Made available in DSpace on 2014-06-11T19:23:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-05-21Bitstream added on 2014-06-13T19:09:19Z : No. of bitstreams: 1 floriano_ea_me_bauru.pdf: 894423 bytes, checksum: af1367103a69a956bc553795ee950833 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dióxido de estanho, 'SNO IND.2', é um material semicondutor com transição de banda de energia (bandgap) larga, sendo que para o cristal (bulk), a energia pode variar de 3,6 até 4,2 eV, dependendo do método utilizado no preparo do material e também do teórico utilizado para o cálculo do bandgap. Suas propriedades ópticas, elétricas e estruturais são responsáveis pela grande quantidade de aplicações tecnológicas, tais como sensores para deteccção de gases, dispositivos óptico-eletrônicos, varistores e mostradores (displays) de cristal liquido entre outras. A natureza de transição de bandas de energia de 'SNO IND.2' tem sido motivo de controvérsia entre vários trabalhos já publicados, tanto teóricos quanto experimentais. Neste trabalho, apresentamos uma revisão de trabalhos teóricos e experimentais, selecionados da literatura, a respeito da natureza da transição direta ou indireta do bandgap do material. Apresentamos também um estudo das propriedades ópticas e estruturais de filmes finos de 'SNO IND.2', depositados sobre substrato de vidro e principalmente sobre substrato de quartzo, pela técnica de dip-coating via sol-gel. A influência dos dopantes foi analisada através de caracterização estrutural por difração de raios-X e também de medidas de absorção óptica. Além disso, também foram realizados cálculos da estrutura de bandas de cristal (bulk), superfície (110) e superfície (101), usando métodos de Primeiros-Princípios. Estes resultados são comparados ao bandgap obtido experimentalmente através de dados de absorção óptica e fotocondutividade em função do comprimento de onda da luz. / Tin dioxide, 'SNO IND.2', is a wide bandagap semiconductor. For the bulk, the bandgap energy may vary in the range 3.6 to 4.2 eV, depending on the method used for its preparation or on the theoretical method employed for the bandgap calculation. The combination of its optical, electrical and structural properties is responsible by the large number of technological applications, such as gas sensors, opto-electronic devices, varistors and liquid crystal display, among others. The bandgap nature has been the focus of controversy among many published papers, either experimental as well as theoretical. In this work, we present a review of published theoretical and experimental papers, selected from the literature, concerning the driect or indirect bandgap nature. A study of optical and structural properties od 'SNO IND.2' thin films, deposited by sol-gel-dip-coating technique, on glass and mainly quartz substrates, is also shown. The influence of doping is also analyzed by the structural characterization through X-ray diffraction data as well as optical absorption measurements. Besides, band structure calculation is also shown, performed on bulk, besides (110) and (101) surfaces, using the First Principles method. These results are compared to experimentally obtained bandgap, through experimental data of optical absorption and photoconductivity as function of light wavelength.

