Syntheses, structures, physical properties, and theoretical studies of CeMxOS (M = Cu, Ag; x ≈ 0.8) and CeAgOS

George H. Chan, Bin Deng, Mariana Bertoni, John R. Ireland, Mark C Hersam, Thomas O Mason, Richard P. Van Duyne, James A. Ibers

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

Black single crystals of the two nonstoichiometric cerium coinage-metal oxysulfide compounds CeCuxOS and CeAgxOS (x ≈ 0.8) have been prepared by the reactions of Ce2S3 and CuO or Ag2O at 1223 or 1173 K, respectively. A black powder sample of CeAgOS has been prepared by the stoichiometric reaction of Ce2S 3, CeO2, Ag2S, and Ag at 1073 K. These isostructural materials crystallize in the ZrSiCuAs structure type with two formula units in the tetragonal space group P4/nmm. Refined crystal structure results and chemical analyses provide evidence that the previously known anomalously small unit-cell volume of LnCuOS for Ln = Ce (Ln = rare-earth metal) is the result of Cu vacancies and the concomitant presence of both Ce 3+ and Ce4+. Both CeCu0.8OS and CeAgOS are paramagnetic with μeff values of 2.13(6) and 2.10(1) μB, respectively. CeCu0.8OS is a p-type semiconductor with a thermal activation energy Ea = 0.22 eV, σ electrical = 9.8(1) 10-3 S/cm at 298 K, and an optical band gap E9 <0.73 eV. CeAgOS has conductivity σconductivity = 0.16(4) S/cm and an optical band gap E 9 = 0.71 eV at 298 K. Theoretical calculations with an on-site Coulomb repulsion parameter indicate that the Ce 4f states are fully spin-polarized and are not localized in CeCuOS, CeCu0.75OS, or CeAgOS. Calculated band gaps for CeCu0.75OS and CeAgOS are 0.6 and 0.8 eV, respectively.

Original languageEnglish
Pages (from-to)8264-8272
Number of pages9
JournalInorganic Chemistry
Volume45
Issue number20
DOIs
Publication statusPublished - Oct 2 2006

Fingerprint

Optical band gaps
Rare Earth Metals
Coinage
Physical properties
physical properties
Cerium
synthesis
Powders
Vacancies
conductivity
p-type semiconductors
Energy gap
metal compounds
Activation energy
Crystal structure
Metals
Single crystals
Semiconductor materials
cerium
rare earth elements

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Syntheses, structures, physical properties, and theoretical studies of CeMxOS (M = Cu, Ag; x ≈ 0.8) and CeAgOS. / Chan, George H.; Deng, Bin; Bertoni, Mariana; Ireland, John R.; Hersam, Mark C; Mason, Thomas O; Van Duyne, Richard P.; Ibers, James A.

In: Inorganic Chemistry, Vol. 45, No. 20, 02.10.2006, p. 8264-8272.

Research output: Contribution to journalArticle

Chan, George H. ; Deng, Bin ; Bertoni, Mariana ; Ireland, John R. ; Hersam, Mark C ; Mason, Thomas O ; Van Duyne, Richard P. ; Ibers, James A. / Syntheses, structures, physical properties, and theoretical studies of CeMxOS (M = Cu, Ag; x ≈ 0.8) and CeAgOS. In: Inorganic Chemistry. 2006 ; Vol. 45, No. 20. pp. 8264-8272.
@article{4356a42766bb4ce38391704f8fa00d90,
title = "Syntheses, structures, physical properties, and theoretical studies of CeMxOS (M = Cu, Ag; x ≈ 0.8) and CeAgOS",
abstract = "Black single crystals of the two nonstoichiometric cerium coinage-metal oxysulfide compounds CeCuxOS and CeAgxOS (x ≈ 0.8) have been prepared by the reactions of Ce2S3 and CuO or Ag2O at 1223 or 1173 K, respectively. A black powder sample of CeAgOS has been prepared by the stoichiometric reaction of Ce2S 3, CeO2, Ag2S, and Ag at 1073 K. These isostructural materials crystallize in the ZrSiCuAs structure type with two formula units in the tetragonal space group P4/nmm. Refined crystal structure results and chemical analyses provide evidence that the previously known anomalously small unit-cell volume of LnCuOS for Ln = Ce (Ln = rare-earth metal) is the result of Cu vacancies and the concomitant presence of both Ce 3+ and Ce4+. Both CeCu0.8OS and CeAgOS are paramagnetic with μeff values of 2.13(6) and 2.10(1) μB, respectively. CeCu0.8OS is a p-type semiconductor with a thermal activation energy Ea = 0.22 eV, σ electrical = 9.8(1) 10-3 S/cm at 298 K, and an optical band gap E9 <0.73 eV. CeAgOS has conductivity σconductivity = 0.16(4) S/cm and an optical band gap E 9 = 0.71 eV at 298 K. Theoretical calculations with an on-site Coulomb repulsion parameter indicate that the Ce 4f states are fully spin-polarized and are not localized in CeCuOS, CeCu0.75OS, or CeAgOS. Calculated band gaps for CeCu0.75OS and CeAgOS are 0.6 and 0.8 eV, respectively.",
author = "Chan, {George H.} and Bin Deng and Mariana Bertoni and Ireland, {John R.} and Hersam, {Mark C} and Mason, {Thomas O} and {Van Duyne}, {Richard P.} and Ibers, {James A.}",
year = "2006",
month = "10",
day = "2",
doi = "10.1021/ic061041k",
language = "English",
volume = "45",
pages = "8264--8272",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "20",

