Die Realstruktur des perowskitischen Modellsystems SrTiO3, welches in der Raumgruppe Pm-3m kristallisiert, wird durch die Sauerstoffvakanz als wichtigstem Defekt dominiert. Durch Temperaturbehandlung unter reduzierenden Bedingungen können Sauerstoffvakanzen in die Kristallstruktur eingebracht werden. Aufgrund ihrer positiven Ladung relativ zum Kristallgitter bewegen sie sich im elektrischen Feld entlang des TiO6-Oktaedernetzwerkes. Die Elektroformierung folgt dabei einem Arrheniuszusammenhang, wobei sowohl die Aktivierungsenergie als auch die Mobilität eine deutliche Abhängigkeit von der Kristallorientierung zeigen. Die Umverteilung der Sauerstoffvakanzen führt zu lokalen reversiblen Strukturänderungen, welche die Ausbildung einer neuen migrationsinduzierten feldstabilisierten polaren (MFP) Phase verursachen. In Abhängigkeit von der elektrischen Feldstärke zeichnet sie sich strukturell durch eine tetragonale Verzerrung der ursprünglich kubischen Elementarzelle aus und geht mit dem Verlust der Inversionssymmetrie einher. Die Polarisation in der Struktur wird durch die erwiesene Pyroelektrizität bestätigt und gilt als Grundlage, um anhand eines kristallographischen Symmetrieabstieges die Herleitung der Raumgruppe P4mm zu ermöglichen. Der durch die Migration hervorgerufene intrinsische Defektkonzentrationsgradient ruft eine elektromotorische Kraft hervor, deren Verwendung in einem elektrochemischen Energiespeicher experimentell nachgewiesen wurde. Diese neuen Funktionalitäten sind durch die Anwendung defektchemischer und kristallphysikalischer Konzepte infolge gezielter Materialmodifizierung unter Einfluss von Temperatur und elektrischem Feld zu verstehen. / The real structure of the perovskite-type model system SrTiO3, crystallizing in space group Pm-3m, is dominated by oxygen vacancies as most important defects. They are introduced in the crystal structure through heat-treatment under reducing conditions. Because of their positive charge relative to the crystal lattice, oxygen vacancies move in an electric field along the TiO6 octahedron network. This electroformation process follows an Arrhenius behavior. Both the activation energy and the mobility show an obvious dependence on the crystal orientation. Redistribution of oxygen defects causes local reversible structural changes, which involve the formation of a migration-induced field-stabilized polar (MFP) phase. In dependence on the electric field strength, this is structurally marked by a tetragonal distortion of the original cubic unit cell and accompanied by a loss of inversion symmetry. The polarisation in the crystal structure is confirmed by the proven pyroelectricity and serves for the argumentation to derive the space group P4mm by means of a crystallographic symmetry descent. The migration-induced intrinsic concentration gradient of oxygen vacancies leads to an electromotive force, whose application as electrochemical energy storage was proven experimentally. These new functionalities are explainable using defect chemistry and crystal physics in consequence of specific material modifications under the influence of temperature and external electric fields.

Orientadores: Peter Alexander Bleinroth Schulz, Ana Luiza Cardoso Pereira / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-18T12:03:32Z (GMT). No. of bitstreams: 1 BahamonArdila_DarioAndres_D.pdf: 15568018 bytes, checksum: 6b550b7e0291945e86b0152735b9ea2c (MD5) Previous issue date: 2011 / Resumo: Neste trabalho analisamos os efeitos das bordas nas propriedades eletrônicas e de transporte em estruturas finitas de grafeno, como nanofitas, pontos quânticos e anéis quânticos de grafeno. Nós focamos essencialmente no acoplamento entre os estados localizados nas bordas externas e estados localizados nas bordas internas, tais como as bordas internas dos anéis, vacâncias ou defeitos estendidos gerados pelas fronteiras de grão. Os cálculos são abordados no formalismo tight-binding para a rede hexagonal do grafeno. Para calcular as propriedades de transporte utilizamos o formalismo de Landauer-Buttiker e as funções de Green da rede. Para anéis quânticos observamos que a evolução dos estados localizados nas bordas internas, em função do campo magnético é oposta à dos estados localizados nas bordas externas. Tanto para anéis quânticos quanto para nanofitas, quando a magnitude do campo magnético gera um comprimento magnético maior do que a metade da separação entre as bordas internas e externas, os estados se acoplam levando à criação de gaps no espectro de auto-energias e ressonâncias de Fano na condutância. Este cenário é enriquecido pelo fato do grafeno ter duas sub-redes (novo grau de liberdade), identi cando que uma mudança na sub-rede dos átomos mais externos ou mais internos dos braços vizinhos de um anel muda a distribuição de carga e que a sub-rede de uma vacância fortemente modifica a forma de linha da condutância em uma nanofita. O mapeamento da densidade local de estados, diferenciada por sub-rede, nos leva a propor uma possível imagem experimental da força de acoplamento, que caracteriza a forma de linha das ressonâncias Fano. Quando consideramos um defeito estendido na rede do grafeno (defeito linear como os recentemente observados experimentalmente) foi encontrado que ele age como uma borda interna, que adiciona um novo canal para elétrons de baixa energia, e que tem aplicações