Hybrid Organic-Inorganic Perovskites

280 Pages·2020·19.389 MB·English

by  Wei Li, Alessandro Stroppa, Zheming Wang, Song Gao

HybridOrganic-InorganicPerovskites
Hybrid Organic-Inorganic Perovskites
WeiLi
AlessandroStroppa
Zhe-MingWang
SongGao
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v
Contents
Preface ix
Acknowledgements xi
1 IntroductiontoHybridOrganic–InorganicPerovskites 1
1.1 PerovskiteOxides 1
1.2 EvolutionfromPerovskiteOxidestoHybridOrganic–Inorganic
Perovskites 3
1.3 ClassificationandChemicalVariationsofHOIPs 4
1.4 Structure,Symmetry,andPropertyFeaturesofHOIPs 5
1.4.1 GeneralTrend 5
1.4.2 IonRadiusMatchabilityandToleranceFactor 7
1.4.3 PhaseTransitions 10
References 12
2 HybridHalidePerovskites 15
2.1 SynthesisandChemicalDiversity 15
2.2 SymmetriesandStructures 19
2.3 PhaseTransitions 24
2.4 PhysicalProperties 29
2.4.1 SemiconductivityandBandgapStructures 29
2.4.2 TransportPropertiesandPhotovoltaics 32
2.4.3 LaserPhysics 49
2.4.4 Light-EmittingDiodes 54
2.4.5 Photodetectors 59
2.4.6 FerroelectricityandRashbaEffect 63
2.4.7 MechanicalProperties 66
2.4.8 ThermalConductivity 70
2.4.9 CaloricEffects 71
2.4.10 OtherPropertiesandApplications 73
References 73
3 HybridFormatePerovskites 79
3.1 SynthesisandChemicalDiversity 79
3.2 SymmetriesandStructures 82
vi Contents
3.3 PhaseTransitionsandOrder–Disorder 91
3.4 PhysicalProperties 94
3.4.1 Magnetism 94
3.4.1.1 Spin-CantingandJTEffect 94
3.4.1.2 Spin-Flop 98
3.4.1.3 QuantumTunnelling 101
3.4.2 Dielectricity 102
3.4.3 Ferroelectricity 105
3.4.4 Ferroelasticity 114
3.4.5 Multiferroicity 118
3.4.6 MechanicalProperties 125
3.4.7 ThermalExpansion 134
3.4.8 CaloricEffects 139
References 145
4 HybridAzidePerovskites 151
4.1 SynthesisandStructures 151
4.2 PhaseTransitions 156
4.3 PhysicalProperties 164
4.3.1 Magnetism 164
4.3.2 Dielectricity 167
4.3.3 Anti-ferroelectricityandFerroelasticity 174
4.3.4 ThermalExpansion 176
4.3.5 MechanicalProperties 177
References 178
5 HybridDicyanamidePerovskites 181
5.1 SynthesisandStructures 181
5.2 PhaseTransitions 185
5.3 PhysicalProperties 188
5.3.1 Dielectricity 188
5.3.2 OpticalPropertiesandSecondHarmonicGeneration(SHG)
Effects 190
5.3.3 Magnetism 191
5.3.4 MechanicalPropertiesandThermalExpansion 193
5.3.5 CaloricEffects 195
References 197
6 HybridCyanidePerovskites 199
6.1 SynthesisandStructures 199
6.2 PhaseTransitions(PT) 204
6.3 PhysicalProperties 211
6.3.1 SecondHarmonicGeneration(SHG) 211
6.3.2 Dielectricity 211
6.3.3 Ferroelectricity 215
References 217
Contents vii
7 HybridDicyanometallateandBorohydridePerovskites 219
7.1 HybridDicyanometallatePerovskites 219
7.1.1 Synthesis,Structures,andPhaseTransitions 219
7.1.2 PhysicalProperties 222
7.2 HybridBorohydridePerovskites 223
References 223
8 HybridHypophosphitePerovskites 225
8.1 Synthesis 225
8.2 SymmetriesandStructures 227
8.3 PhaseTransitions 229
8.4 PhysicalProperties 231
8.4.1 MechanicalProperties 231
8.4.2 Magnetism 231
References 233
9 OtherPerovskite-LikeHybridMaterialsandMetal-Free
Perovskites 235
9.1 HybridOrganic–InorganicPerchlorates 235
9.1.1 Synthesis,Structures,andPhaseTransitions 235
9.1.2 PhysicalProperties 239
9.1.2.1 MechanicalProperties 240
9.1.2.2 DielectricProperties 243
9.1.2.3 HighEnergeticProperties 244
9.2 HybridOrganic–InorganicTetrafluoroborates 246
9.2.1 Synthesis,Structures,andPhaseTransitions 246
9.2.2 PhysicalProperties 248
9.3 Metal-FreePerovskites 249
9.3.1 Synthesis,Structures,andElectronicProperties 249
9.3.2 PhaseTransitions 255
9.3.3 PhysicalProperties 255
9.3.3.1 Photoluminescence 255
9.3.3.2 FerroelectricityandDielectricity 256
9.3.3.3 MechanicalProperties 260
References 265
10 ConcludingRemarksandFuturePerspectives 267
Index 271
ix
Preface
Hybridorganic–inorganicperovskiteshaveattractedsubstantialinterestduring
the past decade because of their chemical variability, structural diversity, and