}

TY - JOUR

T1 - Syntheses, structures, physical properties, and theoretical studies of CeMxOS (M = Cu, Ag; x ≈ 0.8) and CeAgOS

AU - Chan, George H.

AU - Deng, Bin

AU - Bertoni, Mariana

AU - Ireland, John R.

AU - Hersam, Mark C

AU - Mason, Thomas O

AU - Van Duyne, Richard P.

AU - Ibers, James A.

PY - 2006/10/2

Y1 - 2006/10/2

N2 - Black single crystals of the two nonstoichiometric cerium coinage-metal oxysulfide compounds CeCuxOS and CeAgxOS (x ≈ 0.8) have been prepared by the reactions of Ce2S3 and CuO or Ag2O at 1223 or 1173 K, respectively. A black powder sample of CeAgOS has been prepared by the stoichiometric reaction of Ce2S 3, CeO2, Ag2S, and Ag at 1073 K. These isostructural materials crystallize in the ZrSiCuAs structure type with two formula units in the tetragonal space group P4/nmm. Refined crystal structure results and chemical analyses provide evidence that the previously known anomalously small unit-cell volume of LnCuOS for Ln = Ce (Ln = rare-earth metal) is the result of Cu vacancies and the concomitant presence of both Ce 3+ and Ce4+. Both CeCu0.8OS and CeAgOS are paramagnetic with μeff values of 2.13(6) and 2.10(1) μB, respectively. CeCu0.8OS is a p-type semiconductor with a thermal activation energy Ea = 0.22 eV, σ electrical = 9.8(1) 10-3 S/cm at 298 K, and an optical band gap E9 <0.73 eV. CeAgOS has conductivity σconductivity = 0.16(4) S/cm and an optical band gap E 9 = 0.71 eV at 298 K. Theoretical calculations with an on-site Coulomb repulsion parameter indicate that the Ce 4f states are fully spin-polarized and are not localized in CeCuOS, CeCu0.75OS, or CeAgOS. Calculated band gaps for CeCu0.75OS and CeAgOS are 0.6 and 0.8 eV, respectively.

AB - Black single crystals of the two nonstoichiometric cerium coinage-metal oxysulfide compounds CeCuxOS and CeAgxOS (x ≈ 0.8) have been prepared by the reactions of Ce2S3 and CuO or Ag2O at 1223 or 1173 K, respectively. A black powder sample of CeAgOS has been prepared by the stoichiometric reaction of Ce2S 3, CeO2, Ag2S, and Ag at 1073 K. These isostructural materials crystallize in the ZrSiCuAs structure type with two formula units in the tetragonal space group P4/nmm. Refined crystal structure results and chemical analyses provide evidence that the previously known anomalously small unit-cell volume of LnCuOS for Ln = Ce (Ln = rare-earth metal) is the result of Cu vacancies and the concomitant presence of both Ce 3+ and Ce4+. Both CeCu0.8OS and CeAgOS are paramagnetic with μeff values of 2.13(6) and 2.10(1) μB, respectively. CeCu0.8OS is a p-type semiconductor with a thermal activation energy Ea = 0.22 eV, σ electrical = 9.8(1) 10-3 S/cm at 298 K, and an optical band gap E9 <0.73 eV. CeAgOS has conductivity σconductivity = 0.16(4) S/cm and an optical band gap E 9 = 0.71 eV at 298 K. Theoretical calculations with an on-site Coulomb repulsion parameter indicate that the Ce 4f states are fully spin-polarized and are not localized in CeCuOS, CeCu0.75OS, or CeAgOS. Calculated band gaps for CeCu0.75OS and CeAgOS are 0.6 and 0.8 eV, respectively.

UR - http://www.scopus.com/inward/record.url?scp=33750325311&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33750325311&partnerID=8YFLogxK

U2 - 10.1021/ic061041k

DO - 10.1021/ic061041k

M3 - Article

VL - 45

SP - 8264

EP - 8272

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 20

ER -