Halide Perovskites: Photovoltaics, Light Emitting Devices, and Beyond

297 Pages·2019·11.171 MB·English

by  Tze-Chien Sum, Nripan Mathews

HalidePerovskites
Halide Perovskites
Photovoltaics,LightEmittingDevices,andBeyond
EditedbyTze-ChienSumandNripanMathews
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10 9 8 7 6 5 4 3 2 1
G.C.Papavassiliou(31stOct.1940to11thFeb.2018)
wasborninLepiana,asmallremotevillagenearArtain
Greece,twodaysafterthebeginningoftheItalian-Greek
war.Despitethehumbleunderprivilegedlocation
ofhisvillage,whichsuddenlytransformedintoawar
zoneincludingthatofthecivilwar,hemanagedtoset
upasmallchemistrylaboratoryinhisparent’sbasement
whichincludedhomemadeelectroniccircuitsandalso
self-taughtEnglishandFrenchthroughradio-provided
Linguaphonelessons.HegraduatedfromtheChemistry
Department(UniversityofAthens)in1968afterfulfillinghismilitaryservice.
SincethenhewasemployedbytheNationalHellenicResearchFoundation
(TheoreticalandPhysicalChemistryInstitute,TPCI).HisPh.D.wasawardedin
1972titled“Laser-RamanSpectraofAdsorbedMaterials.”Afterasuccessful
careerandmultipleassessments/elections,hebecameDirectorofResearchas
wellasservedtwiceasdirectorofTPCI.Finally,afterhisretirementin2009,he
wasnamedResearcherEmeritusuntilhispassing.
Hispublishedresearchworkfocusedonabroadsetoftopicssuchasmetallic
nanoparticles,TCNQ-basedmetals,mixedvalencemetalcomplexes,
semiconductingnanoparticles,organometallicconductors,charge-transfer
complexesaswellashybridorganic–inorganiclow-dimensionalmaterialswith
semiconducting,conducting,andsuperconductingproperties.
Someofhispioneerworksareinthefieldsofquantumdots,organic
superconductors,andhybridorganicinorganicsemiconductors(knownas
perovskites).Specifically,hepublishedthefirst-everresearchinobservingand
explainingthequantumsizeeffect(blueshift),whichmostlygoesunnoticed,in
theJournalofSolidStateChemistry40,330–335(1981)titled“Luminescence
SpectraandRamanExcitationProfilesinSmallCdSParticles.”Laterhe
publishedthefirstasymmetricalTTF-basedorganicsuperconductorin1988in
twopublicationsinSyntheticMetals,27,373–378and379–383(1988)titled
“ConductingSolidsBasedonSomeNewUnsymmetricalTetraheterofulvalenes”
and“LowTemperatureMeasurementsoftheElectricalConductivitiesofSome
ChargeTransferSaltswiththeAsymmetricDonorsMDT-TTF,EDT-TTFand
EDT-DSDTF(MDT-TTF) AuI ,anewsuperconductor(T =3.5Katambient
2 2 c
pressure),”respectively.Inthefieldofperovskites,hisearlypioneeringworks
dateprecedeby12yearsthemajorityofthecurrentrelatedpublications.Their
noveltyincluded,insomecases,crucialdetailsregardingsynthesis,theuseof
colloidalsuspensions,thenovelexcitonicenergytransferphenomenaobserved
inmixturesofquasi-2D(q2D)perovskites,and,finally,thefirsteffortfor
fabricatingroomtemperatureenergytransferq2D-perovskite-basedLED,
beyondthe2011reported2Dperovskite-basedLED.Overall,hispublished
workcounts177articles,receivingapproximately3000citations.
