Intrinsically ultralow thermal conductivity in all-inorganic superatomic bulk crystals

TL;DR

This study reports the synthesis of all-inorganic superatomic bulk crystals with ultralow thermal conductivity, attributed to anharmonic vibrations and disordered phonon transport, highlighting their potential for energy management.

Contribution

It demonstrates the growth of high-quality superatomic crystals with record-low thermal conductivity and analyzes their phonon transport mechanisms.

Findings

Re6Se8Te7 and Re6Te15 have thermal conductivities of 0.32 and 0.53 W/m·K at room temperature.

Large Grüneisen parameter and low sound speed contribute to ultralow thermal conductivity.

Thermal conductivity behavior aligns with the Debye-Callaway model and approaches glassy-like diffusion limits at high temperatures.

Abstract

Superatomic compounds, composed of atomic clusters interwoven by weak chemical bonds exhibit large anharmonicity vibrations, are excellent candidates for ultralow thermal conductivity (\k{appa}) materials. However, growing bulk superatomic single crystals is challenging due to complex chemical composition and chemical bonds, and studies on their intrinsic thermal property are scarce. Here, we grew high-quality superatomic single crystals of Re6Se8Te7 and Re6Te15, both of which are narrow band gap semiconductors that change into metals under external physical pressure. At room-temperature, the \k{appa} are 0.32 W m-1 K-1 and 0.53 W m-1 K-1 in Re6Se8Te7 and Re6Te15, respectively, ranking among the lowest value reported in all-inorganic bulk crystals. It is mainly attributed to the large Gr\"uneisen parameter (1.93) and low average sound speed (< 1482 m/s), which are due to soft Te7 nets weakly embedded among the rigid Re6Se8 (Re6Te8) quasi-cubic clusters. The appearance of boson peak, i. e., hump of C(T)/T3, verifies the existence of disordered phonon transports. Besides, the temperature dependence of \k{appa} can be described by classic Debye-Callaway model. Notably, above 350 K, the \k{appa} values of Re6Se8Te7 and Re6Te15 are remarkably close to the upper limit derived from glassy-like diffusion model. This finding sets the superatomic compounds as a promising family for searching ultralow-\k{appa} and energy management materials.