The energy requirements of our planet will continue to grow with increasing world population and the modernization of currently underdeveloped countries. This will force us to search for environmental friendly alternative energy resources. Solar energy by far provides the largest of all renewable energy resources with an average power of 120 000 TW irradiated from the sun which can be exploited through solar electricity, solar fuel, and biomass. Nanostructured materials have been the subject of extensive research as the building block for construction of solar energy conversion devices for the past decades. The nanostructured materials sometimes have peculiar electrical and optical properties that are often shape and size dependent and are not expected in the bulk phase. Recent research has focused on new strategies to control nanostructured morphologies and compositions of semiconductor materials to optimize their solar conversion efficiency. In this dissertation, we discuss the synthesis and characterizations of one dimensional nanostructured TiO₂ based materials and their solar energy conversion applications. We have developed a solvothermal synthesis method for growing densely packed, vertical, single crystalline TiO₂ rutile nanowire arrays with unprecedented small feature sizes of 5 nm and lengths up to 4.4 [mu]m. Because of TiO₂'s large band gap, the working spectrum of TiO₂ is limited to the ultra violet region with photons shorter than 420 nm. We demonstrate that the active spectrum of TiO₂ can be shifted to ~ 520 nm with incorporation of N via nitridation of TiO₂ nanowires in NH₃ flow. In addition, we demonstrate a synergistic effect involving hydrogenation and nitridation cotreatment of TiO₂ nanowires that further redshift the active spectrum of TiO₂ to 570 nm. The Ta and N co-incorporated TiO₂ nanowires were also prepared and showed significant enhancement in photoelectrochemical performance compared to mono-incorporation of Ta or N. This enhancement is due to fewer recombination centers from charge compensation effects and suppression of the formation of an amorphous layer on the nanowires during the nitridation process. Finally, we have developed hydrothermal synthesis of single crystalline TiO₂ nanoplatelet arrays on virtually all substrates and demonstrated their applications in water photo-oxidation and dye sensitized solar cells. / text

The sun is a vast source of renewable energy, which can potentially be used to satisfy the world's increasing energy demand. Yet many material challenges need to be overcome before solar energy conversion can be implemented on a larger scale. This dissertation focuses on materials used for solar energy conversion through photo-electrochemical (PEC) processes. It discusses methods for improving PEC materials, namely mixed metal oxide semiconductors, by nanostructuring, incorporation of additional elements, and application surface electrocatalysts. In this dissertation several material synthesis techniques are detailed. A high vacuum synthesis process known as reactive ballistic deposition (RBD) is used to synthesize nanostructured bismuth vanadate (BiVO₄), which is studied for PEC water oxidation. Additionally, ballistic deposition (BD) is used to incorporate Mo and W into nanostructured BiVO₄ to improve the PEC activity. An array dispenser and scanner system is used to incorporate metals into copper oxide (CuO) and copper bismuth oxide (CuBi₂O₄) and over 3,000 unique material compositions are tested for cathodic photoactivity. The system is also used to test 35 elements as single component metal oxides, mixed metal oxides, and dopants for titanium dioxide (TiO₂) for use in dye-sensitized solar cells (DSCs). Lastly, RBD is used to deposit tungsten semicarbide (W₂C) onto p-type silicon (p-type) substrates as an electrocatalyst for PEC proton reduction. In many cases, the synthesis techniques and new material combinations presented in this dissertation result in improved PEC performance. The materials are thoroughly assessed and characterized to gain insights into their nanostructure, chemical composition, light absorption, charge transport properties, catalytic activity, and stability. / text

