Syntheses, structure, magnetism, and optical properties of the interlanthanide sulfides {delta}-Ln {sub 2-} {sub x} Lu {sub x} S{sub 3} (Ln=Ce, Pr, Nd)

Journal Article · Sun Jul 15 00:00:00 EDT 2007 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2007.04.008· OSTI ID:21015883

Bangjin, Geng ^[1]; Sang Choi, Eun ^[2]; Guertin, Robert P ^[3]; Brooks, James S ^[2]; Bray, Travis H ^[1]; Booth, Corwin H ^[4]

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1. Department of Chemistry and Biochemistry and the E.C. Leach Nuclear Science Center, Auburn University, Auburn, AL 36849 (United States)
2. Department of Physics and National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310 (United States)
3. Department of Physics and Astronomy, Tufts University, Medford, MA 02155 (United States)
4. Chemical Sciences Division-Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States)

{delta}-Ln {sub 2-} {sub x} Lu {sub x} S{sub 3} (Ln=Ce, Pr, Nd; x=0.67-0.71) compounds have been synthesized through the reaction of elemental rare-earth metals and S using a Sb{sub 2}S{sub 3} flux at 1000 deg. C. These compounds are isotypic with CeTmS{sub 3}, which has a complex three-dimensional structure. It includes four larger Ln{sup 3+} sites in eight- and nine-coordinate environments, two disordered seven-coordinate Ln{sup 3+}/Lu{sup 3+} positions, and two six-coordinate Lu{sup 3+} ions. The structure is constructed from one-dimensional chains of LnS {sub n} (n=6-9) polyhedra that extend along the b-axis. These polyhedra share faces or edges with two neighbors within the chains, while in the [ac] plane they share edges and corners with other chains. Least square refinements gave rise to the formulas of {delta}-Ce{sub 1.30}Lu{sub 0.70}S{sub 3}, {delta}-Pr{sub 1.29}Lu{sub 0.71}S{sub 3} and {delta}-Nd{sub 1.33}Lu{sub 0.67}S{sub 3}, which are consistent with the EDX analysis and magnetic susceptibility data. {delta}-Ln {sub 2-} {sub x} Lu {sub x} S{sub 3} (Ln=Ce, Pr, Nd; x=0.67-0.71) show no evidence of magnetic ordering down to 5 K. Optical properties measurements show that the band gaps for {delta}-Ce{sub 1.30}Lu{sub 0.70}S{sub 3}, {delta}-Pr{sub 1.29}Lu{sub 0.71}S{sub 3}, and {delta}-Nd{sub 1.33}Lu{sub 0.67}S{sub 3} are 1.25, 1.38, and 1.50 eV, respectively. Crystallographic data: {delta}-Ce{sub 1.30}Lu{sub 0.70}S{sub 3}, monoclinic, space group P2{sub 1} /m, a=11.0186(7), b=3.9796(3), c=21.6562(15) A, {beta}=101.6860(10), V=929.93(11), Z=8; {delta}-Pr{sub 1.29}Lu{sub 0.71}S{sub 3}, monoclinic, space group P2{sub 1} /m, a=10.9623(10), b=3.9497(4), c=21.5165(19) A, {beta}=101.579(2), V=912.66(15), Z=8; {delta}-Nd{sub 1.33}Lu{sub 0.67}S{sub 3}, monoclinic, space group P2{sub 1} /m, a=10.9553(7), b=3.9419(3), c=21.4920(15) A, {beta}=101.5080(10), V=909.47(11), Z=8. - Graphical abstract: Inverse molar neodymium magnetic susceptibility vs. T for {delta}-Nd{sub 1.33}Lu{sub 0.67}S{sub 3} under an applied magnetic field of 0.1T between 2 and 300 K. The straight line represents the fit to Curie-Weiss law in the range of 100-300 K.

• OSTI ID: 21015883
• Journal Information: Journal of Solid State Chemistry, Vol. 180, Issue 7; Other Information: DOI: 10.1016/j.jssc.2007.04.008; PII: S0022-4596(07)00152-1; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANTIMONY SULFIDES
CERIUM COMPOUNDS
CRYSTALLOGRAPHY
CURIE-WEISS LAW
EV RANGE 01-10
LANTHANUM COMPOUNDS
LUTETIUM COMPOUNDS
LUTETIUM IONS
MAGNETIC FIELDS
MAGNETIC SUSCEPTIBILITY
MAGNETISM
MAGNETIZATION
MONOCLINIC LATTICES
NEODYMIUM COMPOUNDS
OPTICAL PROPERTIES
PRASEODYMIUM COMPOUNDS
SPACE GROUPS
SYNTHESIS
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K