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Stability and Degradation of Organic and Polymer Solar Cells PDF

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P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome Stability and Degradation of Organic and Polymer Solar Cells i P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome Stability and Degradation of Organic and Polymer Solar Cells Editor FREDERIK C. KREBS Department of Energy Conversion and Storage, Technical University of Denmark, Roskilde, Denmark A John Wiley & Sons, Ltd., Publication iii P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome Thiseditionfirstpublished2012 ©2012JohnWiley&Sons,Ltd Registeredoffice JohnWiley&SonsLtd,TheAtrium,SouthernGate,Chichester,WestSussex,PO198SQ,UnitedKingdom Fordetailsofourglobaleditorialoffices,forcustomerservicesandforinformationabouthowtoapplyforpermissiontoreuse thecopyrightmaterialinthisbookpleaseseeourwebsiteatwww.wiley.com. TherightoftheauthortobeidentifiedastheauthorofthisworkhasbeenassertedinaccordancewiththeCopyright,Designs andPatentsAct1988. Allrightsreserved.Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmitted,inanyformorby anymeans,electronic,mechanical,photocopying,recordingorotherwise,exceptaspermittedbytheUKCopyright,Designsand PatentsAct1988,withoutthepriorpermissionofthepublisher. Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmaynotbeavailablein electronicbooks. Designationsusedbycompaniestodistinguishtheirproductsareoftenclaimedastrademarks.Allbrandnamesandproduct namesusedinthisbookaretradenames,servicemarks,trademarksorregisteredtrademarksoftheirrespectiveowners.The publisherisnotassociatedwithanyproductorvendormentionedinthisbook.Thispublicationisdesignedtoprovideaccurate andauthoritativeinformationinregardtothesubjectmattercovered.Itissoldontheunderstandingthatthepublisherisnot engagedinrenderingprofessionalservices.Ifprofessionaladviceorotherexpertassistanceisrequired,theservicesofa competentprofessionalshouldbesought. Thepublisherandtheauthormakenorepresentationsorwarrantieswithrespecttotheaccuracyorcompletenessofthecontents ofthisworkandspecificallydisclaimallwarranties,includingwithoutlimitationanyimpliedwarrantiesoffitnessfora particularpurpose.Thisworkissoldwiththeunderstandingthatthepublisherisnotengagedinrenderingprofessionalservices. Theadviceandstrategiescontainedhereinmaynotbesuitableforeverysituation.Inviewofongoingresearch,equipment modifications,changesingovernmentalregulations,andtheconstantflowofinformationrelatingtotheuseofexperimental reagents,equipment,anddevices,thereaderisurgedtoreviewandevaluatetheinformationprovidedinthepackageinsertor instructionsforeachchemical,pieceofequipment,reagent,ordevicefor,amongotherthings,anychangesintheinstructionsor indicationofusageandforaddedwarningsandprecautions.ThefactthatanorganizationorWebsiteisreferredtointhisworkas acitationand/orapotentialsourceoffurtherinformationdoesnotmeanthattheauthororthepublisherendorsestheinformation theorganizationorWebsitemayprovideorrecommendationsitmaymake.Further,readersshouldbeawarethatInternet Websiteslistedinthisworkmayhavechangedordisappearedbetweenwhenthisworkwaswrittenandwhenitisread.No warrantymaybecreatedorextendedbyanypromotionalstatementsforthiswork.Neitherthepublishernortheauthorshallbe liableforanydamagesarisingherefrom. LibraryofCongressCataloging-in-PublicationData Stabilityanddegradationoforganicandpolymersolarcells/editor,FrederikC.Krebs. p.cm. Includesbibliographicalreferencesandindex. ISBN978-1-119-95251-0(cloth) 1.Polymers–Deterioration. 2.Photovoltaiccells. 