The properties of free-standing cubic silicon carbide for optoelectronic applications are explored in this work. The main focus of the work is on boron doped cubic silicon carbide, which is proposed as a highly useful material in several optoelectronic applications. The material is grown using sublimation epitaxy and the doped material is grown homoepitaxially on nominally undoped seeds. It is characterized using the experimental setups of photoluminescence spectroscopy, Nomarski interference spectroscopy and absorption spectroscopy. I have studied seed growth of nominally undoped cubic material on hexagonal (4H) substrates, and the influence on the grown material from the different faces of the substrate. It is found that it is not possible under the explored conditions to completely cover the growth area with the cubic polytype on the carbon face, but it can be done reproducibly on the silicon face. Reasons for this are discussed. Different doping setups are also explored. The influence on the material properties from growth conditions is explored. It is shown from absorption measurements that it is possible to grow boron doped cubic silicon carbide using this growth method, whereas optical microscopy studies show that the sample quality degrades with high doping concentrations. I have explored the luminescence properties of the material. No boron related emission is found with either room temperature or low temperature photoluminescence spectroscopy. Reasons for this are discussed using results from absorption measurements and optical microscopy.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23911号 / 工博第4998号 / 新制||工||1780(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 阿部 竜, 教授 陰山 洋, 教授 藤田 晃司 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Solar hydrogen has the potential to replace fossil fuels with a sustainable energy carrier that can be produced from sunlight and water via &quotewater splitting&quote. This study investigates the use of hematite (Fe&sub2O&sub3) as a photoelectrode for photoelectrochemical water splitting. Fe&sub2O&sub3 has a narrow indirect band-gap, which allows the utilization of a substantial fraction of the solar spectrum. However, the water splitting efficiencies for Fe&sub2O&sub3 are still low due to poor absorption characteristics, and large losses due to recombination in the bulk and at the surface. The thesis investigates the use of nanostructured composite electrodes, where thin films of Fe&sub2O&sub3 are deposited onto a nanostructured metal oxide substrate, in order to overcome some of the factors that limit the water splitting efficiency of Fe&sub2O&sub3. Doped (Si, Ti) and undoped Fe&sub2O&sub3 thin films were prepared using vacuum deposition techniques, and their photoelectrochemical, electrical, optical and structural properties were characterised. The doped Fe&sub2O&sub3 exhibited much higher photoelectrochemical activity than the undoped material, due to an improvement of the surface transfer coefficient and some grain boundary passivation. Schottky barrier modeling of Fe&sub2O&sub3 thin films showed that either the width of the depletion region or the diffusion length is the dominant parameter with a value around 30 nm, and confirmed that the surface charge transfer coefficient is small. An extensive review of the conduction mechanisms of Fe&sub2O&sub3 is presented. ZnO and SnO&sub2 nanostructures were investigated as substrates for the Fe&sub2O&sub3 thin films. Arrays of well-aligned high aspect ratio ZnO nanowires were optimised via the use of nucleation seeds and by restricting the lateral growth of the nanostructures. The geometry of the nanostructured composite electrodes was designed to maximise absorption and charge transfer processes. Composite nanostructured electrodes showed lower quantum efficiencies than equivalent thin films of Fe&sub2O&sub3, though a relative enhancement ofcollection of long wavelength charge carriers was observed, indicating that the nanostructured composite electrode concept is worthy of further investigation. The rate-limiting step for water splitting with Fe&sub2O&sub3 is not yet well understood and further investigations of the surface and bulk charge transfer properties are required in order to design electrodes to overcome specific shortcomings.

Anthropogenic climate change presents an unrivalled threat to environmental stability and the prosperity of future generations. Utilising abundant, renewable resources in energy generation and storage will be essential to halt climate change and its effects. Solar water splitting is an excellent tool in the renewable energy arsenal for countering climate change, as it utilises both sunlight and water, two of the most abundant resources available on earth. Furthermore, the direct formation of a chemical fuel, hydrogen, is thought to be more practical for storing in large quantities than electricity. Work in this thesis covers the investigation of a variety of materials, fabricated by aerosol assisted chemical vapour deposition (AACVD), for their ability to carry out photoelectrochemical water splitting. In one project, thin films of Bi2Ti2O7 (BTO), specifically of the pyrochlore crystal structure, are fabricated by AACVD and analysed for their photoelectrochemical properties. The resulting thin films are found to be phase pure with a band gap of 2.88 eV, which is 0.32 eV smaller than TiO2. Efforts to dope the BTO thin films are further investigated through the addition of iron. Significant modification