<p>   </p> <p>Colloidal cesium lead bromide (CsPbBr₃) quantum dots (QDs) have emerged as an exciting class of quantum emitters due to their near-unity quantum yields, large oscillator strengths, and long coherence time. Ordered superlattices (SLs) grown from these QDs exhibit emergent properties resulting from their assembly. In this work, we explore the self-assembly, disorder, and superradiant properties of 3D superlattices of CsPbBr₃ to understand how structural heterogeneity influences optical properties.</p> <p>A thorough understanding of the competition between coherence and dephasing from phonon scattering and energetic disorder is currently lacking in the literature. Here, we present an investigation of exciton coherence in perovskite QD solids using temperature-dependent photoluminescence linewidth and lifetime measurements. The properties of perovskite QDS described above should also enable them to overcome hurdles experienced by other materials that limit solid-state superradiance, such as fast dephasing processes from inherent disorder and thermal fluctuations. Our results demonstrate that excitons can coherently delocalize in highly ordered CsPbBr₃ superlattices leading to superradiant emission. We observe loss of coherence and exciton localization to a single QD at higher temperatures, resulting from scattering by optical phonons. At low temperatures, static disorder and defects limit exciton coherence, and a wide range of coherence numbers are observed across a self-assembled sample of SLs. These results highlight the promise and challenge in achieving long-range coherence in perovskite QD solids.</p> <p>A thorough understanding of structural heterogeneity in CsPbBr₃ quantum dot superlattices is necessary for the realization of robust exciton coherence in these systems. 3D SLs self-assemble from a colloidal solution of cubic QDs as the solvent evaporates, leading to SLs ranging widely in macroscopic size, shape, and aspect ratio. Scanning transmission electron microscopy (STEM) coupled to fast-Fourier transform (FFT) analysis is utilized to characterize the structural properties of individual SLs, such as the average constituent quantum dot size, size dispersity, and number of crystalline domains. Analysis reveals that SLs are structurally heterogeneous but tend to have a narrower size distribution than the precursor solution due to size selection that occurs during evaporative self-assembly. We directly correlate STEM-FFT structural properties to low-temperature photoluminescence spectra for individual SLs, demonstrating that substructure in the photoluminescence peak arises from multiple, locally-ordered domains within the SL. In addition, we show that long-range structural disorder in a SL does not necessarily impact short-range phenomena such as exciton delocalization.</p> <p>  </p>

Anyone who decides to buy a new mobile phone today is likely to buy a screen made from organic light-emitting diodes (OLEDs). OLEDs are a relatively new display technology and will probably account for the largest market share in the upcoming years. This is due to their brilliant colors, high achievable display resolution, and comparably simple processing. Since they are not based on the rigid crystal structure of classical semiconductors and can be produced as planar thin-film modules, they also enable the fabrication of large-area lamps on flexible substrates – an attractive scenario for future lighting systems. Despite these promising properties, the breakthrough of OLED lighting technology is still pending and requires further research. The charge-carrier dynamics in an OLED determine its device functionality and, therefore, enable the understanding of fundamental physical concepts and phenomena. From the description of charge-carrier dynamics, this work derives experimental methods and device concepts to optimize the efficiency and stability of OLEDs. OLEDs feature an electric current of charge carriers (electrons and holes) that are intended to recombine under the emission of light. This process is preceded by charge-carrier injection and their transport to the emission layer. These three aspects are discussed together in this work. First, a method is presented that quantifies injection resistances using a simple experiment. It provides a valuable opportunity to better understand and optimize injection