The field of thermoelectric materials has flourished over the last two decades. Significant successes achieved in the development of materials notwithstanding, novel and highly efficient materials are in steep demand due to a wide range of potential and current applications, ranging from wearable electronics to space missions. The main challenge in the improvement of the thermoelectric figure of merit ( zT ) is to optimize the intertwined intrinsic charge and thermal transport properties. High electrical conductivity and thermopower, along with low thermal conductivity, need to be achieved simultaneously to excel the thermoelectric efficiency. In this review, the thermoelectric concepts, basics of transport properties, and strategies for zT optimization are discussed in the first section. In the following sections, the predominate structure types associated with high‐performance bulk thermoelectric materials are discussed in detail: Bi 2 Te 3 , PbTe, TAGS/LAST systems, SnSe, Cu 2− x Se, chalcopyrites, tetrahedrites, clathrates, skutterudites, zinc antimonides, Yb 14 MnSb 11 , Heusler and half‐Heusler intermetallics. The basic crystal structures, the possibilities for doping and substitutions to adjust charge carrier concentration and thermal conductivity, baseline thermoelectric properties, and strategies for efficiency improvement are considered for each structure type. Examples of recent work highlighting these strategies are briefly presented.
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