Increasing ubiquity of computational resources has enabled simulation of complex electronic systems and modern materials. The PAOFLOW software package is a tool designed to construct and analyze tight binding Hamiltonians from the solutions of DFT calculations. PAOFLOW leverages localized basis sets to greatly reduce computational costs of post-processing QE simulation results, enabling efficient determination of properties such as electronic density, band structures in the presence of electric or magnetic fields, magnetic or spin circular dichroism, spin-texture, Fermi surfaces, spin or anomalous Hall conductivity (SHC or AHC), electronic transport, and more. PAOFLOW's broad functionality is detailed in this work, and several independent studies where PAOFLOW's capabilities directly enabled research on promising candidates for ferroelectric and spintronic based technologies are described. Today, Quantum computers are at the forefront of computational information science. Materials scientists and quantum chemists can use quantum computers to simulate interacting systems of fermions, without having to perform the iterative methods of classical computing. This dissertation also describes a study where the band structure for silicon is simulated for the first time on quantum hardware and broadens this concept for simulating band structures of generic crystalline structures on quantum machines.

L’interface entre le silicium amorphe (a-Si:H) et le silicium cristallin (c-Si) est un constituent clés de cellules solaires à haut rendement reposant sur des procédés à basse température. Trois propriétés de l’interface déterminent le rendement des cellules solaires à hétérojonction de silicium: les décalages de bandes entre a-Si:H et c-Si, les défauts d’interface et la courbure de bande dans c-Si. Ces trois aspects sont traités dans ces travaux de thèse.Dans un premier un temps, un calcul analytique de la courbure de bande dans c-Si est développé. Il repose sur l’approximation d’une densité d’état (DE) constante dans la bande interdite de a-Si:H. L’influence des principaux paramètres de la structure sur la courbure de bande est étudiée : décalage de bande, densité d’état dans a-Si:H, défaut d’interface, etc. La présence d’un effet de confinement quantique est discutée. Grâce à une comparaison entre ces calculs et des mesures de conductance planaire en fonction de la température sur des structures (p)a-Si:H/(n)c-Si et (n)a-Si:H/(p)c-Si, les décalages de bande de valence et de conduction ont pu être estimés à 0.36 eV et 0.15 eV respectivement. En outre, il est montré que le décalage de la bande de valence est indépendant de la température, alors que le décalage de la bande de conduction suit les évolutions des bandes interdites de c-Si et a-Si:H. Ces mesures tendent à prouver que le ‘branch point’ dans a-Si:H est indépendant du dopage.Ensuite, les calculs analytiques sont approfondis pour prendre en compte différents aspects de la structure complète incorporée dans les cellules : contact avec un oxyde transparent conducteur, présence d’une couche de a-Si:H non-dopée à l’interface. A l’aide de simulations numériques et à la lumière de mesures de conductance planaire conjuguées à des mesures de la qualité de passivation de l’interface, des pistes pour optimiser les cellules à hétérojonction sont commentées. En particulier, il est montré qu’un optimum doit être trouvé entre une bonne passivation et une courbure de bande suffisante. Ceci peut être accompli par un réglage fin des propriétés de la couche tampon (épaisseur, dopage), du contact (travail de sortie élevé) et de l’émetteur (p)a-Si:H (densité de défauts et épaisseur). En particulier, un émetteur avec une DE importante conduit paradoxalement à de meilleures performances.Enfin, un nouveau type d’interface a été développé. La surface de c-Si a été oxydée volontairement dans de l’eau pure dé-ionisée à 80 °C avant le dépôt de (p)a-Si:H afin d’obtenir une structure (p)a-Si:H/SiO2/(n)c-Si. A l’aide d’un modèle de courant par effet tunnel implémenté dans le logiciel de simulation numérique AFORS-HET, l’effet d’une couche à grande bande interdite (comme c’est le cas pour SiO2) sur les performances de cellules est étudié : le facteur de forme et le courant