Made available in DSpace on 2014-06-11T19:23:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-07-07Bitstream added on 2014-06-13T19:29:34Z : No. of bitstreams: 1 pontes_dsl_me_bauru.pdf: 3995495 bytes, checksum: e77735073c68d26d0fbf6d4f3285874a (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho de dissertação de mestrado foram preparadas amostras do sistema 'Pb IND. 1-x-yCa IND. xSr IND.yTiO IND. 3' (PCST) com x = 0.05, 0,15, 0,35 e y = 0,05, 0.15, 0,35, utilizando-se o método dos precursores poliméricos e, a partir desse material, produzir amostras cerâmicas e filmes finos nanoestruturados e caracterizar suas propriedades estruturais, microestruturais e elétricas. A caracterização estrutural foi realizada utilizando as técnicas de difração de raios X, espectroscopia Raman e espectroscopia na região do infravermelho. Os filmes finos foram preparados pela técnica “spin-coating” sobre substrato de 'Si/SiO IND. 2/Ti/Pt'. A temperatura de cristalização foi de 600ºC. A cristalização de todos os filmes finos e pó apresentaram estrutura do tipo perovisquita sem a presença de uma segunda fase. Foi possível obter com sucesso um sistema complexo de incorporação de dois diferentes íons '(Ca POT. 2+ e Sr POT. 2+)' no sitio A, em substituição aos íons 'Pb POT. 2+' para o sistema 'Pb IND. 1-x-yCa IND. xSr IND.yTiO IND. 3' na forma de filme fino e pó, sem a separação de fases tais como 'PbTiO IND. 3, CaTiO IND. 3, SrTiO IND. 3', ou até mesmo fase complexas como '(Pb,Sr)TiO IND. 3' ou '(Pb,Ca)TiO IND. 3'. Os sítios A localizam-se dentro de um dodecaedro '(AO IND. 12)' de doze oxigênios enquanto o sitio B no interior de um octaedro regular '(BO IND.6)' constituído de oito oxigênios. Portanto, as distorções ocorridas nestas estruturas produzem importantes mudanças e surgimento de novas propriedades elétricas que encadeiam grande interesse tecnológico e cientifico. As propriedades ferroelétricas foram fortemente influenciadas pela presença desses dois íons '(Ca POT. 2+ e Sr POT. 2+)' em substituição aos íons 'Pb POT. 2+'. Levando o sistema a uma completa ausência de natureza ferroelétrica a temperatura ambiente. / On this master’s degree dissertation samples of the system 'Pb IND. 1-x-yCa IND. xSr IND.yTiO IND. 3' (PCST) with x = 0.05, 0.15, 0.35 and y = 0.05, 0.15, 0.35 were prepared through the polymeric precursors method. From this material, ceramic samples and thin films were produced and their structure, microstructure and electrical properties were assessed. The structural characterization was done using X-ray diffraction, Raman spectroscopy and spectroscopy techniques on the infrared region. The films were prepared through the spin-coating technique on 'Si/SiO IND. 2/Ti/Pt' substrate and its crystallization temperature was 600ºC. All thin films and powder showed structure like perovskite without a second phase. A complex incorporation system of two different ions '(Ca POT. 2+ e Sr POT. 2+)' at site A was successfully achieved, replacing the 'Pb POT. 2+' ions on the 'Pb IND. 1-x-yCa IND. xSr IND.yTiO IND. 3' system as thin film and powder with no partition of phases such as 'PbTiO IND. 3, CaTiO IND. 3, SrTiO IND. 3', or even more complex ones as '(Pb,Sr)TiO IND. 3' or '(Pb,Ca)TiO IND. 3'. The sites A were found in a '(AO IND. 12)' dodecahedron of twelve oxygens, and the site B was discovered in a regular octahedron formed by eight oxygens. Therefore the distortions on these structures triggered relevant changes and new electrical properties which promote great technological and scientific interest. It is noteworthy that the ferroelectric properties were heavily influenced by the presence of these two ions '(Ca POT. 2+ e Sr POT. 2+)' replacing the 'Pb POT. 2+' ions, leading the system to an absolute absence of ferroelectric nature at room temperature.

