The evolution of the nanoscale dissipative structures in a distribution of defects within the isothermally irradiated f.c.c. crystal

A kinetic model for the influence of external noises such as fluctuations of the vacancies’ generation rate and inhomogeneity of irradiated f.c.c. crystal on the formation of nanoscale modulated dissipative structure in a spatial distribution of vacancies is considered. The generation rate of vacancies all over the sites and a density of their dislocation-type sinks are modelled as independent random uniform stationary fields and with certain defined parameters of fluctuation correlations – spatial and temporal ones. Such stochastic fields can induce a spatial redistribution of vacancies that can lead to their density stationary uniform field or stochastic one. By the average value and correlation functions of these fluctuations, the conditions are determined for interacting fluctuations of the vacancies’ density, under which this homogeneous random field becomes unstable in relation to the stochastic field with a spatially periodic mean distribution of vacancies’ density. For instance, with f.c.c. nickel as a model of the irradiated functional material, the temperature dependence of spatial period d(T) of the modulated dissipative structure of vacancies’ subsystem in f.c.c. crystal is numerically forecasted and analysed, taking into account the total (‘electrochemical’?+?‘strain-induced’) interaction between vacancies. Such d(T)-dependence is also determined by the kinetic characteristics of vacancies’ redistribution.     

The dissipative modulated structures in a distribution of interacting vacancies in the elastically anisotropic body-centred cubic crystals under an isothermal irradiation

ABSTRACT

Dissipative mechanism of formation of a modulated structure of vacancies in a body-centred cubic (b.c.c.) crystal is considered as its intrinsic property under an isothermal irradiation irrespectively of elastic-anisotropy factor sign. Conditions of self-organisation of a precursor of formation of a ‘superlattice’ of nanovoids, namely, the modulated structure in a spatial distribution of the diffusing vacancies generated by irradiation, because of the instability of their homogeneous distribution as a result of interaction between them in a b.c.c. host crystal under irradiation, are analysed. As shown for the first time, the ‘cohesive’ and ‘elastic’ couplings between interacting (and diffusing) vacancies have a crucial role in a pattern-selection process accordingly with different (positive or negative) elastic-anisotropy factors.     

多铁性钙钛矿薄膜的氧空位调控研究进展

精确调控ABO_3钙钛矿结构中氧空位的位置与浓度已被证明可调控多铁性薄膜的不同物理性质,包括输运特性、光学特性和多铁性质等.本文回顾了多种典型的多铁性材料,从氧空位形成机理、氧八面体结构、应变-氧空位关系和具体物性调控效应(多铁、超导和电化学性能)等角度介绍了该体系中氧空位调控效应.同时依托氧空位调控的最新研究进展,尤其是对氧空位调控单相材料多铁性质方面工作的分析,为探索新型磁电功能性材料与器件提供了重要参考.     

S空位调节扶手型二硫化钼纳米带的电子性质

二硫化钼纳米带按边界结构特征可分为锯齿型和扶手型,在制备过程中,不可避免地会存在一定的缺陷,其中硫空位(VS)最为常见,它将改变纳米结构,进而影响其电子性质。本文采用密度泛函理论来研究S空位对扶手型二硫化钼纳米带性质的影响。计算结果表明：纯扶手型二硫化钼纳米带（AMoS2NRs）为非磁性半导体,但其物性受S空位的位置及浓度所调制。当S空位出现在纳米带内部时,其性质不变。但当S空位在纳米带边缘时,AMoS2NRs被调节成半金属;并随着S空位的浓度的增加,其物性从半金属转变为稀磁半导体。这一有趣的发现将使得低维MoS2纳米材料在自旋电子学上有更宽广的应用。     

Mott transition in modulated lattices and parent insulator of (K,Tl)(y)Fe(x)Se(2) superconductors

The degree of electron correlations remains a central issue in the iron-based superconductors. The parent iron pnictides are antiferromagnetic, and their bad-metal behavior has been interpreted in terms of proximity to a Mott transition. We study such a transition in multiorbital models on modulated lattices containing an ordered pattern of iron vacancies, using a slave-rotor method. We show that the ordered vacancies lead to a band narrowing, which pushes the system to the Mott insulator side. This effect is proposed to underlie the insulating behavior observed in the parent compounds of the newly discovered (K,Tl)(y)Fe(x)Se(2) superconductors.     

Twelve-fold quasicrystal and its approximant of Ta62Te38 interpreted as modulated crystals

A transmission electron microscopy study reveals that the twelve-fold quasicrystal and its approximant in Ta62Te38 are crystals subjected to the structure modulation. It is composed of two modulated layers rotated by 30 degrees (or 90 degrees) to each other about their normal. Structures of the twelve-fold quasicrystal and its approximant can be related by modulation waves with the same directions but with slightly different wavelengths. The modulation is considered to be due to the rearrangement of atomic vacancies as a response to the occurrence of charge density waves.     

