First-Principles Study of CuGaO2 Polymorphs: Delafossite α-CuGaO2 and Wurtzite β-CuGaO2
| Autor: | Yuki Iguchi, Hiraku Nagatani, Masao Kita, Chiyuki Sato, Issei Suzuki, Takahisa Omata, Naoki Ohashi, Hiroshi Yanagi |
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| Rok vydání: | 2016 |
| Předmět: |
Chemistry
02 engineering and technology Electronic structure Crystal structure engineering.material 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Inorganic Chemistry Crystal Delafossite Crystallography Atomic orbital Computational chemistry engineering Density functional theory Physical and Theoretical Chemistry Local-density approximation 0210 nano-technology Wurtzite crystal structure |
| Zdroj: | Inorganic Chemistry. 55:7610-7616 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.6b01012 |
| Popis: | The electronic structures of delafossite α-CuGaO2 and wurtzite β-CuGaO2 were calculated based on density functional theory using the local density approximation functional including the Hubbard correction (LDA+U). The differences in the electronic structure and physical properties between the two polymorphs were investigated in terms of their crystal structures. Three major structural features were found to influence the electronic structure. The first feature is the atomic arrangements of cations. In the conduction band of α-CuGaO2 with a layered structure of Cu2O and Ga2O3, Cu and Ga states do not mix well; the lower part of the conduction band mainly consists of Cu 4s and 4p states, and the upper part consists of Ga 4s and 4p states. By contrast, in β-CuGaO2, which is composed of CuO4 and GaO4 tetrahedra, Cu and Ga states are well-mixed. The second feature is the coordination environment of Cu atoms; the breaking of degeneracy of Cu 3d orbitals is determined by the crystal field. Dispersion of the Cu 3d valence band of β-CuGaO2, in which Cu atoms are tetrahedrally coordinated to oxygen atoms, is smaller than those in α-CuGaO2, in which Cu atoms are linearly coordinated to oxygen atoms; this results in a larger absorption coefficient and larger hole effective mass in β-CuGaO2 than in α-CuGaO2. The interatomic distance between Cu atoms-the third feature-also influences the dispersion of the Cu 3d valence band (i.e., the effective hole mass); the effective hole mass decreases with decreasing interatomic distance between Cu atoms in each structure. The results obtained are valuable for understanding the physical properties of oxide semiconductors containing monovalent copper and silver. |
| Databáze: | OpenAIRE |
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