layers. Subsequently, the charge carrier transport at high electrical currents, as required for OLEDs as bright lighting elements, will be investigated. Here, electro-thermal effects are presented that form physical limits for the design and function of OLED modules and explain their sudden failure. Finally, the dynamics and recombination of electro-statically bound charge carrier pairs, so-called excitons, are examined. Various options are presented for manipulating exciton dynamics in such a way that the emission behavior of the OLED can be adjusted according to specific requirements.:List of publications . . . . . . . . . . . . . . . . . v List of abbreviations . . . . . . . . . . . . . . . . . ix 1 Introduction . . . . . . . . . . . . . . . . . 1 2 Fundamentals . . . . . . . . . . . . . . . . . 5 2.1 Light sources and the human society . . . . . . . . . . . . . . . . . 5 2.1.1 Human light perception . . . . . . . . . . . . . . . . . . . . 8 2.1.2 Physical light quantification . . . . . . . . . . . . . . . . . . 10 2.1.3 Non-visual light impact . . . . . . . . . . . . . . . . . . . . . 13 2.1.4 Implications for modern light sources . . . . . . . . . . . . . 15 2.2 Organic semiconductors . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.1 Molecular energy states . . . . . . . . . . . . . . . . . . . . . 18 2.2.2 Intramolecular state transitions . . . . . . . . . . . . . . . . 24 2.2.3 Molecular films . . . . . . . . . . . . . . . . . . . . . . . . . 31 2.2.4 Electrical doping . . . . . . . . . . . . . . . . . . . . . . . . 34 2.2.5 Charge-carrier transport . . . . . . . . . . . . . . . . . . . . 36 2.2.6 Exciton formation and recombination . . . . . . . . . . . . . 38 2.2.7 Exciton transfer . . . . . . . . . . . . . . . . . . . . . . . . . 41 2.3 Organic light-emitting diodes . . . . . . . . . . . . . . . . . . . . . 44 2.3.1 Structure and operation principle . . . . . . . . . . . . . . . 44 2.3.2 Metal-semiconductor interfaces . . . . . . . . . . . . . . . . 47 2.3.3 Typical operation characteristics . . . . . . . . . . . . . . . . 49 2.4 Colloidal nanocrystal emitters . . . . . . . . . . . . . . . . . . . . . 52 2.4.1 Terminology: Nanocrystals and quantum dots . . . . . . . . 52 2.4.2 The particle-in-a-box model . . . . . . . . . . . . . . . . . . 54 2.4.3 Surface passivation . . . . . . . . . . . . . . . . . . . . . . . 55 3 Materials and methods . . . . . . . . . . . . . . . . . 57 3.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 3.1.1 OLED materials . . . . . . . . . . . . . . . . . . . . . . . . . 57 3.1.2 Materials for photoluminescence . . . . . . . . . . . . . . . . 60 3.2 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.2.1 Thermal evaporation . . . . . . . . . . . . . . . . . . . . . . 62 3.2.2 Solution processing . . . . . . . . . . . . . . . . . . . . . . . 64 3.3 Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 3.3.1 Absorbance spectroscopy . . . . . . . . . . . . . . . . . . . . 66 3.3.2 Photoluminescence quantum yield . . . . . . . . . . . . . . . 66 3.3.3 Excitation sources . . . . . . . . . . . . . . . . . . . . . . . 67 3.3.4 Sensitive EQE for absorber materials . . . . . . . . . . . . . 68 3.4 Exciton-lifetime analysis . . . . . . . . . . . . . . . . . . . . . . . . 69 3.4.1 Triplet lifetime . . . . . . . . . . . . . . . . . . . . . . . . . 69 3.4.2 Singlet-state lifetime . . . . . . . . . . . . . . . . . . . . . . 70 3.4.3 Lifetime extraction . . . . . . . . . . . . . . . . . . . . . . . 70 3.5 OLED characterization . . . . . . . . . . . . . . . . . . . . . . . . . 73 3.5.1 Current-voltage-luminance and quantum efficiency . . . . . . 73 3.5.2 Temperature-controlled evaluation . . . . . . . . . . . . . . . 74 4 Charge-carrier injection into doped organic films . . . . . . . . . . . . . . . . . 77 4.1 Ohmic injection contacts . . . . . . . . . . . . . . . . . . . . . . . . 79 4.2 Device architecture . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 4.2.1 Conception . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 4.2.2 Device symmetry . . . . . . . . . . . . . . . . . . . . . . . . 80 4.2.3 Device homogeneity . . . . . . . . . . . . . . . . . . . . . . . 83 4.3 Resistance characteristics . . . . . . . . . . . . . . . . . . . . . . . . 84 4.3.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . 84 4.3.2 Equivalent-circuit development . . . . . . . . . . . . . . . . 