First-principles study of diffusion and interactions of vacancies and hydrogen in hcp-titanium

We present a study of the stability of n-vacancies (V (n)) and hydrogens in the hexagonal close-packed titanium system computed by means of first-principles calculations. In this work, performed by using the generalized gradient approximation of density functional theory, we focused on the formation energies and the processes of migration of these defects. In the first part, the calculated formation energy of the monovacancy presents a disagreement with experimental data, as already mentioned in the literature. The activation energy is underestimated by almost 20%. The stability of compact divacancies was then studied. We show that a divacancy is more stable than a monovacancy if their migration energies are of the same order of magnitude. We also predict that the migration process in the basal plane of the divacancy is controlled by an intermediate state corresponding to a body-centered triangle (BO site). The case of the trivacancies is finally considered from an energetic point of view. In the second part, the insertion of hydrogen and the processes of its migration are discussed. We obtain a satisfactory agreement with experimental measurements. The chemical nature of the interactions between hydrogen and titanium are discussed, and we show that the H-atom presents an anionic behavior in the metal. The trapping energy of hydrogen in a monovacancy as a function of the number of hydrogen atoms is finally presented.     

运用第一性原理研究氧化锌电阻阀片中氧空位与掺杂条件下ZnO晶体电学性质

为了比较Nb_2O_5、MnO_2、MgO三种添加剂对氧化锌电阻阀片电学性能影响,在微观层面模拟Nb、Mn、Mg三种元素分别掺杂ZnO完整超晶胞和带有氧空位缺陷的ZnO超晶胞,并运用第一性原理分析掺杂晶胞的特性.本文计算了晶体结构、掺杂形成能、氧空位形成能、能带结构、态密度、载流子迁移率、电导率等.结果表明,掺入Nb原子的掺杂体系晶格体积最大,Mg掺杂体系的形成能最大,稳定性最弱,Nb掺杂氧空位形成能最低,更容易引入氧空位.Nb掺杂的ZnO超晶胞禁带宽度最小,氧空位缺陷增大掺杂晶体的禁带宽度.在相同掺杂浓度和同等条件下,Mn掺杂的晶体电导率最高.     

First-principles study of the diffusion of hydrogen in ZnO

Zinc oxide, a wide-gap semiconductor, typically exhibits n-type conductivity even when nominally undoped. The nature of the donor is contentious, but hydrogen is a prime candidate. We present ab initio calculations of the migration barrier for H, yielding a barrier of less than approximately 0.5 eV. This indicates isolated hydrogen is mobile at low temperature and that thermally stable H-related donors must logically be trapped at other defects. We argue this is also true for other oxides where H is a shallow donor.     

First-principles study of the co-effect of carbon doping and oxygen vacancies in ZnO photocatalyst

Although tuning band structure of optoelectronic semiconductor-based materials by means of doping single defect is an important approach for potential photocatalysis application,C-doping or oxygen vacancy(Vo)as a single defect in ZnO still has limitations for photocatalytic activity.Meanwhile,the influence of co-existence of various defects in ZnO still lacks sufficient studies.Therefore,we investigate the photocatalytic properties of ZnOx C0.0625(x=0.9375,0.875,0.8125),confirming that the co-effect of various defects has a greater enhancement for photocatalytic activity driven by visible-light than the single defect in ZnO.To clarify the underlying mechanism of co-existence of various defects in ZnO,we perform systematically the electronic properties calculations using density functional theory.It is found that the coeffect of C-doping and Vo in ZnO can achieve a more controllable band gap than doping solely in ZnO.Moreover,the impact of the effective masses of ZnO_xC_0.0625(x=0.9375,0.875,0.8125)is also taken into account.In comparison with heavy Vo concentrations,the light Vo concentration(x=0.875)as the optimal component together with C-doping in ZnO,can significantly improve the visible-light absorption and benefit photocatalytic activity.     

Enhancement of zinc interstitials in ZnO nanotubes grown on glass substrate by the hydrothermal method

In this study, high density well aligned ZnO nanotubes were grown on glass via a two-step growth-then-etching by simple and template-free hydrothermal method. We used etching procedure to introduce additional zinc interstitial defects in the ZnO nanotubes. The optical properties of the ZnO nanotubes have been investigated by depth-resolved cathodluminescence spectroscopy (DRCLS) which provides information about the physical origin and growth dependence of optically active defects together with their spatial distribution. The DRCLS study gives clear evidence about the enhancement of zinc interstitial defects which are responsible for the violet and decrease of the DL emission in ZnO nanotubes when compared to the as grown ZnO nanorods. We observed a variation in the zinc interstitials along the nanotube depth.     

