Photoluminescence and magnetism in the new magnetic semiconductors: K2Cd3(1-x)Mn3xS4

E. A. Axtell, J. Hanko, J. A. Cowen, Mercouri G Kanatzidis

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Abstract

A new family of magnetic semiconductors, K2Cd3(1-x)Mn3xS4, prepared from molten K2Sx is reported. For x ≤ 0.6, the compounds crystallize in the K2Cd3S4 structure type. The cell volumes of the series obey Vegard's Law for solid solutions. The compounds range in color from yellow through orange brown to red and possess platelike morphologies. A structural transformation occurs between x = 0.7 and x = 0.9. Red plates of K2Cd0.4Mn2.6S4 (x = 0.87) crystallize in the space group Ccca with a = 5.9217(8) Å, b = 13.531(1) Å, c = 11.0696(8) Å, and V = 887.0(1) Å3. The end member, K2Mn3S4, crystallizes in the space group Ccca with a = 11.0637(7) Å, b = 26.830(2) Å, c = 5.8180(4) Å, and V = 1727 Å3. For x ≤ 0.6, the compounds form as (M3S4)n2n- layers, interspersed by K+ cations. These layers are composed only of M3S42- units shaped like truncated cubes. When x = 0.87, a new structure related to that of Cs2Mn3S4 is observed. The end member of the series (i.e., x = 1) K2Mn3S4 is revealed to have a related yet surprising structure. The compounds display room-temperature band gaps ranging from 2.79 to 2.92 eV. Absorptions in the mid-gap region, due to Mn2+-based d-d transitions, are also observed. The compounds are strongly emissive in the visible spectrum at room temperature, with the light emission shifted to the red immediately upon the introduction of small amounts of manganese. The magnetic properties of these compounds evolve from classical paramagnetic to spin glass as a function of x. For x ≥ 0.05, the compounds deviate from Curie-Weiss behavior. Antiferromagnetic coupling is observed in all cases. With very high Mn content transitions to magnetically complex phases are observed with possible spin-glass-like behavior.

Original languageEnglish
Pages (from-to)2850-2863
Number of pages14
JournalChemistry of Materials
Volume13
Issue number9
DOIs
Publication statusPublished - 2001

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Magnetic semiconductors
Spin glass
Magnetism
Photoluminescence
Light emission
Manganese
Cations
Molten materials
Solid solutions
Magnetic properties
Energy gap
Positive ions
Color
Temperature

ASJC Scopus subject areas

  • Materials Chemistry
  • Materials Science(all)

Cite this

Photoluminescence and magnetism in the new magnetic semiconductors : K2Cd3(1-x)Mn3xS4. / Axtell, E. A.; Hanko, J.; Cowen, J. A.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 13, No. 9, 2001, p. 2850-2863.

