Free carriers in nanocrystalline titanium dioxide thin films

Abstract

This thesis analyzes the properties of heavily doped nanocrystalline titanium dioxide. Thin films were deposited by magnetron sputtering with either water vapor as reactive gas or a periodically interrupted oxygen supply. The samples were at the same time electrically conducting and transparent. They consisted of mixtures of rutile, anatase and amorphous phases. Titanium dioxide is chemically stable, hard, non-toxic, transparent, and inexpensive. Due to a high refractive index it is often found in optical applications as a thin film coating. For many purposes it is interesting to take advantage of a combination of good transparency and electrical conductivity. An even larger field of applications would open if the electric conductivity of TiO2 could be increased in a controlled manner. Conventional bulk doping is limited, however, by low solubility limits. Highly conducting nanocrystalline TiO2 thin films have been obtained recently by sputtering in presence of water vapor. The present project intends to elucidate the doping mechanisms at work in such films. In addition, an alternative process to achieve grain-boundary doping of TiO2 was explored. Spectrophotometry over a wide spectral range (0.05 to 5 eV) was the main tool in probing the mobile electrical charge carriers. The interpretation of these optical measurements required appropriate models. The models developed took many structural properties into account, such as thickness, surface roughness, density, anisotropy and crystalline phase composition. The phase and morphology of the films were analyzed by X-ray diffraction and reflection, scanning probe microscopy, and electron microscopy. The chemical analyses included electron-probe microanalyses, Rutherford backscattering and elastic recoil detection analysis. The DC electrical properties were measured between room temperature and 250 °C. Most water-deposited samples showed semiconducting behavior with an activation energy of the order of 100 meV. The optical measurements revealed a broad absorption band around 1 eV. The absorption coefficient scaled with conductivity. It was successfully modelled as a Lorentzian. Similar absorption bands have been reported for reduced rutile and anatase single crystals. Water-deposited samples containing anatase exhibited a metallic behavior. In these samples the thermal activation energy was reduced to about 30 meV and the charge carriers displayed a high mobility (3 cm2V-1s-1). The infrared absorption band was about 10 times less important than in the samples devoid of anatase. Thin films of TiO2 intercalated with the equivalent of nanometer-thick layers of Ti were prepared. By changing the period in the oxygen supply the grain size, and thereby the film properties, could be modified. The films obtained in this way had many properties in common with water-deposited films. They showed the same absorption band in the infrared, had comparable charge carrier densities and were electrically conductive (102 to 104 Sm-1 at room temperature). To our knowledge, this was the first time that such high electrical conductivities were achieved by sputtering in an oxygen plasma.