promissórias como um o metálico quântico. Todos os nossos resultados são robustos quando a desordem nas bordas é incluído / Abstract: This work is concerned with the effects of the edges in the electronic and transport properties of nite structures of graphene, such as quantum dots, quantum rings and graphene nanoribbons. We primarily focus on the coupling between states located at the outer edges and states located at the inner edges, as internal edges of rings, vacancies or extended defects generated by the grain boundaries. The calculations are addressed within the tight-binding formalism for the hexagonal lattice. To calculate the transport properties we use the Landauer-B uttiker formalism and the recursive lattice Green's functions. For quantum rings we observed that the evolution of the states located at the inner edges, as a function of magnetic eld is opposite to that of the states located on the outer edges. For quantum rings as well as graphene nanoribbons when the magnitude of the magnetic eld creates a magnetic length larger than a half of the separation between the inner and outer edges, the states are coupled creating gaps in the self-energy spectrum and Fano resonances in the conductance of the graphene nanoribbons. This scenario is enriched when the sublattice is added as a new degree of freedom, identifying that a change in sublattice of the most external or most internal atoms of neighboring arms of a ring changes the charge distribution and the sublattice of a vacancy strongly modify the lineshape of the conductance. Sublattice differentiated Local density of states mapping for different lineshapes leading us to propose a possible experimental imaging of the coupling strength, which characterizes the lineshape of the Fano resonances. When we considered the recently experimentally observed extended defect, we found that it acts as an internal edge, which adds a new channel for low energy electrons, and would have promissory applications as metallic wire. All of our results are robust when edge disorder is included / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Cette these est consacree a l’etude des interactions entre les lacunes et les elements d'alliages d’un acier renforcé par une dispersion de nano-oxydes (ODS (Oxide Dispersion Strengthened)), matériau de structure envisagé pour les réacteurs nucléaires du futur. Ces travaux ont été réalisés pour un système simplifié constitué d'une matrice de fer α contenant de l'oxygène, de l'yttrium, du titane et des lacunes à partir de modélisations multi-échelles. Nous nous sommes attachés en particulier au rôle des lacunes formées en exces au cours de l’elaboration de ces aciers. La stabilite et la mobilite des amas lacunes-solutés ont été examinées à partir de calculs ab initio, d’une part, pour l’oxygene qui a ete compare au carbone et a l’azote, solutes interstitiels egalement presents dans les aciers, et d’autre part, pour le titane et l’yttrium, solutes substitutionnels. Les trois solutés interstitiels ont révélé un comportement tres analogue. L’impact de la mobilité des amas lacunes-solutes a ete etabli en utilisant un modele en dynamique d’amas parametre sur nos résultats ab initio. Il a été ainsi démontré que, en sursaturation de lacunes, la diffusion des solutés interstitiels peut etre acceleree, alors que celle des solutes substitutionnels ne l’est pas forcement. Ces conclusions se sont averees coherentes avec des observations experimentales existantes. L’ensemble de ces résultats ont ensuite été exploité pour améliorer notre compréhension des mécanismes de formation des nanoparticules. Il est apparu que la diffusion relative de l’yttrium et du titane, ainsi que le nombre de noyaux potentiels pour former des nanoparticules dépendent de la concentration en lacunes dans le système. / This PhD thesis is devoted to the study of interactions between vacancies and alloying elements in Oxide Dispersion Strengthened (ODS) steels, which are promising candidate materials for future nuclear reactors. This work is based on multiscale modeling of a simplified system composed by oxygen, yttrium and titanium atoms and vacancies in an α-iron lattice. We particularly focused on the role of vacancies which are created in excess during the fabrication of these steels. The stability and mobility of vacancy-solute clusters have been examined using ab initio calculations for oxygen, on one hand, which has been systematically compared to carbon and nitrogen, interstitial solutes frequently present in iron-based materials, and, on the other hand, for substitutional solutes : titanium and yttrium. The three interstitial solutes show very similar energetic and kinetic behaviors. The impact of small mobile vacancy-solute clusters has been verified using a cluster dynamics model based on our ab initio results. It has been thus demonstrated that with oversaturation of vacancies, diffusion of interstitial solutes may be accelerated, while substitutional solutes do not become necessarily faster. These conclusions are consistent with existing experimental observations. All these results have been then used to complete our understanding of nanoclusters formation mechanisms. It appeared that the relative mobility of yttrium and titanium, as well as the number of potential nuclei to form nanoparticles strongly depend on the total vacancy concentration in the system.

