Ce travail de thèse porte sur l’étude des propriétés optiques et électroniques des puits quantiques de GaN / AlGaN grâce à des techniques classiques de réflectivité résolue en angle et de photoluminescence, ainsi qu’avec la technique de photoluminescence résolue temporellement. Les expériences de photoluminescence en régime continu ont permis d’estimer les énergies des transitions excitoniques qui sont également accessibles en réflectivité. Ces techniques ont ainsi permis de mettre en évidence l’effet Stark dans les puits quantiques GaN / AlGaN. L’effet Stark sur les énergies de transition est cohérent avec la théorie des fonctions enveloppes. Les spectres de réflectivité permettent d’accéder à la force d’oscillateur des excitons grâce à leur modélisation par le formalisme des matrices de transfert, prenant en compte les phénomènes d’élargissement homogène et inhomogènes des transitions optiques. Enfin, les mesures de photoluminescence résolue en temps en fonction de la température, ont également permis d’extraire la force d’oscillateur qui est inversement proportionnelle au temps de recombinaison radiative. Cette étude a également permis de mettre en évidence l’effet Stark responsable de la diminution de la force d’oscillateur en fonction de l’épaisseur du puits quantique mais aussi en fonction de la composition d’aluminium. L’augmentation de l’épaisseur du puits entraîne une diminution du recouvrement des fonctions d’onde, et une augmentation de la composition d’aluminium intensifie le champ électrique et diminue également le recouvrement des fonctions d’onde. / This work deals with the study of optical and electronic properties of GaN / AlGaN quantum wells, by classical techniques of spectroscopy including angle resolved reflectivity or photoluminescence, but also by time resolved photoluminescence. The continuous wave photoluminescence experiments allowed estimating the energies of the excitonic transitions, which are also available through reflectivity. These techniques highlighted the Stark effect in GaN / AlGaN quantum wells. The influence of the Stark effect on the energies of the excitonic transitions is well reproduced by envelop functions theory. Reflectivity spectra give access to the oscillator strength via their fitting by transfer matrix formalism, taking in account both homogeneous and inhomogeneous broadenings of the optical transitions. Finally, time resolved photoluminescence measurements as a function of temperature were performed to extract the oscillator strength, which is proportional to the inverse of the radiative recombination time. This technique also highlighted the Stark effect which is responsible of the vanishing of the oscillator strength with the thickness of the well and the aluminium composition. Increasing of the quantum well’s thickness induces decreasing of wave functions overlap, as well as an increasing of the aluminium composition which intensifies the electric field and splits the wave functions.

Ce travail de thèse porte sur l’étude des propriétés optiques et électroniques des puits quantiques de GaN / AlGaN grâce à des techniques classiques de réflectivité résolue en angle et de photoluminescence, ainsi qu’avec la technique de photoluminescence résolue temporellement. Les expériences de photoluminescence en régime continu ont permis d’estimer les énergies des transitions excitoniques qui sont également accessibles en réflectivité. Ces techniques ont ainsi permis de mettre en évidence l’effet Stark dans les puits quantiques GaN / AlGaN. L’effet Stark sur les énergies de transition est cohérent avec la théorie des fonctions enveloppes. Les spectres de réflectivité permettent d’accéder à la force d’oscillateur des excitons grâce à leur modélisation par le formalisme des matrices de transfert, prenant en compte les phénomènes d’élargissement homogène et inhomogènes des transitions optiques. Enfin, les mesures de photoluminescence résolue en temps en fonction de la température, ont également permis d’extraire la force d’oscillateur qui est inversement proportionnelle au temps de recombinaison radiative. Cette étude a également permis de mettre en évidence l’effet Stark responsable de la diminution de la force d’oscillateur en fonction de l’épaisseur du puits quantique mais aussi en fonction de la composition d’aluminium. L’augmentation de l’épaisseur du puits entraîne une diminution du recouvrement des fonctions d’onde, et une augmentation de la composition d’aluminium intensifie le champ électrique et diminue également le recouvrement des fonctions d’onde. / This work deals with the study of optical and electronic properties of GaN / AlGaN quantum wells, by classical techniques of spectroscopy including angle resolved reflectivity or photoluminescence, but also by time resolved photoluminescence. The continuous wave photoluminescence experiments allowed estimating the energies of the excitonic transitions, which are also available through reflectivity. These techniques highlighted the Stark effect in GaN / AlGaN quantum wells. The influence of the Stark effect on the energies of the excitonic transitions is well reproduced by envelop functions theory. Reflectivity spectra give access to the oscillator strength via their fitting by transfer matrix formalism, taking in account both homogeneous and inhomogeneous broadenings of the optical transitions. Finally, time resolved photoluminescence measurements as a function of temperature were performed to extract the oscillator strength, which is proportional to the inverse of the radiative recombination time. This technique also highlighted the Stark effect which is responsible of the vanishing of the oscillator strength with the thickness of the well and the aluminium composition. Increasing of the quantum well’s thickness induces decreasing of wave functions overlap, as well as an increasing of the aluminium composition which intensifies the electric field and splits the wave functions.

