The Formation of Defect Complexes in a ZnO Grain Boundary

The microscopic properties a ZnO grain boundary containing extrinsic point defects are studied using a density functional computational approach. The results show that the grain boundary acts as a sink for native defects, such as the zinc vacancy and the oxygen interstitial, and also for bismuth substitutional impurities. The defects tend to accumulate at under-coordinated sites in the boundary core and prefer to form small clusters. In particular the segregation of Bi promotes the formation of the other native defects by lowering their formation energies in the boundary. Individually, the native defects and the Bi impurity do not produce deep interface states in the band gap which are electrically active. However, when the defects cluster to form a Bi_Zn-V_Zn-O_i complex, new gap states are created of acceptor type. It is suggested that these new states are caused by defect interactions which compensate one another resulting in the depletion of an occupied impurity state and new bond formation. The results are discussed in terms of the Schottky barrier model commonly used to describe the electrical characteristics of ZnO varistors.     

Electronic conductivity and chemical diffusion in n-conducting barium titanate ceramics at high temperatures

The electronic conductivity as well as the chemical diffusion coefficient of barium titanate ceramics doped with Y and Mn (donor-doped and acceptor co-doped) have been determined by application of conductivity relaxation experiments. The equilibrium values of the electronic conductivity of n-conducting BaTiO₃ have been analyzed by application of a defect chemical model involving electrons and cation vacancies as the predominant defect species at oxidizing conditions (fairly high oxygen partial pressures). The relaxation curves of the electronic conductivity yield the chemical diffusion coefficient of the bulk by employing a spherical grain model where the appropriate diffusion length is the radius of grains (average grain size). The conductivity relaxation experiments have been performed as a function of temperature ranging from 1100 to 1250 °C at oxygen partial pressures between 0.01 and 1 bar. The kinetics of the oxygen exchange process can be interpreted in terms of extremely fast diffusion of oxygen via oxygen vacancies along the grain boundaries and slow diffusion of Ti (cation)-vacancies from the grain boundaries into the grains. The Ti-vacancy diffusion coefficients were extracted from the chemical diffusion coefficients as a function of temperature. Typical values for the Ti-vacancy diffusivity are around 10^− 15 cm² s^− 1 with an activation energy of 3.9 ± 0.7 eV.     

An alternative approach to investigate the origin of p-type conductivity in arsenic doped ZnO

P-type conductivity in MOCVD grown ZnO was obtained by directional thermal diffusion of arsenic from semi-insulating GaAs substrate. The films were single crystalline in nature and oriented along (002) direction. Ab initio calculations in the framework of density functional theory have been carried out with different chemical states of arsenic in ZnO. Present calculations suggested As_Zn–2V_Zn defect is a shallow acceptor and results in ferromagnetism in ZnO. The magnetic measurements of the samples indeed showed ferromagnetic ordering at room temperature. X-ray photoelectron spectra confirmed the presence of As_Zn and V_Zn. The core level chemical shift in binding energy of As_Zn indicated the formation of As_Zn–2V_Zn. Diffused arsenic substitutes zinc atom and creates additional zinc vacancies. The zinc vacancies, surrounding the oxygen atoms, result in unpaired O 2p electrons which in turn induce ferromagnetism in the samples.     

Static and Dynamic Electron Holography of Electrically Active Grain Boundaries in SrTiO3

The dynamics of electrostatic potential barriers at grain boundaries (GBs) in Nb-doped SrTiO₃ bicrystals is investigated using a unique combination of bulk and in-situ TEM electrical measurements across isolated GBs, coupled with electron holography under in-situ applied bias. The Nb bulk-doped bicrystals exhibit a positive GB potential that suppresses reversibly under applied bias greater than the nonlinearity threshold in the current-voltage curve. This suppression is interpreted as break-down of the potential barrier to current transport.The results on Nb bulk-doped bicrystals have been compared to those in which Mn has been added as a grain boundary specific dopant. This acceptor doping of the grain boundary causes an appreciable increase in the grain boundary resistance and extension of the nonlinear regime. A preliminary account of static electron holography shows a relatively flat potential profile across the GB, indicating probable compensation of donor states at the GB core with Mn-acceptors. Interestingly, the phase profile under applied bias in this case exhibits a reversible dip at the GB which is interpreted as an activation of GB trap states due to Mn-acceptor dopants trapping extra electrons (the majority charge carriers) at the GB core, inducing a negative GB potential, and diminishing current transport until the threshold bias is exceeded.The synergistic combination of nanoscale TEM measurements coupled with traditional macroscopic electrical measurements is emphasized.     

