Designing thermoelectric chalcogenides with atom probe tomography

Thermoelectric materials can realize waste heat recovery and solid-state refrigeration, providing sustainable solutions to the energy crisis and environmental pollution. The performance of thermoelectric materials is gauged by the transport of electrons and phonons. Materials with fast electron movement but slow phonon propagation would be ideal thermoelectrics. These transport behaviors of carriers are influenced by the intrinsic chemical bonding mechanism and structural defects of materials. Understanding the bonding and microstructures of materials is of paramount importance to improve their thermoelectric properties. Atom probe tomography (APT) provides a unique combination of characterizing chemical bonding and lattice defects, being a very powerful tool in the study of thermoelectric materials. It has been revealed that many of the high-performance thermoelectric chalcogenides utilize metavalent bonding (MVB), which can be distinguished from other bonding mechanisms by the unconventionally high value (>60%) of “probability of multiple events (PME)” measured by APT. Thus, many new compounds with high thermoelectric performance can be designed by tailoring their chemical bonds, and APT is an indispensable technique to corroborate the bonding transition. Owing to the high spatial and chemical resolution of APT, the local change of chemical bonding at defects such as grain boundaries and precipitates can also be detected by APT. This enables us to better understand the role of chemical bonding in regulating the electron and phonon transport across individual defects. The results in turn provide insights into the tailoring of thermoelectric properties by manipulating the local chemical bonds. For example, the thermoelectric properties of polycrystalline SnSe have been significantly improved by removing the stiff Sn-O bonds at the grain boundary as directly observed by APT. In contrast, the strong bonding connection between thermoelectric and interfacial materials enables a high-efficiency and durable thermoelectric device. Based on APT, in conjunction with other characterization techniques, we can explore some uncharted territories in the design of thermoelectric materials.