L’objectif de cette étude est de mieux comprendre le rôle joué par les défauts dans les propriétés optiques et électroniques des nanostructures d’oxyde de zinc. Pour ce faire, nous avons synthétisé des nanoparticules d’oxyde de zinc de 6 à 18 nm de diamètres pouvant être considérées comme modèle en terme de stœchiométrie, de cristallinité et de qualité de surface par une méthode physique originale : la Low Energy Cluster Beam Deposition.La caractérisation optique des défauts présents dans les nanoparticules de ZnO a été faite grâce à l’analyse des spectres d’émission visible et UV à différentes températures [10K-300K]. En particulier la luminescence excitonique à 3,31 eV, qui est un sujet controversé, a été étudiée en comparant la luminescence excitonique d’échantillons structurés à différentes échelles (nanoparticules, microcristaux et monocristal). Les temps de déclins très rapides des défauts donneurs ont été étudiés par spectroscopie à décalage de fréquence au CELIA à Bordeaux révélant une dépendance en fonction de la taille des NPs du type Giant Oscillator Strenght.Les propriétés de transport électronique des couches minces de NPs, naturellement dopées n, ont été caractérisées grâce à des expériences σ(T). Différents scénarios sont proposés pour expliquer les résultats des expériences de conductivité, et discutés en fonction des propriétés optiques des couches et de leur morphologie. En particulier, il est montré que la surface des NPs, très réactive, influence fortement le transport, ce qui laisse entrevoir la possibilité d’utiliser ces films nanostructurés comme capteurs de gaz. / This study deals with the influence of defects on the electronic properties of ZnO nanoparticles (NPs).In order to perform this study we have synthesized ZnO NPs using an original physical way : the Low Energy Cluster Beam Deposition. The NPs size can be adjusted between 6 and 18 nm depending the synthesis parameters and their analysis shows that the NPs have a good stoichiometry, cristallinity and surface quality.The photoluminescence properties of different ZnO samples structured at different scales (i.e. nanoparticle, microcrystal and monocrystal) have been analyzed at different temperature (10K-300K). The good cristallinity of the NPs is confirmed by the lack of visible luminescence. The comparison of the 3,31 eV excitonic emission of ZnO samples structured at different scales shows that this band is due to extended defect and/or exciton-phonon coupling rather than a surface luminescence. Moreover the lack of the 3.31 eV in the NPs luminescence shows that these defect does not occurs in ZnO NPs. At last, the time resolved study of the donor bounded exciton emission shows a variation of the decay time with the size of NPs suggesting a Giant Oscillator Strenght phenomenon.The transport properties of ZnO NPs assembled thin film are determined by conductivity measurements at variable temperatures. Different possibilities are considered in order to explain the temperature dependence of the conductivity and correlated with the optical properties of the NPs, showing a hopping type conductivity. The huge reactivity of the nanostructured film strongly influences the conductivity showing a possibility to use ZnO NPs as a gas sensor.

