Made available in DSpace on 2017-07-21T20:42:43Z (GMT). No. of bitstreams: 1 Leonardo Pacheco Wendler.pdf: 18625984 bytes, checksum: b24bfd3c491c213c9b049bbfaef17001 (MD5) Previous issue date: 2014-01-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The solid oxide fuel cells (SOFCs) have been considered as one of the most promising power sources to the future, and because that have awakened the interest from the governments and large companies. The large scale utilization of these devices only depends on costs reduction and better systems performance. The anode is one of the most requested components of a SOFC, because maintains direct contact with the fuel. The anode material must presents thermal stability, compatibility with the electrolyte, good catalytic activity and electronic conductivity. A lot of materials have just tested for use as SOFCs anodes, including metals like platinum and nickel. However, many problems were found, mainly because platinum wasn´t able to maintain its integrity in the cell operation conditions, suffering peeling during the process; and nickel particles suffered sintering in the high operation temperatures of the cell, blocking the fuel arrival to reaction sites, causing the loss of system performance. One of the alternatives to these metals are the lanthanumcontaining materials with perovskite structure. To this study it has been proposed the utilization of a lanthanum-based perovskite containing chromium, which provides good stability, and nickel, which provides good catalytic activity. Thus, the aim of the present study is to obtain the perovskite structure LaCr0,5Ni0,5O3, and characterize it to verify if its properties place it like a possible material to utilization as SOFC anode. It was investigated the obtaining of this composition by Pechini method, and the samples were characterized by X-ray diffraction, infrared spectroscopy, thermo gravimetric analysis, differential thermal analysis, He picnometry, specific surface area by BET method, scanning electronic microscopy, energy dispersive X-ray spectrometry, impedance spectroscopy and mercury porosimetry. The synthesized material showed high electrical conductivity at room temperature, and showed potential for use as anode in SOFCs. / As células a combustível de óxido sólido (CaCOS, ou SOFCs, do inglês Solid Oxide Fuel Cells) tem sido consideradas como uma das mais promissoras fontes de energia do futuro, e por isso tem despertado o interesse dos governos e de grandes empresas. A utilização em larga escala desses dispositivos depende unicamente da redução de custos e do aumento do desempenho dos sistemas. O ânodo é um dos componentes mais solicitados de uma CaCOS, pois mantém contato direto com o combustível. O material do ânodo deve então apresentar estabilidade térmica, uma compatibilidade com o eletrólito, boa atividade catalítica e condutividade eletrônica. Muitos materiais já foram testados para utilização como ânodo em CaCOS, incluindo metais como platina e níquel. Porém foram encontrados muitos problemas, principalmente porque a platina não mantinha sua integridade nas condições de operação da célula, sofrendo descamação durante o processo; e o níquel sofria sinterização de suas partículas nas altas temperaturas de operação da célula, impedindo a chegada do combustível nos sítios de reação, causando a perda de desempenho do sistema. Uma das alternativas a estes metais é a utilização de materiais com estrutura perovisquita contendo lantânio Para este trabalho está sendo proposta a utilização de uma perovisquita baseada em lantânio contendo cromo, o qual fornece boa estabilidade, e níquel, o qual fornece boas propriedades catalíticas. Desta forma o objetivo do presente trabalho é estudar a obtenção da estrutura perovisquita LaCr0,5Ni0,5O3, e caracterizá-la para verificar se as suas propriedades a colocam como um possível material para utilização como ânodo em CaCOS. Foi investigada a obtenção desta composição através do método Pechini, e as amostras foram caracterizadas por difração de raios x, espectroscopia no infravermelho, análise termogravimétrica, análise térmica diferencial, picnometria a He, área superficial específica pelo método BET, microscopia eletrônica de varredura, espectrometria de energia dispersiva de raios x, espectroscopia de impedância e porosimetria de mercúrio. O material sintetizado apresentou alta condutividade elétrica à temperatura ambiente, e mostrou potencial para utilização como ânodo em CaCOS.

