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The electrical properties of ZnO and contacts to ZnO have been investigated using different techniques. Temperature dependent Hall (TDH) effect measurements have been used to characterize the as-received melt grown ZnO samples in the 20 – 330 K temperature range. The effect of argon annealing on hydrogen peroxide treated ZnO samples has been investigated in the 200 – 800oC temperature range by the TDH effect measurement technique. The experimental data has been analysed by fitting a theoretical model written in Matlab to the data. Donor concentrations and acceptor concentrations together with the associated energy levels have been extracted by fitting the models to the experimentally obtained carrier concentration data by assuming a multi-donor and single charged acceptor in solving the charge balance equation. TDH measurements have revealed the dominance of surface conduction in melt grown ZnO in the 20 – 40 K temperature range. Surface conduction effects have proved to increase with the increase in annealing temperature. Surface donor volume concentrations have been determined in the 200 – 800oC by use of theory developed by D. C. Look. Good rectifying Schottky contacts have been fabricated on ZnO after treating the samples with boiling hydrogen peroxide. Electrical properties of these Schottky contacts have been investigated using current-voltage (IV) and capacitance-voltage (CV) measurements in the 60 – 300 K temperature range. The Schottky contacts have revealed the dominance of predominantly thermionic emission at room temperature and the existence of other current transport mechanisms at temperatures below room temperature. Polarity effects on the Schottky contacts deposited on the O-polar and Zn-polar faces of ZnO have been demonstrated by the IV technique on the Pd and Au Schottky contacts at room temperature. Results obtained indicate a strong dependence of the Schottky contact quality on the polarity of the samples at room temperature. The quality of the Schottky contacts have also indicated their dependence on the type of metal used with the Pd producing contacts with the better quality as compared to the Au. Schottky barrier heights determined using temperature dependent IV measurements have been observed to increase with increasing temperature and this has been explained as an effect of barrier inhomogeneities, while the ones obtained from CV measurements have proved to follow the negative temperature coefficient of the II – VI semiconductor material, i.e. a decrease in barrier height with increasing temperature. However, the values have proved to be larger than the energy gap of ZnO, an effect that has been explained as caused by an inversion layer. Copyright / Dissertation (MSc)--University of Pretoria, 2010. / Physics / unrestricted

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Dans cette thèse je me suis intéressé au caractère relativiste de matériaux topologiques tridimensionnels : les semi-métaux de Weyl et les isolants topologiques. Après une introduction aux états de surfaces et aux matériaux topologiques, je discute leurs propriétés de covariance sous les rotations trigonométriques et hyperboliques. Ces transformations me permettent de traiter les équations du mouvement d'un électron dans un champ magnétique ou à la surface, sous l'influence d'un champ électrique ou d'une inclinaison de la relation de dispersion. En première partie, je l'illustre dans le cas de la réponse magnéto-optique des semi-métaux de Weyl, en présence d'une inclinaison. Ces calculs sont en lien avec ma collaboration avec les expérimentateurs du LNCMI à Grenoble pour la caractérisation de la structure de bande de Cd₃As₂ où l'on montre que ce matériau est un semi-métal de Kane et non un semi-métal de Dirac dans la gamme de potentiels chimiques expérimentalement accessible. L'autre partie de cette thèse porte sur les états de surface des isolants topologiques où l'on montre qu'il existe des états de surface massifs au-delà de l'état de surface chiral. Ces états semblent avoir été observés par des études en ARPES d'échantillons de Bi₂Se₃ et Bi₂Te₃ oxydés et par des mesures de transport sur HgTe déformé. J'ai ainsi eu l'occasion de travailler avec les expérimentateurs du LPA à Paris sur le comportement des états de surface de HgTe sous forts effets de champ. Je termine par une discussion des états à l'interface entre un semi-métal de Weyl et un isolant dans le cas où le gap de ce dernier est suffisamment petit pour observer l'effet d'un champ magnétique et d'une inclinaison de la relation de dispersion sur les états de surface. / During my PhD studies I focused on the relativistic properties of threedimensional topological materials, namely Weyl semimetals and topological insulators. After introducing surface states and topological materials I discuss their covariance in trigonometric and hyperbolic rotations. These transformations help to solve the equations of motion of an electron in a magnetic field or at the surface with an applied electric field or with a tilt in the band dispersion. In a first place, I illustrate these transformations for the magneto-optical response of tilted Weyl semimetals. This work is related to my collaboration with experimentalists at LNCMI, Grenoble for characterizing the band structure of Cd₃As₂ where we show that this material is a Kane semi-metal instead of a Dirac semi-metal in the experimentally accessible range of chemical doping. The other part of this thesis is concerned with the surface states of topological insulators. I show that massive surface states can also exist in addition to the chiral surface state due to band inversion. Such states may have already been observed in ARPES measurement of oxidized Bi₂Se₃ and Bi₂Te₃ and in transport measurement of strained bulk HgTe. I show the work we performed with experimentalists at LPA, Paris on the behavior of HgTe surface states for strong field effects. Finally, I discuss the states at the interface of a Weyl semimetal and a small gap insulator. In this situation, an applied magnetic field or the tilt of the band dispersion can strongly affect the observed surface states.