Grain boundary potential and charge density at grain boundaries of chemically prepared thin silver sulfide films

The grain boundary potential and interface state charge density at the grain boundaries of silver sulfide (Ag₂S) thin films prepared by chemical conversion of cadmium sulfide (CdS) films have been determined from the dc resistance of the material and are found to be sensitive to annealing. A reduction in the grain boundary potential and the grain boundary charge density of the film has been noticed when the source CdS film is annealed at different temperatures prior to chemical conversion. The variation in the grain boundary charge density of the grown Ag₂S film with source annealing temperature has been found to be similar to that of thin cadmium sulfide film, reported earlier. An additional low temperature heat treatment of the sample results in an enhancement in the charge density at the grain boundaries. The change in the silver vacancy and/or oxygen and sulfur content of the films as revealed from the energy dispersive spectra of the films suggests possible role of film composition on the grain boundary charge density.     

Electronic structure of substitutional defects and vacancies in GaSe

We have investigated the nature of defect states associated with substitutional impurities (Cd, In, Sn) and both Ga and Se vacancies in GaSe using ab initio electronic structure methods within density functional theory. These calculations were done using supercell model allowing for internal atomic relaxation. Binding energies (BEs) of defects obtained in this model are compared with effective mass approximation results. Significant central cell corrections are present for most of the defects. This is consistent with charge densities associated with the defect states that show clearly their strongly localized nature. Because of the difficulties associated with LDA/GGA in giving the correct band gap in semiconductors, we have only compared the acceptor BEs with available experiments. Our theoretical results agree well with the experiment for Cd_Ga and V_Ga. The fundamental role played by the Ga dimers in the formation of defect states is discussed.     

Electronic structure of a model grain boundary

We present a calculation of the electronic structure of a model symmetrical tilt (130) grain boundary in a f.c.c. metal. The local density of states for atoms at and near the boundary is evaluated for a tight-binding s-like Hamiltonian by the transfer matric method. Relaxation of the energy levels of the atoms near the boundary is introduced to preserve charge neutrality. A band of localized states is found above the Fermi level.     

Investigation of impurity levels in thin polycrystalline SmS films

Data obtained in the study of the behavior with temperature of the electrical resistance of thin polycrystalline SmS films (thickness ～0.5–0.8 μm) performed in the temperature region 4.2–440 K have been used to correct the band structure model of this material. It has been shown that the main impurity levels in thin polycrystalline SmS films are levels corresponding to localized states close to the conduction band bottom, as well as the impurity donor levels E _i which belong to Sm ions filling vacancies in the S sublattice. The tail of localized states has been found to extend up to the energy of impurity donor levels.     

Modelling of diffusion and conductivity relaxation of oxide ceramics

A two-dimensional square grain model has been applied to simulate simultaneously the diffusion process and relaxation of the dc conduction of polycrystalline oxide materials due to a sudden change of the oxygen partial pressure of the surrounding gas phase. The numerical calculations are performed by employing the finite element approach. The grains are squares of equal side length (average grain size) and the grain boundaries may consist of thin slabs of uniform thickness. An additional (space charge) layer adjacent to the grain boundary cores (thin slabs) either blocking (depletion layer) or highly conductive for electronic charge carriers may surround the grains. The electronic transport number of the mixed ionic-electronic conducting oxide ceramics may be close to unity (predominant electronic conduction). If the chemical diffusion coefficient of the neutral mobile component (oxygen) of the grain boundary core regions is assumed to be higher by many orders of magnitude than that in the bulk, the simulated relaxation curves for mass transport (diffusion) and dc conduction can deviate remarkably from each other. Deviations between the relaxation of mass transport and dc conduction are found in the case of considerably different electronic conductivities of grain boundary core regions, space charge layers, and bulk. On the contrary, the relaxation curves of mass transport and electronic conductivity are in perfect coincidence, when either effective medium diffusion occurs or the effective conductivity is unaffected by the individual conductivities of core regions and possible space charge layers, i.e. the grain boundary resistivity is negligible.     

