Heterovalent Substitution in Mixed Halide Perovskite Quantum Dots for Improved and Stable Photovoltaic Performance - Ghosh et al. - 2021

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pubs.acs.org/JPCCArticleHeterovalentSubstitutioninMixedHalidePerovskiteQuantumDotsforImprovedandStablePhotovoltaicPerformancePublishedaspartofTheJournalofPhysicalChemistryvirtualspecialissue“D.D.SarmaFestschrift”.††DibyenduGhosh,Md.YusufAli,AnimaGhosh,ArnabMandal,andSayanBhattacharyya*CiteThis:J.Phys.Chem.C2021,125,5485−5493ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Oneofthestrategiestoimprovethedeviceperformanceofmetal-halideperovskitesolarcellsistoaltertheelectronicandopticalpropertiesoftheperovskitelatticebymetaliondoping.Inthiswork,aliovalentdopingofsilverattheleadsiteofCsPbBr1.5I1.5quantumdots(QDs)showsstrikingprospectsinimprovingthephotovoltaic(PV)deviceperformance.Latticedopingcouldbeachievedonlyupto∼3.5atom%Ag+withrespecttoPb2+whichhassignificantimpactontheelectronicandopticalpropertiesoftheQDs.Thebandgapcouldbereducedfrom2.15eVforpristineQDsto2.12eVwith3.5atom%Ag-doping,beyondwhichmidbandgapstatesarecreatedalongwiththeformationofasecondaryAgIphasewithhigherAg+substitution.Densityfunctionaltheory(DFT)showsenhancedopticalabsorptioncoefficientandp-typecharacteroftheAg-dopedQDs.WiththeQDshaving3.5atom%Ag,asignificant∼20%enhancementinphotoconversionefficiency(PCE)isobservedupto9.67±0.12%duetothereductionofsurfaceandintrinsicdefects,decreaseinnonradiativerecombinationleadingtoanincreaseincarrierlifetime,andincreaseinchargetransfer.Althoughingeneralall-inorganicperovskite(AIPSK)QDsareattractivebecauseoftheirhighercrystallinity,betteropticalproperty,andeasysolutionprocessability,thesolutionstabilityofAIPSKQDsisnotthesameasthatinPVdevices.After3.5atom%Ag-doping,ourPVdevicesshowextremelypromisingambientstabilityfor575h(24days)withlessthan5%dropinPCEincomparisonto12%dropforpristineQDdevices.1.INTRODUCTIONNonetheless,AIPSKQDsalonestilllagbehindtheexpectedbenchmarkduetocarrierrecombinationandstabilityissues.ThemonumentalresearchactivitiesonABX3metal-halide+++2+Bothisovalentandaliovalentlatticedopinghasbeenperovskites(whereA=CH3NH3,CH(NH2)2,Cs;B=Pb,Sn2+,andX=Cl−,Br−,I−)areduetotheirbrilliantpropertiesconsideredapromisingapproachtoalleviatetheseadversa-DownloadedviaUNIVOFNEWMEXICOonMay15,2021at21:07:26(UTC).ries.15,16Hybridorganic−inorganicperovskitesaredopedwithsuchasdefecttolerance,highabsorption,andextinctionseveralheteroelementslikeBa2+,Cd2+,Sr2+,Sn2+,andcoefficients,appropriatebandgaps,ambipolarchargetrans-Mn2+,17−21whereaspartialreplacementofPb2+bySn2+inanport,longcarrierdiffusionlengthandlifetime,smallexcitonSeehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.1−4bindingenergy,andsolutionprocessability.PerovskitesolarAIPSKcompositioncouldretainanimpressivePCEof202+celldeviceshavealreadyreachedacertified25.5%efficiencyin∼11.33%.LimitedsubstitutionofPbbyaliovalentmetalaveryshortspanoftime5whichhasunderpinneditsgreatcationssuchasK+,Ce3+,andYb3+hasalsoshownpotentialasafuturecompetitortocommercializedSisolarcell.prospects,22,23whileAl3+dopinghasresultedinimprovingHowever,ambientstabilityofthesePVdevicesfacesaconstantthecrystalqualityandreducingthelatticestrain.24ThechallengeduetotheinevitabledecompositionoftheblackattenuationofcarrierconcentrationbyshiftingtheFermilevelperovskite(α-phase)oforganic−inorganicleadtri-iodideto(E)inAg+dopedorganic−inorganicperovskitewasfirst6Ftheinactiveyellowδ-phase.AlsovolatileorganicspeciesaredemonstratedbytheCaiandChengroupin2017.25ThisAg-formedinhumidenvironmentsleadingtolatticedeformationdopingstrategywasfollowedbyafewotherresearchgroupswhichdecreasesthephotoluminescence(PL)quantum7,8yield.AIPSKQDsprovidearemedyforbeingmoremoisture,air,light,andheatresistant,9,10alongsidesuperiorReceived:December14,2020optoelectronicpropertiesreaching100%quantumyield,11Revised:February21,2021achievingsolarcellPCE∼10.77%12andreachingbeyond13%Published:March9,202113withCsPbI2Brcomposition.TheQDsalsohelpinincreasingthestabilityoforgano-leadhalideperovskitebulkfilmsby14fillingthepin-holesandfacilitatingchargetransport.©2021AmericanChemicalSocietyhttps://dx.doi.org/10.1021/acs.jpcc.0c111225485J.Phys.Chem.C2021,125,5485−5493

1TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticledemonstratingthebettermentofchargetransportandimpurities,theQDsolutionwascentrifugedagainwithan26−28lesseningthedetrimentaloxidativedegradation.WithappropriateamountofMeOAcat7000rpmfor10min.Thesmallernanoparticles,inparticularQDs,thediffusionofprecipitatewasdissolvedinhexaneandstoredat4°Cfor12dopantionsbecomeincreasinglychallengingduetoaself-h.Thesupernatantwascentrifugedandtheprecipitatewas29,30purificationmechanismoftheQDs.StartingfromII−VI,driedundervacuum.3132I−III−VIsemiconductors,toPSKs,thereisalow-to-high2.6.PreparationofCompactTiO2(c-TiO2)Precursor.dopantconcentrationthresholdforexclusivelatticedoping;AcidicsolutionofethanolanddiluteHClwasaddeddropwisebeyondaparticularlimit,eitherthedopantionsareexpelledtounderconstantstirringinanethanolicsolutionofTTIP.ThetheQDsurfacewithamoreioniccharacterorthedopantisresultingsolutionwasstirredforanother30mintoyieldasegregatedasclusters.BoththesizeofthedopantionandQDtransparenthomogeneousprecursorsolution.sizedeterminethisthreshold.2.7.FabricationofPVDevices.FTOglasseswithsheetHerein,westudytheeffectofAgincorporationinAIPSKresistance∼5−6Ωcm−1werecleanedstepwisewithsoapCsPbBr1.5I1.5QDsontheirstructuralandphotophysicalwater,distilledwater,acetone,andisopropanoleachfor10minpropertiesandfinallyonthePVdeviceefficiencyandambientinanultrasonicbathfollowedbydryingunderN2flow.Thestability.CsPbBr1.5I1.5compositionischosensinceitissubstrateswereexposedunderUVozonelampfor5mintorelativelymorestableunderhumidenvironmentandelevatedremoveresidualorganicimpuritiesandthentransferredinsidetemperatures.Ag+issuitableasthedopantionbecauseofitstheN2filledglovebox.Fordepositingc-TiO2electroncloserionicradius(115pm)tothatofPb2+(119pm)andtransportinglayer(ETL),TiO2precursorsolutionwasspinbecausepartialsubstitutionofPb2+byAg+doesnotperturbcoatedat2000rpmfor30s,andthecoatedsubstrateswere25+thecrystalstructuresignificantly.WeobservethatAgfirstdriedonapreheatedhotplateat100°Cfor10minanddopingupto3.5atom%withrespecttoPb2+helpstoreducethenannealedat550°Cinsideaboxfurnacefor50min.theintrinsicdefectstatesandcarrierrecombination,therebyChlorobenzenewasusedfordispersingtheas-synthesizedincreasingthelifetimeofchargecarriersforbetterchancesofCPBIorAg-CPBIQDs(50mg/mL)ontoc-TiO2at1000rpmextractioninthePVdevice.PSKlatticedopingwith3.5atomfor30s.Thesubstrateswerethendippedinleadnitrate%Agenables∼20%increaseinPCEandsustainsthePVdissolvedinmethylacetateforremovalofligandsanddriedatperformanceforatleast575h(24days)withlessthan5%60°Cfor2min.Theabovestatedprocesswasrepeated