Heightened global concern over greenhouse gas emissions has led to an increased demand for clean energy conversion technologies. Thermoelectric materials convert directly between thermal and electrical energy and can increase the efficiency of existing processes via waste heat recovery and solid-state climate control applications. The conversion efficiency of available thermoelectric materials and the devices comprised of them is unfortunately quite low, and thus new materials must be developed in order for thermoelectrics to keep pace with competing technologies. One approach to increasing the conversion efficiency of a given material is to decrease its lattice thermal conductivity, which has traditionally been accomplished by introducing phonon scattering centers into the material. These scattering centers also tend to degrade electronic transport in the material, thereby minimizing the overall effect on the thermoelectric performance. The purpose of this work is to develop materials with inherently low lattice thermal conductivity such that no extrinsic modifications are required. A novel approach in which complex ternary semiconductors are derived from well-known binary or elemental semiconductors is employed to identify candidate materials. Ternary diamond-like compounds, namely Cu2SnSe3 and Cu3SbSe4, are synthesized, characterized, and optimized for thermoelectric applications. It is found that sample-to-sample variations in hole concentration limits the plausibility of Cu2SnSe3 as a thermoelectric material. Cu3SbSe4 is found to be a promising material that can achieve thermoelectric performance comparable to state-of-the-art materials when optimized. This work uncovers anomalous thermal conductivity in several Cu-Sb-Se ternary compounds, which is used to develop a set of guidelines relating crystal structure to inherently low lattice thermal conductivity.
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