Dye-sensitized, quantum-dot sensitized, quantum-dot, and hybrid organic/inorganic solar cells are promising excitonic photovoltaic devices for the generation of low cost, carbon free energy. Wide-band gap semiconductor nanowire photoanodes have the potential to increase the efficiencies of these excitonic solar cells. Controlling and tailoring the dimensions of the nanowires (i.e. nanowire height, diameter, and planar number density) for each solar cell type is important for efficiency improvement. Obtaining such control will require a detailed and fundamental understanding of the nanowire growth process. Towards this end, the synthesis of TiO2 and ZnO nanowire films in aqueous solutions was studied.
Anatase TiO2 nanowire films were grown on flexible titanium foil substrates using a three step hydrothermal synthesis. First, the top surface of the titanium foil was transformed to Na2Ti2O4(OH)2 nanotubes through hydrothermal oxidation in NaOH. Next, the Na2Ti2O4(OH)2 nanotubes were converted to H2Ti2O4(OH)2 nanotubes by ion exchange. Finally, the H2Ti2O4(OH)2 nanotubes were converted to polycrystalline anatase nanowires through a topotactic transformation. The film morphology evolution, crystal structure transformations, and growth mechanism were examined in detail. Dye-sensitized solar cells (DSSCs) were assembled from these TiO2 nanowire films. Transient photocurrent and photovoltage spectroscopies were used to measure the electron transport and recombination rates in these solar cells. Compared to TiO2 nanoparticle DSSCs the electron collection efficiency in the TiO2 nanowire DSSCs was increased due to decreased electron recombination. However, the electron transport in the nanowire DSSCs was similar to that of TiO2 nanoparticle DSSCs.
The synthesis of ZnO nanowires from aqueous solutions of methenamine (HMT) and zinc nitrate hexahydrate on substrates was studied in detail. A ZnO nanowire growth mechanism was proposed which predicts that the precursor is a zinc-methenamine complex (Zn-HMT2+ and Zn-HMT-Zn4+) which reacts at the hydroxyl terminated nanowire surface. This growth mechanism was supported by examining the growth with several experimental techniques, kinetic modeling, and thermodynamic calculations. In addition, the ZnO nanowire film growth, on ZnO seeded substrates, was found to be mass transport limited. This results in an inverse relationship between the nanowire planar number density and the height and diameter of the nanowires. By stirring the solution the growth rate is increased by approximately a factor of four.
University of Minnesota Ph.D. dissertation. August 2009. Major: Chemical Engineering. Advisor: Eray S. Aydil. 1 computer file (PDF); ix, 193 pages, appendix 1.
Boercker, Janice Elaine.
Synthesis of titanium dioxide and zinc oxide nanowires for excitonic solar cells..
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