Structure and physical properties of layered double perovskite NdBaCo2O5.50 + δ (δ ≈ 0.25)

Magnetic, electric, and elastic properties of the crystal and magnetic structure of double layered perovskite NdBaCo₂O_{5.50 + δ} are studied by the neutron diffraction method at various temperatures. The data are analyzed using two models of crystal structure. In the first model, the sample consists of two crystal-structure phases with ordered and disordered arrangements of oxygen vacancies. In the second model, a new crystal-structure phase is formed in this compound, which is characterized by ordering of oxygen vacancies in the plane of the rare-earth ion in the 1c crystallographic position (0, 0, 1/2) of space group Pmmm. Two crystal-structure models correspond to different types of magnetic ordering (a mixture of a ferromagnetic phase and a G-type antiferromagnetic phase is presumed in the two-phase crystal-structure model, while a canted antiferromagnetic structure is presumed in the one-phase crystal structure model). The behavior of electric and elastic parameters is better described in the first model, while neutron diffraction studies are in better agreement with the second model.     

Phase field simulation of spinodal decomposition under external magnetic field

A computational model was developed to simulate the spinodal decomposition process of ferromagnetic alloys under an external magnetic field. In this model, the temporal evolution of the modulated structure was described by a phase field method, and the magnetic configuration was solved by using a micromagnetic method. The spinodal decomposition and coarsening processes of a single magnetic particle and an A-B hypothetical system under an external magnetic field were simulated using the proposed model. The simulation results show that the precipitated particles were elongated along the direction of the external magnetic field. The dependence of the modulated structure of an A-B hypothetic system on external magnetic field is much more sensitive than that of the single particle structure. The simulation results also demonstrate that the modulation of the external magnetic field is effective even if the spinodal decomposition has been completed and a stable modulated structure was formed.     

Study of the surface segregation of carbon vacancies in TiCx

Density functional theory (DFT) calculations have been performed to study the surface segregation of carbon vacancies in TiC_x in this work. The results confirm that the vacancies in the surface have the smaller formation energy and less effect on the electronic structure of TiC_x than those in the bulk, which indicates that the carbon vacancies in TiC_x prefer to segregate on the surface. It is also found that energy barriers for the migration of the vacancies are dependent on their locations, and the deeper the location of vacancies is in the bulk, the higher is the diffusion energy barrier needed.     

Defect structure of β-LiAl

Lattice parameter and density measurements have been made on a series of Li-Al alloys extending over the LiAl β-phase. The lattice parameter of the slowly cooled β-phase alloys varied almost linearly with composition within the phase field. Theoretical density calculations for several single-defect models from lattice parameter data did not yield a good fit with the experimental density data. Rather, a model based on the coexistence of two types of defects, namely, vacancies in the lithium sublattice and lithium antistructure atoms in the aluminum sublattice, characterized the defect structure. Calculated concentrations of these defects varied with departure from stoichiometry and showed good agreement with the concentration of lithium vacancies estimated from NMR measurements. Compositional dependence of the vacancy concentration and the lithium diffusion coefficient produced a good correlation and strongly suggested that the lithium atoms diffuse via a vacancy mechanism. It is hypothesized that the defect structure of this compound may be related to the electronic structure of this so-called NaTl phase.     

Microscopic description of an Ising spin glass near the percolation threshold

Monte Carlo results using a microscopic model to describe FexZn(1-x)F2 indicate that its spin-glass phase at x=0.25 and zero magnetic field is characterized by the presence of antiferromagnetic fractal domains, separated by random vacancies and strongly correlated in time. The effective local random-field distribution corroborates this glassy behavior, which emerges irrespective of ab initio competing interactions and is a consequence of the fractal domain structure near the percolation threshold, x(p)=0.24. The aging properties of the system are in agreement with predictions of short-range stochastic spin-glass models and with the droplets model for spin glass close to percolation.     

Electronic structure and XPS spectra for the stoichiometric and substoichiometric Hf monocarbide-nitride system

We present results of electronic structure calculations for stoichiometric and substoichiometric HfC_xN_1-x (for x=0, 0.42, 0.6 and 1) obtained with the relativistic Korringa-Kohn-Rostocker Greens function (RKKR-GF) method. The mixed crystal and the finite concentrations of vacancies are treated within the coherent potential approximation (CPA), of which athree component version is needed to treat both chemical disorder and vacancies on the anion sublattice. We calculate X-ray photoemission intensities for all cases and find that, provided vacancies are taken into account, they agree rather well with experiment. We find that the densities of states at the Fermi level are but little affected by the presence of vacancies and briefly discuss the implications for the superconductivity in this series of compounds.     

