OverviewofOrganicHalidePerovskites

BenMorris
NathanielLee
PaulKeith
GunAn

MCHE3310
Dr.Wang
December1,2015

Introduction
OrganicHalidePerovskitesarearelativelynewareaofresearchinmaterialscience.The
familyofmaterialsisofparticularinteresttoenvironmentalscientistsandenergyengineersfora
fewreasons.Firstly,thematerialshavegreatpotentialforefficientlyharnessingsolarenergy.
Secondly,theyarethefastestgrowingfieldofsolarenergyresearchtodate(Collavinietal.).
Thirdly,theyaremuchlessexpensiveanddifficulttoproducethanprevioustechnologies.For
thesethreereasons,OrganicHalidePerovskitesareaninterestingandpotentiallypowerfulnew
technology.
Structure
Perovskiteisageneraltermthatreferstoanymaterialwithacrystalstructuresimilarto
CaTiO
.NamedafterRussianmineralogistLevPerovski,Perovskiteisasimplecubiccompound
3
withtheformulaABX

(webmineral).Theelement/compoundA(GreenAtoms)isalwayslarger
3
thantheBelement/compoundandarepositionedonall4cornersofthecrystalstructure(hence
thesimplecubicstructure).TheB(Greyatoms)element/compoundislocatedoneachfaceofthe
structure,andthefinalelement,X(Redatom)isplacedinthecenterofthecrystal.

Figure1(IdealPerovskiteStructureCaTiO
)
3
1

RegularPerovskite
Fortheregular,nonmodifiedPerovskite,Aistypicallyanalkalineearthmetal(group
2),Bistypicallyoneofthetransitionmetalsinthefirstthreecolumns(3d5d)withchargeof
4+,andtheXcompoundisalmostalwaysoxygen.

Figure2(PeriodicTableforreference)
OrganicInorganicHalidePerovskite
LikethePerovskitepreviouslystated,organichalidePerovskitehasanABX
structure,
3
buttheA,B,andXcompoundsaredifferent.CompoundAwillnowbeanorganic
(containingcarbon)compoundwithatotalelectronicchargeof2+.CompoundBwillnowbean
inorganiccompoundwithatotalelectronicchargeof4+,andfinally,elementXhaschanged
frombeingalmostalwaysanoxygenatomtoahalogen(group17)atom.Anexampleofsucha
compoundismethylammoniumleadiodide(CH
NH
PbI
),(Mottaetal.)whichisavery
3
3
3
innovativematerialinsolarenergy.

Figure3Modelof
CH
NH
PbI
3
3
3
MechanicalProperties
Wewillcomparebrass(familiarmetal)toorganichalideperovskitesoweknowexactly
theextentofperovskitesmechanicalproperties.Organichalideperovskitehasalowshear
capacityandYoungsmodulusrangingfrom3to12GPaand15to37GPa(Feng),respectively.
Forcomparison,brasshasayoungsmodulusof97GPaandshearmodulusof37GPa.This
showsperovskitewilldeformandshearatlowerstressesthanbrass.Poissonsratiofor
perovskiterangesfrom0.4to0.5whichsuggeststhatitisaductilematerialandallowsfor
extensivedeformationbeforefailing,(Feng)Brassisaductilematerialthathasapoissonsratio
of0.31makingitlessductilethanperovskite.PerovskiteslowYoungsmodulusgivesitalow
tensilestress,whichmeansitwillfailwithasmallerforcethanbrass.
ElectricalandThermalProperties
Themainreasonthatorganichalideperovskitesaresointerestingisthattheyexhibitthe
photovoltaiceffect,meaningtheygenerateelectriccurrentwhentheyareexposedtolight.

Additionally,thesematerialsarerelativelyefficientatthisconversionfromlighttoelectricity.In
2015,asolarcellwascreatedusingahybridhalideperovskitecalledmethylammoniumlead
iodide(CH
NH
PbI
)whichexhibitedanefficiencyofabout20%(Mottaetal.).Asa
3
3
3
comparison,themostefficientconsumergradesolarpanelstodatehaveanefficiencyof
approximately21%(TheEcoExperts).However,hybridhalideperovskitesaresignificantlyless
expensivetoproducethanotherphotovoltaicmaterials,andsosolarpanelsmadefromthem
wouldbelessexpensivethanexistingconsumergradesolarpanels.
Inastudyconductedin2009,methylammoniumleadiodidewasfoundtohaveasolar
energyconversionefficiencyof3.8%(Kojimaetal.).Thisefficiencyissmallincomparisonwith
theefficiencyof20%foundforthesamematerialonlysixyearslaterin2015,indicatingthefast
paceofresearchanddevelopmentfororganichalideperovskites.Theefficiencyofthese
materialswilllikelycontinuetoincreaseasmoreresearchisconducted.However,thereisa
theoreticallimittotheefficiency.Ina2015study,ateamdevelopedadetailedbalancemodelfor
methylammoniumleadiodidewhichpredictedanefficiencylimitforthematerialof
approximately31%(Shaetal.).Thisimpliesthatthesolarconversionefficiencyofthematerial
mayneverexceed31%.However,theproductioncostsofthematerialmaycontinuetodecline
oncetheefficiencylimitisapproachedorreached.
Organichalideperovskites,althoughusefulforconvertinglightintoelectricity,possess
certaininherentinstabilities.Onepropertywhichmakesthematerialsunstableinsolarpower
applicationsistheirthermalconductivities,whichareunusuallylowforceramics.Alowthermal
conductivityisundesirableforsolarpowerapplicationsbecause,byFourierslaw,amaterial
withalowthermalconductivityhasahightemperaturegradient,whichdoesnotallowheatto

transferuniformlythroughoutthematerialaseasily.Thisintroducesthermalstressesthat
significantlyshortenthelifeofthesolarcells.Thethermalconductivityofmethylammonium
1 1
leadiodidewasexperimentallydeterminedtobe0.5W(K
m
)atroomtemperature(Pisoniet

al.).OthervaluesofthermalconductivityforselectedmaterialsaregiveninTable1.