Hehasbeenabeloved,humble,modestandlow-profileresearcher,amentor
tohisstudentsaswellasmanycolleaguestowhomheeffortlessly
communicatedhisknowledge.Finally,throughouttheyearshislaboratoryand
infrastructurewerefreelyandkindlyprovidedtoanyonewhoneededthose.
vii
Contents
PartI BasicPropertiesandEarlyWorksin
Organic–InorganicPerovskites 1
1.1 Structural,Optical,andRelatedPropertiesofSomePerovskites
BasedonLeadandTinHalides:TheEffectsonGoingfromBulk
toSmallParticles 3
GeorgeC.Papavassiliou,GeorgeA.Mousdis,andIoannisKoutselas
1.1.1 Introduction 3
1.1.2 MaterialsBasedonSaturatedOrganicMoiety 4
1.1.2.1 BulkPerovskites(SC)MX 4
3
1.1.2.2 ParticulatePerovskites(SC)MX 5
3
1.1.2.3 BulkPerovskitesoftheType(BC) MX 8
2 4
1.1.2.4 ParticulatePerovskitesoftheType(BC) MX 8
2 4
1.1.2.5 BulkPerovskitesoftheType(SC) (BC) M X 10
n−1 2 n 3n+1
1.1.2.6 ParticulatePerovskitesoftheType(SC) (BC) M X 11
n−1 2 n 3n+1
1.1.2.7 SomeCommonFeaturesinthePropertiesof3Dandq-2D
Systems 13
1.1.2.8 Low-Dimensional(LD)Perovskites 15
1.1.2.9 RelatedProperties 15
1.1.3 PerovskitesConsistingofNon-saturatedOrganicMoietyBC 16
1.1.4 OtherPerovskiteStructures 18
References 18
1.2 AbInitioandFirstPrinciplesStudiesofHalidePerovskites 25
JackyEvenandClaudineKatan
1.2.1 IntroductiontoAbInitioandDFTStudiesofAll-inorganic,3Dand
LayeredHybridOrganicMetalHalidePerovskites 25
1.2.2 BrillouinZoneFolding,LatticeStrain,andTopologyoftheElectronic
Structure 28
1.2.3 ImportanceofSpin–OrbitCoupling(SOC) 33
1.2.4 InterplayofSOCandLossofInversionSymmetry:Rashbaand
DresselhausEffects 36
viii Contents
1.2.5 CollectiveVibrations,StochasticCationReorientations,andMolecular
Dynamics 40
References 47
1.3 Excitonicsin2DPerovskites 55
WeeKiangChong,DavidGiovanni,andTze-Chien Sum
1.3.1 IntroductiontoTwo-dimensionalPerovskites 55
1.3.2 ExcitonicPropertiesandOpticalTransitionsin2D-OIHPs 56
1.3.3 WhiteLightEmission(WLE)from2D-OIHPs 57
1.3.3.1 EnergyTransferMechanism 59
1.3.3.2 BroadbandDefectEmission 60
1.3.3.3 Self-trappedExcitons 61
1.3.3.4 RoleofOrganicFrameworkinBroadband2D-OIHPEmitters 63
1.3.4 StrongExciton–PhotonCouplingin2D-OIHPs 64
1.3.4.1 Jaynes–CummingsModel 64
1.3.4.2 Exciton–PhotonCouplingin2DPerovskitesThinFilms:OpticalStark
Effect 65
1.3.4.3 Exciton–PhotonCouplingin2DPerovskiteMicrocavities:
Exciton–Polariton 66
1.3.5 ConcludingRemarks 73
References 74
PartII Organic–InorganicPerovskiteSolarCells 81
2.1 WorkingPrinciplesofPerovskiteSolarCells 83
PabloP.Boix,SoniaR.Raga,andNripanMathews
2.1.1 Introduction 83
2.1.2 ChargeGeneration 84
2.1.3 ChargeTransport 86
2.1.4 ChargeRecombination 89
2.1.5 ChargeExtraction/Injection:InterfacialEffects 93
2.1.6 IonicMechanisms 95
2.1.7 ConcludingRemarks 96
References 97
2.2 ThePhotophysicsofHalidePerovskiteSolarCells 101
MingjieLi,BoWu,andTze-ChienSum
