Large Thermal Conductivity Drops in the Diamondoid Lattice of CuFeS₂ by Discordant Atom Doping

Doping in a lattice refers to the introduction of very small quantities of foreign atoms and has a generally small effect on decreasing the lattice thermal conductivity, unlike alloying which involves large fractions of other elements and strongly enhances point defect phonon scattering. Here, we report that, by alloying only 3% of In on the Cu sites of the diamond-like lattice of CuFeS₂ chalcopyrite compound (Cu_1-InFeS₂, x = 0.03) has a disproportionally large effect in reducing the lattice thermal conductivity of the compound from 2.32 to 1.36 Wm^-1K^-1 at 630 K. We find that In is not fully ionized to +3 when on the Cu sublattice and exists mainly in the +1 oxidation state. The 5s² lone pair of electrons of In⁺ makes this atom incompatible (referred to as discordant) with the tetrahedral geometry of the crystallographic site. This causes strong local bond distortions thereby softening the In-S and Cu-S chemical bonds and introducing localized low frequency vibrations. The latter couple with the base phonon frequencies of the CuFeS₂ matrix enhancing the anharmonicity and decreasing the phonon velocity, and consequently the lattice thermal conductivity. The control material in which the In doping is on the Fe³⁺ site of the structure at the same doping level (and found in the site-compatible In³⁺ state), has a far smaller effect on the phonon scattering.