Design, crystal growth, and physical properties of low-temperature thermoelectric materials

Abstract

Thermoelectric materials serve as the foundation for two important modern technologies, namely 1) solid-state cooling, which enables small-area refrigeration without vibrations or moving parts, and 2) thermoelectric power generation, which has important implications for waste heat recovery and improved sources of alternative energy. Although the overall field of thermoelectrics research has been active for decades, and several consumer and industrial products have already been commercialized, the design and synthesis of new thermoelectrics that outperform long-standing state of the art materials has proven extremely challenging. This is particularly true for low-temperature refrigeration applications, which is the focus of this work; however, scientific advances in this area generally support power generation as well. In order to achieve more efficient materials for virtually all thermoelectric applications, improved materials design principles must be developed and synthetic procedures must be better understood. We aim to contribute to these goals by studying two classes of materials, namely 1) the tetradymites Bi2TeSe2 and Bi2Te2Se, which are close relatives of state of the art thermoelectric cooling materials, and 2) Kondo insulating (-like) FeSb2 and FeSi, which possess anomalously enhanced low-temperature thermoelectric properties that arise from exotic electronic and magnetic properties. The organization of this dissertation is as follows: Chapter 1 is a brief perspective on solid-state chemistry. Chapter 2 presents experimental methods for synthesizing and characterizing thermoelectric materials. In Chapter 3, two original research projects are discussed: first, work on the tetradymite Bi2TeSe2 doped with Sb to achieve an n- to p-type transition, and second, the tetradymite Bi2Te2Se with chemical defects through two different methods. Chapter 4 gives the magnetic and transport properties of FeSb2-RuSb2 alloys, a family of compounds exemplifying what we consider to be the next generation of thermoelectric materials for low-temperature cooling due to their anomalously enhanced low-temperature thermoelectric properties, along with an outlook for seeking additional materials with similarly enhanced properties. Lastly, in Chapter 5, a brief outlook on the future of thermoelectrics is discussed, along with our current and future work on FeSi-RuSi alloys.