Dissertations / Theses on the topic 'Cerium oxide films'

The physical properties of thin nanocrystalline cerium oxide films have been studied with the purpose of their application as a functional material of different microelectronic transducers for biosensors: highperformance photoresistors and photodiodes for bioluminescence registration, ion-selective field-effect transistors (ISFET) and MOS-varactors indicating the pH changes as a result of biochemical processes. The effect of technological factors on the photoelectrical, optical, temperature and electrophysical properties of cerium oxide films has been studied. We established the technological conditions which allow to obtain СеОх-films with desired functional characteristics. On the basis of the synthesized nanocrystalline СеОх-films obtained by the "explosive evaporation" method we developed new types of photodetectors for registration of bioluminescent signal (photoresistors and photodiodes) with enhanced photosensitivity (310- 330 mA/lm∙V) in the visible range. Application of cerium oxide based photoresistors in the bioluminometers instead of photomultiplier tubes and avalanche photodiodes allows to significantly reduce the cost of bioluminometer and increase its sensitivity when measuring at alternating signal. On the basis of nanocrystalline СеОх-films obtained by the "metallic mirrors oxidation" method we developed potentiometric biosensory transducers (ion-selective field-effect transistors and MOS-varactors) with CeOx as gate dielectric. It yields higher sensitivity and stability as compared to the use of the SiO2 and Si3N4 films. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/34964

Cerium oxide (ceria)-based materials in the nanoscale regime are of significant fundamental and technological interest. Nanoceria in pure and doped forms has current and potential use in solid oxide fuel cells, catalysis, UV- screening, chemical mechanical planarization, oxygen sensors, and bio-medical applications. The characteristic feature of Ce to switch between the +3 and + 4 oxidation states renders oxygen buffering capability to ceria. The ease of this transformation was expected to be enhanced in the nanoceria. In most the practical scenarios, it is necessary to have a stable suspension of ceria nanoparticles (CNPs) over longer periods of time. However, the existing literature is confined to short term studies pertaining to synthesis and property evaluation. Having understood the need for a comprehensive understanding of the CNP suspensions, this dissertation is primarily aimed at understanding the behavior of CNPs in various chemical and physical environments. We have synthesized CNPs in the absence of any surfactants at room temperature and studied the aging characteristics. After gaining some understanding about the behavior of this functional oxide, the synthesis environment and aging temperature were varied, and their affects were carefully analyzed using various materials analysis techniques such as high resolution transmission electron microscopy (HRTEM), UV-Visible spectroscopy (UV-Vis), and X-ray photoelectron spectroscopy (XPS). When the CNPs were aged at room temperature in as-synthesized condition, they were observed to spontaneously assemble and evolve as fractal superoctahedral structures. The reasons for this unique polycrystalline morphology were attributed to the symmetry driven assembly of the individual truncated octahedral and octahedral seed of the ceria. HRTEM and Fast Fourier Transform (FFT) analyses were used to explain the agglomeration behavior and evolution of the octahedral morphology. Some of the observations were supported by molecular dynamic simulations. Poly (ethylene glycol) (PEG) and ethylene glycol (EG) were used to control the kinetics of this morphology evolution. The ability to control the agglomeration of CNPs in these media stems from the lower dielectric constant and an increased viscosity of the EG and PEG based solvents. CNPs when synthesized and aged in frozen conditions, i.e. in ice, were found to form one dimensional, high aspect ratio structures. A careful analysis has provided some evidence that the CNPs use the porous channels in ice as a template and undergo oriented attachment to form nanorods. When the aging treatment was done near freezing temperature in solution, the nanorods were not observed, confirming the role of channels in ice. When synthesized in aqueous media such as DI water, PEG and EG; CNPs were observed to exhibit a reversible oxidation state switching between +3 and +4. Band gap values were computed from the optical absorption data. The changes in the band gap values observed were attributed to the changes in the oxidation state of CNPs as opposed to the quantum confinement effects, as expected in other nanoparticle systems. The work presented in this dissertation demonstrates, with evidence, that in order to obtain a comprehensive understanding of the properties of nanoscale materials it is of paramount importance to monitor their behavior over relatively longer periods of time under various ambient environments. While the solution based techniques offer a versatility and low cost route to study the fundamental properties of nanomaterials, they suffer some inherent problems such as precursor contamination and uncontrolled chemical reactions. Especially when analyzing the behavior of ceria-based materials for applications like solid oxide fuel cells, a great control in the density and crystalline quality are desired. In order to achieve this, as a first step pure ceria thin films were synthesized using oxygen plasma assisted molecular beam epitaxy (OPA-MBE). The ceria films were analyzed using various in situ and ex situ techniques to study the crystal structure, growth mode and epitaxial quality of the films. It was observed that the epitaxial orientation of the ceria films could be tuned by varying the deposition rate. When the films were grown at low deposition rate (< 8 Å/min) ceria films with epitaxial (200) orientation were observed where as the films grown at high deposition rates (up to 30 Å/min) showed (111) orientation. Theoretical simulations were used to confirm some of the experimental facts observed in both nanoparticles and thin films.
Ph.D.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Materials Science & Engr PhD

