Hybrid organic-inorganic solar photovoltaic (PV) cells capable of directly converting sunlight to electricity have attracted much attention in recent years. Despite evident technological advancements in the PV industry, the widespread commercialisation of solar cells is still being mired by their low conversion efficiencies and high cost per Watt. Perovskites are an emerging class of semiconductors providing a low-cost alternative to silicon-based photovoltaic cells, which currently dominate the market. This thesis develops a series of studies on “all-solid state perovskite solar cells” fabricated via vapour deposition which is an industrially-accessible technique, to achieve planar heterojunction architectures and efficient PV devices. Chapter 2 presents a general outlook on the operating principles of solar cells, delving deeper into the specific operational mechanism of perovskite solar cells. It also explores the usual methods employed in the fabrication of perovskite thin films. Chapter 3 describes the experimental procedures followed during the fabrication of the individual components constituting the device from the synthesis of the precursors to the construction of the functioning perovskite PV devices. Chapter 4 demonstrates pioneering work involving the dual-source vapour deposition (DSVD) of planar heterojunction perovskite solar cells which generated remarkable power conversion efficiency values surpassing 15%. These significant results pave the way for the mass-production of perovskite PVs. To further expand the range of feasible vapour deposition techniques, a two-layer sequential vapour deposition (SVD) technique is explored in Chapter 5. This chapter focusses on identifying the factors affecting the fundamental properties of the vapour-deposited films. Findings provide an improved understanding of the effects of precursor compositions and annealing conditions on the films. Chapter 5 concludes with a comparison between SVD and DSVD fabricated films, highlighting the benefits of each vapour deposition technique. Furthermore, hysteretic effects are analysed in Chapter 6 for the perovskite PV devices fabricated based on different structural configurations. An interesting discovery involving the temporary functioning of compact layer-free perovskite PV devices suggests the presence of a built-in-field responsible for the hysteresis of the cells. The observations made in this chapter yield a new understanding of the functionality of individual cell layers. Combining the advantages of the optimum vapour deposition technique established in Chapter 4 and Chapter 5, with the enhanced understanding of perovskite PV cell operational mechanism acquired from Chapter 6, an ongoing study on an “all-perovskite” tandem solar cell is introduced in Chapter 7. This demonstration of the “all-perovskite” tandem devices confirms the versatility of perovskites for a broader range of PV applications.

Submitted by Maike Costa (maiksebas@gmail.com) on 2017-06-21T13:34:41Z No. of bitstreams: 1 arquivototal.pdf: 8365560 bytes, checksum: 9864dee1c44924e2f7a2db5c50f4a7aa (MD5) / Made available in DSpace on 2017-06-21T13:34:41Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 8365560 bytes, checksum: 9864dee1c44924e2f7a2db5c50f4a7aa (MD5) Previous issue date: 2016-08-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The bentonite term designates gross clays containing at least 50% of smectite and particularly montmorillonite. The smectite have features like lamellar structures, ion exchange capacity, variability of the chemical composition and the electrical charge of the lamellae, which determine the properties in interactions with organic and inorganic substances. Changes in physical and chemical properties of these materials after intercalation of organic compounds has drawn attention due to wide applicability by these hybrids. polar organic molecules such as amines, may replace the water molecules that occupy the interlayer space, resulting in organofílicos materials. Within this perspective, we obtained hybrid bentonite intercalation / amines using bentonite exchanged with sodium and calcium cations. In this case we have used two cyclic diamines of pharmacological importance, an aliphatic, piperazine (PPZ) and an aromatic, pyrazine (PRZ) for hybrid formation by several synthesis routes. Then the drug amiloride hydrochloride, which has in its structure the pyrazine ring is loaded in calcium bentonite sample for subsequent emissions testing. The characterization techniques such as, XRD, IR, TEM, inter alia, the efficiency in all cases. Thus, the results indicate a possible application of such hybrids for obtaining the metal complexes and the use of these systems for controlled