Native defects in cuprous oxide Cu2O are investigated by using first-principles calculations based on density-functional theory. Considering the formation of copper and oxygen vacancies, antisites and interstitials, and a copper split-vacancy complex defect, we analyze the electronic structure and calculate their respective formation energies as a function of the change in Fermi level under both copper-rich and oxygen-rich conditions. We find that, under both growth conditions, the defect with the lowest formation energy is the simple copper vacancy, followed by the copper split-vacancy complex. Both low-energy copper defects produce hole states at the top of the valence band, largely accounting for the p -type conductivity in this material. In spite of the creation of dangling bonds at the nearest-neighbor O atoms, these copper defects are found to be spin neutral. Under oxygen-rich conditions, oxygen interstitials have low formation energies and are found to exhibit a ferromagnetic ordering with a total magnetic moment of 1.38 μB and 1.36 μB at the octahedral and tetrahedral sites, respectively. Considering the possibility of native defect formation at the surface of this material, we investigate the relative stability of both low- and high-index copper-oxide surfaces by comparing their surface free energies as a function of the change in oxygen chemical potential. Using the technique of ab initio atomistic thermodynamics, we then correlate the dependence of the calculated Gibbs free-surface energy as a function of oxygen pressure and temperature via the oxygen chemical potential. We identify two low-energy surface structures, namely, Cu2O (110): CuO and Cu2O (111) -CuCUS, with the former marginally more stable for oxygen-rich conditions and the latter more stable for oxygen-lean (or copper-rich) conditions. Cu2O (110): CuO is calculated to be nonmagnetic and Cu2O (111) -CuCUS is calculated to be a ferromagnetic ordering, with a total magnetic moment of 0.91 μB per defect. With the results for both bulk and surface native defects, we find that under oxygen-lean conditions, a ferromagnetic behavior could be attributed mainly to copper vacancy formation in the (111) surface of Cu2O while under oxygen-rich conditions, low-energy bulk oxygen interstitial defects induce a ferromagnetic character in the same material. This highlights the complementary role of bulk and surface native magnetic defects under different pressure and temperature conditions, especially at the nanoparticle scale where surface properties dominate.
|Journal||Physical Review B - Condensed Matter and Materials Physics|
|Publication status||Published - 2009 Jan 5|
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Condensed Matter Physics