Direct Probing of Gap States and their Passivation in Halide Perovskites by High-Sensitivity , Variable Energy Ultraviolet Photoelectron

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SupportingInformationforPublication:DirectProbingofGapStatesandtheirPassivationinHalidePerovskitesbyHigh-Sensitivity,VariableEnergyUltravioletPhotoelectronSpectroscopyIgalLevine1*,KoheiShimizu2,AlbertoLomuscio3,MichaelKulbak4,CarolinRehermann1,AravaZohar4,MojtabaAbdi-Jalebi5,BaodanZhao6,7,SusanneSiebentritt3,FengshuoZu8,NorbertKoch1,8,AntoineKahn9,GaryHodes4,RichardH.Friend6,HisaoIshii2*andDavidCahen4,101Helmholtz-ZentrumBerlinfürMaterialienundEnergieGmbH,Kekulé-Str.5,12489Berlin,Germany2CenterforFrontierScience,ChibaUniv.,1-33,Yayoi-cho,Inage-ku,Chiba-shi,263-8522Chiba,Japan3Lab.forPhotovoltaics,Univ.duLuxembourg,41,rueduBrill,L-4422Belvaux,Luxembourg4Dept.ofMaterials&Interfaces,WeizmannInst.ofScience,Rehovot76100,Israel5InstituteforMaterialsDiscovery,UniversityCollegeLondon,MaletPlace,London,WC1E7JEUK6CavendishLaboratory,UniversityofCambridge,JJThomsonAvenue,Cambridge,CB30HEUK7StateKeyLaboratoryofModernOpticalInstrumentation,CollegeofOpticalScienceandEngineering;InternationalResearchCenterforAdvancedPhotonics,ZhejiangUniversity,Hangzhou,China8InstitutfürPhysik&IRISAdlershof,Humboldt-UniversitätzuBerlin,12489Berlin,Germany9Dept.ofElectricalEngineering,PrincetonUniversity,Princeton,NJ08544,USA10Bar-IlanInst.forNanotechnol.&Adv.Mater.(BINA)andDept.ofChemistry,Bar-IlanUniv.,RamatGan,IsraelS1

1FigureS1:VariableenergyHS-UPSmeasurementsofaCr/AufilmdepositedonaSi/SiO2wafer.Longpassfiltercut-off0.005Au/PTAA/MixAPbBr3FTO/TiO2/2D-3D0.0040.0030.002SPVamplitude[mV]0.0010.0000.60.81.01.21.41.61.82.02.22.4Photonenergy[eV]FigureS2:ModulatedSPVmeasurementsinthefixedcapacitorarrangementofaMixAPbBr3filmdepositedonAu/PTAAsubstrate(showninteal,illuminationusingahalogenlampthroughtheHaPS2

2side)andofa2D/3DHaPfilmdepositedonFTO/TiO2substrate(showninred,illuminationusingahalogenlampthroughtheFTOside).FigureS3:VariableintensityHe-1UPSmeasurementsofMixAPbBr3onFTO/TiO2(right)andonAu/PTAA(left)FittingofSPVresultstoCFSinFigure3.FittingfunctionwasthesumoffourGaussianfunctionswhichpeakatthedefectenergiespreviouslyobtainedbymodulatedSPV,expressedas:4(?VL−?)2VLB??(?B)=∑??exp[−2]2(2.36??)?=1where?VLiselectronbindingenergywithrespecttovacuumlevel,?normalizationconstant,?B??defectenergy,and??thefullwidthathalfmaximum(FWHM)oftheGaussianfunction.S3

3WeusedgraphingsoftwareIgorPro(Wavemetrics,Inc.),whichemploysLevenberg–Marquardtalgorithmforsolvingnonlinearcurve-fittingproblems.Boundsandinitialvaluesforfittingparametersweresetasfollows:ThepeakpositionswereinitiallysettotheenergyobtainedbySPV(4.7,4.45,4.1,and3.95eV)and,sincethemodulatedSPVhaveuncertaintyof0.1eVindeterminingdefectenergy,allowedtovarywithintherangeof±0.1eV.FWHMofeachdefectstateisassumedasandfixedto0.2eV,theresolutionofHS-UPSandhencetheminimumlinewidthofthestate.Weimposednoboundaryconditiononnormalizationconstantsandchosetheirinitialvaluesas1.0*104fordefectsat4.7eVand4.45eV,1.0*103for4.1eV,and1.0*102for3.95eV.ThefittingfunctionsoftheindividualdefectsareshownasdashedlinesinFigureS4.FigureS4:FittingfunctionsoftheindividualdefectsaddedtoFigure3ofthemaintextThefittingresultsareshownasthicklinesinFigureS4anddashedlinesinFigure3ofthemaintext,redoneforMixAPbBr3onTiO2andblueoneonPTAA.ThevaluesoftheparametersatconvergencearelistedinTableS1.ThefittingwasnotconvergedforMAPbBr3and2D/3Dperovskitesduetotheinsufficientnumberofdatapoints.TableS1:TheparametersatconvergenceS4

4Parameters?(x10-4)?(x10-4)?(x10-4)?(x10-4)?(eV)?(eV)?(eV)?(eV)12341234Range±∞±∞±∞±∞4.68±0.14.45±0.14.10±0.13.95±0.1MixAPbBr3onPTAA9.3±1.68.9±1.46.6±2.11.5±2.14.78±0.024.50±0.024.2±0.14.0±0.2onTiO21.5±0.21.7±0.40.37±0.180.03±0.24.78±0.024.51±0.024.2±0.13.9±0.8S5