La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus. / Understanding the interrelations between microstructure and electronic processes in polymeric semiconductors is of great importance for their use in bulk heterostructures, as the active part of power-converting devices such as organic photovoltaic cells or light emitting diodes, as well as for quantum optoelectronics applications. In this doctoral thesis, two different systems are investigated; each of these systems represents a different approach to optimize materials in terms of microstructure and their ability to order on the molecular level. In the first system, by means of quasi-steady-state photoinduced absorption (PIA) and pump-modulation-frequency-dependent PIA spectroscopy, I performed a comprehensive analysis of the working principles of a hybrid photovoltaic cell based on nanocrystals of zinc oxide (ZnO) and poly(3-hexylthiophene) (P3HT). The interface surface area between donor (polymer P3HT) and acceptor (ZnO nanocrystals), where charge generation occurs, plays a significant role in the performance of the hybrid photovoltaic cells. To improve the charge generation mechanism of P3HT: ZnO, it is therefore essential to modify the P3HT: ZnO interface area. We demonstrated that molecular interface modification with cis-bis(4,40-dicarboxy-2,20bipyridine) ruthenium (II) (N3-dye) and a-Sexithiophen-2-yl-phosphonic Acid (6TP) as interface modifiers enhanced the photocurrent and performance in P3HT: ZnO cells. 6TP and N3 attach to the ZnO interface, thus increasing the donor:acceptor interface area that contributes to enhanced charge separation. Furthermore, 6TP and N3 reduce the ZnO traps that reduces recombination. In the second part, I introduced a processed solid-like ultra-high-molecular-weight polystyrene polymeric host matrix to trap and protect poly [2-methoxy, 5-(2’-ethylhexoxy)- 1,4-phenylene vinylene-PPV] (MEH-PPV) solution for use in quantum optoelectronic devices. Previous work by others has shown that MEH-PPV in solution undergoes a conformation transition from coiled conformation at high temperatures (blue-phase) to a chain-extended conformation at low temperatures (red-phase). The chain-extended conformation of MEH-PPV solution favours the characteristics needed to improve quantum optoelectronic devices, however the solution cannot be incorporated into the device. We demonstrated that the red-phase feature of MEH-PPV in solution maintains in a processed solid-like ultra-high-molecular-weight polystyrene polymeric host matrix (MEH-PPV/UHMWPS gels), by means of temperature-dependent photoluminescence (PL) spectroscopy (ranged from 290K down to 80 K). The red-phase of MEH-PPV/UHMW PS gels manifest itself as narrow linewidths and enhanced 0-0 line strength in the PL spectrum as well as a small stokes shifts between the PL and absorption spectra at low temperatures. These approaches demonstrate that microstructure manipulation and electronic properties of polymeric semiconductors have a direct impact on the device performance for their continued technological developments.

Der erste Teil dieser Arbeit ist dem Kondogittermodell gewidmet. Für ein Elektron, das in einen ferromagnetisch gesättigten Hintergrund aus lokalen Spinmomenten eingebracht wird (ferromagnetisches Polaron), wird die stationäre Schrödingergleichung gelöst und das vollständige Eigenwertspektrum im endlichen und unendlichen Gitter abgeleitet. Danach wird die zeitabhängige Schrödingergleichung für beliebige Anfangsbedingungen gelöst und eine detaillierte Analyse des Down-Elektron-Zerfalls vorgenommen. Für endliche Bandfüllungen wird im Anschluss das magnetische Grundzustandsphasendiagramm mit Hilfe einer Molekularfeldtheorie bestimmt. Der Einfluss von Verdünnung/Unordnung im lokalen Momentensystem auf die auftretenden Phasen wird analysiert. Im zweiten Teil der Arbeit wird das Hubbardmodell untersucht. Für dieses wird mit Hilfe einer modifizierten Störungstheorie (englisch: modified perturbation theory, MPT) eine wellenzahlabhängige (nicht-lokale) Selbstenergie abgeleitet, die sowohl für schwache als auch für starke Coulombwechselwirkungen gute Ergebnisse liefert. Mit dieser werden dann Spektraldichten und Quasiteilchenzustandsdichten berechnet, wobei insbesondere die nicht-lokalen Korrelationseffekte im Fokus stehen. Daneben werden Ergebnisse für die optische Leitfähigkeit, die in einer renormierten diagrammatischen Ein-Schleifen-Näherung berechnet wurden, besprochen. Es wird dann gezeigt, dass nur unter Beachtung der nicht-lokalen Korrelationseffekte ein ferromagnetisches