First-principles study of ground-state properties and high pressure behavior of ThO2

The mechanical properties, electronic structure and phonon dispersion of ground state ThO2 as well as the structure behavior up to 240 GPa are studied using first-principles density-functional theory. Our calculated elastic constants indicate that both the ground-state fluorite structure and high pressure cotunnite structure of ThO2 are mechanically stable. The bulk modulus, shear modulus, and Young's modulus of cotunnite ThO2 are all smaller by approximately 25% compared with those of fluorite ThO2. The Poisson's ratios of both structures are approximately equal to 0.3 and the hardness of fluorite ThO2 is 22.4 GPa. The electronic structure and bonding nature of fluorite ThO2 are fully analyzed, and show that the Th-O bond displays a mixed ionic/covalent character. The phase transition from the fluorite to cotunnite structure is calculated to occur at the pressure of 26.5 GPa, consistent with recent experimental measurement by ldiri et al. [1]. For the cotunnite phase it is further predicted that an isostructural transition takes place in the pressure region of 80-130 GPa.

Structural, mechanical, thermodynamic, and electronic properties of thorium hydrides from first-principles

We perform first-principles calculations of the structural, electronic, mechanical, and thermodynamic properties of thorium hydrides (ThH2 and Th4H15) based on the density functional theory with generalized gradient approximation. The equilibrium geometries, the total and partial densities of states, charge density, elastic constants, elastic moduli, Poisson's ratio, and phonon dispersion curves for these materials are systematically investigated and analyzed in comparison with experiments and previous calculations. These results show that our calculated equilibrium structural parameters are well consistent with experiments. The Th-H bonds in all thorium hydrides exhibit weak covalent character, but the ionic properties for ThH2 and Th4H15 are different due to their different hydrogen concentration. It is found that while in ThH2 about 1.5 electrons transfer from each Th atom to H, in Th4H15 the charge transfer from each Th atom is around 2.1 electrons. Our calculated phonon spectrum for the stable body-centered tetragonal phase of ThH2 accords well with experiments. In addition we show that ThH2 in the fluorite phase is mechanically and dynamically unstable.

Defects in gallium nitride nanowires: First principles calculations

Atomic configurations and formation energies of native defects in an unsaturated GaN nanowire grown along the [001] direction and with (100) lateral facets are studied using large-scale ab initio calculation. Cation and anion vacancies, antisites, and interstitials in the neutral charge state are all considered. The configurations of these defects in the core region and outermost surface region of the nanowire are different. The atomic configurations of the defects in the core region are same as those in the bulk GaN, and the formation energy is large. The defects at the surface show different atomic configurations with low formation energy. Starting from a Ga vacancy at the edge of the side plane of the nanowire, a N-N split interstitial is formed after relaxation. As a N site is replaced by a Ga atom in the suboutermost layer, the Ga atom will be expelled out of the outermost layers and leaves a vacancy at the original N site. The Ga interstitial at the outmost surface will diffuse out by interstitialcy mechanism. For all the tested cases N-N split interstitials are easily formed with low formation energy in the nanowires, indicating N-2 molecular will appear in the GaN nanowire, which agrees well with experimental findings.

First-principle study of native defects in CuScO2 and CuYO2

This paper studies the electronic structure and native defects intransparent conducting oxides CuScO2 and CuYO2 using the first-principle calculations. Some typical native copper-related and oxygen-related defects, such as vacancy, interstitials, and antisites in their relevant charge state are considered. The results of calculation show that, CuMO2 (M = Sc, Y) is impossible to shown-type conductivity ability. It finds that copper vacancy and oxygen interstitial have relatively low formation energy and they are the relevant defects in CuScO2 and CuYO2. Copper vacancy is the most efficient acceptor, and under O-rich condition oxygen antisite also becomes important acceptor and plays an important role in p-type conductivity.

