TY - JOUR
T1 - Vast Structural and Polymorphic Varieties of Semiconductors AMM′Q4(A = K, Rb, Cs, Tl; M = Ga, In; M′ = Ge, Sn; Q = S, Se)
AU - Friedrich, Daniel
AU - Hao, Shiqiang
AU - Patel, Shane
AU - Wolverton, Chris
AU - Kanatzidis, Mercouri G.
N1 - Funding Information:
This work was supported mainly by the National Science Foundation Grant DMR-2003476. D.F. would like to thank the German Research Foundation (DFG) for financial support (reference number: FR 4094/1-1).
Publisher Copyright:
© 2021 American Chemical Society.
PY - 2021/8/24
Y1 - 2021/8/24
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.chemmater.1c02211
DO - 10.1021/acs.chemmater.1c02211
M3 - Article
AN - SCOPUS:85113491950
VL - 33
SP - 6572
EP - 6583
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 16
ER -