85 4.4 Impedance spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 92 4.4.1 Measurement fundamentals . . . . . . . . . . . . . . . . . . 92 4.4.2 Thickness dependence . . . . . . . . . . . . . . . . . . . . . 93 4.4.3 Temperature dependence . . . . . . . . . . . . . . . . . . . . 95 4.5 Depletion zone variation . . . . . . . . . . . . . . . . . . . . . . . . 97 4.6 Molybdenum oxide as a case study . . . . . . . . . . . . . . . . . . 99 5 Charge-carrier transport and self-heating in OLED lighting . . . . . . . . . . . . . . . . .101 5.1 Joule self-heating in OLEDs . . . . . . . . . . . . . . . . . . . . . . 104 5.1.1 Electrothermal feedback . . . . . . . . . . . . . . . . . . . . 104 5.1.2 Thermistors . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 5.1.3 Cooling strategies . . . . . . . . . . . . . . . . . . . . . . . . 106 5.2 Self-heating causes lateral luminance inhomogeneities in OLEDs . . 108 5.2.1 The influence of transparent electrodes . . . . . . . . . . . . 108 5.2.2 Luminance inhomogeneities in large OLED panels . . . . . . 110 5.3 Electrothermal OLED models . . . . . . . . . . . . . . . . . . . . . 112 5.3.1 Perceiving an OLED as thermistor array . . . . . . . . . . . 112 5.3.2 The OLED as a single three-layer thermistor . . . . . . . . . 114 5.3.3 A numerical 3D model of heat and current flow . . . . . . . 116 5.4 OLED stack and experimental conception . . . . . . . . . . . . . . 118 5.5 The Switch-back effect in planar light sources . . . . . . . . . . . . 120 5.5.1 Predictions from numerical 3D modeling . . . . . . . . . . . 121 5.5.2 Experimental proof . . . . . . . . . . . . . . . . . . . . . . . 124 5.5.3 Variation of vertical heat flux . . . . . . . . . . . . . . . . . 127 5.5.4 Variation of the OLED area . . . . . . . . . . . . . . . . . . 131 5.6 Electrothermal tristabilities in OLEDs . . . . . . . . . . . . . . . . 133 5.6.1 Observing different burn-in schematics . . . . . . . . . . . . 133 5.6.2 Bistability and tristability in organic semiconductors . . . . 134 5.6.3 Experimental indications for attempted branch hopping . . . 138 5.6.4 Saving bright OLEDs from burning in . . . . . . . . . . . . 144 5.6.5 Taking another view onto the camera pictures . . . . . . . . 145 6 Charge-carrier recombination and exciton management . . . . . . . . . . . . . . . . .147 6.1 Optical down conversion . . . . . . . . . . . . . . . . . . . . . . . . 149 6.1.1 Spectral reshaping of visible OLEDs . . . . . . . . . . . . . 149 6.1.2 Infrared-emitting OLEDs . . . . . . . . . . . . . . . . . . . . 155 6.2 Dual-state Förster transfer . . . . . . . . . . . . . . . . . . . . . . . 158 6.2.1 Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 6.2.2 Verification . . . . . . . . . . . . . . . . . . . . . . . . . . . 159 6.3 Singlet fission and triplet fusion in rubrene . . . . . . . . . . . . . . 161 6.3.1 Photoluminescence of pure and doped rubrene films . . . . . 163 6.3.2 Electroluminescence transients of rubrene OLEDs . . . . . . 172 6.4 Charge transfer-state tuning by electric fields . . . . . . . . . . . . . 177 6.4.1 CT-state tuning via doping variation . . . . . . . . . . . . . 177 6.4.2 CT-state tuning via voltage . . . . . . . . . . . . . . . . . . 180 6.5 Excursus: Exciton-spin mixing for wavelength identification . . . . 183 6.5.1 Characteristics of the active film . . . . . . . . . . . . . . . . 184 6.5.2 Conception . . . . . . . . . . . . . . . . . . . . . . . . . . . 186 6.5.3 Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187 6.5.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188 6.5.5 Application demonstrations . . . . . . . . . . . . . . . . . . 192 6.5.6 All-organic device . . . . . . . . . . . . . . . . . . . . . . . . 195 6.5.7 Device limitations and prospects . . . . . . . . . . . . . . . . 198 7 Conclusion and outlook . . . . . . . . . . . . . . . . . 207 7.1 Charge-carrier injection into doped films . . . . . . . . . . . . . . . 207 7.2 Charge-carrier transport in hot OLEDs . . . . . . . . . . . . . . . . 208 7.2.1 Prospects for OLED lighting facing tristable behavior . . . . 209 7.2.2 Outlook: Accessing the hidden PDR 2 region . . . . . . . . . 210 7.3 Charge-carrier recombination and spin mixing . . . . . . . . . . . . 211 7.3.1 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 7.3.2 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 Bibliography. . . . . . . . . . . . . . . . . 