Interlaced crystals having a perfect Bravais lattice and complex chemical order revealed by real-space crystallography

Abstract

The search for optimal thermoelectric materials aims for structures in which the crystalline order is disrupted to lower the thermal conductivity without degradation of the electron conductivity. Here we report the synthesis and characterisation of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystalline order: an uninterrupted, perfect, global Bravais lattice, in which the two cations exhibit a wide array of distinct ordering patterns within the cation sublattice, forming interlaced domains and phases. Partitioning into domains and phases is not unique; the corresponding boundaries have no structural defects or strain and entail no energy cost. We call this form of crystalline order ‘interlaced crystals’ and present the example of hexagonal CuInS2. Interlacing is possible in multi-cation tetrahedrally bonded compound with an average of two electrons per bond. Interlacing has minimal effect on electronic properties, but should strongly reduce phonon transport, making interlaced crystals attractive for thermoelectric applications.