Phasendiagramm konstruiert werden kann, das in Einklang mit dem Mermin-Wagner-Theorem steht. / The first part of this work deals with the Kondo-lattice model. The stationary Schrödinger equation is solved for the case of one electron in a ferromagnetically saturated local moment system (the magnetic polaron). The complete eigensystem is derived for the finite and infinite lattice. The time-dependent Schrödinger equation is then solved for arbitrary initial conditions and a detailed analysis of the down-electron decay dynamics is given. For finite band occupations the magnetic ground-state phase diagram is constructed within a mean-field theory. The effect of disorder/dilution in the local moment system on the phase diagram is discussed. The second part concentrates on the investigation of the Hubbard model. A nonlocal self-energy is derived within a modified perturbation theory that interpolates between weak and strong Coulomb repulsion. Results for the spectral density and quasiparticle density of states are shown with special attention to the effects of nonlocal correlations. Results for the optical conductivity within a renormalized one-loop approximation are also discussed. The main result of this section is the importance of nonlocal correlations for the fulfillment of the Mermin-Wagner theorem. A phase diagram that shows regions of ferromagnetic order is calculated for the simple cubic lattice.

Nesta tese, analisamos dois sistemas de semicondutores magnéticos: um semicondutor magnético cristalino de EuTe e uma heteroestrutura formada por um poço quântico de GaAs/AlGaAs ao lado uma barreira tipo delta de Mn, que, ao difundir-se, forma o semicondutor magnético diluído de (Ga,Mn)As. Nossos estudos foram focados na possibilidade de manipularmos oticamente a orientação magnética de ambos os sistemas. No semicondutor magnético de EuTe, a indução de magnetização se dá pela formação de polarons magnéticos ao redor de elétrons fotoexcitados. Para o estudo dos polarons, um modelo teórico elaborado foi adaptado para a construção de um sistema computacional baseado no método de Monte Carlo. Essa sistema permitiu o cálculo do momento magnético e do raio do polaron em temperaturas finitas, muito acima da temperatura de Néel. O modelo foi elaborado para reproduzir tanto as propriedades do EuTe sem o polaron (temperatura de Néel e campo crítico), quanto o deslocamento da linha de fotoluminescência devido a formação do polaron. Além do desenvolvimento do próprio método computacional, que pode ser utilizado para estudar outros sistemas, o conhecimento adquirido com o estudo do EuTe serviu como base para o estudo de um sistema mais complexo, que é a heteroestrutura de GaAs/AlGaAs + dMn. O estudo da heteroestrutura de GaAs/AlGaAs + dMn foi feito em cima de medidas experimentais de rotação de Kerr com resolução temporal. O sistema de medição construído permite, também, medidas de rotação de Kerr com resolução espacial, que servem para o estudo de transporte e hélice de spin em semicondutores, e está detalhadamente descrito em um dos capítulo desta tese. Na amostra estudada, o controle da magnetização dos íons de Mn é feito através da interação de troca com o elétron fotoexcitado no poço quântico. Os resultados obtidos das medidas de rotação de Kerr mostram uma frequência de precessão dependente do tempo, que revela a existência de dois processos com dinâmicas diferentes: uma primeira orientação do spin dos íons de Mn devido à polarização do par elétron-buraco no poço quântico, seguida por um realinhamento desses spins com o campo magnético externo, a partir do momento em que a coerência dos spins dos buracos desaparece. Esse resultado sugere que a interação entre os elétrons fotoexcitados e os íons de Mn ocorre por intermédio dos buracos fotoexcitados, ao contrário do que havia sido proposto em estudos anteriores de estruturas similares, mas de acordo com o modelo de interação sp-d, utilizado para explicar o ferromagnetismo do (Ga,Mn)As. / In this thesis we analyzed two magnetic semiconductor systems: one intrinsic magnetic semiconductor crystal of EuTe and one GaAs-based heterostructure with a GaAs/AlGaAs quantum well close to delta-type Mn barrier, that forms a diluted magnetic semiconductor of (Ga,Mn)As after diffusion. Our studies on both systems were focused on the possibility of optical manipulation of magnetic order. In EuTe pure semiconductor, the magnetization control occurs due to de formation od magnetic polarons around photo-excited electrons. To study magnetic polarons we adapted a theoretical model to build