Thermal Conductivity of Sm3S4 System with Mixed Valence Sm Ions

The thermal conductivity () and electrical resistivity () of mixed-valence compound Sm₃S₄ have been measured in the temperature range 5 to 300 K. The present results and those presented previously 1] for the thermal conductivity between 80 to 850 K are interpreted in terms of the temperature-dependent fluctuating valence of Sm ions. Sm₃S₄ crystallizes in the cubic Th₃P₄ structure, and the cations with different valences occupy equivalent lattice sites. Divalent and trivalent Sm ions are randomly distributed in the ratio of 1:2 over all possible crystallographic cation positions (Sm²⁺ ₂Sm³⁺ ₂S^2– ₄). The behavior of the Sm₃S₄ lattice thermal conductivity _ph is extraordinary since valences of Sm ions are fluctuating (Sm³⁺Sm²⁺) with a temperature dependent frequency. In the interval 20 to 50 K (low hopping frequencies), _ph of Sm₃S₄ varies as _ph T ^–1 (it is similar to materials with static distribution of cations with different valences): at 95 to 300 K (average hopping frequencies 10⁷ to 10¹¹ Hz), _ph changes as _ph T ^–0.3 (it is similar to materials with defects). Defects in Sm₃S₄ appear because of local strains in the lattice by the electrons hopping from Sm²⁺ ions (with big ionic radii) to Sm³⁺ ions (with small ionic radii) and back (Sm²⁺Sm³⁺), at T>300 K (high hopping frequencies), _ph becomes similar to materials with homogenous mixed valence states 1].