RESUMO
The quaternary transition metal oxyselenide La(2)O(2)ZnSe(2) has been shown to adopt a ZrCuSiAs-related structure with Zn(2+) cations in a new ordered arrangement within the [ZnSe(2)](2-) layers. This cation-ordered structure can be derived and described using the symmetry-adapted distortion mode approach. La(2)O(2)ZnSe(2) is an direct gap semiconductor with an experimental optical band gap of 3.4(2) eV, consistent with electronic structure calculations.
RESUMO
Rare earth oxyselenides A4O4Se3 (A = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb and Y) were synthesised using solid state reactions and three new structure types (ß, γ, and δ) were observed. A4O4Se3 materials adopt either the α (A = Nd, Sm), ß (A = Eu), γ (A = Gd, Tb) or δ (A = Dy, Ho, Er, Yb, Y) structure depending on the rare earth radius. Each structure type contains alternating [A2O2](2+) and Se(2-)/Se2(2-) layers. Different ordered and disordered arrangements of Se(2-) and [Se-Se](2-) give the Se layer flexibility and lead to the four different structure types observed. The volume coefficients of expansion for A4O4Se3 ranged from +1.746(9) × 10(-5) to +2.237(3) × 10(-5) K(-1) from 12 to 300 K; no structural phase transitions were observed in this temperature range. Diffuse reflection spectra show A4O4Se3 are semiconductors with band gap Eg 1.02-1.46 eV. Gd4O4Se3, Dy4O4Se3, and Tb4O4Se3 samples show antiferromagnetic ordering with Néel temperature, TN, of 7-9 K. DFT calculations confirm the two different valence states of Se(2-) and Se2(2-) in Eu4O4Se3.