Effects of oxygen partial pressure on packing density and laser damage threshold of TiO2 thin films

TiO2 films are deposited by electron beam evaporation as a function of oxygen partial pressure. The packing density, refractive index, and extinction coefficient all decrease with the increase of pressure, which also induces the change of the film's microstructure, such as the increase of voids and H2O concentration in the film. The laser-induced damage threshold (LIDT) of the film increases monotonically with the rise of pressure in this experiment. The porous structure and low nonstoichiometric defects absorption contribute to the film's high LIDT. The films prepared at the lowest and the highest pressure show nonstoichiometric and surface-defects-induced damage features, respectively.(C) 2007 American Institute of Physics.

Effects of annealing on laser-induced damage threshold of TiO2/SiO2 high reflectors

The mechanism of improving 1064 nm, 12 ns laser-induced damage threshold (LIDT) of TiO2/SiO2 high reflectors (HR) prepared by electronic beam evaporation from 5.1 to 13.1 J/cm(2) by thermal annealing is discussed. Through optical properties, structure and chemical composition analysis, it is found that the reduced atomic non-stoichiometric defects are the main reason of absorption decrease and LIDT rise after annealing. A remarkable increase of LIDT is found at 300 degrees C annealing. The refractive index and film inhomogeneity rise, physical thickness decrease, and film stress changes from compress stress to tensile stress due to the structure change during annealing. (c) 2007 Elsevier B.V. All rights reserved.

Laser-induced damage of Ti O2 Si O2 high reflector at 1064 nm

A high laser-induced damage threshold (LIDT) TiO2/SiO2 high reflector (HR) at 1064 nm is deposited by e-beam evaporation. The HR is characterized by optical properties, surface, and cross section structure. LIDT is tested at 1064 nm with a 12 ns laser pulse in the one-on-one mode. Raman technique and scanning electron Microscope are used to analyze the laser-induced modification of HR. The possible damage mechanism is discussed. It is found that the LIDT of HR is influenced by the nanometer precursor in the surface, the intrinsic absorption of film material, the compactness of the cross section and surface structure, and the homogeneity of TiO2 layer. Three typical damage morphologies such as flat-bottom pit, delamination, and plasma scald determine well the nanometer defect initiation mechanism. The laser-induced crystallization consists well with the thermal damage nature of HR. (C) 2008 American Institute of Physics.

Effects of annealing on microstructure and optical properties of TiO2 sculptured thin films

The evolution of microstructure and optical properties of TiO2 sculptured thin films under thermal annealing is reported. XRD, field emission SEM, UV-Vis-NIR spectra are employed to characterize the microstructural and optical properties. It is found that the optimum annealing temperature for linear birefringence is 500 degrees C. The maximum of transmission difference for linear birefringence is up to 18%, which is more than twice of that in as-deposited thin films. In addition, the sample annealed at 500 degrees C has a minimum of column angle about 12 degrees C. The competitive process between the microstructural and optical properties is discussed in detail. Post-annealing is a useful method to improve the linear birefringence in sculptured thin films for practical applications.

Investigation on properties of TiO2 thin films deposited at different oxygen pressures

TiO2 thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on optical, mechanical and structural properties of TiO2 thin films were studied. The results showed that with the increase of oxygen partial pressure, the optical transmittance gradually increased, the transmittance edge gradually shifted to short wavelength, and the corresponding refractive index decreased. The residual stresses of all samples were tensile, and the value increased as oxygen partial pressure increasing, which corresponded to the evolutions of the packing densities. The structures of TiO2 thin films all were amorphous because deposition particles did not possess enough energy to crystallize. (C) 2007 Elsevier Ltd. All rights reserved.

Effects of deposition rates on laser damage threshold of TiO2/SiO2 high reflectors

TiO2 single layers and TiO2/SiO2 high reflectors (HR) are prepared by electron beam evaporation at different TiO2 deposition rates. It is found that the changes of properties of TiO2 films with the increase of rate, such as the increase of refractive index and extinction coefficient and the decrease of physical thickness, lead to the spectrum shift and reflectivity bandwidth broadening of HR together with the increase of absorption and decrease of laser-induced damage threshold. The damages are found of different morphologies: a shallow pit to a seriously delaminated and deep crater, and the different amorphous-to-anatase-to-rutile phase transition processes detected by Raman study. The frequency shift of Raman vibration mode correlates with the strain in. film. Energy dispersive X-ray analysis reveals that impurities and non-stoichiometric defects are two absorption initiations resulting to the laser-induced transformation. (C) 2008 Elsevier B. V. All rights reserved.

Investigation on thermal stability of TiO2 films for application at high temperature

The thermal stability of electron beam deposited TiO2 monolayers and TiO2/SiO2 high reflectors (HR) during 300 to 1100 degrees C annealing is studied. It is found that the optical loss of film increases with the increase in annealing temperature, due to the phase change, crystallisation and deoxidising of film. Scattering loss dominates the optical property degradation of film below 900 degrees C, while the absorption is another factor at 1100 degrees C. The increase in refractive index and decrease in physical thickness of TiO2 layer shift the spectra of HR above 900 degrees C. The possible crack mechanism on the surface of HR during annealing is discussed. Guidance for application on high temperature stable optical coatings is given.