First-principles study of p-type transparent conductive oxides CuXO2 (X=Y, Sc, and Al)

Using first-principles methods we have calculated electronic structures, optical properties, and hole conductivities of CuXO2 (X=Y, Sc, and Al). We show that the direct optical band gaps of CuYO2 and CuScO2 are approximately equal to their fundamental band gaps and the conduction bands of them are localized. The direct optical band gaps of CuXO2 (X=Y, Sc, and Al) are 3.3, 3.6, and 3.2 eV, respectively, which are consistent with experimental values of 3.5, 3.7, and 3.5 eV. We find that the hole mobility along long lattice c is higher than that along other directions through calculating effective masses of the three oxides. By analyzing band offset we find that CuScO2 has the highest valence band maximum (VBM) among CuXO2 (X=Y, Sc, and Al). In addition, the approximate transitivity of band offset suggests that CuScO2 has a higher VBM than CuGaO2 and CuInO2 [Phys. Rev. Lett. 88, 066405 (2002)]. We conclude that CuScO2 has a higher p-type doping ability in terms of the doping limit rule. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2991157]

First-principles study on rutile TiO2 quantum dots

The electronic structure of rutile TiO2 quantum dots (QDs) are investigated via the first-principles band structure method. We first propose a model to passivate the rutile TiO2 surfaces for the local density approximation calculations. In this model pseudohydrogen atoms are used to passivate the surface dangling bonds, which remove the localized in-cap surface states in the TiO2 QDs. As the size of the QD decreases, the band gap evolves as E-g(dot) = E-g(bulk) + 73.70/d(1.93), where E-g(dot) and d are the band gap and diameter of the QD, and E-g(bulk) is the band gap of the bulk rutile TiO2. The valence band maximum and the conduction band minimum states of the QDs are distributed mostly in the interior of the QDs, and they well inherit the atomic characteristics of those states of the bulk rutile TiO2.

First-principles study of defects in CuGaO2

Using the first-principles methods, we study the electronic structure, intrinsic and extrinsic defects doping in transparent conducting oxides CuGaO2. Intrinsic defects, acceptor-type and donor-type extrinsic defects in their relevant charge state are considered. The calculation result show that copper vacancy and oxygen interstitial are the relevant defects in CuGaO2. In addition, copper vacancy is the most efficient acceptor. Substituting Be for Ga is the prominent acceptor, and substituting Ca for Cu is the prominent donors in CuGaO2. Our calculation results are expected to be a guide for preparing n-type and p-type materials in CuGaO2.

First-principle study of extrinsic defects in CuScO2 and CuYO2

Using first-principles methods, we studied the extrinsic defects doping in transparent conducting oxides CuMO2 (M=Sc, Y). We chose Be, Mg, Ca, Si, Ge, Sn as extrinsic defects to substitute for M and Cu atoms. By systematically calculating the impurity formation energy and transition energy level, we find that Be-Cu is the most prominent extrinsic donor and Ca-M is the prominent extrinsic acceptor. In addition, we find that Mg atom substituting for Sc is the most prominent extrinsic acceptor in CuSCO2. Our calculation results are expected to be a guide for preparing n-type and p-type materials through extrinsic doping in CuMO2 (M=SC, y). (C) 2008 Elsevier B.V. All rights reserved.

First-principles study of transition metal impurities in Si

By using ab initio electronic structure calculations within density functional theory, we study the structural, electronic, and magnetic properties of Si doped with a transition metal impurity. We consider the transition metals of the 3d series V, Cr, Mn, Fe, Co, and Ni. To get insight into the level filling mechanism and the magnetization saturation, we first investigate the transition metal-Si alloys in the zinc-blende structure. Next, we investigate the doping of bulk Si with a transition metal atom, in which it occupies the substitutional site, the interstitial site with tetrahedral symmetry, and the interstitial site with hexagonal symmetry. It is found that all of these transition metal impurities prefer an interstitial position in Si. Furthermore, we show that it is possible to interpret the electronic and magnetic properties by using a simple level filling picture and a comparison is made to Ge doped with the same transition metal atoms. In order to get insight into the effect of a strained environment, we calculate the formation energy as a function of an applied homogeneous pressure and we show that an applied pressure can stabilize the substitutional position of transition metal impurities in Si. Finally, the energies of the ferromagnetic states are compared to those of the antiferromagnetic states. It is shown that the interstitial site of the Mn dopant helps us to stabilize the nearest neighbor substitutional site to realize the ferromagnetic state. For doping of Si with Cr, a ferrimagnetic behavior is predicted.