Kimberlitos são rochas vulcânicas que, frequentemente, contêm diamante, grafite e/ou carbonato, sendo a presença destes componentes diretamente influenciada pela variabilidade da fugacidade de oxigênio (fO2) do magma durante a sua ascenção. Segundo Chakhmouradian and Mitchell (2000), CaTiO3-perovskitas podem ser usadas para revelar as condições de alguns dos múltiplos estágios de cristalização da história magmática destas rochas. No intuito de estabelecer a fugacidade de oxigênio de magmas kimberlíticos naturais, CaTiO3-perovskitas foram cristalizadas experimentalmente em equilíbrio com um líquido kimberlítico sintético em altas temperaturas e diferentes condições de pressão e de fugacidade de oxigênio. Os experimentos mostraram que a perovskita incorporou maiores quantidades de Fe3+ com o aumento da fO2. A equação do oxigênio barômetro desenvolvida neste estudo pode ser aplicada em rochas kimberlíticas de diferentes condições de fO2, que contêm CaTiO3-perovskita e olivina. Na presente pesquisa, nós aplicamos este oxigênio barômetro em amostras do kimberlito Rosário do Sul, que é um kimberlito transicional localizado no limite sudoeste da Bacia do Paraná. Os dados de minerais deste kimberlito sugerem que sua fonte é um produto da reação de um líquido silicático-carbonatítico com o manto. Idades U-Pb de ~ 128Ma em CaTiO3-perovskitas (Conceição et al., in prep.) revelam que o kimberlito Rosário do Sul provavelmente entrou em erupção logo após o vulcanismo da Província Paraná-Etendeka. Temperaturas de cristalização, pressões e fO2 dos kimberlitos Rosário do Sul e Alfeu-I, outro importante kimberlito situado no sul do Brasil, foram calculadas. As condições de suas fontes foram estimadas usando diferentes métodos a partir das composições de olivinas, espinélios, CaTiO3-perovskitas, granadas, ortopiroxênios e clinopiroxênios. As temperaturas, pressões e condições de fO2 dos kimberlitos Rosário do Sul e Alfeu-I sugerem que eles foram transportados para a superfície em condições nas quais fluidos ricos em CO2 podem reagir com o manto silicático e produzir carbonatos. A composição mineral e as condições de formação do kimberlito Rosário do Sul indicam que a sua fonte pode ter sido metassomatizada por fluidos provenientes da reciclagem de uma placa oceânica subductada durante a quebra do Gondwana e abertura do Atlântico Sul, logo depois do vulcanismo da Província Paraná-Etendeka. As condições de formação dos kimberlitos Rosário do Sul e Alfeu-I são usadas também para estimar o potencial destes kimberlitos em preservar diamantes. / Kimberlites are volcanic rocks which often contain diamonds, graphite and/or carbonate, and the stability of these minerals is directly influenced by the variability of oxygen fugacity (fO2) of the magma during its ascent. Second Chakhmouradian and Mitchell (2000), CaTiO3-perovskites may be used to unravel the conditions of some of the multiple stages of crystallization in the magmatic history of these rocks. In order to establish oxygen fugacities of natural kimberlititic magmas, we experimentally equilibrated CaTiO3-perovskites with synthetic kimberlitic melts at high temperatures, different oxygen fugacities and different pressures. The experiments show that perovskite incorporates increasing amounts of Fe3+ with increasing fO2. The oxygen barometer equation developed in this study can be applied in kimberlite rocks that contain CaTiO3-perovskite and olivine from different fO2 conditions. In the present research, we applied this oxygen barometer in the Rosário do Sul kimberlite samples, which is a transitional kimberlite located in the southwestern edge of the Paraná Basin. The mineral data of this kimberlite suggest that its source is a product of the reaction of a silicate-carbonate liquid in the mantle. U-Pb ages of ~ 128 Ma on CaTiO3-perovskites (Conceição et al., in prep.) reveal that the Rosário do Sul kimberlite probably erupted just after the volcanism of Paraná-Etendeka Province. We calculated crystallization temperatures, pressures and oxygen fugacities (fO2) of Rosário do Sul and Alfeu-I kimberlites, another important kimberlite situated in the South of Brazil. Their source conditions are estimated using different methods from olivines, spinels, CaTiO3-perovskites, garnets, orthopyroxenes and clinopyroxenes compositions. The calculated temperature, pressure and fO2 values of Rosário do Sul and Alfeu-I kimberlites suggest that they were transported to the surface under fO2 conditions in which CO2-rich fluids may react with mantle silicates to produce carbonates. The mineral composition and fO2 conditions of Rosário do Sul kimberlite indicate that its source may have been metasomatized by fluids generated from the recycling of a subducted oceanic plate during the Gondwana breakup and the South Atlantic opening, just after the Paraná-Etendeka Province volcanism. The source conditions of Rosário do Sul and Alfeu-I kimberlites are also used to estimate the potential of these kimberlites to preserve diamonds.