Solid Oxide Fuel Cells (SOFCs) are devices that directly convert chemical energy into electrical energy, without proceeding through a Carnot combustion cycle. These devices are based on the usage of solid oxide electrolytes operating at relatively elevated temperatures. Two major hurdles must be overcome in order to decrease the operating temperatures of practical SOFCs. The first relates to reducing ohmic losses within solid electrolytes. The second relates to the need for developing high performance electrodes since electrolyte reaction rates at both anode and cathode are affected detrimentally as operating temperatures fall. This PhD project has focussed on addressing the first hurdle in two innovative ways: 1. the implementation of solid electrolytes with higher ionic conductivity than zirconia, 2. the development of very thin film electrolytes as thick as 5ƒÝm. Several thin films with novel electrode-electrolyte structures were fabricated and evaluated in order to demonstrate the viability of low temperature SOFC operations. Development of such thin films was innovative and challenging to achieve. The approach taken in this work involved fabricating a dense and thin gadolinia doped ceria (10GDC - Gd 10wt%, Ce 90wt%) oxide electrolyte. 10GDC is an electrolyte exhibiting higher conductivities than conventional materials during low temperature operations. A research contribution of this PhD was the demonstration of the deposition of 10GDC thin films using RF magnetron sputtering for the first time. 10GDC thin film electrolytes with thickness in a range between 0.1 to 5ƒÝm were fabricated on 10 yttrium stabilised zirconium (10YSZ) substrates by using a RF magnetron sputterer. The primary parameters controlling 10GDC thin film deposition using this method were explored in order to identify optimal conditions. The fabricated films were subsequently analysed for their morphology, composition and stoichiometry using a variety of methods, including Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectrometry (EDS), optical microscopy, X-ray Photoelectron Spectroscopy (XPS), and X-ray Diffraction (XRD). A preliminary test was conducted in order to examine the function of 10GDC thin film electrolytes together with the cathode and anode substrates at intermediate temperatures (700oC). A complete planar single cell was designed and assembled for this purpose. However, when fully assembled and tested, the cell failed to generate any voltage or current. Consequently, the remainder of the PhD work was focused on systematically exploring the factors contributing to the assembled fuel cell failure. As fabrication failure analysis is seldom reported in the scientific literature, this analysis represents a significant scientific contribution. This analysis proceeded in a series of steps that involved several different methods, including SEM, red dye analysis, surface morphology and cross section analysis of the cell. It was found that pinholes and cracks were present during the fuel cell operating test. Cathode delamination was also found to have occurred during the test operation. This was determined to be due to thermal expansion mismatch between the cathode substrate and the 10GDC electrolyte thin film. A series of suggestions for future research are presented in the conclusion of this work.