Cette thèse est consacrée à l'étude expérimentale par spectroscopie pompe-sonde femtoseconde des propriétés optiques hors-équilibre de solutions micellaires de nanotubes de carbone. Les propriétés des nanotubes de carbone sont profondément affectées par leur géométrie unidimensionnelle. Les interactions coulombiennes exaltées du fait du confinement quantique des électrons à une dimension donnent naissance à des excitons fortement liés. L'analyse des spectres d'absorption transitoire par la méthode des moments permet une étude des interactions entre excitons. La relaxation des excitons s'avère gouvernée par les collisions entre excitons, limitées par la diffusion à 1D dans le nanotube. La présence d'excitons dans une sousbande conduit à un décalage uniforme vers le bleu de l'ensemble des transitions excitoniques et à un élargissement de même ampleur. Ainsi, les interactions croisées entre excitons de sousbandes différentes sont de même amplitude qu'entre excitons de même sousbande, en accord avec une modélisation simple.Par ailleurs, les nanotubes sont constitués uniquement d'atomes de surface, ce qui leur confère une forte sensibilité à l'environnement. Cette sensibilité est mise à profit dans des composés hybrides où la fonctionnalisation non-covalente par des colorants ouvre une nouvelle voie d'excitation des nanotubes. Notre étude montre que le transfert d'énergie entre les colorants et les nanotubes permet une excitation monochromatique efficace et uniforme de l'ensemble des espèces de nanotubes. Une fois l'exciton transféré au nanotube, sa relaxation s'avère ensuite identique à celle observée dans les nanotubes nus. / This thesis is devoted to the experimental study by femtosecond pump-probe spectroscopy of micellar solutions of carbon nanotubes. The properties of carbon nanotubes are greatly affected by their 1D geometry. Quantum confinement of electrons in 1D leads to enhanced coulomb interactions giving rise to strongly bound excitons. Many-body effects between excitons is investigated by the moment method analysis of the transient absorption spectra. The relaxation of excitons is controlled by diffusion-limited collisions between excitons. The presence of excitons in the lowest subband results in a broadening and an uniform blue-shift of the excitonic energy spectrum. Intra and intersubband interactions turn out to be of the same magnitude, in agreement with a simple mean field theory of excitonic interactions.Moreover, the one-layer structure of nanotubes results in strong interaction with the environment. We take advantage of the environmental sensitivity of nanotubes in hybrid compounds where the non-covalent functionalization with dyes opens a new extrinsic monochromatic excitation channel of the nanotubes through an efficient and ultrafast energy transfer between dyes and nanotubes. Once the exciton transferred to the nanotube, its relaxation is similar to the one observed in bare nanotubes.

Les propriétés optiques de nanotubes de carbone sont décrites idéalement parla physique d’un objet unidimensionnel, donnant lieu notamment à l’apparition des excitons pour décrire les transitions optiques de ces objets. Les expériences d’optique(émission, absorption) réalisées sur ces objets à température ambiante et sur des ensemble d’objets ont permis de confirmer les prédictions théoriques basées sur la physique des objets 1D. Mais à température cryogénique et à l’échelle de l’objet unique,les propriétés optiques observées expérimentalement sont systématiquement très éloignées de celles d’un objet 1D. On peut notamment citer l’apparition de propriétés comme l’émission de photons uniques, qui a largement contribué à l’intensification de la recherche sur ces objets pour des applications en photonique quantique. Ces propriétés sont attribuées à la localisation des excitons le long de l’axe des nanotubes dans des puits de potentiel créés aléatoirement par l’interaction des nanotubes avec leur environnement. Les propriétés optiques sont alors proches de celles des objets0D, et sont fortement modulées par l’environnement. Les mécanismes et l’origine de la localisation et la connaissance physique de ces puits sont encore très limités. Ce travail montre d’une part le développement d’une technique d’absorption sur objet individuel et la caractérisation de sa sensibilité, et d’autre part l’étude statistique de l’émission de nanotubes à température cryogénique. Les résultats obtenus par une technique de super-résolution couplée à une imagerie hyper-spectrale montrent les grandeurs caractéristiques des puits de potentiels au sein de nanotubes individuels.Un dispositif expérimental de photoluminescence résolue en excitation implémenté au cours de ce travail a également montré une modification de l’état excitonique fondamental par l’environnement, avec l’apparition d’une discrétisation spatiale et spectrale de l’état fondamental délocalisé en une multitude d’états localisés. / The optical properties of carbon nanotubes are ideally described by the physicsof a one-dimensional object, giving rise in particular to the emergence of excitons todescribe the optical transitions of these objects. The optical experiments (emission,absorption) carried out on these objects at ambient temperature and on ensemblesconfirm the theoretical predictions based on the physics of 1D objects. But atcryogenic temperature and at the single emitter scale, the optical properties observedexperimentally are systematically different from those of a 1D object. One can citethe emergence of properties such as photon antibunching, which largely contributed tothe intensification of research on these objects for applications in quantum photonics.These properties are attributed to the localization of excitons along the nanotube axisin local potential wells (traps) created randomly by the interaction of nanotubes withtheir environment. The optical properties are then close to those of 0D objects, andare strongly modulated by the environment. The mechanisms and the origin of thelocalization and the physical knowledge of these traps are still very limited. This workshows on the one hand the development of an absorption setup on individual objectand the characterization of its sensitivity, and on the other hand the statistical studyof the emission of nanotubes at cryogenic temperature in a micro-photoluminescencesetup. The results obtained in the later setup by a super-resolution technique coupledwith hyper-spectral imaging show the characteristic quantities of potential wellswithin individual nanotubes. An experimental excitation-resolved photoluminescencesetup implemented during this work also showed a modification of the fundamentalexcitonic state by the environment, with the emergence of a spatial and spectraldiscretization of the delocalized ground state in a multitude of localized states.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: See full text / AFRIKAANSE OPSOMMING: Sien volteks

