In HIOS-Strukturen, die auf einem Quantengraben und einer angrenzenden organischen Deckschicht basieren, wurde eine effiziente Umwandlung von Wannier-Exzitonen in Frenkel-Exzitonen mittels resonantem Förster Energietransfer (FRET) demonstriert. Das hier verwendete Design besteht aus einem spiro-annulierten Quarter-phenyl (L4P-SP3), das auf einen ZnO-Quantengraben (SQW) aufgewachsen wurde, um inkohärente Kopplung zu erreichen. Mittels optischer Spektroskopie haben wir demonstriert, dass diese hybriden Strukturen Energietransfer vom SQW zu den organischen Molekülen mit einer Effizienz von bis zu 77% zeigen. Allerdings zeigen UPS-Messungen eine typ-II-artige Energieniveau-Anpassung zwischen ZnO und der molekularen Schicht, die zu einem sehr effizienten Ladungstrennungsvorgang (ηCT=0.9) führt, der die molekulare Emission unterdrückt. Die erste beruht auf einer schnellen und hocheffizienten Energietransfer-Kaskade: nach der ersten Transferstufe wird die Anregungsenergie von der hybriden Grenzfläche weggeleitet, indem eine zweite Energietransferstufe eingeführt wird, bevor die Dissoziation der Exzitonen an der Grenzfläche statt-finden kann. Wir verwenden Sexiphenyl, L6P als endgültigen Akzeptor. In solch einer Struktur können wir eine Wiederherstellung der molekularen Emission um einen Faktor acht demonstrieren und zeigen, dass der Energietransferprozess zwischen L4P-SP3 und L6P den Ladungstrennungsprozess fast vollständig überholt. Als andere Option haben wir die Energieniveaus angepasst, indem eine organometallische Donor-Monolage [RuCp*mes] ergänzt wird. Diese Zwischenschicht senkt die Austrittsarbeit von ZnO deutlich ab und führt so zu einer Anpassung der Niveaus zwischen die zwei Halbleiter. Während die Effizienz des Energietransfers unverändert bleibt, steigen die Emission von L4P-SP3 sowie die Lebenszeit der molekularen Photoluminescenz um einen Faktor sieben verglichen mit entsprechenden Strukturen ohne Zwischenlage. / In HIOS structures based on a quantum well and an adjacent organic overlayer, efficient conversion of Wannier excitons into Frenkel excitons via Förster-type resonant energy transfer (FRET) has been demonstrated. The design here in use consists of a spiro-annulated ladder-type quarter-phenyl (L4P-SP3), deposited on ZnO-based single quantum wells (SQW) to obtain incoherent electronic coupling. The SQWs we use are grown with extremely thin (2 nm) capping layer. With photoluminescence excitation and time-resolved spectroscopy, we demonstrate that these hybrid structures exhibit energy transfer from the inorganic material to the organic molecules with an efficiency up to 77%. However, UPS measurements show a type-II energy level alignment between ZnO and the molecular layer, resulting in a very efficient charge separation process (ηCT=0.9) that suppresses the molecular emission. The first idea relies on a fast and highly efficient cascade FRET: following the primary transfer step from the QW, the excitation is conveyed away from the hybrid interface by a secondary transfer-step within the organic layer. As final acceptor we select ladder-type sexiphenyl (L6P). In such a structure, we demonstrate a recovery of the molecular emission by a factor eight, showing that the intermolecular FRET outpaced almost entirely the charge separation process. As alternative option, we tune the energy levels at the interface by introducing an organometallic donor monolayer [RuCp*mes]. The interlayer reduces substantially the ZnO work function, aligning the frontier levels of the inorganic and organic semiconductor. Optical experiments show the benefits of the interlayer: while the FRET efficiency is unaffected, the L4P-SP3 emission and its photoluminescence lifetime increase by a factor of seven, when compared to the same structure without interlayer.