High refractive index TiO2 film deposited by electron beam evaporation

The well known 'crystal seed' theory is first applied in this work to prepare TiO2 film: a high refractive index rutile TiO2 film is grown by electron beam evaporation on the rutile seed formed by 1100 degrees C annealing. The average n is larger than 2.4, by far the highest in all the authors' TiO2 films. The films are characterised by optical properties, microstructure and surface morphologies. It is found that the refractive index shows positive relation with the crystal structure, grain size, and packing density and roughness of the film. The film has lower density of granularity and nodule defects on the surface than those of the film deposited by magnetron sputtering. The result shows attractive application in complex filter and laser coatings.

Modification of the biological intercept model to account for ontogenetic effects in laboratory-reared delta smelt (Hypomesus transpacificus)*

We investigated age, growth, and ontogenetic effects on the proportionality of otolith size to fish size in laboratory-reared delta smelt (Hypomesus transpacificus) from the San Francisco Bay estuary. Delta smelt larvae were reared from hatching in laboratory mesocosms for 100 days. Otolith increments from known-age fish were enumerated to validate that growth increments were deposited daily and to validate the age of fish at first ring formation. Delta smelt were found to lay down daily ring increments; however, the first increment did not form until six days after hatching. The relationship between otolith size and fish size was not biased by age or growth-rate effects but did exhibit an interruption in linear growth owing to an ontogenetic shift at the postflexon stage. To back-calculate the size-at-age of individual fish, we modified the biological intercept (BI) model to account for ontogenetic changes in the otolith-size−fish-size relationship and compared the results to the time-varying growth model, as well as the modified Fry model. We found the modified BI model estimated more accurately the size-at-age from hatching to 100 days after hatching. Before back-calculating size-at-age with existing models, we recommend a critical evaluation of the effects that age, growth, and ontogeny can have on the otolith-size−fish-size relations

Síntese e caracterização de TiO2 puro e modificado para aplicações ambientais

Fotocatalisadores baseados em nanopartículas de dióxido de titânio modificados fornecem soluções em potencial para a mineralização de poluentes orgânicos em meio aquoso. Agentes modificadores têm sido amplamente investigados com o objetivo de promover a fotoativação pela luz visível. Foram estudadas a nível fundamental até aqui, as modificações estruturais, texturais e óticas causadas pela introdução de silício e nitrogênio na rede da titânia. Titânias puras (TiO2) e modificadas nanoestruturadas, particularmente titânias modificadas com silício (TiO2-SiO2), com razões atômicas Si/Ti de 0,1, 0,2 e 0,3 foram sintetizadas pelo método sol-gel a partir da hidrólise ácida de isopropóxido de titânio(IV) e tetraetoxisilano. As metodolo-gias sintéticas desenvolvidas tentaram aderir aos princípios da Química Verde, dispensando o uso de atmosfera inerte e temperatura e pressão elevadas, o que foi alcançado utilizando-se, principalmente, a agitação ultrassônica. Titânias modificadas com silício e dopadas com ni-trogênio (TiO2-SiO2-N) foram obtidas a partir do pré-tratamento de TiO2-SiO2 a 500 C ao ar e então submetidas ao fluxo de amônia (NH3) a 600 C por 1-3 h e, após resfriamento, foram recozidas a 400 C ao ar. Amostras distintas foram caracterizadas, na forma de pó seco e após calcinação entre 400600 C, por difração de raios X, adsorção de nitrogênio, microscopia eletrônica de varredura e espectroscopia de refletância difusa no UV-Visível. As titânias pu-ras, obtidas principalmente variando-se a razão de hidrólise, foram cristalizadas na forma de anatásio como fase predominante até 600 C, além de traços de brookita presente até 500 C. O rutilo foi identificado a partir de 600 C como fase minoritária, embora apresentando tama-nhos de cristal significativamente maiores que os estimados para o cristal de anatásio. As titâ-nias modificadas com até 20% de silício apresentaram notável estabilidade térmica, evidenci-ada pela presença exclusiva de anatásio até 900 C. Foi também observado o aparecimento de macroporos com diâmetro médio em torno de 55 nm após calcinação a 400 C, diferentemente do que se observou nas amostras em geral. A introdução de baixo teor de silício assegurou às titânias calcinadas valores elevados de área específica, atribuído ao efeito de contenção acentuada na taxa de crescimento do cristal. As titânias modificadas com silício e as titânias puras obtidas com taxa de hidrólise 25:1 para a razão H2O : Ti apresentaram mesoporos com diâmetros médios de mesma dimensão do cristal. As titânias modificadas com silício e dopa-das com nitrogênio apresentaram absorção na região visível entre 400-480 nm, com discreta redução da energia de band gap para as transições eletrônicas consideradas. Titânias calcina-das a 300−400 C apresentaram desempenho fotocatalítico semelhante ao TiO2 P25 da De-gussa sob irradiação UV, na degradação do azo corante Reactive Yellow 145 em soluções a-quosas em pH 5 a 20 1C