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

<p>To fully optimize devices for solar energy conversion, a comprehensive understanding of how excitons migrate in materials for solar cell devices is crucial. Understanding the mechanisms behind exciton diffusion and energy transfer will enable the fabrication of highly efficient devices. However to thoroughly study exciton properties, techniques implementing high spatial (nm sizes) and temporal (fs time scales) resolution is required. Herein, we utilize transient absorption microscopy (TAM) with 50 nm spatial resolution and 200 fs temporal resolution to elucidate exciton diffusion in polymeric materials for solar energy conversion.</p> <p>While organic devices are inexpensive and require simpler fabrication procedures than inorganic materials, their device efficiencies often suffer due to their semi-crystalline nature, lending to short diffusion lengths which lead to trap sites and inevitably recombination. It has been demonstrated that achieving long-range exciton diffusion lengths is possible through coherence effects. Coherence can be found in an intermediate electronic coupling region where delocalization and localization compete.</p> <p>To exploit coherence effects, we study polymeric systems in which polymer chains are highly aligned via simple and scalable procedures; semiconducting fibers and solution coated films. In studying the fiber, we first implement polarized photoluminesce (PL) to determine optical ansitropy. From the polarized PL and PL images, it is observed that emission intensities are largest when probing along the transition dipole moment of the polymer. This suggests a type of Förester Resonance Energy Transfer mechanism in which excitons hop from one polymer chain to another.</p> <p>Solution coated polymer films are also studied to understand exciton diffusion as a function of deposition methods. By varying the solution concentration as well as coating rate, we are able to tune the morphology of the film. We observe a strong dependence between diffusion constant and deposition parameters, with diffusion constants of <i>ca.</i> 9, 13 and 33 cm²/s for three different films. The results obtained in this thesis are preliminary steps in an effort to elucidate energy transfer mechanisms and rates.</p><br>

Ressonância magnética detectada eletricamente (RMDE) de banda-X (9 GHz) e de banda-K (24 GHz) foram usadas para estudar diversos diodos baseados em tris-8(hidroxiquinolinolato) de alumínio III (Alq3). A técnica de RMDE consiste, basicamente, em medir a variação da condutividade quando o sistema entra na condição de ressonância magnética; assim, é possível relacionar propriedades de transporte elétrico com as funções de onda das moléculas envolvidas no processo. Para este estudo foram confeccionados diodos eletroluminescentes e unipolares de multicamadas no Laboratoire d'Optoélectronique des Materiaux Moléculaire (LOMM), da École Polytechnique Fédérale de Lausane (EPFL), Suíça, pelo Dr. Frank Nüesch. Faz parte também deste trabalho a montagem experimental do sistema de RMDE de banda-K, onde a maior parte dos dados foram obtidos. O sinal de RMDE dos diodos unipolares, da ordem de 1E-6, é atribuído ao processo dependente de spin de saltos eletrônicos que ocorre próximo às interfaces. O sinal típico de RMDE dos diodos eletroluminescentes é mais intenso, da ordem de 1E-4, e é atribuído à ressonância de spin-1/2 na formação dos éxcitons. O espectro de RMDE, por meio de ajuste de curvas, pôde ser decomposto em duas gaussianas: uma com largura de linha pico-a-pico DHPP de 1,6 mT, independente do campo elétrico aplicado no dispositivo, e outra variando de 2,0 mT a 3,4 mT. A componente mais estreita se deve à ressonância do radical positivo de Alq3, enquanto que a componente mais larga àquela do negativo. O estudo da forma de linha e de sua dependência com o campo elétrico dos espectros de RMDE de diodos unipolares dão suporte à ambas as atribuições. Neste trabalho, a questão da eficiência quântica e da zona de recombinação também são discutidas. / Electrically Detected Magnetic Resonance (EDMR) at X-band (9GHz) and K-band (24 GHz) were used to investigate Alq3 based diodes. EDMR technique consists basically of measuring conductivity variation at magnetic resonance conditions; thus, it is possible to correlate electrical transport properties with wave functions of the molecules involved in the process. Electroluminescent and unipolar multilayer diodes were prepared in the Laboratoire d'Optoélectronique des Materiaux Moléculaire (LOMM), at on École Polytechnique Fédérale de Lausane EPFL, Switzerland by Dr. Frank Nüesch. The experimental setup of the K-band EDMR system, where most of the data were obtained, was also part of this work. The unipolar diodes EDMR signal is of the order of 1E-6 and is attributed to spin dependent hopping process close to the interfaces. The electroluminescent diodes typical EDMR signal is more intense, of the order of 1E-4 , and is attributed to exciton´s formation spin-1/2 resonance. The EDMR spectrum can be decomposed into two Gaussians: one with peak-to-peak line width (DHPP) of 1.6 mT, independent of the electrical field applied to the devices, and other one whit DHPP of 2.0 mT to 3.4 mT. The narrower component is due to the resonance of positive Alq3 radical, while the larger component is due to the negative. Both attributions are supported by the investigation of line shape and its dependence of electrical field in the unipolar diodes EDMR spectra. In this work, the quantum efficiency and the recombination zone issues are also discussed.

