Thesis advisor: Cyril P. Opeil / Thermoelectric (TE) energy conversion is an all-solid-state technology which can convert waste thermal energy into useful electric power and cool ambience without using harmful gases like CFC. Due to their several advantages over traditional energy conversion technologies, thermoelectric generators (TEG) and coolers (TEC) have drawn enormous research efforts. The objective of this work is to find promising materials for thermoelectric cooling applications and optimize their thermoelectric performances. Finding a material with a good value for the thermoelectric figure-of-merit (ZT) at cryogenic temperatures, specifically below 77 K, has been of great interest. This work demonstrates that FeSb2, CeCu6 and CeAl3, all belonging to a class of materials with strongly correlated electron behavior; exhibit promising thermoelectric properties below 77 K. In general, ZT of a TE material can be increased using two basic approaches: lattice thermal conductivity reduction and power factor (PF) enhancement. The results of this study indicate that nanostructuring effectively decreases the thermal conductivity of FeSb2, CeCu6 and CeAl3 leading to improved ZT. The approach of introducing point-defect scattering to further reduce the thermal conductivity is successfully implemented for Te-substituted FeSb2 nanostructured samples. A semiconductor/metal interface has long been proposed to exhibit enhanced thermoelectric properties. We use this technique by introducing Ag-nanoparticles in the host FeSb2 which further increases ZT by 70%. Additionally, a detailed investigation is made on the phonon-drag effect as a possible mechanism responsible for the large value of the Seebeck coefficient of FeSb2. We show that the phonon-drag mechanism contributes significantly to the large Seebeck effect in FeSb2 and hence this effect cannot be minor as was proposed in literatures previously. A model based on Kapitza-resistance and effective medium approach (EMA) is used to analyze the thermal conductivities of nanostructured FeSb2 samples. We find a notably large value for Kapitza length at low temperatures indicating the dominance of inter-grain thermal resistance over bulk thermal resistance in determining the thermal properties of FeSb2. / Thesis (PhD) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.