À travers l’histoire, la lumière a suscité le plus vif intérêt chez de nombreuses personnes curieuses, qu’il s’agisse de philosophes questionnant sa nature ou de scientifiques cherchant à interpréter les phénomènes qui lui sont associés. L’optique joue un rôle essentiel dans nombre de nos applications quotidiennes. L’indice de réfraction est l’un des facteurs les plus importants en photonique. Il est possible d’améliorer l’efficacité des dispositifs photoniques, comme les diodes électroluminescentes, les cellules photovoltaïques, etc., en réduisant la disparité des indices de réfraction des matériaux utilisés dans les dispositifs optiques. Cette thèse apporte quelques éclaircissements sur l’adaptation de l’indice de réfraction des matériaux, détaillant des aspects de l’indice de réfraction et de son ingénierie à l’aide de nanocomposites de polymère. Ce chapitre d’introduction évolue vers une discussion plus large sur l’indice de réfraction, ses différentes valeurs, et les avantages potentiels que son ingénierie pourrait générer. De minces films polymères ont été préparés et les nanoparticules ont été introduites de façon à modifier l’indice de réfraction. De la même manière, des films épais ont été préparés en utilisant du PMMA et du polystyrène, ceux-ci ayant été utilisés pour caractériser optiquement et morphologiquement les échantillons préparés. De nombreuses méthodes ont été employées pour préparer les films polymères. Des films polymères ultraminces ont également été préparés en utilisant la technique de revêtement par centrifugation, puis l’épaisseur du film de polystyrène a été modifiée afin d’étudier son impact sur l’indice de réfraction. Il a fallu surmonter plusieurs obstacles lors des recherches, comme la préparation d’un substrat ultra pur, l’uniformité du film polymère mince préparé, l’adhérence du film polymère mince sur les substrats après le coulage au solvant, etc. Tous ces défis ont été relevés grâce aux innovations détaillées dans cette thèse
Historically, light was a centre of interest for numerous inquisitive people: the philosophers who were interested in its nature and the scientists who wanted to interpret its associated phenomena. Optics is playing a pivotal role in many of our day to day applications.The refractive index is one of the most significant parameters in photonics. An increase in the efficiency of the photonic devices, like Light Emitting Diodes, Solar Cells, etc., can be achieved by reducing the refractive index mismatch of materials used in the optical devices.This thesis throws some light into the tailoring the refractive index of materials, by giving detailed aspects of refractive index and engineering of the refractive index using polymer nanocomposite. This introductory chapter evolves into a wider discussion on the refractive index and the types of refractive index and the potential leverage that can be obtained by engineering the refractive index. Polymer thin films were prepared and the nanoparticles were introduced so as to modify the refractive index. Similarly, thick polymer films were prepared using PMMA and Polystyrene and these were utilized to optically and morphologically characterize the prepared samples. Multiple methods have been utilized to prepare the polymer films. Ultra thin polymer films were also prepared using the spin coating technique and later the thickness of the polystyrene film was changed so as to understand its impact on the refractive index. There were multiple challenges to overcome while carrying out the research like the preparation of ultra pure substrate, uniformity in the prepared polymer thin film, adherence of the polymer thin film on to the substrates after solvent casting etc. All the challenges were overcome using the innovations, which are detailed in the thesis

Ce travail de thèse concerne l’élaboration et la caractérisation chimique et structurale de couches minces d’oxyde de silicium dopées avec des terres rares ainsi que l’étude de leurs propriétés de photoluminescence. Les films sont dopées avec du cérium. Le co-dopage cérium et ytterbium est également étudié dans le cas des couches de SiO2. Il est montré que dans les oxydes de composition SiO1, le cérium joue un rôle important dans la structure et l’organisation chimique de l’oxyde, notamment en favorisant la démixtion de l’oxyde. L’exposition à un faisceau laser focalisé engendre une démixtion locale favorisée par le cérium. Pour les films minces de SiO1,5 contenant à la fois du cérium et des nanocristaux de silicium, les différentes étapes de la séparation de phase entre nanocristaux de Si et agrégats riches en Ce ont été mises en évidence, notamment par sonde atomique tomographique et par microscopie électronique à balayage en transmission. Les propriétés de luminescence des dopants sont discutées en lien avec la microstructure de la matrice hôte. Pour tous ces systèmes, la formation d’un silicate de cérium de composition Ce2Si2O7 à haute température (> 1100°C) a été mise en évidence. Le cérium présent sous forme d’ions isolés ou dans un silicate émet intensément dans le bleu (400 nm) à température ambiante ce qui pourrait être intéressant pour le développement de diodes bleues en filière Si. Enfin, un transfert d’énergie des ions Ce3+ vers les ions Yb3+ a été mis en évidence dans les films minces de SiO2 ouvrant ainsi la voie à de possibles applications dans le domaine du solaire photovoltaïque
This thesis concerns the structural characterization and the photoluminescence properties of thin silicon oxide films doped with rare earths The films are doped with cerium. The co-doping with both cerium and ytterbium is also studied in the case of SiO 2 layers. It is shown that in oxides with composition SiO1, cerium plays an important role in the structure and chemical organization of the oxide, in particular by promoting phase separation of the oxide. The exposure to a focused laser beam generates a local demixtion favored by cerium. For thin SiO1,5 films containing both cerium and silicon nanocrystals, we are able to follow the phase separation occuring between Si nanocrystals and Ce rich aggregates using both atom probe tomography and scanning transmission electron microscopy. The luminescence properties of dopants are discussed in connection with the microstructure of the host matrix. For all these systems, the formation of a cerium silicate with composition Ce2Si2O7 is observed at high temperature (> 1100 ° C). The cerium present either as isolated Ce3+ ions or in a silicate emits intensely at 400 nm (blue) at room temperature, which might be of interest for the development of blue light emitting diodes fully compatible with the Si technology. Finally, an energy transfer from Ce3+ ions to Yb3+ ions is demonstrated in thin SiO2 films opening the route to possible applications in the field of photovoltaics