Quantum diffusion of light interstitials

The diffusion rate of light interstitials is calculated avoiding the usual adiabatic and Condon approximations for the phonons. The method employed is a generalization of the standard small polaron theory taking explicitely account of the strongly coupled interstitial-host vibrations.     

Resonant modes due to anion interstitials and anion vacancies in fluorites

The resonant modes due to anion interstitials and anion vacancies in fluorites are computed on the basis of a Green's function formalism. The Green's functions are calculated on the basis of shell model fitted to the phonon dispersion curves of the respective crystals. The force constant changes are calculated by finding the relaxations of the different host atoms and then using the short range potential due to Catlow and Norgett. The calculated frequencies of the resonant mode due to anion interstitials in BaF₂; shows good agreement with the experimental results. The results discussed in a comparative fashion for the three crystals CaF₂, SrF₂; and BaF₂; along with the possibility of their experimental detection.     

Diffusion coefficients of vacancies and interstitials along tilt grain boundaries in molybdenum

The diffusion coefficients of vacancies and interstitials along symmetrical tilt grain boundaries in molybdenum have been calculated using the molecular dynamics method. The migration energies of defects have been obtained. The activation energy and coefficients of grain boundary self-diffusion have been deter-mined. A comparison of the obtained results with the studies of other authors indicates that boundaries formed between particles in the powder in sintering experiments have a higher diffusion activity as compared to stable grain boundaries in polycrystals.     

Electric quadrupole interaction due to vacancies and interstitials in cubic host metals

A procedure has been developed to evaluate from first principle the electric field gradient (efg) due to vacancies and interstitials in cubic host metals. For this purpose the screening charge distribution in the valence-effect has been constructed in scattering theory using appropriate muffin-tin potential. In the size-effect, the efg has been evaluated in a more realistic model of the lattice than the commonly used elastic continuum. Unlike other calculations, no adjustable parameter has been used in the present procedure.     

Quantum diffusion of light interstitials in metals

A quantum theory of diffusion of self-trapped light interstitials in metals is presented. The theory encompasses both coherent and incoherent tunneling, but the approximation used neglects the dependence of the interstitial transfer matrix element on the vibrational state of the crystal. The coherent tunneling contribution is estimated by fitting the incoherent diffusion rate to experimental data for hydrogen and muon diffusion. It is predicted that coherent diffusion should be dominant below ～ 80 K for H in Nb and below ～ 190 K for μ⁺ in Cu. Experimental verifications of these predictions would require high purity strain free samples and low concentrations of the diffusing species.     

Ag-N共掺p型ZnO的第一性原理研究

采用基于密度泛函理论的第一性原理赝势法对Ag-N共掺杂ZnO体 系以及间隙N和间隙H掺杂p型ZnO: (Ag, N)体系的缺陷形成能和离化能进行了研究. 结果表明, 在Ag_Zn和N_O所形成的众多受主复合体中, Ag_Zn-N_O受主对不仅具有较低的缺陷形成能同时其离化能也相对较小, 因此, Ag_Zn-N_O受主对的形成是Ag-N共掺ZnO体系实现p型导电的主要原因. 研究发现, 当ZnO: (Ag, N)体系有额外间隙N原子存在时, Ag_Zn-N_O受主对容易与N_i形成Ag_Zn-(N₂)_{m O}施主型缺陷, 该施主缺陷的形成降低了Ag-N共掺ZnO的掺杂效率因而不利于p型导电. 当间隙H引入到ZnO: (Ag, N)体系时, H_i易与Ag_Zn-N_O受主对形成 受主-施主-受主复合结构(Ag_Zn-H_i-N_O), 此复合体的形成不仅提高了Ag_Zn-N_O受主对在ZnO中的固溶度, 同时还能使其受主能级变得更浅而有利于p型导电. 因此, H辅助Ag-N共掺ZnO可能是一种有效的p型掺杂手段. 关键词： p型ZnO 缺陷形成能 受主离化能 第一性原理     

First-principles study of diffusion behaviour of point defects in the O-terminated (0001) surface in wurtzite ZnO

A detailed first-principles study of the diffusion behaviour of point defects in the O-terminated (0001) surface in wurtzite ZnO was performed. The O vacancy and interstitial are found to diffuse much more easily in surface than in bulk. The Zn vacancy has a similar migration barrier for both bulk and surface, but has much smaller barrier for the diffuse-in process. The Zn interstitial is difficult to diffuse in the surface directly, but it can diffuse into the bulk relatively easily. Specific values of corresponding migration barriers are obtained.     