2.2.1 IntroductiontoPhotophysicsStudiesofHalidePerovskites 101
2.2.2 OpticalPropertiesofCH NH PbI PolycrystallineThinFilms 102
3 3 3
2.2.2.1 ElectronicBandStructureandOpticalTransitions 102
2.2.2.2 ExcitonBindingEnergiesandPhotoexcitedSpecies:ExcitonsVersus
FreeCarriers 103
2.2.2.3 CarrierDiffusionLengths,CarrierMobilities,andDefects 104
2.2.2.4 TransientSpectralFeaturesandChargeDynamics 107
2.2.2.5 PhotophysicalProcessesandTheirRecombinationConstants 108
Contents ix
2.2.2.6 HotCarriersinPerovskites 111
2.2.2.7 SummaryandOutlook 112
2.2.3 EnergeticsandChargeDynamicsatPerovskiteInterfaces 112
2.2.3.1 Introduction 112
2.2.3.2 EnergeticsatthePerovskite/ChargeTransportLayerInterfaces 112
2.2.3.3 Charge-TransferDynamicsatthePerovskite/Charge-TransportLayer
Interface 115
2.2.3.4 SummaryandOutlook 117
2.2.4 TowardPerovskiteSingle-CrystalPhotovoltaics 117
2.2.4.1 AbsorptionandEmissionProperties 118
2.2.4.2 SurfaceVersusBulkOpticalProperties 120
2.2.4.3 CarrierLifetimes,DiffusionLengths,andDiffusionCoefficients 121
2.2.4.4 TransientSpectralFeaturesandExcitationDynamics 122
2.2.4.5 RecombinationConstantsintheSurfaceandBulkRegionsof
PerovskiteSingleCrystals 126
2.2.5 ConcludingRemarks 127
References 128
2.3 Charge-SelectiveContactMaterialsforPerovskiteSolarCells
(PSCs) 131
PengGaoandMohammadKhajaNazeeruddin
2.3.1 Hole-SelectiveElectron-BlockingMaterials(HTMs) 132
2.3.1.1 OrganicHTMs 132
2.3.1.1.1 MolecularHTMs 132
2.3.1.1.2 PolymericHTMs 135
2.3.1.1.3 OrganometallicComplexHTMs 136
2.3.1.2 InorganicHole-SelectiveElectron-BlockingMaterials 138
2.3.2 Electron-SelectiveHole-BlockingMaterials 139
2.3.2.1 InorganicElectron-SelectiveHole-BlockingMaterials 140
2.3.2.1.1 TiO 140
2
2.3.2.1.2 ZnO 144
2.3.2.1.3 SnO 144
2
2.3.2.2 OrganicElectron-SelectiveHole-BlockingMaterials 146
2.3.2.3 CompositeETMs 147
2.3.3 Conclusion 147
References 148
2.4 BeyondMethylammoniumLeadIodidePerovskite 155
TeckM.Koh,BiplabGhosh,PadinhareC.Harikesh,SubodhMhaisalkar,and
NripanMathews
2.4.1 Introduction:BeyondCH NH PbI 155
3 3 3
2.4.1.1 MultidimensionalPerovskites 155
2.4.1.2 MultidimensionalPerovskitePhotovoltaics 157
2.4.2 TheoreticalCalculationsforPb-FreeHalidePerovskites 161
2.4.2.1 ASnX Perovskites:3DPb-FreeStructures 161
3
2.4.2.2 A SnX Perovskites:Metal-DeficientStructures 165
2 6
2.4.2.3 Germanium-BasedPerovskites 166
x Contents
2.4.2.4 Bismuth/Antimony-BasedPerovskites 168
2.4.2.5 DoublePerovskites:HybridBinaryMetalStructures 170
2.4.3 ExperimentalEffortsinPb-FreePerovskitePhotovoltaics 170
2.4.3.1 Sn2+andGe2+asReplacementsforPb2+ 172
2.4.3.2 A SnX asaStableAlternativetoASnX 174
2 6 3
2.4.3.3 Cu2+:anAlternativeDivalentMetalCation 175
2.4.3.4 Bi3+andSb3+:TowardTrivalentMetalCations 175
2.4.4 ConcludingRemarksandOutlook 176
References 178
2.5 HalidePerovskiteTandemSolarCells 183
TeodorK.Todorov,OkiGunawan,andSupratikGuha