Ce travail de thèse concerne l’élaboration et la caractérisation structurale de couches minces d’oxyde d’étain dopées avec des terres rares ainsi que l’étude de leurs propriétés de photoluminescence. Les couches sont dopées avec du cérium, du terbium ou de l’ytterbium. Les films sont élaborés par évaporation sous vide d’une poudre de SnO2 sur un substrat de silicium monocristallin, et nécessitent un recuit post-dépôt à 600°C à l’air pour cristalliser en phase SnO2 de type rutile. Dans une première partie du travail a consisté caractériser le matériau non dopé. La caractérisation microstructurale a révélé qu’une oxydation du substrat conduisant à une réaction entre l’oxyde d’étain et le silicium avait lieu, conduisant à une microstructure complexe. Afin de limiter les interactions chimiques, des substrats recouverts de silice thermique ont également été utilisées. Les films non dopés présentent des propriétés de luminescence, mise en évidence et discutées en lien avec la microstructure. Pour les films dopés, l’étude structurale a mis en évidence la cristallisation d’une seconde phase de SnO2 de type orthorhombique. Une étude approfondie en STEM-EELS a permis de localiser les ions de terre rare dans la couche. Enfin les propriétés de luminescence des terres rares ont été étudiées en fonction de leur concentration dans le film et de la température de recuit. Après des recuits à 700°C, les couches dopées au Tb émettent intensément dans le vert à température ambiante, ce qui pourrait être intéressant pour le développement de diodes vertes à base de SnO2
This thesis concerns the structural characterization and the photoluminescence properties of tin oxide thin films doped with rare earths. The films are doped with cerium, terbium and ytterbium. The films were obtained by evaporation of SnO2 on silicon substrates. The as-deposited films were sub-stoichiometric and the films were then annealed in air at 600°C to reach rutile phase. The microstructural study reveals a substrate oxidation leading to a chemical reaction between tin oxide and silicon, and a complex microstructure. To limit the chemical interaction during annealing, silicon substrate coated with thermal silica were used. Undoped films show a broad luminescent band, which is discussed and linked with the microstructure. On the other hand, the structural study of doped films demonstrated the crystallization of a second phase of SnO2, which is orthorhombic. A STEM-EELS study allow to localize the rare earths ions in the films. Finally, the luminescence properties of the rare earths were study with respect to their concentration and the temperature of annealing. After annealing at 700°C, the Tb-doped films emit intensively in the green region, which might be of interest for the development of SnO2-based green light emitting diodes

