Semiconducting properties and related defect disorder for well defined TiO2 single crystal were studies. Semiconducting properties have been determined using simultaneous measurements of two independent electrical properties, including electrical conductivity, ??, and thermoelectric power, S, at elevated temperatures (1073-1323 K) in the gas phase of controlled oxygen activity (10-10 Pa < p(O2) < 75 kPa). Measurements of s and S were conducted (i) in the gas/solid equilibrium and (ii) during equilibration. Oxygen vacancies have been identified as the predominant defects in TiO2 over a wide range of p(O2). Individual conductivity components related to electrons, electron holes and ions, were determined from the obtained ?? data. The effect of p(O2) on these individual components was considered in the form of a diagram. This work led to the discovery of the formation and diffusion of Ti vacancies. However, the obtained diffusion data indicate that, in the temperature ranges commonly used in studies of semiconducting properties (1000-1400K), the Ti vacancies concentration is quenched and may thus be assumed constant. In addition it was shown that Ti vacancies in appreciable concentrations form only during prolonged oxidation. It was determined that the discrepancies in the reported n-p transition point are related to the concentration and spectrum of impurities as well as the concentration of Ti vacancies. It has been shown that the n-p transition point in high-purity TiO2 is determined by the Ti vacancy concentration. A well defined chemical diffusion coefficient, Dchem, was determined using kinetic data obtained during equilibration. A complex relationship between p(O2) and Dchem was observed. These data showed a good agreement between the obtained diffusion data and defect disorder. Examination of the determined equilibration kinetics, led to the discovery of two kinetic regimes, the result of the transport of defects at different mobilities. The determined data are considered well defined due to the following reasons: 1. The studied specimen was of exceptionally high purity and free of grain boundaries (single crystal) 2. The specimen was studied in the gas phase of controlled and well defined oxygen activity which was continuously monitored. 3. Whenever the experimental data were measured in equilibrium, the gas/solid equilibrium has been verified experimentally. 4. A good agreement between the two, self-confirmatory, electrical properties, including ?? and S has been determined simultaneously and independently. The defect disorder model derived in the present work may be used for tailoring controlled semiconducting properties through the selection of annealing conditions involving the temperature and oxygen activity.
| Identifer | oai:union.ndltd.org:ADTP/257237 |
| Date | January 2006 |
| Creators | Nowotny, Maria, Materials Science & Engineering, Faculty of Science, UNSW |
| Publisher | Awarded by:University of New South Wales. School of Materials Science and Engineering |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | Copyright Maria Nowotny, http://unsworks.unsw.edu.au/copyright |
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