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The search for new functional materials with tunable properties remains a central challenge in chemistry, particularly for applications in energy and electronics. In this work, we present a framework for predictive crystal design in alkali metal chalcogenides that enables controlled dimensional reduction of a parent covalent motif, yielding a broad range of electronic structures, which systematically evolve from one parent to the other. We present 11 new members of the AnCu4–nSnS4 family (A = alkali metal; n = 0–4), which reduce the three-dimensional (3D) covalent network of Cu4SnS4 into various 3D, 2D, 1D, and 0D [Cu4–nSnS4]n− motifs through the substitution of Cu with alkali metals of various radii. The end members of the family set the range in achievable band gaps at 0.99 eV for fully covalent Cu4SnS4 (n = 0) and 3.38 eV for K4SnS4 (n = 4) with 0D [SnS4]n− tetrahedra. As the dimensionality of [Cu4–nSnS4]n− systematically reduces within AnCu4–nSnS4 (n = 1–3), a stepwise increase in band gap energy occurs through a gradual decrease in the energy of the valence band maximum and an increase in the conduction band minimum, with an increase in the effective masses of charge carriers. Furthermore, irrespective of the alkali metal, the thermal stability decreases with decreasing [Cu4–nSnS4]n− dimensionality within the quaternary members. Most importantly, we demonstrate that predictable crystal structure and property evolution for a given composition space is possible by deriving a general formula based on substituting the covalent metals of a parent structure with alkali metals.
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A selenium-based “alkahest”: reactive dissolutions of metals and metal compounds with n -alkylammonium polyselenide solutions
The solution-processing of metal chalcogenides offers a promising route to improve the manufacturing of semiconductor devices. The amine–thiol solvent system has been deemed an “alkahest” for its ability to dissolve a wide range of metals and metal chalcogenides. Therefore, it enables convenient synthesis of metal sulfides. However, in the literature there are limited reports of analogous selenium-based “alkahest” chemistry. Here we show that solutions containing n-alkylammonium polyselenides can dissolve a wide range of metals and metal compounds through the formation of soluble metal polyselenides. These metal polyselenides can subsequently be utilized as precursors for the synthesis of a wide range of binary and multinary metal selenide thin films and nanoparticles, including Cu(In,Ga)Se2, Cu2ZnSnSe4, and Ag2ZnSnSe4.
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- Award ID(s):
- 1855882
- PAR ID:
- 10532407
- Publisher / Repository:
- Inorganic Chemistry Frontiers
- Date Published:
- Journal Name:
- Inorganic Chemistry Frontiers
- Volume:
- 10
- Issue:
- 20
- ISSN:
- 2052-1553
- Page Range / eLocation ID:
- 6032 to 6044
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d3qi01632c