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Este trabalho apresenta e discute o uso do óxido de cério na fabricação de filmes espessos por “screen printing” para aplicações em sensores de gás. Nesse estudo o CeO2 puro foi obtido pelo método dos precursores poliméricos utilizando como resina precursora o citrato de céria. O “puff” – espuma resultante da primeira fase do tratamento térmico da resina- foi calcinado a 550, 600, 700 e 750°C. O pó foi caracterizado por termogravimetria (TG) e as propriedades estruturais, morfológicas foram avaliadas por difratometria de raios X (DRX), espectroscopia Raman, área de superfície por isotermas Brunauer, Emmett e Taller (BET) e microscopia eletrônica de varredura (MEV). A resposta sensora foi estudada em uma câmara de teste construída no Laboratório de Catálise e Superfícies do Instituto de Ciência de Tecnologia de Materiais (INTEMA) da Universidade de Mar del Plata. A TG mostrou a formação de óxido de cério a 550°C, temperatura relativamente baixa quando comparada com outros métodos. Mediante DRX todas as amostras mostraram picos correspondentes à fase pura de CeO2 o qual cristaliza em uma estrutura cúbica do tipo fluorita, entretanto, maiores temperaturas de calcinação mostraram aumento da cristalinidade e tamanho do cristalito. No espectro Raman, um forte pico em torno do 461 cm-1 foi detectado, atribuído às vibrações simétricas do Ce-O. A área de superfície BET dos pós foi de 301, 77 m2/g o que evidencia a formação de partículas muito pequenas e altamente reativas. As micrografias obtidas por MEV mostram a presença de diferentes tamanhos na forma de aglomerados. A caracterização da resposta sensora mostrou que o sensor fabricado a partir de pós de CeO2 puro apresenta um bom tempo de resposta, alcançando a melhor performance com temperatura de trabalho de 400 °C, tanto em atmosferas redutoras e oxidantes. A característica principal observada foi que os resultados são dependentes dos ciclos anteriores, a reprodutibilidade do sistema é garantida quando se apaga a “memória” do sistema, expondo-o ao vácuo.
This paper presents and discusses the use of cerium oxide in the production of thick films for "screen printing" for applications in gas sensors. In this study the pure CeO2 was obtained by the polymeric precursor method using as a precursor resin citrate ceria. The "puff" - resulting foam from the first stage of thermal treatment of the resin-calcined at 550, 600, 700 and 750 °C. The powder was characterized by thermogravimetry (TG) and structural, morphological were evaluated by X-ray diffraction (XRD), Raman spectroscopy, isothermal Brunauer surface area, Emmett and Taller (BET) and scanning electron microscopy (SEM) . The sensor response was studied in a test chamber built in the Laboratory of Catalysis and Surface Materials Technology Institute of Science (INTEMA), University of Mar del Plata. The thermogravimetry showed the formation of cerium oxide at 550° C, relatively low temperature compared with other methods. Upon XRD all samples showed peaks corresponding to pure CeO2 phase which crystallizes in a cubic fluorite type structure, however, higher calcination temperatures showed increased crystallinity and crystallite size. In the Raman spectrum, a strong peak around 461 cm-1 was detected, assigned to symmetric vibrations of the Ce-O. The BET surface area of the powders was 301, 77 m2 /g which shows the formation of very small and highly reactive particles. The SEM micrographs show the presence of different sizes in the form of agglomerates. The characterization of the sensor response showed that the sensors manufactured from pure CeO2 powder has a good response time, achieving better performance at 400 °C working temperature in both reducing and oxidizing atmospheres. The main feature observed was that the results are dependent on previous cycles, the system reproducibility is guaranteed when it deletes the "memory" of the system, exposing it to vacuum.

Orientador: Miguel Angel Ramírez Gil
Coorientadora: Maria Olívia Berengue
Banca: José Vitor Candido de Souza
Banca: Miguel Adolfo Ponce
Resumo: Este trabalho apresenta e discute o uso do óxido de cério na fabricação de filmes espessos por "screen printing" para aplicações em sensores de gás. Nesse estudo o CeO2 puro foi obtido pelo método dos precursores poliméricos utilizando como resina precursora o citrato de céria. O "puff" - espuma resultante da primeira fase do tratamento térmico da resina- foi calcinado a 550, 600, 700 e 750°C. O pó foi caracterizado por termogravimetria (TG) e as propriedades estruturais, morfológicas foram avaliadas por difratometria de raios X (DRX), espectroscopia Raman, área de superfície por isotermas Brunauer, Emmett e Taller (BET) e microscopia eletrônica de varredura (MEV). A resposta sensora foi estudada em uma câmara de teste construída no Laboratório de Catálise e Superfícies do Instituto de Ciência de Tecnologia de Materiais (INTEMA) da Universidade de Mar del Plata. A TG mostrou a formação de óxido de cério a 550°C, temperatura relativamente baixa quando comparada com outros métodos. Mediante DRX todas as amostras mostraram picos correspondentes à fase pura de CeO2 o qual cristaliza em uma estrutura cúbica do tipo fluorita, entretanto, maiores temperaturas de calcinação mostraram aumento da cristalinidade e tamanho do cristalito. No espectro Raman, um forte pico em torno do 461 cm-1 foi detectado, atribuído às vibrações simétricas do Ce-O. A área de superfície BET dos pós foi de 301, 77 m2/g o que evidencia a formação de partículas muito pequenas e altamente reativas. As microgra... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: This paper presents and discusses the use of cerium oxide in the production of thick films for "screen printing" for applications in gas sensors. In this study the pure CeO2 was obtained by the polymeric precursor method using as a precursor resin citrate ceria. The "puff" - resulting foam from the first stage of thermal treatment of the resin-calcined at 550, 600, 700 and 750 °C. The powder was characterized by thermogravimetry (TG) and structural, morphological were evaluated by X-ray diffraction (XRD), Raman spectroscopy, isothermal Brunauer surface area, Emmett and Taller (BET) and scanning electron microscopy (SEM) . The sensor response was studied in a test chamber built in the Laboratory of Catalysis and Surface Materials Technology Institute of Science (INTEMA), University of Mar del Plata. The thermogravimetry showed the formation of cerium oxide at 550° C, relatively low temperature compared with other methods. Upon XRD all samples showed peaks corresponding to pure CeO2 phase which crystallizes in a cubic fluorite type structure, however, higher calcination temperatures showed increased crystallinity and crystallite size. In the Raman spectrum, a strong peak around 461 cm-1 was detected, assigned to symmetric vibrations of the Ce-O. The BET surface area of the powders was 301, 77 m2 /g which shows the formation of very small and highly reactive particles. The SEM micrographs show the presence of different sizes in the form of agglomerates. The characterization of the sensor response showed that the sensors manufactured from pure CeO2 powder has a good response time, achieving better performance at 400 °C working temperature in both reducing and oxidizing atmospheres. The main feature observed was that the results are dependent on previous cycles, the system reproducibility is guaranteed when it deletes the "memory" of the system, exposing it to vacuum
Mestre