Correlation between green luminescence and morphology evolution of ZnO films

Photoluminescence and atomic force microscopy have been used to characterize ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD) at varied growth pressures. The surface morphology with different grain structures has strong influence on the green photoluminescence of ZnO. When large discrete islands or structureless overgrowth cover the rough surface, broad green emissions around 500 nm go beyond the ultraviolet (UV) emission band; whereas, when the surface is packed closely with small grains, only weak green emission is observed with a red-shift to 528 nm. This variation of green emissions is ascribed to changes in the charge states of oxygen vacancies, which is strongly dependent on the surface morphology and grain structures. Based on the grain boundary defect model, two possible recombination processes for the green emission are proposed and discussed in detail. PACS 68.55.Jk; 78.55.Et; 81.05.Dz     

Magnetically tunable nonlinear current–voltage characteristics in oxygen deficient manganite perovskites

La_0.667Ca_0.333Mn_1−xM_xO_3−δ (M=Mg, Li or Re) exhibit insulating behaviour and nonlinear current–voltage (J–E) relationship with voltage-limiting characteristics at temperatures below the ferromagnetic transition (T_c). The high current region is set in at field strengths <60 V/cm. Nonlinearity exponent, α in the relation J=kE^α increases inversely with temperature. In presence of an external magnetic field, the J–E curves show higher current density at lower field strengths. Microstructural studies indicate that there is no segregation of secondary phases in the grain boundary regions. There is remarkable changes in ρ(T) as well as J–E curves with the grain size. Annealing studies in lower p_O2 atmospheres indicate that there is significant out-diffusion of oxygen ions through the grain boundary layer (GBL) regions creating oxygen vacancies in the GBL regions. The concentration of Mn⁴⁺ ions is lowered at the GBL due to oxygen vacancies, reducing the probability of hopping and resulting in insulating behaviour. Therefore an insulating barrier is introduced between two conducting grains and the carrier motion between the grains is inhibited. Thus below T_c, where sufficient increase in resistivity is observed the conduction may be arising as a result of spin dependent tunneling across the barrier. External electric field lowers the barrier height and establishes carrier transport across the barrier. Above certain field strength, barrier height diminishes significantly and thereby allowing large number of carriers for conduction, giving rise to highly nonlinear conductivity.     

Analysis of electro-active regions and conductivity of BaMnO3 ceramic by impedance spectroscopy

Polycrystalline BaMnO₃ ceramic powders were prepared using the conventional mixed oxide route accompanied with several milling processes. Single phase formation was verified by recording the X-ray diffraction pattern of the powder as well as sintered pellet at room temperature. Scanning electron micrograph and energy dispersive X-ray spectrum of cross-sectional view have shown that sintered pellet is highly porous and contains only Ba, Mn and O elements, respectively. Analysis of impedance spectroscopy was carried out via the complex impedance and complex modulus formalisms. These results have shown that BaMnO₃ behave as semiconducting material. Furthermore, as a consequence of electrically inhomogeneous nature of the sample, it was observed that the electroactive regions (such as grain, grain boundary and sample-electrode interface) are overlapped in the applied frequency domain with dominant grain boundary effect. An equivalent circuit model (R _g C _g)(R _gb Q _gb)(R _e Q _e) was employed to fit the temperature dependent impedance spectroscopy data. Study of grain and grain boundary conductivities suggest that grains are more conductive than grain boundaries and conduction mechanism followed correlated barrier hopping (CBH) model.     

Ab initio studies of isolated hydrogen vacancies in graphane

We present a density functional study of various hydrogen vacancies located on a single hexagonal ring of graphane (fully hydrogenated graphene) considering the effects of charge states and the position of the Fermi level. We find that uncharged vacancies that lead to a carbon sublattice balance are energetically favorable and are wide band gap systems just like pristine graphane. Vacancies that do create a sublattice imbalance introduce spin polarized states into the band gap, and exhibit a half-metallic behavior with a magnetic moment of 1.00 μ_B per vacancy. The results show the possibility of using vacancies in graphane for novel spin-based applications. When charging such vacancy configurations, the deep donor (+1/0) and deep acceptor (0/−1) transition levels within the band gap are noted. We also note a half-metallic to metallic transition and a significant reduction of the induced magnetic moment due to both negative and positive charge doping.     

Grain Boundary Diffusion and Mechanisms of Creep of Nanostructured Metals

Comparative investigations of diffusion in coarse-grained (d = 20 μm), nanocrystalline (d = 0.04 μm) and nanostructured nickel (d = 0.3 μm) have been carried out in a temperature interval of 0.2–0.3 melting temperature. The reasons for difference of parameters of copper grain-boundary diffusion in the above materials are discussed. The effect exerted by grain boundary state and grain boundary diffusion fluxes of impurity on creep mechanisms of nanostructured nickel and copper in the temperature interval of 373–473 K have been studied. Significant change in the apparent creep activation energy under copper grain boundary diffusion fluxes is described as a consequence of different contribution of grain boundary sliding to overall deformation.     