de court-circuit sont extrêmement réduits. En revanche, une couche de SiO2 n’a que peu d’impact sur les propriétés optiques de la structure. Expérimentalement, les échantillons réalisés montrent une qualité de passivation à mi-chemin entre le cas sans couche tampon et le cas avec (i)a-Si:H : ceci est expliqué par la présence d’une charge fixe négative dans l’oxyde. La courbure de bande dans c-Si est moins affectée par la présence d’une couche d’oxyde que d’une couche de (i)a-Si:H. Les cellules solaires réalisées démontrent que le concept a le potentiel d’aboutir à de hauts rendements : sur des structures non-optimisées, une tension de court-circuit supérieure à 650 mV a été démontrée, alors que l’oxyde ne semble pas limiter le transport de charge. / The interface between amorphous silicon (a-Si:H) and crystalline silicon (c-Si) is the building block of high efficiency solar cells based on low temperature fabrication processes. Three properties of the interface determine the performance of silicon heterojunction solar cells: band offsets between a-Si:H and c-Si, interface defects and band bending in c-Si. These three points are addressed in this thesis.First, an analytical model for the calculation of the band bending in c-Si is developed. It assumes a constant density of states (DOS) in the a-Si:H band gap. The influence of most parameters of the structure on the band bending is studied: band offsets, DOS in a-Si:H, interface defects, etc. The presence of quantum confinement at the interface is discussed. Analytical calculations and temperature dependent planar conductance measurements are compared such that the band offsets on both (p)a-Si:H/(n)c-Si and (n)a-Si:H/(p)c-Si can be estimated: the valence band offset amounts 0.36 eV while the conduction band offset is 0.15 eV. In addition, it is shown that the valence band offset is independent of temperature whereas the conduction band offset follows the evolutions of c-Si and a-Si:H band gaps with temperature. A discussion of these results in the frame of the branch point theory for band line-up leads to the conclusion that the branch point in a-Si:H is independent of the doping.Then, analytical calculations are developed further to take into account the real solar cell structure where the a-Si:H/c-Si structure is in contact with a transparent conductive oxide and an undoped buffer layer is present at the interface. Measurements of the planar conductance and of the interface passivation quality are interpreted in the light of analytical calculations and numerical simulations to open a way towards a method for the optimization of silicon heterojunction solar cells. It is particularly shown that a trade-off has to be found between a good passivation quality and a significant band bending. This can be realized by tuning the buffer layer properties (thickness, doping), the TCO-contact (high work function) and the emitter (defect density and thickness). Interestingly, an emitter with a high DOS leads to better cell performances.Finally, a new type of interface has been developed, that was not applied to heterojunction solar cells so far. The c-Si surface has been oxidized in deionized water at 80 °C before the (p)a-Si:H emitter deposition such that (p)a-Si:H/SiO2/(n)c-Si structures were obtained. A tunneling current model has been developed, implemented in the 1D numerical device simulator AFORS-HET and used to study the effect of a wide band gap interfacial layer (as it is the case for SiO2) on cell performance: the fill-factor and the short-circuit current are dramatically reduced for thick and high barriers. However, a SiO2 layer has only little impact on optical properties. Fabricated samples show a passivation quality halfway between samples with no buffer layer and with an (i)a-Si:H buffer layer: this is explained by the presence of a negative fixed charge in the oxide. The band bending in (n)c-Si is higher with an oxide layer than with an (i)a-Si:H buffer layer. Solar cells demonstrate that this new concept has the potential to achieve high power conversion efficiencies: for non-optimized structures, an open-circuit voltage higher than 650 mV has been demonstrated, while the oxide does not seem to create a barrier to charge transport.

