Crystal growth and electrical properties of lithium, rubidium, and cesium molybdenum oxide bronzes

Pierre Strobel; Martha Greenblatt

doi:10.1016/0022-4596(81)90444-8

Crystal growth and electrical properties of lithium, rubidium, and cesium molybdenum oxide bronzes

Pierre Strobel, Martha Greenblatt

School of Arts and Sciences, Chemistry & Chemical Biology

Research output: Contribution to journal › Article › peer-review

19 Scopus citations

Abstract

Crystals of Li_0.33 MoO₃ (blue), Rb_0.23MoO₃ (blue) and Cs_0.31MoO₃ (red) were grown by electrolysis from MoO₃{single bond}M₂MoO₄ melts (M =alkali metal) with composition 70-77 mole% MoO₃. Melts richer in M₂MoO₄ produced MoO₂ only. Correlation is made between bronze formation and the coordination of Mo in the melt and in the equilibrium solid phase M₂Mo₄O₁₃. Li_0.33MoO₃ and Cs_0.31MoO₃ are semiconductors with high-temperature-range activation energies 0.16 and 0.12 eV. Rb_0.23MoO₃ has an electrical behavior similar to that of blue K_xMoO₃ with a semiconductor-metal transition at (170 ± 5) K. ESR spectra observed in Li_0.33MoO₃ and Rb_0.23MoO₃ single crystals at 4.2 K show extensive delocalization of the 4d¹ electron associated with Mo(V) centers. Attempts to grow molybdenum bronzes containing Ca or Y were unsuccessful.

Original language	English (US)
Pages (from-to)	331-338
Number of pages	8
Journal	Journal of Solid State Chemistry
Volume	36
Issue number	3
DOIs	https://doi.org/10.1016/0022-4596(81)90444-8
State	Published - Mar 1 1981

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/0022-4596(81)90444-8

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title = "Crystal growth and electrical properties of lithium, rubidium, and cesium molybdenum oxide bronzes",

abstract = "Crystals of Li0.33 MoO3 (blue), Rb0.23MoO3 (blue) and Cs0.31MoO3 (red) were grown by electrolysis from MoO3{single bond}M2MoO4 melts (M =alkali metal) with composition 70-77 mole% MoO3. Melts richer in M2MoO4 produced MoO2 only. Correlation is made between bronze formation and the coordination of Mo in the melt and in the equilibrium solid phase M2Mo4O13. Li0.33MoO3 and Cs0.31MoO3 are semiconductors with high-temperature-range activation energies 0.16 and 0.12 eV. Rb0.23MoO3 has an electrical behavior similar to that of blue KxMoO3 with a semiconductor-metal transition at (170 ± 5) K. ESR spectra observed in Li0.33MoO3 and Rb0.23MoO3 single crystals at 4.2 K show extensive delocalization of the 4d1 electron associated with Mo(V) centers. Attempts to grow molybdenum bronzes containing Ca or Y were unsuccessful.",

author = "Pierre Strobel and Martha Greenblatt",

note = "Funding Information: The authors wish to thank Professor J. H. Pifer for his help with the ESR measurementsP, rofessor A. Wold for valuable discussions on the electrolytic Process, and Drs. C. Hurd and S. P. McAlister for their help with the electrical measurements,w hich were performed at the National Research Council, Ottawa.T his materiali s basedu pon work supportedb y the National ScienceF oundationu nderG rant DMR78-08554a ndb y the RutgersU niversity ResearchC ouncil.",

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T1 - Crystal growth and electrical properties of lithium, rubidium, and cesium molybdenum oxide bronzes

AU - Strobel, Pierre

AU - Greenblatt, Martha

N1 - Funding Information: The authors wish to thank Professor J. H. Pifer for his help with the ESR measurementsP, rofessor A. Wold for valuable discussions on the electrolytic Process, and Drs. C. Hurd and S. P. McAlister for their help with the electrical measurements,w hich were performed at the National Research Council, Ottawa.T his materiali s basedu pon work supportedb y the National ScienceF oundationu nderG rant DMR78-08554a ndb y the RutgersU niversity ResearchC ouncil.

PY - 1981/3/1

Y1 - 1981/3/1

N2 - Crystals of Li0.33 MoO3 (blue), Rb0.23MoO3 (blue) and Cs0.31MoO3 (red) were grown by electrolysis from MoO3{single bond}M2MoO4 melts (M =alkali metal) with composition 70-77 mole% MoO3. Melts richer in M2MoO4 produced MoO2 only. Correlation is made between bronze formation and the coordination of Mo in the melt and in the equilibrium solid phase M2Mo4O13. Li0.33MoO3 and Cs0.31MoO3 are semiconductors with high-temperature-range activation energies 0.16 and 0.12 eV. Rb0.23MoO3 has an electrical behavior similar to that of blue KxMoO3 with a semiconductor-metal transition at (170 ± 5) K. ESR spectra observed in Li0.33MoO3 and Rb0.23MoO3 single crystals at 4.2 K show extensive delocalization of the 4d1 electron associated with Mo(V) centers. Attempts to grow molybdenum bronzes containing Ca or Y were unsuccessful.

AB - Crystals of Li0.33 MoO3 (blue), Rb0.23MoO3 (blue) and Cs0.31MoO3 (red) were grown by electrolysis from MoO3{single bond}M2MoO4 melts (M =alkali metal) with composition 70-77 mole% MoO3. Melts richer in M2MoO4 produced MoO2 only. Correlation is made between bronze formation and the coordination of Mo in the melt and in the equilibrium solid phase M2Mo4O13. Li0.33MoO3 and Cs0.31MoO3 are semiconductors with high-temperature-range activation energies 0.16 and 0.12 eV. Rb0.23MoO3 has an electrical behavior similar to that of blue KxMoO3 with a semiconductor-metal transition at (170 ± 5) K. ESR spectra observed in Li0.33MoO3 and Rb0.23MoO3 single crystals at 4.2 K show extensive delocalization of the 4d1 electron associated with Mo(V) centers. Attempts to grow molybdenum bronzes containing Ca or Y were unsuccessful.

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Crystal growth and electrical properties of lithium, rubidium, and cesium molybdenum oxide bronzes

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