An understanding of the structural features and bonding of a particular material, and the properties these features impart on its physical characteristics, is essential in the search for new systems that are of technological interest. For several relevant applications, the design or discovery of low thermal conductivity materials is of great importance. We report on the synthesis, crystal structure, thermal conductivity, and electronic-structure calculations of one such material, PbCuSbS3 . Our analysis is presented in terms of a comparative study with Sb2 S3 , from which PbCuSbS3 can be derived through cation substitution. The measured low thermal conductivity of PbCuSbS3 is explained by the distortive environment of the Pb and Sb atoms from the stereochemically active lone-pair s(2) electrons and their pronounced repulsive interaction. Our investigation suggests a general approach for the design of materials for phase-change-memory, thermal-barrier, thermal-rectification and thermoelectric applications, as well as other functions for which low thermal conductivity is purposefully sought.
Keywords: ELF (Electron Localization Function); chalcogenides; density functional theory; thermal conductivity; thermoelectricity.
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