No description available.

No description available.

Nous considérons le problème d’un électron sur des pavages quasipériodiques en une et deux dimensions. Nous introduisons tout d’abord les pavages quasipériodiques d’un point de vue géométrique, et défendons en particulier l’idée que ces pavages sont les pavages apériodiques les plus proches de la périodicité. Nous concentrant plus particulièrement sur l’un des pavages quasipériodiques les plus simples, la chaîne de Fibonacci, nous montrons à l’aide d’un groupe de renormalisation que la multifractalité des états électroniques découle directement de l’invariance d’échelle de la chaîne. Élargissant ensuite notre champ d’étude à un ensemble de chaînes quasipériodiques, nous nous intéressons au théorème de label des gaps, qui décrit comment la géométrie d’une chaîne donnée contraint les valeurs que peut prendre la densité d’états intégrée dans les gaps du spectre électronique. Plus précisément, nous nous intéressons à la façon dont l’énoncé de ce théorème est modifié lorsque l’on considère une séquence d’approximants périodiques approchant une chaîne quasipériodique. Enfin, nous montrons comment des champs de hauteurs géométriques peuvent être utilisés pour construire des états électroniques exacts sur des pavages en une et deux dimensions. Ces états sont robustes aux perturbations du hamiltonien, sous réserve que ces dernières respectent les symétries du pavage sous-jacent. Nous relions les dimensions fractales de ces états à la distribution de probabilités des hauteurs, que nous calculons de façon exacte. Dans le cas des chaînes quasipériodiques, nous montrons que la conductivité suit une loi d’échelle de la taille de l’échantillon, dont l’exposant est relié à cette même distribution de probabilités. / We consider the problem of a single electron on one and two-dimensional quasiperiodic tilings. We first introduce quasiperiodic tilings from a geometrical point of view, and point out that among aperiodic tilings, they are the closest to being periodic. Focusing on one of the simplest one-dimensional quasiperiodic tilings, the Fibonacci chain, we show, with the help of a renormalization group analysis, that the multifractality of the electronic states is a direct consequence of the scale invariance of the chain. Considering now a broader class of quasiperiodic chains, we study the gap labeling theorem, which relates the geometry of a given chain to the set of values the integrated density of states can take in the gaps of the electronic spectrum. More precisely, we study how this theorem is modified when considering a sequence of approximant chains approaching a quasiperiodic one. Finally, we show how geometrical height fields can be used to construct exact eigenstates on one and two-dimensional quasiperiodic tilings. These states are robust to perturbations of the Hamiltonian, provided that they respect the symmetries of the underlying tiling. These states are critical, and we relate their fractal dimensions to the probability distribution of the height field, which we compute exactly. In the case of quasiperiodic chains, we show that the conductivity follows a scaling law, with an exponent given by the same probability distribution.

This master's thesis studies the electronic properties changes of graphene caused by substrate SiO2, adsorbed molecules of water and atoms of gallium. There are tested different geometrical configurations of these systems and consequently calculated band structures to derive the changes of the electronic properties: the doping effect and band gap opening of graphene layer.

