Importance of spin-orbit coupling in hybrid

organic/inorganic perovskites for photovoltaic

applications
JackyEven,Laurent.Pedesseau,JeanmarcJancu,andClaudineKatan*

UniversitEuropennedeBretagne,INSA,FOTON,UMR6082,35708Rennes,France

CNRS,InstitutdesSciencesChimiquesdeRennes,UMR6226,35042Rennes,France

CorrespondingAuthor
ClaudineKatan

Threedimensionalorganic/inorganicperovskiteshaverecentlybeensuggestedasanovelclass
ofmaterialsfordyesensitizedsolarcells(DSSC)withimprovedphotoconversionefficiency.
Thesecompoundsaremodeledinthisworkwithinthedensityfunctionaltheory(DFT).The
bandgapsaredominatedbyagiantspinorbitcoupling(SOC)intheconductionband,whichhas

beenlargelyoverlookedsofar.Directandisotropicopticaltransitionsatroomtemperatureare
associatedtoaspinorbitsplitoffbandrelatedtoatriplydegeneratedconductionbandofthe
cubiclatticewithoutSOC.Itisshownthat,duetothestrongSOC,theelectronicstatesinvolved
intheopticalabsorptionareonlyslightlyperturbedbylocaldistortionsofthelattice.Inaddition,
bandoffsetcalculationsconfirmthatCH3NH3PbX3/TiO2 (X=Br,I)isareferencematerialfor
driving electrons towardthe electrode indyesensitizedsolarcells.Twodimensional hybrid
perovskitesarealsosuggestedtoreachfurtherflexibilityforlightconversionefficiency.This
studyisamajorsteptowardstheunderstandingoftheoptoelectronicpropertiesofthesenovel
class of DSSC at the level of knowledge already achieved in the field of conventional
semiconductors.

TOCGRAPHICS

Hybridmaterials,optoelectronics,titanateoxyde,densityfunctionaltheory

Photovoltaic(PV)solarelectricityisoneofthekeytechnologiesofthe21stcenturytoreducethe
worldsrelianceonfossilfuelsforenergygeneration.Reducedcostsandhigherconversion
efficienciesareofcrucialimportancetomakePVbasedtechnologieseconomicallymore
competitive.Thequestforqualityandperformancesoffuturesolarcellshasattractedavast
researcheffortoverthelastdecadeinthefieldofsemiconductorheterostructures,nanostructured
materials,andthinfilms.Variousapproachesrangingfromhighcost/highperformanceIIIV
technologies,multiplejunctionsandconcentratorsystems,tolowcostthinfilmstechnologies14

havebeeninvestigated.Obviously,thedesignofnoveland/orefficientPVdevicesrequiresa
realisticmodelingofunderlyingmaterialspropertiesincludingchemicalcomposition,
mechanical,electricalandopticalfeatures.Thiscanbegainedwithstateoftheartabinitio
approaches.Inaddition,suchknowledgeisdesirabletoreachPVcellscomposedofearth
abundantelementsbasedmaterials.
Threedimensionalorganic/inorganicperovskites,basedonrelativelysmallorganiccations,have
recentlybeensuggestedasanovelclassofmaterialsfordyesensitizedsolarcells(DSSC)with
improvedphotoconversionefficiency.517Indeed,withananoporousTiO2electrode,ultrahigh
lightpowerconversionefficiencieshavebeendemonstrated.Comparedtoalternativestrategies
basedoninorganicsemiconductorquantumdots(QDs)orextremelythinabsorberscoatedupon
theinternalsurfaceofamesoporousTiO2electrode,hybridperovskitesofferseveralbenefits.In
particular,theeaseofsynthesis,tailoringoftheopticalabsorptionbychemicalsubstitution,
electronictransport,andhighstabilityindryair,areamongthemostfeaturedpropertiesofthese
systems.Interestingly,whereasconductionbandandvalencebandalignmentsbetween
absorbersandTiO2areofcrucialimportanceinunderstandingchargetransferandcharge
transport,7,8,16,18theirmodelingisstillscanty.
Conversely,twodimensionalhybridorganic/inorganicmaterialshaveattractedincreasing
interestoverthepastdecadeduetotheirpotentialoptoelectronicapplications.19Oncemore,the
versatilityoftheorganicpartaffordsthepossibilityoffinetuningmaterialsproperties.For
example,ithasbeenshownthattheopticalspectraofleadhalideorganic/inorganicperovksites
canbeeasilytailoredbyvaryingtheorganiccation,whichimprovestheopticalefficienciesand
tuningoftheemissionwavelength.19Amongthem,selfassembledlayeredstructureshave