First-principles study of electronic structure and ferromagnetism in Ti-doped ZnO

We perform first-principles spin polarized calculations of the electronic structure of Ti-doped in ZnO. Ferromagnetism in Ti-doped ZnO is identified, which is in agreement with recent experimental and calculated results. A net magnetic moment of 0.715μ_B is found per Ti. At a Ti concentration of 12.5%, total energy calculations show that the ferromagnetic state is 68 meV lower than the antiferromagnetic state. The electronic states near Fermi energy are dominated by strong hybridization between O 2p and Ti 3d, which is just the origin of impurity band in Ti-doped ZnO and also implies that the Ti-O bond is quite covalent instead of purely ionic. Since there is no magnetic element in this compound, Ti-doped ZnO appears to be an unambiguous dilute magnetic semiconductor.     

First-principles study of optical properties in Ca-doped ZnO alloys

Various electronic and optical properties of Zn_1?x Ca _x O ternary alloys of wurtzite structure are calculated using a first-principles approach based on the framework of the generalized gradient approximation to density-functional theory. In particular, on-site Coulomb interactions are introduced, which can reasonably well predict the electronic properties and band gaps of the Zn_1?x Ca _x O (0??x??0.25) system. The imaginary part of the calculated dielectric function indicates that the optical transition between O 2p states in the valence band and Zn 4s states in the conduction band shifts to the high-energy range as the Ca concentration increases. The calculated band gap shows a significant increase with increasing Ca concentration. Therefore, Zn_1?x Ca _x O ternary alloys may be a potential candidate alloy for optoelectronic materials, and especially for light-emitters and detectors.     

第一性原理研究Te-N共掺p型ZnO

采用基于密度泛函理论的第一性原理赝势法对Te-N共掺杂ZnO体系的晶格结构、 杂质态密度和电子结构进行了理论分析.研究表明, N掺杂引起晶格收缩,而Te的掺入引起晶格膨胀, 从而减小晶格应力促进N的掺杂,并且Te由于电负性小于O而带正电, Te在ZnO中作为等电子施主而存在.研究发现, N掺杂体系中在费米能级附件形成窄的深受主能级, 而Te-N共掺体系中, N杂质带变宽,空穴更加离域,同时,空穴有效质量变小,受主能级变浅, 更有利于实现p型特性.因此, Te-N共掺有望成为一种更为有效的p型掺杂手段.     

First-principles study of photoconductivity in BaTiO3 with oxygen vacancies

The photoconductivity of BaTiO_2.5 with oxygen vacancy has been studied by the linear muffin-tin orbital method in the atomic sphere approximation (LMTO-ASA). The ground-state structure of BaTiO_2.5 is obtained by minimization of the total energy. The partial densities of states show that the occupied states at the bottom of the conduction band have primarily Ti d orbital character. The photoconductivity shows that two novel features, in the low energy side, can be attributed to the intraband transition of free electronic carriers in the vicinity of the Fermi level and the interband transition of the Ti 3d(yz) related band states, to the Ti 3d(xy,xz) related band states, respectively. In addition, it is also found that the anisotropy of photoconductivity is enhanced because of the introduction of oxygen vacancy. The system can show the conductive behavior of electronic carriers, which is qualitatively in agreement with a recent experimental finding.     

Sb complexes and Zn interstitials in Sb-implanted ZnO epitaxial films

In the present work, post-annealing is adopted to investigate the formation and the correlation of Sb complexes and Zn interstitials in Sb-ion implanted ZnO films, by using Raman scattering technique and electrical characterizations. The damage of Zn sublattice, produced by ion bombardment process is discerned from the unrecovered E2 (L) peak in annealed high Sb+ dose implanted samples. It is suggested that the Zn sublattice may be strongly affected by the introduction of Sb dopant because of the formation of SbZn-2VZn complex acceptor. The appearance of a new peak at 510 cm 1 in the annealed high dose Sb+ implanted samples is speculated to result from (Zn interstitials-O interstitials) Zni-Oi complex, which is in a good accordance with the electrical measurement. The p-type ZnO is difficult to obtain from the Sb+ implantation, however, which can be realized by in-situ Sb doping with proper growth conditions instead.