L'efficacité du processus photovoltaïque dépend du matériau actif à travers la structure de bande et la dynamique des porteurs de charge. Dans cette thèse, nous avons relié les propriétés électroniques et la dynamique de relaxation à la structure atomique des matériaux utilisés pour deux technologies différentes de cellules solaires, celle à base d’hétérostructures de silicium, et celle à base de pérovskites hybrides organiques-inorganiques. Dans les cellules solaires de silicium, nous avons analysé l'influence des défauts sur les propriétés électroniques des hétérostructures de silicium amorphe (a-Si:H/a-SIC:H/c-Si) par spectroscopies des niveaux de coeur et de la bande de valence. En particulier, nous avons quantifié le nombre de liaisons pendantes induites dans la couche a-Si:H par irradiation, et nous avons identifié les états électroniques qui leur sont associés. Enfin nous avons expliqué les transitions précédemment observées par photoluminescence. Dans les cellules solaires à pérovskite hybride, nous avons corrélé la structure atomique, la structure électronique et la dynamique électronique pour des pérovskites bi- et tridimensionnelles. Dans ce but nous avons utilisé tout un panel de techniques complémentaires: diffraction des rayons X, spectroscopie de photoémission résolue en angle, spectroscopie de photoémission inverse et photoémission à deux photons résolue en temps. Pour la pérovskite bidimensionnelle (C₆H₅C₂H₄NH₃)₂PbI₄, nous avons déterminé expérimentalement les bandes de valence et de conduction et nous les avons comparées aux simulations de la fonction spectrale. Pour la pérovskite tridimensionnelle CH₃NH₃PbI₃, nous avons aussi déterminé les structures de bande expérimentale et simulée. Des signatures spectrales très larges ont été observées expérimentalement, ce qui relaxe les conditions de transition optique avec un impact éventuel sur l'efficacité des cellules solaires. Tant dans les expériences que dans les calculs, nous observons que le poids spectral suit une périodicité cubique alors que le système est structurellement dans une phase tétragonale. Cette contradiction apparente s'explique par la largeur spectrale des bandes, qui cache le repliement dû à la distorsion tétragonale. En ce qui concerne la dynamique de relaxation, nous avons observé que les porteurs photoexcités se thermalisent dans une échelle de temps subpicoseconde par couplage aux vibrations des cations organiques. À des échelles de temps plus longues (10~100 picosecondes), la diffusion électronique contrôle la dynamique. Cette dynamique est affectée par les défauts induits par recuit, qui localisent les électrons photoexcités pendant plus de 300 picosecondes. / The efficiency of the photovoltaic process depends on the electronic band structure of the active material and the charge carrier dynamics. In this thesis, we have studied how these issues are related to the atomic structure in materials for two different technologies of solar cells, namely silicon heterostructure solar cells, and hybrid organic-inorganic perovskite solar cells. In silicon heterostructure solar cells, we have analyzed the impact of defects on the electronic properties of amorphous silicon heterostructures (a-Si:H/a-SIC:H/c-Si) by core level and valence band spectroscopies. In particular, we have quantified the number of dangling bonds inside a-Si:H layer upon irradiation, we have identified the electronic states associated to them, and we have understood the transitions previously observed by photoluminescence. In perovskite solar cells, we have correlated the atomic structure, the electronic structure and the electronic dynamics for two- and three-dimensional hybrid organic-inorganic perovskites. We have used with this goal a whole panel of complementary techniques: X-ray diffraction, angle-resolved photoemission spectroscopy, inverse photoemission spectroscopy, and time-resolved two-photon photoemission. In the two-dimensional perovskite (C₆H₅C₂H₄NH₃)₂PbI₄, the valence and conduction bands have been determined experimentally and compared to spectral function simulations. In the three-dimensional perovskite CH₃NH₃PbI₃, we have again determined the band structure and simulated it. Very broad spectral features have been experimentally observed, which relax the optical transition conditions impacting in the solarcell efficiencies. In both experiments and calculations, we observe that the spectral weight follows a cubic periodicity while the system is structurally in the tetragonal phase. This apparent contradiction is explained by the band broadness, which hides the band folding of the tetragonal distortion. As for the relaxation dynamics, we have observed that the photoexcited carriers thermalize in a subpicosecond time scale through the coupling to organic cation vibrations. At longer timescales (10~100 picoseconds), the electron diffusion controls the dynamics. This dynamics is affected by the annealing-induced defects, which localize the photoexcited electrons for more than 300 picoseconds.

In order to study the electronic and optical properties of complex materials an approach providing a reliable estimate of band gaps in combination with the reasonable description of the ground state is required. In the present study of pure and defective perovskite crystals, the fulfillment of such requirements is clearly demonstrated using a simple hybrid HF/DFT scheme containing an admixture of non-local Fock exchange. In present theoretical investigations, a wide class of perovskite oxides is represented by three, the most attractive (from a scientific point of view) crystals of SrTiO3, BaTiO3, and PbTiO3 in their high symmetry cubic phases. These perovskite crystals present a great technological and fundamental interest due to their numerous applications related to ferroelectricity, non-linear and electro-optics, superconductivity, and catalysis. Although the above-mentioned perovskite-type materials have been intensively investigated theoretically and experimentally at least in the last fifteen years, a proper description of their electronic properties is still an area of active research. In order to make a contribution to the explanation of various electro-optical effects observed in perovskite materials, their ground-state properties have been calculated from first principles and analyzed in the present study.