3dropinPCE.times.OntopoftheQDperovskitelayer,spiro-MeOTADholetransportlayer(HTL)wasdepositedbyspincoatingofa2.EXPERIMENTALSECTIONsolutioncontaining72.3mg/mLofspiro-MeOTADin2.1.Materials.Lead(II)bromide(PbBr2,99.999%tracechlorobenzene,28.8μLof4-tert-butylpyridine,and17.5μLmetalbasis),lead(II)iodide(PbI2,99.999%tracemetalbasis),oflithiumbis(trifluoromethanesulfonyl)imide(LiTFSI)(520cesiumcarbonate(Cs2CO3,reagentplus,99%),silvernitratemg/mLinacetonitrile)at2000rpmfor30s.Anyresidual(AgNO3,Vetec,>99.5%),octadecene(ODE,technicalgrade,solventwasremovedbyheatingthesubstrateat60°Cfor590%),oleylamine(OAm,70%),oleicacid(OAc,90%),min.TennanometersofMoO3(atadepositionrateof0.1−0.3titaniumisopropoxide(TTIP,>97%),spiro-MeOTADÅ/s)andAg(100nmatadepositionrate0.3−1Å/s)were(>99%),bis(trifluoromethane)sulfonimidelithiumsaltsequentiallydepositedontopofHTLinsidethethermalevaporator(basepressureof5.5×10−6Torr).Thedeposited(99.95%),4-tert-butylpyridine(TBP,96%),andanhydrouschlorobenzene(99.8%)werepurchasedfromSigma-Aldrich.filmthicknessofMoO3andAgtopelectrodewasestimatedinFTO(TCO22-7,2.2mmthickness)andTi-nanoxide(T/SP,situviaquartzcrystalthicknessmonitor.Theactivedeviceareawasmaintainedat0.06cm2.particlesize20nm)werepurchasedfromSolaronix.Hexane(fractionfrompetroleum)andmethylacetate(MeOAc,2.8.CharacterizationandMeasurements.TheX-raySynthesisgrade)werepurchasedfromMerck.diffraction(XRD)measurementswerecarriedoutwitha2.2.SynthesisofCs-Oleate.InatypicalsynthesisRigakupowderX-raydiffractometerhavingCuKα=1.54059protocol,0.18gofCs2CO3,8mLofODE,and1mLofÅradiation.UV−visabsorbancespectrawererecordedbyOAcweretakenina50mLthree-neckedround-bottomflaskJascoV-670spectrophotometer.PLspectraweremeasuredandkeptundervacuumfor30min,followedbyheatingat120withaHoribaJobinYvonFluorologusingaXelampasthe°Cforanother30min.N2gaswaspurgeduntilthesolutionexcitationsourcewithanexcitationwavelengthof450nm.PLbecameclear.Thissolutionwaskeptatthistemperatureunderquantumyield(PLQY)wasmeasuredwiththehelpofaN2forfurtheruse.standarddyeCoumarin153.Thefluorescencelifetimeswere2.3.SynthesisofCsPbBr1.5I1.5(CPBI)QDs.Thesynthesisrecordedbytime-correlatedsingle-photoncountingspectro-33fluorimeterfromHORIBAJobinYvonIBH.ThefluorescenceofCPBIissimilartoourpreviousreport.PbBr2andPbI2(0.5mmoleach)in50mLODEweredissolvedstepwisefirstlifetimewascalculatedbyfittingthedecaycurveswithaat120°Cfor1hundervacuumandthenat140°CunderN2programinstalledbyIBH.Fieldemissionscanningelectronforanother30minfollowedbyadding5mLeachofOAmandmicroscopy(FESEM)imageswererecordedinCarlZeissOAc.Inthefinalstep,4mLofCs-OleatewasaddedintotheSUPRA55VPFESEM.Transmissionelectronmicroscopysolution,andafter5sthesolutionwasquenchedinice-cooled(TEM)imageswererecordedwiththeDST-FISTfacility,waterbath.IISERKolkata,JEOL,JEM-2100Fequippedwiththeenergy2.4.SynthesisofAg-CPBIQDs.Ag-incorporatedCPBIdispersiveanalysisofX-rays(EDAX)setup.TorecordtheQDsweresynthesizedbythesameprocedureasaboveexceptTEMandscanningTEM−highangleannulardarkfieldforthestoichiometricadditionofAgNOastheAg+source.(STEM-HAADF)images,selectedareaelectrondiffraction32.5.IsolationofCPBIandAg-CPBIQDs.Freshly(SAED),EDAX,andelementalmapping,theQDswerepreparedQDswerecentrifugedat7000rpmfor10min,anddispersedinhexane.Atomicforcemicroscope(AFM)imagestheprecipitatewasdissolvedinhexane.TogetridofweretakenwiththesamedispersionbyNT-MDTNTEGRA5486https://dx.doi.org/10.1021/acs.jpcc.0c11122J.Phys.Chem.C2021,125,5485−5493

2TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure1.(a)SchematicrepresentationofthepristineandAg-dopedCsPbBr1.5I1.5crystalstructuresobtainedbyRietveldrefinementofXRDpatterns.Vacindicatesanionvacancy.(b)XRDpatternsofQDpowdersandzoomed-inviewof(110)plane.(c)UV−vis-NIRabsorption,(d)PLemission,and(e)transientPL(TCSPC)spectraofpristineandAg-dopedCPBIQDs.instrumentfromNT-MDT(SantaClara,CA).SolarcelltheAgatomthereisaslightchangeinthecrystalstructure.So,measurementswerecarriedoutusingsteadystateAM1.5Ginadditiontospin−orbitcoupling(SOC)wehaveconsideredSolarSimulatorClassAAAModel:PEC-L01(Batsol)andthespinpolarizationeffectforsupercellstructureoptimizationBioLogicelectrochemicalworkstation(ModelNo.SP-300).andelectronicpropertyevaluations.2.9.ComputationalDetails.SystematicelectronicstructurewascalculatedwithintheframeworkofDFT3.RESULTSANDDISCUSSIONS34formalismasimplementedinWien2kcode.Inourmodeling,3.1.StructuralCharacterization.ThepristineandAg-wehaveconsideredAgincorporationindopedCsPbBr1.5I1.5colloidalQDsweresynthesizedbyhotCsPbI1.5Br1.5(CsPb1−xAgxI1.5Br1.5)withconstituentelementsinjectionat140°CwheretheQDsarestabilizedbyOAmandinthesupercellas8Cs,8Pb,12Br,and12I,where8PbOAcligandcapping(SupportingInformation,FigureS1).Onatomswerevariedincombinationof(1Ag,7Pb)and(2Ag,6thebasisofourpreviousfindings,33wehavechosenmixedPb-Pb)forvariousdopingconcentrations.ThePerdew−Burke−halideperovskiteQDsasthehoststructuresincehalf-Ernzerhof(PBE)exchangecorrelationpotentialofthesubstitutionofI−byBr−helpsinelevatingthediffusiongeneralizedgradientapproximation(GGA)35andTranand−barrierofImigrationwhichfavorablyhindersdecomposition36BlahamodifiedBeckeandJohnson(TB-mBJ)potentialhaveoftheperovskitelatticetotheyellowphase.ThetotalAg37beenusedthroughoutthecalculations.ThesizeofK-pointloadingineachsamplewasquantitativelyverifiedbyEDAXmeshesoftheCsPbI1.5Br1.5supercellandCsPb1−xAgxI1.5Br1.5analysis(FigureS2andTableS1).Hereafter,pristinestructureissetto6×6×6.Theself-consistentconvergenceCsPbBr1.5I1.5QDsarereferredtoasCPBI,andbasedonthecalculationswereconsideredsimilartotheearliercalculationofAgatom%withrespecttoPbobtainedfromtheEDAXatotalenergytoleranceof10−5Ry.38Thesimilarionicradiusanalysis(TableS1)theQDsaredesignatedasAg0.01-CPBI,ofAg+(115pm)andPb2+(119pm)helpedtoincreasetheAg0.02-CPBI,Ag0.035-CPBIandAg0.057-CPBI,respectively.tolerancefactor,andthedeviceperformanceisbetterthanthatRietveldrefinementoftheXRDpatternsvalidatesphaseofotherelementalsubstitutions(e.g.,Sn2+,Sr2+,In3+,andsopurityoftheQDsexceptthatforAg0.057-CPBIwhere∼2.5wtforth).However,duetoanoddnumberofvalenceelectronsin%AgIisfoundsegregatedalongwiththecubicQDphase5487https://dx.doi.org/10.1021/acs.jpcc.0c11122J.Phys.Chem.C2021,125,5485−5493

3TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticle(FigureS3andTableS2).OuranalysisshowsthattheupperthresholdoftheAg+substitutionlimitatthePb2+siteis∼3.5atom%(CsPb0.965Ag0.035Br1.5I1.5),beyondwhichAgIispresentasaminorsecondaryphase.Itisinterestingtonotethatwith5.7atom%Ag(EDAXdata),∼2.5%contributionisfromAgI(XRDRietveldanalysis),thusindicatingthelatticedopinglimitof3−3.5%.Moreover,theAg/Pbratioof4atom%obtainedbyXRDanalysisisagoodmatchwith3.5atom%obtainedbyEDAXanalysis(TableS1).Thisclearlymanifeststheself-purificationmechanisminQDswhereexcessAg+isexpelledfromthelattice.TheRietveldrefinedcrystalstructuresinFigure1avalidatesthelimitedaliovalentsubstitutionofPb2+byAg+withinthePbX4−octahedra.6TheXRDpatternsofthecubicα-phase(JCPDSNo.54-0752)donotshowanynoticeablealterationswiththeincreaseofAgconcentrationintheperovskitelattice(Figure1b),wherebythespacegroupPm3̅misalwaysmaintained.However,theincorporationofAg+atthePb2+siteisevidentfromthehigher2θshiftoftheXRDreflectionsinparticulartheΔ2θshiftof(110)peakisby0.3°fromCPBItoAg0.057-CPBI(zoomedviewofFigure1b).ThisshiftcanbewellunderstoodfromthesubstitutionoflargerPb2+ofionicradius119pmbysmallerAg+of115pmwhichleadstoaloweringoftheinterplanard-Figure2.(a)TEMand(b)HRTEMimagesand(c)SAEDpatternofspacingvaluesandadecreaseofunitcellvolume(TableS1).pristineCPBIQDs.(d)TEMand(e)HRTEMimagesand(f)SAED3.2.OpticalCharacterization.TheabsorptionandpatternofAg0.035-CPBIQDs.Latticefringesinpanels(b,e)showtheemissionspectrawererecordedwiththepurifiedcolloidal(110)planeandprominentreflectionsofthecubiclatticeareQDsdispersedinhexane.TheabsorptiononsetshiftsfromobservedintheSAEDpatterns(c,f).(g)STEM-HAADFimageand2.12eV(583nm)forCPBIto2.04eV(605nm)forAg0.035-thecorrespondingelementalmapsofCs,Pb,Br,I,andAg.(h)Self-CPBIwhichsignifies∼0.1eVdecreaseinthebandgap(FigureorganizationoftheQDsintoplateletsafter7and14daysinhexane1c).ThebandgapofCPBI,Ag0.01-CPBI,Ag0.02-CPBI,Ag0.035-medium.CPBI,andAg0.057-CPBIQDsare2.15,2.14,2.13,2.12,and2.09eV,respectively.ThePLspectrainFigure1dalsoshowaFigure2f.TheSTEM-HAADFimageanditscorrespondingconsistentredshiftwithhigherAg+substitutionsandanelementalmappingconfirmtheuniformdistributionoftheadditionalshoulderpeakforAg0.057-CPBIduetothecreationelements,inparticularAgwithoutanyobservablephase39ofmidbandgapstatesandformationofsecondaryAgIphase.segregation(Figure2g).WealsoobservethatirrespectiveofPLQYalsoshowsanenhancementfrom72%forpristineCPBIAgdoping,thenanocubesagedinsidetheparentcolloidalto78%with3.5%Ag+substitution(TableS3).Thetransientsolutioncanself-assembleintotwo-dimensionalstructuresofPLspectraclearlydemonstratetheimprovementincarrierseveralnanometerstomicronsinlateraldimensionwithoutlifetimeofAg-dopedCPBIQDs(Figure1eandTableS3).anychangeincrystalstructure.Figure2hshowssuchaself-TheaveragelifetimeofchargecarriersisthemaximuminorganizationofrepresentativeCPBIQDsafter1and2weeksAg0.035-CPBI(16.9ns)butdecreasessignificantlyto5.1nsinhexanemedium.AFMimagingreflectstheself-organizedwithfurtherincreaseinAgcontent(Ag0.057-CPBI)duetotheQDsafter2weeksofaginghavingasheetdimensionof100−increaseinnonradiativerecombinationinaslightlyimpure150nmandheightof8−9nm(FigureS4).Thisself-constitutionoftheQDsasreflectedfromtheτ1andτ3organizationprocessoftengovernedbyanisotropicdipolarcomponentsinTableS3.internanocubeforceshaslongbeenconsideredtobeextremely3.3.MorphologicalAnalysisoftheQDs.Figure2beneficialforpracticalrealizationofbottom-upfabricationprovidesamicroscopicviewofthepristineanddopedCBPI40−42technologies.QDs,theanalysisofwhichcorroboratestheXRDresults.3.4.DFTAnalysisoftheQDs.TheconsequencesofAgTransmissionelectronmicroscope(TEM)imageofpristinedopingontheelectronicpropertiesofCPBIQDsareCPBIQDsinFigure2ashowsmonodispersenanocubesofcomputationallyelucidatedwiththreecompositionsofsidelength8.1−8.4nm.Thehigh-resolutionTEM(HRTEM)CsPb1−xAgxI1.5Br1.5(x=0,0.125,0.25).ThecalculatedimageinFigure2brevealsthecubicα-phaseofthenanocubesformationenergyoftheoptimizedCPBIcubicunitcelliswherethelatticespacingof0.43nmcorrespondsto(110