Fabrication of Thin Films by Pulsed Laser Deposition for Clean Energy Applications

Pulsed laser deposition (PLD) is a physical vapor deposition technique for thin film fabrication. Compared with other techniques, pulsed laser deposition technique has advantages such as stoichiometry, flexibility, versatility, lower deposition temperature, ability to grow metastable materials. Because of these advantages, pulsed laser deposition has been widely used in materials research. In this dissertation, pulsed laser deposition has been used to grow thin films for solid oxide fuel cell, light-emitting diode, and solar cell applications./nFirstly, yttria-stabilized zirconia (YSZ) and cerium dioxide (CeO2) thin films are deposited in oxygen-deficient environments; their properties are compared to those deposited in oxygen-rich environments. Oxygen-deficient films are highly (001)-oriented, which corresponds to a surface that is expected to be forbidden based on Tasker's theoretical calculation of stoichiometric ionic crystals. A model considering non-stoichiometry-induced surface relaxation and surface atomic density is proposed to explain the orientation phenomenon observed under oxygen-deficient deposition conditions. This model is consistent with previous experimental results for indium tin oxide (ITO), SnO2 and NiO thin films deposited under similar conditions. Detailed studies of the preferred orientation of these oxygen-deficient ionic crystals are of direct relevance to the fabrication of films for use in solid oxide fuel cells./nSecondly, undoped, Cu-doped, Se-enriched, Cu2Se-doped, Ag-doped, Ag2Se-doped, and nitrogen-doped ZnSe films have been grown on fused quartz substrates by pulsed laser deposition. It is found that adding a small amount (~2 mol%) of Cu2Se can significantly improve crystallinity and (111) texturing of ZnSe films. While the other films are highly resistive, Cu2Se-doped ZnSe films are p-type conducting with hole concentrations of ~ cm-3 and resistivity of ~0.098 ohm*cm (compared with previous reports of ~ cm-3 and 0.75 ohm*cm, respectively). The successful heavy p-type doping of ZnSe films is attributed to substitution of Zn atoms with Cu while limiting selenium-vacancy-associated compensating defects with additional selenium. Nitrogen doping has turned ZnSe films more favorable to wurtzite structures. Two newly observed Raman peaks at 555 cm-1 and 602 cm-1 are assigned to N local vibrational modes of hexagonal ZnSe structures. The nitrogen-doped ZnSe films are not conductive, which might be due to compensating defects arising from the presence of native defects or other impurities. This work is of importance to solve doping difficulties and contact problems of wide-bandgap semiconductors./nFinally, batch growth of thin films by pulsed laser deposition has been tried. Using the natural temperature gradient, films with different deposition temperatures have been fabricated together. With change of deposition temperatures, ZnSe films are shown to have problems associated with crystalline defects, selenium loss, or phase separation. ZnSe films with improved crystallinity and no phase separation have been achieved using a 16 mol% Se enriched target. Multi-plume pulsed laser deposition has been proposed and discussed. With directionality of PLD plumes and non-uniformity of PLD films, this system is supposed to be more suitable for high-throughput compound thin film fabrication, which makes it very promising for efficient materials optimization and exploration. High-throughput fabrication of compound thin films has been successfully achieved using this system.

Advisor: Mao, Samuel S.
Zhang, Xiang