Perovskites: crystal structure, important compounds and ...

1 Perovskites: crystal structure , important compounds and propertiesPeng GaoGMF Group Meeting12,04,2016 Solar energy resourceTerrestrial sun lightGlobal Power DemandPV instillationsTo start We have to solve the energy problem. Any technology that has good potential to cut carbon emissions by > 10 % needs to be explored aggressively. Researchers should not be deterred by the struggles some companies are having. Someone needs to invest in scaling up promising solar cell And Historyof perovskite compoundsPerovskite is calcium titanium oxide or calcium titanate, with the chemical formula CaTiO3. The mineral was discovered by Gustav Rose in 1839 and is named after Russian mineralogist Count Lev AlekseevichPerovski(1792 1856). Allmaterialswith thesamecrystalstructureasCaTiO3,namelyAB X3,are termedperovskites: Very stable structure , large number of compounds , variety of properties, many practical applications.

2 Key role of the BO6octahedrain ferromagnetism and ferroelectricity. Extensive formation of solid solutions material optimization by composition control and phase transition +B4+O2-Ideal cubic perovskite structure (ABO3)Origin And Historyof perovskite compoundsPerovskiteSystemsInorganic Oxide PerovskitesIntrinsic PerovskitesDoped PerovskitesHalide PerovskitesAlkali-halide PerovskitesA2Cl(LaNb2)O7 Organo-Metal Halide PerovskitesClassification of perovskite SystemStructurededuced1959:KongeligeDans keVidenskabernesSelskab, Matematisk-FysikeMeddelelser(1959)32, p1-p17 Author:Moller, :The structure of cesiumplumboiodideCsPbI31892: 1stpaper on lead halide perovskitesReference compoundPropertiesExisting and potential applications NotesBaTiO3 Ferroelectricity, piezoelectricity, high dielectric constantMultilayer ceramic capacitors (MLCCs), PTCR resistors, embedded capacitanceMost widely used dielectric ceramicTC= 125 C(Ba,Sr)TiO3 Non-linear dielectric propertiesTunable microwave devicesUsed in the paraelectric statePb(Zr,Ti)O3 Ferroelectricity, piezoelectricityPiezoelectric transducers and actuators, ferroelectric memories (FERAMs)PZT.

3 Most successful piezoelectric materialBi4Ti3O12 Ferroelectric with high Curie temperatureHigh-temperature actuators, FeRAMsAurivillius compound TC= 675 C( )NbO3, , piezoelectricityLead-free piezoceramicsPerformances not yet comparable to PZT but rapid progress(Pb,La)(Ti,Zr)O3 Transparent ferroelectricOptoelectronic devicesFirst transparent ferroelectric ceramicBiFeO3 Magnetoelectric coupling, high Curie temperatureMagnetic field detectors,memoriesMost investigated multiferroic compound . TC= 850 CPbMg1/3Nb2/3O3 Relaxor ferroelectricCapacitors, actuatorsHigh permittivity, large electrostrictive coefficients, frequency-dependent propertiesSrRuO3 FerromagnetismElectrode material for epitaxial ferroelectric thin films(La, A)MnO3A = Ca, Sr, BaFerromagnetism, giant magnetoresistance, spin-polarized electronsMagnetic field sensors, spin electronic devicesSrTiO3 Incipient ferroelectricity, thermoelectric power, metallic electronic conduction when n-doped, mixed conduction when p-doped, photocatalystAlternative gate dielectric material, barrier layer capacitors, substrate for epitaxial growth, photoassisted water splittingMultifunctional materialLaGaO3 BaIn2O5 Oxyde-ion conductionElectrolyte in solid oxide fuel cells (SOFCs)BaIn2O5is an oxygen deficient perovskite with brownmillerite , BaZrO3 Proton conductionElectrolyte in protonic solid oxide fuel cells (P-SOFCs)

