High-Pressure Synthesis and Physical Properties of a Spinel Compound FeAl2S4

Inorg Chem. 2022 Aug 22;61(33):13184-13190. doi: 10.1021/acs.inorgchem.2c02034. Epub 2022 Aug 9.

Abstract

A spinel compound FeAl2S4 was successfully synthesized under high-pressure and high-temperature conditions and was systematically characterized via the structural, magnetic, and specific heat measurements. It crystallizes into a cubic structure with the space group Fdm (no. 227) and the lattice constant a = 10.0207(2) Å. A Fe/Al site inversion is found; that is, the molecular formula can be rewritten as (Fe1-xAlx)(Al2-xFex)S4, and the inversion parameter x is about 0.22. Magnetic susceptibility measurements indicate that FeAl2S4 undergoes a spin glass behavior, which is confirmed by ac susceptibility and specific heat measurements. The freezing temperature Tf ∼ 10.5 K and Weiss temperature Tθ ∼ -107.4 K lead to a high frustration parameter f = |Tθ/Tf| of about 10, which suggests that FeAl2S4 is a high-frustration magnet. Our results indicate that high pressure can help stabilize the spinel structure with small σ and the cation inversion plays an important role in the formation of the spin glass state.