a computer simulation system based on Monte Carlo\'s method. This system allowed us to calculate the magnetic moment and radius of the polaron at finite temperatures fair above Néel Temperature. The computational model was tested to reproduce EuTe properties without polarons (Néel Temperature and critical magnetic field) and with polarons (photoluminescence line shift). Beside the development of this computational model, that can be used to study other systems, the knowledge acquired during the studies on EuTe helped us to better understand the more complex system of the GaAs/AlGaAs +dMn heterostructure. The studies about the GaAs/AlGaAs + dMn heterostructure were based on experimental measurements of time-resolved Kerr rotation. The measurement system we built also allows us to perform spatial-resolved Kerr rotation measurements to study spin transport and spin helix on semiconductors and it is described in details in one chapter of this thesis. The optical manipulation of Mn ions magnetization on the studied sample is consequence of the exchange interaction with the photoexcited electron inside the quantum well. The results of Kerr rotation measurements show a time-dependent precession frequency that reveals the existence of two process with distinct dynamics: the initial orientation of Mn ions spins with the photoexcited electron-hole pair, followed by the realignment of these spins with the external magnetic field, as soon as the photoexcited hole spins loose its coherence. These results indicate that the exchange interaction between the photoexcited electron inside the quantum well and the Mn ions is mediated by the photoexcited holes, in opposition of what was being proposed in previous studies of similar structures, but in agreement with the sp-d model, used to explain the (Ga,Mn)As ferromagnetism.

Nós calculamos o efeito da interação elétron-fonons longitudinais óticos (LO) sobre a energia de transição ls &#8594 2p+ entre os níveis de uma impureza doadora, localizada em um poço quântico de GaAs-AlxGa1-xAs. Nossos resultados para a energia de transição em função do campo magnético aplicado mostram claramente, que a saturação da energia de transição (efeito pinning) ocorre na energia dos fônons LO, em boa concordância com recentes dados experimentais. Obtemos também a massa de cíclotron de polarons confinados em fios quânticos quase-unidimensionais, com potencial de confinamento parabólico. Observamos que o comportamento da massa é diferente daquele para sistemas bi-dimensionais e que esta diferença é maior quanto maior o potencial de confinamento. Para a heterojunção de GaAs-AlGaAs e GaAs-GaSb, investigamos a importância da interação elétron-fonons interfaciais sobre a massa de cíclotron. Verificamos que a contribuição dos fonons interfaciais é fundamental nas regiões próximas às resonâncias, onde domina o espectro. Finalmente, calculamos a energia de ligação de uma impureza hidrogenóide, localizada no centro de um ponto quântico circular de GaAs-AlGaAs. Na ausência de campo magnético aplicado, obtivemos uma expressão analítica para a função de onda do elétron ligado. Notamos, que a influência do campo magnético sobre a energia de ligação é fraca nas regiões de pequenos raios, devido ao forte potencial de confinamento. / We calculate the effects of the electron-longitudinal optical (LO) phonons interaction on the intra donor ls &#8594 2p+ transition energy in GaAs-AlGaAs quantum wells structures. Our results to the transition energy as a function of the magnetic Field strength, show that the pinning effect occur in the phonon LO energy in good agreement with recent experimental data. The cyclotron mass of polarons confined in quasi.one.dimensional quantum-well wires with parabolic confinement potential, is also obtained. The behavior of electrons effective mass with magnetic field is different, of the two-dimensional systems, and the difference increase when the confinement potential increase. To heterojunctions of GaAs-AlAs and GaAs-GaSb, we investigate the electroninterfacials optical (IO) phonons interactions on the effective cyclotron mass. We find that the electron-IO-phonons interaction is fundamental near the resonances, where they dominate the spectra. Finally, the ground state binding energy of donor impurity, placed in the center of a circular quantum dot is calculated. Without magnetic field, we obtained the analytic expression to the bound electron wave function. The influence of the magnetic field on the donor binding energy is weaker, when the radius of the quantum dot became smaller.

