N‐Type CuIn₅Se₈‐Based Thermoelectric Materials with All‐Scale Hierarchical Architectures

AbstractCopper (Cu)‐based thermoelectric (TE) materials have attracted great attention from both scientific and industrial societies, but for a long time, their real applications are greatly limited by the lack of high‐performance n‐type Cu‐based TE materials. Most recently, the novel n‐type Cu‐based TE material, CuIn5Se8, has been discovered to show a record‐high TE figure‐of‐merit (zT) to match the state‐of‐the‐art p‐type Cu‐based TE materials. However, the physical origin of such high zT is still unclear due to its complex phase compositions and crystal structures. In this work, it is revealed that the excellent TE performance is mainly contributed by the intrinsically ultralow lattice thermal conductivity originating from the unique all‐scale hierarchical architecture. It covers the ranges from atomic‐scale cation disorder in the tetragonal CuIn5Se8 phase and nanoscale diversified stacking units and stacking sequences in the hexagonal CuIn5Se8 phase, to mesoscale grain boundaries between the tetragonal phase and hexagonal phase. Doping Br at the Se‐sites can largely tune the electrical transports of CuIn5Se8 while maintaining the ultralow lattice thermal conductivity, leading to high zT reaching the optimal value predicted by the single parabolic model. This work will guide the investigation of n‐type Cu‐based TE materials in the future.