Role of Partial Vacancy and Structural Distortion in the Stability of Nonstoichiometric Phases Ni7-δInSe2-xSx (1.26 ≥ δ ≥ 0.94; 0 ≤ x ≤ 1.33).

ABSTRACT

This study explores the structure and stability of partly disordered sulfur-substituted Ni5.74InSe2 (I4/mmm, a = 3.6766(1) Å, c = 18.8178(10) Å, Z = 2). The structure of Ni7-δInSe2-xSx (x = 0.2, 0.36, 0.66, 0.80, 0.94) compounds is isotypic to their parent Ni5.74InSe2 and can be viewed as alternating heterometallic Cu3Au-type ∞2[Ni3In] slabs and defective Cu2Sb-type ∞2[Ni4-δ(Se/S)2] slabs along the [001]-axis. Similar to the parent Se-compound, the Ni-Ch (Ch = chalcogen) fragment is non-stoichiometric and possesses a partially occupied Ni-site. It was observed that with sulfur insertion at the selenium site of Ni5.74InSe2, the interatomic distance between the partially occupied nickel and mixed (S/Se) sites decreases from ∼2.24 to ∼1.95 Å, and the occupancy of the disordered nickel site simultaneously increases. The limiting composition Ni6.06InSe0.67S1.33 (x = 1.33, δ = 0.94) is formed in the sulfur-rich region. Its average structure resembles the Ni6SnS2-type and has a similar motif to Ni5.74InSe2; the only difference is that Cu3Au-type ∞2[Ni3In] alternates with two types of Ni-Ch fragments (Cu2Sb or Li2O type units). By using first-principles electronic structure calculations, we explained the presence of partially disordered nickel sites in the Ni-Ch fragment and rationalized why the nickel site occupancy increases with sulfur insertion.