Journal
JOURNAL OF SOLID STATE CHEMISTRY
Volume 187, Issue -, Pages 264-268Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jssc.2012.01.020
Keywords
Lanthanide chalcogenides; Lanthanide antimony chalcogenides; Flux synthesis; Tunnel structure; Lone-pair effects
Funding
- National Science Foundation, Division of Materials Research [DMR-1004459]
- Division Of Materials Research
- Direct For Mathematical & Physical Scien [1004459] Funding Source: National Science Foundation
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Dark red and dark brown crystals of Yb4Sb2S11.25 and Tm8Sb4Se11.68, respectively, were obtained from the reaction of the elements in Sb(2)Q(3) (Q=S, Se) fluxes. Both non-stoichiometric compounds are orthorhombic and crystallize in the same space group Pnnm, with two formula units per unit cell (a=12.446(2), b=5.341(1), c=12.058(2) for sulfide and a=13.126(2), b=5.623(1), c=12.499(2) for the selenide). Their crystal structures are dominated by lanthanide-chalcogenide polyhedra (CN = 7 and 8), which share corners, edges, triangular- and square-faces to form a three-dimensional framework embedding antinomy cations. The latter are coordinated by three sulfide anions with 5(1+2+2) secondary contacts forming basically infinite chains running along [0 1 0]. The chalcogens in both compounds form chalcogenide Q(2-) and dichalcogenide (Q(2))(2-) anionic units. The optical analysis made on those compounds shows that both are semiconductors with band gap of 1.71 and 1.22 eV for Yb4Sb2S11.25 and Tm4Sb2Se11.75. respectively. (C) 2012 Elsevier Inc. All rights reserved.
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