En viabilité hivernale, la prévision de l’état de surface des infrastructures s’avère indispensable, et permet une anticipation, une meilleure coordination et une efficacité d’intervention des services d’exploitation. La majorité des pays dispose de modèles de prévision de la température de surface d'infrastructures et des routes en particulier (TSR). La complexité de ces outils d’aide à la décision est croissante, pour servir au mieux les usagers et l’exploitant. Le microclimat urbain influence le bilan énergétique de surface selon différents processus : radiatifs, aérodynamiques et hydrologiques. Néanmoins, d’autres processus physiques anthropiques influencent cette TSR, tel que le trafic. Des travaux ont été menés par le passé concernant l’apport énergétique du trafic dans le bilan thermique de la ville. Celui-ci a fait l’objet d’études sur les périodes estivales et les îlots de chaleur urbains associés. Cependant, dans les cas de dégradations des conditions hivernales de circulation, ces apports énergétiques ont été intégrés de façon marginale dans la modélisation des paramètres de surface de la route. L’absence de cette contribution du trafic dans la modélisation du bilan énergétique de surface explique, dans une certaine limite, la prévision imparfaite de l’état de surface de la route. La bibliographie recense plusieurs études conduites afin d’identifier et de quantifier ces effets du trafic. Elles n'ont pas ou peu traité la perte ou le gain d'énergie causé par le passage des véhicules sur le bilan énergétique de surface, ou sur la modélisation de la TSR. Dans la présente étude, deux approches ont été proposées pour paramétrer le trafic dans le modèle numérique Town Energy Balance (TEB), l'une globale et la seconde détaillée. Leur analyse comparée indique que la seconde a significativement amélioré les résultats de la modélisation de la TSR. Les apports thermiques du trafic ont augmenté la TSR de 2 à 4°C pour la rapprocher des mesures expérimentales (écart de 0.5 à 1°C en moyenne). Elle est le résultat de l’effet cumulatif des différents processus physiques associés au trafic, et varie en fonction de ses paramètres (densité, vitesse de circulation, fluidité, etc.). Une étude de sensibilité a été menée afin d’apprécier les processus physiques responsables de l’amélioration de la TSR. Les résultats indiquent que l’effet turbulent, la densité de flux radiatif ainsi que la densité de flux due aux frottements des pneumatiques contribuent le plus à l'augmentation la TSR. Néanmoins la contribution énergétique de chacun de ces processus dépend à la fois des paramètres du trafic et des conditions météorologiques. Cette étude a présenté également une analyse préliminaire de l’influence de la lame d’eau présente en surface sur la TSR. Cette dernière décroit en fonction de l’épaisseur de la lame d’eau. Les facteurs anthropiques tels que le trafic et l’adjonction de fondants routiers sur la lame d’eau présente en surface sont décrits et discutés, et une paramétrisation proposée en perspectives / In winter maintenance, forecasting the infrastructure surface status is mandatory, to allow anticipation, better coordination and efficiency of services. The majority of countries have forecast models of the infrastructure surface temperature and especially roads one (RST). The complexity of these decision tools is growing, to best serve the users and managers. The urban microclimate influences the surface energy balance according to various processes: radiative, aerodynamic and hydrologic. However, other anthropogenic physical processes influence this RST, such as traffic. Studies have been carried out in the past about the traffic heat input in the town heat balance. These were conducted on the summer periods and associated urban heat islands. However, in case of traffic in adverse winter conditions, these energy contributions were marginally integrated into the modeling of the road surface parameters. The absence of this traffic's contribution in the surface energy balance modeling explains, to a given limit, the imperfect forecasting of road surface status. The literature identifies several studies conducted to identify and to quantify these effects of traffic. They have insufficiently or not treated the loss or gain on energy caused by circulating vehicles on the surface energy balance, or on modeling the RST. In this study, two approaches have been proposed to parameterize