies 217
7.4 HydrogenationattheEdges 219
7.4.1 StabilityofNanoribbons 219
7.4.2 DihydrogenatedEdges 219
7.5 NovelProperties 226
7.6 Outlook 231
Acknowledgements 231
References 231
8 Stone–WalesDefectsinGrapheneandRelatedTwo-Dimensional
Nanomaterials 235
SharmilaN.ShirodkarandUmeshV.Waghmare
8.1 Introduction 235
8.2 ComputationalMethods 236
8.3 Graphene:Stone–Wales(SW)Defects 237
8.3.1 Structural,Electronic,Magnetic,andVibrationalPropertiesof
GraphenewithSWDefect 238
8.3.1.1 StructuralChangesatanSWDefect 238
8.3.1.2 InteractionbetweenSWDefects 239
Contents IX
8.3.1.3 ElectronicStructureofGrapheneandEffectsofSW
Defects 239
8.3.1.4 MagnetizationduetoTopologicalDefects 245
8.3.1.5 EffectsonVibrationalProperties 246
8.3.2 LatticeThermalConductivityofGraphenewithSWDefect 252
8.3.2.1 TheoreticalModel 252
8.3.2.2 κ:Results 253
8.3.3 Discussion 254
8.4 C1−x(BN)x/2:C–BNInterfaces 255
8.4.1 SWDefectattheC–BNInterface 256
8.4.2 Discussion 259
8.5 Two-DimensionalMoS andMoSe 259
2 2
8.5.1 PointDefects 259
8.5.2 StackingFaults 261
8.5.3 IRRadiationAbsorption 261
8.5.4 Discussion 265
8.6 Summary 265
Acknowledgments 266
References 266
9 GrapheneandGraphene-Oxide-BasedMaterialsforElectrochemical
EnergySystems 269
GanganahalliKotturappaRameshaandSrinivasanSampath
9.1 Introduction 269
9.2 Graphene-BasedMaterialsforFuelCells 270
9.2.1 Graphene-BasedCatalystSupportforSmallMoleculeRedox
Reactions 271
9.2.2 Graphene-Oxide-BasedProtonConductingMembranes 278
9.2.3 Graphene-BasedBiofuelCells 279
9.3 Graphene-BasedSupercapacitors 280
9.4 GrapheneinBatteries 289
9.5 ConclusionsandFuturePerspectives 296
References 297
10 HeterogeneousCatalysisbyMetalNanoparticlesSupportedon
Graphene 303
M.SamyEl-Shall
10.1 Introduction 303
10.2 SynthesisofGrapheneandMetalNanoparticlesSupportedon
Graphene 304
10.2.1 ChemicallyConvertedGraphenebyMicrowave-AssistedChemical
ReductionofGrapheneOxide 304
10.2.1.1 MetalNanoparticlesSupportedonGraphenebyMicrowave
Synthesis 307
X Contents
10.2.2 Laser-ConvertedGraphenebyLaserReductionofGraphene
Oxide 308
10.2.2.1 Laser-AssistedPhotoreductionofGrapheneOxideinDifferent
Solvents 313
10.2.3 PhotochemicalReductionofMetalIonsandGrapheneOxide 315
10.2.3.1 PhotoreductionofGoldIonsandGOinDifferentSolvents 315
10.2.3.2 PhotoreductionofSilverIonsandGOinDifferentSolvents 316
10.2.3.3 MechanismofPhotocatalyticReduction 318
10.3 Pd/GrapheneHeterogeneousCatalystsforCarbon–Carbon
Cross-CouplingReactions 319
10.3.1 Pd/GrapheneCatalystsPreparedbyMicrowave-AssistedChemical
ReductionofGO 319
10.3.1.1 CatalyticActivityandRangeofUtility 320
10.3.1.2 CatalystRecyclability 322
10.3.2 Pd/PRGOCatalystsPreparedbyLaserPartialReductionofGO 323
10.3.2.1 LaserSynthesisofPdNanoparticlesonStructuralDefectsin
Graphene 323
10.3.2.2 MechanismofPartialReductionofGOandDefectGeneration 325
10.3.2.3 ApplicationofPd/PRGONanocatalyststoSuzukiReaction 326
10.3.2.4 RecyclabilityofthePd/PRGONanocatalystsinSuzuki
Reaction 328
10.3.2.5 ApplicationsofthePd/PRGOCatalystAtoHeckandSonogashira
Reactions 329
10.4 COOxidationbyTransition-Metal/Metal-OxideNanoparticles
SupportedonGraphene 330
10.5 ConclusionsandOutlook 334
Acknowledgment 335
References 335
11 GraphenesinSupramolecularGelsandinBiologicalSystems 339
SantanuBhattacharyaandSumanK.Samanta
11.1 Introduction 339
11.1.1 Overviewof2D-Nanomaterials 339
11.1.2 OverviewofPhysicalGels 339
11.1.3 DifferentTypesofGraphenes,TheirPreparation,Functionalization,
andGelation 340
11.2 TowardtheGelationofGO 341
11.2.1 EffectofpHontheGelationofGO 342
11.2.2 EffectoftheDimensionofGOtowardGelation 343
11.2.3 Cross-Linker(SmallMolecule/Polymer)-InducedGOGels 343
11.2.4 Cation-InducedGOGels 345
11.2.5 Surfactant-InducedGOGels 346
11.2.6 Ionic-Liquid-InducedGOGels 347
11.2.7 GelationofHemoglobinbyGOandSensing 347