ThermalConductivity mW*K

Material

MaterialClass

Copper

398

Metal

FusedSilica

1.4

Ceramic

MethylammoniumLead
Iodide

0.5

Ceramic

Alumina

39

Ceramic

Polystyrene

.13

Polymer

Table1.ThermalConductivities(Callister789)
Becauseorganichalideperovskitesgenerallyhavelowthermalconductivitiesforceramics,they
needtobestabilizedforuseundernormalconditionstoreducethermalstresses.
Anothersourceofinstabilityfororganichalideperovskitesisthattheydegradeinair
becausetheyreactwithoxygen(Youetal.).Oncethematerialstartsdegrading,itsconversion
efficiencydecreases(Youetal.).Onemethodofstabilizationinvolvescreatingasolutionofan
organichalideperovskiteandametaloxide(Youetal.).Themetalinthenewcompositeshields
thehalideperovskitefromoxygen,andthereforesignificantlyreducesdegradationofthe
material(Youetal.).
Byaddingametaltotheorganichalideperovskite,thethermalstressespresentinthe
materialundernormalusewouldalsolikelybesomewhatreduced.Becausemetalshavethe

highestthermalconductivitiesofallthematerialclasses(normallybetween10and250
1 1
W(K
m
)),themetalpresentinthecompositewouldlikelymakethetemperaturedistribution

insidethematerialmoreuniform,thereforereducingthermalstresses(Callister789).This
reductioninstresswouldmakethematerialmoresuitedtonormaluse.

Applications
ThemainapplicationofOrganicHalidePerovskitesisinsolarcelltechnologyduetothe
photovoltaiceffectpresentinthematerial.
Usinghybridorganicinorganicleador
tin
halidebasedmaterialasthelightharvestingactivelayer,thesecellscurrentlyhaveareported
efficiencyof20%
(Mottaetal.),howeverthesematerialshaveaprojectedpeakefficientlyof
approximately31%(Shaetal.).Thesesolarcellsaresignificantlylessexpensivethanother
modernphotovoltaicsolarcellsduetolowmanufacturingcostsandabundanceofmaterials.The
potentialforcheaperandmoreefficientsolarcellshasleadtoseveralstartupcompaniessuchas
DyesolandSauleTechnologies,whichhaveinvestedinandstartedproducingthesesolarcells
forcommercialuse.
SauleTechnologies
isresearchingOrganicHalidePerovskitesforuseintheirperovskite
solarcelltechnology.Aperovskitesolarcellusesaperovskitestructuredcompoundasthe
lightharvestingactivelayer.Duetothebroadabsorptionspectrum,fastchargerate,cheap
manufacturingcosts,andtransparentnatureofperovskites,
SauleTechnologiesplanstocreate
solarcellsthatcanbeintegratedintobuildingsseamlessly.Thisisincontrasttomodernsilicon

basedsolarpanels,whicharegenerallyanunsightlyadditiontomostbuildings.Theirkeygoalis
toturnwindowsofbuildingsintophotovoltaiccellswithoutlosingtransparency.Alsoduetoits
flexibility,theywanttouseperovskitecellsinroofingandwallstomaximizetheamountofsolar
energythatisabsorbedandconvertedintoelectricalenergy.
Dyesolisresearching
organichalideperovskitesforuseinperovskitedyesolarcell
technology.Thesecellsaresimilartotheirdyesensitizedsolarcells,buttheperovskiteisused
insteadofsensitizeddyetoabsorblightenergy.Theadvantageperovskitedyesolarcellshold
overdyesensitizedcellsisthattheyarecheapertoproduce,flexible,andtransparent,thus
allowingthemtobeusedinmanyplaceswheretraditionaldyesensitizedsolarcellswouldbe
unsuitable.

Figure4:Workingofa
PerovskiteSolarCell

Figure4parta)isaschematicofasensitizedperovskitesolarcell.Thentypematerial

extractstheelectronsandaptypematerialreplacesthem.Partb)isaschematicofathinfilm

perovskitesolarcell,whichisjustaflatlayerofperovskitesandwichedbetweentwoselective
contacts.Partc)showschargegenerationandextractioninthesensitizedarchitecture,whilepart
d)showsthechargegenerationandextractioninthethinfilmarchitecture.
Conclusion
Organichalideperovskitesareanewandpromisingareaofmaterialscienceresearch.
Althoughtherearecurrentlyseveralmajorstabilityissuesinherentinthefamilyofmaterials,
theyshowpromiseasaneffective,inexpensivealternativetoothermodernmaterialscurrently
usedforsolarpowergeneration.Theirlowthermalconductivities,althoughadetrimenttosolar
powerapplications,areaninterestingandsomewhatuniquepropertythatcouldmakehalide
perovskitesusefulforotherapplicationsinthefuture.Becausethesematerialsarerelativelynew,
theirpropertiesandpotentialusefulnesshavenotbeenfullyrealized.However,theyareoneof
thefastestgrowingareasofmaterialresearchtodate.Therewilllikelybemanyinteresting
applicationsoforganichalideperovskitesinthenearfuture.

Credits:
BenMorrisIntroduction,ElectricalandThermalProperties,Conclusion,Powerpoint
PaulKeithApplications,CoverPage,Powerpoint
GunWooAnMechanicalProperties,MaterialStudio,Submission,Powerpoint
NathanielLeeStructure,MaterialStudio,Powerpoint

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