Chemical bath deposition of semiconductor thin films & nanostructures in novel microreactors.

摘要

Chemical bath deposition (CBD) offers a simple and inexpensive route to deposit semiconductor nanostructures and thin films, but lack of fundamental understanding and control of the underlying chemistry has limited its versatility. CBD is traditionally performed in a batch reactor, requiring only a substrate to be immersed in a supersaturated solution of aqueous precursors such as metal salts, complexing agents, and pH buffers. Highlights of CBD include low cost, operation at low temperature and atmospheric pressure, and scalability to large area substrates.;In this dissertation, I explore CBD of semiconductor thin films and nanowire arrays in batch and continuous flow microreactors. Microreactors offer many advantages over traditional reactor designs including a reduction in mass transport limitations, precise temperature control and ease of production scale-up by "numbering up". Continuous flow micoreactors offer the unique advantage of providing reaction conditions that are time-invariant but change smoothly as a function of distance down the reaction channel. Growth from a bath whose composition changes along the reactor length results in deposited materials whose properties vary as a function of position on the substrate, essentially creating a combinatorial library. These substrates can be rapidly characterized to identify relationships between growth conditions and material properties or growth mechanisms.;I have used CBD in a continuous flow microreactor to deposit ZnO nanowire arrays and CdZnS films whose optoelectronic properties vary as a function of position. The spatially-dependent optoelectronic properties of these materials have been correlated to changes in the composition, structure or growth mechanisms of the materials and ultimately their growth conditions by rigorous spatial characterization. CBD in a continuous flow microreactor, coupled with spatial characterization, provides a new route to understanding the connection between CBD growth conditions and the resulting optoelectronic properties of the film.;The high surface-to-volume ratio of a microreactor also lends itself to in situ characterization studies. I demonstrated the first in situ x-ray absorption fine-structure spectroscopy (XAFS) study of CBD. The high sensitivity and ability to characterize liquid, amorphous and crystalline materials simultaneously make in situ XAFS spectroscopy an ideal tool to study the CBD of inorganic nanomaterials.