In this study photocatalytic antibacterial and self-cleaning activities of TiO2-SiO2 thin films as a function of TiO2/SiO2 ratios were investigated. TiO2-SiO2 mixed oxides were synthesized by sol-gel method and coated over soda-lime glass plates by dip coating technique. Escherichia coli was used as a model microorganism for the photocatalytic antibacterial tests. Degradation rate of methylene blue (MB) molecules was used to characterize photocatalytic self-cleaning activities of thin film surfaces. The maximum antibacterial activity was achieved over 92 wt% SiO2 containing thin films. However, when the SiO2 content exceeds 92 wt%, photocatalytic antibacterial activity decreased considerably, which was explained by the dilution of TiO2 phase and inaccessibility of TiO2. Increase in photocatalytic antibacterial activity was attributed to increases in the relative surface area, roughness, hydroxyl (OH-) groups and bacterial adhesion. The favored bacterial adhesion enhanced direct contact of bacteria with TiO2 particles and surface reactive oxygen species. The highest initial decomposition rate of MB was obtained for 60 wt% SiO2 and the activity decreases as SiO2 concentration increases. The increase in photocatalytic activity by the SiO2 addition can be explained by the increase of the amount of MB per unit area of TiO2-SiO2 thin films. Different adsorption capability of thin films against MB molecule and E. coli cell was explained as the first reason why the antibacterial and self-cleaning activities reached their maximum values at different SiO2 ratios. The second reason could be related with the different control mechanisms of self-cleaning and antibacterial activities by different textural and surface properties.

Entre l'enfournement des matières premières sur le bain liquide et le verre la sortie du four, on peut s'interroger sur les étapes par lesquelles le mélange vitrifiable passe avant d'être transformé en un liquide homogène. D'un point de vue chronologique, l'élaboration du verre peut être considérée en trois étapes : l'état initial du mélange granulaire avant réaction ; l'étape de réaction chimique entre les différents constituants ; un liquide avec ses inclusions gazeuses et solides (bulles et quartz résiduel). Chacune de ces étapes concerne un domaine spécifique, avec un fort couplage entre physique et chimie. Aborder la façon dont réagissent ces matières premières ensemble et comment la microstructure peut influencer le chemin réactionnel suivi globalement par le mélange est indispensable pour savoir a chaque moment de la transformation quels mécanismes sont mis en jeu. Cela permettrait de corriger certains problèmes liés à l'élaboration d'un verre industriel (bulles piégé es dans le liquide, grains de quartz non incorporés au liquide, hétérogénéité chimique du liquide). La variété de phénomènes possibles lors de la fusion d'un mélange vitrifiable industriel nous poussera à simplifier le système un maximum, afin d'être capable de relier l'évolution de la microstructure à celle de la chimie du matériau. C'est la raison pour laquelle nous avons décidé d'étudier le système SiO2-Na2CO3. Nous avons de plus utilisé des grains tamisés dans des tranches précises, afin de pouvoir relier la transformation chimique du mélange à la répartition spatiale initiale du mélange granulaire.

ON A ETUDIE LES EQUILIBRES ENTRE DES SOLUTIONS AQUEUSES CHLORUREES OU NON ET DES MINERAUX DU SYSTEME SIO::(2)-AL::(2)O::(3)-NA::(2)O-K::(2)O. LES DONNEES THERMODYNAMIQUES SUR LES PHASES SOLIDES ET LA DISTRIBUTION DES ESPECES ALCALINES ENTRE IONS ET MOLECULES DANS LES SOLUTIONS CONCENTREES DE CHLORURES DE SODIUM ET DE POTASSIUM SONT L'OBJET DE LA PREMIERE PARTIE; LA SECONDE PARTIE TRAITE DE L'IMPORTANCE DES COMPLEXES QUE LES ALCALINS FORMENT AVEC LA SILICE ET SURTOUT L'ALUMINE DANS LE SYSTEME ETUDIE