the traffic in the Town Energy Balance (TEB) numerical model, this first one being overall and the second one detailed. Their comparative analysis indicates that the second significantly improved the results of the RST modeling. The traffic heat inputs increased RST by 2 to 4°C, results being then closer to experimental measurements (average difference of 0.5 to 1°C). It is the result of the cumulative effect of the various traffic physical processes, and varies according to its parameters (density, vehicle velocity, fluidity, etc.). A sensitivity analysis was conducted to assess the physical processes responsible for the improvement of the RST. The results indicate that the turbulent effect, the radiative heat flux and flux density due to tires friction represent the greatest contribution to RST increase. Nevertheless the energy contribution of each of these processes depends both traffic parameters and weather conditions. This study also presented a preliminary analysis of the influence of a water layer over the surface on the RST. The latter decreases as a function of the thickness of the water layer. Anthropogenic factors such as traffic and the addition of de-icing products into the water layer present on the surface are described and discussed, and a parameterization proposed as a perspective

Über die besonders hohe Effizienz von Halid-Perowskit (HaP)-basierten optoelektronischen Bauteilen wurde bereits in der Literatur berichtet. Um die Entwicklung dieser Bauteile voranzutreiben, ist ein umfassendes und verlässliches Verständnis derer elektronischen Struktur, sowie der Energielevelanordnung (ELA) an HaP Grenzflächen von größter Bedeutung. Demzufolge beschäftigt sich die vorliegende Arbeit mit der Untersuchung i) der Bandstruktur von Perowskit-Einkristallen, um ein solides Fundament für die Darlegung der elektronischen Eigenschaften von polykristallinen Dünnschichten zu erarbeiten, und mit ii) den Einflüssen von Oberflächenzuständen auf die elektronische Struktur der Oberfläche, sowie deren Rolle bei der Kontrolle von ELA an HaP Grenzflächen. Die Charakterisierung erfolgt überwiegend mithilfe von Photoelektronenspektroskopie (PES) und ergänzenden Messmethoden wie Beugung niederenergetischer Elektronen an Oberflächen, UV-VIS-Spektroskopie, Rasterkraftmikroskopie und Kelvin-Sonde. Erstens weist die Banddispersion von zwei prototypischen Perowskit-Einkristallen eine starke Dispersion des jeweiligen oberen Valenzbandes (VB) auf, dessen globales Maximum in beiden Fällen am R-Punkt in der Brillouin-Zone liegt. Dabei wird eine effektive Lochmasse von 0.25 m0 für CH3NH3PbBr3, bzw. von ~0.50 m0 für CH3NH3PbI3 bestimmt. Basierend auf diesen Ergebnissen werden die elektronischen Spektren von polykristallinen Dünnschichten konstruiert und es wird dadurch aufgezeigt, dass eine Bestimmung der Valenzbandkantenposition ausgehend von einer logarithmischen Intensitätsskala aufgrund von geringer Zustandsdichte am VB Maximum vorzuziehen ist. Zweitens stellt sich bei der Untersuchung der elektronischen Struktur von frisch präparierten Perowskit-Oberflächen heraus, dass die n-Typ Eigenschaft eine Folge der Bandverbiegung ist, welche durch donatorartige Oberflächenzustände hervorgerufen wird. Des Weiteren weisen die PES-Messungen an Perowskiten mit unterschiedlichen Zusammensetzungen aufgrund von Oberflächenphotospannung eine Anregungslichtintensitätsabhängigkeit der Energieniveaus von bis zu 0.7 eV auf. Darüber hinaus wird die Kontrolle von ELA durch gezielte Variation der Oberflächenzustandsdichte gezeigt, wodurch sich unterschiedliche ELA-Lagen (mit Abweichungen von über 0.5 eV) an den Grenzflächen mit organischen Akzeptormolekülen erklären lassen. Die vorliegenden Ergebnisse verhelfen dazu, die starke Abweichung der in der Literatur berichteten Energieniveaus zu erklären und somit ein verfeinertes Verständnis des Funktionsprinzips von perowskit-basierten Bauteilen zu erlangen. / Optoelectronic devices based on halide perovskites (HaPs) and possessing remarkably high performance have been reported. To push the development of such devices even further, a comprehensive and reliable understanding of their electronic structure, including the energy level alignment (ELA) at HaPs interfaces, is essential but presently not available. In an attempt to get a deep insight into the electronic properties of HaPs and the related interfaces, the work presented in this thesis investigates