Made available in DSpace on 2014-06-11T19:27:13Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-09-20Bitstream added on 2014-06-13T20:55:53Z : No. of bitstreams: 1 mabuchi_gh_me_bauru.pdf: 1920924 bytes, checksum: f08f31db69b94fc1bdc144ed68ccce09 (MD5) / Neste trabalho de mestrado foram preparadas amostras do sistema SrTiO3, Sr1-xFexTiO3 e Sr1-xNixTiO3 com x = 0,05 e 0,10, no qual foi utilizado o método dos precursores polímeros e, a partir desse método, foram produzidas amostras na forma de pós e filmes finos nanoestruturados e caracterizar suas propriedades estruturais, morfológicas, elétricas e ópticas. As caracterizações estruturais e morfológicas foram realizadas utilizando as técnicas difração de raios X, método de Rietveld, espectroscopia micro-Raman, espectroscopia na região do infravermelho, microscopia eletrônica de emissão de campo (FEG) e microscopia de força atômica (MFA). Os filmes finos foram preparados pela técnica spin-coating sobre substrato de Si/SiO2/Ti/Pt e SiO2. O tratamento térmico das amostras na forma de pó e filme foram de 400ºC/4horas/5ºCmin-1 e 700ºC/2horas/5ºCmin-1. Os pós e os filmes finos apresentaram estrutura do tipo Perovskita sem a presença de segunda fase. Foi possível obter uma solução sólida incorporação do íon Fe e Ni no sitio A na forma de pós e filmes finos. Os sítios A localizam-se dentro de um dodecaedro (A012) de doze oxigênios enquanto o sitio B no interior de um octaedro regular (BO6) constituído de oito oxigênios. Portanto, as distorções ocorridas nestas estruturas produzem importantes mudanças e surgimento de novas propriedades. A introdução dos íons Fe e ni não alteram a característica paraelétrica do SrTiO3 a temperatura ambiente, no entanto, apresentaram constante a perda dielétrica estáveis podendo ser considerada um grande candidato a aplicação que requerem estabilidade a altas frequências. Além disso, os filmes filmes finos depositados sobre substratos de SiO2 apresentaram altas transmitância na região do UV-visível e diminuição do band gap e aumento do índice de refração dos filmes finos substituídos em relação ao puro / In this master's degree work, samples of the systems SrTiO3, Sr-1x-FexTiO3 and Sr1-xFeTiO3 and Sr1-xNiTiO3 (with x = 0,05 and 0,10) were synthsized by the polymeric precursors' method, and from this material, powder and nanostructured thin films samples were produced to have their structural, morphological, electical and optical properties characterized. The structural characterization and morphological was done by using x-ray diffraction techniques, Rietveld Method, micro-Raman spectroscopy, infrared region's spectroscopy techniques, field emission's electronic microscopy (FEG) and atomic force microscopy (AFM). The thin films were prepared by the spin-croating technique on Si/SiO2/Ti/Pt and SiO2 substrates. The thermal treatment of the samples, in powder and film forms, was of 400ºC/4H/5ºCmin-1 and 700ºC/2h/5ºCmin1. The powders and thin films presented a Perovskite type of structure without the presence of the second phase. It was possible to obtain a complex incorporation system of the ions Fe and Ni at the site A as powder and thin films. The sites A are located inside a docecahedron (AO12) of twelve oxygens, with the site B, inside a regular octahedron (BO6), formed by eight oxygens. Therefore, the distortion occurred on these structures produce important changes and the emergence of new properties. The introduction of the Fe and Ni ions don't change the SrTiO3 paraelectric characteristics at room temperature, but, they presented stable constant and dielectric loss, what can be considered a great candidate to an application that requires stability and high frequencies. Moreover, the thin films that were deposited on the SiO2, presented high transmittance in the visible UV's region and the diminution of the STO's band gap, due to the doped-material

Made available in DSpace on 2014-06-11T19:28:35Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-07-10Bitstream added on 2014-06-13T19:16:39Z : No. of bitstreams: 1 bueno_je_me_guara.pdf: 4834367 bytes, checksum: aaf1ac72afcdf02ebd179c37cd676523 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Sendo um importante e emergente ramo dentro da área dos novos materiais, a deposição de filmes de diamante CVD tem despertado cada vez mais interesse na comunidade científica internacional. O propósito principal dessa dissertação é contribuir com os trabalhos de pesquisa sobre deposição de filmes de diamante CVD, assistidos por filamento quente. O desenvolvimento dos experimentos ocorreu utilizando-se amostras com substratos de Si, sobre as quais foram depositados diamante CVD, com adição de baixa concentração de N2 à mistura gasosa precursora. Optou-se pela baixa concentração, sendo esta uma condição desafiadora, com poucas informações disponíveis. As amostras resultantes dos experimentos foram caracterizadas através do MEV, DRX e EDX revelando, respectivamente uma morfologia com mesmo tamanho e formato dos cristais, confirmando ainda a presença de filme de diamante CVD, cujos cristais apresentaram dimensões uniformes e o filme formado teve cobertura de toda amostra. Assim verificou-se que com a adição de 0,75% em volume de N2 houve a deposição de diamante CVD de alta pureza cristalina, ou seja, de alta qualidade. / As an important and emergent material the CVD diamond has got the attention of the international scientific communities. This study is aimed at continuing the research about CVD diamond using a hot-filament reactor, analyzing its potential and possibilities of its technological applications. The development of the experiments were done on Si substrate samples and the growth process was studied with the introduction of small concentration of N2 in the feed gas mixture, during the diamond growth, in the hot-filament reactor by the chemical vapor deposition technique. The decision to choose a small concentration of N2 was taken because there are few papers and published results. The diamond samples were characterized by scanning electron microscopy and X-ray to verify the properties of the sample and also its morphology. The diamond growth in the nitrogen atmosphere resulted in crystals and thin films with similar morphology and dimensions. Therefore, by the characterization techniques it was verified that the addition of 0,75% in volume of N2 has resulted in a high crystalline purity CVD diamond deposition.