A proposta desse estudo é investigar as propriedades de migração do éxciton, transferência de energia e transporte de cargas em heteroestruturas orgânicas ultrafinas compostas pela integração de um polímero semicondutor com moléculas de clorofila. A sintonização dos estados eletrônicos desses materiais torna possível a obtenção de heteroestruturas com modulação energética capazes de aprisionar éxcitons e cargas apresentando potencialidade de aplicação em Diodos Orgânicos Emissores de Luz (OLEDs). Para tal filmes de polifuoreno (PFO) (camada transportadora de carga) totalmente amorfo e filmes de clorofila (camada ativa na forma de poço de potencial) foram preparados utilizando a técnica e automontagem (LBL) combinada com spin-coating, caracterizados por microscopia confocal por varredura a laser e técnicas espectroscópicas de absorção e emissão. Investigou-se os processos fotofísicos utilizando microscopia confocal e de tempo de vida. Os resultados foram interpretados com base no modelo de transferência de energia de Förster combinado com as taxas de Miller-Abrahams e com a equação de difusão excitônica. Com essa abordagem, obteve-se uma relação entre a migração do éxciton no PFO e a transferência de energia não radiativa deste polímero para as moléculas de clorofila. Observou-se uma eficiente transferência de energia igual a 94% no regime de filmes ultrafinos. Para compreender os mecanismos de transporte de carga, implementamos e validamos o método de simulação de Monte Carlo para o transporte de carga em sistemas orgânicos desordenados. Com essa abordagem investigou-se a dinâmica das cargas em filmes poliméricos desordenados com e sem a camada de poço de potencial. Propriedades elétricas, tais como, mobilidade elétrica e coeficiente de difusão, foram obtidas e estão de acordo com os reportados na literatura. Obteve-se uma taxa de preenchimento de cargas no poço de potencial igual a 1010 buracos/s para campo elétrico de 1 MV/cm e constatou-se que a taxa aumenta com o campo elétrico. Tal abordagem apresenta-se como uma alternativa interessante para auxiliar o planejamento experimental de OLEDs baseados em heteroestruturas orgânicas. / In this study the exciton migration, energy transfer and charge transport in ultrathin organic heterostructure formed by semiconductor polymer and chlorophyll molecules were investigated. The energetic tuning between these materials promotes organic heterostructures with energetic modulation capable of trapping excitons and charges showing an application potential in Organic Light Emitting Diodes (OLEDS). Amorphous polyfluorenes (PFO) and chlorophyll a (chla) were prepared using self-assembly combined with spin-coating methods and characterized by confocal laser scanning microscopy and spectroscopic techniques. Photophysical processes were investigated using confocal and life-time microscopy and the results interpreted from the model of Förster energy combined with the Miller-Abrahams rate as well as the exciton diffusion equation. These results provided a relationship between the exciton migration in the PFO film and the non-radiative energy transfer from polymer to chla molecules. An efficient transfer of energy equal to 94% was observed. Method of the Monte Carlo simulation were implemented to investigate the charge transport in this disordered organic system. Using this method, the charge dynamics with and no potential well layer was studied. Electrical properties obtained, such as electric mobility and diffusion coefficient, are in agreement with literature. It was estimated a charge fill rate in the potential well equal to 1010 holes/s for 1 MV/cm and this parameter increases with the electric field. This approach has been shown to be an interesting alternative for the experimental design of OLEDs composed by organic heterostructure.