)−14.32eVwhichimprovesto−15.03eVfortheAg0.125-CPBIreflection,whichisalsothehighestintensitypeakintheXRDstructure,thusemphasizingtheprogressivestabilizationofthepattern(Figure1b).TheselectedareaelectrondiffractioncubiclatticewithAgdoping.Furthermore,inordertoexplore(SAED)patternsupportstheplaneindexingandcubiccrystaltheeffectofAg+dopingontheelectronicandopticalstructure(Figure2c).ThemonodispersityoftheQDsispropertiesofCPBI,thetotalandpartialdensityofstatesretainedafterAg+substitutionattheB-siteoftheperovskite(DOS)wereevaluated(Figure3).Apparently,foreachQDs(Figure2d).Figure2eshowstheHRTEMimageofstructurebothspin-upandspin-downDOSaresimilar,representativeAg-CPBIQDswithaslightlyreducedlatticewhichindicatesthatspinpolarizationeffectsinducedbyAg+0.035spacing∼0.41nmofthe(110)plane,whichisinagreementsubstituentisnegligibleandtheresultantnetspinmagneticwiththehigher2θshiftoftheXRDpeaks.Theunchangedmomentsarezero.Therefore,onlythespin-uptotalandpartialcubiccrystalstructureisreflectedfromtheSAEDpatterninDOSisdisplayedhere.InpristineCPBI,I5sandPb6sorbitals5488https://dx.doi.org/10.1021/acs.jpcc.0c11122J.Phys.Chem.C2021,125,5485−5493

4TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure3.TotalandpartialDOSof(a,b)CPBI,(c,d)Ag0.125-CPBI,(e,f)Ag0.25-CPBI.havedominatingcontributionstothevalencebandmaximareductionofbandgapofthesystemandtherebytherequiredwhereasI5pandPb6porbitalscontributemoretothebottomenergyforelectrontransitionsfromAg4dstatestoPb6pstatesideoftheconductionband(Figure3a,b).AsshowninFigureisreduced.TheopticalbandgapofpristineCBPIstructureis3c,e,afterAgsubstitution,thetotalDOSbarelychange.The2.1eVwithscissorcorrectionincludingSOCandTb-mBJdeeplocalizationofAg4dorbitalat−4to0eVshowsthepotential,whereasthebandgapforAg0.125-CPBIstructureisabsenceofanydopantstateswithinthebandgap(Figure3d,f),1.98eV(Figure3a,c).Thebandgapdecrementby∼0.12eVunlikethatobservedinFigure1d.Althoughtheconductionsupportstheobservedredshiftofabsorptionandemissionbandremainsunchanged,thevalencebandshiftstowardhighbands(Figure1c,d).Moreover,theabsorptioncoefficientenergylevelsandasaresultFermienergyentersthevalencespectraofpristineandAg-substitutedstructuresclearlyband,demonstratingthep-typenatureofAg-CPBI.ThisisindemonstratethehigherabsorbanceofAgsubstitutedsystemcontrasttothen-typecharacterofalkaline-earthmetal-dopedascomparedtothepristinestructure(FigureS5).15metalhalideperovskites.3.5.DeviceCharacterization.WhilethesolarcellAlso,thetotalDOSreduceswiththeincreaseinAgfabricationwasdoneinsidetheN2filledglovebox,thedeviceconcentrationfromAg0.125-CPBI(Figure3c)toAg0.25-CBPImeasurementswerecarriedoutinairwitharelativehumidity(Figure3e),wheretheshiftofvalencebandtowardlowenergyof55%andlaboratorytemperatureof25°C.TheAIPSKsolarlevelsisclearlyvisible.ThepartialDOSinFigure3a,cshowthecellswerefabricatedwithCBPIandAg-CPBIQDabsorbershybridizationofI5p,Pb6pandAg4dfrom−4to0eVandawithc-TiO2(thickness∼50nm)asETLandspiro-OMeTADlocalphenomenonleadingtowideningofthevalenceband.asHTL(Figure4a)wherethethicknessisaround350−400ThevalencebandmaximumisnotcontrolledeitherbyI5pornm(Figure4b).WiththeincreaseindopedAgcontentinthePb6pbutratheraffectedbyAg4dorbitalwhichshiftstowardCPBIabsorberlayer,theshort-circuitcurrentdensity(Jsc)andhigherenergylevels.Thiseventuallyleadstoanoverallopen-circuitvoltage(Voc)increaseuptoAg0.035-CPBI5489https://dx.doi.org/10.1021/acs.jpcc.0c11122J.Phys.Chem.C2021,125,5485−5493

5TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleFigure4.(a)SchematicrepresentationofatypicalAg-dopedCPBIQDdevice,and(b)cross-sectionalFESEMimageofanactualdevice.Solarcellcharacterizationdataintermsof(c)J−Vcharacteristicplots,(d)Nyquistplots(withequivalentcircuitastheinset),and(e)stabilityplotsforthedevicesmonitoredfor575h(24days)underambientenvironment.Table1.PVParametersoftheDevicesFabricatedwithPristineandAg-DopedCPBIQDAbsorbers2asamplesVoc(V)Jsc(mA/cm)fillfactorefficiency(%)Rs(Ω)Rct(Ω)CPBI1.0011.350.718.07±0.1548.91064Ag0.01-CPBI1.0211.560.738.66±0.2047.7921Ag0.02-CPBI1.0212.110.739.08±0.1643.5709Ag0.035-CPBI1.0412.510.749.67±0.1241.3312Ag0.057-CPBI0.9812.050.698.13±0.2341.5475aAverageestimationwasperformedwithsamplesize5of.composition(Figure4c).With3.5atom%AgsubstitutioninnotonlymodifiesthebandstructurebutalsodecreasestheAg0.035-CPBI,theincreaseinJscisby∼10.22%(from11.35tointrinsicvacanciesintheQDswhichincreasetheJsc.Onthe12.51mA/cm2)andVincreasesfrom1.0to1.04V.contrary,nonradiativepathwaysaremorefavoredwhenaocConsequentlyPCEincreasesfrom8.07±0.15%forCPBItosecondaryphaseappearsandthelatticeAgisincreasedupto9.67±0.12%forAg0.035-CPBIQDs.AhigherAg/Pbratioof5.7atom%.ThisisalsoobservedfromthePLdecayprofile5.7atom%alongwiththeAgIphaseinAg0.057-CPBIQDswhichultimatelyleadstoadecreaseinJsc.TheNyquistplotshoweverhasanegativeimpactonthedeviceperformanceobtainedbytheelectrochemicalimpedance(EIS)measure-(Table1).TheseresultsclearlysuggestthatincorporationofmentsonthedevicesindicatenoticeabledecreaseintheAg+atalowconcentrationof3.5atom%attheB-siteofCPBIsemicirclediameteruptoAg-CPBI,suggestingadecrease0.0355490https://dx.doi.org/10.1021/acs.jpcc.0c11122J.Phys.Chem.C2021,125,5485−5493

6TheJournalofPhysicalChemistryCpubs.acs.org/JPCCArticleinchargetransferresistance(Rct)(Figure4d).TheNyquist■ASSOCIATEDCONTENTplotswerefittedbyaparallelcombinationofcapacitance(C1),*sıSupportingInformationRctwithaseriesresistance(Rs)(insetofFigure4d).RctTheSupportingInformationisavailablefreeofchargeatdecreasesfrom1064ΩforCPBIto312ΩforAg0.035-CPBIhttps://pubs.acs.org/doi/10.1021/acs.jpcc.0c11122.andincreasesagainforAg0.057-CPBI(Table1).RsalsoExperimentaltechnique,XRDRietveldplotsanddecreasesfrom48.9ΩforpristineCPBIto41.3ΩforAg0.035-analysis,EDAXanalysis,PLdecayparameters,absorp-CPBI.ThedecreaseinRctattributestotheremovalofsurfacetioncoefficientfromDFTcalculation,solutionstabilitydefectsandtrapstateswhereasthedecreaseinRssuggeststheofQDs(PDF)removalofintrinsicdefects.ThetrendintransientPLspectraisfullyconsistentwiththeEISresultswheretheenhancement■ofcarrierlifetimeisduetothisremovalofdefectstates.AUTHORINFORMATION3.6.PVDeviceStability.TheeffectofAg+substitutioninCorrespondingAuthorCPBIQDshasdirectimplicationsontheQDstabilityaswellSayanBhattacharyya−DepartmentofChemicalSciences,andasthedevicestability.TheabsorptionandemissionspectraofCentreforAdvancedFunctionalMaterials,IndianInstituteofAg-CBPIQDsrecordedatregularintervalsfor20hshowthatScienceEducationandResearch(IISER)Kolkata,Mohanpur741246,India;orcid.org/0000-0001-8074-965X;thestabilityofCPBIQDsisunalteredafterAgdoping(FigureEmail:sayanb@iiserkol.ac.inS6).ThePVdevicesshowexcellentambientstabilityunder55%humidityand25°C(Figure4e).ThestabilitymeasuredAuthorsfor575hintermsofPCE(η%)showlessthan5%dropinDibyenduGhosh−DepartmentofChemicalSciences,andPCEforAg0.035-CPBIincomparisonto∼12%dropinthecaseCentreforAdvancedFunctionalMaterials,IndianInstituteofofpristineCPBIQD-baseddevices.ThisriseinstabilityoftheScienceEducationandResearch(IISER)Kolkata,MohanpurAg-dopedCPBIQDdevicesisquiteencouraging.Becauseof741246,India;orcid.org/0000-0002-8885-1365thepresenceofasecondaryAgIphase,excessAgdopinghasMd.YusufAli−DepartmentofChemicalSciences,andCentrenopositiveimpactonthestabilityandthereforethedropinforAdvancedFunctionalMaterials,IndianInstituteofSciencePCEforAg0.057-CPBIQD-baseddevicescloselymatchestoEducationandResearch(IISER)Kolkata,MohanpurthatofpristineCPBIQDdevices.Ininorganicperovskites,the741246,IndiaoxygenadsorptionissufficientlyreducedinanAg-dopedAnimaGhosh−DepartmentofChemicalSciences,andCentresamplewhichinturnabatestheoveralloxidationandhelpstoforAdvancedFunctionalMaterials,IndianInstituteofincreasethelong-termstabilityofthesolarcell,27whichisScienceEducationandResearch(IISER)Kolkata,ratherauniversaloccurrenceinnanostructuresbeyondQDs.43Mohanpur741246,IndiaArnabMandal−DepartmentofChemicalSciences,andCentreforAdvancedFunctionalMaterials,IndianInstituteof4.CONCLUSIONSScienceEducationandResearch(IISER)Kolkata,Insummary,wehavesuccessfullyincorporatedAg+attheB-Mohanpur741246,IndiasiteoftheCsPbBr1.5I1.5(ABX3)QDswhichhasasignificantCompletecontactinformationisavailableat:impactontheelectronicandopticalpropertiesoftheQDsashttps://pubs.acs.org/10.1021/acs.jpcc.0c11122wellasontheAIPSKQDsolarcells.Ag+couldreplacethePb2+cationsintheQDlatticeuptoaAg/PbdopingratioofAuthorContributions∼4.6atom%.However,anattempttocreateQDswith†D.G.andM.Y.A.contributedequally.maximumpossiblelatticedopingisaccompaniedbytheNotesaccumulationof2.5wt%ofasecondaryphaseofAgIwithinaTheauthorsdeclarenocompetingfinancialinterest.sampletotalAgatom%of5.7whichhasdetrimentalconsequencesontheopticalpropertiesandPVdevice■ACKNOWLEDGMENTSperformance.DFTcalculationsshowanenhancedopticalD.G.andA.G.acknowledgeNationalPostdoctoralFellowshipabsorptioncoefficientandbetterp-typecharacterduetoAg+(NPDF)SchemeunderDepartmentofScienceandTechnol-incorporation.Ag+substitutionhelpsinreducingthebandgapogy(DST),M.Y.A.thanksIISERKolkataandA.M.thanksfrom2.15to2.12eVfromCPBItoAg0.035-CPBIUniversityGrantsCommission(UGC),NewDelhifortheir(CsPb0.965Ag0.035Br1.5I1.5)QDsfacilitatinghigheropticalfellowships.ThefinancialsupportfromScienceandEngineer-absorptionwhereasmidbandgapstatesarecreatedalongingResearchBoard(SERB)undersanctionNo.CRG/2020/withtheformationofAgIphasewithhigherAg+substitution.000084isdulyacknowledged.ThesolarcelldevicesfabricatedwithAg0.035-CPBIQDsshowasignificant∼20%enhancementinPCE.Theenhancementin■REFERENCESPCEcouldbewellunderstoodduetothereductionofsurface(1)Bi,E.;Chen,H.;Xie,F.;Wu,Y.;Chen,W.;Su,Y.;Islam,A.;defectsaswellasintrinsicdefects,decreaseinnonradiativeGrätzel,M.;Yang,X.;Han,L.DiffusionEngineeringofIonsandrecombinationleadingtoanincreaseincarrierlifetime,andChargeCarriersforStableEfficientPerovskiteSolarCells.Nat.increaseinchargetransferfromtheAIPSKQDabsorberlayerCommun.2017,8,15330.toETLandHTL.ThePVdevicestabilityalsoshowsvery(2)Xing,G.;Mathews,N.;Sun,S.;Lim,S.S.;Lam,Y.M.;Gratzel,M.;Mhaisalkar,S.;Sum,T.C.Long-RangeBalancedElectron-andpromisinglong-termoperationfor575h(24days).ThisworkHole-TransportLengthsinOrganic-InorganicCH3NH3PbI3.Sciencedemonstratesthetremendousbenefitofasuitablealiovalent2013,342,344−347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