An onset coarsening-coalescence event based on the incubation time of cylindrical mesopore formation and a significant decrease of specific surface area by a certain fraction relative to the dry pressed samples was determined by N2 adsorption-desorption hysteresis isotherm for amorphous SiO2 nanoparticles (ca. 40 nm in size). In the temperature range of 1150-1300oC, the nanoparticles with binder (PVA) additive underwent onset sintering coupled with coarsening-coalescence without appreciable crystallization. The apparent activation energy of such a rapid process for amorphous SiO2 nanoparticles was estimated as 177 ¡Ó 31.5 kJ/mol, based on 30% change of specific surface area. As a comparison, in much lower temperature range of 600-900oC, the amorphous Zn2SiO4 nanoparticles underwent onset sintering coupled with coarsening-coalescence accompanied more or less with the formation of ZnO The apparent activation energy of such a rapid process for a amorphous Zn2SiO4 was estimated as 105 ¡Ó 3.8 kJ/mol based on 50% change of specific surface area. The minimum temperatures for sintering/coarsening/coalescence of the amorphous SiO2 and Zn2SiO4 are 1120¢J and 635oC, respectively based on the extrapolation of steady specific surface area reduction rates to null. PLA fragmentation of amorphous and nearly spherical SiO2 nanoparticles (40 nm in size) in water (i.e. PLAL process) with optional NaCl addition was conducted under Q-switch mode (532 nm, 400 mJ per pulse) having laser focal point fixed at ca. 10 mm beneath the water level for an accumulation time of 20 and 30 min at 10 Hz. The 532 nm laser incidence suffered little water absorption and was effective to produce irregular shaped amorphous nanocondensates as small as 10nm~20nm in diameter with accompanied change of medium range order (MRO) as indicated by single rather than two broad x-ray diffractions at low 2theta angle. Whereas the Na+ uptake in the amorphous silica from the salty water account for a lower wave number of FTIR bands. The combined effects of nanosize, MRO change and H+ -signature may cause a lower minimum band gap of the amorphous products (analogous to opal-A) which become partially crystallized as £]-cristobalite (analogous to opal-CT) with additional £\-tridymite when Na+ is present.

This study indicate that the chemical inter-diffusion between the Cr-doped glass/glass ceramic and quartz (SiO2) influence the fluorescence properties of glass, mainly because of Cr4+ replacing by tetrahedral of Si4+. Cr4+ fluorescence intensity was reduced and its emission band was shifted to longer wavelength (red shift). We selected the SiO2-based glass composition: Mg2SiO4 glass-ceramic and reduced a ratio of SiO2 sintered into the ceramic powder. This paper used diffusion characteristics of quartz (SiO2) to compensate for reduced SiO2 in the ceramic powder. After diffusing with quartz (SiO2), ceramics powder changed into glasses. The intensity of fluorescence and the crystal field had been improved. The center of Cr4+ fluorescence is about 1100nm belonging to Cr4+:Mg2SiO4 crystal. The ratio of Cr4+ in Mg2SiO4 crystal/Cr4+ in MgO-SiO2 glass increases from 0.33 to 1.74. The goal is to develop a novel glass which is resistant to SiO2 inter-diffusion degradation during fiber fabrication, and provide the new fiber technology to avoid the influence of inter-diffusion This study provides new types of treatment: Laser induced crystallization. Laser heat-treatment can more quickly induce crystals in glass during seconds, than traditional heat-treatment which require several hours. This study also indicate that one step laser heat-treatment induce micro-crystals, but one step laser heat-treatment induce nano-crystals. We successfully produced nano-crystallization during seconds.

The resistance random access memory (RRAM) is one of the most popular of the next generation memories with the high operating speed, reliability and the smallest miniature size. RRAM has metal-insulator-metal structure that can greatly reduce the difficulty of entry, but the biggest problem is how to choose the insulator. We selected silicon-based materials to match the intergrated circuits manufacturing process. In this work, sputtering titanium doping in the silicon oxide thin film has a stable characteristic of resistance switching. By material analyzing, we found that supercritical carbon dioxide fluid (SCCO2) treatment can passivate the silicon oxide defect and the self-reduction of titanium oxide, but it also brought OH group into our thin film. So we observed the interface type characteristic of resistance switching. Using constant voltage sampling experiment extract the reaction rate constant (k) and the active energy, prove that the reaction is caused by OH injection. Double-layer structure with titanium-doped and carbon-doped silicon oxide RRAM promote lower operating current by hopping conduction, which is caused by graphite oxide doping. The Space-Charge Limited Current mechanism for high limited current is proven by COMSOL electric field simulation.

In this study,The bottom electrode(TiN),middle insulator(Hf:SiOx),and top electrode(Pt) were deposited respectively by sputtering technique for fabricating the RRAM with MIM structure.The mole fraction of hafnium were about 5%.Instead of non-doped SiO2 base device has no switching characteristic,the Hf-doped SiO2 RRAM could be operator over 100 times and resistive state was kept stable over 104 second. In this researches,the double layer structure(Pt/Hf:SiO2/Hf:SiO2(doped N2 and NH3)).The Resistance switching characteristics of double layer structure device has particular I-V characteristics due to the doping of N.The doping of NH3 cause hydrogen plasma treatment on double layer device also bring about particular I-V characteristics. The physical mechanism we had proposed were proof by the Current-Voltage fitting and the material analysis.By control stop-voltage,the double layer structure device can operation by multi-bit. The detail physical mechanism is studied by the stable RRAM device(Ti/HfO2/TiN).In this study,the model of reset process we had proposed were proof by the special measurement methods(Constant-voltage sampling) and the principle of chemical reaction mechanism.