3.Organiccompounds–Biodegradation. I.Krebs,FrederikC. QD381.9.D47S732012 621.3815(cid:2)42–dc23 2011051140 AcataloguerecordforthisbookisavailablefromtheBritishLibrary. PrintISBN:9781119952510 Setin10/12ptTimesbyAptaraInc.,NewDelhi,India. iv P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome Contents Preface xi Acknowledgements xiii ListofContributors xv 1. TheDifferentPVTechnologiesandHowTheyDegrade 1 FrederikC.Krebs 1.1 ThePhotovoltaicEffectandtheOverview 1 1.2 ThePhotovoltaicTechnologies 2 1.3 IntrinsicVersusExtrinsicStability 3 1.3.1 IntrinsicStability 3 1.3.2 ExtrinsicStability 3 1.4 Degradation–TheCulprits,theWhat,theWhyandtheHow 3 1.5 SomeRepresentativeTechnologiesandHowTheyDegrade 4 1.5.1 Mono-andPolycrystallineSiliconSolarCells 5 1.5.2 Amorphous,Micro-andNanocrystallineSiliconSolarCells 6 1.5.3 CIS/CIGSSolarCells 8 1.5.4 CdS/CdTeSolarCells 9 1.5.5 Dye-SensitizedSolarCells(DSSC) 10 1.5.6 OrganicandPolymerSolarCells(OPV) 11 References 12 2. ChemicalandPhysicalProbesforStudyingDegradation 17 BirgittaAndreasenandKionNorrman 2.1 Introduction 17 2.2 PhysicalProbes 18 2.2.1 UV-visSpectroscopy 18 2.2.2 AtomicForceMicroscopy(AFM) 18 2.2.3 InterferenceMicroscopy 20 2.2.4 ScanningElectronMicroscopy(SEM) 21 2.2.5 FluorescenceMicroscopy 23 2.2.6 Light-BeamInduced-CurrentMicroscopy(LBIC) 24 2.2.7 ElectroluminescenceandPhotoluminescenceImaging Microscopy(ELIandPLI) 25 2.2.8 X-rayReflectometry 26 v P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome vi Contents 2.3 ChemicalProbes 27 2.3.1 InfraredSpectroscopy(IR) 27 2.3.2 Time-of-FlightSecondaryIonMassSpectrometry(TOF-SIMS) 28 2.3.3 X-rayPhotoelectronSpectroscopy(XPS) 32 2.4 SummaryandOutlook 35 References 36 3. ImagingTechniquesforStudyingOPVStabilityandDegradation 39 MarcoSeeland,RolandRo¨schandHaraldHoppe 3.1 IntroductiontoImagingTechniques 39 3.1.1 MicroscopyandOpticalScanning 39 3.1.2 LuminescenceImaging 40 3.1.3 Lock-InThermography 43 3.1.4 Light-BeamInducedCurrent 45 3.2 Reports 46 3.2.1 Background:DegradationofOLEDDevices 46 3.2.2 Light-BeamInducedCurrent 50 3.2.3 LuminescenceImaging 54 3.2.4 OpticalMicroscopy 57 3.2.5 DarkLock-InThermographyandLBIC 58 3.2.6 DarkLock-InThermographyandOpticalScanningforFailure Analysis 62 3.3 Discussion:ComparisonofImagingTechniques 63 3.4 Summary 66 Acknowledgement 66 References 66 4. PhotochemicalStabilityofMaterialsforOPV 71 MatthieuManceau,Agne`sRivatonandJean-LucGardette 4.1 Introduction 71 4.2 Methods 72 4.2.1 AgingCondition 72 4.2.2 DegradationMonitoring 74 4.3 State-of-the-Art 82 4.3.1 Degradationoftheπ-ConjugatedPolymer 82 4.3.2 AcceptorMaterialAgingandBlendDegradation 99 References 102 5. DegradationofSmall-Molecule-BasedOPV 109 MartinHermenau,MoritzRiedeandKarlLeo 5.1 ComparisontoSmall-MoleculeOLEDs 110 5.1.1 NumberofPhotoexcitationsperMolecule 113 5.2 ComparisontoPolymerSolarCells 115 5.2.1 SensitivitytoAir 115 5.2.2 TemperatureStability 115 P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome Contents vii 5.3 Small-MoleculeOrganicMaterials 116 5.3.1 ActiveMaterials 116 5.3.2 Transport-andExciton-BlockingMaterials 119 5.4 DegradationConditions 125 5.4.1 OxygenandWater 125 5.4.2 UVRadiation 132 5.5 State-of-the-ArtinLifetimeStudies 134 5.6 SummaryandOutlook 138 References 139 6. DegradationofPolymer-BasedOPV 143 MikkelJørgensenandFrederikC.Krebs 6.1 FocusontheDegradationandStabilityofPolymer SolarCells 143 6.2 AChartofDegradationandStabilityofPolymer SolarCells 143 6.3 AShortAccountoftheOPVStability/Degradation History 144 6.3.1 TheDivisionsofDegradationMechanisms 146 6.3.2 TheMethodologies 148 6.4 ModusOperandiforEvolvingOPV 148 6.5 TheRecentDevelopments 149 6.5.1 ThePhotocatalyticOxides 149 6.5.2 Interlayers 150 6.5.3 TheInvertedStructure 151 6.5.4 R2RProcessing 152 6.5.5 LaminationandEncapsulation 153 6.5.6 WaterProcessing 154 6.5.7 MechanicalDegradation–Delamination 155 6.6 InterlaboratoryStudiesandRoundRobins 156 6.7 OutsideStudies 157 6.8 HowFarCanOPVBeTakeninTermsofStability? 