i) the fundamental band structure of perovskite single crystals, in order to establish solid foundations for a better understanding the electronic properties of polycrystalline thin films and ii) the effects of surface states on the surface electronic structure and their role in controlling the ELA at HaPs interfaces. The characterization is mostly performed using photoelectron spectroscopy, together with complementary techniques including low-energy electron diffraction, UV-vis absorption spectroscopy, atomic force microscopy and Kelvin probe measurements. Firstly, the band structure of two prototypical perovskite single crystals is unraveled, featuring widely dispersing top valence bands (VB) with the global valence band maximum at R point of the Brillouin zone. The hole effective masses there are determined to be ~0.25 m0 for CH3NH3PbBr3 and ~0.50 m0 for CH3NH3PbI3. Based on these results, the energy distribution curves of polycrystalline thin films are constructed, revealing the fact that using a logarithmic intensity scale to determine the VB onset is preferable due to the low density of states at the VB maximum. Secondly, investigations on the surface electronic structure of pristine perovskite surfaces conclude that the n-type behavior is a result of surface band bending due to the presence of donor-type surface states. Furthermore, due to surface photovoltage effect, photoemission measurements on different perovskite compositions exhibit excitation-intensity dependent energy levels with a shift of up to 0.7 eV. Eventually, control over the ELA by manipulating the density of surface states is demonstrated, from which very different ELA situations (variation over 0.5 eV) at interfaces with organic electron acceptor molecules are rationalized. Our findings further help to explain the rather dissimilar reported energy levels at perovskite surfaces and interfaces, refining our understanding of the operational principles in perovskite related devices.

Cette thèse présente une étude des propriétés électroniques de systèmes de basse dimension à base de métaux et de semiconducteurs. La première partie de l'étude traite le confinement de l'état de Shockley dans des nanostructures tridimensionnelles d'Ag(111), par des mesures STM/STS à très basse température (5 K). Nous avons d'abord analysé en détail la structure en énergie et la distribution spatiale des modes confinés. Nous avons ensuite mis à profit la nature discrète du spectre en énergie pour étudier le temps de vie des quasiparticules. Un comportement typique de liquide de Fermi est mis en évidence, et nous montrons que le mécanisme de diffusion dominant est associé au couplage électron-phonon. La contribution extrinsèque provenant du confinement partiel de l'onde électronique a également été obtenue. Une loi d'échelle est observée avec la taille des nanostructures, ce qui permet d'extraire un coefficient de réflexion plus important que dans de simples ilôts monoatomiques. La seconde partie de l'étude est consacrée aux couches ultra-minces semiconductrices obtenues par dépôts d'alcalins (K, Rb, Cs) sur la surface Si(111):B-[racine]3. Ce travail résout la controverse concernant la nature de l'état fondamental de ce système, et notamment l'origine de la reconstruction 2[racine]3 obtenue à la saturation du taux de couverture. La compréhension en amont de la structure cristallographique permet d'élucider les propriétés électroniques. Nous montrons qu'une approche à un électron, conduisant à un isolant de bandes, décrit le système de manière convaincante, malgré l'indication de forts effets polaroniques. Ce résultat est le fruit d'une étude approfondie combinant des techniques diverses et complémentaires (LEED, ARPES, XPS, STM/STS et calcul DFT) / This thesis is devoted to the electronic properties of low-dimensional systems based on metal and semiconducting materials. The first part deals with the Shockley state confinement in Ag(111) nanostructures, by means of very-low temperature (5 K) STM/STS measurements. We study the electronic structure and spatial distribution of the confined modes. Then the discrete nature of the electronic spectrum allows one to yield the quasiparticule lifetime. A Fermi-liquid behaviour is evidenced and we show that the dominant decay mechanism is attributed to the electron-phonon coupling. The extrinsic contribution arising from the partial confinement of the electronic wave is