• Calcium;
  • Iron;
  • Arsenic;
  • Superconductors;
  • Intermetallic phases;
  • Solid-state reactions;
  • Thermal stability


CaFe4As3 is a new intermetallic structure type that can be described as a framework comprising of FeAs4 tetrahedra. The structure has similarities to the 1-2-2 superconducting phase in that the Fe/As network is related to the ThCr2Si2 structure. In addition, this phase shows magnetic transitions associated with spin density waves. This phase was prepared from a Sn flux, and it has recently been reported that further expansion of this structure type via chemical substitution is limited. We have developed a solid-state synthesis route for the preparation of CaFe4As3 that involves reacting a stoichiometric combination of the constituent elements. The thermal stability of this material was investigated over the 298–1473 K temperature range. An initial investigation of the Sn grown CaFe4As3 crystals showed that residual Sn that was present on the surface of the crystals reacted with the crystals at temperatures above 1173 K to form new phases. A thermal stability study of Sn-free CaFe4As3 indicated that it decomposed to give CaFe2As2 and Fe2As. The thermal behavior of CaFe2As2 was also investigated and the data showed that it can also form CaFe4As3 at high temperatures. The solid-state synthesis route presented herein and additional solid solution studies may provide opportunities for the prepartion of materials with this structure type with improved electronic properties.