recentlyshownenhancednonlinearopticalpropertiesinmicrocavities.20Interestingly,inthese
materialsDFTcalculationspredictreversedorderingofbandedgestatesascomparedto
tetrahedrallybondedsemiconductors.21Consistentlywithimportantrelativisticeffectsexpected
forlead,suchcalculationshavealsoevidencedthemajorroleofspinorbitcoupling(SOC)that
significantlyreducesthebandgapbyinducingalargesplittingofthefirstdegenerated
conductionlevels.21
Surprisingly,forthehybrid3DmaterialsrecentlyproposedasefficientDSSC,5,7,8,1416theeffect
ofSOChasbeenlargelyoverlooked,especiallyfromthetheoreticalpointofview.Optical
absorption22andreflectivity23measurementsbroughtclearexperimentalevidenceofsizeable
SOCsplittingsinsuchmaterialsmorethanadecadeago.EvensoeffectsofSOChavebeen
stressedinarecentcomputationalwork,15tothebestofourknowledgetheyhavenotyetbeen
accountedforincalculatedbandstructuresreportedintheliterature.
ThispaperaimstoinvestigatetheroleofSOContheelectronicbandstructureoftwo3Dhybrids
recentlyinvestigatedforPVdevices,namelyMAPbX3compoundswhereX=Br,IandMAstands
formethylammonium(CH3NH3).Moreover,asthedesignofefficientDSSCrequiresagood
understandingofVBalignments,wesuggestaprotocoltoderivethebandalignmentbetweenthe
MAPbX3absorbersandTiO2.Itinvolvescalculationsonaslabofarelated2Dhybrid,namely
2(C4H9NH3+)(PbI42).24Suchanalogsalsoallowfurthercomparisonandoffercomplementary
routesforbandgapengineering.Actually,bymixingthecompositionofhalogenatomsin
MAPb(I1xBrx)3structures,ithasrecentlybeenshownthatthebandgapcanbecontrollablytuned
tocovertheentirevisiblespectrum.14

Thesemixedcompoundsexhibitanaverageddisorderedcubicphase(spacegroupPm3m)at
roomtemperature.25Thestructuraldisorderisbothassociatedtotherotationofammonium
cationsandtiltofleadhalideoctaedra.Atlowtemperature,MAPbBr3andMAPbI3presentan
orderedorthorhombicstructureofspacegroupPnma,withacelldoublingwhencomparedtothe
roomtemperaturephase(Figure1).15,26

Figure1.OverviewofthecrystalstructuresofMAPbI3(left)andMAPbBr3(right)atlow
temperature.Thestructuresarebothorthorhombic(spacegroupPnma),15,26withacelldoubling
whencomparedtotheroomtemperaturecubicphase.

Theseorderedcrystallinestructuresareusedtoperformthepresenttheoreticalstudy.Figure2
showsthebandstructuresofMAPbBr3andMAPbI3withandwithouttheSOCinteraction.

Figure2.ElectronicbandstructuresofMAPbI3(top)andMAPbBr3(bottom),without(a)and
with(b)thespinorbitcouplinginteraction.Theoriginoftheenergyscaleistakenatthetopof
thevalenceband(VBM).
LetusfirstanalyzetheresultsobtainedwithoutSOC.Consistentlywithearlierresultsonthe
roomtemperaturecubicphase,27thegroundstatetransitionsareofdirecttypebutatthepoint
insteadoftheRpoint.15OurstudyshowsthattheymainlyinvolveeightactiveBlochlevels:two
levelsforthevalencebandmaximum(VBM12)andsixlevelsfortheconductionband
minimum(CBM16).Thisapparentcomplexsequenceatpointisassociatedtothelow
temperaturesymmetrybreakingwhichleadsbothtounitcelldoublingandstrain.26Infact,a