obtained as well. A scaling law with the nanostructure width is demonstrated, from which we deduce a higher reflection amplitude than in monoatomic islands. In the second part of the thesis, we study semiconducting ultra-thin films produced by alkali (K, Rb, Cs) deposition on the Si(111):B-[root of]3 surface. This work solves the controversy concerning the ground state of this system, and especially the nature of the 2[root of]3 surface recontruction obtained at saturation coverage. Prior understanding of the crystallographic structure allows to elucidate the electronic properties. We show that a one-electron picture, leading to a band insulator scenario, gives a good description of the system, in spite of strong polaronic effects. This conclusion results from an in-depth, combined study of complementary techniques (LEED, ARPES, XPS, STM/STS and DFT calculations).

Substitutional dopants in III-V semi-conductors, such as Si atoms in GaAs, are of great interest for the applications in transistors, Schottky diodes, and doping super-lattices which have been widely employed to control the electrical properties of semi-conductors. Although Si doped GaAs systems have been intensively investigated theoretically and experimentally in the last several decades, some properties are still debated. In order to give a further explanation of Si doped GaAs systems, we systematically studied DX center in bulk GaAs and in GaAs(110), as well as the relative stabilities of different charged systems for Si atom replacing Ga atom at the substitutional site near GaAs(110) surface from first principles ground state method. We show that DX centre is a metastable state in bulk GaAs and completely unstable in the top few layers of GaAs(110). When Si atom replaces Ga atom at the surface, Charge states have an important influence on the stability of the system, and the additional charge is mainly concentrated on the Si atom for charged system. In addition, we studied the STM images of clean GaAs(110) and charged Si:GaAs(110) by employing Tersoff-Hamann approximation. The calculated STM images are in good agreement with experimental results. We show that at the positive bias voltage the positively charged Si atom presents a bright feature while the negatively charged Si atom shows a dark feature. In a semi-conductor, all bands are either completely full or completely empty. It is well known that DFT underestimates the band gaps of semi-conductors, a simple rigid shift can be used to correct the band energies of semi-conductors. Unlike semi-conductor, the fermi energies of metals lie in some bands. Furthermore, it turned out that some noble metals such as Cu and Ag depend on the considered band and k point , therefore, the so-called scissors operator can not be used for the metallic systems. The most successful approach within theoretical method for these metals is the many body perturbation theory. On the other hand, an interesting study for metals is quasi-particle excitations, which play an important role in a rich variety of physical and chemical phenomena such as energy transfer in photochemical reaction, desorption and oxidation of molecules at surfaces, spin transport within bulk metals, across interfaces, and at surfaces. One of the crucial properties of quasi-particle excitation is their lifetimes which determine the duration of these excitations. We carried out the calculations of quasi-particle band-structures and lifetimes for noble metals Cu and Ag within the GW approximation. For Cu, both the calculated positions of the d bands and the width of the d bands is within 0.1 eV compared to the experimental results. For Ag, partial core correction should be included in the pseudo-potential to get reliable positions of the d bands. The calculated lifetime agree with the experiment in the energy region away from the Fermi level, but deviates from the experimental results near the Fermi level where short range interactions which GW approach fails to describe play an important role. For a better description of the lifetime near the Fermi level, higher terms beyond the GW approximation in the many body perturbation theory need to be considered. In addition, the image potential state lifetimes in Cu(100) have been calculated using GW approximation based on the localized Gaussian basis set, and the calculated n=1, 2 imagepotential state lifetimes are in good agreement with experimental results.