Magnetic coupling properties of mn-doped ZnO nanowires: First-principles calculations

Based on the density functional theory, we study the magnetic coupling properties of Mn-doped ZnO nanowires. For the nanowires with passivated surfaces, the antiferromagnetic state is found and the Mn atoms have a clustering tendency. When the distance between two Mn atoms is large, the system energetically favors the paramagnetic or spin-glass state. For the nanowires with unpassivated surfaces, the ferromagnetic (FM) coupling states appear between the two nearest Mn atoms, and the zinc vacancies can further stabilize the FM states between them. The electrons with enough concentration possibly mediate the FM coupling due to the negative exchange splitting of conduction band minimum induced by the s-d coupling, which could be useful in nanomaterial design for spintronics. (C) 2008 American Institute of Physics.

Origin of the doping bottleneck in semiconductor quantum dots: A first-principles study

Doping difficulty in semiconductor nanocrystals has been observed and its origin is currently under debate. It is not clear whether this phenomenon is energetic or depends on the growth kinetics. Using first-principles method, we show that the transition energies and defect formation energies of the donor and acceptor defects always increase as the quantum dot sizes decrease. However, for isovalent impurities, the changes of the defect formation energies are rather small. The origin of the calculated trends is explained using simple band-energy-level models.

First-principles study of the electronic structures and magnetic properties of 3d transition metal-doped anatase TiO2

We study the electronic structures and magnetic properties of the anatase TiO2 doped with 3d transition metals (V, Cr, Mn, Fe, Co, Ni), using first-principles total energy calculations based on density functional theory (DFT). Using a molecular-orbital bonding model, the electronic structures of the doped anatase TiO2 are well understood. A band coupling model based on d-d level repulsions between the dopant ions is proposed to understand the chemical trend of the magnetic ordering. Ferromagnetism is found to be stabilized in the V-, Cr-, and Co-doped samples if there are no other carrier native defects or dopants. The ferromagnetism in the Cr- and Co-doped samples may be weakened by the donor defects. In the Mn-, and Fe-doped samples, the ferromagnetism can be enhanced by the acceptor and donor defects, respectively.

First-principles study of native defects in rutile TiO2

Native point defects in the rutile TiO2 are studied via first-principles pseudopotential calculations. Except for the two antisite defects, all the native point defects have low formation energies. Under the Ti-rich growth condition, high concentrations of titanium interstitials and oxygen vacancies would form spontaneously in p-type samples; whereas high concentrations of titanium vacancies would form spontaneously in n-type samples regardless of the oxygen partial pressure. (c) 2007 Elsevier B.V. All rights reserved.

Electronic structures and mechanical properties of uranium monocarbide from first-principles LDA plus U and GGA plus U calculations

The electronic structure, elastic constants, Poisson's ratio, and phonon dispersion curves of UC have been systematically investigated from the first-principles calculations by the projector-augmented-wave (PAW) method. In order to describe precisely the strong on-site Coulomb repulsion among the localized U 5f electrons, we adopt the local density approximation (LDA) + U and generalized gradient approximation (GGA) + U formalisms for the exchange correlation term. We systematically study how the electronic properties and elastic constants of UC are affected by the different choice of U as well as the exchange-correlation potential. We show that by choosing an appropriate Hubbard U parameter within the GGA + U approach, most of our calculated results are in good agreement with the experimental data. Therefore. the results obtained by the GGA + U with effective Hubbard parameter U chosen around 3 eV for UC are considered to be reasonable. (C) 2009 Elsevier B.V. All rights reserved.

Structural, elastic, and electronic properties of cubic perovskite BaHfO3 obtained from first principles

We investigated the structural, elastic, and electronic properties of the cubic perovskite-type BaHfO3 using a first-principles method based on the plane-wave basis set. Analysis of the band structure shows that perovskite-type BaHfO3 is a wide gap indirect semiconductor. The band-gap is predicted to be 3.94 eV within the screened exchange local density approximation (sX-LDA). The calculated equilibrium lattice constant of this compound is in good agreement with the available experimental and theoretical data reported in the literatures. The independent elastic constants (C-11, C-12, and C-44), bulk modules B and its pressure derivatives B', compressibility beta, shear modulus G, Young's modulus Y, Poisson's ratio nu, and Lame constants (mu, lambda) are obtained and analyzed in comparison with the available theoretical and experimental data for both the singlecrystalline and polycrystalline BaHfO3. The bonding-charge density calculation make it clear that the covalent bonds exist between the Hf and 0 atoms and the ionic bonds exist between the Ba atoms and HfO3 ionic groups in BaHfO3. (C) 2009 Elsevier B.V. All rights reserved.