In this thesis, original theoretical and numerical investigations into the interaction of light with excitonic nanostructures are presented, in a bid to demonstrate that excitonic nanostructures are viable alternatives to the use of plasmonic nanostructures where electric field enhancement and confinement are sought. In particular, the field enhancement and confinement around excitonic nanostructures on resonance is shown to be comparable if not in excess of that around noble metal nanoparticles such as gold and silver. These excitonic modes, when set in the context of a core-shell geometry, are shown to offer tunability through nanoparticle design and through the index of the environment. In addition, hybrid `hyperbolic' and `plexcitonic' modes are shown to offer similar properties in metallic-excitonic nanostructures. Altogether, these excitonic and hybrid excitonic modes are shown to have potential in nanophotonic applications.

No description available.

In two dimensions, non-trivial topology and enhanced correlation lead to amazing physical phenomena. Graphene offers a high-quality, ultra-tunable and integratable two dimensional electron system in the study of interacting and topological quantum fluids. In this thesis we studied in detail various emergent quantum phenomena of electron fluids due to both strong in-plane and out-of-plane interaction between electrons in single and multi-layer graphene systems. Using magnetoresistance measurement in the corbino disk geometry, we manged to quantitatively measure the viscosity of electrons in monolayer and bilayer graphene as a function of carrier density and temperature. We demonstrated a crossover between degenerate Fermi liquid and non-degenerate electron-hole liquid. In the quantum Hall regime, we applied the corbino geometry as a probe of the incompressible sample bulk, improving significantly the resolution of fragile quantum Hall states compared to Hall bar devices. The improved resolution enables quantitative studies over a much broader parameter space in both singlelayer and multi-layer graphene system. In double-layer graphene where two vertically stacked graphene layers are in close proximity but electrically separated by a thin hBN tunnel barrier, we observed sequence of FQHS which can be perfectly described by two-component composite fermion theory. Using a combination of different measurement configuration, we found evidence for a novel type of two-component non-abelian FQHS. At \nu = 1 in double-layer graphene where ground states of indirect excitons occur, we mappped out the entire phase diagram. We realized BEC-BCS crossover in the exciton condensation phase tunable with both magnetic field and electrostatic gating. At small exciton filling fraction, we discovered Wigner crystal of excitons. Lastly, we realized a strongly correlated triple-layer quantum Hall system with independent control of carrier density in each layer and demonstrated three-layer coherent quantum Hall effect at total integer filling fraction and possibly fractional filling fraction.

Singlet fission, the conversion of one photoexcited singlet exciton into two triplet excitons, is a promising mechanism to overcome theoretical efficiency limits in single-junction solar cells. Intramolecular singlet fission materials based on molecular dimers are a powerful platform to study singlet fission since triplet dynamics can be fine-tuned through chemical structure. This thesis describes the critical nature of the molecular bridge between singlet fission chromophores in determining the fate of the triplet pair. We demonstrate how bridge energetics, connectivity, length, and planarity are tunable handles for controlling rates of triplet pair generation and recombination. These rates can even be modulated independent of each other, furnishing materials with desirable properties such as fast triplet generation and long triplet lifetimes. This thesis establishes key design principles to provide greater control over triplet pair formation, dephasing, and decay in intramolecular singlet fission materials. Chapter 1 introduces the process of singlet fission and provides an overview of the progress and challenges in the field. In Chapters 2 and 3, we detail the significance of bridge frontier molecular orbital energies and connectivity patterns in mediating triplet pair formation in bridged pentacene and tetracene dimers. We highlight key observables in the linear absorption spectra to predict relative rates of triplet pair formation, and demonstrate how quantum interference graphical models from single-molecule electronics can successfully be applied to explain triplet pair formation behavior in singlet fission. In Chapter 4, we investigate triplet pair recombination in these materials and propose that electronic coupling alone does not dictate triplet pair dephasing and decay. In Chapter 5, we present a new singlet fission chromophore and identify important triplet population signatures distinguishing singlet fission from intersystem crossing in contiguous dimers. Lastly, in Chapter 6, we explore dendrimers as a controlled macromolecular architecture to study singlet fission.

No description available.