to the band gap is observed, leading to a confirmed pyrochlore thin film exhibiting a band gap of 2.5 eV, a reduction of 0.38 eV from undoped BTO. The resulting thin film had a photocurrent 5 times higher than that of undoped BTO. Finally, efforts to fabricate Fe2Ti2O7 are outlined. It is discovered that a stable phase of Fe2TiO5 is preferentially formed over the pyrochlore phase, even with dramatic modification to the deposition parameters and precursor stoichiometry. The high stability of this phase, coupled with the limiting features of the glass substrates, highlights the challenges with forming certain pyrochlore thin films. In a second project, the effect of depositing titanium nanoclusters onto the surface of bismuth vanadate is investigated. Nanoclusters are of huge interest because their properties lie between those of atoms and bulk materials. Additionally, nanoscale clusters can be fabricated with incredible precision, allowing one to select discrete diameter particles for deposition on surfaces. Ti nanoclusters over a range of sizes are deposited onto BiVO4 photoanodes. It is discovered that the deposition of ultralow loadings of Ti2000 clusters results in an 80 % enhancement in the photocurrent of the BiVO4 substrates. Further experimentation highlights that the photocurrent enhancement is linked to the size of the nanocluster and the density of the clusters on the surface. A mechanism is outlined, whereby the Ti nanoclusters partially reduce the surface of the BiVO4, leading to enhanced electron transport within the thin films due to the presence of oxygen vacancies. In a final project, polycrystalline InN, GaN and systematically controlled InxGa1-xN composite thin films are fabricated on FTO glass by a facile, low-cost and scalable aerosol assisted chemical vapor deposition technique. Variation of the indium content in the composite films leads to a dramatic shift in the optical absorbance properties, which correlates with the band edges shifting between those of GaN to InN. Moreover, the photoelectrochemical properties are shown to vary with indium content, with the 50 % indium composite having an external quantum efficiency of around 8 %. Whilst the overall photocurrent is found to be low, the photocurrent stability is shown to be excellent, with little degradation seen over 1 hour. Subsequent attempts to modify the morphology by conducting vertical-AACVD are also outlined. Thin films fabricated using vertical-AACVD are found to grow via a different mechanism, leading to undesired split phase growth, where two different compositions form on the same substrate.

abstract: Photocatalytic water splitting is a promising technique to produce H2 fuels from water using sustainable solar energy. To better design photocatalysts, the understanding of charge transfer at surfaces/interfaces and the corresponding structure change during the reaction is very important. Local structural and chemical information on nanoparticle surfaces or interfaces can be achieved through characterizations on transmission electron microscopy (TEM). Emphasis should be put on materials structure changes during the reactions in their “working conditions”. Environmental TEM with in situ light illumination system allows the photocatalysts to be studied under light irradiation when exposed to H2O vapor. A set of ex situ and in situ TEM characterizations are carried out on typical types of TiO2 based photocatalysts. The observed structure changes during the reaction are correlated with the H2 production rate for structure-property relationships. A surface disordering was observed in situ when well-defined anatase TiO2 rhombohedral nanoparticles were exposed to 1 Torr H2O vapor and 10suns light inside the environmental TEM. The disordering is believed to be related to high density of hydroxyl groups formed on surface oxygen vacancies during water splitting reactions. Pt co-catalyst on TiO2 is able to split pure water producing H2 and O2. The H2 production rate drops during the reaction. Particle size growth during reaction was discovered with Z-contrast images. The particle size growth is believed to be a photo-electro-chemical Ostwald ripening. Characterizations were also carried out on a more complicated photocatalyst system: Ni/NiO core/shell co-catalyst on TiO2. A decrease of the H2 production rate resulting from photo-corrosion was observed. The Ni is believed to be oxidized to Ni2+ by OH• radicals which are intermediate products of H2O oxidation. The mechanism that the OH• radicals leak into the cores through cracks on NiO shells is more supported by experiments. Overall this research has done a comprehensive ex situ and in situ TEM characterizations following some typical TiO2 based photocatalysts during reactions. This research has shown the technique availability to study photocatalyst inside TEM in photocatalytic conditions. It also demonstrates the importance to follow structure changes of materials during reactions in understanding deactivation mechanisms. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2015