2.5.1 Introduction 183
2.5.2 TandemDeviceTypeandPerformanceLimitations 184
2.5.2.1 SingleTCE/Two-Terminal(2-T)MonolithicStack 184
2.5.2.2 Multi-TCE/Two-Terminal(2-T)MechanicalStack 185
2.5.2.3 Multi-TCE/Three-Terminal(3-T)MechanicalStack 185
2.5.2.4 Multi-TCE/Four-Terminal(4-T)MechanicalStack 186
2.5.2.5 Multi-TCE/Four-Terminal(4-T)SpectrumSplit 186
2.5.3 PerovskiteTandemPhotovoltaicDeviceResearch 188
2.5.4 ConclusionandOutlook 194
References 194
PartIII PerovskiteLightEmittingDevices 199
3.1 PerovskiteLight-EmittingDevices–Fundamentalsand
WorkingPrinciples 201
MicheleSessolo,Maria-GraziaLa-Placa,LauraMartínez-Sarti,and
HenkJ.Bolink
3.1.1 Excitons,FreeCarriers,andTrapStatesinHybridPerovskiteThin
Films 202
3.1.2 HybridPerovskiteLight-EmittingDiodes 205
3.1.3 HybridPerovskiteNanostructuresandNanoparticles 209
3.1.3.1 InorganicCesiumLeadHalideQuantumDots 212
3.1.3.2 Quasi-2DHybridLeadHalidePerovskites 215
3.1.3.3 FinalConsiderations 218
References 218
3.2 TowardElectricallyDrivenPerovskiteLasers–Prospectsand
Obstacles 223
SongtaoChenandArtoNurmikko
3.2.1 Introduction 223
3.2.2 ElectricalInjectioninPerovskite-BasedLight-EmittingDiodes
(LEDs) 225
3.2.3 OpticalGaininThin-filmSolid-statePerovskites 228
3.2.4 IntegratingOpticalResonatorsandPerovskiteGainMedia 234
Contents xi
3.2.5 TheWayForwardTowardElectricalInjection 239
3.2.6 Summary 241
References 242
PartIV BeyondPerovskitePhotovoltaics 249
4.1 NovelSpinPhysicsinOrganic–InorganicPerovskites 251
ChuangZhang,DaliSun,andZeevV.Vardeny
4.1.1 Introduction 251
4.1.2 MagneticFieldEffect(MFE)onPhotocurrent(PC),
Photoluminescence(PL),andElectroluminescence(EL) 252
4.1.2.1 ObservationofMFEintheCH NH PbI ClxFilmsandDevices 253
3 3 3−x
4.1.2.2 MFEinHybridPerovskites;MorphologyDependence 255
4.1.2.3 The“Universal”PlotandtheSpin-mixingProcessviaΔgofElectrons
andHoles 258
4.1.3 HighMagneticFieldOpticalPhenomena 260
4.1.3.1 DirectMeasurementofΔgbyField-InducedCircularlyPolarized
Emission 260
4.1.3.2 Magneto-absorptionSpectroscopyatUltrahighMagneticField 263
4.1.4 Spin-PolarizedCarrierDynamics 263
4.1.4.1 DirectMeasurementofSpin-pairLifetimebyPicosecond
Pump–ProbeSpectroscopy 263
4.1.4.2 DeterminationofSpinRelaxationTimefromCircularPump–Probe
Technique 265
4.1.5 ConclusionandOutlook 265
Acknowledgements 268
References 268
4.2 PerovskiteSolarCellsforPhotoelectrochemicalWaterSplitting
andCO Reduction 273
2
Gurudayal,JoelAger,andNripanMathews
4.2.1 Introduction 273
4.2.1.1 PhotoelectrochemicalGenerationofH 275
2
4.2.1.2 PECElectrodeMaterials 276
4.2.2 TandemConfigurations 277
4.2.2.1 Photoanode–PhotocathodeStrategy 278
4.2.2.2 PEC-PVTandemSystem 282
4.2.2.3 Photovoltaic-Electrocatalyst(PV-EC)Structure 285
4.2.3 EC/PEC-PVApproachforCO Reduction 287
2
4.2.4 ConcludingRemarksandOutlook 288
References 290
Index 293