Cette thèse théorique s'inscrit dans l'univers de l'Informatique quantique et celui du transfert d'énergie. Nous étudions le transport quantique d'un exciton utilisé dans le but de véhiculer une information quantique, ou de l'énergie, sur des graphes moléculaires complexes. Dans ce contexte, nous nous intéressons aux effets de différents environnements quantiques pouvant moduler le transport excitonique. Une première partie du manuscrit porte sur le transport d'information quantique en pré­sence d'un environnement de phonons locaux. Dans ce contexte, nous introduisons une ap­proche théorique appelée PT* permettant de traiter sur un pied d'égalité exciton et pho­nons. Cette théorie est tout d'abord appliquée au cas particulier du graphe en étoile. Par la suite, PT* est comparée à des calculs exacts menés sur une collection de graphes variés. Nous montrons ainsi que la théorie PT* possède une très grande force de prédictibilité et de multiples avantages théoriques et numériques ( durée de simulation, interprétations liées à l'intrication ... ) . Dans une deuxième partie du manuscrit, nous étudions le transport quantique d'énergie sur un graphe complexe en contact avec un système externe absorbant. Nous nous intéressons tout particulièrement à la caractérisation du phénomène d'absorption énergétique et son opti­misation (transition de superradiance). Nous mettons en évidence l'impact de la topologie du réseau sur l'évolution du processus d'absorption. Pour étendre cette étude, nous considérons ensuite la présence d'un désordre local brisant la symétrie du réseau de base. Nous montrons alors que le désordre peut influencer positivement l'évolution du processus d'absorption. / The scope of this PhD is twofold and can be integrated simultaneously in quantum infor­mation theory and energy transport. We theoretically study the excitonic quantum transport in order to transmit either quantum information or energy on complex molecular networks. In this context, we pay a special attention to the modulations that different quantum envi­ronments can generate on the excitonic transport. In a first part of the manuscript, we focus on the quantum transport of information in the presence of a local phononic environment. In this context, we introduce a theoretical approach, named PT*, treating on an equal footing exciton and phonons. Firstly, this theory is applied to a particular case : the star graph. Then, PT* is compared to exact numerical calculations realized on a collection of different graphs. In this context, we demonstrate that the PT* approach shows a very strong predictability but also several theoretical and numerical advantages (simulation duration, entanglement interpretations ... ). In a second part of the manuscript, we study the quantum transport of energy on a complex graph in contact with an external absorbing system. We focus on the optimisation of the absorption process ("superradiance transition"). We demonstrate that the topology of the considered network influences the absorption evolution. In order to extend this study, we then consider the presence of a local disorder breaking the inner symetry of the graph. In this context, we show that the disorder can benefically influence the absorption process.

