Flux synthesis and isostructural relationship of cubic Na(1.5)Pb(0.75)PSe4, Na(0.5) Pb(1.75)GeS4, and Li(0.5)Pb(1.75)GeS4

Jennifer A. Aitken, Gregory A. Marking, Michel Evain, Lykourgos Iordanidis, Mercouri G Kanatzidis

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Abstract

Na(1.5)Pb90.75)PSe4 was synthesized by the reaction of Pb with a molten mixture of Na2Se/P2Se3/Se at 495°C. Na(0.5)Pb(1.75)GeS4 was synthesized by reacting Pb and Ge in molten Na2S(x) at 530°C. Likewise, L(0.5)Pb(1.75)GeS4 can be synthesized in a Li2S(x) flux at 500°C. Na(0.5)Pb(1.75)GeS4 and Li(0.5)Pb(1.75)GeS4 are relatively air- and water-stable, while Na(1.5)Pb(0.75)PSe4 is only stable in air and water for less than 1 day. The structures of all three compounds were determined by single-crystal X-ray diffraction. The compounds crystallize in the cubic, noncentrosymmetric space group I43d with a = 14.3479(2) Å, Z = 16, R1 = 0.0226, and wR2 = 0.0517 for Na(1.5)Pb(0.75)PSe4, a = 14.115(1) Å, Z= 16, RI = 0.0284, and wR2 = 0.0644 for Na(0.5)Pb(1.75)GeS4, and a = 14.0163(6) Å, Z = 16, RI = 0.0273, and wR2 = 0.0637 for Li(0.5)Pb(1.75)GeS4. The compounds adopt a structure that is similar to that of Ba3CdSn2S8 and feature [PSe4 3- or [GeS4 4- tetrahedral building blocks. In this three-dimensional structure, there are two types of metal sites. In each structure, these sites are occupied differently because of a disorder between the alkali and lead cations. All three compounds are semiconductors with band gaps around 2 eV. The observation of a large second harmonic generation (SHG) signal for Na(0.5)Pb(1.75)GeS4 indicates that it may be a potential nonlinear optical (NLO) material. Infrared and Raman spectroscopic characterization is also reported. (C) 2000 Academic Press.

Original languageEnglish
Pages (from-to)158-169
Number of pages12
JournalJournal of Solid State Chemistry
Volume153
Issue number1
DOIs
Publication statusPublished - 2000

Fingerprint

Molten materials
Fluxes
Optical materials
Water
air
Alkalies
optical materials
synthesis
Harmonic generation
Air
water
Cations
alkalies
harmonic generations
Energy gap
Lead
Positive ions
Metals
Single crystals
disorders

Keywords

  • Chalcogenides
  • Molten salt fluxes
  • Second harmonic generation
  • Selenophosphate
  • Thiogermanate

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Flux synthesis and isostructural relationship of cubic Na(1.5)Pb(0.75)PSe4, Na(0.5) Pb(1.75)GeS4, and Li(0.5)Pb(1.75)GeS4 . / Aitken, Jennifer A.; Marking, Gregory A.; Evain, Michel; Iordanidis, Lykourgos; Kanatzidis, Mercouri G.

In: Journal of Solid State Chemistry, Vol. 153, No. 1, 2000, p. 158-169.

Research output: Contribution to journalArticle

Aitken, Jennifer A. ; Marking, Gregory A. ; Evain, Michel ; Iordanidis, Lykourgos ; Kanatzidis, Mercouri G. / Flux synthesis and isostructural relationship of cubic Na(1.5)Pb(0.75)PSe4, Na(0.5) Pb(1.75)GeS4, and Li(0.5)Pb(1.75)GeS4 In: Journal of Solid State Chemistry. 2000 ; Vol. 153, No. 1. pp. 158-169.
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abstract = "Na(1.5)Pb90.75)PSe4 was synthesized by the reaction of Pb with a molten mixture of Na2Se/P2Se3/Se at 495°C. Na(0.5)Pb(1.75)GeS4 was synthesized by reacting Pb and Ge in molten Na2S(x) at 530°C. Likewise, L(0.5)Pb(1.75)GeS4 can be synthesized in a Li2S(x) flux at 500°C. Na(0.5)Pb(1.75)GeS4 and Li(0.5)Pb(1.75)GeS4 are relatively air- and water-stable, while Na(1.5)Pb(0.75)PSe4 is only stable in air and water for less than 1 day. The structures of all three compounds were determined by single-crystal X-ray diffraction. The compounds crystallize in the cubic, noncentrosymmetric space group I43d with a = 14.3479(2) {\AA}, Z = 16, R1 = 0.0226, and wR2 = 0.0517 for Na(1.5)Pb(0.75)PSe4, a = 14.115(1) {\AA}, Z= 16, RI = 0.0284, and wR2 = 0.0644 for Na(0.5)Pb(1.75)GeS4, and a = 14.0163(6) {\AA}, Z = 16, RI = 0.0273, and wR2 = 0.0637 for Li(0.5)Pb(1.75)GeS4. The compounds adopt a structure that is similar to that of Ba3CdSn2S8 and feature [PSe4 3- or [GeS4 4- tetrahedral building blocks. In this three-dimensional structure, there are two types of metal sites. In each structure, these sites are occupied differently because of a disorder between the alkali and lead cations. All three compounds are semiconductors with band gaps around 2 eV. The observation of a large second harmonic generation (SHG) signal for Na(0.5)Pb(1.75)GeS4 indicates that it may be a potential nonlinear optical (NLO) material. Infrared and Raman spectroscopic characterization is also reported. (C) 2000 Academic Press.",
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T1 - Flux synthesis and isostructural relationship of cubic Na(1.5)Pb(0.75)PSe4, Na(0.5) Pb(1.75)GeS4, and Li(0.5)Pb(1.75)GeS4