Submitted by Arianne Vellasco Gomes (ariannevellasco@gmail.com) on 2018-06-15T18:52:22Z No. of bitstreams: 1 Arianne_Vellasco_Gomes_TESE_POSMAT_2018.pdf: 4211125 bytes, checksum: 16221f3149817fbc6e4db2f2026f2f14 (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-06-18T17:39:32Z (GMT) No. of bitstreams: 1 gomes_av_dr_bauru.pdf: 3510911 bytes, checksum: 2abe98b4f93107bb6dc267a184ebef70 (MD5) / Made available in DSpace on 2018-06-18T17:39:32Z (GMT). No. of bitstreams: 1 gomes_av_dr_bauru.pdf: 3510911 bytes, checksum: 2abe98b4f93107bb6dc267a184ebef70 (MD5) Previous issue date: 2018-04-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Tópicos fundamentais da estrutura eletrônica de materiais cristalinos, são investigados de forma generalizada mediante o Cálculo Fracionário. São calculadas as bandas de energia, as funções de Bloch e as funções de Wannier, para a equação de Schrödinger fracionária com derivada de Riesz. É apresentado um estudo detalhado do caráter não local desse tipo de derivada fracionária. Resolve-se a equação de Schrödinger fracionária para o modelo de Kronig-Penney e estuda-se os efeitos da ordem da derivada e da intensidade do potencial. Verificou-se que, ao passar da derivada de segunda ordem para derivadas fracionárias, o comportamento assintótico das funções de Wannier muda apreciavelmente. Elas perdem o decaimento exponencial, e exibem um decaimento acentuado em forma de potência. Fórmulas simples foram dadas para as caudas das funções de Wannier. A banda de energia mais baixa mostrou-se estar relacionada ao estado ligado de um único poço quântico. Sua função de onda também apresentou decaimento em lei de potência. As bandas de energia superiores mudam de comportamento em função da intensidade do potencial. No caso inteiro, a largura de cada uma dessas bandas diminui. No caso fracionário, diminui inicialmente e depois volta a aumentar, aproximando-se de um valor infinito à medida que a intensidade do potencial tende ao infinito. O grau de localização das funções de Wannier, expresso pelo desvio padrão da posição, mostra um comportamento similar ao da largura das bandas de energia. Além dos cristais perfeitos a Ciência de Materiais estuda cristais com defeito. Os defeitos são responsáveis por muitas propriedades de interesse tecnológico e podem induzir estados localizados. Neste trabalho, calculado o estado localizado de menor energia no modelo de Kronig-Penney fracionário com defeito, mediante método das transformadas de Fourier e das funções de Wannier. Verificou-se que este estado também decai em forma de lei de potência. / Basics topics on the electronic structure of crystalline materials are investigated in a generalized fashion through Fractional Calculus. The energy bands, the Bloch and Wannier functions for the fractional Schr odinger equation with Riesz derivative are calculated. The non-locality of the Riesz fractional derivative is analyzed. The fractional Schr odinger equation is solved for the Kronig-Penney model and the e ects of the derivative order and the potential intensity are studied. It was shown that moving from the integer to the fractional order strongly a ects the asymptotic behavior of the Wannier functions. They lose the exponential decay, gaining a strong power-law decay. Simple formulas have been given for the tails of the Wannier functions. A close relatim between the lowest energy band and the bound state of a single quantum well was found. The wavefunction of the latter decays as a power law. Higher energy bands change their behavior as the periodic potential gets stronger. In the integer case, the width of each one of those bands decreases. In the fractional case, it initially decreases and then increases. The width approaching a nite value as the strength tends to in nity. The degree of localization of the Wannier functions, as expressed by the position standard deviation, behaves similarly to the width of the energy bands. In addition to perfect crystals, Materials Science studies defective crystals. Defects are responsible for many properties of technological interest and can induce localized states. In this work, the localized state of lowest energy in the fractional Kronig-Penney model with defect is calculated through of the Fourier transform method and the Wannier functions. It was shown that is decays as a power law.