Les piles à membrane polymère à échange de protons (PEMFC) sont une des techniques les plus prometteuses pour une production d'électricité propre et efficace à partir d'hydrogène. Les applications de cette nouvelle génération de piles à combustibles concernent aussi bien des applications portables et nomades telles que smartphones, ordinateurs portables, électronique embarquée que des applications domestiques ou dans les transports. A ce jour, le platine utilisé comme catalyseur est considéré comme le seul choix possible pour un rendement élevé et stable. En conséquence, suite à des ressources limitées en platine, la fabrication des piles à combustible reste coûteuse et la production industrielle généralisée impossible. Pour cette raison, une diminution substantielle de la quantité de Pt incorporée et donc la recherche de nouveaux matériaux d'anode à faible coût avec une activité élevée sont nécessaires. Des systèmes à base d’oxyde de cérium dopés au platine avaient été présentés comme étant des catalyseurs actifs pour l'oxydation du CO, la production d'hydrogène, l'oxydation de l'éthanol et la décomposition de méthanol. Au cours de ce travail, de nouveaux concepts pour la fabrication des piles à combustible ont été développés : la quantité de platine incorporée a été fortement diminuée conduisant à la production de nouveaux matériaux d'anode. Enfin, des catalyseurs à base de platine ont été déposés non pas sous la forme usuelle de nanopoudres mais sous forme de films minces fortement poreux sur substrat silicium.Au cours de cette thèse, le système Pt-CeOx a été étudié. Des échantillons non dopés puis dopés avec une faible quantité de platine ont été élaborés puis caractérisés en vue d'une application comme catalyseurs pour piles à combustibles. L'obtention de ces matériaux avec des propriétés sur mesure implique la maîtrise totale de leurs conditions de croissance. Afin d’étudier ces nouveaux composés de taille nanométrique, la microscopie électronique en transmission (MET) a été un outil précieux, qui a permis d'apporter des informations très précises sur la morphologie des films minces, la composition chimique et la structure à l'échelle atomique. Le cérium possède un double degré d'oxydation (+III/+IV), ce qui explique ses très bonnes propriétés catalytiques. Des analyses par spectrométrie dephotoélectrons X (XPS) ainsi que par spectroscopie de pertes d'énergie des électrons (EELS) ont été effectuées afin de déterminer son degré d'oxydation
Present doctoral thesis is focused on investigation of novel metal-oxide anode catalyst for fuel cell application by electron microscopy and associated spectroscopies. Catalysts based on Pt-doped cerium oxide in form of thin layers prepared by simultaneous magnetron sputtering deposition on intermediate carbonaceous films grown on silicon substrate have been studied. The influence of the catalyst support composition (a-C and CNx films), deposition time of CeOx layer and other deposition parameters, as deposition rate, composition of working atmosphere and Pt concentration on the morphology of Pt-CeOx layers has been investigated mainly by Transmission Electron Microscopy (TEM). The obtained results have shown that by combination of suitable preparation conditions we are able to tune the final morphology and composition of the catalysts. The composition of carbonaceous films and Pt-CeOx layers was examined by complementary spectroscopy techniques – Energy Dispersive X-ray Spectroscopy (EDX), Electron Energy Loss Spectroscopy (EELS) and X-ray Photoelectron Spectroscopy (XPS). Such prepared porous structures of Pt-CeOx are promising as anode catalytic material for real fuel cell application
Předložená dizertační práce se zabývá studiem nových katalyzátorů na bázi kov-oxid vhodných pro použití v palivových článcích na straně anody. Platinou dopovaný oxid ceru připravený magnetronovým naprašováním ve formě tenkých vrstev na uhlíkových mezivrstvách nesených křemíkovým substrátem byl zkoumán prostřednictvím mikroskopických a spektroskopických metod. Vliv složení uhlíkového nosiče (a-C a CNx filmy), depozičního času CeOx vrstvy a dalších depozičních parametrů, např. depoziční rychlosti, složení pracovní atmosféry a Pt koncentrace na morfologii Pt-CeOx vrstev byl studován převážně pomocí transmisní elektronové mikroskopie (TEM). Získané výsledky ukazují, že vhodnou kombinací depozičních podmínek jsme schopni vyladit výslednou morfologii a kompozici katalyzátoru. Složení uhlíkových filmů a Pt-CeOx vrstev bylo studováno spektroskopickými technikami – energiově-disperzní spektroskopií (EDX), spektroskopií charakteristických ztrát elektronů (EELS) a rentgenovou fotoelektronovou spektroskopií (XPS). Takto připravené porézní struktury vrstev Pt-CeOx jsou slibným katalytickým materiálem na straně anody pro reálné aplikace v palivových článcích