Nesta tese, analisamos dois sistemas de semicondutores magnéticos: um semicondutor magnético cristalino de EuTe e uma heteroestrutura formada por um poço quântico de GaAs/AlGaAs ao lado uma barreira tipo delta de Mn, que, ao difundir-se, forma o semicondutor magnético diluído de (Ga,Mn)As. Nossos estudos foram focados na possibilidade de manipularmos oticamente a orientação magnética de ambos os sistemas. No semicondutor magnético de EuTe, a indução de magnetização se dá pela formação de polarons magnéticos ao redor de elétrons fotoexcitados. Para o estudo dos polarons, um modelo teórico elaborado foi adaptado para a construção de um sistema computacional baseado no método de Monte Carlo. Essa sistema permitiu o cálculo do momento magnético e do raio do polaron em temperaturas finitas, muito acima da temperatura de Néel. O modelo foi elaborado para reproduzir tanto as propriedades do EuTe sem o polaron (temperatura de Néel e campo crítico), quanto o deslocamento da linha de fotoluminescência devido a formação do polaron. Além do desenvolvimento do próprio método computacional, que pode ser utilizado para estudar outros sistemas, o conhecimento adquirido com o estudo do EuTe serviu como base para o estudo de um sistema mais complexo, que é a heteroestrutura de GaAs/AlGaAs + dMn. O estudo da heteroestrutura de GaAs/AlGaAs + dMn foi feito em cima de medidas experimentais de rotação de Kerr com resolução temporal. O sistema de medição construído permite, também, medidas de rotação de Kerr com resolução espacial, que servem para o estudo de transporte e hélice de spin em semicondutores, e está detalhadamente descrito em um dos capítulo desta tese. Na amostra estudada, o controle da magnetização dos íons de Mn é feito através da interação de troca com o elétron fotoexcitado no poço quântico. Os resultados obtidos das medidas de rotação de Kerr mostram uma frequência de precessão dependente do tempo, que revela a existência de dois processos com dinâmicas diferentes: uma primeira orientação do spin dos íons de Mn devido à polarização do par elétron-buraco no poço quântico, seguida por um realinhamento desses spins com o campo magnético externo, a partir do momento em que a coerência dos spins dos buracos desaparece. Esse resultado sugere que a interação entre os elétrons fotoexcitados e os íons de Mn ocorre por intermédio dos buracos fotoexcitados, ao contrário do que havia sido proposto em estudos anteriores de estruturas similares, mas de acordo com o modelo de interação sp-d, utilizado para explicar o ferromagnetismo do (Ga,Mn)As. / In this thesis we analyzed two magnetic semiconductor systems: one intrinsic magnetic semiconductor crystal of EuTe and one GaAs-based heterostructure with a GaAs/AlGaAs quantum well close to delta-type Mn barrier, that forms a diluted magnetic semiconductor of (Ga,Mn)As after diffusion. Our studies on both systems were focused on the possibility of optical manipulation of magnetic order. In EuTe pure semiconductor, the magnetization control occurs due to de formation od magnetic polarons around photo-excited electrons. To study magnetic polarons we adapted a theoretical model to build a computer simulation system based on Monte Carlo\'s method. This system allowed us to calculate the magnetic moment and radius of the polaron at finite temperatures fair above Néel Temperature. The computational model was tested to reproduce EuTe properties without polarons (Néel Temperature and critical magnetic field) and with polarons (photoluminescence line shift). Beside the development of this computational model, that can be used to study other systems, the knowledge acquired during the studies on EuTe helped us to better understand the more complex system of the GaAs/AlGaAs +dMn heterostructure. The studies about the GaAs/AlGaAs + dMn heterostructure were based on experimental measurements of time-resolved Kerr rotation. The measurement system we built also allows us to perform spatial-resolved Kerr rotation measurements to study spin transport and spin helix on semiconductors and it is described in details in one chapter of this thesis. The optical manipulation of Mn ions magnetization on the studied sample is consequence of the exchange interaction with the photoexcited electron inside the quantum well. The results of Kerr rotation measurements show a time-dependent precession frequency that reveals the existence of two process with distinct dynamics: the initial orientation of Mn ions spins with the photoexcited electron-hole pair, followed by the realignment of these spins with the external magnetic field, as soon as the photoexcited hole spins loose its coherence. These results indicate that the exchange interaction between the photoexcited electron inside the quantum well and the Mn ions is mediated by the photoexcited holes, in opposition of what was being proposed in previous studies of similar structures, but in agreement with the sp-d model, used to explain the (Ga,Mn)As ferromagnetism.

