Device Architecture and Materials for Organic Light-Emitting Devices Sarah Schols Device Architecture and Materials for Organic Light- Emitting Devices Targeting High Current Densities and Control of the Triplet Concentration SarahSchols LargeAreaElectronics(LAE) Imec Kapeldreef75 3000Leuven,VlaamsBrabant Belgium [email protected] ISBN978-94-007-1607-0 e-ISBN978-94-007-1608-7 DOI10.1007/978-94-007-1608-7 SpringerDordrechtHeidelbergLondonNewYork LibraryofCongressControlNumber:2011928673 ©SpringerScience+BusinessMediaB.V.2011 Nopartofthisworkmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorby anymeans,electronic,mechanical,photocopying,microfilming,recordingorotherwise,withoutwritten permissionfromthePublisher,withtheexceptionofanymaterialsuppliedspecificallyforthepurpose ofbeingenteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework. Coverdesign:VTeXUAB,Lithuania Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface This book is a reprint of the manuscript entitled “Device architecture and mate- rials for organic light-emitting devices”, that was submitted to the jury deciding on the achievement of my PhD at the Katholieke Universiteit Leuven in Belgium. It is the result of five years fascinating research at imec in Leuven, Belgium, be- tween2004and2009.DifferentpeoplecontributedtomyworkandIwanttoshow gratitude to all of them. First, I would like to thank my two promoters, Prof. Paul Heremans(KUL/imec)andProf.RobertMertens(KUL/imec)whogavemetheop- portunitytostartaPhDinaninspiringenvironmentasimec.Iamalsoverygrateful totheotherPhDjurymemberswhotookthetimetocarefullyreadmymanuscript: Prof.MarkvanderAuweraer(KUL),Prof.JanEngelen(KUL),Prof.HenningSir- ringhaus(UniversityofCambridge),Prof.UliLemmer(UniversitätKarlsruhe)and Prof. Adhemar Bultheel (KUL). My special thanks go to Andrey Kadashchuk for introducingmeintotheexcitingworldofspectroscopyandforthemanyscientific discussions, but of course also all other colleagues of the Polymer and Molecular ElectronicsgroupatimecwithwhomIworkedtogetherduringmyPhDaregrate- fully acknowledged. Besides, I would like to thank Thilo Stöferle (IBM Research Zurich),TobiasPlötzing(RWTHAachen)andThorstenWahlbrink(AMOGmbH) forthenicecollaboration.TheFWOisacknowledgedforthefinancialsupport.Fi- nally, I warmly thank my family for their continuous support and interest in my work. SarahSchols v Contents 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.1 OrganicSemiconductors . . . . . . . . . . . . . . . . . . . . . . . 1 1.1.1 SemiconductingPropertiesofOrganicMaterials . . . . . . 2 1.1.2 ChargeTransportinOrganicMaterials . . . . . . . . . . . 4 1.1.3 OpticalTransitionsinOrganicMaterials . . . . . . . . . . 6 1.2 StateoftheArtOrganicLight-EmittingDevices . . . . . . . . . . 9 1.2.1 OrganicLight-EmittingDiodes . . . . . . . . . . . . . . . 9 1.2.2 OrganicLight-EmittingTransistors . . . . . . . . . . . . . 11 1.3 OrganicSemiconductorLasers . . . . . . . . . . . . . . . . . . . 13 1.3.1 GeneralAspectsofLaserAction . . . . . . . . . . . . . . 13 1.3.2 MotivationforPlasticLasers . . . . . . . . . . . . . . . . 15 1.3.3 LasinginOrganicSemiconductors . . . . . . . . . . . . . 17 1.3.4 ProspectsforElectricallyPumpedOrganicLasers . . . . . 27 1.4 Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 2 MaterialsandExperimentalTechniques . . . . . . . . . . . . . . . . 33 2.1 SampleFabrication . . . . . . . . . . . . . . . . . . . . . . . . . 33 2.1.1 MaterialsUsedinthisWork . . . . . . . . . . . . . . . . . 33 2.1.2 DepositionTechniques. . . . . . . . . . . . . . . . . . . . 34 2.1.3 FabricationofPhotonicFeedbackStructures . . . . . . . . 37 2.2 DeviceCharacterization . . . . . . . . . . . . . . . . . . . . . . . 41 2.2.1 TransistorMeasurementandParameterExtraction . . . . . 41 2.2.2 CharacterizationofOLEDs . . . . . . . . . . . . . . . . . 42 2.2.3 Time-ResolvedPhotoluminescenceMeasurements . . . . . 