symmetryanalysisindicatesthattheCBM16statesarerelatedtotheconductionbandminimum
(CBM)attheRpointintheroomtemperaturePm3mcubicphasewhichcorrespondstoatriply
degeneratelevelassociatedtothevectorialrepresentationofthesimplegroup.25Thesame
electronicbandstructureisobtainedaroundthebandgapfortherelatedCsPbI3compoundwhere
theorganicpartofMAPbI3isreplacedbyaCsatominthelowtemperaturePnmaphase(figure
S1).Wecanfurtherdeveloptheanalysisoftheelectronicstatesusingthecompletephase
sequenceofMAPbI3andCsPbI3structures(videinfra).Similarenergydispersionsoccuratlow
temperaturealongtheU(1/2,0,1/2),YandU(1/2,0,1/2)directionsinfigure2,whichis
inherenttothesmalldistortionoftheperovskitelattice.Thedirectbandgapcalculatedat
pointisinagreementwiththestrongabsorbanceobservedatroomtemperature.7,22Thesix
CBM16statescorrespondtoantibondinghybridizationsof6porbitalsofleadandbelongtothe
irreduciblerepresentationsoftheD2hpointgroup(factorgroupforthePnmaspacegroupat
point).VBM12consistinantibondinghybridizationsofthe6sorbitalsofleadand5porbitals
ofiodineandareassociatedtononpolarirreduciblerepresentationsofthepointgroup.Optical
activityisrelatedtothedipolarmatrixelementsbetweenthefirstvalenceandconductionband

M VBM ,CBM 13 VBM i

statesasdefinedby:

CBM 13
xi

where xi representsthecrystal

axis.21ThesematrixelementstakesimilarvaluesfortheCBMstatesintheMAPbX3family.A
strongandalmostisotropicopticalactivityisexpectedfromsymmetryandenhancedatroom
temperaturebythedisorderofthecubicphase.SimilarresultsareobtainedforMAPbI3,although

thestraininducedconductionbandsplittingislarger.Wepointoutthatastraineffectwasalso
reportedinrelatedMASnX3compounds.32
Figure2revealslargechangesoftheelectronicbandstructurewhenaccountingforSOC.Indeed,
thefundamentaltransitionsofMAPbI3andMAPbBr3lowerto0.5eVand0.8eVrespectively.
WhiletheVBarenearlyunaffected,thesixfirstCBundergoadramaticsplitting.Thebandgap
remainsdirectandlocatedatthecenteroftheBrillouinzone.Thesefindingsareconsistentwith
thevaluereportedforarelated2Dorganicinorganichybrid,2(pFC6H5C2H4NH3)PbI4,for
whichthecorrectionisofabout1eV,leadingtoabandgapreductionbyafactoroftwo.21This
2Dperovskitecrystalizessimilarlytothe2(AA)PbX4family(AA=CnH2n+1NH3)24,29,30forwhich
wehaveemployedthesameleveloftheory.Forn=412andX=I,thespinorbitcouplinginduces
alargebandgapcorrectionofabout0.8eV,againmainlylocalizedontheCBlevels.Moreover,
whenappliedtorelatedinorganicstructuressuchasCsPbX3,comparablecorrectionsare
obtained,asillustratedfigure3(top)fortheinorganiccubicphaseofCsPbI3(asimilarresult
(figureS2)isobtainedforthecubicphaseofCsPbBr3.25)

10

11

Figure3..ElectronicbandstructuresofCsPbI3inthecubicphase(top)andtetragonalphase
(bottom),without(a)andwith(b)thespinorbitcouplinginteraction.Theoriginoftheenergy
scaleistakenatthetopofthevalenceband(VBM).
OnecannoticethatthecalculatedbandgapattheGGAPBElevelisequalto1.3eVingood
agreementwithprevioussimulations.36.ThecalculatedbandgapsattheLDAlevelareequalto
1.2eVforCsPbI3and1.3eVforCsPbBr3,andthespinorbitcouplinginducesalargebandgap
correctionofabout1.1eVinbothcases(figure3(top)).Alltheseresultsdemonstratethatthe
effectofSOConbandgapsishugeandcannotbereasonablydisregarded.Evenifcomparison
withavailableexperimentaldataisnotstraightforward,ourresultsareinqualitativegood
agreementwithevidenceofSOCeffectsintheopticalabsorption22andreflectivity23spectra

12

reportedforMAPbX3.Furthermore,theopticaltransitionoccursattheRpointintheroom
temperaturePm3mcubicphase.ForthePm3msymmorphicspacegroup,itispossibletodirectly
analyzetheirreduciblerepresentationsatRpointusingtheOhpointgroup.31Thetriply
degenerate(CBM13)(figure3a(top))statesareassociatedtothevectorialrepresentationofthe

simplegroupcommonlydescribed21,32bythe

symbols.Inthecorresponding

doublegroupincludingspinors,itissplittedbySOCintotwofolddegeneratestatesandfourfold
degeneratestates(figure3b(top)).Thissituationisusuallyencounteredinthevalencebandof
cubicconventionalsemiconductors.21,31TheconductionbandminimumofCsPbX3andMAPbX3
atroomtemperatureareassociatedtothetwofolddegeneratespinorbitsplitoff(SO)states