Neste trabalho, foram investigados os processos de migração e dissociação do éxciton em filmes ultrafinos de poli(9,9 dioctilfluoreno) (PFO) com espessura menores que o raio típico de migração excitônica (10 nm) próximos de interface semicondutora orgânica e inorgânica. Os filmes de PFO foram produzidos utilizando a técnica de <span style=\'color:black;font-style:italic;language:PT-BR\'>spin-coating<span style=\'color:black;language:PT-BR\'> a partir de soluções de PFO em clorofórmio e em tolueno. Sabe-se que ao se utilizar o clorofórmio como solvente, os filmes de PFO apresentam uma estrutura amorfa. Com isso foi possível obter filmes com espessuras menores que o raio de migração do éxciton com qualidades ideais para o estudo de processos fotofísicos. Esses filmes foram depositados sobre uma camada de nanopartículas de dióxido de titânio (TiO<span style=\'color:black;language:PT-BR\'>2<span style=\'color:black;language:PT-BR\'>) formando assim uma interface orgânica/inorgânica. Técnicas espectroscópicas, tais como, microscopia confocal de fluorescência (LSCM), microscopia de imagem do tempo de vida (FLIM), fotoluminescência de onda contínua e resolvida no tempo bem como espectroscopia de absorção foram utilizadas no presente trabalho. Inicialmente o espectro de fotoluminescência dos filmes de PFO foram caracterizados através da dependência da intensidade da transição puramente eletrônica <span style=\'color:black;font-style:italic;language:PT-BR\'>I<span style=\'color:black;language:PT-BR\'>, largura da linha a meia altura <span style=\'font-family:Symbol;color:black;language:PT-BR\'>G<span style=\'color:black;language:PT-BR\'>o<span style=\'color:black; language:PT-BR\'>, energia da transição puramente eletrônica <span style=\'color:black;font-style:italic;language:PT-BR\'>E<span style=\'color:black;language:PT-BR\'> e parâmetro de Huang-Rhys <span style=\'color:black;font-style:italic;language:PT-BR\'>S<span style=\'color:black;language:PT-BR\'> variando a temperatura. Verificou-se que a intensidade pode ser descrita em termos da ativação térmica da migração do éxciton. Além disso, a temperatura introduz uma desordem térmica que afeta diretamente o tamanho dos segmentos conjugados que é observado em termos dos parâmetros, <span style=\'font-family:Symbol;color:black;language:PT-BR\'>G<span style=\'color:black;language:PT-BR\'>o<span style=\'color:black; language:PT-BR\'>, <span style=\'color:black;font-style:italic; language:PT-BR\'>E<span style=\'color:black;language:PT-BR\'> e <span style=\'color:black;font-style:italic;language:PT-BR\'>S<span style=\'color:black;language:PT-BR\'>. Com os filmes de PFO produzidos com o solvente tolueno foi observado que frações de fase <span style=\'font-family:\"Times New Roman\";color:black;font-style:italic; language:EL\'>&#946;<span style=\'font-family:\"Times New Roman\"; color:black;language:EL\'> <span style=\'color:black;language:PT-BR\'>já são induzidas nesses filmes e que esta fase não está dispersa na matriz amorfa e sim em forma de domínios formados por moléculas na fase <span style=\'font-family:\"Times New Roman\";color:black;font-style:italic; language:EL\'>&#946; <span style=\'color:black;language:PT-BR\'>que correspondente ao ordenamento nos anéis aromáticos do PFO. Também foi observado que nos filmes com espessura menor que 10 nm preparados em clorofórmio, a fase <span style=\'font-family:\"Times New Roman\";color:black;font-style:italic; language:EL\'>&#946;<span style=\'font-family:\"Times New Roman\"; color:black;language:EL\'> <span style=\'color:black;language:PT-BR\'>é induzida e sugerimos que isso ocorre devido a forte interação filme/substrato. Além disso, outros métodos bem conhecidos na literatura, tais como, tratamento a vapor de tolueno e ciclos térmicos de resfriamento/aquecimento foram utilizados para induzir a fase <span style=\'font-family:\"Times New Roman\";color:black;font-style:italic; language:EL\'>&#946;<span style=\'font-family:\"Times New Roman\"; color:black;language:EL\'> <span style=\'color:black;language:PT-BR\'>em filmes de PFO amorfo. Com relação aos filmes contendo a interface TiO<span style=\'color:black;language:PT-BR\'>2<span style=\'color:black;language:PT-BR\'>/PFO, a dissociação do éxciton na interface foi observada através da redução da intensidade da fotoluminescência. Em filmes ultrafinos, a eficiência do processo de dissociação do éxciton na interface é superior a 90%. A partir desses resultados, obteve-se que o raio de migração do éxciton no PFO é de (13 <span style=\'font-family:Symbol;color:black;language:PT-BR\'>±<span style=\'color:black;language:PT-BR\'> 3) nm. Além disso, devido à alta fluência (~ 10<span style=\'color:black;language:PT-BR\'>25<span style=\'color:black;language:PT-BR\'> fótons/cm<span style=\'color:black;language:PT-BR\'>2<span style=\'color:black;language:PT-BR\'>s), efeitos de autoaniquilamento de éxcitons em filmes ultrafinos foram observados nas medidas de tempo de decaimento radiativo. Por fim, em filmes de PFO (contendo a fase <span style=\'font-family:\"Times New Roman\";color:black;font-style:italic; language:EL\'>&#946;<span style=\'font-family:\"Times New Roman\"; color:black;language:EL\'>) <span style=\'color:black;language:PT-BR\'>depositados sobre o TiO<span style=\'color:black;language:PT-BR\'>2<span style=\'color:black;language:PT-BR\'>, somente os éxcitons das regiões amorfas migram até a interface do TiO<span style=\'color:black;language:PT-BR\'>2<span style=\'color:black;language:PT-BR\'> e são dissociados por ela. A energia térmica a temperatura ambiente promove uma maior eficiência da dissociação do éxciton do que em baixas temperaturas (~5 K). No entanto, mesmo em temperatura ambiente, as moléculas de fase <span style=\'font-family:\"Times New Roman\";color:black;font-style:italic; language:EL\'>&#946;<span style=\'font-family:\"Times New Roman\"; color:black;language:EL\'> <span style=\'color:black;language:PT-BR\'>atuam como centros de captura dos éxcitons competindo com o processo de dissociação. A partir desses resultados, obteve-se que o raio de transferência de energia no PFO é igual a (3,5 <span style=\'color:black;text-decoration:underline;language:PT-BR\'>+<span style=\'color:black;language:PT-BR\'> 0,5) nm.