In this work, a quantum well intermixing(QWI) technology, called impurity free vacancy diffusion(IFVD), is used to do the bandgap engineering in an optoelectronic monolithic integration. The monolithic integration of SOAs and EAMs is taken as an example. By IFVD, the transition energy levels of EAM quantum wells can be shifted to shorter wavelength region, while SOA quantum wells are kept the same. Therefore, the overall SOA-integrated EAM efficiency can be improved. We use dielectric film¡XSiO2 and Si3N4 to control the impurity free vacancy diffusion, both of these two dielectric layer will induce stress on the wafer, but they will come to the totally different result base on the difference atom chemistry with the substrate. Using Ga atom diffusion into SiO2 to relax stress, the IFVD will be operated to enhance quantum well intermixing, leading to energy bang transition change. On the other hand, with Si3N4 film, no significant intermixing is observed, implying atom chemistry dominates the whole process. Also, a super critical fluid technique by H2O2 is also employed to further improving SiO2 quality, a as large as 180nm blue shift is obtained, further improving such mechanism. Through difference properties between SiO2 and Si3N4 dielectric layers, different bandgap transitions in one single chip can be controlled in an area of 30£gm¡Ñ50£gm, leading to a planar bandgap engineering. Use these techniques, an EAM-SOA integration is designed and fabricated, obtaining an wavelength offset of 40nm with good quality of material structure. In the future, we can use this technique on large scale chip, tuning the bandgap to make photonic integration circuit without re-growth.

The aim of this study was to investigate the viability of patterning by immobilization, photocatalytic removal, and re-immobilization steps of the enzyme on photocatalytically active thin films for biosensor fabrication purposes. For this aim, TiO2-SiO2-Au sol-gel colloids were synthesized and deposited on glass substrates as thin films by dip coating. Cysteamine linker was assembled on gold nanoparticles to functionalize thin films with amine groups for immobilization of model enzyme invertase. Effect of immobilization temperature, enzyme concentration of the immobilization solution and immobilization period on invertase immobilization were investigated. The immobilized invertase activity was found independent from the immobilization temperature in the range tested (4oC-room temperature). The optimum enzyme concentration and period for immobilization was determined as 10&micro / g/ml and 12 hours respectively. The resulting invertase immobilized thin films showed high storage stability retaining more that 50% of their initial activity after 9 weeks of storage. Photocatalytic enzyme removal and re-immobilization studies were carried out by irradiating the invertase immobilized thin films with blacklight. Upon 30 minutes of irradiation, immobilized invertase was completely and irreversibly inactivated. Initial immobilized invertase activity (before the irradiation) was attained when invertase was re-immobilized on thin films that were irradiated for 5 hours. Thus it was inferred that with sufficient exposure, enzymes can be completely removed from the surfaces which makes the re-immobilization possible. The possibility of enzyme removal with photocatalytic activity and re-immobilization can pave the way to new patterning techniques to produce multi-enzyme electrode arrays.

The aim of this study was to immobilize the redox enzyme laccase over TiO2-SiO2-Au thin film coated ITO glass substrates in order to prepare electrochemically active surfaces for biosensor applications. Colloidal TiO2-SiO2-Au solution was synthesized by sol-gel route and thin film was deposited onto the substrates by dipcoating method. The cysteamine was utilized as a linker for immobilization of enzyme covalently through gold active sites. Preliminary studies were conducted by using invertase as model enzyme and Pyrex glasses as substrates. The effect of immobilization parameters such as immobilization temperature, concentration of enzyme deposition solution, immobilization time for laccase were examined. Leakage studies were conducted and storage stability of immobilized laccase was determined. Highest laccase activity was achieved when immobilization was performed with 50 &micro / g/ml solution at 4&deg / C for 2 hours. Laccase activity decreased after 4 hours of impregnation in enzyme solution. Laccase leakage was observed in the first usage of substrates and 55% activity decrease was determined in the subsequent use which might be attributed to the presence of uncovalently adsorbed enzyme on the fresh samples. In air and in buffer storage stabilities were also tested. It was found that the activity of samples almost vanished after 6 days regardless of storage conditions. Both enzymes had more activity on ITO substrate.