emission tests in view of the PPZ have pharmacological properties while PRZ is a base molecule for various drugs, such as amiloride, for example. / O termo bentonita designa as argilas brutas contendo pelo menos 50% de esmectitas e particularmente montmorillonita. As esmectitas possuem características como: estrutura lamelar, capacidade de troca iônica, variabilidade da composição química e da carga elétrica das lamelas, que determinam as propriedades nas interações com substâncias orgânicas e inorgânicas. As alterações nas propriedades físicas e químicas desses materiais após a intercalação de compostos orgânicos tem chamado atenção devido à vasta aplicabilidade apresentada por esses híbridos. Moléculas orgânicas polares, como aminas, podem substituir as moléculas de água, que ocupam o espaço interlamelar, resultando em materiais organofílicos. Dentro dessa perspectiva, foram obtidos híbridos de intercalação bentonitas/aminas utilizando bentonitas trocadas com cátions de sódio e cálcio. Neste caso foram utilizadas duas diaminas cíclicas de importância farmacológica, uma alifática, piperazina (PPZ) e uma aromática, pirazina (PRZ) para a formação de híbridos por diversas rotas de síntese. Em seguida o fármaco cloridrato de amilorida, que tem em sua estrutura o anel pirazínico, foi carregado na amostra cálcica da bentonita para consequentes ensaios de emissão. As técnicas de caracterização como, DRX, IV, MET, entre outros, comprovaram a eficiência em todos os casos. Sendo assim, os resultados indicam uma possível aplicação desses híbridos para obtenção de complexos metálicos, bem como o uso destes sistemas para ensaios de emissão controlada tendo em vista que a PPZ tem propriedades farmacológicas, enquanto a PRZ é uma molécula base para diversos fármacos, como a amilorida, por exemplo.

Made available in DSpace on 2015-05-14T13:21:47Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2304381 bytes, checksum: 383faaa5d2a0cb26ce8f49ef357849d1 (MD5) Previous issue date: 2009-03-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The selective leaching of clay minerals is an important method in the preparation of porous silicates presenting as a simple, effective and low cost route. In this study, vermiculite was submitted to acid treatment at concentrations 1, 2, 3, and 4 mol dm-3, resulting the precursor solids named as VacX (x=1 a 4), respectively. The lixiviated matrices and vermiculite reacted covalently with the organosilanes aminepropyl-, propyletilenediamine-, propyldietilenetriamine- and glycidoxypropyltrimethoxisilane (GPTS). The hybrid Vac3G, derived from silanization reaction between Vac3 and GPTS, was submitted to subsequent reactions with ethyl, propyl, butyldiamines and 2- aminepiridine resulting in the entrance of new basic centres. The products were characterized by chemical analysis, infrared spectroscopy, X-ray diffraction, 29Si and 27Al NMR in solid state, SEM, and pore volume and surface area determination. The lixiviation of sodic vermiculite originated the restructured porous solids with high superficial area showing the values133, 334, 673 e 575 m2 g-1 for VacX where X = 1,2,3,4, respectively. These solids and sodic vermiculite reacted covalently with each organosilane through methoxyl groups of silane and the hydroxyl surface of matrices. Independently of solid, it was observed that the lixiviation favored the reactivity of activated matrices compared with sodic vermiculite, showing the Vac3 as more reactive comparing with others solids. All modified solids presented high nitrogen content showing the values of 6,31 %. The set of modified vermiculites containing aminepropyl group was applied as adsorbent for divalent cations as copper and nickel in aqueous solution. These solid showed highest affinity for Ni2+ than Cu2+ ions as illustrated by Nf values of 2,97 and 1,23 mmol g-1, respectively. Clay porous solids obtained of leaching treatment of vermiculite are potential substrates for grafting of silanes showing important applications as adsorbents for contaminant species as heavy metals. / A lixiviação seletiva de argilominerais é um método importante na preparação de silicatos porosos constituindo-se em uma rota simples, efetiva e de baixo custo. Neste estudo a vermiculita foi submetida a tratamento ácido com acido nítrico nas concentrações 1, 2, 3 e 4 mol dm- 3, originando os sólidos precursores denominados VacX (x=1 a 4), respectivamente. As matrizes ativadas e a vermiculita reagiram covalentemente com os organosilanos aminopropil-, propiletilenodiamino-, propildietilenotriamino- e glicidóxipropiltrimetoxissilano (GPTS) através dos grupos metoxilas do silano e as hidroxilas da superfície das matrizes. O híbrido Vac3G, derivado da silanização do