| Electrochemical deposition of active materials such as Si, Mo and Ge is notoriously difficult, so they are typically deposited using expensive vacuum methods such as chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), and magnetron sputtering. However, for most materials, electrochemical deposition has significant advantages of cost, scalability, and manufacturability. There are two main challenges in depositing these materials from aqueous electrolytes at room temperature, namely their highly cathodic standard reduction potential and the formation of native oxides. This has led researchers to use non-aqueous electrolytes such as organic solvents, room temperature ionic liquids (RTILs), and high temperature molten salts. However, these have drawbacks over aqueous electrolytes such as high cost, low conductivity, flammability, and corrosive behavior. During my PhS studies, these two challenges were overcome by using the galvanic method of deposition and by including HF in the electrolyte.;Si thin films are employed in a variety of technologies, including microelectronic and photovoltaic devices, Li ion battery anodes, and corrosion-resistant coatings. A galvanic and a combined galvanic/electroless method of Si deposition were developed using aqueous electrolytes at room temperature to obtain nanoporous and compact films, respectively. These films were characterized to understand the surface morphology, thickness, crystallinity, growth rate, composition and nucleation behavior. Approximately 7-10 µm thick compact Si films were achieved with a deposition time of around 28 hours.;The galvanic method of deposition was also extended to deposit compact Mo films. Mo thin films have a number of technological applications, including back contacts for CIGS/CZTS photovoltaic devices and corrosion-resistant coatings. Mo thin films were also thoroughly characterized and approximately 4.5 µm thick films were obtained after 3 hours. Similar to Si depostion, a galvanic method of deposition and the galvanic/electroless method of deposition was tested for the deposition of Ge. However no Ge deposit could be consistently obtained, probably due to oxyanion formation in aqueous hexaflurogermante solution. |