remarkable physical properties. However, to date, there has been no book
that covers the synthesis, structures, and functionalities of these fascinating
materials. This important book, by Wei Li, Alessandro Stroppa, Zhe-Ming
Wang,andSongGao,whoareinternationalleadersinthefield,fillsthisgapby
summarizing the recent advances in all the known 3D hybrid perovskite sub-
classes,whichincludehalides,azides,formates,hypophosphites,dicyanamides,
cyanides,dicyanometallates,andevensomemetal-freesystems.Italsopresents
a comprehensive account of their intriguing physical properties, including
photovoltaicandoptoelectronicproperties,magnetism,dielectricity,ferroelec-
tricity,ferroelasticity,andmultiferroicity.Suchatimelybookwillgivereadersa
comprehensivesummaryofthecurrentlyknown3Dhybridperovskitesandalso
illustratethemanyopportunitiesthatliebeyondthepopularhalidematerials.
SantaBarbara,May2020 AnthonyK.Cheetham,KBEFRS
xi
Acknowledgements
ThisbookwassupportedbytheNationalNaturalScienceFoundationofChina
(grantnos21571072,21671008,21975132,and21991143)andtheFundamental
ResearchFundsfortheCentralUniversities(no.63196006).Theauthorsarealso
grateful to Nankai University, CNR-SPIN, Peking University, and South China
UniversityofTechnologyfortheirfinancialsupport.
1
1
IntroductiontoHybridOrganic–InorganicPerovskites
1.1 PerovskiteOxides
Perovskiteisacalciumtitaniumoxidemineral,whichhasthechemicalformula
of CaTiO . It was discovered in 1839 by the Prussian mineralogist Gustav
3
Rose in a piece of skarn collected from the Ural Mountains and named in
honour of the Russian Count, Lev A. Perovskiy [1]. Nowadays, perovskites
broadly denote any materials that have the same type of structure as CaTiO ,
3
and their general chemical formula can be expressed as ABX [2]. The A and
3
B represent two metal ions that have different ionic radii, and the X denotes
an anion that is six-coordinated to the B-site. Adjacent BX octahedra are
6
three dimensionally linked via sharing their corners to generate a framework
structure in which the A-site counterbalancing cations are located in the
frameworkcavities(Figure1.1).Theperovskitestructurecanalsobeconsidered
as a cubic close-packed system in which the A- and X-sites are stacked in a
cubic-close-packedmanneralongthebody-diagonaldirection.
Perovskiteoxideshavediversecompositions,whichcanaccommodateagreat
dealofelementsintheperiodictable,andthecorrespondingchemicalvariations
enable many physical properties that have important industrial applications
[3].Perovskitematerialswereonlylimitedtoapplicationsaspigmentsinitially;
however,thesurgeofmilitaryneedforferroelectricmaterialsduringthe1940s
ledtotheinventionofBaTiO andthestartoftheelectroniceraofperovskites
3
[4].ThecrystalstructureofBaTiO wassolvedbyHelenD.Megawin1945,and
3
thisseminalworkinitiatedthefundamentalunderstandingofstructuralevolu-
tion and associated properties of synthetic perovskite oxides [5]. As illustrated
inFigure1.2a,theB-siteTi4+ displacesfromthecentreofTiO intheambient
6
trigonalphase ofBaTiO (R3m),which inducestheoccurrence ofspontaneous
3
polarization and therefore ferroelectric ordering. BaTiO is one of the most
3
commonlyusedferroelectricceramicsinavarietyofindustrialfieldsnowadays.
Researchin1950sledtotheinventionofanotherimportantperovskiteceramic,
leadzirconatetitanate(PbZr Ti O ,PZT,0<x<1),whichisasolidsolutionof
x 1−x 3
PbZrO andPbTiO (Figure1.2b)[6].PZTshowsastrikingpiezoelectriceffect
3 3
in addition to its intrinsic ferroelectricity and has been being widely utilized
as transducers, capacitors, and actuators in industry. Lanthanum manganite
(LaMnO , Figure 1.2c) is another very important perovskite oxide, which
3
HybridOrganic-InorganicPerovskites,FirstEdition.
WeiLi,AlessandroStroppa,Zhe-MingWang,andSongGao.
©2020Wiley-VCHVerlagGmbH&Co.KGaA.Published2020byWiley-VCHVerlagGmbH&Co.KGaA.