<span style=\'color:black; language:PT-BR\'> <![if !vml]> <![endif]> / In this work, we investigated the process of exciton dissociation and migration in ultra-thin films of poly (9,9 dioctilfluoreno) (PFO) with a thickness smaller than the typical radius of excitonic migration (10 nm) and near to organic and inorganic semiconductor interface. The PFO films were produced using the spin-coating technique from a PFO solution in chloroform and toluene. It is known that when using chloroform as solvent, the PFO films have an amorphous structure. Thus, it was possible to obtain films that have thicknesses smaller than the radius of the exciton migration qualities, which is ideal to study photophysical processes. These films were deposited on the titanium dioxide (TiO<span style=\'language:EN\'>2<span style=\'language:EN\'>) nanoparticles layer forming an organic/inorganic interface. Spectroscopic techniques such as fluorescence confocal microscopy (LSCM), fluorescence lifetime imaging microscopy (FLIM), continuous wave photoluminescence and time resolved and absorption spectroscopy were used in this study. First, the photoluminescence spectrum of PFO films were characterized by the dependence of the purely electronic transition intensity <span style=\'font-style:italic;language:EN\'>I<span style=\'language:EN\'>, full width at half maximum <span style=\'font-family:Symbol;language:EN\'>G<span style=\'language: EN\'>o<span style=\'language:EN\'>, purely electronic transition energy <span style=\'font-style:italic;language:EN\'>E<span style=\'language:EN\'> and Huang-Rhys parameter <span style=\'font-style:italic;language:EN\'>S <span style=\'language:EN\'>with the temperature. It was showed that the intensity can be described according to thermal activation of the exciton migration. Furthermore, the temperature introduces a thermal disorder affecting directly the conjugated segment length which is observed according to the parameters, <span style=\'font-family:Symbol;language:EN\'>G<span style=\'language: EN\'>o<span style=\'language:EN\'>, <span style=\'font-style: italic;language:EN\'>E<span style=\'language:EN\'> e <span style=\'font-style:italic;language:EN\'>S<span style=\'language:EN\'>. The PFO films produced with the solvent toluene analysis showed that the fractions of <span style=\'font-family:\"Times New Roman\";font-style:italic;language:EN\'>&#946;<span style=\'language:EN\'> phase are already induced and that this phase is not dispersed in the amorphous matrix. On the order hand, they are shaped domains formed by <span style=\'font-family:\"Times New Roman\";font-style:italic;language:EN\'>&#946;<span style=\'language:EN\'> phase molecules that are related to the PFO aromatic rings organization. It was also observed that the films with thickness smaller than 10 nm prepared using chloroform, the <span style=\'font-family:\"Times New Roman\";font-style:italic;language:EN\'>&#946;<span style=\'language:EN\'> phase is induced, which may be occurring due to the strong interaction observed between film and substrate. Other methods reported in the literature, such as toluene steam treatment and thermal cycles of cooling/heating were used to induce <span style=\'font-family:\"Times New Roman\";font-style:italic;language:EN\'>&#946;<span style=\'language:EN\'> phase in amorphous PFO films as well. The exciton dissociation at the interface in films containing TiO<span style=\'language:EN\'>2<span style=\'language:EN\'>/PFO interface were observed by reduction of photoluminescence intensity; and this same efficiency in ultra-thin films is higher than 90%. From these results, it was reported that the exciton migration radius in PFO is (13 <span style=\'font-family:Symbol;language:EN\'>±<span style=\'language:EN\'> 3) nm. Furthermore, effects of excitons annihilation in ultra-thin films were observed in the decay time radiative measurements due to high fluency (~ 10<span style=\'language:EN\'>25<span style=\'language:EN\'> photons/cm<span style=\'language:EN\'>2<span style=\'language:EN\'>s). Finally, in PFO films (with the <span style=\'font-family:\"Times New Roman\";font-style:italic;language:EN\'>&#946;<span style=\'language:EN\'> phase) deposited on the TiO<span style=\'language:EN\'>2 <span style=\'language:EN\'>just the exciton of amorphous regions migrates to the TiO<span style=\'language:EN\'>2<span style=\'language:EN\'> interface, which dissociates them. The thermal energy at room temperature promotes higher efficiency than the exciton dissociation at low temperatures (~ 5 K). However, even at room temperature, the <span style=\'font-family:\"Times New Roman\";font-style:italic;language:EN\'>&#946;<span style=\'language:EN\'> phase molecules act as the most important molecules to capture exciton, competing to the exciton dissociation process. These results conducted to conclude that the energy transfer radius in PFO is equal to (3.5 <span style=\'text-decoration:underline;language:EN\'>+<span style=\'language: EN\'> 0.5) nm. <![if !vml]> <![endif]>