Der Erste dieser Arbeit befasst sich mit der STM Untersuchung einer Grenzschicht in umgebender Atmosphäre, welche sich durch die Adsorption von Graphen auf einer Glimmeroberfläche ausbildet. Durch die umgebene Luftfeuchtigkeit interkalieren Wassermoleküle in diese Grenzschicht. Durch die Variation der relativen Luftfeuchtigkeit gibt diese Wasser ab bzw. nimmt auf, und es manifestieren sich sternförmig wachsende Fraktale, in denen Graphen etwa um den Durchmesser eines Wassermoleküls an Höhe absinkt. Die STM Untersuchung, welche primär sensitiv auf die Zustandsdichte von Graphen reagiert, zeigte, dass sich anders als in den SFM Untersuchungen, zusätzliche signifikante Höhenänderungen von Graphen innerhalb der Fraktale bildeten. Dieses deutet auf eine Wasserschicht hin, welche Domänen mit signifikant unterscheidbaren Polarisationsrichtungen aufweisen, welche die Zustandsdichte von Graphen verändern kann. Dies ist aber gleichbedeutend mit der Annahme, dass sich in jener Grenzschicht mindestens zwei oder mehr lagen Wasser bilden müssen. Der zweiten Teil befasst sich mit der STM Untersuchung einer funktionalisierten Oberfläche die charakterisiert ist durch eine leitende Oberfläche (Graphen und HOPG) adsorbierten funktionalisierte Dyade an einer Fest-Flüssig Grenzfläche. Diese Dyade besteht im Wesentlichen aus einem Zink-Tetraphenylporphyrin (ZnTPP) und mit diesem über einem flexiblen Arm verbundenen Spiropyranderivat. Letztere ändert seine Konformation durch die Einstrahlung mit Licht geeigneter Wellenlänge, womit sich das Dipolmoment stark ändert. Es zeigte sich, dass das Schaltverhalten auf einen Graphen mit dem Schaltverhalten einer Dyade in Lösung vergleichbar ist. Dieses lässt den Schluss zu, dass das Schalteigenschaften einer einzelnen Dyade auf das adsorbierte Kollektiv übertragen werden kann, da es keine signifikanten beeinflussenden Wechselwirkungen durch die leitende Oberfläche und der benachbarten Dyaden auswirkte. / The first of this two-part work deals with the STM investigation of an interface in the surrounding natural atmosphere, which is formed by the adsorption of the conductive graphene onto the mica surface. In this interface, water molecules may intercalate by the surrounding humidity. By varying the relative humidity, the interface is rewetted, respectively, dewetted and it manifests itself in a star shape growing fractals, where the height of graphene is decreased by approximately the diameter of one water molecule. The STM investigation - which is primarily sensitive to the density of states of graphene - shows that additional significant changes in the height of graphene are formed within the fractal, unlike in the SFM investigations. This suggests that there is a water layer by which the density of graphene is differently affected by domains with significant distinguishable polarisation alignments. However, this is equivalent to the assumption that there are two or more water layers exist within the interface. The second part of this work deals with the STM investigation of a functionalized surface characterised by a functionalized dyad adsorbed onto a conductive surface (graphene and HOPG) at a solid-liquid interface. This dyad essentially comprises a zinc-tetraphenylporphyrin (ZnTPP) and is connected with a spiropyran derivative via a flexible linker. This changes its conformation through irradiation with light with a suitable wavelength, by which the dipole moment is also strongly changed. It was found that the switching behaviour of a graphene-based conductive surface is comparable with the switching behaviour of a dyad, which itself can move freely in solution. This leads to the conclusion that the switching properties of a single dyad can be transmitted to its collective because it affected no significant influence interactions by the conductive surface and the adjacent dyads.

No description available.