Le développement actuel des piles à combustible SOFC fonctionnant à température intermédiaire suppose l'optimisation des méthodes de synthèse et de mise en forme pour les matériaux nouveaux développés au cours des dernières années. En effet, les propriétés électrochimiques de ces dispositifs sont étroitement liées aux caractéristiques des poudres de départ ainsi qu'à la microstructure des électrodes (ou de l'électrolyte) après leur mise en forme. Une amélioration significative des dites propriétés peut être obtenue par la nanostructuration des matériaux. Dans ce contexte, ce travail de thèse est consacré à l’élaboration du matériau de cathode Nd2NiO4+d ainsi que du matériau d'électrolyte Ce1-xAxO2-d. Les méthodes mises en œuvre sont la synthèse de nanopoudres en milieux éthanol/eau supercritiques et par voie pyrosol ainsi que le dépôt de couches minces en milieu CO2 supercritique. Les objets obtenus ont enfin été caractérisés par spectroscopie d'impédance électrochimique afin de quantifier leur performance pour l’application SOFC
The ongoing development of Intermediate Temperature Solid Oxide Fuel Cells implies the optimization of the synthesis and deposition methods for the new materials developed these past years. Indeed, electrochemical properties of these materials are closely linked to the initial powder characteristics as well as the electrode (or electrolyte) microstructure after deposition. Significant improvement of the aforementioned properties can be obtained via nanostructuration of the materials. Thus, this thesis is dedicated to the synthesis of the cathode material Nd2NiO4+d and the electrolyte material Ce1-xAxO2-d. Methods employed are namely nanopowder synthesis in water/ethanol supercritical mixtures and spray pyrolysis as well as thin film deposition in supercritical fluids. The obtained objects have finally been characterized by electrochemical impedance spectroscopy in order to assess their performance for the SOFC application

This diploma thesis studies magneto-optical (MO) response of epitaxial thin films of Co-doped ceria. Thin films were characterized by XPS, LEED, STM, spectroscopic ellipsometry and measurement of MO activity. The work focuses on studying MO response of the films depending on film thickness, cobalt concentration, oxidation state of cerium and chemical state of cobalt. Spectra of MO response consist of low energy region where the MO activity is mediated by transitions from defect induced states to conduction band and high energy region where a peak of MO activity appears which we attribute to transitions from valence band to conduction band. In this work we qualitatively explain the effects of the physico- chemical states of the thin films on the structure of the obtained MO spectra, mainly on the appearance of the MO activity in the low energy region, and on the changes of the position of the MO peak. Compared to other preparation methods the epitaxial thin films allow achieving a shift of the MO peak in the direction of higher photon energy.

Concentration of Ce3+ is one of the most important parameters that influence the reactivity of ceria based catalyst. In this work we examine different experimental approaches for controlling Ce3+ concentration in cerium oxide model catalyst systems such as: i) influencing the stoichiometry of ceria, ii) introducing high valence doping agent, and iii) growing ultra thin ceria films with a strong metal substrate interaction. Structure, morphology and chemical state of prepared reduced ceria based systems were examined by means of surface science techniques: scanning tunneling microscopy, low-energy electron diffraction and X-ray photoelectron spectroscopy. In the present work an original method of ceria film reduction was introduced that allows stepwise control on stoichiometry and degree of film reduction (i). Further we introduce preparation procedures for well-ordered tungsten doped ceria model system (ii) and for the high quality 2D ultrathin ceria system on Cu (1 1 1) (iii). Preparation methods and model systems introduced in this work incorporate different physicochemical principles of Ce3+ induction and provide a variety of model systems useful for examining different effects that diversely prepared Ce3+ ions have on the activity of the catalyst.

