American Chemical Society
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Infinitely Adaptive Transition Metal Oxychalcogenides: The Modulated Structures of Ce2O2MnSe2 and (Ce0.78La0.22)2O2MnSe2

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journal contribution
posted on 2015-04-28, 00:00 authored by Chun-Hai Wang, Chris M. Ainsworth, Dong-Yun Gui, Emma E. McCabe, Matthew G. Tucker, Ivana R. Evans, John S. O. Evans
This article reports the syntheses, structures, and physical properties of the oxychalcogenides (Ce1–xLax)2O2MnSe2 with x = 0–0.7. These materials have a layered structure related to that of the LaOFeAs-derived superconductors but with the transition metal sites 50% occupied. Ce2O2MnSe2 contains alternating layers of composition: [Ce2O2]2+ and [MnSe2]2–. The size mismatch between the layers leads to an incommensurate structure with a modulation vector of q = αa*+ 0b*+0.5c* with α = 0.158(1), which can be described with a (3 + 1)­D superspace structural model in superspace group Cmme(α,0,1/2)­0s0 [67.12]. There is a strong modulation of Mn site occupancies, leading to a mixture of corner- and edge-sharing MnSe4/2 tetrahedra in the [MnSe2]2– layers. The modulation vector can be controlled by partial substitution of Ce3+ for larger La3+, and a simple commensurate case was obtained for (Ce0.78La0.22)2O2MnSe2 with α = 1/6. The materials respond to the change in relative size of the oxide and chalcogenide blocks by varying the ratio of corner- to edge-sharing tetrahedra. The superspace model lets us unify the structural description of the five different ordering patterns reported to date for different Ln2O2MSe2 (Ln = lanthanide) materials. Mn moments in Ce2O2MnSe2 and (Ce0.78La0.22)2O2MnSe2 order antiferromagnetically below TN = 150 K, and Ce moments order below ∼70 K. The magnetic structures of both materials have been determined using neutron diffraction. Both materials are semiconductors; Ce2O2MnSe2 has σ = 9 × 10–6 Ω–1 cm–1 at room temperature and an activation energy for charge carrier mobility from RT to 170 °C of ∼0.4 eV.