As a result of the computing power provided by the current technology, computational methods now play an important role in modeling and designing materials at the nanoscale. The focus of this dissertation is two-fold: first, new computational methods to model nanoscale transport are introduced, then state-of-the-art tools based on density functional theory are employed to explore the properties of phosphorene, a novel low dimensional material with great potential for applications in nanotechnology. A Wannier function description of the electron density is combined with a generalized Slater-Koster interpolation technique, enabling the introduction of a new computational method for constructing first-principles model Hamiltonians for electron and hole transport that maintain the density functional theory accuracy at a fraction of the computational cost. As a proof of concept, this new approach is applied to model polythiophene, a polymer ubiquitous in organic photovoltaic devices. A new low dimensional material, phosphorene - a single layer of black phosphorous - the phosphorous analogue of graphene was first isolated in early 2014 and has attracted considerable attention. It is a semiconductor with a sizable band gap, which makes it a perfect candidate for ultrathin transistors. Multi-layer phosphorene transistors have already achieved the highest hole mobility of any two-dimensional material apart from graphene. Phosphorene is prone to oxidation, which can lead to degradation of electrical properties, and eventually structural breakdown. The calculations reported here are some of the first to explore this oxidation and reveal that different types of oxygen defects are readily introduced in the phosphorene lattice, creating electron traps in some situations. These traps are responsible for the non-ambipolar behavior observed by experimental collaborators in air-exposed few-layer black phosphorus devices. Calculation results predict that air exposure of phosphorene creates a new family of two-dimensional oxides, which has been later confirmed by X-ray photoemission measurements. These oxides can form protective coatings for phosphorene and have interesting tunable electronic properties. Finally, Wannier function interpolation has been used to demonstrate that a saddle-point van Hove singularity is present near the phosphorene Fermi energy, as observed in some layered cuprate high temperature superconductors; this leads to an intriguing strain-induced ferromagnetic instability.

This thesis employs experimental and theoretical methods to characterise carbon nitride solids and proposes a generalstructural model for amorphous carbon nitride (a-C:N). It finds that a-C:N deposited by several methods is essentially identical, with similar bonding environments for carbon and nitrogen atoms. Using evidence from several techniques, the saturation of nitrogen in an sp2 carbon matrix is discussed. The experimental studies on a range of carbon nitride solids show no evidence for a crystalline form of carbon nitride. In addition to the experimental characterisation of a-C:N, ab initio molecular dynamics were used to investigate bonding and structure in carbon nitride. These simulations show that the most common form of nitrogen bonding was three-fold sites with a lone pair of electrons. Two-fold nitrogen sites were also found in agreement with experimental findings. An increase of nitrogen in a-C:N decreases the sp3-carbon fraction, but this is not localised on the nitrogen and the effect is most severe at high densities. A simulation of a low density/high nitrogen content network shows that the nitrogen saturation seen experimentally may be due to the formation of N2 dimers and C-N molecules which are easily driven out of the structure. The ab initio simulations also explore the nature of charged nitrogen and carbon sites in a-C:N. An analysis based on Wannier Function centres provided further information about the bonding and allowed for a detailed classification of these sites. The removal of electrons from the networks caused structural changes that could explain the two-state conductivity in ta-C:N memory devices. Finally, a theoretical study of the electron energy-loss near-edge structure (ELNES) calculated using multiple scattering theory is presented. The calculated ELNES of diamond, graphite and boron, silicon and carbon nitride structures compare well to experiment and supports the experimental finding that no crystalline carbon nitride had (or has) been produced. These ELNES calculations will however, provide a means of identifying crystalline beta-C3N4 should it be synthesised.