Effects of particle size on the structural and hyperfine properties of tin dioxide nanoparticles

In this work, we report on the study of SnO ₂ nanoparticles prepared by a polymer precursor method. X-ray diffraction (XRD) data analysis evidenced the formation of only the tetragonal rutile-type phase for the as-grown and thermally annealed samples. A mean grain size of about 11 nm for the as-prepared sample has been determined. This mean size increases after the thermal annealing and with the annealing temperature. The room temperature M?ssbauer spectra (MS) were well fitted using a quadrupole splitting (QS) distribution. The isomer shift (IS) tends to increase when the grain size decreases. That increase has been associated to the extra s-electron density generated by the oxygen vacancies.     

An extended read model for grain boundaries in GaAs

The space charging properties of grain boundaries in GaAs are discussed using an extended Read dislocation model. Model calculations for medium to high angle grain boundaries show: (1) the core-site occupational probability for a dislocation at the grain boundary is at least an order of magnitude lower than would be expected on the basis of simple Read theory; (2) due to the strong core-core interaction of the dislocations, the depletion width W decreases with an increase in tilt angle θ: and (3) W is approximately independent of θ in highly doped (N_D ? 10₁₇/cm³) material. Comparisons between model predictions and experimentally determined depletion widths of grain boundaries in GaAs are presented.     

Defect structure and transport properties of manganous sulphide

It has been shown that above 800 K manganous sulphide demonstrates a simple defect structure which can be described in terms of a point defect model. Over the major part of the phase field of MnS the predominant defects are doubly ionized cation vacancies and electron holes (Mn_1?yS) while near and at the Mn/MnS phase boundary doubly ionized interstitial cations and quasi-free electrons predominate (Mn_1+yS). In the intermediate range intrinsic ionic defects predominate at lower temperatures and intrinsic electronic disorder prevails at higher temperatures.     

Theoretical study of the critical current of YBa2Cu3O7−δ bicrystals with hole-deficient grain boundaries

We develop a theory of the critical current across grain boundaries in YBa₂Cu₃O_7−δ bicrystals. Experiments have shown that there is hole depletion near a boundary and the concentration profiles have been determined for specific cases. These results mean that the critical temperature is a function of distance from the boundary. Taking this function from experiment as input into the theory, we study two specific boundaries: a boundary with a 7° misorientation angle about [100] which is known to be strongly coupled for the purposes of current flow, and a 31° boundary which is known to be weakly coupled. Using Ginzburg-Landau theory, we determine the dependence of the critical current density (j_c) on temperature and the spatial dependence of the order parameter for these boundaries. The results show that the oxygen depletion can account for a major portion of the change from weak to strong coupling of boundaries as the misorientation angle is increased.     

Defect chemistry of grain boundaries in proton-conducting solid oxides

The defect chemistry of charged grain boundaries in an acceptor-doped oxide in equilibrium with water vapour is examined theoretically. The basis of the theoretical approach is that the formation of charged grain boundaries and attendant space-charge zones is governed by differences in the standard chemical potentials of oxygen vacancies and hydroxide ions between bulk and grain-boundary core, that is, by the thermodynamic driving energies for defect redistribution. A one-dimensional continuum treatment is used to predict the space-charge potential and defect concentrations in the grain-boundary core as a function of water partial pressure, temperature and acceptor dopant concentration for various values of the two thermodynamic driving energies. The results are discussed with respect to experimental data in the literature for acceptor-doped perovskite oxides (e.g. BaZrO₃) and fluorite oxides (e.g. CeO₂).     

ZnO薄膜微结构变化对光电特性的影响

使用脉冲激光淀积(PLD)技术在n型Si衬底上沉积氧化锌(ZnO)薄膜,在O2气氛下对样品进行了500℃(Sample1,S1),600℃(Sample2,S2),700℃(Sample3,S3)和800℃(Sample4,S4)退火,随后进行了X射线衍射(XRD)谱,椭偏光折射率,热激电流(TSC)和电容-电压(C-V)的测量。研究发现:S1中晶界的电子陷阱由高浓度的深能级杂质(Zni)提供的电子填充,该能级位于ET=EC-0.24±0.08eV。S3中出现与中性施主(D0)有关的深能级中心,其ET=EC-0.13±0.03eV,推测D0的出现与高温氧气条件退火下晶界处形成的复合体缺陷有关。XRD和椭偏光折射率测量结果表明:氧气对ZnO薄膜微结构的修饰是改变ZnO/Si结构光电特性的主要因素。