Vast Structural and Polymorphic Varieties of Semiconductors AMM′Q4(A = K, Rb, Cs, Tl; M = Ga, In; M′ = Ge, Sn; Q = S, Se)

Daniel Friedrich, Shiqiang Hao, Shane Patel, Chris Wolverton, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Nine new chalcogenide semiconductors AInM′Q4 (A+ = K+, Rb+, Cs+, Tl+ M′4+ = Ge4+, Sn4+ Q2- = S2-, Se2-) have been prepared by solid-state syntheses and structurally characterized by single-crystal X-ray diffraction techniques. These new phases fill in the missing links in these quaternary systems and crystallize in various two-dimensional layered polymorphs, while combinations containing large M3+ and M′4+ cations also adopt an extended three-dimensional (3D) network structure. The AMM′Q4 materials exhibit a wide range of band gaps with colored selenides (1.8 eV < Eg < 2.3 eV) and mostly white sulfides (2.5 eV < Eg < 3.6 eV). These phases have direct band gaps except for the thallium analogues and the cubic AGaSnSe4-cP84. First-principles theoretical calculations of the electronic band structures reveal critical insight into the structure/property relationships of these materials. The distinct polymorphism of these quaternary phases is studied by discussing kinetic and thermodynamic factors responsible for the crystallization, structural considerations, and complementary density functional theory (DFT) calculations.

Original languageEnglish (US)
Pages (from-to)6572-6583
Number of pages12
JournalChemistry of Materials
Volume33
Issue number16
DOIs
StatePublished - Aug 24 2021

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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