Nous présentons des résultats mathématiques obtenus pour un nouveau modèle de champ moyen dédié à la description d'électrons quantiques interagissant dans des cristaux comportant des défauts locaux. Ce modèle est dérivé du modèle dit de supercellule par un procédé de limite thermodynamique. ous travaillons avec un modèle de Hartree-Fock réduit, obtenu à partir du modèle de Kohn-Sham étendu en négligeant le terme d'échange-corrélation. Les modèles utilisés et les résultats obtenus sont présentés au chapitre 2 puis démontrés au chapitre 4. Les chapitres 3 et 5 sont consacrés à la simulation numérique de notre modèle. Notre approche consiste à mettre en œuvre une approximation variationnelle dans une base précalculée de fonctions de Wannier du cristal parfait de référence. Nous présentons quelques résultats numériques obtenus sur un modèle uni dimensionnel avec un potentiel d'interaction de Yukawa.

We performed ab initio studies of the electronic excitation spectra of the ferro- magnetic, Mott-insulator YTiO3 using density functional theory (DFT) and time- dependent density functional theory (TDDFT). In the ground state description, we included a Hubbard U to account for the strong correlations present within the d states on the cation. The excitation spectra was calculated using TDDFT linear response formalism in both the optical limit and the limit of large wavevector transfer. In order to identify the local d-d transitions in the response, we also computed the density response of YTiO3 using a novel technique where the basis included Wannier functions generated for the Ti and Y sites. Also, we describe the first implementation of the all-electron Kohn-Sham density functional equations in a periodic system using multi-wavelets and fast integral equations using MADNESS (multiresolution adaptive numerical environment for scientific simulation; http://code.google.com/p/m-a-d-n- e-s-s). This implementation is highlighted by the real space lattice sums involved in the application of the Coulomb and bound state Helmlholtz integral operators.

Le champ électromagnétique térahertz (THz) se situe dans l'intervalle de fréquence entre l'infrarouge et les micro-ondes, à peu près entre 1 THz à 10 THz. Ce domaine est hautement souhaitable tant pour la recherche fondamentale que pour les applications. Pourtant des sources THz compacts et accordables ne sont pas encore disponibles. Depuis la première proposition en 1970, les superréseaux semiconducteurs, dans lequel deux couches semi-conductrices atomiques avec bande interdite différente sont disposés périodiquement, fournissent de nouvelles possibilités. De nouvelles techniques et de nouveaux dispositifs deviennent réalisables. Dans cette thèse, les oscillations de Bloch dans des mini-bandes électroniques d'un superréseau polarise et la dispersion du gain associée sont utilisées pour réaliser une source THz compacte et accordable : l'oscillateur de Bloch THz. Un premier ensemble de dispositifs utilisent des réseaux dopes spécifiquement conçus pour éviter la formation de domaine d'accumulation de charges. Ces dispositifs utilisent une surface semi-isolante ou deux surfaces métalliques permettant un guidage par plasmon de surface. Cependant, malgré la réalisation de couplage par les bords ou par un réseau diffractant en surface et des mesures directes ou avec un interféromètre a transformation de Fourrier (FTIR), l'électroluminescence a été observée dans le domaine térahertz, avec un gain qui n'a pas pu etre relie aux oscillations de Bloch. Avec des superréseaux non dope, l'émission THz des oscillations de Bloch a été détectée par spectroscopie dans le domaine temporel. La dépendance de la fréquence d'émission avec le champ électrique appliqué constitue une preuve directe des oscillations de Bloch. L'échelle de Wannier Stark des trous sous pompage optique continu a aussi été observe dans les superréseaux non dopes. Avec l'augmentation de la puissance de pompage optique, les pics du photocourant se décalent et leurs formes deviennent asymétriques. L'évolution est attribue a l'accumulation des porteurs photogénérés dans les deux couches encadrant le superréseau. En outre, pour une puissance de pompage élevée, la bistabilité du photocourant a été également observée.