Le graphène est un cristal bidimensionnel composé d'atomes de carbone arrangés sur un réseau en nids d'abeille. Ce matériau présente des propriétés électroniques intéressantes tant au niveau fondamental qu'en vue d'applications avec notamment une structure de bande exotique en « cône de Dirac » et de grandes mobilités de porteurs. Sa fabrication par graphitisation du SiC est particulièrement adaptée aux applications électroniques. Nous avons étudié ce système par microscopie à effet tunnel (STM) et simulations numériques ab initio avec comme objectif la caractérisation au niveau atomique de l'interface graphène - SiC(000-1) (face carbone) et l'étude de l'impact du substrat sur la structure électronique du graphène. Après un chapitre introductif à la thématique du graphène, suivi d'un chapitre présentant les deux techniques utilisées au cours de ce travail, nous présentons nos échantillons faiblement graphitisés obtenus sous ultra-vide. Nous avons identifié deux types d'interfaces, les reconstructions natives de la surface du SiC(000-1) appelées (2x2)C et (3x3), sur lesquelles reposent les ilots monoplan de graphène, avec un fort désordre rotationnel donnant lieu à des figures de moiré sur les images STM. Nous montrons par imagerie STM et spectroscopie tunnel que l'interaction graphène/(3x3) est très faible. Nous étudions ensuite le cas d'interaction plus forte graphène/(2x2) successivement du point de vue des états du graphène et des états de la reconstruction, dans l'espace direct et réciproque, de façon expérimentale et théorique. Enfin, nous considérons l'effet de défauts observés par STM à l'interface des ilots sur (2x2), modélisés par des adatomes d'hydrogène, sur le dopage et la structure de bande électronique du graphène. / Graphene refers to a two-dimensional crystal made of carbon atoms arranged on a honeycomb lattice. This material presents interesting electronic properties regarding fundamental physics as well as industrial applications, such as an exotic low-energy band structure and high charge carrier mobility. Its fabrication through the graphitization of SiC is a promising method for electronics. We studied this system using scanning tunnelling microscopy (STM) and ab initio numerical simulations with the aim of characterizing the graphene - SiC(000-1) (carbon face) interface and studying the impact of the substrate on graphene's electronic structure. After an introduction to the graphene topic and a description of our investigation techniques, we present our lightly graphitized samples obtained under ultra-high vacuum. We identify two interface structures, the native SiC(000-1) surface reconstructions named (2x2)C and (3x3), on top of which lie graphene monolayer islands with a high rotational disorder leading to various moiré patterns on STM images. Using STM, we show that the graphene/(3x3) interaction is very weak. We then study the stronger graphene/(2x2) interaction successively from the point of view of the graphene and the reconstruction states, in the direct and reciprocal space, using both our experimental and theoretical methods. Finally, we consider the impact of interfacial defects observed by STM through graphene/(2x2) islands and modelled with hydrogen adatoms on the electronic band structure and doping of graphene

A new approach to the discovery of high absorbing semiconductors for solar cells was taken by working under a set of design principles and taking a systemic methodology. Three transition metal chalcogenides at varying states of development were evaluated within this framework. Iron pyrite (FeS���) is well known to demonstrate excellent absorption, but the coexistence with metallic iron sulfides was found to disrupt its semiconducting properties. Manganese diselenide (MnSe���), a material heavily researched for its magnetic properties, is proposed as a high absorbing alternative to iron pyrite that lacks destructive impurity phases. For the first time, a MnSe��� thin film was synthesized and the optical properties were characterized. Finally, CuTaS���, a known but never characterized material, is also proposed as a high absorbing semiconductor based on the design principles and experimental results. / Graduation date: 2013

Kohlenstoffnanoröhrchen (engl. carbon nanotubes, CNTs) sind Dank ihrer außergewöhnlichen elektrischen Eigenschaften Kandidaten für eine Vielzahl von Anwendungen im Bereich der Mikroelektronik. Ihre ballistischen Transporteigenschaften und die geringe Anfälligkeit auf Elektromigration sind vorteilhaft für die Anwendung von CNTs in Interconnectsystemen. Die Abhängigkeit der elektrischen Transporteigenschaften von mechanischer Verformung bildet weiterhin die Grundlage für die Produktion neuartiger Sensoren auf CNT-Basis. Durch die Besetzung mit Adatomen können diese Eigenschaften dabei weiter verbessert und bei der Herstellung gezielt eingestellt werden. Die Verformung besetzter CNTs ist dabei ein noch relativ unerforschtes Gebiet. In dieser Arbeit wird dieses Verhalten untersucht. Zu Beginn wird gezeigt, dass die Eigenschaften von CNTs durch die Besetzung mit verschiedenen Metallen auf unterschiedliche Weise beeinflusst werden können. Dazu gehören auch Unterschiede zwischen den Spinzuständen, welche bei einigen der untersuchten Metalle auftreten. Durch die axiale Verformung der CNTs wird abschließend gezeigt, dass die Sensoreigenschaften von CNTs auch nach der Besetzung mit Metallen erhalten bleiben.

