Syntheses, crystal structures, and physical properties of La 5Cu6O4S7 and La5Cu 6.33O4S7

George H. Chan; Ming Ling Liu; Li Dong Chen; Fu Qiang Huang; Daniel E. Bugaris; Daniel M. Wells; John R. Ireland; Mark C. Hersam; Richard P. Van Duyne; James A. Ibers

doi:10.1021/ic7024796

Syntheses, crystal structures, and physical properties of La ₅Cu₆O₄S₇ and La₅Cu _6.33O₄S₇

George H. Chan, Ming Ling Liu, Li Dong Chen, Fu Qiang Huang, Daniel E. Bugaris, Daniel M. Wells, John R. Ireland, Mark C. Hersam, Richard P. Van Duyne, James A. Ibers

Northwestern University

Research output: Contribution to journal › Article

14 Citations (Scopus)

Abstract

Single crystal and bulk powder samples of the quaternary lanthanum copper oxysulfides La₅Cu_6.33O₄S₇ and La₅Cu₆O₄S₇ have been prepared by means of high-temperature sealed-tube reactions and spark plasma sintering, respectively. In the structure of La₅Cu_6.33O ₄S₇, Cu atoms tie together the fluorite-like _∞²[La₅O₄S⁵⁺] and antifluorite-like _∞²[Cu₆S ₆^5-] layers of La₅Cu₆O ₄S₇. The optical band gap, E_g, of 2.0 eV was deduced from both diffuse reflectance spectra on a bulk sample of La ₅Cu₆O₄S₇ and for the (010) crystal face of a La₅Cu_6.33O₄S₇ single crystal. Transport measurements at 298 K on a bulk sample of La ₅Cu₆O₄S₇ indicated p-type metallic electrical conduction with σ_electrical = 2.18 S cm ^-1, whereas measurements on a La₅Cu_6.33O ₄S₇ single crystal led to σ_electrical = 4.5 10^-3 S cm^-1 along [100] and to semiconducting behavior. In going from La₅Cu₆O₄S₇ to La₅Cu_6.33O₄S₇, the disruption of the _∞²[Cu₆S₆^5-] layer and the decrease in the overall Cu²⁺ (3d⁹) concentration lead to a significant decrease in the electrical conductivity.

Original language	English
Pages (from-to)	4368-4374
Number of pages	7
Journal	Inorganic Chemistry
Volume	47
Issue number	10
DOIs	https://doi.org/10.1021/ic7024796
Publication status	Published - May 19 2008

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Chan, G. H., Liu, M. L., Chen, L. D., Huang, F. Q., Bugaris, D. E., Wells, D. M., Ireland, J. R., Hersam, M. C., Van Duyne, R. P., & Ibers, J. A. (2008). Syntheses, crystal structures, and physical properties of La ₅Cu₆O₄S₇ and La₅Cu _6.33O₄S₇. Inorganic Chemistry, 47(10), 4368-4374. https://doi.org/10.1021/ic7024796

Syntheses, crystal structures, and physical properties of La ₅Cu₆O₄S₇ and La₅Cu _6.33O₄S₇. / Chan, George H.; Liu, Ming Ling; Chen, Li Dong; Huang, Fu Qiang; Bugaris, Daniel E.; Wells, Daniel M.; Ireland, John R.; Hersam, Mark C.; Van Duyne, Richard P.; Ibers, James A.

In: Inorganic Chemistry, Vol. 47, No. 10, 19.05.2008, p. 4368-4374.

Research output: Contribution to journal › Article

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title = "Syntheses, crystal structures, and physical properties of La 5Cu6O4S7 and La5Cu 6.33O4S7",

abstract = "Single crystal and bulk powder samples of the quaternary lanthanum copper oxysulfides La5Cu6.33O4S7 and La5Cu6O4S7 have been prepared by means of high-temperature sealed-tube reactions and spark plasma sintering, respectively. In the structure of La5Cu6.33O 4S7, Cu atoms tie together the fluorite-like ∞2[La5O4S5+] and antifluorite-like ∞2[Cu6S 65-] layers of La5Cu6O 4S7. The optical band gap, Eg, of 2.0 eV was deduced from both diffuse reflectance spectra on a bulk sample of La 5Cu6O4S7 and for the (010) crystal face of a La5Cu6.33O4S7 single crystal. Transport measurements at 298 K on a bulk sample of La 5Cu6O4S7 indicated p-type metallic electrical conduction with σelectrical = 2.18 S cm -1, whereas measurements on a La5Cu6.33O 4S7 single crystal led to σelectrical = 4.5 10-3 S cm-1 along [100] and to semiconducting behavior. In going from La5Cu6O4S7 to La5Cu6.33O4S7, the disruption of the ∞2[Cu6S65-] layer and the decrease in the overall Cu2+ (3d9) concentration lead to a significant decrease in the electrical conductivity.",

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AU - Chan, George H.

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AU - Bugaris, Daniel E.

AU - Wells, Daniel M.

AU - Ireland, John R.

AU - Hersam, Mark C.

AU - Van Duyne, Richard P.

AU - Ibers, James A.

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N2 - Single crystal and bulk powder samples of the quaternary lanthanum copper oxysulfides La5Cu6.33O4S7 and La5Cu6O4S7 have been prepared by means of high-temperature sealed-tube reactions and spark plasma sintering, respectively. In the structure of La5Cu6.33O 4S7, Cu atoms tie together the fluorite-like ∞2[La5O4S5+] and antifluorite-like ∞2[Cu6S 65-] layers of La5Cu6O 4S7. The optical band gap, Eg, of 2.0 eV was deduced from both diffuse reflectance spectra on a bulk sample of La 5Cu6O4S7 and for the (010) crystal face of a La5Cu6.33O4S7 single crystal. Transport measurements at 298 K on a bulk sample of La 5Cu6O4S7 indicated p-type metallic electrical conduction with σelectrical = 2.18 S cm -1, whereas measurements on a La5Cu6.33O 4S7 single crystal led to σelectrical = 4.5 10-3 S cm-1 along [100] and to semiconducting behavior. In going from La5Cu6O4S7 to La5Cu6.33O4S7, the disruption of the ∞2[Cu6S65-] layer and the decrease in the overall Cu2+ (3d9) concentration lead to a significant decrease in the electrical conductivity.

AB - Single crystal and bulk powder samples of the quaternary lanthanum copper oxysulfides La5Cu6.33O4S7 and La5Cu6O4S7 have been prepared by means of high-temperature sealed-tube reactions and spark plasma sintering, respectively. In the structure of La5Cu6.33O 4S7, Cu atoms tie together the fluorite-like ∞2[La5O4S5+] and antifluorite-like ∞2[Cu6S 65-] layers of La5Cu6O 4S7. The optical band gap, Eg, of 2.0 eV was deduced from both diffuse reflectance spectra on a bulk sample of La 5Cu6O4S7 and for the (010) crystal face of a La5Cu6.33O4S7 single crystal. Transport measurements at 298 K on a bulk sample of La 5Cu6O4S7 indicated p-type metallic electrical conduction with σelectrical = 2.18 S cm -1, whereas measurements on a La5Cu6.33O 4S7 single crystal led to σelectrical = 4.5 10-3 S cm-1 along [100] and to semiconducting behavior. In going from La5Cu6O4S7 to La5Cu6.33O4S7, the disruption of the ∞2[Cu6S65-] layer and the decrease in the overall Cu2+ (3d9) concentration lead to a significant decrease in the electrical conductivity.

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