In this PhD thesis, the physics of vacancies in two-dimensional ordered Heisenberg antiferromagnets is investigated. We use semi-classical methods to study the influence of a single vacancy in long-range ordered states, with a focus on non-collinear order. Here, on a classical level, a magnetic distortion is created as the spins readjust in response to the vacancy. We use the non-collinear $120^\\circ$ state on the frustrated triangular lattice as an example, where we determine the impurity contributions to the magnetization and susceptibility. An important discovery is the vacancy moment not being quantized due to non-universal partial screening. The resulting effective moment $m_0 \\ll S$ can be observed as a fractional prefactor to an impurity-induced Curie response $m_0^2/(3k_BT)$ at finite temperature. This is in sharp contrast to collinearly ordered states. Here the moment is always quantized to the bulk spin value, $m_0=S$. Furthermore, we present a detailed analysis of the vacancy-induced distortion cloud. Due to Goldstone modes, it decays algebraically as $r^{-3}$ with distance $r$ to the vacancy. Using leading-order $1/S$-expansion, we determine the quantum corrections to both size and direction of the distorted magnetic moments. Secondly, we study the same problem in the presence of an external magnetic field $h$, both for the square and triangular lattice. For the triangular lattice we use a biquadratic exchange term $K$ to stabilize a unique ground state from a degenerate manifold. The finite-field vacancy moment $m(h)$ is generated by field-dependent screening clouds, as different non-collinear bulk states evolve with increasing field. These distortion clouds decay exponentially on a magnetic length scale $l_h\\propto 1/h$. Most importantly, we find that the magnetic-field linear-response limit $h \\rightarrow 0^+$ is generically singular for $SU(2)$ ordered local-moment antiferromagnets, as the vacancy moment in zero field differs fundamentally from even an infinitesimal but finite field, $m(h \\rightarrow 0^+)\\neq m_0$. Moreover, a part of the screening cloud itself becomes universally singular. Particularly for spin-flop states, this leads to a semi-classical version of perfect screening. We present general arguments to support these claims, as well as microscopic calculations. Another remarkable result is an impurity-induced quantum phase transition for overcompensated vacancies in the $M=1/3$ plateau phase on the triangular lattice with $K<0$. We close our analysis with a discussion about important limits for finite vacancy concentrations, as well as a possible experimental verification of our predictions.

Die Realstruktur des perowskitischen Modellsystems SrTiO3, welches in der Raumgruppe Pm-3m kristallisiert, wird durch die Sauerstoffvakanz als wichtigstem Defekt dominiert. Durch Temperaturbehandlung unter reduzierenden Bedingungen können Sauerstoffvakanzen in die Kristallstruktur eingebracht werden. Aufgrund ihrer positiven Ladung relativ zum Kristallgitter bewegen sie sich im elektrischen Feld entlang des TiO6-Oktaedernetzwerkes. Die Elektroformierung folgt dabei einem Arrheniuszusammenhang, wobei sowohl die Aktivierungsenergie als auch die Mobilität eine deutliche Abhängigkeit von der Kristallorientierung zeigen. Die Umverteilung der Sauerstoffvakanzen führt zu lokalen reversiblen Strukturänderungen, welche die Ausbildung einer neuen migrationsinduzierten feldstabilisierten polaren (MFP) Phase verursachen. In Abhängigkeit von der elektrischen Feldstärke zeichnet sie sich strukturell durch eine tetragonale Verzerrung der ursprünglich kubischen Elementarzelle aus und geht mit dem Verlust der Inversionssymmetrie einher. Die Polarisation in der Struktur wird durch die erwiesene Pyroelektrizität bestätigt und gilt als Grundlage, um anhand eines kristallographischen Symmetrieabstieges die Herleitung der Raumgruppe P4mm zu ermöglichen. Der durch die Migration hervorgerufene intrinsische Defektkonzentrationsgradient ruft eine elektromotorische Kraft hervor, deren Verwendung in einem elektrochemischen Energiespeicher experimentell nachgewiesen wurde. Diese neuen Funktionalitäten sind durch die Anwendung defektchemischer und kristallphysikalischer Konzepte infolge gezielter Materialmodifizierung unter Einfluss von Temperatur und elektrischem Feld zu verstehen. / The real structure of the perovskite-type model system SrTiO3, crystallizing in space group Pm-3m, is dominated by oxygen vacancies as most important defects. They are introduced in the crystal structure through heat-treatment under reducing conditions. Because of their positive charge relative to the crystal lattice, oxygen vacancies move in an electric field along the TiO6 octahedron network. This electroformation process follows an Arrhenius behavior. Both the activation energy and the mobility show an obvious dependence on the crystal orientation. Redistribution of oxygen defects causes local reversible structural changes, which involve the formation of a migration-induced field-stabilized polar (MFP) phase. In dependence on the electric field strength, this is structurally marked by a tetragonal distortion of the original cubic unit cell and accompanied by a loss of inversion symmetry. The polarisation in the crystal structure is confirmed by the proven pyroelectricity and serves for the argumentation to derive the space group P4mm by means of a crystallographic symmetry descent. The migration-induced intrinsic concentration gradient of oxygen vacancies leads to an electromotive force, whose application as electrochemical energy storage was proven experimentally. These new functionalities are explainable using defect chemistry and crystal physics in consequence of specific material modifications under the influence of temperature and external electric fields.

