An Instant Change of Elastic Lattice Strain during Cu2Se Phase Transition: Origin of Abnormal Thermoelectric Properties

The superionic conductor Cu2Se is a promising thermoelectric material due to its low thermal conductivity. An abnormal but clear change in the thermoelectric parameters has been observed during the phase transformation from the ordered and non‐cubic α‐Cu2Se to the disordered and cubic β‐Cu2Se. However, the microstructural origin of the abnormal change and its implications for thermoelectric applications remain largely unknown. Herein, by mimicking the real working conditions of thermoelectrics, the phase transition from α‐ to β‐Cu2Se induced by the rising temperature has been carefully investigated by in situ transmission electron microscopy. It is observed that an abrupt and anisotropic volume‐change in the Se‐sublattice occurs when the temperature is raised to the phase transition point. The abnormal change in the crystalline volume versus temperature, which is caused by the local migration of Cu‐ions, induces an instant and uncommon strain‐field, which reduces the carrier’s mobility and increases the electrical resistance. Local migration of Cu‐ions is responsible for a quite low thermal conductivity. Such effects exist only at the instance of the phase transition. Observing the thermoelectric response of the structure during the phase transition may provide insights into the development of high performance thermoelectric materials, which fall beyond the traditional approaches.By applying in situ TEM, a dynamic evolution of the crystalline structure and the strain fields during Cu2Se phase transformation have been studied. The instant generation and release of a large elastic strain is identified as one of the main origins of the abnormal thermoelectric behavior of Cu2Se in the moment of phase transition.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/167752/1/adfm202100431_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/167752/2/adfm202100431.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/167752/3/adfm202100431-sup-0001-SuppMat.pd