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.

A systematic study has been made of the electrical conduction processes through electrically etched porous silicon (PS) films sandwiched between two metal electrodes. The PS layers were formed by anodisation of p-type silicon wafers in a hydrofluoric (HF) acid solution. The effect of fabrication conditions on the structural and electrical properties of PS have been investigated. The thickness of PS layers was found to depend on the anodisation time, whereas porosity was regarded to be controlled by the current density and HF acid concentration. The dark current-voltage I(V) characteristics at fixed temperature and the variation of current as a function of temperature have been established. The characteristics for all devices, regardless the metal contact, show a rectifying behaviour with ideality factor close to unity. It was found that PS films fabricated from p-type silicon substrates behave like n-type silicon due to the depletion of electronic holes. The results suggest that a pn heterojunction between PS and p-Si is responsible for the rectifying behaviour. A value of 0.7 eV was obtained for the barrier height at the interface between PS and p-Si at room temperature. The barrier height was found to increase with rising temperature. Recombination conduction process was found to be dominant at low temperatures as the activation energy did not exceed 0.22 eV. At high temperatures, thermionic emission diffusion process was found to be responsible for the current transport in the PS structures. A band model was proposed for metal/PS/p-Si/metal structures in order to explain the observed characteristics. A.c. dark current measurements revealed that the a.c. conductivity varies as ws where w is the angular frequency and s' is an index which depends on temperature and having a value less than unity. A.c. activation energy was interpreted in terms of hopping conduction at low temperatures (less than 200 K) and diffusion transport of charge carriers through PS layers at higher temperatures. Measurements of capacitance as a function of frequency and temperature showed a decrease with increasing frequency and increase with increasing temperature. The photoconduction behaviour of PS was characterised by high dark resistivity, a clear photosensitivity for visible light, and a bias voltage dependence of the spectral response.

No description available.