Nós calculamos o efeito da interação elétron-fonons longitudinais óticos (LO) sobre a energia de transição ls &#8594 2p+ entre os níveis de uma impureza doadora, localizada em um poço quântico de GaAs-AlxGa1-xAs. Nossos resultados para a energia de transição em função do campo magnético aplicado mostram claramente, que a saturação da energia de transição (efeito pinning) ocorre na energia dos fônons LO, em boa concordância com recentes dados experimentais. Obtemos também a massa de cíclotron de polarons confinados em fios quânticos quase-unidimensionais, com potencial de confinamento parabólico. Observamos que o comportamento da massa é diferente daquele para sistemas bi-dimensionais e que esta diferença é maior quanto maior o potencial de confinamento. Para a heterojunção de GaAs-AlGaAs e GaAs-GaSb, investigamos a importância da interação elétron-fonons interfaciais sobre a massa de cíclotron. Verificamos que a contribuição dos fonons interfaciais é fundamental nas regiões próximas às resonâncias, onde domina o espectro. Finalmente, calculamos a energia de ligação de uma impureza hidrogenóide, localizada no centro de um ponto quântico circular de GaAs-AlGaAs. Na ausência de campo magnético aplicado, obtivemos uma expressão analítica para a função de onda do elétron ligado. Notamos, que a influência do campo magnético sobre a energia de ligação é fraca nas regiões de pequenos raios, devido ao forte potencial de confinamento. / We calculate the effects of the electron-longitudinal optical (LO) phonons interaction on the intra donor ls &#8594 2p+ transition energy in GaAs-AlGaAs quantum wells structures. Our results to the transition energy as a function of the magnetic Field strength, show that the pinning effect occur in the phonon LO energy in good agreement with recent experimental data. The cyclotron mass of polarons confined in quasi.one.dimensional quantum-well wires with parabolic confinement potential, is also obtained. The behavior of electrons effective mass with magnetic field is different, of the two-dimensional systems, and the difference increase when the confinement potential increase. To heterojunctions of GaAs-AlAs and GaAs-GaSb, we investigate the electroninterfacials optical (IO) phonons interactions on the effective cyclotron mass. We find that the electron-IO-phonons interaction is fundamental near the resonances, where they dominate the spectra. Finally, the ground state binding energy of donor impurity, placed in the center of a circular quantum dot is calculated. Without magnetic field, we obtained the analytic expression to the bound electron wave function. The influence of the magnetic field on the donor binding energy is weaker, when the radius of the quantum dot became smaller.

Gegenstand der vorliegenden Dissertation ist die Untersuchung von Ca-dotierten PrMnO3 (PCMO) als Katalysator für die (photo)elektrochemische Wasseroxidation. Im Fokus der Untersuchungen stehen die folgenden elementaren Schritte des Gesamtprozesses: i) Die optische Absorption in PCMO wird zunächst als Funktion der Ca-Dotierung und der Temperatur untersucht mit dem Ziel, den Einfluß von Korrelationseffekten auf die optischen Eigenschaften zu verstehen. Die präsentierten Ergebnisse zeigen, dass die Bildung kleiner Polaronen im PCMO als Folge starker Korrelationswechselwirkungen in breites Absorptionsmaximum im Nah-Infrarot bis sichtbarem Energiebereich verursacht, welches im Rahmen eines Photonen-assistierten Polaronenhüpfprozesses und einer Anregung zwischen Jahn-Teller-aufgespaltenen Zuständen diskutiert wird. Weiterhin legt die Dotierungsabhängigkeit der Spektren nahe, dass O 2p und Mn 3d Hybridzustände die Fermienergie-nahe elektronische Struktur bestimmen, wobei der relative Anteil von O 2p mit der Ca-Dotierung variiert. ii) Der aktive Zustand von PCMO in Kontakt mit Wasser bzw. Wasserdampf wird mit Hilfe von Zyklovoltammetrie und in situ ‚environmental‘ Transmissionselektronenmikroskopie (ETEM) für verschiedene Dotierlevels untersucht. Die Ergebnisse beider Methoden ergeben, dass die katalysierte Wasseroxidation gemäß $2\text{H}_2\text{O} \rightarrow \text{O}_2 + 4 \text{H}^+$ mit einem Korrosionsprozess in Form einer Pr/Ca Verarmung und