215 Acknowledgements . . . . . . . . . . . . . . . . . 249 / Wer sich heute für ein neues Mobiltelefon entscheidet, kauft damit wahrscheinlich einen Bildschirm aus organischen Leuchtdioden (OLEDs). Durch ihre brillanten Farben, die hohe erreichbare Auflösung und eine vergleichsweise einfache Prozessierung werden OLEDs als relativ neue Bildschirmtechnologie in den nächsten Jahren wohl den größten Marktanteil ausmachen. Da sie nicht auf der starren Kristallstruktur klassischer Halbleiter beruhen und als planare Dünnschichtmodule produziert werden können, ermöglichen sie außerdem die Fertigung großer Flächenstrahler auf flexiblen Substraten – ein sehr attraktives Szenario für zukünftige Beleuchtungssysteme. Trotz dieser vielversprechenden Eigenschaften steht der Durchbruch der OLED-Technologie als Leuchtmittel noch aus und erfordert weitere Forschung. Die Dynamik der Ladungsträger (Elektronen und Löcher) in einer OLED charakterisiert wichtige Teile der Bauteilfunktion und ermöglicht daher das Verständnis grundlegender physikalischer Konzepte und Phänomene. Diese Arbeit leitet anhand dieser Beschreibung experimentelle Methoden und Bauteilkonzepte ab, um die Effizienz und Stabilität von OLEDs zu optimieren. OLEDs zeichnen sich dadurch aus, dass ein elektrischer Strom aus Ladungsträgern (Elektronen und Löchern) möglichst effizient unter Aussendung von Licht rekombiniert. Diesem Prozess geht eine Ladungsträgerinjektion und deren Transport zur Emissionsschicht voraus. Diese drei Aspekte werden in dieser Arbeit zusammenhängend diskutiert. Als erstes wird eine Methode vorgestellt, die Injektionswiderstände anhand eines einfachen Experimentes quantifiziert. Sie bildet eine wertvolle Möglichkeit, Injektionsschichten besser zu verstehen und zu optimieren. Anschließend wird der Ladungsträgertransport bei hohen elektrischen Strömen untersucht, wie sie für OLEDs als helle Beleuchtungselemente nötig sind. Hier werden elektro-thermische Effekte vorgestellt, die physikalische Grenzen für das Design und die Funktion von OLED Modulen bilden und deren plötzliches Versagen erklären. Abschließend wird die Dynamik der stark elektrostatisch gebundenen Ladungsträgerpaare, sogenannter Exzitonen, kurz vor deren Rekombination untersucht. Es werden verschiedene Möglichkeiten vorgestellt sie so zu manipulieren, dass sich das Abstrahlverhalten der OLED anhand bestimmter Anforderungen einstellen lässt.:List of publications . . . . . . . . . . . . . . . . . v List of abbreviations . . . . . . . . . . . . . . . . . ix 1 Introduction . . . . . . . . . . . . . . . . . 1 2 Fundamentals . . . . . . . . . . . . . . . . . 5 2.1 Light sources and the human society . . . . . . . . . . . . . . . . . 5 2.1.1 Human light perception . . . . . . . . . . . . . . . . . . . . 8 2.1.2 Physical light quantification . . . . . . . . . . . . . . . . . . 10 2.1.3 Non-visual light impact . . . . . . . . . . . . . . . . . . . . . 13 2.1.4 Implications for modern light sources . . . . . . . . . . . . . 15 2.2 Organic semiconductors . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.1 Molecular energy states . . . . . . . . . . . . . . . . . . . . . 18 2.2.2 Intramolecular state transitions . . . . . . . . . . . . . . . . 24 2.2.3 Molecular films . . . . . . . . . . . . . . . . . . . . . . . . . 31 2.2.4 Electrical doping . . . . . . . . . . . . . . . . . . . . . . . . 34 2.2.5 Charge-carrier transport . . . . . . . . . . . . . . . . . . . . 36 2.2.6 Exciton formation and recombination . . . . . . . . . . . . . 38 2.2.7 Exciton transfer . . . . . . . . . . . . . . . . . . . . . . . . . 41 2.3 Organic light-emitting diodes . . . . . . . . . . . . . . . . . . . . . 44 2.3.1 Structure and operation principle . . . . . . . . . . . . . . . 44 2.3.2 Metal-semiconductor interfaces . . . . . . . . . . . . . . . . 47 2.3.3 Typical operation characteristics . . . . . . . . . . . . . . . . 49 2.4 Colloidal nanocrystal emitters . . . . . . . . . . . . . . . . . . . . . 52 2.4.1 Terminology: Nanocrystals and quantum dots . . . . . . . . 52 2.4.2 The particle-in-a-box model . . . . . . . . . . . . . . . . . . 54 2.4.3 Surface passivation . . . . . . . . . . . . . . . . . . . . . . . 55 3 Materials and methods . . . . . . . . . . . . . . . . . 57 3.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 3.1.1 OLED materials . . . . . . . . . . . . . . . . . . . . . . . . . 