Spectroscopic Investigation of the Chemical and Electronic Properties of Chalcogenide Materials for Thin-film Optoelectronic Devices

摘要

Chalcogen-based materials are at the forefront of technologies for sustainable energy production. This progress has come only from decades of research, and further investigation is needed to continue improvement of these materials.For this dissertation, a number of chalcogenide systems were studied, which have applications in optoelectronic devices, such as LEDs and Photovoltaics. The systems studied include Cu(In,Ga)Se2 (CIGSe) and CuInSe2 (CISe) thin-film absorbers, CdTe-based photovoltaic structures, and CdTe-ZnO nanocomposite materials. For each project, a sample set was prepared through collaboration with outside institutions, and a suite of spectroscopy techniques was employed to answer specific questions about the system. These techniques enabled the investigation of the chemical and electronic structure of the materials, both at the surface and towards the bulk.CdS/Cu(In,Ga)Se2 thin-films produced from the roll-to-roll, ambient pressure, Nanosolar industrial line were studied. While record-breaking efficiency cells are usually prepared in high-vacuum (HV) or ultra-high vacuum (UHV) environments, these samples demonstrate competitive mass-production efficiency without the high-cost deposition environment. We found relatively low levels of C contaminants, limited Na and Se oxidation, and a S-Se intermixing at the CdS/CIGSe interface. The surface band gap compared closely to previously investigated CIGSe thin-films deposited under vacuum, illustrating that roll-to-roll processing is a promising and less-expensive alternative for solar cell production.An alternative deposition process for CuInSe2 was also studied, in collaboration with the University of Luxembourg. CuInSe2 absorbers were prepared with varying Cu content and surface treatments to investigate the potential to produce an absorber with a Cu-rich bulk and Cu-poor surface. This is desired to combine the bulk characteristics of reduced defects and larger grains in Cu-rich films, while maintaining a wide surface band gap, as seen in Cu-poor films. A novel absorber was prepared Cu-rich with a final In-Se treatment to produce a Cu-poor surface, and compared directly to Cu-poor and Cu-rich produced samples. Despite reduced Cu at the surface, the novel absorber was found to have a surface band gap similar to that of traditional, Cu-poor grown absorbers. Furthermore, estimation of the near-surface bulk band gap suggests a narrowing of the band gap away from the surface, similar to highly efficient, Cu-poor grown absorbers.Long-term degradation is another concern facing solar cells, as heat and moistures stress can result in reduced efficiencies over time. The interface of the back contact material and absorber layer in (Au/Cu)/CdTe/CdS thin-film structures from the University of Toledo were investigated after a variety of accelerated stress treatments with the aim of further understanding the chemical and/or electronic degradation of this interface. Sulfur migration to the back contact was observed, along with the formation of Au-S and Cu-S bonds. A correlation between heat stress under illumination and the formation of Cu-Cl bonds was also found.Nanocomposite materials hold promise as a next-generation photovoltaic material and for use in LED devices, due in part to the unique ability to tune the absorption edge of the film by adjusting the semiconductor particle size, and the prospective for long-range charge-carrier (exciton) transport through the wide band gap matrix material. Thin films of CdTe were sputter deposited onto ZnO substrates at the University of Arizona and studied before and after a short, high temperature annealing to further understand the effects of annealing on the CdTe/ZnO interface. A clumping of the CdTe layer and the formation of Cd- and Te-oxides was observed using surface microscopy and photoelectron spectroscopy techniques. These findings help to evaluate post-deposition annealing as a treatment to adjust the final crystallinity and optoelectronic properties of these films.Through publication and/or discussion with collaborators, each project presented in this dissertation contributed to the understanding of the chemical and electronic properties of the material surface, near-surface bulk, and/or interfaces formed. The information gained on these unique chalcogenide materials will assist in designing more efficient and successful optoelectronic devices for the next generation of solar cells and LEDs.