AU - Aitken, Jennifer A.

AU - Marking, Gregory A.

AU - Evain, Michel

AU - Iordanidis, Lykourgos

AU - Kanatzidis, Mercouri G

PY - 2000

Y1 - 2000

N2 - Na(1.5)Pb90.75)PSe4 was synthesized by the reaction of Pb with a molten mixture of Na2Se/P2Se3/Se at 495°C. Na(0.5)Pb(1.75)GeS4 was synthesized by reacting Pb and Ge in molten Na2S(x) at 530°C. Likewise, L(0.5)Pb(1.75)GeS4 can be synthesized in a Li2S(x) flux at 500°C. Na(0.5)Pb(1.75)GeS4 and Li(0.5)Pb(1.75)GeS4 are relatively air- and water-stable, while Na(1.5)Pb(0.75)PSe4 is only stable in air and water for less than 1 day. The structures of all three compounds were determined by single-crystal X-ray diffraction. The compounds crystallize in the cubic, noncentrosymmetric space group I43d with a = 14.3479(2) Å, Z = 16, R1 = 0.0226, and wR2 = 0.0517 for Na(1.5)Pb(0.75)PSe4, a = 14.115(1) Å, Z= 16, RI = 0.0284, and wR2 = 0.0644 for Na(0.5)Pb(1.75)GeS4, and a = 14.0163(6) Å, Z = 16, RI = 0.0273, and wR2 = 0.0637 for Li(0.5)Pb(1.75)GeS4. The compounds adopt a structure that is similar to that of Ba3CdSn2S8 and feature [PSe4 3- or [GeS4 4- tetrahedral building blocks. In this three-dimensional structure, there are two types of metal sites. In each structure, these sites are occupied differently because of a disorder between the alkali and lead cations. All three compounds are semiconductors with band gaps around 2 eV. The observation of a large second harmonic generation (SHG) signal for Na(0.5)Pb(1.75)GeS4 indicates that it may be a potential nonlinear optical (NLO) material. Infrared and Raman spectroscopic characterization is also reported. (C) 2000 Academic Press.

AB - Na(1.5)Pb90.75)PSe4 was synthesized by the reaction of Pb with a molten mixture of Na2Se/P2Se3/Se at 495°C. Na(0.5)Pb(1.75)GeS4 was synthesized by reacting Pb and Ge in molten Na2S(x) at 530°C. Likewise, L(0.5)Pb(1.75)GeS4 can be synthesized in a Li2S(x) flux at 500°C. Na(0.5)Pb(1.75)GeS4 and Li(0.5)Pb(1.75)GeS4 are relatively air- and water-stable, while Na(1.5)Pb(0.75)PSe4 is only stable in air and water for less than 1 day. The structures of all three compounds were determined by single-crystal X-ray diffraction. The compounds crystallize in the cubic, noncentrosymmetric space group I43d with a = 14.3479(2) Å, Z = 16, R1 = 0.0226, and wR2 = 0.0517 for Na(1.5)Pb(0.75)PSe4, a = 14.115(1) Å, Z= 16, RI = 0.0284, and wR2 = 0.0644 for Na(0.5)Pb(1.75)GeS4, and a = 14.0163(6) Å, Z = 16, RI = 0.0273, and wR2 = 0.0637 for Li(0.5)Pb(1.75)GeS4. The compounds adopt a structure that is similar to that of Ba3CdSn2S8 and feature [PSe4 3- or [GeS4 4- tetrahedral building blocks. In this three-dimensional structure, there are two types of metal sites. In each structure, these sites are occupied differently because of a disorder between the alkali and lead cations. All three compounds are semiconductors with band gaps around 2 eV. The observation of a large second harmonic generation (SHG) signal for Na(0.5)Pb(1.75)GeS4 indicates that it may be a potential nonlinear optical (NLO) material. Infrared and Raman spectroscopic characterization is also reported. (C) 2000 Academic Press.

KW - Chalcogenides

KW - Molten salt fluxes

KW - Second harmonic generation

KW - Selenophosphate

KW - Thiogermanate

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