Neste trabalho, apresentamos estudos sobre o transporte eletrônico de cargas e diagramas de fase no plano ns-B em bicamadas eletrônicas ou poços quânticos duplos, formados de ligas semiconductoras de AlxGa1-xAs e GaAs, assim como também em poços quânticos triplos de GaAs. Para esta finalidade, amostras de poços duplos com diferentes concentrações de Al (x) dentro de cada poço e triplos de GaAs foram crescidas. Inicialmente, se apresenta um estudo teórico, o qual mostrou que, em poços quânticos duplos em que em cada poço a concetração de Al é diferente, a aplicação de tensões de porta permite a modulação do fator g de Landé dos elétrons confinados nesses poços. Em especial, estudou-se o caso de concentrações de Al que correspondem a valores do fator g com sinal oposto, em cada poço. Posteriormente se faz um estudo teórico da estrutura eletrônica das amostras de poços duplos e triplos, em seguida apresenta-se os fundamentos teóricos que serão de base para a interpretação de nosso resultados experimentais. Na primeira parte de nosso trabalho, medidas de magnetotransporte (Shubnikov-de Haas (SdH) e Hall), foram realizadas em todas as amostras de estudo. Na amostra de poço duplo 3242, com fator g de Landé de sinais opostos foi encontrado o colapso do gap de spin nas oscilações SdH com o incremento do campo magnético, ou seja, a soma da energia de Zeeman mais a energia de troca e correlação é igual ao potencial de desordem. Este colapso é atribuido à competição entre as energias de troca, intracamadas e intercamadas. Foi realizada uma análise das oscilações SdH através da transformada de Fourier (FFT), para mostrar que as propriedades eletrônicas tais como a concentração e mobilidade dos elétrons, nas amostras de poços duplos, decrescem à medida que aumenta a concentracão de Al. As propriedades eletrônicas nas amostras de poços triplos dependem dos parâmetros de crescimento, tal como a largura dos poços e barreira. Na segunda parte, são apresentados diagramas de fase ns-B, obtidos através da justaposição dos espectros de magnetorresistência, em amostras de poços duplos e triplos em campo magnético perpendicular e certos valores de campo inclinado. Mostra-se que, em campo magnético perpendicular, o modelo de uma partícula sem interações descreve com boa aproximação o aparecimento dos anéis no diagrama de fase para a amostra de poço duplo com g = -0,44. No entanto, na amostra com g ~ 0 o modelo não descreve em boa aproximação os diagramas de fase em campo magnético perpendicular e inclinado, precisando de um modelo que inclua termos de interação de muitos corpos para uma possível explicação. Também se prediz a existência de um estado canted antiferromagnético. O modelo também mostrará que os diagramas de fase das amostras de poços triplos têm um comportamento semelhante ao das amostras de poços duplos, quando a densidade de elétrons do poço central é baixa comparada com a densidade dos poços laterais. / In this work, we present studies about the electronic transport of charges and phase diagrams in the ns-B plane in electronic bilayers or double quantum wells formed of both AlxGa1-xAs and GaAs semiconductor alloys, also in GaAs triple quantum wells. For this purpose, double quantum wells with different aluminium compositions (Al(x)) in each well and triple quantum wells samples were growth. Firstly, a theoretical study was presented, which showed that in double quantum wells with different Al compositions, the aplication of gate voltages allow the modulation of the Landé g factor of the electrons confined within each well. In particular, the case where the quantum wells have different Al compositions was studied, which lead to the opposite signs of the electronic g-factor in each well. After this, a theoretical study of the electronic structure has been presented of both double and triple quantum wells, then, a basic theory has been presented, which will be the base for the interpretation of our experimental results. At the frst part of our work, magnetotransport measurements (Shubnikov-de Haas (SdH) and Hall) were performed in all the studied samples. In the double quantum well sample (3242), wich has Landé g-factor with opposite signs in each well, was found the spin gap collapse at the Shubnikov-de Haas oscillations with an increase in the magnetic field, that is, the sum of the bare Zeeman energy and exchange potencial energy has the same magnitude of the disorder potencial. This collapse was attributed to the competition between the interlayer and intralayer exchange energies. Fast Fourier transform (FFT) of the Shubnikov-de Haas oscillations was performed in the double and triple quantum well samples to show that the electronic properties, such as electron density and mobility decrease with the increase of the Al compositions. On the other hand, the electronic properties on the triple quantum well samples depend on growth parameters, such as width and heigh barriers of the wells. At the second part ns- B phase diagrams were determined through the superposed longitudinal magnetoresistance, in the double and triple quantum wells samples at the perpendicular magnetic field and certain values of tilted magnetic fields. It has been shown that in a perpendicular magnetic field a single particle model describes in a good aproximation the appearance of ring structures in the phase diagram of the double quantum well with g = -0:44. Meanwhile, at the sample with vanishing Landé g-factor (g ~ 0) the single particle model can not describe in a good approximation the phase diagram, being a requirement a many particle model for an possivel explanation. It has also been predicted the existence of a canted antiferromagnetic state. Finally, the model will also showed the phase diagram of triple quantum wells are similar to double quantum wells, when the electron density of the middle well is low compared to the side wells.

