@phdthesis{Goetzendoerfer2010, author = {G{\"o}tzend{\"o}rfer, Stefan}, title = {Synthesis of Copper-Based Transparent Conductive Oxides with Delafossite Structure via Sol-Gel Processing}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-51601}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2010}, abstract = {Starting off with solubility experiments of possible precursors, the present study reveals the whole development of a sol gel processing route for transparent p type semiconductive thin films with delafossite structure right to the fabrication of functional p-n junctions. The versatile sol formulation could successfully be modified for several oxide compositions, enabling the synthesis of CuAlO2, CuCrO2, CuMnO2, CuFeO2 and more. Although several differences in the sintering behaviour of powders and thin films could be observed, the powder experiments significantly contributed to the clearification of the intricate phase development during thermal annealing and also to optimization of the annealing sequence for thin film processing. Two different ternary systems turned out to be the most promising candidates for p-TCO application: Copper aluminum oxide for its high optical transmittance and copper chromium oxide for its low synthesis temperature, which allowed thin film deposition on low-cost borosilicate substrates. In order to combine the advantages of these two systems, the quaternary oxide composition CuAl1-xCrxO2 was investigated. With a higher optical transmittance than CuCrO2, a lower synthesis temperature than CuAlO2 and a lower resistivity than both parent systems, the optimum composition of the quaternary oxide is reached for x = 0.50. Compared to physical vapour deposition techniques, the undoped thin films presented here still need to make up some deficites in their optoelectronic performance. Although the best sol-gel samples are able to compete with RF sputtered samples or sampes deposited by PLD in transmittance, their resistivity is almost two orders of magnitude higher. The most probable reasons for this are the characteristic imperfections of sol-gel thin films like porosity and small crystallite size, which create barriers like grain boundaries and bottlenecks like barely connected particles. By additional effort such shortcomings can be repelled to a certain extend, but nevertheless the density of undoped sol-gel material always stays behind its pendants processed by physical vapour deposition.[246] Furthermore, such additional endeavour is likely to annihilate the advantage of sol-gel technique in processing costs. Extrinsic doping is a common method to decrease the resistivity of delafossite materials. Partially replacing the trivalent cations by divalent ones creates additional holes and thus generates additional charge carriers for p-type semiconductivity. This can improve the conductivity of delafossites by up to three orders of magnitude. Due to the compositorial flexibility of sol-gel processing, dopants could be introduced easily in this study by soluble precursors. However, improving the conductivity of CuAlO2 and CuAl0.5Cr0.5O2 via this method failed. Actually, this seems to be due to the fact that instead of being incorporated into the delafossite phase the dopant ions form intransparent phase impurities like spinels, which interfere with optical transmittance of the thin films. On the contrary, doping had a positive effect on the conductivity and the optical transmittance of copper chromium oxide, with magnesium being the most effective dopant. The resistivity could be decreased by more than three orders of magnitude, but in order to achieve this, much higher Mg concentrations than by other thin film deposition methods were necessary. This indicates a low doping efficiency in sol gel processed thin films, but also the ability of sol gel processing to incorporate more magnesium into the oxide than any other processing method. The extensive substitution of the chromium ions also increases the optical transmittance and allows sol gel processed thin films to draw level with thin films deposited by sputtering methods or PLD. Finally, the applicability of the delafossite thin films was proven by the asymmetric current voltage characteristics of heterojunctions between ITO and the delafossites. Shunting problems of the metallic contacts, on the other hand, reveal structural deficites of the delafossites, which should be the subject of further investigations.}, subject = {Transparent-leitendes Oxid}, language = {en} } @phdthesis{Schumm2008, author = {Schumm, Marcel}, title = {ZnO-based semiconductors studied by Raman spectroscopy: semimagnetic alloying, doping, and nanostructures}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-37045}, school = {Universit{\"a}t W{\"u}rzburg}, year = {2008}, abstract = {ZnO-based semiconductors were studied by Raman spectroscopy and complementary methods (e.g. XRD, EPS) with focus on semimagnetic alloying with transition metal ions, doping (especially p-type doping with nitrogen as acceptor), and nanostructures (especially wet-chemically synthesized nanoparticles).}, subject = {Wide-gap-Halbleiter}, language = {en} }