43 2.2.4 Time-ResolvedPump-ProbeExperiments. . . . . . . . . . 45 2.2.5 AmplifiedSpontaneousEmissionandLossMeasurements . 46 2.2.6 DeterminationofThermallyStimulatedLuminescence . . . 47 3 OrganicLight-EmittingDiodeswithField-EffectElectronTransport 49 3.1 DeviceFabrication . . . . . . . . . . . . . . . . . . . . . . . . . . 50 3.2 DeviceOperation . . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.3 DevicePerformance . . . . . . . . . . . . . . . . . . . . . . . . . 56 vii viii Contents 3.3.1 OpticalandElectricalCharacterization . . . . . . . . . . . 56 3.3.2 Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 3.4 ImprovementoftheExternalQuantumEfficiency . . . . . . . . . 60 3.5 SummaryandConclusions . . . . . . . . . . . . . . . . . . . . . 62 4 DevicesBasedonDiperfluorohexyl-quaterthiopheneDerivatives . . 65 4.1 CharacterizationoftheElectron-TransportingMaterialsDFH-4T andDFHCO-4T . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 4.2 DevicesBasedonDFH-4T . . . . . . . . . . . . . . . . . . . . . 69 4.2.1 TransistorsBasedonDFH-4T . . . . . . . . . . . . . . . . 69 4.2.2 DFH-4TinOLEDswithField-EffectElectronTransport . . 70 4.3 DevicesBasedonDFHCO-4T. . . . . . . . . . . . . . . . . . . . 72 4.3.1 HighPerformanceDFHCO-4TTransistors . . . . . . . . . 72 4.3.2 DFHCO-4TinOLEDswithField-EffectElectronTransport 76 4.4 Comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 4.5 SummaryandConclusions . . . . . . . . . . . . . . . . . . . . . 78 5 ControloftheTripletConcentrationinOrganicLight-Emitting Devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 5.1 PulsedExcitationofOLEDswithField-EffectElectronTransport . 82 5.1.1 Pulse-WidthDependenceofOrganicLight-Emitting Devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 5.1.2 EffectsInfluencingthePulsedExcitationBehaviorof OLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 5.2 TripletExcitationScavenginginFilmsofConjugatedPolymers . . 86 5.2.1 TripletScavenginginLiquid-StateOrganicDyeLasers . . 86 5.2.2 TripletScavenginginSolid-StateOrganicThinFilms . . . 88 5.3 SummaryandConclusions . . . . . . . . . . . . . . . . . . . . . 94 6 Triplet-EmitterDopedOrganicMaterials . . . . . . . . . . . . . . . 97 6.1 TripletDynamicsandChargeCarrierTrappinginTriplet-Emitter DopedConjugatedPolymers . . . . . . . . . . . . . . . . . . . . 97 6.1.1 SpectroscopicCharacterization . . . . . . . . . . . . . . . 99 6.1.2 ThermallyStimulatedLuminescenceinCNPPPDoped withBtp Ir(acac) . . . . . . . . . . . . . . . . . . . . . . 110 2 6.2 OpticalPumpingofTriplet-Emitters . . . . . . . . . . . . . . . . 111 6.2.1 AttemptstoObserveASEUsingBtp Ir(acac) . . . . . . . 112 2 6.2.2 AttemptstoObserveASEUsingF5PhandGDP16b . . . . 113 6.3 SummaryandConclusions . . . . . . . . . . . . . . . . . . . . . 114 7 ValueofOLEDswithField-EffectElectronTransportforLasing Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 7.1 PotentialofOLEDswithField-EffectElectronTransportasLaser DeviceConfiguration . . . . . . . . . . . . . . . . . . . . . . . . 117 7.1.1 HighCurrentDensities . . . . . . . . . . . . . . . . . . . 118 7.1.2 ReducedAbsorptionLosses . . . . . . . . . . . . . . . . . 119 Contents ix 7.2 OpticallyPumpedLasingExperiments . . . . . . . . . . . . . . . 123 7.2.1 StimulatedEmissioninAlq :DCM . . . . . . . . . . . . 124 3 2 7.2.2 StimulatedEmissioninStacksComprisingAlq :DCM . . 126 3 2 7.2.3 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 131 7.3 DevicewithIntegratedField-EffectandPhotonicFeatures . . . . . 131 7.4 SummaryandConclusions . . . . . . . . . . . . . . . . . . . . . 133 8 GeneralConclusionsandFutureOutlook . . . . . . . . . . . . . . . 135 8.1 OverviewoftheMainResults . . . . . . . . . . . . . . . . . . . . 135 8.2 SuggestionsforFurtherResearch . . . . . . . . . . . . . . . . . . 137 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139