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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 (β, γ, and δ) were observed. A4O4Se3 materials adopt either the α (A = Nd, Sm), β (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.

Synthesis, characterisation and properties of rare earth oxyselenides A4O4Se3(A = Eu, Gd, Tb, Dy, Ho, Er, Yb and Y)

Synthesis, characterisation and properties of rare earth oxyselenides A₄O₄Se₃(A = Eu, Gd, Tb, Dy, Ho, Er, Yb and Y)