Submitted by Luciana Sebin (lusebin@ufscar.br) on 2016-09-19T13:34:59Z No. of bitstreams: 1 TeseIAC.pdf: 3635782 bytes, checksum: af0cdbb8c8caf2d9a90377d533f6b0ca (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-20T18:14:48Z (GMT) No. of bitstreams: 1 TeseIAC.pdf: 3635782 bytes, checksum: af0cdbb8c8caf2d9a90377d533f6b0ca (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-20T18:14:55Z (GMT) No. of bitstreams: 1 TeseIAC.pdf: 3635782 bytes, checksum: af0cdbb8c8caf2d9a90377d533f6b0ca (MD5) / Made available in DSpace on 2016-09-20T18:15:04Z (GMT). No. of bitstreams: 1 TeseIAC.pdf: 3635782 bytes, checksum: af0cdbb8c8caf2d9a90377d533f6b0ca (MD5) Previous issue date: 2015-12-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / The use of semiconductors for environmental applications and solar photoconversion has been widely explored recently. Due the intensive researches on renewable energy such as the photoelectrochemical H2 evolution from water splitting reaction, the design of new catalysts has been investigated. In this context, tungsten oxide – WO3 – is a promising catalyst for such application, however its conduction band is located at a more positive potential than the potential of water reduction, as a result WO3 does not have the ability to reduce H+ to H2. In the first part, this work deal with the synthesis of WO3 by the oxidant peroxide method, as a promising catalyst for this reaction. Tuning of the band-edge levels for the different synthesized catalysts was verified from Mott Schottky plot, and it represents the effective photoelectrocatalytic water splitting.In the second part, the study of heterostructuring TiO2 with WO3was investigated because of the possibility to mitigate the recombination of electron–hole pairs and therefore obtain more active systems for photocatalytic applications. The synthesis of WO3/TiO2 heterostructures was evaluated by hydrothermal method using three different routes: (I) precursors used as peroxo-complexes; (II) tungsten peroxo-complex and TiO2 pre-formed oxide; (III) pre-formed oxides as building blocks. The results showed by electrochemical characterization demonstrated how the electronic parameters (band edge positions, Fermi level energy and charge migration) affect the photocatalytic activity of heterostructures obtained by the distinct synthetic routes. The as-synthesized materials was investigated toward the photodegradation of organic dye (Rhodamine-B) under visible and UV illumination. The growth mechanism was observed to play a significant role in governing surface and interfacial properties, which has a direct influence on xvi materials photoactivity. The band edge positions for the materials was determined from Mott Schottky plot and the experimentally determined energy diagram is consistent with the formation of a type II heterostructure for WO3/TiO2 and it is well correlated to recent reports in literature. As a result, the photogenerated electrons and holes can be spatially distributed in two different crystalline phases in contact and the charge recombination is inhibited, which is efficient for photocatalytic reactions.Additionally, regarding the energy diagram obtained for the heterostrucutres, it is possible from the thermodynamic aspect the use of those structures as promising candidates for the photoelectrocatalytic water splitting, since the band positions are sufficiently large to overcome the character of this reaction. / O uso de semicondutores para aplicações ambientais e na fotoconversão solar tem sido amplamente explorado recentemente. Devido a pesquisas intensivas sobre energias renováveis como a reação de produção fotoeletroquímica de H2 a partir da água, o desenvolvimento de novos catalisadores tem sido investigado. O óxido de tungstênio – WO3– é um material promissor para tais aplicações, entretanto, a posição da sua banda de condução possui valores mais positivos que o potencial de redução da água, e desta forma este material não tem a habilidade de reduzir diretamente o H+ para H2. Na primeira parte, este trabalho aborda a síntese de WO3 pelo método dos peróxidos oxidantes (OPM), como um catalisador promissor para esta reação. Foi observado deslocamento nas bandas de energia para o filme de WO3 obtido pela rota OPM em relação ao óxido obtido pela rota convencional, determinado pela da relação de Mott Schottky e estes resultados caracterizam a efetiva reação water splitting. Na segunda parte, foi investigado a formação de heteroestruturas de TiO2 com WO3, no acoplamento entre as estruturas eletronicas dos óxidos semicondutores para obtenção de sistemas mais ativos em processos fotocatalíticos. A