Vac3 com GPTS, sofreu reações subseqüentes com as diaminas etil, propil, butildiamina e 2- aminopiridina, possibilitando a entrada de novos centros básicos. Os diversos sólidos foram caracterizados por análise química, espectroscopia na região do IV, DRX, RMN 29Si e 27Al, MEV, volume de poro e área superficial. A lixiviação da vermiculita sódica originou sólidos porosos reestruturados com elevadas áreas superficiais cujos valores foram 133, 334, 673 e 575 m2 g-1 para os sólidos Vac1, Vac2, Vac3 e Vac4, respectivamente. Independentemente do sólido, observou-se que à medida que a lixiviação se torna mais acentuada, houve um aumento na reatividade das matrizes ativadas em relação à vermiculita original, sendo a matriz Vac3 a mais reativa diante das reações aqui propostas. Todos os sólidos modificados apresentaram altos teores de grupos orgânicos incorporados. A série de vermiculitas modificadas com o grupo aminopropil foi utilizada para a adsorção de cátions divalentes de cobre e níquel em solução aquosa, mostrando maior afinidade para os íons de Ni2+ (aq) do que para Cu2+ (aq) como ilustrado pelos valores Nf de 2,97 e 1,23 mmol g-1, respectivamente. Os sólidos porosos argilosos derivados de tratamento ácido da vermiculita são substratos potenciais para imobilização de silanos apresentando importantes aplicações como adosrventes para espécies poluentes como metais pesados.

Tesis por compendio / [EN] The doctoral thesis presented under the title "Hybrid inorganic-organic materials for the optical recognition of neutral and anionic species" has had as its main objective the synthesis and characterization of organic-inorganic hybrid materials based on the combination of the principles of Supramolecular Chemistry and Materials Science. Recent studies confirm that cooperation between these two areas of Chemistry allow the simulation of what natural living beings have been doing for millions of years in a natural way. At cellular level, many vital functions are related to the ability of a particular receptor to recognize a particular species, giving a specific answer. But what is more interesting is that in living organisms, most of these systems do not exist as dissolved molecules, but are bounded to a (bio)organic skeleton with more or less flexibility. When we imitated these systems bearing in mind the supramolecular and analytical chemistry, we find that we need a sensory molecule able to join with the specie that we want to detect and at the same time, this union must produce a change in its physico-chemical properties giving as a result a signal. But moreover, if we take advantatge of the fact that siliceous nanostructured materials present a high physical and chemical stability and that they have cavities where the sensor system can be incorporated into, we have the synthetic hybrid organic-inorganic combination similar to the natural one. In order to develop this idea, we have used sensor systems widely studied in molecular recognition processes in aqueous media and we have applied them to the inorganic-organic hydrid materials. Therefore, the present work thesis has been structured in two parts: on the one hand, the synthesis and characterization of the functionalized inorganic porous solid materials by the study and detection of amines using the "chemodosimeter" approach. On the other hand, we have made the synthesis and characterization of the organic functionalized inorganic porous solid materials for the study and detection of anionic species through the displacement assays approach. / [ES] La tesis doctoral que se presenta bajo el título "Hybrid inorganic-organic materials for the optical recognition of neutral and anionic species" ha tenido como objetivo principal la síntesis y caracterización de materiales híbridos orgánico-inorgànicos basados en la combinación de los principios de la Química Supramolecular y la Ciencia de los Materiales. Recientes estudios corroboran que la cooperación entre estas dos áreas de la Química permite simular lo que ya hace millones de años realizan de forma natural los organismos vivos. A nivel celular, muchas de las funciones vitales están relacionadas con la habilidad de un receptor concreto para reconocer una determinada especie, dando una respuesta específica. Pero lo que resulta más interesante, es que en los organismos vivos, la mayoría de estos sistemas no existen en forma de moléculas disueltas, sino que están unidos con mayor o menor flexibilidad a un esqueleto bio(in)orgánico. Cuando imitamos estos sistemas teniendo en cuenta la química supramolecular y analítica, nos encontramos que necesitamos de una molécula indicadora que sea capaz de unirse a la especie que queremos detectar y que a su vez, esta unión produzca un cambio