Kohlenstoffnanoröhrchen (engl. carbon nanotube, CNT) sind vielversprechende Kandidaten für den Ersatz von Kupferleitbahnen die bei weiterer Strukturverkleinerung von integrierten Schaltkreisen notwendig wird. In dieser Arbeit wird mit Hilfe von ab-initio Simulationen auf Basis der Dichtefunktionaltheorie die elektronische Struktur von halbleitenden CNTs beispielhaft anhand des (8,4)-CNTs untersucht. Nach Besetzung des CNT mit Metallatomen, hier Kobalt, zeigen sich massive Änderungen der Bandstruktur. Es reichen bereits überraschend kleine Mengen des Metalls aus, um einen starken Effekt zu erreichen. Die Änderungen der elektronischen Struktur sind stark abhängig von der genauen Position der Metallatome relativ zum Kohlenstoffgerüst der CNTs, der Einfluss der mechanischen Verformung des CNTs als Reaktion auf die Anlagerung ist hingegen sehr gering. Die relevanten Bänder der Kobaltatome liegen leicht unterhalt der Fermi-Energie und sorgen bei der Integration in die Bandstruktur des CNTs für die Schließung der Bandlücke und somit für die Transformation eines vorher halbleitenden CNTs in ein leitendes. Diese Transformation konnte auch mit Simulationsrechnungen zum Elektronentransport bestätigt werden. Ferner wurden bei weiteren Rechnungen eine ausgeprägte Spinabhängigkeit der Bandstruktur ermittelt, welche noch weiterer Untersuchung bedarf.

This work investigates the defect energies, band alignments, and charge carrier recombination in polycrystalline Cu(In1-xGax)(Se1-ySy)2 chalcopyrite thin films and the interrelationship with the alloy composition. Photoluminescence spectroscopy of investigated Cu-poor Cu(In,Ga)(Se,S)2 layers generally shows broad emission lines with the corresponding maxima shifting towards higher energies under decreasing temperature or under increasing excitation power. Admittance spectroscopy of Cu-poor ZnO/CdS/Cu(In,Ga)(Se,S)2 chalcopyrite devices shows that the activation energies of the dominant defect distributions involving donors at the CdS/absorber interface and deep acceptors in the chalcopyrite bulk, increase upon alloying CuInSe2 with S. The band alignments within the Cu(In1-xGax)(Se1-ySy)2 system are determined using the energy position of the bulk acceptor state as a reference. The band gap enlargement under Ga alloying is accommodated almost exclusively in the rise of the conduction band edge, whereas the increase of band gap upon alloying with S is shared between comparable valence and conduction band offsets. The extrapolated band discontinuities [delta]EV(CuInSe2/CuInS2) = -0.23 eV, [delta]EC(CuInSe2/CuInS2) = 0.21 eV, [delta]EV(CuInSe2/CuGaSe2) = 0.036 eV, and [delta]EC(CuInSe2/CuGaSe2) = 0.7 eV are in good agreement with theoretical predictions. Current-voltage analysis of Cu-poor ZnO/CdS/Cu(In,Ga)(Se,S)2 devices reveals recombination barriers which follow the band gap energy of the absorber irrespective of alloy composition, as expected for dominant recombination in the chalcopyrite bulk. In turn, the recombination at the active junction interface prevails in Cu-rich devices which display substantially smaller barriers when compared to the band gap energy of the absorber. The result indicates that the Cu-stoichiometry is the driving compositional parameter for the charge carrier recombination in the chalcopyrite heterojunctions under investigations.

Im Rahmen dieser Doktorarbeit werden de Haas-van Alphen-Untersuchungen an den nichtmagnetischen Borkarbidsupraleitern LuNi2B2C und YNi2B2C präsentiert. Aus den Quantenoszillationen in der normalleitenden Phase in Kombination mit Bandstrukturrechnungen konnten Informationen über die verzweigte Fermiflächenarchitektur und über die Elektron-Phonon-Kopplung der Borkarbide gewonnen werden. Die Kopplung ist stark anisotrop und fermiflächenabhängig. Dies spricht für einen Mehrbandmechanismus der Supraleitung in der Materialklasse. Zusätzlich konnten de Haas-van-Alphen-Oszillationen mehrerer Fermiflächen unterhalb von Bc2 tief in der Shubnikov-Phase beobachtet werden. Das Verhalten dieser Oszillationen lässt sich nicht mit bisher bekannten Theorien beschreiben. Allerdings weist das Bestehen der Oszillationen weit unterhalb von Bc2 auf ein Bestehen von elektronischen Zuständen in der Shubnikov-Phase hin.