Research output: Contribution to journalArticle

Axtell, E. A. ; Hanko, J. ; Cowen, J. A. ; Kanatzidis, Mercouri G. / Photoluminescence and magnetism in the new magnetic semiconductors : K2Cd3(1-x)Mn3xS4. In: Chemistry of Materials. 2001 ; Vol. 13, No. 9. pp. 2850-2863.
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title = "Photoluminescence and magnetism in the new magnetic semiconductors: K2Cd3(1-x)Mn3xS4",
abstract = "A new family of magnetic semiconductors, K2Cd3(1-x)Mn3xS4, prepared from molten K2Sx is reported. For x ≤ 0.6, the compounds crystallize in the K2Cd3S4 structure type. The cell volumes of the series obey Vegard's Law for solid solutions. The compounds range in color from yellow through orange brown to red and possess platelike morphologies. A structural transformation occurs between x = 0.7 and x = 0.9. Red plates of K2Cd0.4Mn2.6S4 (x = 0.87) crystallize in the space group Ccca with a = 5.9217(8) {\AA}, b = 13.531(1) {\AA}, c = 11.0696(8) {\AA}, and V = 887.0(1) {\AA}3. The end member, K2Mn3S4, crystallizes in the space group Ccca with a = 11.0637(7) {\AA}, b = 26.830(2) {\AA}, c = 5.8180(4) {\AA}, and V = 1727 {\AA}3. For x ≤ 0.6, the compounds form as (M3S4)n2n- layers, interspersed by K+ cations. These layers are composed only of M3S42- units shaped like truncated cubes. When x = 0.87, a new structure related to that of Cs2Mn3S4 is observed. The end member of the series (i.e., x = 1) K2Mn3S4 is revealed to have a related yet surprising structure. The compounds display room-temperature band gaps ranging from 2.79 to 2.92 eV. Absorptions in the mid-gap region, due to Mn2+-based d-d transitions, are also observed. The compounds are strongly emissive in the visible spectrum at room temperature, with the light emission shifted to the red immediately upon the introduction of small amounts of manganese. The magnetic properties of these compounds evolve from classical paramagnetic to spin glass as a function of x. For x ≥ 0.05, the compounds deviate from Curie-Weiss behavior. Antiferromagnetic coupling is observed in all cases. With very high Mn content transitions to magnetically complex phases are observed with possible spin-glass-like behavior.",
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N2 - A new family of magnetic semiconductors, K2Cd3(1-x)Mn3xS4, prepared from molten K2Sx is reported. For x ≤ 0.6, the compounds crystallize in the K2Cd3S4 structure type. The cell volumes of the series obey Vegard's Law for solid solutions. The compounds range in color from yellow through orange brown to red and possess platelike morphologies. A structural transformation occurs between x = 0.7 and x = 0.9. Red plates of K2Cd0.4Mn2.6S4 (x = 0.87) crystallize in the space group Ccca with a = 5.9217(8) Å, b = 13.531(1) Å, c = 11.0696(8) Å, and V = 887.0(1) Å3. The end member, K2Mn3S4, crystallizes in the space group Ccca with a = 11.0637(7) Å, b = 26.830(2) Å, c = 5.8180(4) Å, and V = 1727 Å3. For x ≤ 0.6, the compounds form as (M3S4)n2n- layers, interspersed by K+ cations. These layers are composed only of M3S42- units shaped like truncated cubes. When x = 0.87, a new structure related to that of Cs2Mn3S4 is observed. The end member of the series (i.e., x = 1) K2Mn3S4 is revealed to have a related yet surprising structure. The compounds display room-temperature band gaps ranging from 2.79 to 2.92 eV. Absorptions in the mid-gap region, due to Mn2+-based d-d transitions, are also observed. The compounds are strongly emissive in the visible spectrum at room temperature, with the light emission shifted to the red immediately upon the introduction of small amounts of manganese. The magnetic properties of these compounds evolve from classical paramagnetic to spin glass as a function of x. For x ≥ 0.05, the compounds deviate from Curie-Weiss behavior. Antiferromagnetic coupling is observed in all cases. With very high Mn content transitions to magnetically complex phases are observed with possible spin-glass-like behavior.

AB - A new family of magnetic semiconductors, K2Cd3(1-x)Mn3xS4, prepared from molten K2Sx is reported. For x ≤ 0.6, the compounds crystallize in the K2Cd3S4 structure type. The cell volumes of the series obey Vegard's Law for solid solutions. The compounds range in color from yellow through orange brown to red and possess platelike morphologies. A structural transformation occurs between x = 0.7 and x = 0.9. Red plates of K2Cd0.4Mn2.6S4 (x = 0.87) crystallize in the space group Ccca with a = 5.9217(8) Å, b = 13.531(1) Å, c = 11.0696(8) Å, and V = 887.0(1) Å3. The end member, K2Mn3S4, crystallizes in the space group Ccca with a = 11.0637(7) Å, b = 26.830(2) Å, c = 5.8180(4) Å, and V = 1727 Å3. For x ≤ 0.6, the compounds form as (M3S4)n2n- layers, interspersed by K+ cations. These layers are composed only of M3S42- units shaped like truncated cubes. When x = 0.87, a new structure related to that of Cs2Mn3S4 is observed. The end member of the series (i.e., x = 1) K2Mn3S4 is revealed to have a related yet surprising structure. The compounds display room-temperature band gaps ranging from 2.79 to 2.92 eV. Absorptions in the mid-gap region, due to Mn2+-based d-d transitions, are also observed. The compounds are strongly emissive in the visible spectrum at room temperature, with the light emission shifted to the red immediately upon the introduction of small amounts of manganese. The magnetic properties of these compounds evolve from classical paramagnetic to spin glass as a function of x. For x ≥ 0.05, the compounds deviate from Curie-Weiss behavior. Antiferromagnetic coupling is observed in all cases. With very high Mn content transitions to magnetically complex phases are observed with possible spin-glass-like behavior.

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