Summary: | The microstructures of Cu2Zn0.2Sn0.8S3 ceramics with high electrical conductivity and low thermal conductivity were investigated by a combination of selected area electron diffraction, high-resolution transmission electron microscopy, X-ray energy dispersive spectroscopy and atom force microscopy techniques. The plate-like tetragonal metastable Cu2S nanoprecipitates with elongated and equiaxed shape were embedded in a distinctive mosaic nanostructure with roughly 10 nm wide facetted domains (fully disordered phase) surrounded by a ∼5 nm wide connective phase (a semi-ordered monoclinic-Cu4ZnSn2S7 phase) were observed. These metastable Cu2S nanoprecipitates show clear orientation relationships with the matrix that the plates align with three crystal axes of cubic lattice. A combination of conductive atomic force microscopy and Kelvin probe force microscopy reveals that the nanoprecipitates have higher electrical conductivity than the matrix due to the higher carrier density, which can inject into the matrix and enhance the total electric conductivity of the sample. Furthermore, a mechanism of phonon scattering is proposed based on the effects of the occupation disorder of Cu atoms in Cu2S nanoprecipitates, coherent heterointerfaces between Cu2S and matrix, and the extended strain field in the matrix regions adjacent to the Cu2S nanoprecipitates.
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