Synthesis and characterization of germanium nanoparticles for flexible thin-film photovoltaics

Photovoltaic cells based on low-cost polycrystalline and nanocrystalline materials are of great interest for both scientific and industrial purposes because of their intriguing properties found in semiconductor nanoparticles as well as the need to make high-energy conversion photovoltaics. The main theme of this dissertation is the synthesis of such nanoparticles of elemental germanium.; Butyl-capped crystalline germanium nanoparticles were synthesized at room temperature in dimethoxymethane via the reduction of germanium tetrachloride with sodium naphthalide and the subsequent reaction with n-butyl Grignard. The nanoparticles were isolated in hexane and characterized by transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray spectroscopy, elemental analysis, X-ray powder diffraction, ultraviolet-visible spectroscopy, and photoluminescence spectroscopy. When heated under vacuum between 300--550°C, the as prepared nanoparticles become amorphous and grow in size. At 561°C, a phase change is observed which is associated with the change from the amorphous to crystalline. Numerous exothermic peaks were found in between 900--950°C under thermogravimetric analysis.; Detailed studies of this reduction synthesis have been performed to optimize the synthetic route. The germanium nanoparticle nucleation is influenced by variations of reductant, concentration, temperature, and synthesis. Results indicate that the reduction route of germanium nanoparticles follows similar kinetics at room temperature, as does the related II-VI nanoparticle synthetic route.; The reduction route was also found to produce a polymeric side product that can be removed at 300°C under vacuum. Under an in-situ heating experiment, this germanium containing polymer acts as a germanium source for the formation of small germanium nanoparticles at temperatures above 300°C. At temperatures above 400°C the polymer further acts to build germanium films.; The metathesis reaction of magnesium germanide and germanium tetrachloride was shown to be another feasible method to synthesize germanium nanoparticles. The effect of surface termination was studied by comparing the alkyl and amine terminations. However, the amine terminated germanium nanoparticles display only short term stability, therefore a better synthetic route is still needed.