en las propiedades físico-químicas de la entidad para producir una señal. Pero además, si aprovechamos el hecho de que los materiales silíceos nanoestructurados presentan una alta estabilidad física y química y que proporcionan cavidades donde alojar al sistema sensor, tenemos la combinación híbrida orgánico-inorgánico sintética similar a la natural. Con el objetivo de desarrollar esta idea, hemos utilizado sistemas sensores ampliamente estudiados en procedimientos de reconocimiento molecular en disolución acuosa y los hemos aplicado a los materiales híbridos orgánico-inorgànicos. De esta manera, el trabajo de tesis se ha estructurado en dos partes: por una parte, la síntesis y caracterización de materiales sólidos inorgánicos porosos funcionalizados para el estudio y detección de aminas utilizando el procedimiento de "dosímetro químico", y en una segunda parte, se ha llevado a cabo la síntesis y caracterización de sólidos inorgánicos porosos funcionalizados para el estudio y detección de especies aniónicas mediante el procedimiento de "ensayos por desplazamiento". / [CA] La tesis doctoral que es presenta sota el títol "Hybrid inorganic-organic materials for the optical recognition of neutral and anionic species" ha tingut com objectiu principal la síntesi i caracterització de materials híbrids orgànic-inorgànics basats en la combinació dels principis de la Química Supramolecular i la Ciència dels Materials. Estudis recents corroboren que la cooperació entre aquestes dues àrees de la Química permet simular el que ja fa milions d'anys realitzen de forma natural els organismes vius. A nivell cel·lular, moltes de les funcions vitals estan relacionades amb l'habilitat d'un receptor concret per a reconèixer una espècie determinada, donant una resposta específica. Però el que és més interessant, és que als organismes vius, la majoria d'aquests sistemes no existeixen en forma de molècules dissoltes, sinó que estan units amb major o menor flexibilitat a un esquelet bio(in)orgànic. Quan imitem aquests sistemes tenint en compte la química supramolecular i analítica, ens trobem que necessitem d'una molècula indicadora que sigui capaç d'unir-se a l'espècie que volem detectar i que alhora, aquesta unió produeixi un canvi en les propietats fisico-químiques de l'entitat per produir una senyal. Però a més, si aprofitem el fet que els materials silícics nanoestructurats presenten una alta estabilitat física i química i que proporcionen cavitats on es pot allotjar el sistema sensor, tenim la combinació híbrida orgànica-inorgànica sintètica semblant a la natural. Per tal de desenvolupar aquesta idea, hem utilitzat sistemes sensors ampliament estudiats en procediments de reconeixement molecular en dissolució aquosa i els hem aplicat als materials híbrids orgànic-inorgànics. Així el present treball de Tesis s'ha estructurat en dues parts: per una banda, la síntesis i caracterització de materials sòlids inorgànics porosos funcionalitzats per l'estudi i detecció d'amines utilitzant el procediment de "dosímetre químic", i en una segona part, s'ha realitzat la síntesis i caracterització de sòlids inorgànics porosos funcionalitzats per a l'estudi i detecció d'espècies aniòniques mitjançant el procediment "d'assajos per desplaçament". / Comes Navarro, M. (2016). Hybrid inorganic-organic materials for the optical recognition of neutral and anionic species [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/62153 / Compendio

Hybride anorganische/organische Systeme (HIOS) sind von großem Interesse für Grundlagenforschung und neue (opto)-elektronische Bauteile. Um effiziente Bauteile zu entwickeln, ist ein Verständnis der Energielevelanordnung (ELA) an der Grenzfläche von entscheidender Bedeutung. Es wird demonstriert, wie Oberflächen mit heterogener Austrittsarbeit die Resultate von ultravioletter Photoelektronenspektroskopie (UPS) beeinflussen. Durch den Vergleich experimenteller Daten mit Berechnungen zeigt sich, dass das lokale elektrostatische Potential oberhalb der Oberfläche zur Ausbildung einer zusätzlichen Energiebarriere für Elektronen über Bereichen mit niedriger Austrittsarbeit führt, was die gemessene Sekundärelektronenkante zu höheren kinetischen Energien verschiebt. Der Einfluss von Streifengröße und experimentellen Parametern wird theoretisch und experimentell gezeigt. Im zweiten Teil dieser Arbeit wird gezeigt, wie man dünne organische Donator/Akzeptor Zwischenschichten nutzen kann, um die ELA zwischen typischen anorganischen und organischen Halbleitern zu kontrollieren. Die Austrittsarbeit von anorganischen Substraten lässt sich so zwischen 2.2-6.0 eV variieren. Der Einfluss von Zuständen in der Bandlücke des anorganischen Halbleiters auf die Bandverbiegung wird im Detail