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The dissociation of the CNHicomplex in GaN is studied in detail using photoluminescence measurements and first‐principles calculations. The blue luminescence (BL2) band with a maximum at 3.0 eV is caused by electron transitions from an excited state located at 0.02 eV below the conduction band to the ground state of the CNHidonor with the 0/+ level 0.15 eV above the valence band. The dissociation releases hydrogen atom, and the remaining CNdefect with the −/0 state at 0.92 eV above the valence band is responsible for the yellow band (YL1) with a maximum at about 2.2 eV. The dissociation of the CNHicomplex can be caused by the photoinduced defect reaction mechanism under UV illumination at low temperature (≈20 K), leading to the bleaching of the BL2 band and simultaneous rise in the YL1 band. The bleaching is reversible. Alternatively, the complex dissociates after annealing at temperatures above 600 °C. The activation energy of this process (3–4 eV, depending on the annealing geometry) corresponds to the removal of hydrogen from the sample and not to the dissociation of the complex itself.
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This content will become publicly available on August 7, 2026
Dimensional Reduction Guides Electronic Structure Evolution in the A n Cu 4–n SnS 4 Semiconductor Series
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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- Award ID(s):
- 2305731
- PAR ID:
- 10627021
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- ISSN:
- 0002-7863
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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