Electronic Structure and Stability of Quaternary Chalcogenide Semiconductors Derived from Cation Cross-Substitution of II-VI and I-III-VI2 Compounds

Journal Article · Thu Jan 01 04:00:00 EST 2009 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.79.165211· OSTI ID:1023091

Chen, S; Gong, X G; Walsh, A; Wei, S H

Sequential cation cross-substitution in zinc-blende chalcogenide semiconductors, from binary to ternary to quaternary compounds, is systematically studied using first-principles electronic structure calculations. Several universal trends are found for the ternary and two classes of quaternary chalcogenides, for example, the lowest-energy structure always has larger lattice constant a, smaller tetragonal distortion parameter {eta} = c/2a, negative crystal-field splitting at the top of the valence band, and larger band gap compared to the metastable structures for common-row cation substitution. The band structure changes in the cation substitution are analyzed in terms of the band offsets and band character decomposition, showing that although the band gap decreases from binary II-VI to ternary I-III-VI{sub 2} are mostly due to the p-d repulsion in the valence band, the decreases from ternary I-III-VI{sub 2} to quaternary I{sub 2}-II-IV-VI{sub 4} chalcogenides are due to the downshift in the conduction band caused by the wave-function localization on the group IV cation site. We propose that common-row-cation I{sub 2}-II-IV-VI{sub 4} compounds are more stable in the kesterite structure, whereas the widely assumed stannite structure reported in the literature for experimental samples is most likely due to partial disorder in the I-II (001) layer of the kesterite phase.

• Research Organization: National Renewable Energy Laboratory (NREL), Golden, CO.
• Sponsoring Organization: USDOE
• DOE Contract Number: AC36-08GO28308
• OSTI ID: 1023091
• Journal Information: Physical Review. B, Condensed Matter and Materials Physics, Journal Name: Physical Review. B, Condensed Matter and Materials Physics Journal Issue: 16, 2009 Vol. 79
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
CATIONS
CHALCOGENIDES
CRYSTAL FIELD
Computational Sciences
ELECTRONIC STRUCTURE
Materials Science and Semiconductors
STABILITY
VALENCE