untersucht und es wird ein Model vorgeschlagen, welches das Pinning des Fermi-Niveaus an diesen Zuständen beschreibt. Es wird experimentell gezeigt, dass die Dotierung des anorganischen Halbleiters kaum Einfluss auf die ELA hat. Weiterhin wird die ELA zwischen dem Übergangsmetall-Dichalcogenid WSe2 und dem organischen Akzeptor C60F48 untersucht. Mit Hilfe von STM und STS Messungen wurde gezeigt, dass C60F48 geschlossene Domänen auf WSe2 bei Bedeckung mit Submonolagen bildet und dass sich die Energielevel von WSe2 drastisch ändern. Durch Auswerten der Potentialänderung als Funktion des Abstandes von einer C60F48 Kante im STS konnte die Thomas-Fermi-Abschirmlänge von WSe2 auf etwa 2 nm bestimmt werden. / Hybrid inorganic/organic systems (HIOS) have attracted a lot of interest for fundamental studies and novel (opto)-electronic devices during the past decade. For developing efficient devices, an understanding and control of the energy level alignment (ELA) at the hybrid interface is of paramount importance. Firstly, it is demonstrated how surfaces with non-uniform local work function influence the measurement results obtained by ultraviolet photoelectron spectroscopy (UPS). By comparing the measured results with calculations, it is found that the electrostatic potential above the surface leads to an additional energy barrier for electrons above low work function areas, shifting the secondary electron cut-off (SECO) to higher kinetic energies in UPS (averaging effect). The influence of pattern size and measurement conditions on the SECO is shown theoretically and experimentally. In the second part it is shown how thin organic donor/acceptor interlayers can be employed to manipulate the ELA between prototypical inorganic and organic semiconductors. The work function of the inorganic substrate can be tuned between 2.2-6.0 eV. The influence of gap states within the inorganic band gap on the band bending change is investigated in detail and a model is proposed, which describes the pinning of the inorganic energy levels as a function of surface state density. It is further shown experimentally that the bulk doping concentration of the inorganic semiconductor has only little effect on the energetic alignment. Finally, the ELA of the transition metal dichalcogenide monolayer WSe2 with the organic acceptor molecule C60F48 is investigated. Using STM and STS measurements, it is revealed that the C60F48 forms domains on WSe2 in the sub-monolayer regime. By evaluating the potential change as a function of distance from a C60F48 edge in STS, it is possible to derive a value for the Thomas-Fermi screening length of WSe2 of about 2 nm.

Organische Solarzellen bieten die Aussicht auf eine ökologische und zugleich ökonomische Energiequelle. Nachteile des Konzepts liegen in der z.T. geringen Stabilität der für Absorption und Ladungstransport verwendeten Moleküle und einer unvollständigen Ausnutzung des Sonnenspektrums. Zur Verbesserung beider Merkmale werden in dieser Arbeit einzelne organische Bestandteile durch anorganische Materialien mit hoher Stabilität und breiten Absorptionsbanden ersetzt. Insbesondere werden als Absorber kolloidale Quantenpunkte (QP) verwendet, denen aufgrund nicht-linearer und durch Größeneffekte steuerbarer optischer Eigenschaften in der Photovoltaik der dritten Generation großes Interesse gilt. Dazu werden dünne anorganisch-organische Filme mit einem Verfahren hergestellt, das auf Wechselwirkungen zwischen Partikeln in Lösung und geladenen Oberflächen beruht (electrostatic layer-by-layer self-assembly). TiO2-Nanokristalle als Elektronenleiter, kolloidale CdTe- und CdSe-QP als Absorber und konjugierte Polymere als Lochleiter werden in die Filme integriert und diese als aktive Schichten in photovoltaischen Zellen verwendet. Die Struktur der Filme wird zunächst mittels AFM, SEM, XPS sowie durch eine Beladung mit organischen Farbstoffen untersucht. Sie weisen Porosität auf einer Skala von Nanometern sowie eine kontrollierbare Dicke und Mikrostruktur auf. Darauf aufbauend werden durch weitere lösungsbasierte Prozessschritte photovoltaische Zellen gefertigt und Zusammenhänge zwischen Struktur und Zellenleistung elektronisch und spektroskopisch untersucht. Einflussfaktoren der Zelleffizienz wie die Ladungsträgererzeugung und interne Widerstände können so bestimmt und die Effizienz von CdSe-QP als Sensibilisatoren nachgewiesen werden. Die Arbeit demonstriert die Eignung der gewählten Methoden und Zelldesigns zur Herstellung von photovoltaischen Zellen und eröffnet neue Ansätze für die Entwicklung und Fertigung insbesondere auf QP basierender Zellen. / Organic solar cells offer the prospect of a both ecological and economical energy source. Drawbacks of the concept are low