With the discovery of appreciable room temperature magnetoresistance (MR) in high Curie temperature (Tc) ferrimagnetic double perovskites such as Sr2FeMoO6, research surrounding other materials of this type has expanded. Most ferrimagnetic double perovskites of the formula A2BB'O6 have non-magnetic A-site cations, such as Sr2+, Ca2+ or Ba2+. Replacing non-magnetic cations with magnetic variants offers further possibilities to tune magnetic effects. This thesis focuses on the substitution of non-magnetic A-site cations with relatively small magnetic Mn2+ cations. This substitution is made possible through the use of high-pressure/temperature (P/T) synthesis, and the characterisation of structural and magnetic properties of new phases discovered through these syntheses. The first of these new phases to be reported herein is Mn2FeReO6, which can be described as the Mn analogue of the well-known ferrimagnetic double perovskite Ca2FeReO6. These materials are well ordered with Fe3+/Re5+ on B-sites and crystallise in a P21/n structure. Mn2FeReO6 shows a high Tc of 520 K due to ferrimagnetic Fe/Re magnetic order above RT, and a large saturated magnetisation of 5.0 μB, which peaks at 75 K. Interestingly, the A-site Mn2+ (3d5) magnetic order has the effect of causing a spin reorientation of the Fe/Re sublattice observed by neutron powder diffraction (NPD) at temperatures below ~75 K. This causes the MR to exhibit the expected negative intergrain tunnelling behaviour above the transition and colossal positive behaviour below. Also reported are a series of perovskite related structures with formulae CaxMn2- xFeReO6 (x = 0.5, 1.0, 1.5). Of particular note among these is CaMnFeReO6, which exhibits 1:1 A-site ordering of Ca/Mn and adopts the P42/n space group. This material belongs to a family of newly discovered 'double double' perovskites, in which Ca/Mn order in columns pointing along the c-axis and Mn has alternating tetrahedral and square planar coordination environments. MR in this material remains negative down to 20 K, potentially due to the presence of Ca disrupting magnetic interactions between Mn2+ cations and suppressing the spin transition. Alternating coordination environments in the double double perovskite structure type were exploited in the synthesis of Ca(Mn0.5Cu0.5)FeReO6. This material also crystallises in the P42/n structure and is well ordered on B-sites, as evidenced by X-ray powder diffraction. Neutron diffraction yields, in addition to columnar order, a slight preference for Cu to occupy the square planar sites and for Mn to occupy tetrahedral sites. This doping of square planar sites with Cu has the effect of enhancing magnetic properties compared to CaMnFeReO6, increasing the saturated magnetisation, raising the ferrimagnetic ordering temperature of the B-sites from 500 to 560 K, and also having a profound effect on the observed MR effects, as a switch in the sign of the MR is observed in this material through a magnetic transition. Finally, B-site substitution has been experimented with in the synthesis of CaMnMnReO6. This also possesses the combined A and B-site orders observed in CaMnFeReO6 and an unusual magnetic structure, with perpendicular A and B-site magnetism due to frustration, deviating greatly from the magnetic structures of materials with B-site Fe/Re. In summary, this thesis compiles the synthesis and analysis of a series of new double perovskites, double double perovskites and a new 'triple double' five-fold cation ordered structure with a general formula of AA'0.5A''0.5BB'O6. These materials show that new types of structural ordering can be used to increase the number of degrees of freedom available for tuning the interplay between many different magnetic cations in different coordination environments.

