Nanostructured semiconductors for thermoelectric energy conversion: Synthesis and transport properties

Increasing energy demands and decreasing natural energy resources have sparked search for alternative clean and renewable energy sources. For instance, currently there is a tremendous interest in thermoelectric and photovoltaic solar energy production technologies. Half-Heusler (HH) alloys are among the most popular material systems presently under widespread investigations for high temperature thermoelectric energy conversion. Approaches to increase the thermoelectric figure of merit (ZT) of HH range from (1) chemical substitution of atoms with different masses within the same atomic position in the crystal structure to optimize carrier concentration and enhance phonon scattering via mass fluctuation and (2) embedding secondary phonon scattering centers in the matrix (nanostructuring) to further reduce thermal conductivity.;This work focuses on three material systems. The first part describes the synthesis and properties (thermal conductivity, electrical conductivity, magnetic) of various oxide nanostructures (NiO, Co3O4) which were subsequently used as inclusion phases in a HH matrix to reduce the thermal conductivity. Detailed reviews of the past efforts along with the current effort to optimize synthetic routes are presented. The effects of the synthesis conditions on the thermoelectric properties of compacted pellets of NiO and Co3O4 are also discussed. The second part of the work discusses the development of synthetic strategies for the fabrication of p-type and n-type bulk nanostructured thermoelectric materials made of a half-Heusler matrix based on (Ti,Hf)CoSb, containing nanostructures with full-Heusler (FH) compositions and structures coherently embedded inside the half-Heusler matrix. The role of the nanostructures in the regulation of phonon and charge carrier transports within the half-heusler matrix is extensively discussed by combining transport data and electron microscopy images. It was found that the FH nanoinclusions form staggered heterojunctions with a valence band (VB) offset energy at the HH/FH phase boundaries. The resulting energy barrier discriminates existing holes with respect to their energy by trapping low energy holes, while promoting the transport of high energy holes through the VB of the FH-quantum dots. This "carrier culling" results in surprisingly large increase in the mobility and the effective mass of high energy holes contributing to electronic conduction. The simultaneous reduction in the density and the increase in the effective mass of holes resulted in large enhancements of the thermopower, whereas the increase in the mobility minimizes the drop in the electrical conductivity. In the third part, the application of this concept of nanostructuring on the Copper Selenide material system is described. Various synthetic approaches such as liquid assisted solid-state reaction and mechanical alloying are utilized for the fabrication of copper selenide compositions. We found that the mechanical alloying clearly decreases the thermal conductivity of the composition as well increases the Seebeck due to decrease in carrier concentrations.