The Stockholm office market segment have for a long time been considered a safe haven when it comes to withstand negative turmoil in the form of rental compression due to economic fluctuation, especially in the CBD demographic. Recently however, a large number of banks and institutions, amounting to some 200000 square meters, have decided to relocate to more peripheral locations with the aim of cost reductions on rent. This mass exodus is studied with focus on rental dynamics as the result of increased vacancies. Other variables are stock changes and employment. The method is econometric combined with an interview series. The data is a panel dataset containing 900 observations. The different models that are being used is the vacancy gap model, an Error Correction Model and a dynamic lag model in the form of a first difference model. Due to non-stationary variables, some models were rejected. A prognosis model has been created for the economic calculations. The results are displayed in a number of scenarios ranging from unchanged rents to severe rental drops. As a comprehensive result this study concludes that a rental drop in the range of 10-20 percent is to be expected. A number of positive side effects are expected to unfold as a result of the relocations. / Stockholmsmarknadens kontorssegment har länge setts på som säker vad gäller att kunna motstå negativ turbulens i form av hyres press på grund av ekonomiska svängningar, och då speciellt marknaden för City eller CBD. Nyligen har dock en stor mängd banker och institutioner om cirka 200000 kvadratmeter bestämt sig för att lokalisera sig i mer perifera lokaler med kostnads reduceringar i form av lägre hyror som mål. Den här massutflyttningen har studerats med fokus på hyresdynamik som ett resultat av ökade vakanser. Andra variabler är ändringar i stocken och sysselsättning. Metoden är ekonometrisk och kombineras med en intervjuserie. Data består av ett paneldatasett innehållande 900 observationer. De olika modellerna som används är en vakansgapsmodell, en Error Correction modell (ECM) och en första differens modell. På grund av icke stationära variabler har vissa modeller förkastats. En prognostiseringsmodell har skapats för de ekonomiska beräkningarna. Resultaten redovisas i olika scenarion som består i allt från att hyrorna inte ändras alls till svåra hyresfall. Ett samlat resultat av studien föreslår ett hyresfall på 10-20 procent. En mängd positiva bieffekter förväntas uppstå som ett resultat av om lokalisationerna.

Thin film metal–insulator–metal capacitors with undoped HfO₂ as the insulator are fabricated by sputtering from ceramic targets and subsequently annealed. The influence of film thickness and annealing temperature is characterized by electrical and structural methods. After annealing, the films show distinct ferroelectric properties. Grazing incidence X-ray diffraction measurements reveal a dominant ferroelectric orthorhombic phase for thicknesses in the 10–50 nm range and a negligible non-ferroelectric monoclinic phase fraction. Sputtering HfO₂ with additional oxygen during the deposition decreases the remanent polarization. Overall, the impact of oxygen vacancies and interstitials in the HfO₂ film during deposition and annealing is correlated to the phase formation process.