4 High protonic conduction at 500-700 C(La,Sr)BO3(B = Mn, Fe, Co)Mixed conduction, catalystCathode material in SOFCs, oxygen separation membranes, membrane reactors, controlled oxidation of hydrocarbons,Used for SOFC cathodesLaAlO3 YAlO3 Host materials for rare-earth luminescent ions,LasersSubstrates for epitaxial film depositionUseful salts with perovskite structureEarly publications on lead halide perovskites1stSolar Cell ReportsSolid-State DSCS olid hole conductor PCER edox electrolyte PCEdyeDSSC using hole transport material DSSC using redox electrolyteTiO2 TiO2light harvesterdye or pigment filmEvolution of device structuresVarious device fabrication methodsa) , , , , , ,NatMater 2014,13,897-903. b)M. Xiao, F. Huang, W. Huang, Y. Dkhissi, Y. Zhu, J. Etheridge, A. Gray-Weale, U. Bach, Cheng, L. Spiccia, Angew. ChemieInt. Ed. 2014, 53, 9898 9903. Anti-solvent the key to optimum morphologyPerovskite vs silicon technologyProduction of silicon and silicon wafersExpensive, high-energy process, generating high levels of waste materialProduction of perovskite cellSimpler, lower cost, lower embodied energy, massively reduced environmentalimpactToxicityAbundanceMedi umMediumLowHighLowLowHighHighLow bandgap q VocLoss in perovskite Solar CellsMaterialBandgap (eV)q Voc(eV)Energy loss (eV) ~ (CH3NH3 PbI3) Green et al.

5 Solar cell efficiency tables (version 42) July 2013 The hybridePerovskite is a Strongly-Absorbing Direct band Gap SemiconductorThe perovskite bandgap can be tuned by Chemical SubstitutionThe band gap can be tuned from eV to eV by substituting bromine for iodine in CH3NH3Pb(BrxI1-x)3 Noh et al., Nano Lett. 2013 For hybrid tandem with CIGSeVBut the morphology is not stable!Lead-free:CH3NH3 SnI3 perovskite Tuning the structure of perovskites from 3D to 2D When will a 3D perovskite form? When the A, B and X components fit together neatly in the crystal lattice. Assuming ionic radii of RAetc, For a close packed cubic perovskite the structure is possible, provided:Low dimensional perovskite with more possibilitiesThe basic structures of 2D organic inorganic perovskite with bilayer and single layer intercalated organic moleculesSchematic representations of hydrogen-bond styles between NH3+heads with an inorganic framework<110>-oriented (C6H13N3)PbBr4(API-PbBr4) that is prepared by reacting N-(3-amino-propyl)imidazole (API) with PbBr2in hydrobromicacid.

6 <110> oriented 2D organic-inorganic hybrid perovskite5,5 -bis(2-aminoethyl)-2,2 :5 ,2 :5 ,2 -quaterthiophene (AEQT) based 2D organic-inorganic hybrid perovskiteRoom temperature photoluminescence excitation ( em= 540 nm) and emission ( ex= 370 nm) spectra for thermally ablated thin films of (AEQT)PbX4with (a) X = Cl and (b) X = within the organic layer of perovskite structures6-amino-2,4-trans,trans-hexadi enoic acid, within a cadmium (II) chloride perovskite framework, polymerizes under ultraviolet (UV) rigid and stable perovskite structure !B. Tiekeand G. Chapuis, Mol. Cryst. Liq. Cryst., 1986, 137, 101Ni(bipy)3as cations for 2D perovskite as hybridmagnetic home message Being toxic and instable, Lead-Halide perovskite is an excellent MODLE material for electronic application. 3D type , Lead-Halide perovskite has found prevailing application in PV field. 3D type , Lead-Halide perovskite can be strong competitor to silicon PV 2D or 1D type perovskite provide more possibility for more broad applications.

7 Alignment of the hybrid halide perovskites CH3NH3 PbCl3, CH3NH3 PbBr3 and T. Butler, JarvistM. Frost and Aron progress in efficient hybrid lead halide perovskite solar cells JinCui, HualiangYuan, Hong Lin et; and Chemistry of Perovskites Mats Johnssonand Peter Lemmens(Dept. Inorg. Chemistry, Stockholm University) Solar cells: An emerging photovoltaic technology Nam-GyuPark (SKKU) Solar Cells: Film Formation and properties-TzeBin Song, Qi Chen, HuanpingZhou, et organic inorganic tin halide perovskites for photovoltaic applications -NakitaK. Noel, Samuel D. Stranks, Antonio Abate, Christian Wehrenfennig, Simone Guarnera, Amir-Abbas Haghighirad, Aditya Sadhanala, Giles E. Eperon, Sandeep K. Pathak, Michael B. Johnston, AnnamariaPetrozza, Laura M. Herzaand Henry J. Layered Hybrid perovskite Solar-Cell Absorber with Enhanced Moisture Stability-Ian C. Smith, Eric T. Hoke, Diego Solis-Ibarra,Michael D.

8 McGehee, and HemamalaI. KarunadasaThank you for your attention!