Ces travaux de thèse ont pour but d'étudier les propriétés électroniques de cellules photovoltaïques à base de couches minces de CZTSSe. L'objectif principal est d'identifier les défauts cristallographiques et de déterminer leur influence sur le fonctionnement des cellules solaires afin de mettre en oeuvre des stratégies de synthèse du CZTSSe pour le rendre compétitif par rapport aux autres matériaux en couches minces du photovoltaïque. La première phase du travail a consisté à élaborer le matériau et à l?intégrer dans une cellule solaire. Le CZTSSe est synthétisé par un procédé en deux étapes: le dépôt des précurseurs sous vide suivi d'un recuit sous atmosphère de sélénium. La deuxième phase du travail a concerné la caractérisation électrique des cellules sous obscurité. Pour cela des mesures de capacité en fonction de la tension et des mesures d'admittance sont effectuées en température. Les interprétations brutes des mesures sont menées en assimilant la cellule à une jonction n+p. Ce modèle s'avère insuffisant pour expliquer complètement les mesures expérimentales, ce qui nous a conduit, dans une troisième phase à une analyse plus détaillée. Pour cela, un calcul de l'admittance à partir des équations de base des semi-conducteurs a été développé. De cette manière, il est possible de sélectionner les contributions au signal qui sont incorporées au modèle. Initialement seule la contribution des défauts est intégrée. La prise en compte de fluctuations de potentiel améliore l'ajustement entre les données expérimentales et calculées. Toutefois une troisième composante doit être incluse pour rendre compte de la réponse diélectrique du CZTSSe. Cette composante à l'origine d'une variation en puissance de la conductivité avec la fréquence est caractéristique d'un mécanisme de hopping. L'incorporation de cette contribution dans la modélisation de l'admittance met en évidence que la conductivité dans le CZTSSe est due à un transport par états localisés, expliquant ainsi sa faible valeur. / This PhD work aims at studying the electronic properties of thin films CZTSSe solar cells. The final purpose is to identify crystallographic defects and determine their influence on the solar cells behavior in order to improve the efficiency and make CZTSSe competitive with other thin film technologies. The first part of the work deals with the fabrication of the CZTSSe thin films and solar cells. CZTSSe is synthetized using a two step process : vacuum deposition of precursors followed by an annealing under selenium atmosphere. The second part of the PhD work is the electrical characterization of the cells in the dark. Capacitance versus voltage measurements and admittance measurements are carried out at different temperatures. The results cannot be fully explained by usual models. As a consequence, further analysis has been conducted in a third part. Admittance has been calculated based on the classical equations that describe charge carriers in semi-conductor. The first interpretation only takes into account the contribution of defects. When the influence of potential fluctuations is added to the model, the adjustment between experimental measurements and calculated data is improved. However, a third component has to be included to fit the CZTSSe dielectric response. This component, causing a power variation of the conductivity with frequency is related to hopping mechanism. Adding this contribution to the admittance calculation allows to show that the CZTSSe conductivity is dominated by a localized states transport and can explain the low conductivity value.

abstract: Thin films of ever reducing thickness are used in a plethora of applications and their performance is highly dependent on their microstructure. Computer simulations could then play a vital role in predicting the microstructure of thin films as a function of processing conditions. FACET is one such software tool designed by our research group to model polycrystalline thin film growth, including texture evolution and grain growth of polycrystalline films in 2D. Several modifications to the original FACET code were done to enhance its usability and accuracy. Simulations of sputtered silver thin films are presented here with FACET 2.0 with qualitative and semi-quantitative comparisons with previously published experimental results. Comparisons of grain size, texture and film thickness between simulations and experiments are presented which describe growth modes due to various deposition factors like flux angle and substrate temperature. These simulations provide reasonable agreement with the experimental data over a diverse range of process parameters. Preliminary experiments in depositions of Silver films are also attempted with varying substrates and thickness in order to generate complementary experimental and simulation studies of microstructure evolution. Overall, based on the comparisons, FACET provides interesting insights into thin film growth processes, and the effects of various deposition conditions on thin film structure and microstructure. Lastly, simple molecular dynamics simulations of deposition on bi-crystals are attempted for gaining insight into texture based grain competition during film growth. These simulations predict texture based grain coarsening mechanisms like twinning and grain boundary migration that have been commonly reported in FCC films. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

abstract: There is an inexorable link between structure and stress, both of which require study in order to truly understand the physics of thin films. To further our knowledge of thin films, the relationship between structure and stress development was examined in three separate systems in vacuum. The first was continued copper thin film growth in ultra-high vacuum after adsorption of a sub-monolayer quantity of oxygen. Results showed an increase in compressive stress generation, and theory was proposed to explain the additional compressive stress within the films. The second system explored was the adsorption of carbon monoxide on the platinum {111} surface in vacuum. The experiments displayed a correlation between known structural developments in the adsorbed carbon monoxide adlayer and the surface stress state of the system. The third system consisted of the growth and annealing stresses of ice thin films at cryogenic temperatures in vacuum. It was shown that the growth stresses are clearly linked to known morphology development from literature, with crystalline ice developing compressive and amorphous ice developing tensile stresses respectively, and that amorphous ice films develop additional tensile stresses upon annealing. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011