Made available in DSpace on 2014-12-17T15:41:57Z (GMT). No. of bitstreams: 1 VitorRMM_DISSERT.pdf: 2544703 bytes, checksum: 4453e8b3e10e994e669daf77efdaa72b (MD5) Previous issue date: 2012-08-04 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Perovskites oxides win importance by its properties and commercials applications, they have a high thermal stability, have conductive properties, electrical, catalytic, electro catalytic, optical and magnetic, and are thermally stable. Because of these properties, are being widely studied as carriers of oxygen in the process of power generation with CO2 capture. In this work, the base carrier system La1-xMexNiO3 (Me = Ca and Sr) were synthesized by the method via the combustion reaction assisted by microwave. were synthesized from the combustion reaction method by microwave process. This method control the synthesi`s conditions to obtain materials with specific characteristics. The carriers calcined at 800 ? C/2h were analyzed by thermal analysis (TG-DTA), to verify its thermal stability, X-ray diffraction (XRD) to verify the phase formation, with subsequent refinement by the Rietveld method, to quantify the percentage of phases formed, the surface area by BET method was determined, scanning electron microscopy (SEM) was obtained to evaluate the material morphology and temperature programmed reduction (TPR) was done to observe the metallic phase of the nickel. After all proposed characterization and analysis of their results can be inferred to these oxides, key features so that they can be applied as carriers for combustion reactions in chemical cycles. The final products showed perovskite-type structures K2NiF4 (main) and ABO3. / ?xidos com estrutura tipo perovsquita destacam-se por suas diversas propriedades e aplica??es comerciais, pois possuem alta estabilidade t?rmica, apresentam propriedades condutoras, el?tricas, catal?ticas, eletrocatal?ticas, ?pticas e magn?ticas, al?m de serem termicamente est?veis. Devido a estas propriedades, est?o sendo amplamente estudados como carreadores de oxig?nio em processos de gera??o de energia com captura de CO2. Neste trabalho, carreadores a base do sistema La1-xMexNiO3 ( Me = Ca e Sr) foram sintetizados a partir do m?todo via rea??o de combust?o assistida por microondas. Este m?todo controla as condi??es de s?ntese para obten??o de materiais com caracter?sticas espec?ficas. Os carreadores calcinados a 800?C/2h foram analisados atrav?s de an?lise t?rmica (TG-DTA), para verifica??o de sua estabilidade t?rmica; difra??o de raios-X (DRX), para verifica??o das fases formadas, com posterior refinamento atrav?s do m?todo de Rietveld, para quantificar o percentual das fases formadas; ?rea superficial pelo m?todo BET; microscopia eletr?nica de varredura (MEV) e redu??o ? temperatura programada (TPR). Ap?s toda caracteriza??o proposta e an?lise dos seus resultados pode-se inferir a esses ?xidos, caracter?sticas fundamentais para que os mesmos possam ser aplicados como carreadores em rea??es de combust?o por ciclos qu?micos. Os carreadores de oxig?nio obtidos possuem estruturas perovsquitas do tipo K2NiF4 (principal) e ABO3.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-05T19:36:02Z No. of bitstreams: 1 AnaQueirozSilva.pdf: 6863169 bytes, checksum: e47ae4d9bb4d9f8cffde413e5eecd620 (MD5) / Made available in DSpace on 2017-05-05T19:36:02Z (GMT). No. of bitstreams: 1 AnaQueirozSilva.pdf: 6863169 bytes, checksum: e47ae4d9bb4d9f8cffde413e5eecd620 (MD5) Previous issue date: 2016-07-19 / In recent years, research has increased in order to develop new materials processing methods have more advantages over conventional methods currently used which are quicker and cheaper. It has become common to use ceramics to obtain electronic devices, dielectric or piezoelectric. The CaTiO3 ceramic material has been widely used in electronic devices. The objective of this study was to synthesize and characterize perovskite ceramic-based CaTiO3 (Titanate Calcium) replaced with