stabilities of the molecules used for absorption and charge transport and an incomplete utilization of the solar spectrum. In order to improve both these characteristics, individual organic components are replaced by inorganic materials with a high stability and broad absorption bands in this work. In particular, colloidal quantum dots (QDs) are used as absorbers, the non-linear and size controllable optical properties of which are attracting great interest in third generation photovoltaics. For this application, inorganic/organic thin films are produced with a method based on interactions between particles in solution and charged surfaces (electrostatic layer-by-layer self-assembly). TiO2-nanocrystals as electron conductors, colloidal CdTe- and CdSe-QDs as absorbers and conjugated polymers as hole conductors are integrated into the films, which are used as active layers in photovoltaic cells. The structure of the films is investigated by AFM, SEM, XPS and by loading the films with organic dye molecules. The films show porosity on a nanometer scale as well as a controllable thickness and microstructure. Complemented by further solution based processing steps, photovoltaic cells are manufactured and correlations between the structure and performance of the cells are investigated both electronically and spectroscopically. Individual factors that determine the cell efficiency, such as carrier generation and internal resistances, are determined and the efficiency of CdSe-QDs as sensitizers is demonstrated. This work proves the suitability of the chosen methods and cell designs for manufacturing photovoltaic cells and opens up new approaches for the development and manufacture of in particular QD-based solar cells.

ZnO hat wegen seiner potenziellen Anwendung in elektronischen Geräten und als Katalysator viel Aufmerksamkeit erhalten. Die Struktur und Reaktivität von ZnO-Oberflächen haben eine direkte Bedeutung für die Leistung und Funktionalität dieser Geräte. Daher ist die Definition und das Verständnis der atomistischen Details von ZnO-Oberflächenstrukturen von besonderer Bedeutung. Die atomistischen Details von ZnO-Oberflächen hängen von den Präparationsverfahren ab. Nach der Kristallpräparation ist es notwendig, eine Oberflächencharakterisierung durchzuführen, um eine Verbesserung der Funktionalität und Effizienz von ZnO-basierten opto-elektronischen Bauelementen und Katalysatoren zu erreichen. Die atomistische Wahrnehmung der Reaktion zwischen einem organischen Molekül und ZnO-Oberflächen spielt eine entscheidende Rolle bei der Optimierung der Wasserstoff-on-demand-Lieferung in Brennstoffzellen. Das Verständnis der atomistischen Details von Adsorption, Diffusion und Dissoziation eines organischen Moleküls ebnet den Weg, um die Vorgänge bei der Wasserstofffreisetzung für Brennstoffzellen zu enträtseln. Mit dem Ziel, die Struktur- und Stöchiometriebestimmung mit Hilfe der XPS zu ermöglichen, präsentiere ich in dieser Arbeit die Ergebnisse einer umfassenden theoretischen Studie über die Kernniveauverschiebungen von ZnO-Oberflächenrekonstruktionen. Darüber hinaus biete ich eine gründliche Untersuchung der gemischt-terminierten Oberfläche, indem ich zunächst die Bedingungen untersuche, unter denen sich Methanol-Monolagen auf dieser Kristallfläche bilden können, und dann alle möglichen Wege für deren Reaktion erforsche. Diese Studie liefert ein umfassendes Bild, um die wahrscheinlichsten Reaktionsschritte zu identifizieren, die zur Interpretation der experimentellen Ergebnisse herangezogen werden können. Sie wird zukünftigen theoretischen Studien für ähnliche Reaktionen wie die Dehydrierung und die Kinetik der Monolagenbildung, die hier untersucht wurden, helfen. / Zinc-Oxide (ZnO) has been getting much attention over the past decades because of its potential application in electronic devices and as a catalyst. The structure and reactivity of ZnO surfaces have direct relevance for the performance and functionality of these devices. Therefore, defining and understanding the atomistic details of ZnO surface structures is of particular importance. The atomistic details of ZnO surfaces depend on the preparation procedures. After the crystal preparation, it is necessary to perform a surface characterization, to achieve an improvement in the functionality and efficiency of ZnO-based opto-electronic devices and catalysts. The atomistic perception of the reaction between an organic molecule and ZnO surfaces plays a crucial role in optimizing hydrogen-on-demand delivery in fuel cells, and understanding the atomistic details of adsorption, diffusion, and dissociation of a simple organic molecule paves the way towards unraveling the procedures involved in the hydrogen liberation for fuel