1 is a suitable material for thin-film gas sensors. Higher sensitivity could be achieved by platinum dopping of the layer. This work focuses on the optimalization of and thin film preparation by radio-frequency magnetron sputtering method. Subsequent analysis by means of XPS, AFM, SEM and XRD was carried out to determine physicochemical attributes of resulting layers. It appears that after the deposition, platinum within the layer is present in the metalic , as well as in the mixed chemical state. After the annealing process mixed state dominates over metalic state and after additional annealing platinum is present solely in oxidized form. Sensory response of layers for presence of hydrogen were examined on two different chip platforms (glass with chromium contacts and sapphire with platinum contacts). Contrary to expectations, the platinum dopped layers performed worse in comparison to the pure tin dioxide layers. This could be explained by the fact, that after annealing platinum within the layer was present mainly in the non-metalic form. Both and layers were more sensitive on sapphire platform, which could be associated with the crystal structure formed on its surface or with presence of metalic contacts.

博士
國立臺灣大學
化學研究所
96
Ce0.8Gd0.2O2-δ (CGO) powder samples were synthesized using citrate sol-gel combustion method, and then the composite electrolyte materials were prepared by a small amount of 1mol% Bi2O3, GeO2, Nb2O5 to CGO. The results show that the densification and conductivity of composite electrolyte were improved. In addition, undergoing 10% H2/N2 for ~ 85h, the conductivity at 700°C in air of the samples could be retained nearly at their starting conductivity. The fabrication of anode-supported intermediate temperature solid oxide fuel cell (IT-SOFC) was carry out by using sandwiched dry-pressed technique with flour layers, because of humid environment in Taiwan, ultrafine CGO powder as electrolyte material. The single cell showed that electrolyte was 16 ± 2 μm in most thin thickness, anode (60wt%-NiO/CGO) and cathode (La0.8Sr0.2Co0.8Fe0.2O3-δ) were 493 ± 7 and 152 ± 4 μm in thickness, respectively. At our best knowledge to build the electrochemical testing device, and the performances of single cell were ~ 450 mW/cm2 (PPD) and ~ 0.79V (OCV), while 100%H2 and air with optimum flow rate of 50 and 150 mL/min at 700°C. On the other hand, under 100%H2 and 100%O2 with optimum flow rate of 50 and 90 mL/min, the the performances were ~ 504 mW/cm2 and ~ 0.82V. The rate-determining step (RDS) was depended on operation temperature: Under 550°C, RDS was oxygen reduction reaction. Above 600°C, RDS was ohmic loss. To exchange of electrolyte material, the addition of 1mol% GeO2 to CGO film was made, under the optimum flow rate through air and 100%O2 in turn, the PPD of single cell were ~ 462 and ~ 521 mW/cm2, respectively, which were improving ~ 12 and ~ 17 mW/cm2, respectively. To exchange of cathode material, the addition of 5.02wt% Pt to LSCF cathode was made, under the optimum flow rate through air and 100%O2 in turn, the PPD of single cell were ~ 526 and ~ 582 mW/cm2, respectively, which were improving ~ 76 and ~ 78 mA/cm2, respectively. To exchange of anode material, the addition of 2.5wt% Mn to Ni/CGO anode was made, under flow rate of 5mL/min through 100%H2 and 100%CH4 at 700°C in turn, the sample displayed about one-third and three-fifth times of the performances of pure Ni/CGO anode, in addition, the performance decreased with long-time. The primary reasons were suggested following: the addition of 1mol% GeO2 to CGO was improving oxide-ion conductivity of electrolyte, thus the influence improved the performance of single cell. However, a small amount of 1mol% Bi2O3 or Nb2O5 to CGO was deteriorating short-circuit short-circuit of electrolyte. For composite Pt/LSCF cathode, the adequate amount of Pt to LSCF was selected due to low oxide-ion conductivity and optimum microstructure surface of self. For composite Mn-Ni/CGO anode, the dense microstructure on surface was observed by the addition of Mn to Ni/CGO , thus the performance of single cell was deteriorating for the direct electrochemical oxidation of methane.

In this work the structural transitions of the rare earth oxides praseodymia and ceria grown on Si(111) are investigated. It is demonstrated that several of the rare earth intermediate phases can be stabilizied by post deposition annealing in ultra high vacuum. However, in most cases no single phased but coexisting species are observed. In addition, the surface structure and morphology of hex-Pr2O3(0001) as well as reduced ceria films are investigated.