síntese de heteroestruturas WO3/TiO2 foi avaliada pelo método hidrotérmico utilizando três rotas distintas: (I) precursores na forma de peroxo-complexos estáveis; (II) peroxo-complexo de tungstênio e óxido pré-formado de TiO2 e (III) óxidos pré-formados como “blocos de construção”. De acordo com os resultados obtidos por caracterização eletroquímica, os parâmetros eletrônicos (posições de banda de energia, nível de Fermi e migração de cargas) influenciaram na atividade fotocatalítica de heteroestruturas obtidas por rotas sintéticas distintas. Os materiais foram investigados na reação defotodegradação do corante orgânico (Rodamina-B) sob xiv iluminação visível e UV. Observou-se que o mecanismo de crescimento das estruturas desempenha um papel significativo nas propriedades finais dos catalisadores produzidos, e uma influência direta sobre a fotoatividade destes. As posições do nível de Fermi para os materiais foi determinada a partir da caracterização eletroquímica pela relação de Mott Schottky e o diagrama de energia determinado experimentalmente é consistente com a formação de uma heteroestrutura tipo II para WO3/TiO2 e está de acordo com relatos recentes na literatura. Como consequência, os elétrons e buracos fotogerados podem estar espacialmente distribuídos nas fases cristalinas em contato e a taxa de recombinação é inibida, o que é eficaz para reações catalíticas. Além disso, em relação ao diagrama de energia obtida para as heteroestruturas, é possível do ponto de vista termodinâmico, a utilização como candidatos promissores para a reação fotoeletrocatalítica de water splitting, uma vez que os potenciais são energeticamente favoráveis para esta reação. / FAPESP: 2011/07484-8 / CAPES: 8218-13-7

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21590号 / 理博第4497号 / 新制||理||1646(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 島川 祐一, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

L’étude de la cinétique de la photodissociation de l’eau assistée par lumière visible a été l’objectif principal de ce travail. En tant que matériau photo-excitable, le semi-conducteur SrTiO₃ dopé au Rh a été utilisé. Le dopage permet l’absorption de lumière visible et donc la transformation d’énergie solaire en combustibles chimiques. Le 1er Chapitre de cette thèse est consacré à une étude bibliographique couvrant les méthodes de caractérisation et les modèles de la cinétique photo-électrochimique. Le 2ème Chapitre traite la description des matériaux et méthodes expérimentaux. Le 3ème Chapitre concerne la caractérisation de la cinétique de la photodissociation de l’eau sur photo-électrodes à base de Rh:SrTiO₃, modifiées en surface par ajout d’un clathrochélate modèle, ou avec du Cu ou du Pt métalliques. Le 4ème Chapitre décrit une étude théorique du mécanisme de la réaction de dégagement d’hydrogène, catalysée par un clathrochélate modèle. Le spectre EXAFS du complexe a été analysé et modélisé, et les intermédiaires importants du mécanisme ont été mis en évidence. Le 5ème Chapitre est consacré à l’étude dynamique de photo-électrodes à base de Rh:SrTiO₃ en utilisant la technique de la photo-tension à lumière modulée. Ce Chapitre présente des résultats inattendus, qui sont rapportés pour la première fois. Ce comportement bizarre a été modélisé par un système d’équations différentielles usuellement utilisées pour décrire ce type de système photo-électrochimique. / The kinetics of water photo-dissociation assisted by visible light was the main topic of this work. The Rh doped SrTiO₃ semiconductor was employed as photo-excitable material. It can absorb visible light and therefore transform solar energy into useful chemical fuels. In this manuscript, a wide bibliographic overview is provided in the 1st Chapter, covering a description of the characterization methods and current models for photoelectrochemical kinetics. The 2nd Chapter is devoted to the description of the materials and methods. The 3rd Chapter deals with the full photoelectrochemical kinetic characterization of water splitting with Rh:SrTiO₃ photoelectrodes, surface-modified by addition of a model clathrochelate or with metallic Cu or Pt. In the 4th Chapter, a theoretical study of the mechanism of hydrogen evolution catalyzed by a model clathrochelate is provided. During the discussion, the EXAFS spectrum of the organometallic complex was thoroughly analyzed and modelled, and the relevant protonated intermediates involved in the mechanism were identified. The 5th Chapter deals with the photoelectrochemical dynamics of illuminated Rh:SrTiO₃ -based photo-electrodes, characterized by the light-modulated photovoltage technique. Unusual results were obtained and are reported in this thesis for the first time. This unexpected dynamic behavior has been modelled by a set of classical differential equations usually used to describe such photo-processes.