鈣鈦礦太陽能電池的研究進(jìn)展

18September2023Perovskite-based

SolarCellsCYQExplorationofsolid,cheap,stabledyeassensitizersforDSSCsCH3NH3PbBr3isthefirstperovskitecompoundasdyetobeintroducedinDSSCs,theefficiencyis2.2%anef?ciencyof3.8%onaCH3NH3PbI3-basedcellwasrealizedPrincipleofDSSCsPerovskite-basedsolarcellJ.

Am.Chem.Soc.131,6050–6051(2009).Organometaltrihalideperovskitesemiconductors(whichhavetheformula(CH3NH3)PbX3,wherePbisleadandXcanbeiodine,bromineorchlorine)basedsolarcellshavehighphotovoltagescloseto1.0V,muchlargethanSi-basedsolarcell’s0.7V.Lifetimeisshort.Continuousirradiationcausedaphotocurrentdecayforanopencellexposedtoair.Comparingtherateofincrease

inperovskitesolarcellefficienciesHodes,G.(2013)."Perovskite-BasedSolarCells."Science342(6156):317-318.◆19.3%@2014TimelineofPerovskitesolarcellsAl2O3ase-collectionlayerScience,2013,338(2012)643-647.PerovskiteasadyeinDSSCJACS,131(2009)6050-6051.PerovskiteQDsasdyeinDSSCNanoscale,2011,3(10):4088-4093.SequentialsolutiondepositionNature499,316–319(2013).FirstplanarheterostructureNature501,395–398(2013).InterfaceengineeringScience,345(2014)542-546.Firstintroductionofspiro-MeOTADasHTM(η:9.7%)Sci.Rep.2,591(2012)論文發(fā)表情況Keyword:perovskiteANDsolarcellPerovskiteMaterialsforPhotoAbsorbersOrganic-InorganicHybridMaterialsStructure:ABX3A:CH3NH3+,B:Pb2+,X:I-,Br-,orCl-