Neste trabalho, apresentamos estudos sobre o transporte eletrônico de cargas e diagramas de fase no plano ns-B em bicamadas eletrônicas ou poços quânticos duplos, formados de ligas semiconductoras de AlxGa1-xAs e GaAs, assim como também em poços quânticos triplos de GaAs. Para esta finalidade, amostras de poços duplos com diferentes concentrações de Al (x) dentro de cada poço e triplos de GaAs foram crescidas. Inicialmente, se apresenta um estudo teórico, o qual mostrou que, em poços quânticos duplos em que em cada poço a concetração de Al é diferente, a aplicação de tensões de porta permite a modulação do fator g de Landé dos elétrons confinados nesses poços. Em especial, estudou-se o caso de concentrações de Al que correspondem a valores do fator g com sinal oposto, em cada poço. Posteriormente se faz um estudo teórico da estrutura eletrônica das amostras de poços duplos e triplos, em seguida apresenta-se os fundamentos teóricos que serão de base para a interpretação de nosso resultados experimentais. Na primeira parte de nosso trabalho, medidas de magnetotransporte (Shubnikov-de Haas (SdH) e Hall), foram realizadas em todas as amostras de estudo. Na amostra de poço duplo 3242, com fator g de Landé de sinais opostos foi encontrado o colapso do gap de spin nas oscilações SdH com o incremento do campo magnético, ou seja, a soma da energia de Zeeman mais a energia de troca e correlação é igual ao potencial de desordem. Este colapso é atribuido à competição entre as energias de troca, intracamadas e intercamadas. Foi realizada uma análise das oscilações SdH através da transformada de Fourier (FFT), para mostrar que as propriedades eletrônicas tais como a concentração e mobilidade dos elétrons, nas amostras de poços duplos, decrescem à medida que aumenta a concentracão de Al. As propriedades eletrônicas nas amostras de poços triplos dependem dos parâmetros de crescimento, tal como a largura dos poços e barreira. Na segunda parte, são apresentados diagramas de fase ns-B, obtidos através da justaposição dos espectros de magnetorresistência, em amostras de poços duplos e triplos em campo magnético perpendicular e certos valores de campo inclinado. Mostra-se que, em campo magnético perpendicular, o modelo de uma partícula sem interações descreve com boa aproximação o aparecimento dos anéis no diagrama de fase para a amostra de poço duplo com g = -0,44. No entanto, na amostra com g ~ 0 o modelo não descreve em boa aproximação os diagramas de fase em campo magnético perpendicular e inclinado, precisando de um modelo que inclua termos de interação de muitos corpos para uma possível explicação. Também se prediz a existência de um estado canted antiferromagnético. O modelo também mostrará que os diagramas de fase das amostras de poços triplos têm um comportamento semelhante ao das amostras de poços duplos, quando a densidade de elétrons do poço central é baixa comparada com a densidade dos poços laterais. / In this work, we present studies about the electronic transport of charges and phase diagrams in the ns-B plane in electronic bilayers or double quantum wells formed of both AlxGa1-xAs and GaAs semiconductor alloys, also in GaAs triple quantum wells. For this purpose, double quantum wells with different aluminium compositions (Al(x)) in each well and triple quantum wells samples were growth. Firstly, a theoretical study was presented, which showed that in double quantum wells with different Al compositions, the aplication of gate voltages allow the modulation of the Landé g factor of the electrons confined within each well. In particular, the case where the quantum wells have different Al compositions was studied, which lead to the opposite signs of the electronic g-factor in each well. After this, a theoretical study of the electronic structure has been presented of both double and triple quantum wells, then, a basic theory has been presented, which will be the base for the interpretation of our experimental results. At the frst part of our work, magnetotransport measurements (Shubnikov-de Haas (SdH) and Hall) were performed in all the studied samples. In the double quantum well sample (3242), wich has Landé g-factor with opposite signs in each well, was found the spin gap collapse at the Shubnikov-de Haas oscillations with an increase in the magnetic field, that is, the sum of the bare Zeeman energy and exchange potencial energy has the same magnitude of the disorder potencial. This collapse was attributed to the competition between the interlayer and intralayer exchange energies. Fast Fourier transform (FFT) of the Shubnikov-de Haas oscillations was performed in the double and triple quantum well samples to show that the electronic properties, such as electron density and mobility decrease with the increase of the Al compositions. On the other hand, the electronic properties on the triple quantum well samples depend on growth parameters, such as width and heigh barriers of the wells. At the second part ns- B phase diagrams were determined through the superposed longitudinal magnetoresistance, in the double and triple quantum wells samples at the perpendicular magnetic field and certain values of tilted magnetic fields. It has been shown that in a perpendicular magnetic field a single particle model describes in a good aproximation the appearance of ring structures in the phase diagram of the double quantum well with g = -0:44. Meanwhile, at the sample with vanishing Landé g-factor (g ~ 0) the single particle model can not describe in a good approximation the phase diagram, being a requirement a many particle model for an possivel explanation. It has also been predicted the existence of a canted antiferromagnetic state. Finally, the model will also showed the phase diagram of triple quantum wells are similar to double quantum wells, when the electron density of the middle well is low compared to the side wells.