57 3.1.2 Materials for photoluminescence . . . . . . . . . . . . . . . . 60 3.2 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.2.1 Thermal evaporation . . . . . . . . . . . . . . . . . . . . . . 62 3.2.2 Solution processing . . . . . . . . . . . . . . . . . . . . . . . 64 3.3 Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 3.3.1 Absorbance spectroscopy . . . . . . . . . . . . . . . . . . . . 66 3.3.2 Photoluminescence quantum yield . . . . . . . . . . . . . . . 66 3.3.3 Excitation sources . . . . . . . . . . . . . . . . . . . . . . . 67 3.3.4 Sensitive EQE for absorber materials . . . . . . . . . . . . . 68 3.4 Exciton-lifetime analysis . . . . . . . . . . . . . . . . . . . . . . . . 69 3.4.1 Triplet lifetime . . . . . . . . . . . . . . . . . . . . . . . . . 69 3.4.2 Singlet-state lifetime . . . . . . . . . . . . . . . . . . . . . . 70 3.4.3 Lifetime extraction . . . . . . . . . . . . . . . . . . . . . . . 70 3.5 OLED characterization . . . . . . . . . . . . . . . . . . . . . . . . . 73 3.5.1 Current-voltage-luminance and quantum efficiency . . . . . . 73 3.5.2 Temperature-controlled evaluation . . . . . . . . . . . . . . . 74 4 Charge-carrier injection into doped organic films . . . . . . . . . . . . . . . . . 77 4.1 Ohmic injection contacts . . . . . . . . . . . . . . . . . . . . . . . . 79 4.2 Device architecture . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 4.2.1 Conception . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 4.2.2 Device symmetry . . . . . . . . . . . . . . . . . . . . . . . . 80 4.2.3 Device homogeneity . . . . . . . . . . . . . . . . . . . . . . . 83 4.3 Resistance characteristics . . . . . . . . . . . . . . . . . . . . . . . . 84 4.3.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . 84 4.3.2 Equivalent-circuit development . . . . . . . . . . . . . . . . 85 4.4 Impedance spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 92 4.4.1 Measurement fundamentals . . . . . . . . . . . . . . . . . . 92 4.4.2 Thickness dependence . . . . . . . . . . . . . . . . . . . . . 93 4.4.3 Temperature dependence . . . . . . . . . . . . . . . . . . . . 95 4.5 Depletion zone variation . . . . . . . . . . . . . . . . . . . . . . . . 97 4.6 Molybdenum oxide as a case study . . . . . . . . . . . . . . . . . . 99 5 Charge-carrier transport and self-heating in OLED lighting . . . . . . . . . . . . . . . . .101 5.1 Joule self-heating in OLEDs . . . . . . . . . . . . . . . . . . . . . . 104 5.1.1 Electrothermal feedback . . . . . . . . . . . . . . . . . . . . 104 5.1.2 Thermistors . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 5.1.3 Cooling strategies . . . . . . . . . . . . . . . . . . . . . . . . 106 5.2 Self-heating causes lateral luminance inhomogeneities in OLEDs . . 108 5.2.1 The influence of transparent electrodes . . . . . . . . . . . . 108 5.2.2 Luminance inhomogeneities in large OLED panels . . . . . . 110 5.3 Electrothermal OLED models . . . . . . . . . . . . . . . . . . . . . 112 5.3.1 Perceiving an OLED as thermistor array . . . . . . . . . . . 112 5.3.2 The OLED as a single three-layer thermistor . . . . . . . . . 114 5.3.3 A numerical 3D model of heat and current flow . . . . . . . 116 5.4 OLED stack and experimental conception . . . . . . . . . . . . . . 118 5.5 The Switch-back effect in planar light sources . . . . . . . . . . . . 120 5.5.1 Predictions from numerical 3D modeling . . . . . . . . . . . 121 5.5.2 Experimental proof . . . . . . . . . . . . . . . . . . . . . . . 124 5.5.3 Variation of vertical heat flux . . . . . . . . . . . . . . . . . 127 5.5.4 Variation of the OLED area . . . . . . . . . . . . . . . . . . 131 5.6 Electrothermal tristabilities in OLEDs . . . . . . . . . . . . . . . . 133 5.6.1 Observing different burn-in schematics . . . . . . . . . . . . 133 5.6.2 Bistability and tristability in organic semiconductors . . . . 134 5.6.3 Experimental indications for attempted branch hopping . . . 138 5.6.4 Saving bright OLEDs from burning in . . . . . . . . . . . . 144 5.6.5 Taking another view onto the camera pictures . . . . . . . . 145 6 Charge-carrier recombination and exciton management . . . . . . . . . . . . . . . . .147 6.1 Optical down conversion . . . . . . . . . . . . . . . . . . . . . . . . 149 6.1.1 Spectral reshaping of visible OLEDs . . . . . . . . . . . . . 