Amorphisierung der PCMO-Elektrode konkurriert. Die höchste katalytische Aktivität sowie Korrosionsstabilität werden im mittleren Dotierungsbereich gefunden. Auf Basis der in situ ETEM Ergebnisse wird außerdem gezeigt, dass durch Zufügen von Monosilan zu Wasserdampf-basierten Elektrolyten im ETEM eine Elektronenstrahl-induzierte Wasseroxidation an aktiven PCMO Oberflächen über die Sekundärreaktion $\text{SiH}_4+2\text{O}_2\rightarrow\text{SiO}_2+2\text{H}_2\text{O}$ nachgewiesen werden kann. Elektronenenergieverlustspektroskopie von PCMO vor und nach der Reaktion in Wasserdampf ergeben, dass der aktive Zustand von PCMO die Bildung und Ausheilung von Sauerstoffleerstellen im Rahmen einer Interkalation des bei der Wasseroxidation freiwerdenden Sauerstoffs beinhaltet. Die Rolle des Elektronenstrahls als Triebkraft für die Wasseroxidation im ETEM wird mithilfe von Elektronenholographie und elektrischen Experimenten sowie theoretischer Modellierung basierend auf Sekundärelektronenemissionen als ein positives Elektronenstrahl-induziertes elektrisches Potential identifiziert.

In dieser Arbeit wird Terahertzspektroskopie (THz) eingesetzt, um nichtlineare niederfrequente Anregungen von kondensierter Materie zu untersuchen. Insbesondere die Anwendung zweidimensionaler (2D) THz-Spektroskopie ermöglicht es, verschiedene Beiträge zu nichtlinearen Signalen zu entflechten. Zunächst wird die nichtlineare polaronische Antwort solvatisierter Elektronen und umliegenden Lösungsmittelmolekülen in der polaren Flüssigkeit Isopropanol erforscht. Solvatisierte Elektronen werden durch Multiphotonen-Ionisation erzeugt. Longitudinale Polaronoszillationen mit THz-Frequenzen werden während der ultraschnellen Lokalisierung der Elektronen impulsiv angeregt. Die Störung solcher Polaronschwingungen mit einem externen THz-Impuls führt zu nichtlinearen Änderungen der transversalen Polaron-Polarisierbarkeit, die sich in deutlichen Änderungen der Oszillationsphase zeigen. Darüber hinaus wird die Erzeugung monozyklischer THz-Impulse in asymmetrischen Halbleiter-Quantentrögen bei resonanter Intersubband-Anregung im Mittelinfraroten (MIR) demonstriert. Die zeitliche Form des emittierten elektrischen THz-Feldes wird durch die Steuerung der Impulsdauer und des elektrischen Feldes der MIR Impulse verändert. Phasenaufgelöste 2D-MIR-Experimente bestätigen, dass die THz-Emission vorrangig auf einen nichtlinearen Verschiebungsstrom bei Femtosekunden-Intersubband-Anregung zurückzuführen ist. Der Einfluss von Intra- und Interbandströmen auf Symmetrieeigenschaften wird in 2D-THz-Experimenten an Wismut demonstriert. Nichtperturbative langwellige Anregung von Ladungsträgern nahe der L-Punkte führt zu einer anisotropen Ladungsträgerverteilung, die sich in einer hexagonalen Winkelabhängigkeit der pump-induzierten THz Transmission manifestiert. Eine damit einhergehende Symmetrieverringerung für bestimmte elektrische Feldpolarisationen erlaubt die Anregung von Zonenrand-Phononen, welche sich in in oszillierenden Signalen in der nichtlinearen 2D-THz-Antwort manifestieren. / This thesis exploits techniques of terahertz (THz) spectroscopy to investigate nonlinear low-frequency excitations of condensed matter. In particular, application of two-dimensional (2D) THz spectroscopy allows to disentangle different nonlinear signal contributions. The nonlinear polaronic response of solvated electrons and their surrounding solvent molecules in the polar liquid isopronal is studied. Solvated electrons are generated via multiphoton ionization. Longitudinal polaron oscillations with THz frequencies are impulsively excited during the ultrafast localization of the electrons. Perturbation of such polaron oscillations with an external THz pulse induces nonlinear changes of the transverse polaron polarizability, reflected in distinct modifications to the oscillation phase as mapped in 2D-THz experiments. Further, the generation of mono-cycle THz pulses from asymmetric semiconductor quantum wells upon resonant intersubband excitation in the mid-infrared (MIR) range is demonstrated. The temporal shape of the emitted THz electric field is modified by controlling pulse duration and peak electric field of the MIR driving