rare earths. The synthesis and replacement of perovskite were made from the starting materials Ca(OH)2, TiO2, Er2O3 and Yb2O3 by mechanical milling in a ball mill for 30 min at 250 rpm to homogenization and then was taken calcination in a muffle furnace. The obtained material powder showed perovskite phase to the orthorhombic space group Pbnm 62. The unit cell of the crystal lattice parameters showed a = 5.378 Å, b = 5.441 Å and c = 7.640 Å for the CaTiO3, which has four per unit cell formula. The number and type of modes provided for each frame can be given by the factor groups having a total of 24 vibrational modes Raman for CaTiO3 with said structure. The morphological characteristics were observed for the samples CTO (calcium titanate) prepared by solid state reaction, demonstrating the formation of small, round grain vacancies, which may be caused by distortions in the crystal lattice. The CTO replaced with Er2O3 and Yb2O3 showed typical bands of green light at 525 and 547 nm corresponding to the transition 4H11/2 → 4I15/2. The two smaller emission bands in the red, correspond to transition 4F9/2 to the ground state 4I15/2. The results obtained for the ceramic systems were satisfactory as the method used for synthesis, who presented with lower cost compared to existing processes. / Nos últimos anos, as pesquisas têm aumentado com o propósito de desenvolver novos métodos de processamento de materiais que apresentem mais vantagens em relação aos processos convencionais utilizados atualmente e que sejam mais rápidos e baratos. Tem se tornado comum utilizar cerâmicas para a obtenção de dispositivos eletrônicos, dielétricos ou piezoelétricos. O material cerâmico CaTiO3 tem sido amplamente utilizado em dispositivos eletrônicos. O objetivo deste trabalho foi sintetizar e caracterizar cerâmicas perovskitas à base de CaTiO3 (Titanato de Cálcio) substituída com terras raras. A síntese e a substituição da perovskita foram feitas à partir dos materiais de partida Ca(OH)2, TiO2, Er2O3 e Yb2O3 por moagem mecânica em um moinho de bolas por 30 min, a 250 rpm para homogeneização e em seguida, foi feita calcinação em um forno tipo mufla. O pó obtido do material apresentou fase de perovskita com grupo espacial ortorrômbica Pbnm 62. A célula unitária da rede cristalina apresentou os parâmetros a=5,378 Å, b=5,441 Å e c=7,640 Å para o CaTiO3, a qual possui quatro fórmulas por célula unitária. O número e tipo de modos previstos para cada estrutura pode ser dado pelo fator de grupos, havendo um total de 24 modos vibracionais Raman para o CaTiO3 com a estrutura citada. Foram observadas as características morfológicas para as amostras de CTO (Titanato de Cálcio), preparadas por reação no estado sólido, demonstrando a formação de grãos pequenos e redondos com vacâncias, que podem ser causadas por distorções na rede cristalina. O CTO substituído com Er2O3 e Yb2O3 apresentou bandas típicas da luz verde em 525 e 547 nm que correspondem à transição 4H11/2→4I15/2. As duas bandas menores de emissão no vermelho, correspondem à transição 4F9/2 para o estado fundamental 4I15/2. Os resultados obtidos para os sistemas cerâmicos mostraram-se satisfatórios quanto ao método utilizado para síntese, que, apresentou-se com menor custo comparado aos processos existentes.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-08-10T15:19:49Z No. of bitstreams: 1 SergioAzevedo.pdf: 3063334 bytes, checksum: ac4355642257682013f550aad3b1a89a (MD5) / Made available in DSpace on 2017-08-10T15:19:49Z (GMT). No. of bitstreams: 1 SergioAzevedo.pdf: 3063334 bytes, checksum: ac4355642257682013f550aad3b1a89a (MD5) Previous issue date: 2015-07-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Strontium titanate, SrTiO3 (ST) is a mixed oxide from the group of perovskites, has a cubic structure and a band gap of 3.2 eV. In this study systems SrTiO3(ST), SrTi0,90Fe0,10O3(STF), Sr0,90Ag0,10TiO3(SAT) and Sr0,95Ag0,05Ti0,90Fe0,10O3(SATF) were synthesized by the Pechini method in which the