cells. In this work, with the aim of enabling structure and stoichiometry determination by using X-ray photoelectron spectroscopy, I present the results of a comprehensive theoretical study on the core-level shifts of ZnO surface reconstructions. Moreover, I provide a thorough investigation of the mixed-terminated (10-10) surface by first examining the conditions under which methanol monolayers can form on this crystal face and by then exploring all possible pathways for its adsorption, diffusion, and initial dehydrogenation. This study provides a comprehensive picture to identify the most probable reaction steps that can be used to interpret experimental findings and will help future theoretical studies for reactions similar to dehydrogenation of organic molecules and monolayer-formation kinetics that were studied here.

Hybride anorganisch/organischen Systeme können die individuellen Vorteile, etwa eine hohe elektronische Mobilität in anorganischen und starke Licht-Materie-Wechselwirkung in organischen Halbleitern, kombinieren. Ein sinnvoller Nutzen dieser Heterostrukturen benötigt ein umfassendes Verständnis der Grenzfläche. Zwei Grenzflächenprozesse werden in dieser Arbeit behandelt. Förster-Resonanzenergietransfer (FRET) wird zwischen einem InGaN/GaN Quantengraben und dem Polymer Cn-ether PPV untersucht. Trotz des hohen internen elektrischen Feldes im Quantengraben, ist effizienter Energietransfer möglich, solange andere nicht-strahlende Zerfallsprozesse unterdrückt werden. Dies wird mittels temperaturabhängiger PL und PLE Spektroskopie gezeigt. PLE demonstriert eine eindeutige Erhöhung der Emission des Akzeptors. Bei höheren Temperaturen dominieren nicht-strahlende Zerfallskanäle. Ladungstransfer wird zwischen MoS2 und dem Molekül H2Pc untersucht. Die Kombination mit organischen Molekülen kann die Funktionalität von MoS2 erweitern. Photoelektronenspektroskopie (PES) zeigt einen Typ-II Heteroübergang an der MoS2/H2Pc Grenzfläche. Angeregte Elektronen gehen von den H2Pc Molekülen in die MoS2 Monolage über, wie mittels einer Verkürzung der PL Lebenszeit von H2Pc gezeigt wird. Photostrommessungen demonstrieren zudem, dass die transferierten Elektronen zu einer erhöhten Photoleitfähigkeit beitragen. Zusätzlich werden auch einzelne 2D Übergangsmetall Dichalkogenide (TMDCs) untersucht. Um TMDCs von hoher Qualität herzustellen, wurde intern eine Wachstumsmethode entwickelt. Mittels PL Spektroskopie werden die so hergestellten Schichten charakterisiert. Die Vielseitigkeit der Methode wird anhand des Wachstums von Mischkristallen und Heterostrukturen gezeigt. Der Einfluss der dielektrischen Funktion des Substrates wird erforscht. Durch die Kombination von PES und Reflexionsmessungen kann eine gleichzeitige Abnahme sowohl der Bandlücke als auch der Exzitonen Bindungsenergie gezeigt werden. / Hybrid inorganic/organic systems can combine the advantages of both materials such as high carrier mobilities in inorganic semiconductors and large light-matter interaction in organic ones. In order to benefit from these heterostructures, a thorough understanding of the interface is needed. Two processes occurring at the interface are looked at in this thesis. Förster resonance energy transfer (FRET) is studied between a single InGaN/GaN quantum well and the polymer Cn-ether PPV. Despite the large internal electric fields in the quantum well, efficient FRET is possible as long as other non-radiative decay channels are suppressed. This is shown by temperature dependent PL and PLE spectroscopy. PLE spectra clearly demonstrate an enhanced light emission from the acceptor. At elevated temperatures, non-radiative decay pathways become dominant. Excited-state charge transfer is studied on MoS2 in combination with the molecule H2Pc. The combination with molecules can extend the functionality of MoS2. Photoelectron spectroscopy (PES) reveals a type II energy level alignment at the MoS2/H2Pc interface. Excited electrons are transferred from H2Pc to MoS2, deduced from a shortening of the H2Pc PL decay time. Photocurrent spectra further show that the transferred electrons contribute to an enhanced photoconductivity. Additionally, bare 2D transition-metal dichalcogenides (TMDCs) are studied. In order to fabricate high-quality TMDC monolayers, a growth method was developed in-house. The grown monolayers are characterised by optical spectroscopy. The versatility of the method is demonstrated by the growth of alloys and heterostructures. The influence of the substrate dielectric function is investigated by comparing band-gaps measured by PES with the exciton transition energies obtained by reflectance measurements. An almost equal reduction in both energies with the substrate dielectric constant is seen.