158 References 158 7. TestEquipmentforOPVStability 163 OlivierHaillant 7.1 Introduction 163 7.2 ReliabilityandDurabilityTestingofPVProducts 165 7.2.1 Reliability,aFunctionofDurability 165 7.2.2 EnvironmentalDurability 166 7.2.3 DurabilityandWeatheringTesting 167 7.3 LaboratoryWeatheringTesting 168 7.3.1 Acceleration 168 7.3.2 Relevance 169 7.3.3 Precision 170 7.3.4 IntroductiontoDeterminationofAccelerationFactors 170 P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome viii Contents 7.4 DurabilityTestingTechniques 172 7.4.1 OutdoorWeathering 172 7.4.2 LaboratoryWeathering 175 7.4.3 LaboratoryPhotoaging 180 7.4.4 Others 183 7.5 Conclusion 185 References 186 8. CharacterizationandReportingofOPVDeviceLifetime 193 SurenA.Gevorgyan 8.1 Introduction 193 8.2 PhotoelectricCharacterizationofOPVDevices 194 8.2.1 PhotoelectricCharacterizationTools 194 8.2.2 CharacterizationinControlledEnvironments 197 8.3 InterlaboratoryStudiesofOPVs 202 8.3.1 Introduction 202 8.3.2 InterlaboratoryStudiesofFlexibleLarge-AreaRoll-to-Roll ProcessedPolymerSolarCellModules 203 8.3.3 InterlaboratoryStabilityStudiesofOPVs 204 8.4 LifetimeTestingandReporting:StandardizedApproach 213 8.4.1 Introduction 213 8.4.2 ProceduresforStandardLifetimeMeasurements 214 8.4.3 ReportingLifetime 235 8.5 Conclusions 238 ListofAbbreviations 238 References 238 9. ConcentratedLightforOrganicPhotovoltaics 243 ThomasTromholt 9.1 Introduction 243 9.2 Light-ConcentrationSetups 245 9.2.1 RefractiveSunlightConcentration 245 9.2.2 ReflectiveSunlightConcentration 246 9.2.3 ConcentratedSolarSimulation 249 9.3 ExperimentalWorkPerformedwithConcentratedLight 251 9.3.1 IPVResponsetoConcentratedSunlight 251 9.3.2 PolymerResponsetoConcentratedLight 253 9.3.3 OrganicSolarCellResponsetoConcentratedLight 257 9.4 PhysicalCharacterizationbyConcentratedSunlight 261 9.5 Conclusion 265 References 265 10. BarrierTechnologyandApplications 269 LarsMu¨ller-Meskamp,JohnFahlteichandFrederikC.Krebs 10.1 EncapsulationRequirements 269 10.1.1 TypesofEncapsulation 270 P1:TIX/XYZ P2:ABC JWST161-fm JWST161-Krebs February1,2012 20:45 Printer:Yettocome Contents ix 10.1.2 Glass/GlassEncapsulation 271 10.1.3 LaminationofBarrierFilms 272 10.1.4 Thin-FilmEncapsulation 273 10.1.5 PerimeterSealing 273 10.2 Thin-FilmPermeationPhysics 274 10.2.1 Solid-StateDiffusionandDiffusioninPolymers 274 10.2.2 Fick’sFirstLawofDiffusion 275 10.2.3 Sorption 276 10.2.4 PermeationinThinFilms 277 10.2.5 ModelsforthePermeationBarrierCoatedPolymerFilms 278 10.2.6 TemperatureDependenceofPermeation 279 10.2.7 DependenceofWaterPermeationonLayerThickness 280 10.2.8 TimeDependenceofPermeation 282 10.2.9 PermeationinMultilayerBarriers 284 10.2.10 PinholesinMultilayerSystems 287 10.3 MeasurementofBarrierProperties 288 10.3.1 GravimetricCup 289 10.3.2 Carrier-Gas-BasedCoulometricBarrierMeasurement 289 10.3.3 MassSpectrometer 290 10.3.4 DirectPressureMeasurement 291 10.3.5 RadioactiveIsotopes 292 10.3.6 CalciumTest(OpticalorElectrical) 293 10.3.7 DeviceTesting 294 10.3.8 StandardsandTypicalMeasurementConditions 295 10.3.9 TestMethodOverview 295 10.4 BarrierTechnologies 295 10.4.1 Single-LayerTechnologies 297 10.4.2 MultilayerTechnologies 309 10.5 BarrierApplicationinOPV 315 10.5.1 Products 316 10.5.2 BarrierCostandManufacturability 318 10.6 Conclusion 321 References 322 11. SummaryandOutlook 331 FrederikC.Krebs Index 333 P1:TIX/XYZ P2:ABC JWST161-Preface JWST161-Krebs February2,2012 21:24 Printer:Yettocome Preface Photovoltaic cells or solar cells made out of organic materials have become the subject ofintensestudybymanyresearchgroupsandasignificantindustrialactivityisemerging withinseveralareasspanningfromsuppliersofmaterials,substratesandbarriers,through inkdevelopmenttofullmanufactureandintegrationoforganicphotovoltaics(OPV).The traditionalphotovoltaicindustryiswellestablishedandthephotovoltaicasausefulenergy- producing unit has been around for nearly 60 years. The interest in OPV technology is thatitpotentiallyprovidesanefficientsolutiontomanyofthestrugglesthatthetraditional PV technologies have been fighting for decades. OPV also has its share of problems but theyaredifferentandtheinterestemergesinthebeliefthatthesenewproblemsforanew