Directbandgap[1]largeabsorptioncoefficient(similartosilicon)[2]highelectricalmobility[3,4]Largee/htransportlength(100~1000nm)[5,6]PropertiesofPerovskiteabsorbersBandgap（eV）Permittivityε激子束縛能(meV)Mobility擴(kuò)散長度CH3NH3PbI31.54.85010~66~100nm[1]CH3NH3PbBr32.36.576CH3NH3PbCl3CH3NH3PbI3–xClx~1000nm[2]CH3NH3PbI3–xClx中擴(kuò)散長度高達(dá)1μm，高出材料的吸收長度近一個數(shù)量級。AdvantagesofPerovskite-basedSolarCellsEasyFabricated(spincoated/Sinteredat80℃)Withgoodcrystalproperties.ThebulktrapdensityofCH3NH3PbI3isnTPF~5×1016/cm3，vsorganicthinfilm:1019/cm3.[NatMater,2014,13(5):476-480.]verylonge–hdiffusionlengthsofCH3NH3PbI3-xClxperovskites(ontheorderof1mm)[Science,342(2013)341-344.]HighVoc:~1V.vsVOC(siliconsolarcell):0.7VMonojunctionsolarcellefficiencyupto20%[J.Phys.Chem.Lett.,4(2013)2423-2429]StackingwithSi-basedsolarcellefficiencyupto32%.[Science,2014,344(6183):458-458. ]LowCostToputthingsinperspective,foraproductioncapacityof1000GWperyear,lessthan10,000tonsofleadwouldbeneeded.Comparethiswiththe4milliontonsperyearofleadusedforlead-acidbatteries.ShortagesofPerovskite-basedSolarCellsOxygensensitized[1]Hydrolysiseasily[2]DegradationDifficultytofabricatelargeareacontinuouslyperovskitefilmArchitectureofperovskitesolarcellsMesoporousStructurePlanarStructureFabricationMethodsSolutionsPbI2與CH3NH3I混合沉積先PbI2后CH3NH3I溶液法方便，但不可控、有針孔、重復(fù)性低Co-evaporationPbI2與CH3NH3I氣相共蒸發(fā)沉積（真空下）雜質(zhì)缺陷少、致密、一致性VASP浸漬PbI2后氣相CH3NH3I反應(yīng)高覆蓋率、低粗糙度、大晶粒（微米級），so低表面復(fù)合率、高開路電壓AbsorptionspectraEnergyEnviron.Sci.7,399–407(2014).ElectronselectivelayerTiO2SiO2ZrO2Al2O3ZnOOptimization:Graphene/TiO2[1](15.6%)DepositionmethodsSinteringtemperatureMicrostructureHoletransportlayerspiro-OMeTAD[1,5]ExpensiveThelowmobility(about10-6–10-5cm2/Vs)[1]DopingwithcobaltelectrolyteandLisaltThehighestefficiency(19.3)tillnow[5]Pyrenederivatives[2]Thiopenederivatives[3]PFB&TFB[4]CuSCNorCuIP3HTPTAACuSnI3PCPDTBTEnergylevelsfordifferentmaterials-3.62-4.92CuSnI3e-selectivematerialsphotoabsorbersh-transportmaterialsMaterialsToday2014,17(1):16-23.Al2O3ase-selectivelayerMaterialsToday2014,17(1):16-23.Al2O3spiro-OMeTADCH3NH3PbI3Graphene/TiO2ase-collectionlayersNanoLetters2014,14(2):724-730.Graphene:ReduceseriesresistanceIncreaserecombinationresistanceHoletransportlayerChemicalstructureoftheHTL:Poly(9,9-dioctylfluorenyl-2,7-diyl(PFO)poly[(9,9-dioctyl?uorenyl-2,7-diyl)-co-(4,4′-(N-(4-sec-butylphenyl)diphenylamine)](TFB)poly(9,9-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,N-phenyl-1,4-phenylenediamine)(PFB).Adv.Funct.Mater.2014,DOI:10.1002/adfm.201401557HTLfilmsperformance:spiro-OMeTAD>TFB>PFB>PFOTheorderofelectricalconductivitiesareσTFB>σspiro-OMeTAD>σPFB>σPFO.SubstratesITOonglassFTOonglassITOonPETFTOonPETGrapheneCNTCounterelectrodeAgAuPtGraphite/carbonblackOptimizationstrategiesforperovskitesolarcellsfine-tuningtheperovskitechemicalcompositiontoimprovefilmquality,suppressionoftherecombinationcouldleadtoVOCofaround1.1Vtuningtheenergylevelsofthecharge-extractionmaterialsusedinthecellharvestingabroaderpartofthesolarspectrumbyusingstackedcellsnon-toxicperovskitesInterfaceofdifferentlayersInterfaceengineeringHow:Planarheterojunctionperovskitesolarcells.CH3NH3PbI3–xClxfilmdepositionthroughanenhancedreconstructionprocessincontrolledhumidityconditions(30%).(lessdefects:decreasedcarrierrecombination)(energylevel:5.3and3.75eV)(ThePLdecaytimewas736nscomparedwiththereferencelifetimeof382ns.)DopingtheTiO2ETLwithYttriumtooptimizecarrierconcentrationandelectroncollectionefficiency(conductionbandminimum(CBM)of4.0eV)ModifyingtheITOelectrodewithpolyethyleneimineethoxylated(PEIE)toreduceitsworkfunction(4.6eVto4.0eV)Cobaltandlithiumco-dopedspiro-OMeTAD(energylevel:5.22eV)Science2014,345(6196):542-546.PlanarstructureProblem1:HydrolysiseasilyDopingBrorCldopingCH3NH3PbI3

[1]AllsolidsolarcellPackagingProblem2:FlexibilityTiO2,Al2O3,ZrO2

RequireahightemperaturesinteringprocessZnOSinteringat50℃Organice/htransportlayerFlexiblesubstrateITOonPETGraphene/CNTMetalnanowireProblem2:Flexibilityexampledepositionfromorganicsolutionslowtemperatures(temperaturesfrom150

°CdowntoRT)formamaterialwithhighcrystallineandelectronicquality.Alayerallowelectronstoflow,butblockholes------theelectron-selectivecontactTiO2layerrequiresafairlytemperaturetemperature(~500°C)sinteringstep.aluminananoparticleslayersinteredatlowertemperature(<150°C)gaveefficienciesofover12%.

[J.EnergyEnviron.Sci.6,1739–1743(2013).]ZnO2layerprocessingbelow100oC.

[Chem.Commun.49,11089–11091(2013).]NaturePhotonics

8(2):87-88.Flexibledevice:ITO/ZnO/CH3NH3PbI3/spiro-OMeTAD/AgdeviceL