149 6.1.2 Infrared-emitting OLEDs . . . . . . . . . . . . . . . . . . . . 155 6.2 Dual-state Förster transfer . . . . . . . . . . . . . . . . . . . . . . . 158 6.2.1 Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 6.2.2 Verification . . . . . . . . . . . . . . . . . . . . . . . . . . . 159 6.3 Singlet fission and triplet fusion in rubrene . . . . . . . . . . . . . . 161 6.3.1 Photoluminescence of pure and doped rubrene films . . . . . 163 6.3.2 Electroluminescence transients of rubrene OLEDs . . . . . . 172 6.4 Charge transfer-state tuning by electric fields . . . . . . . . . . . . . 177 6.4.1 CT-state tuning via doping variation . . . . . . . . . . . . . 177 6.4.2 CT-state tuning via voltage . . . . . . . . . . . . . . . . . . 180 6.5 Excursus: Exciton-spin mixing for wavelength identification . . . . 183 6.5.1 Characteristics of the active film . . . . . . . . . . . . . . . . 184 6.5.2 Conception . . . . . . . . . . . . . . . . . . . . . . . . . . . 186 6.5.3 Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187 6.5.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188 6.5.5 Application demonstrations . . . . . . . . . . . . . . . . . . 192 6.5.6 All-organic device . . . . . . . . . . . . . . . . . . . . . . . . 195 6.5.7 Device limitations and prospects . . . . . . . . . . . . . . . . 198 7 Conclusion and outlook . . . . . . . . . . . . . . . . . 207 7.1 Charge-carrier injection into doped films . . . . . . . . . . . . . . . 207 7.2 Charge-carrier transport in hot OLEDs . . . . . . . . . . . . . . . . 208 7.2.1 Prospects for OLED lighting facing tristable behavior . . . . 209 7.2.2 Outlook: Accessing the hidden PDR 2 region . . . . . . . . . 210 7.3 Charge-carrier recombination and spin mixing . . . . . . . . . . . . 211 7.3.1 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 7.3.2 Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 Bibliography. . . . . . . . . . . . . . . . . 215 Acknowledgements . . . . . . . . . . . . . . . . . 249

In this work, electronic excitations in organic semiconductors were investigated with electron energy-loss spectroscopy and optical absorption spectroscopy. Excitons are bound electron-hole pairs, which mostly determine the photophysical properties of the material. Excitons in organic semiconductors can interact with each other with two different mechanisms: Coulomb and charge-transfer coupling and a respective mix of both. Depending on which is dominating, different optical properties and a change of the exciton’s energy as a function of momentum are the consequences. This is called the exciton dispersion E(k) and can be measured by electron energy-loss spectroscopy. The obtained data were analysed with the assistance of calculations of the point dipole model, which is based on Coulomb coupling only. Four different materials were chosen, which all revealed new, unexpected insights into the field of exciton dynamics in organic crystals. The main focus of this work are molecular crystals, of which two were grown with physical vapor transport within this work. Dibenzopentacene, a pentacene derivative, was grown and characterized as a single crystal for the first time. A strong structural and optical anisotropy was revealed, which indicates, that the determination of the optical properties arises not only from the intermixing of the excitons with themselves, but also with vibrational modes. The exciton dispersion showed a smaller exciton bandwidth, than in the close relative pentacene, which suggests weaker exciton interaction parameters. As a further material, para-quaterphenyl single crystals were grown. According to the measurements a strong polarization dependence can be seen, which is underlined by calculations. Momentum dependent measurements displayed a strong dispersion of the first excitation, which could not be explained by the interaction of a molecule with the nearest neighbours, instead the next-nearest neighbours must be included to describe the dispersion appropriately. Single crystals of perylene were provided by Xianjie Liu’s group from the Linköping University. They also showed a strong anisotropy in polarization dependent optical absorption measurements. As the point dipole calculations result in a wrong polarization dependence of the first two excitations, it can be assumed that an additional contribution in the form of charge-transfer coupling between the molecules, which can flip this polarization dependence, is necessary to model the spectra properly. Contrary to the optical absorption data, the exciton dispersion is behaving similar as Coulomb coupled systems, which is confirmed by point dipole calculations. This work is completed with a momentum and temperature dependent series of pentacene thin films. It was shown that thin film spectra can represent single crystal spectra at small momenta. The according study revealed a strong temperature dependence of the exciton dispersion.