and different technology might be easier to tackle than the ones we have failed to tackle efficiently for the traditional PV technologies. Traditional PV in the form of crystalline PV was born as an environmentally and inherently stable technology and many of the laterdevelopmentsneverknewdifferent.However,theyallsufferfromthesameproblem of a massive energy input being required in their manufacture, and sometimes also from scarcityoftheelementsemployedorsignificanttoxicityofthecomponentsthatconstitute themorintheprocessesleadingtothem.OPVinitsintendedformdoesnotshareeither oftheseproblemsandpotentiallyallowsforveryshortenergypaybacktimesastheyare very thin, common elements can be employed and very little energy is required for their manufacture.Theyalsohaveaweaknessandthatistheirinstabilityduringoperationand sensitivity to some of the atmospheric components that are evidently present on earth. The early OPVs were not very stable and had a duration of operation in air measured in seconds or some minutes at most. Today, many thousands of hours is common place, however,itisstilllaggingbehindthestabilitypresentedbyforinstancecrystallinesilicon. This book is dedicated to a description of what this instability is, where it has its roots, how it is measured and characterized, the physical means available to investigate it and also how it can be countermeasured through removal or elimination of the source of the problemorthroughdesignofthematerialsanddevice.Thisbookisdedicatedtothetopic ofdegradationofOPVandshouldserveasasourceofreferenceforthestudent,theexpert, theexperimentalist,theinterestedandthegeneralist.Iwishyouapleasantreadandhope thatyouwillfindmostofthequestionsonthetopicansweredorfindapathtowardsfurther development. FrederikC.Krebs xi P1:TIX/XYZ P2:ABC JWST161-back JWST161-Krebs January20,2012 11:3 Printer:Yettocome Acknowledgements Duringthewritingofthisbooktheauthorshavebeensupportedbyseveralfunding organisationsandwouldliketoexpressthanksto: – TheDanishStrategicResearchCouncil(2104-07-0022)andEUDP(j.no.64009-0050). – TheDresdnerInnovationszentrumEnergieeffizienz,fundedbytheEuropeanUnion,the StateSaxonyandtheFraunhoferGesellschaftforfundingencapsulationresearchatIAPP andIPMS. – TheThuringianMinistryofCultureintheframeworkofFIPVII. – TheEuropeanCommission,theGermanMinistryforEducationandResearch(BMBF), Deutsche Forschungsgemeinschaft (DFG), Free State of Saxony, and further funding agencies.K.LeothankstheDFGforthesupportviatheLeibnizPrize. – Public-fundedresearchprojectssupportedbytheGermanFederalMinistryforEducation andResearchunderreferencenumber13N8858and01RI0628andbytheSaxonyState MinistryforEconomicAffairs,LaborandTransportunderreferencenumber3957/623 Several people have supported the authors and we would like to express sincere gratitudeto: – Toni Mu¨ller and Bert Ma¨nnig from Heliatek GmbH for supporting this work with data andknowledge.Furthermore,wewanttothanktheFraunhoferIPMSandthecompanies CreaphysGmbH,HeliatekGmbH,NovaledAG,andSim4TecGmbHforcontinuedgood collaboration.Thisworkwouldnothavebeenpossiblewithoutthehelpofthetechnical and scientific staff of the organic solar cell group at the IAPP, especially Sven Kunze, CarstenWolf,TobiasGu¨nther,InesRabelodeMoraesandSebastianScholz. – SylvioSchubert,HannesKlumbiesandClaudiaKeiblerfortheircontributionstoencap- sulationatIAPPandIPMS,KarlLeo,OlafHildandChristianMayfortheirsupport. – Colleagues from Fraunhofer FEP, especially, Nicolas Schiller, Steffen Straach, Steffen Gu¨nther,MatthiasFahland,OlafZywitzkiandThomasModesfortheirworkonsingle and multilayer barriers as well as for providing some of the figures being used for this bookchapter,AllessandroPatellifromCIVEN,Italy,forallowingreproductionofSEM imagesofthemultilayerbarrierpresentedbyCIVEN. – MarkusHo¨selisthankedfortakingphotographsforthecoverarttothisbook. xiii

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