Lattice thermal conductivity of compounds with inhomogeneous intermediate rare-earth ion valence

The thermal conductivity κ (within the range 4–300 K) and electrical conductivity σ (from 80 to 300 K) of polycrystalline Sm₃S₄ with the lattice parameter a=8.505 Å (with a slight off-stoichiometry toward Sm₂S₃) are measured. For T>95 K, charge transfer is shown to occur, as in stoichiometric Sm₃S₄ samples, by the hopping mechanism (σ ～ exp(?ΔE/kT) with ΔE ～ 0.13 eV). At low temperatures up to the maximum in the lattice thermal conductivity κ_ph(T)], κ_ph ～ T ^2.6; in the range 20–50 K, κ_ph ～ T ^?1.2; and for T>95 K, where the hopping charge-transfer mechanism sets in, κ_ph ～ T ^?0.3 and a noticeable residual thermal resistivity is observed. It is concluded that in compounds with inhomogeneous intermediate rare-earthion valence, to which Sm₃S₄ belongs, electron hopping from Sm²⁺ (ion with a larger radius) to Sm³⁺ (ion with a smaller radius) and back generates local stresses in the crystal lattice which bring about a change in the thermal conductivity scaling of κ_ph from T ^?1.2 to T ^?0.3 and the formation of an appreciable residual thermal resistivity.