same, favor the production of nanostructured materials with a high stoichiometric accordingly. The precursors used were titanium isopropoxide, citric acid, strontium nitrate, ferric nitrate, silver nitrate and ethylene glycol. For the formation of the precursor powder, the resin is calcined at 300 °C for 1 hour with a ramp of 10 °C min-1. The precursor powder was characterized by TG/DTA. For the formation of calcined systems we used different temperatures of 400 °C / 500 °C/ 600 °C/ 700 °C/ 2h with a ramp of 10 °C min-1. The sample composition was calcined in ST 550 °C/ 2h to examine the formation of the phase. The samples were characterized by X-Ray Diffraction (XRD) spectroscopy, FTIR, UV-Vis spectroscopy, Raman spectroscopy and B.E.T. the sample STF showed a peak shift DTA higher intensity to lower temperature, resulting in a more rapid decomposition. The x-ray diffractograms show the formation of perovskite phase at low temperature of 600 °C with secondary phase SrCO3 and TiO2, the SAT and SATF samples occurred and formation of metal pranta as a secondary phase. Infrared spectra show that the material exhibits short-range organization and having SrCO3 as a secondary phase. Raman spectra show first order band which is characteristic of tetragonal structure ST. The samples are mesoporous, the substitution Ti / Fe and Sr / Ag promoted the reduction of the surface area of the samples. The addition of iron as a substituent ST caused a reduction of the optical band gap 3.21(2) to 2.31(2) in PBS and 2.16(1) composition in SATF composition. It can be concluded that the method is efficient in the synthesis of structural organization samples with short and long range, using calcination temperatures above 600 °C, and that the substitution by Ti/Fe promotes the reduction of the band gap and the surface area of the ST. / O Titanato de estrôncio, SrTiO3 (ST) é um óxido misto do grupo das perovskitas, apresenta estrutura cúbica e um “band gap” de 3,2 eV. Neste estudo, os sistemas SrTiO3(ST), SrTi0,90Fe0,10O3(STF), Sr0,90Ag0,10TiO3(SAT) e Sr0,95Ag0,05Ti0,90Fe0,10O3(SATF) foram sintetizados pelo método Pechini, o mesmo favorece a obtenção de materiais com alta conformidade estequiométrica. Os precursores utilizados foram: isopropóxido de titânio, ácido cítrico, nitrato de estrôncio, nitrato férrico, nitrato de prata e etileno glicol. Para a formação do pó precursor, calcinou-se a resina a 300ºC por 1 hora com rampa de 10 ºC.min-1. O pó precursor foi caracterizado por TG/DTA. Para a formação dos sistemas calcinados utilizou-se diferentes temperaturas de 400 ºC/500 ºC/600 ºC/700 ºC/2h com rampa de 10 ºC.min-1. A amostra com composição ST foi calcinada em 550 ºC/2h para analisar a formação da fase. As amostras foram caracterizadas por Difração de Raios-X (DRX), Espectroscopia FTIR, Espectroscopia UV-VIS, Espectroscopia Raman e B.E.T. A amostra STF apresentou um deslocamento do pico DTA de maior intensidade, para temperatura menor, resultando em uma decomposição mais rápida. Os difratogramas de Raios-x comprovam a formação da fase perovskita a partir da temperatura de 600ºC, com fase secundaria de SrCO3 e TiO2, nas amostras SAT e SATF ocorreu e formação de pranta metálica como fase secundaria. Os espectros infravermelhos mostram que o material apresenta organização a curto alcance e que apresenta SrCO3 como fase secundária. Os espectros Raman apresentam banda de primeira ordem que é característico da fase tetragonal da estrutura ST. As amostras são mesoporosas, as substituições Ti/Fe e Sr/Ag promoveram a redução da área superficial das amostras. A adição de ferro como substituinte promoveu a redução do band gap óptico do ST de 3,21(2) para 2,31(2) na composição STF e 2,16(1) na composição SATF. Pode se concluir que o método é eficiente na síntese das amostras com organização estrutural a curto e longo alcance, utilizando temperaturas de calcinação acima de 600 ºC, e que a substituição Ti por Fe promove a redução do “band gap” e da área superficial do ST.

