The role of native point defects and donor impurities in the electrical properties of ZnSb2O4: a hybrid density-functional study.

The ceramic material zinc antimony oxide ZnSb2O4 has promising electrical and magnetic properties, making it suitable for various applications such as electrochemical and energy storage. However, the effects of point defects and impurities on its electrical properties have never been revealed. Here, we employ hybrid density-functional calculations to investigate the energetics and electronic properties of native point defects and donor impurities in ZnSb2O4. The energetically favorable configurations of native point defects under selected growth conditions (O-rich and O-poor) are identified based on the calculated formation energies. The study finds no shallow donor and shallow acceptor defects with low formation energies. Still, the oxygen vacancy (VO) has the lowest formation energy among the donor-type defects under O-rich and O-poor conditions. However, it acts as a very deep acceptor, making it unlikely to provide free electron carriers to the conduction band. Moreover, electron carriers are likely to be compensated by the formation of zinc vacancies (VZn) and the zinc substituted for antimony (ZnSb), which behave as dominant acceptors. Our analysis of the charge neutrality conditions estimates that the Fermi level of undoped ZnSb2O4 would be pinned in a range that is 2.60 eV to 3.12 eV above the VBM for O-rich to O-poor growth conditions, respectively, suggesting that this material is semi-insulating. The possibility of enhancing free electron carriers by doping with Al, Ga, In, and F impurities is also investigated. Our results, however, indicate that high n-type conductivity is hindered by self-compensation in which the impurities additionally act as electron killers. Our results suggest that other impurity candidates and approaches may need to be considered to efficiently dope this material into n-type. Overall, this work paves the way for point defect engineering in this class of ternary oxides.

Effects of oxygen pressure on the morphology and surface energetics of ß-PbO2: insight from DFT calculations.

For over a century, lead dioxide (PbO2) has been investigated in lead-acid batteries and extensively utilized in a variety of applications. Identifying the surface properties and equilibrium morphology of ß-PbO2 (rutile phase) particles is mandatory for industrial utilization and surface engineering. Using density-functional calculations within the generalized gradient approximation revised for solids (PBEsol), we investigate a variety of surface properties of ß-PbO2. The surface energies of low-Miller-index stoichiometric surfaces are firstly determined, and the (110) surface is found to be the most thermodynamically stable. The relative energetics of these surfaces are represented by a Wulff construction which shows an acicular shape, mostly dominated by the (110) and (100) surfaces. Besides, we investigate the surface chemistry of ß-PbO2 under reduction and oxidation conditions as a function of oxygen pressure, finding that most surfaces except for (100) and (110) are likely to be oxidized. Under oxygen pressure at 1 atm and oxygen-rich limit, the (101) surface is the most thermodynamically stable, dominating the Wulff construction with pyramidal shapes. Our results indicate that the growth conditions that cause non-stoichiometry of the surface could modify the equilibrium Wulff shape of ß-PbO2. Our predicted Wulff shapes and dominant facets agree with the experimental results in which the pyramidal shape of the ß-PbO2 grains has often been observed with the (101) preferred orientation.

Energetics and optical properties of carbon impurities in rutile TiO2.

Titanium dioxide is one of the most promising materials for many applications such as photovoltaics and photocatalysis. Non-metal doping of TiO2 is widely used to improve the photoconversion efficiency by shifting the absorption edge from the UV to visible-light region. Here, we employ hybrid density-functional calculations to investigate the energetics and optical properties of carbon (C) impurities in rutile TiO2. The predominant configurations of the C impurities are identified through the calculated formation energies under O-poor and O-rich growth conditions. Under the O-poor condition, we find that C occupying the oxygen site (CO) is energetically favorable for Fermi-level values near the conduction band minimum (n-type TiO2), and acts as a double acceptor. Under the O-rich condition, the Ci-VTi complex is energetically favorable, and is exclusively stable in the neutral charge state. We also find that interstitial hydrogen (Hi) can bind to CO, forming a CO-Hi complex. Our results suggest that CO and CO-Hi are a cause of visible-light absorption under oxygen deficient growth conditions.

Energetics of native defects in anatase TiO2: a hybrid density functional study.

The energetics and electronic structures of native defects in anatase TiO2 are comprehensively studied using hybrid density functional calculations. We demonstrate that oxygen vacancies (VO) and titanium interstitials (Tii) act as shallow donors, and can form at substantial concentrations, giving rise to free electrons with carrier densities from 1011 to 1019 cm-3 under oxygen-rich and oxygen-poor conditions, respectively. The titanium vacancies (VTi), identified as deep acceptors and induced hole carriers, are incapable of fully compensating for the free electrons originating from the donor-type defects at any oxygen chemical potential. Even under extreme oxygen-rich conditions, the Fermi level, which is determined from the charge neutrality condition among charge defects, electron and hole carriers, is located 2.34 eV above the valence band maximum, indicating that p-type conductivity can never be realized under any growth conditions without external doping. This is consistent with common observations of intrinsic n-type conductivity of TiO2. At a typical annealing temperature and under a typical oxygen partial pressure, the carrier concentration is found to be approximately 5 × 1013 cm-3.

Electronic properties of highly-active Ag3AsO4 photocatalyst and its band gap modulation: an insight from hybrid-density functional calculations.

The electronic structures of highly active Ag-based oxide photocatalysts Ag3AsO4 and Ag3PO4 are studied by hybrid-density functional calculations. It is revealed that Ag3AsO4 and Ag3PO4 are indirect band gap semiconductors. The Hartree-Fock mixing parameters are fitted for experimental band gaps of Ag3AsO4 (1.88 eV) and Ag3PO4 (2.43 eV). The smaller electron effective mass and the lower valence band edge of Ag3AsO4 are likely to be responsible for the superior photocatalytic oxidation reaction to Ag3PO4. The comparable lattice constant and analogous crystal structure between the two materials allow the opportunities of fine-tuning the band gap of Ag3AsxP1-xO4 using a solid-solution approach. The development of Ag3AsxP1-xO4 should be promising for the discovery of novel visible-light sensitized photocatalysts.

Mechanism of photocatalytic activities in Cr-doped SrTiO3 under visible-light irradiation: an insight from hybrid density-functional calculations.

We used hybrid density-functional calculations to clarify the effect of substituting chromium for titanium (Cr(Ti)) on photocatalytic activities of Cr-doped SrTiO(3). A singly negative Cr(Ti)⁻, which is relevant to a lower oxidation state of Cr, is advantageous for the visible light absorption without forming electron trapping centers, while other charge states are inactive for the photocatalytic reaction. Stabilizing the desirable charge state (Cr(Ti)⁻) is feasible by shifting the Fermi level towards the conduction band. Our theory sheds light on the photocatalytic properties of metal-doped semiconductors.

Evidence for native-defect donors in n-type ZnO.

Recent theory has found that native defects such as the O vacancy V(O) and Zn interstitial Zn(I) have high formation energies in n-type ZnO and, thus, are not important donors, especially in comparison to impurities such as H. In contrast, we use both theory and experiment to show that, under N ambient, the complex Zn(I)-N(O) is a stronger candidate than H or any other known impurity for a 30 meV donor commonly found in bulk ZnO grown from the vapor phase. Since the Zn vacancy is also the dominant acceptor in such material, we must conclude that native defects are important donors and acceptors in ZnO.