No / The objective of this review is to provide an overview concerning what the authors believe to be the most important photoelectrochemical techniques for the study of semiconductor nanoparticles. After a short historical background and a brief introduction to the area of photoelectrochemistry, the working principles and experimental setups of the various static and dynamic techniques are presented. Experimental details which are of crucial importance for their correct execution are emphasized, and applications of the techniques as found in the recent research literature as applied to semiconductor nanoparticles are illustrated.

No description available.

No description available.

No description available.

No description available.

No description available.

Strongly correlated systems have been a major challenge for a long time in the field of theoretical chemistry. For such systems, the relevant portion of the Hilbert space scales exponentially, preventing efficient simulation on large systems. However, in many cases, the Hilbert space can be partitioned into clusters on the basis of strong and weak interactions. In this work, we mainly focus on an approach where we partition the system into smaller orbital clusters in which we can define many-particle cluster states and use traditional many-body methods to capture the rest of the inter-cluster correlations. This dissertation can be mainly divided into two parts. In the first part of this dissertation, the clustered ansatz, termed as tensor product states (TPS), is used to study large strongly correlated systems. In the second part, we study a particular type of strongly correlated system, correlated triplet pair states that arise in singlet fission. The many-body expansion (MBE) is an efficient tool that has a long history of use for calculating interaction energies, binding energies, lattice energies, and so on. We extend the incremental full configuration interaction originally proposed for a Slater determinant to a tensor product state (TPS) based wavefunction. By partitioning the active space into smaller orbital clusters, our approach starts from a cluster mean-field reference TPS configuration and includes the correlation contribution of the excited TPSs using a many-body expansion. This method, named cluster many-body expansion (cMBE), improves the convergence of MBE at lower orders compared to directly doing a block-based MBE from an RHF reference. The performance of the cMBE method is also tested on a graphene nano-sheet with a very large active space of 114 electrons in 114 orbitals, which would require 1066 determinants for the exact FCI solution. Selected CI (SCI) using determinants becomes intractable for large systems with strong correlation. We introduce a method for SCI algorithms using tensor product states which exploits local molecular structure to significantly reduce the number of SCI variables. We demonstrate the potential of this method, called tensor product selected configuration interaction (TPSCI), using a few model Hamiltonians and molecular examples. These numerical results show that TPSCI can be used to significantly reduce the number of SCI variables in the variational space, and thus paving a path for extending these deterministic and variational SCI approaches to a wider range of physical systems. The extension of the TPSCI algorithm for excited states is also investigated. TPSCI with perturbative corrections provides accurate excitation energies for low-lying triplet states with respect to extrapolated results. In the case of traditional SCI methods, accurate excitation energies are obtained only after extrapolating calculations with large variational dimensions compared to TPSCI. We provide an intuitive connection between lower triplet energy mani- folds with Hückel molecular