Metal-halide perovskites show great promise as solution-processable semiconductors for efficient solar cells and LEDs. In particular, the diffusion range of photogenerated carriers is unexpectedly long and the luminescence yield is remarkably high. While much effort has been made to improve device performance, the barriers to improving charge transport and recombination properties remain unidentified. I first explore charge transport by investigating a back-contact architecture for measurement. In collaboration with the Snaith group at Oxford, we develop a new architecture to isolate charge carriers. We prepare thin films of perovskite semiconductors over laterally-separated electron- and hole-selective materials of SnOₓ and NiOₓ, respectively. Upon illumination, electrons (holes) generated over SnOₓ (NiOₓ) rapidly transfer to the buried collection electrode, leaving holes (electrons) to diffuse laterally as majority carriers in the perovskite layer. We characterise charge transport parameters of electrons and holes, separately, and demonstrate that grain boundaries do not prevent charge transport. Our results show that the low mobilities found in applied-field techniques do not reflect charge diffusivity in perovskite solar cells at operating conditions. We then use the back-contact architecture to investigate recombination under large excess of one charge carrier type. Recombination velocities under these conditions are found to be below 2 cm s⁻¹, approaching values of high quality silicon and an order of magnitude lower than under common bipolar conditions. Similarly, diffusion lengths of electrons and holes exceed 12 μm, an order of magnitude higher than reported in perovskite devices to date. We report back-contact solar cells with short-circuit currents as high as 18.4 mA cm⁻², giving 70% external charge-collection efficiency. We then explore the behaviour of charge carriers in continuously illuminated metal-halide perovskite devices. We show that continuous illumination of perovskite devices gives rise to a segregated charge carrier population, and we find that the distance photo-induced charges travel increases significantly under these conditions. Finally, we examine intermittancy in the photoluminescence intensity of metal-halide perovskite films.

Sung, Siu Chung = 鎂矽酸鹽(MgSiO₃)在核幔邊界條件下的第一性原理研究 / 宋紹聰. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (p. 110-115). / Abstracts in English and Chinese. / Sung, Siu Chung = Mei xi suan yan (MgSiO₃) zai he man bian jie tiao jian xia de di yi xing yuan li yan jiu / Song Shaocong. / Chapter 1 --- Introduction --- p.1 / Chapter 2 --- Review on MgSiO3 --- p.5 / Chapter 2.1 --- Interior of the Earth --- p.5 / Chapter 2.1.1 --- The importance of MgSiO3 in geosciences --- p.6 / Chapter 2.1.2 --- "Anomalies in lower mantle, D"" layer and the core-mantle boundary" --- p.7 / Chapter 2.2 --- Review on experimental and theoretical studies on MgSiO3 --- p.9 / Chapter 2.2.1 --- The perovskite structure --- p.9 / Chapter 2.2.2 --- MgSiO3 pv --- p.12 / Chapter 2.3 --- ppv structure --- p.14 / Chapter 2.3.1 --- MgSiO3 ppv --- p.15 / Chapter 2.3.2 --- MgSiO3 liquid --- p.18 / Chapter 3 --- Physical quantities in geoscience and molecular dynamics sim- ulations --- p.20 / Chapter 3.1 --- Equation of state --- p.21 / Chapter 3.2 --- Gruneisen parameter --- p.22 / Chapter 3.3 --- Thermoelasticity --- p.22 / Chapter 3.4 --- Phase transition --- p.24 / Chapter 3.5 --- Correlation function --- p.25 / Chapter 3.5.1 --- Pair Distribution function --- p.25 / Chapter 3.5.2 --- Coordination number --- p.27 / Chapter 3.5.3 --- Time correlation function and mean square displacement --- p.27 / Chapter 3.6 --- Seismic velocities --- p.28 / Chapter 4 --- Theoretical Methods --- p.30 / Chapter 4.1 --- Density Functional Theory --- p.30 / Chapter 4.2 --- Approximating exchange-correlation energy functional --- p.33 / Chapter 4.3 --- Car-Parrinello Molecular Dynamics --- p.34 / Chapter 4.4 --- Variable cell dynamics --- p.36 / Chapter 4.5 --- Nose-Hoover Thermostat --- p.37 / Chapter 5 --- Simulation method and details --- p.39 / Chapter 5.1 --- Structure at 0 K --- p.40 / Chapter 5.1.1 --- Initialization of simulation cells --- p.40 / Chapter 5.1.2 --- Convergence test --- p.41 / Chapter 5.1.3 --- "Electronic minimization, fictitious electronic mass and time step" --- p.42 / Chapter 5.2 --- Electronic and ionic minimization --- p.43 / Chapter 5.3 --- Cell optimization and structure at 0 K --- p.44 / Chapter 5.3.1 --- Optimized simulation cell of pv and ppv --- p.44 / Chapter 5.4 --- Equation of state and stability of solid --- p.46 / Chapter 5.5 --- Melting --- p.48 / Chapter 5.6 --- Statistical average --- p.50 / Chapter 6 --- MgSiO3 perovskite and post-perovskite at CMB conditions --- p.51 / Chapter 6.1 --- Equations of state of pv and ppv at 0 K --- p.51 / Chapter 6.2 --- Enthalpy of pv and ppv at 0 K --- p.54 / Chapter 6.3 --- Equations of state of pv and ppv at different temperatures --- p.55 / Chapter 6.4 --- Fluctuation of stress components of pv and ppv --- p.59 / Chapter 6.5 --- Pair distribution function of pv and ppv --- p.61 / Chapter 6.5.1 --- Pair distribution function at different temperatures with similar cell volume --- p.61 / Chapter 6.5.2 --- Pair distribution function at 4000 K and different volumes --- p.66 / Chapter 6.5.3 --- Pair distribution function at 6000 K and different volumes --- p.70 / Chapter 6.5.4 --- Coordination numbers --- p.74 / Chapter 7 --- Liquid structure at CMB conditions --- p.78 / Chapter 7.1 --- Equations of state of liquid --- p.78 / Chapter 7.2 --- Stress components of liquid --- p.80 / Chapter 7.3 --- Pair distribution function of liquid --- p.83 / Chapter 7.4 --- Coordination numbers of liquid --- p.88 / Chapter 7.4.1 --- Mean square displacement --- p.88 / Chapter 8 --- Phase diagram of MgSiO3 --- p.92 / Chapter 8.1 --- Pressure-temperature relations --- p.92 / Chapter 8.1.1 --- Enthalpy --- p.94 / Chapter 8.2 --- Internal energy --- p.96 / Chapter 8.3 --- Phase boundaries and phase diagram --- p.99 / Chapter 9 --- Discussions --- p.105 / Chapter 9.1 --- Phase diagram --- p.105 / Chapter 9.2 --- LDA vs GGA --- p.107 / Chapter 9.3 --- Pv and ppv at low pressure --- p.107 / Chapter 9.4 --- Two-phase method --- p.108 / Bibliography --- p.110 / Chapter A --- Rotation and shape optimization --- p.116

Ce manuscrit présente l?étude par diffusion de neutrons aux petits angles des inhomogénéités magnétiques de l?échelle nanométrique à l?échelle mésoscopique à basse température dans les composés manganites à effet CMR de la série Pr1-xCaxMnO3, x proche de 1/3, et son évolution sous champ magnétique appliqué. <br />Ces systèmes montrent une séparation de phase à grande échelle entre une phase ferromagnétique isolante (FI) et une phase antiferromagnétique isolante (AFI) correspondant à deux phases cristallines distinctes. Ils se transforment en une troisième phase cristalline, ferromagnétique métallique (FM), sous l?effet du champ magnétique. Nous avons tenté de comprendre par quel mécanisme. <br />Nous avons mis en évidence l?existence d?inhomogénéités magnétiques nanométriques dans chacune des phases FI et AFI. Notre étude sous champ révèle l?apparition d?un fort signal de diffusion dû à une nucléation de clusters de phase FM mésoscopiques (quelques centaines de nanomètres) lors de la transition I-M induite par le champ, faisant ainsi disparaître la diffusion par les objets nanométriques. L?effet CMR n?est donc pas dû à une nucléation à l?échelle nanométrique mais mésoscopique.

Dans une première partie, de nouveaux hydrures ternaires ont été préparés et caractérisés. Les systèmes étudiés sont AH-MH₂ (A = K, Rb, Cs et M = Mg, Ca). Dans les systèmes AH-MgH₂ l'évolution structurale a été discutée en fonction du caractère iono-covalent de la liaison magnésium-hydrogène. Dans une deuxième partie, plusieurs nouveaux fluorohydrures ont été mis en évidence. L'effet de la substitution de l'hydrogène au fluor dans ces phases a été étudiée en utilisant la RMN, la spectroscopie Mössbauer, la conductivité ionique et les mesures magnétiques.