Thermo-chemical properties and electrical resistivity of Zr-based arsenide chalcogenides

Ternary phases in the systems Zr–As–Se and Zr–As–Te were studied using single crystals of ZrAs1.40(1)Se0.50(1) and ZrAs1.60(2)Te0.40(1) (PbFCl-type of structure, space group P4/nmm) as well as ZrAs0.70(1)Se1.30(1) and ZrAs0.75(1)Te1.25(1) (NbPS-type of structure, space group Immm). The characterization covers chemical compositions, crystal structures, homogeneity ranges and electrical resistivities. At 1223 K, the Te-containing phases can be described with the general formula ZrAsxTe2–x, with 1.53(1)≤x≤1.65(1) (As-rich) and 0.58(1)≤x≤0.75(1) (Te-rich). Both phases are located directly on the tie-line between ZrAs2 and ZrTe2, with no indication for any deviation. Similar is true for the Se-rich phase ZrAsx–ySe2–x with 0.70(1)≤x≤0.75(1). However, the compositional range of the respective As-rich phase ZrAsx–ySe2–x (0.03(1)≤y≤0.10(1); 1.42(1)≤x≤1.70(1)) is not located on the tie-line ZrAs2–ZrSe2, and exhibits a triangular region of existence with intrinsic deviation of the composition towards lower non-metal contents. Except for ZrAs0.75Se1.25, from the homogeneity range of the Se-rich phase, all compounds under investigation show metallic characteristics of electrical resistivity at temperatures >20 K. Related uranium and thorium arsenide selenides display a typical magnetic field-independent rise of the resistivity towards lower temperatures, which has been explained by a non-magnetic Kondo effect. However, a similar observation has been made for ZrAs1.40Se0.50, which, among the Zr-based arsenide chalcogenides, is the only system with a large concentration of intrinsic defects in the anionic substructure.