1 / 2,1 / 2

1
3

X iY

1
3

1 / 2,1 / 2

and

1
3

X iY

1
3

(figure

3b(top)).TheSOstatesleadtoastrong21andisotropic32opticaltransitionwiththeeven

likeVBMstates.Tounderstandtheinfluenceofthecubictetragonal(Pm3mI4mcm)transition
ofMAPbI333onitsoptoelectronicproperties,wehavealsoperformedDFTcalculationson
CsPbI3inthetetragonalphaseofMAPbI3includingtheSOC.WithoutSOC,thetriply
degenerateCBMstatesandtheVBMstatearefoldedbackfromtheRpointatthepointcases
(figure3a,bottom).InadditionandaccordingtotheD4hpointgroup,thestrainalongthezaxis
inducesasmallsplittingoftheCBMandthebandgapreducesto1.0eV.TheCBMvectorial

representationsplitsintoanondegenerate

stateatlowerenergyandtwofolddegenerate

13

states.TheSOCeffectishowevermuchlargerthantheeffectofstrain,andleadstoa

verysmallbandgap(figure3b(bottom)).ThestateorderingincludingSOCatthepointofthe
I4mcmphaseremainssimilartotheoneofthePm3mcubicphase,theCBMstatesbeingagain

relatedtothetwofolddegenerateSOstates

1 / 2,1 / 2

and

1 / 2,1 / 2

BasedonthebandstructureofCsPbI3,wecanalsoinvestigatethecubicorthorhombic(Pm3m
Pnma)transition.ThistransitionisassociatedtoacelldoublingandfoldingbackfromtheR
pointtothepoint.ThetriplydegenerateCBMaredoubledandsplittedbythestrainalongthe
threedirections.ThesixCBMstatescorrespondtoonedimensionalrepresentationsofthesimple
D2hpointgroupwhichyieldtwofolddegeneraterepresentationsofthecorrespondingdouble
group.ThestraineffectisnomorenegligiblewhencomparedtotheSOCeffect,buttheCBM
stateoflowestenergyhasanelectronicdensitysimilartotheoneofcubicSOstate.
Now,onecanwonderwhythefundamentaltransitionscalculatedwithoutSOCforthelow
temperaturePnmastructures,1.5eVand1.9eVrespectivelyforMAPbI3andMAPbBr3(figure
2)comparenicelywiththevaluesobtainedexperimentally,i.e.1.5eVand2.3eVrespectivelyfor
MAPbI3andMAPbBr3.5,14,22,23Thisagreementisfortuitousandstemsfromlargeerror
cancellations.Indeed,thebandgapisknowntobeunderestimatedintheDFTgroundstate
computations.ThiscanbecorrectedbyincludingmanybodyeffectsbymeansofGWself
energycorrectionforthebandgap34orusingtheBetheSalpeterequationresolutionforthe
exciton.35Unfortunately,suchcalculationsarebeyondavailablecomputationalresourcesfor
largesystems.InordertogaugetheimportanceoftheGWcorrections,wehaveconsideredthe

14

cubicphaseofCsPbI3.AoneshotGWselfenergycorrectionontheLDAlevelamountstoa0.6
eVincreaseofthebandgap.Thisvalue,althoughnotselfconsistent,showsthatGWcorrections
arelargeandintheoppositedirectiontoSOCeffects.Unfortunately,afulltreatmentincluding
bothSOCandmanybodyeffectsisfarbeyondavailablecomputationalresources.
Efficientelectricalpowergenerationreliesonthequalityoftheabsorberandthebandgap
energy.Theseconditionsappeartobefulfilledandunderstoodfromthetheoreticalpointofview.
ThisefficiencyalsoreliesontheabilityofthePVdevicetodrivethecarrierstowardthe
electrodes.Acorrectbandalignmentbetweenthesensitizerandtheelectrodematerialsisthusa
keyparametertopredictperformancesofPVdevices.InthecaseofDSSC,withaTiO2
electrode,hybridMAPbX3perovskitesappeartogreatlyimprovetheelectrontransport.8To
evaluatethevalencebandalignmentbetweentheanatasestructureofTiO28andhybrid
perovskites,aslabcalculation37wasperformedforthe2(AA)PbI4withn=4.Thisallows
estimatingtheoffsetsbetweenthevacuumlevelanditsbulkpotential(figure4).

