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Mitchell, Kwasi
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article
Syntheses, Structure, and Selected Physical Properties of CsLnMnSe 3 (Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y) and AYbZnQ3 (A = Rb, Cs; Q = S, Se, Te)
Abstract
<p>CsLnMnSe<sub>3</sub> (Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y) and AYbZnQ<sub>3</sub> (A = Rb, Cs; Q = S, Se, Te) have been synthesized from solid-state reactions at temperatures in excess 1173 K. These isostructural materials crystallize in the layered KZrCuS<sub>3</sub> structure type in the orthorhombic space group Cmcm. The structure is composed of LnQ<sub>6</sub> octahedra and MQ<sub>4</sub> tetrahedra that share edges to form <sup>2</sup><sub>∞</sub>[LnMQ<sub>3</sub>] layers. These layers stack perpendicular to [010] and are separated by layers of face- and edge-sharing AQ<sub>8</sub> bicapped trigonal prisms. There are no Q-Q bonds in the structure of the ALnMQ<sub>3</sub> compounds so the formal oxidation states of A/Ln/M/Q are 1+/3+/2+/2-. The CsLnMnSe<sub>3</sub> materials, with the exception of CsYbMnSe<sub>3</sub>, are Curie-Weiss paramagnets between 5 and 300 K. The magnetic susceptibility data for CsYbZnS<sub>3</sub>, RbYbZnSe <sub>3</sub>, and CsYbMSe<sub>3</sub> (M = Mn, Zn) show a weak cusp at approximately 10 K and pronounced differences between field-cooled and zero-field-cooled data. However, CsYbZnSe<sub>3</sub> is not an antiferromagnet because a neutron diffraction study indicates that CsYbZnSe<sub>3</sub> shows neither long-range magnetic ordering nor a phase change between 4 and 295 K. Nor is the compound a spin glass because the transition at 10 K does not depend on ac frequency. The optical band gaps of the (010) and (001) crystal faces for CsYbMnSe<sub>3</sub> are 1,60 and 1.59 eV, respectively; the optical band of the (010) crystal faces for CsYbZnS<sub>3</sub> and RbYbZnSe<sub>3</sub> are 2,61 and 2,07 eV, respectively.</p>