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Title: Crystallographic and magnetic properties of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} (x{approx}0.3) single crystals with the layered defect NiAs structure synthesized under high pressure

Abstract

We report on the reproducible growth of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} single crystals of sizable dimensions ({approx}0.3 mm) and homogeneous composition (x{approx}0.3) by means of high-pressure synthesis. The refinement of single crystal X-ray diffraction data indicates that the crystal structure is of the monoclinic defect NiAs-type, which consists of a stacking of VS{sub 2} layers with CdI{sub 2}-type structure and chains of edge-sharing (Cu{sub 1-x}V{sub x})S{sub 6} octahedra. Layers and chains form a network of face-sharing octahedra with no Cu-V intra-chain ordering. A combined X-ray photoelectron spectroscopy and bond valence sum analysis indicates that the valence of the V and Cu ions are 3+ and 1+, respectively. Magnetic susceptibility measurements unveil the coexistence of a large Pauli-like and of a small Curie-like paramagnetic contributions, with no evidence of any long range order down to 2 K. This result suggests a picture of predominantly itinerant 3d V electrons with significant electron-electron correlations. - Graphical Abstract: Crystallographic structure of (Cu{sub 0.69}V{sub 0.31})V{sub 2}S{sub 4}. For clarity, the octahedral environment of (Cu{sub 0.69}V{sub 0.31}) site is not shown. Highlights: > Synthesis of new single-crystals in the Cu-V-S system using high pressure and high temperature. > Structural analysis revealed the single-crystals to bemore » of the defect NiAs-type structure. > Bond valence sum analysis combined to X-ray photoemission spectroscopy revealed Cu{sup 1+} and a majority of V{sup 3+}. > Magnetic susceptibility has been measured. > Charge carriers are of two types, localized and itinerant.« less

Authors:
 [1]; ; ; ;  [1]; ;  [2];  [1]
  1. Institut de Mineralogie et Physique des Milieux Condenses, Universite Pierre et Marie Curie, CNRS UMR 7590, Campus Jussieu, 4 place Jussieu 75005 Paris (France)
  2. Institut Lavoisier Versailles, Universite de Versailles Saint-Quentin, CNRS UMR 8180, Batiment Lavoisier, 45 avenue des Etats-Unis 78035 Versailles Cedex (France)
Publication Date:
OSTI Identifier:
21580259
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 184; Journal Issue: 9; Other Information: DOI: 10.1016/j.jssc.2011.06.034; PII: S0022-4596(11)00362-8; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CADMIUM IODIDES; CHARGE CARRIERS; CRYSTALLOGRAPHY; ELECTRON CORRELATION; MAGNETIC SUSCEPTIBILITY; MONOCLINIC LATTICES; MONOCRYSTALS; PARAMAGNETISM; PRESSURE RANGE MEGA PA 10-100; SYNTHESIS; TEMPERATURE RANGE 0400-1000 K; TRANSITION ELEMENTS; X RADIATION; X-RAY DIFFRACTION; X-RAY PHOTOELECTRON SPECTROSCOPY; CADMIUM COMPOUNDS; CADMIUM HALIDES; COHERENT SCATTERING; CORRELATIONS; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; DIFFRACTION; ELECTROMAGNETIC RADIATION; ELECTRON SPECTROSCOPY; ELEMENTS; HALIDES; HALOGEN COMPOUNDS; IODIDES; IODINE COMPOUNDS; IONIZING RADIATIONS; MAGNETIC PROPERTIES; MAGNETISM; METALS; PHOTOELECTRON SPECTROSCOPY; PHYSICAL PROPERTIES; PRESSURE RANGE; PRESSURE RANGE MEGA PA; RADIATIONS; SCATTERING; SPECTROSCOPY; TEMPERATURE RANGE

Citation Formats

Klein, Y., E-mail: yannick.klein@impmc.upmc.fr, Moutaabbid, H., Soyer, A., D'Astuto, M., Rousse, G., Vigneron, J., Etcheberry, A., and Gauzzi, A. Crystallographic and magnetic properties of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} (x{approx}0.3) single crystals with the layered defect NiAs structure synthesized under high pressure. United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.06.034.
Klein, Y., E-mail: yannick.klein@impmc.upmc.fr, Moutaabbid, H., Soyer, A., D'Astuto, M., Rousse, G., Vigneron, J., Etcheberry, A., & Gauzzi, A. Crystallographic and magnetic properties of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} (x{approx}0.3) single crystals with the layered defect NiAs structure synthesized under high pressure. United States. doi:10.1016/j.jssc.2011.06.034.
Klein, Y., E-mail: yannick.klein@impmc.upmc.fr, Moutaabbid, H., Soyer, A., D'Astuto, M., Rousse, G., Vigneron, J., Etcheberry, A., and Gauzzi, A. Thu . "Crystallographic and magnetic properties of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} (x{approx}0.3) single crystals with the layered defect NiAs structure synthesized under high pressure". United States. doi:10.1016/j.jssc.2011.06.034.
@article{osti_21580259,
title = {Crystallographic and magnetic properties of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} (x{approx}0.3) single crystals with the layered defect NiAs structure synthesized under high pressure},
author = {Klein, Y., E-mail: yannick.klein@impmc.upmc.fr and Moutaabbid, H. and Soyer, A. and D'Astuto, M. and Rousse, G. and Vigneron, J. and Etcheberry, A. and Gauzzi, A.},
abstractNote = {We report on the reproducible growth of (Cu{sub 1-x}V{sub x})V{sub 2}S{sub 4} single crystals of sizable dimensions ({approx}0.3 mm) and homogeneous composition (x{approx}0.3) by means of high-pressure synthesis. The refinement of single crystal X-ray diffraction data indicates that the crystal structure is of the monoclinic defect NiAs-type, which consists of a stacking of VS{sub 2} layers with CdI{sub 2}-type structure and chains of edge-sharing (Cu{sub 1-x}V{sub x})S{sub 6} octahedra. Layers and chains form a network of face-sharing octahedra with no Cu-V intra-chain ordering. A combined X-ray photoelectron spectroscopy and bond valence sum analysis indicates that the valence of the V and Cu ions are 3+ and 1+, respectively. Magnetic susceptibility measurements unveil the coexistence of a large Pauli-like and of a small Curie-like paramagnetic contributions, with no evidence of any long range order down to 2 K. This result suggests a picture of predominantly itinerant 3d V electrons with significant electron-electron correlations. - Graphical Abstract: Crystallographic structure of (Cu{sub 0.69}V{sub 0.31})V{sub 2}S{sub 4}. For clarity, the octahedral environment of (Cu{sub 0.69}V{sub 0.31}) site is not shown. Highlights: > Synthesis of new single-crystals in the Cu-V-S system using high pressure and high temperature. > Structural analysis revealed the single-crystals to be of the defect NiAs-type structure. > Bond valence sum analysis combined to X-ray photoemission spectroscopy revealed Cu{sup 1+} and a majority of V{sup 3+}. > Magnetic susceptibility has been measured. > Charge carriers are of two types, localized and itinerant.},
doi = {10.1016/j.jssc.2011.06.034},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 9,
volume = 184,
place = {United States},
year = {2011},
month = {9}
}