A theory of the carrier transport, optical emission, and photoconductivity from optoelectronic devices based on ambipolar long-channel carbon-nanotube (CNT) field-effect transistors (FETs) is presented in this dissertation. In optical emitters based on ambipolar long-channel CNT FETs, an analytic diffusive-transport model for various recombination mechanisms is provided for the first time. The relationship and the scaling of emitted light-spot size and emitted optical power are clearly depicted for the first time as well. We also implement a numerical diffusive-transport approach for the light emission, in which the focus is on the effects of radiative and nonradiative recombination in the channel, with the movement of the spatial recombination profile in response to the gate and drain voltages. For the first time, we find that the emitted light-spot size and the emitted optical power depend sensitively on the operative nonradiative recombination mechanisms. We implement a numerical diffusive-transport approach including exciton photogeneration as well for photoconductors based on ambipolar long-channel CNT FETs with uniform and near-field photoexcitation. We show that the photocurrents are typically much smaller than the dark currents, and explain some possible reasons. Moreover, the exciton densities in CNTs are calculated and the effect of exciton diffusion is presented.

I present a detailed study of many-body effects associated with the interband 1s transition and intraband 1s-2p transition in two- and three-dimensional photo-excited semiconductors. I employ a previously developed excitonic model to treat effects of exchange and phase space filling. I extend the scope of the model to include static free-carrier screening. I also develop a factorization scheme to obtain a consistent set of excitonic dynamical equations. The exciton transition energies are renormalized by many-body interactions, and the excitonic dynamical equations provide simple expressions for the individual contributions of screening, phase space filling and exchange. The effects of exchange and phase space filling are quantified by a set of excitonic coefficients. I first calculate these coefficients analytically by omitting screening effects. In contrast, the screened coefficients involve multi-dimensional integrals which must be evaluated numerically. I present a detailed discussion of the numerical methods used to evaluate these integrals, which include a novel algorithm for segmenting multi-dimensional integration regions. The excitonic model correctly predicts the blue shift and bleaching of the 1s exciton resonance due to exchange and phase space filling. Free-carrier screening is found to enhance these effects by lowering the exciton binding energy. In contrast, the effects of free-carrier screening on the 1s-2p transition energy are more subtle. In the absence of free-carrier screening, exchange and phase space filling lead to a blue shift of the transition energy. However, screening decreases the 1s binding energy faster than the 2p binding energy, which in turn decreases the transition energy. Thus, screening effects oppose exchange and phase space filling, and the overall magnitude and sign of the 1s-2p transition energy shift depends on the free-carrier density. Specifically, for low-moderate excitation densities exchange and phase space filling can be dominated by screening, leading to a net red shift of the transition energy. The results for two- and three-dimensional systems are qualitatively similar, although the magnitudes of the shifts are much smaller in three dimensions. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2011-05-31 15:58:27.222

Les polaritons de microcavité sont des états hybrides lumière-matière à caractère bosonique.Dans les dernières décennies, un grand intérêt a été accordé à leur phase de condensation de Bose-Einstein.Nous avons développé dans ce travail des outils théoriques et numériques pour comprendre et interpréter la dynamique spatiale et temporelle de la formation des condensats de polaritons.Nous avons proposé une approche numérique pour la résolution complète des équations couplées du modèle Gross-Pitaevskii généralisé à deux dimensions en coordonnées cartésiennes.Nous avons cherché à comprendre les aspects du seuil de condensation sous différentes configurations spatiales et temporelles d'excitation optique non résonante.Nous avons en particulier proposé une nouvelle approche pour définir le seuil.Enfin, pour une condensation sous exciation focalisée, dans une microcavité ZnO, nous avons pu accéder à, et comprendre, quelques propriétés vues dans les expériences. / Microcavity polaritons are hybrid light-material states of a bosonic nature.In the last decades, an enormous interest has been paid to their Bose-Einstein condensation phase.We develop, in this work the theoretical and numerical tools to understand and interpret the spatial and temporal dynamics of the formation of condensates of polaritons.We propose a numerical approach for the comprehensive resolution of the generalized Gross-Pitaevskii model in two-dimensions in Cartesian coordinates.We sought to understand the aspects of the condensation threshold under different spatial and temporal configurations of non-resonant optical excitation.In particular, we propose a new approach to define the threshold.Finally, for a condensation under a focal exciation in a ZnO microcavity, we were able to access, and understand, some of the experimentally observed properties.