pulses. Phase-resolved 2D-MIR experiments confirm that the THz emission is predominantly due to a nonlinear shift current generated upon femtosecond intersubband excitation. The influence of combined intra- and interband currents on symmetry properties, which opens novel quantum pathways for phonon excitation in narrow-band-gap materials, is demonstrated by 2D-THz experiments on bismuth. Nonperturbative long-wavelength excitation of charge carriers close to the L points leads to an anisotropic carrier distribution, reflected in a six-fold azimuthal angular dependence of the pump-induced change of THz transmission. A concomitant symmetry reduction for certain electric-field polarizations allows for the excitation of phonons at the zone boundary which are reflected in oscillatory signals in the nonlinear 2D-THz response.

Dans un semiconducteur polaire, la propagation d'un phonon optique longitudinal s'accompagne d'un champ électrique macroscopique qui se couple aux porteurs libres pour donner naissance à l'effet magnéto-polaron résonant. Cet effet est une des manifestations les plus spectaculaires de l'interaction électron-phonon dans un milieu polaire et devrait se manifester par un comportement d'anti croisement entre les niveaux de Landau. Du point de vue expérimental, les résultats sont souvent masqués par la forte absorption du substrat et cette interaction n'a jamais été clairement observée. Nous avons pu résoudre ce problème en décollant les structures de leur substrat originel de GaAs pour les recoller sur un substrat de silicium qui est transparent dans l'infrarouge lointain. Ces structures décollées nous permettent de mesurer, de manière absolue, la transmission dans la région énergétique des phonons optiques de GaAs. Je présenterai des expériences de transmission infra rouge effectuées sur une série de puits quantiques de GaAs de haute mobilité et fortement dopées en configuration de Faraday perpendiculaire et de Faraday oblique. Les résultats seront interprétés dans le formalisme de la fonction diélectrique.

The fact that loosely bonded DNA bases could tolerate large structural fluctuations, form a dissipative environment for a charge traveling through the DNA. Nonlinear stochastic nature of structural fluctuations facilitates rich charge dynamics in DNA. We study the complex charge dynamics by solving a nonlinear, stochastic, coupled system of differential equations. Charge transfer between donor and acceptor in DNA occurs via different mechanisms depending on the distance between donor and acceptor. It changes from tunneling regime to a polaron assisted hopping regime depending on the donor-acceptor separation. Also we found that charge transport strongly depends on the feasibility of polaron formation. Hence it has complex dependence on temperature and charge-vibrations coupling strength. Mismatched base pairs, such as different conformations of the G・A mispair, cause only minor structural changes in the host DNA molecule, thereby making mispair recognition an arduous task. Electron transport in DNA that depends strongly on the hopping transfer integrals between the nearest base pairs, which in turn are affected by the presence of a mispair, might be an attractive approach in this regard. I report here on our investigations, via the I –V characteristics, of the effect of a mispair on the electrical properties of homogeneous and generic DNA molecules. The I –V characteristics of DNA were studied numerically within the double-stranded tight-binding model. The parameters of the tight-binding model, such as the transfer integrals and on-site energies, are determined from first-principles calculations. The changes in electrical current through the DNA chain due to the presence of a mispair depend on the conformation of the G・A mispair and are appreciable for DNA consisting of up to 90 base pairs. For homogeneous DNA sequences the current through DNA is suppressed and the strongest suppression is realized for the G(anti)・A(syn) conformation of the G・A mispair. For inhomogeneous (generic) DNA molecules, the mispair result can be either suppression or an enhancement of the current, depending on the type of mispairs and actual DNA sequence.