orbital theory, providing a many-body version of Hückel theory for excited triplet states. The n-body Tucker ansatz (which is a truncated TPS wavefunction) developed in our group provides a good approximation to the low-lying states of a clusterable spin system. In this approach, a Tucker decomposition is used to obtain local cluster states which can be truncated to prune the full Hilbert space of the system. As a truncated variational approach, it has been observed that the self-consistently optimized n-body Tucker method is not size- extensive, a property important for many-body methods. We explore the use of perturbation theory and linearized coupled-cluster methods to obtain a robust yet efficient approximation. Perturbative corrections to the n-body Tucker method have been implemented for the Heisenberg Hamiltonian and numerical data for various lattices and molecular systems has been presented to show the applicability of the method. In the second part of this dissertation, we focus on studying a particular type of strongly correlated states that occurs in singlet fission material. The correlated triplet pair state 1(TT) is a key intermediate in the singlet fission process, and understanding the mechanism by which it separates into two independent triplet states is critical for leveraging singlet fission for improving solar cell efficiency. This separation mechanism is dominated by two key interactions: (i) the exchange interaction (K) between the triplets which leads to the spin splitting of the biexciton state into 1(TT),3(TT) and 5(TT) states, and (ii) the triplet-triplet energy transfer integral (t) which enables the formation of the spatially separated (but still spin entangled) state 1(T...T). We develop a simple ab initio technique to compute both the triplet-triplet exchange (K) and triplet-triplet energy transfer coupling (t). Our key findings reveal new conditions for successful correlated triplet pair state dissociation. The biexciton exchange interaction needs to be ferromagnetic or negligible compared to the triplet energy transfer for favorable dissociation. We also explore the effect of chromophore packing to reveal geometries where these conditions are achieved for tetracene. We also provide a simple connectivity rule to predict whether the through-bond coupling will be stabilizing or destabilizing for the (TT) state in covalently linked singlet fission chromophores. By drawing an analogy between the chemical system and a simple spin-lattice, one is able to determine the ordering of the multi-exciton spin state via a generalized usage of Ovchinnikov's rule. In the case of meta connectivity, we predict 5(TT) to be formed and this is later confirmed by experimental techniques like time-resolved electron spin resonance (TR-ESR). / Doctor of Philosophy / The study of the correlated motion of electrons in molecules and materials allows scientists to gain useful insights into many physical processes like photosynthesis, enzyme catalysis, superconductivity, chemical reactions and so on. Theoretical quantum chemistry tries to study the electronic properties of chemical species. The exact solution of the electron correlation problem is exponentially complex and can only be computed for small systems. Therefore, approximations are introduced for practical calculations that provide good results for ground state properties like energy, dipole moment, etc. Sometimes, more accurate calculations are required to study the properties of a system, because the system may not adhere to the as- sumptions that are made in the methods used. One such case arises in the study of strongly correlated molecules. In this dissertation, we present methods which can handle strongly correlated cases. We partition the system into smaller parts, then solve the problem in the basis of these smaller parts. We refer to this block-based wavefunction as tensor product states and they provide accurate results while avoiding the exponential scaling of the full solution. We present accurate energies for a wide variety of challenging cases, including bond breaking, excited states and π conjugated molecules. Additionally, we also investigate molecular systems that can be used to increase the efficiency of solar cells. We predict improved solar efficiency for a chromophore dimer, a result which is later experimentally verified.