Quaternary rare-earth arsenides REAg1−Zn As2 (RE=La–Nd, Sm, Gd–Dy) with tetragonal SrZnBi2- and HfCuSi2-type structures

Reactions of the elements at 800 °C with the nominal compositions RE Ag 1 − x Zn x As 2 resulted in quaternary arsenides RE Ag 1 − x Zn y As 2 in which the combined Ag and Zn content deviates increasingly from unity in the Zn-richer phases, reflecting the transition from the fully stoichiometric ternary silver-containing arsenides RE AgAs 2 to the substoichiometric zinc-containing ones RE Zn 0.67 As 2 . Powder X-ray diffraction analysis indicated SrZnBi 2 -type (space group I 4/ mmm , Z =4; RE =La, Ce) and HfCuSi 2 -type structures (space group P 4/ nmm , Z =2; RE =Pr, Nd, Sm, Gd, Tb, Dy). Single-crystal X-ray diffraction analysis performed on LaAg 0.5 Zn 0.5 As 2 , PrAg 0.5 Zn 0.5 As 2 , and NdAg 0.5 Zn 0.5 As 2 indicated that the Ag and Zn atoms are disordered within metal-centred tetrahedra and provided no evidence for distortion of the square As nets. The small electron excess tolerated in these quaternary arsenides and the absence of distortion in the square nets can be traced to the occurrence of As–As states that are only weakly antibonding near the Fermi level. PrAg 0.5 Zn 0.5 As 2 and NdAg 0.5 Zn 0.5 As 2 are paramagnetic with effective magnetic moments consistent with trivalent RE species.