15

Figure4.Potentialprofileinanalkylammonium(AA)2Dhybridperovskitecrystal(darkline)
andinaslab(reddottedline)withthesamecrystallographicstructure24surroundedbyvacuum.
Anupwardenergyshiftequalto0.93eVhasbeenappliedtothecrystalprofileinordertomatch
theslabprofile.WhenthesameshiftisappliedtothecomputedVBM,anabsoluteVBMof
5.6eVisfound.
Itleadstoanabsolutevalencebandenergyof5.6eV.Moreover,onecanusethepositionofthe
5dlevelsofleadasacommonelectronicmarkerbothfor3Dand2Dhybridperovskites.The
relativepositionofthe5dorbitalswithrespecttotheirVBMamountrespectivelyto16.4and
16.2eV.Thisleadstoanabsolutevalencebandenergyof5.4eVforbothMAPbX3crystals
thatnicelyagreeswiththeabsolutevalencebandenergylevelsdeducedfromtheexperimental

16

workfunctions:5.44and5.38eVforX=IandX=Br,respectively.5Thecompleteband
alignmentdiagramisgivenfigure5,basedontheabsolutevalencebandenergy(7.3eV)
commonlyusedforTiO2.8

Figure5.EnergyleveldiagramderivedfromthepositionofPb5dorbitals,computedVBM
(figure4)andexperimentalbandgapsofMAPbI3(1.5eV),MAPbBr3(2.3eV)5,14andanalkyl
ammonium(AA)2Dhybridperovskite(2,5eV).24CommonlyacceptedvaluesforTiO2electron
affinityof4.1eVandabsolutevalencebandenergyof7.3eVareused.
Itclearlydemonstratesthattheconductionbandoffsetsarefavorablefortheelectroninjection
fromabsorbertoelectrode.Inaddition,thisdiagramsuggeststhatcombining2Dand3Dhybrid
perovskitesmayprovideanalternativewayforthedesignofcolorfulsolarcellsthatcoverthe
entirevisiblespectrum.

17

Insummary,basedonDFTcalculations,theelectronicpropertiesof3Dleadhalide
organic/inorganicperovskitesusedasabsorbersinDSSC5,7,8havebeenthoroughlyinvestigated.
TheirbandgapisdominatedbyagiantSOCeffectactingmainlyontheconductionband,aswas
alreadydemonstratedforrelated2Dhybrids.21Atroomtemperature,theirremarkableoptical
propertiescanberelatedtodirectandisotropicopticaltransitionsbetweenatriplydegenerated
conductionbandandasinglevalencebandinasimplegrouprepresentation.Valenceband
offsets5confirmthatthegatheringofMAPbX3hybridsandTiO2isarelevantchoicefordriving
theelectronstowardtheelectrode.Ourcalculationsonalkylammoniumbased2Dhybridsalso
suggestacomplementaryroutetothechemicaltuning14recentlyproposedforthedesignof
colorfulsolarcellswithenhancedlightconversionefficiency.
ThepresenttheoreticalstudywasperformedusingtheDFTimplementationavailableinthe
ABINITpackage,38withtheLDAortheGGAPBEgradientcorrectionforexchange
correlation39andrelativistic,normconserving,separable,dualspaceGaussiantype
pseudopotentialsofGoedecker,Teter,andHutterforallatoms40orFritzHaberInstitutes
pseudpotentials.41TheSIESTAcodewasusedforthesimulationofslabsattheDFTGGA
level.42Wehaveverifiedthatthebandstructuresnearthebandgapdonotdependonthe
inclusionof5dorbitalsforPb.Theelectronicwavefunctionsareexpandedontoaplanewave
basissetwithanenergycutoffof950eV.4x4x4and4x4x1MonkhorstPackgridsareusedfor
reciprocalspaceintegrationin3Dand2Dstructuresrespectively.Calculationswereperformed
withandwithoutSOC.

18

CorrespondingAuthor
*Email:claudine.katan@univrennes1.frTel:+33(0)223235682
Notes
Theauthorsdeclarenocompetingfinancialinterests.
ThisworkwasperformedusingHPCresourcesfromGENCICINES/IDRISgrant2013
c2012096724.TheworkissupportedbyAgenceNationalepourlaRecherche(PEROCAI
projectANR1004).

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