This article corrects the following: 'Origin of Ferroelectric Phase in Undoped HfO2 Films Deposited by Sputtering' Advanced Materials Interfaces 6(11) 2019, first Published online: April 29, 2019

The discovery of the ferroelectric orthorhombic phase in doped hafnia films has sparked immense research efforts. Presently, a major obstacle for hafnia's use in high-endurance memory applications like nonvolatile random-access memories is its unstable ferroelectric response during field cycling. Different mechanisms are proposed to explain this instability including field-induced phase change, electron trapping, and oxygen vacancy diffusion. However, none of these is able to fully explain the complete behavior and interdependencies of these phenomena. Up to now, no complete root cause for fatigue, wake-up, and imprint effects is presented. In this study, the first evidence for the presence of singly and doubly positively charged oxygen vacancies in hafnia–zirconia films using thermally stimulated currents and impedance spectroscopy is presented. Moreover, it is shown that interaction of these defects with electrons at the interfaces to the electrodes may cause the observed instability of the ferroelectric performance.

[pt] Esta tese investigou a síntese de metanol via hidrogenação do CO2 empregando dois conjuntos de catalisadores. O primeiro é composto pelos tradicionais catalisadores de Cu/ZnO/Al e o segundo aborda os catalisadores de In2O3 e ZrO2. Com relação ao Cu/ZnO/Al, foram preparados quatro amostras via coprecipitação. Os resultados mostraram que há um teor ótimo (3,8 por cento at.) de Al para a qual se observa uma maior taxa de formação de metanol. Os catalisadores foram caracterizados por fisissorção de N2, titulação com N2O,espectroscopia de absorção atômica, ICP, DRX, XPS, TPD-(CO2,NH3 e H2O), TPSR-CO2/H2, TEM/HRTEM/EDS. Uma correlação entre a taxa de formação de metanol e a quantidade de vacâncias de oxigênio superficiais do catalisador foi observada. Foi verificado que o Al atua como um promotor na geração de vacâncias de oxigênio. Com relação aos sistemas de In2O3, foi realizado um screening e selecionado nove catalisadores. Esses sólidos foram caracterizados pelas seguintes técnicas: DRX, TPD-NH3, TPD-CO2, TPR-H2 e TPSR-CO2/H2. Foi realizado um estudo em dinâmica molecular clássica investigando os efeitos da dopagem do In2O3 e da interação entre o In2O3 e o ZrO2 e relacionando os resultados com a performance dos catalisadores. O melhor desempenho catalítico foi obtido para o inédito catalisador de 0,6Pt-In2O3+6ZnZrO2, sendo esse desempenho associado à presença de vacâncias. Além disso, pelos cálculos teóricos de dinâmica molecular foi verificado que tanto a mistura física quanto a dopagem do In2O3 podem promovem a mobilidade de oxigênio da rede dos óxidos, o que facilita a formação de vacâncias de oxigênio. Sendo assim, os dois conjuntos de catalisadores estudados mostram que as vacâncias de oxigênio têm papel central na formação do metanol a partir da hidrogenação do CO2. As informações geradas neste trabalho contribuirão para o desenvolvimento de catalisadores promissores para a futura exploração industrial da geração de metanol a partir de CO2. / [en] This thesis investigated methanol synthesis via CO2 hydrogenation using two sets of catalysts. The first set consists of the traditional Cu/ZnO/Al catalysts and the second set involves In2O3 and ZrO2 catalysts. Concerning Cu/ZnO/Al, four samples were prepared via coprecipitation. The results showed that there is an optimum Al content (3.8 percent at.) for which a higher methanol formation rate is observed. The catalysts were characterized by N2 physisorption, titration with N2O, atomic absorption spectroscopy, ICP, XRD, XPS (CO2,NH3 and H2O)-TPD, CO2/H2-TPSR, TEM/HRTEM/EDS. A correlation was observed between the rate of methanol formation and the amount of surface oxygen vacancies on the catalyst. It was found that Al acts as a promoter in the generation of oxygen vacancies. Regarding the In2O3 systems, a screening was carried out and nine catalysts were selected. These solids were characterized using the following techniques: XRD, NH3- TPD, CO2-TPD, TPR-H2 and CO2/H2-TPSR. A classical molecular dynamics study was carried out investigating the effects of doping In2O3 and the interaction between In2O3 and ZrO2 and relating the results to the performance of the catalysts. The best catalytic performance was obtained for the new 0,6Pt-In2O3+6ZnZrO2 catalyst, and this performance was associated with the presence of vacancies. In addition, molecular dynamics calculations showed that both the physical mixture and the doping of In2O3 can promote the mobility of oxygen in the oxide lattice, facilitating the formation of oxygen vacancies. Thus, the two sets of catalysts studied show that oxygen vacancies play a central role in the formation of methanol from the hydrogenation of CO2. The information generated in this work will contribute to the development of promising catalysts for the future industrial exploitation of methanol generation from CO2.