The search for alternate and renewable energy resources as well as the efficient use of energy and development of such systems that can help to save the energy consumption is needed because of exponential growth in world population, limited conventional fossil fuel resources, and to meet the increasing demand of clean and environment friendly substitutes. Hydrogen being the simplest, most abundant and clean energy carrier has the potential to fulfill some of these requirements provided the development of efficient, safe and durable systems for its production, storage and usage. Chemical hydrides, complex hydrides and nanomaterials, where the hydrogen is either chemically bonded to the metal ions or physiosorbed, are the possible means to overcome the difficulties associated with the storage and usage of hydrogen at favorable conditions. We have studied the structural and electronic properties of some of the chemical hydrides, complex hydrides and functionalized nanostructures to understand the kinetics and thermodynamics of these materials. Another active field relating to energy storage is rechargeable batteries. We have studied the detailed crystal and electronic structures of Li and Mg based cathode materials and calculated the average intercalation voltage of the corresponding batteries. We found that transition metal doped MgH2 nanocluster is a material to use efficiently not only in batteries but also in fuel-cell technologies. MAX phases can be used to develop the systems to save the energy consumption. We have chosen one compound from each of all known types of MAX phases and analyzed the structural, electronic, and mechanical properties using the hybrid functional. We suggest that the proper treatment of correlation effects is important for the correct description of Cr2AlC and Cr2GeC by the good choice of Hubbard 'U' in DFT+U method. Hydrogen is fascinating to physicists due to predicted possibility of metallization and high temperature superconductivity. On the basis of our ab initio molecular dynamics studies, we propose that the recent claim of conductive hydrogen by experiments might be explained by the diffusion of hydrogen at relevant pressure and temperature. In this thesis we also present the studies of phase change memory materials, oxides and amorphization of oxide materials, spintronics and sulfide materials.

In this work, the electronic band structure of III (In, Al, Ga) - V (N, As, Sb) compounds and their ternary alloys have been investigated by density functional theory (DFT) within generalized gradient approximation (GGA) and empirical tight binding (ETB) calculations, respectively. The present DFT-GGA calculations have shown direct band gap structures in zinc-blende phase for InN, InAs, InSb, GaN, and GaAs. However, indirect band gap structures have been obtained for cubic AlN, AlSb and AlAs com- pounds / here, the conduction band minima of both AlN and AlAs are located at X symmetry point, while that of AlSb is at a position lying along Gamma- X direction. An important part of this work consists of ETB calculations which have been parameterized for sp3d2 basis and nearest neighbor interactions to study the band gap bowing of III(In / Al)- V(N / As / Sb) ternary alloys. This ETB model provides a satisfactory electronic properties of alloys within reasonable calculation time compared to the calculations of DFT. Since the present ETB energy parameters reproduce successfully the band structures of the compounds at &iexcl / and X symme- try points, they are considered reliable for the band gap bowing calculations of the ternary alloys. In the present work, the band gap engineering of InNxAs1&iexcl / x, InNxSb1&iexcl / x, InAsxSb1&iexcl / x, Al1&iexcl / xInxN, Al1&iexcl / xInxSb and Al1&iexcl / xInxAs alloys has been studied for total range of constituents (0 &lt / x &lt / 1). The downward band gap bowing seems the largest in InNxAs1&iexcl / x alloys among the alloys considered in this work. A metallic character of InNxAs1&iexcl / x, InNxSb1&iexcl / x and InAsxSb1&iexcl / x has been ob- tained in the present calculations for certain concentration range of constituents (N / As) as predicted in the literature. Even for a small amount of contents (x), a decrease of the electronic e&reg / ective mass around &iexcl / symmetry point appears for InNxAs1-x, InNxSb1-x and InAsxSb1-x alloys manifesting itself by an increase of the band curvature. The calculated cross over from indirect to direct band gap of ternary Al alloys has been found to be consistent with the measurements. As a last summary, the determinations of the band gaps of alloys as a function of contents, the concentration range of con- stituents leading to metallic character of the alloys, the change of the electronic effective mass around the Brillioun zone center (Gamma) as a function of alloy contents, the cross over from indirect to direct band gap of the alloys which are direct on one end, indirect on the other end, are main achievements in this work, indispensable for the development of mate- rials leading to new modern circuit components.