Die Entwicklung optoelektronischer Geräte wurde stark durch organische Donor-Akzeptor-Komplexe beeinflusst, die eine zentrale Rolle in der modernen Optoelektronik spielen. Diese Materialien ermöglichen ein komplexes Zusammenspiel elektronischer, optischer und phononischer Eigenschaften. Frühe Arbeiten zu konjugierten Polymeren in OLEDs und Bulk-Heterojunktionen in organischen Photovoltaikzellen legten das Fundament für praktikable OLEDs und verbesserten die Effizienz in OPVs. Kürzlich hat sich das Forschungsfeld auf hybride anorganisch-organische Systeme ausgeweitet. Diese Materialien kombinieren die hohe Ladungsträgerdichte und -mobilität der anorganischen Komponenten mit den Lichtausbeute- und Emissionscharakteristika organischer Moleküle. Die Integration von Übergangsmetall-Dichalcogenid-Monoschichten hat bedeutende Fortschritte gebracht, besonders für die Feineinstellung der Ladungstransferdynamik. Diese Entwicklungen stellen neue Herausforderungen dar, insbesondere bei der Modellierung laserinduzierter, ultraschneller Ladungstransferdynamik. RT-TDDFT hat sich als effizientes und genaues Werkzeug erwiesen, das für die Untersuchung großer Systeme geeignet ist und die Simulation zeitaufgelöster Phänomene ermöglicht. Diese Dissertation analysiert die laserinduzierte Ladungstransferdynamik in vollständig organischen und hybriden anorganisch-organischen Grenzflächen. Sie untersucht die Komplexität stark und schwach gebundener Grenzflächen und deren Verhalten unter externen Laserpulsen sowie den Temperatureffekten auf die Ladungstransferdynamik. Die Nutzung von RT-TDDFT zur Modellierung ultraschneller Elektronendynamik und vibronischer Kopplung hat das Verständnis in diesem Feld vertieft und die Effektivität bei der Modellierung optoelektronischer Geräte demonstriert. / The development of optoelectronic devices has been significantly influenced by organic donor-acceptor complexes, which play a central role in modern optoelectronics. These materials enable a complex interplay of electronic, optical, and phononic properties. Early work on conjugated polymers in OLEDs and bulk heterojunctions in organic photovoltaic cells laid the foundation for practical OLEDs and improved efficiency in OPVs. Recently, the field of research has expanded to hybrid inorganic-organic systems. These materials combine the high charge carrier density and mobility of inorganic components with the light yield and emission characteristics of organic molecules. The integration of transition metal dichalcogenide monolayers has brought significant advances, particularly in fine-tuning charge transfer dynamics. These developments present new challenges, especially in modeling laser-induced, ultrafast charge transfer dynamics. RT-TDDFT has proven to be an efficient and accurate tool suitable for studying large systems and enabling the simulation of time-resolved phenomena. This dissertation analyzes the laser-induced charge transfer dynamics in fully organic and hybrid inorganic-organic interfaces. It investigates the complexity of strongly and weakly bound interfaces and their behavior under external laser pulses, as well as the temperature effects on charge transfer dynamics. The use of RT-TDDFT to model ultrafast electron dynamics and vibronic coupling has deepened the understanding in this evolving field and demonstrated its effectiveness in modeling optoelectronic devices.