This thesis employs experimental and theoretical methods to characterise carbon nitride solids and proposes a generalstructural model for amorphous carbon nitride (a-C:N). It finds that a-C:N deposited by several methods is essentially identical, with similar bonding environments for carbon and nitrogen atoms. Using evidence from several techniques, the saturation of nitrogen in an sp2 carbon matrix is discussed. The experimental studies on a range of carbon nitride solids show no evidence for a crystalline form of carbon nitride. In addition to the experimental characterisation of a-C:N, ab initio molecular dynamics were used to investigate bonding and structure in carbon nitride. These simulations show that the most common form of nitrogen bonding was three-fold sites with a lone pair of electrons. Two-fold nitrogen sites were also found in agreement with experimental findings. An increase of nitrogen in a-C:N decreases the sp3-carbon fraction, but this is not localised on the nitrogen and the effect is most severe at high densities. A simulation of a low density/high nitrogen content network shows that the nitrogen saturation seen experimentally may be due to the formation of N2 dimers and C-N molecules which are easily driven out of the structure. The ab initio simulations also explore the nature of charged nitrogen and carbon sites in a-C:N. An analysis based on Wannier Function centres provided further information about the bonding and allowed for a detailed classification of these sites. The removal of electrons from the networks caused structural changes that could explain the two-state conductivity in ta-C:N memory devices. Finally, a theoretical study of the electron energy-loss near-edge structure (ELNES) calculated using multiple scattering theory is presented. The calculated ELNES of diamond, graphite and boron, silicon and carbon nitride structures compare well to experiment and supports the experimental finding that no crystalline carbon nitride had (or has) been produced. These ELNES calculations will however, provide a means of identifying crystalline beta-C3N4 should it be synthesised.

Stuttgart, Univ., Diss., 2002.

Made available in DSpace on 2014-06-11T19:30:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-04-18Bitstream added on 2014-06-13T20:20:42Z : No. of bitstreams: 1 romano_mc_me_bauru.pdf: 1627459 bytes, checksum: 18d280916e43c7dadfd84a8bfbb6e9f0 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Os cristais fotônicos são novos materiais em que a permissividade dielétrica e a permeabilidade magnética apresentam a periodicidade de uma rede de Bravais. No caso dos sólidos cristalinos, é a energia potencial de cada elétron que apresenta esse tipo de periodicidade. Por conta das semelhanças que existem entre as equações que descrevem os sintomas eletrônicos e fotônicos, muitos dos conceitos e métodos da teoria de estados eletrônicos vêm sendo aplicados na investigação de cristais fotônicos. Dentre esses conceitos, as funções de Wannier apresentam vantagens para o tratamento de estados eletrônicos e modos fotônicos localizados. Este trabalho aborda o caso de cristais fotônicos unidimensionais com simetria de inversão. Primeiramente são calculados e analisadas funções de Wannier bem localizadas. Em seguida são investigados os modos eletromagnéticos localizados produzidos por defeitos em cristais fotônicos, utilizando o método de matriz de transferência e o método da combinação linear das funções de Wannier. Finalmente, é feita a comparação dos resultados obtidos mediante esses métodos e são discutidas as vantagens do uso de funções de Wannier / Photonic crystal are new materials where both the dielectric permittivity and the magnetic permeability present the periodicity of a Bravais lattice. In the case of electronic states, this property is shown by the mono-eletronic potential energy. Due to the similarities between the eletronic and photonic problems, many concepts and methods of theory of electronic states are being applied to investigate photonic crystals. Among such concepts, the Wannier functions are advantageous to deal with either localized photonic modes. This work addresses the case of one-dimensional photonic crystals with inversion symmetry. First, well-localized Wannier functions are calculated and analyzed. Then, the localized modes produced by defects in photonic crystals are investigated by using either transfer matrices or linear combination Wannier functions. Finally, the results obtained by the two methods are compared and the advantages of using Wannier functions are discussed