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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

50 Scopus citations


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 [PSe43- or [GeS44- 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 (US)
Pages (from-to)158-169
Number of pages12
JournalJournal of Solid State Chemistry
Issue number1
StatePublished - 2000


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

ASJC Scopus subject areas

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


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