Phase Transitions of a Dilute O(n) Model

We investigate tricritical behavior of the O(n) model in two dimensions by means of transfer-matrix and finite-size scaling methods. For this purpose we consider an O(n) symmetric spin model on the honeycomb lattice with vacancies; the tricritical behavior is associated with the percolation threshold of the vacancies. The vacancies are represented by face variables on the elementary hexagons of the lattice. We apply a mapping of the spin degrees of freedom model on a non-intersecting-loop model, in which the number n of spin components assumes the role of a continuously variable parameter. This loop model serves as a suitable basis for the construction of the transfer matrix. Our results reveal the existence of a tricritical line, parametrized by n, which connects the known universality classes of the tricritical Ising model and the theta point describing the collapse of a polymer. On the other side of the Ising point, the tricritical line extends to the n=2 point describing a tricritical O(2) model.     

Computational simulation of δ-Bi2O3. II. Charge migration

The fluorite phase of Bi₂O₃ has an extremely high ionic conductivity and although this is connected with the 75% average occupancy of the oxygen sites it is not due solely to isolated jumps of oxygen vacancies. Static lattice simulations depend on the existence of a structure based on a periodic lattice and it was shown in paper I that the Sillén structure, which involves a <111> superlattice of vacancies, is a satisfactory model for δ-Bi₂O₃. However, the Sillén structure is highly defective and includes a large number of <110> defects. Near-perfect Sillén domains, separated by changed boundaries, are shown not to have a particularly low energy, so that a domain mechanism of charge transport is unlikely. Instead, the charged defects in δ-Bi₂O₃ are vacancies and pseudo-interstitials (that is oxygen ions occupying normally-vacant sites in the <111> superlattice) associated with <110> defect chains. It is proposed that these defects have a high mobility due to two mechanisms of charge transport. One of these involves the transfer of charge carriers between collinear <110> defects; the other depends on the delocalization of charge that accompanies the addition of a vacancy or a pseudo-interstitial to a chain of <110> defects and is thus quite analogous to the mechanism of proton conduction in water.     

Possible path to a new class of ferromagnetic and half-metallic ferromagnetic materials

We introduce a path to a possibly new class of magnetic materials whose properties are determined entirely by the presence of a low concentration of specific point defects. Using model Hamiltonian and ab initio band structure methods we demonstrate that even large band gap nonmagnetic materials as simple as CaO with a small concentration of Ca vacancies can exhibit extraordinary properties. We show that such defects will initially bind the introduced charge carriers at neighboring sites and depending on the internal symmetry of the clusters so formed, will exhibit "local" magnetic moments which for concentrations as low as 3% transform this nonmagnetic insulator into a half-metallic ferromagnet.     

Analysis of vacancies produced at non-equilibrium concentrations by interdiffusion

In this paper, we address the fundamental problem of chemical interdiffusion in binary alloys for the case where vacancies at non-equilibrium concentrations may be generated during the interdiffusion process. We take a very general phenomenological approach to interdiffusion but develop it in a new way. Both high vacancy and low vacancy concentrations are dealt with. For the commonly encountered small vacancy concentration case our strategy centres on directing the information about the driving force associated with the non-equilibrium vacancies (which is effectively not measurable) onto the velocity of inert marker(s) in the diffusion zone. Assuming access to independent knowledge of the two tracer diffusivities we derive expressions for the transport coefficient (for the case of non-equilibrium vacancies) using an analysis along Boltzmann–Matano lines. Using the random alloy model we show that in principle it is possible to measure the relative concentration of non-equilibrium vacancies produced during interdiffusion.     

Structure of the magnetic-field-induced modulated phase of an α-Fe2O3: Ga single crystal

The field and orientational dependences of magnetic linear birefringence in α-Fe₂O₃: Ga single crystals are investigated. The experimental results make it possible to refine and specify the structure and reveal the features of technical magnetization of the modulated magnetic phase of this weak ferromagnet. It is shown that the model of the modulated magnetic structure used in this study adequately describes the experimental situation.     

Applications of the CPA to elemental tetrahedrally bonded amorphous semiconductors

It is pointed out that the CPA can easily be coupled with multiband, nearest-neighbor tight-binding Bethe-lattice Hamiltonians to fruitfully study the electronic structure of tetrahedrally bonded elemental amorphous semiconductors. Results are presented which illustrate the effects on the model semiconducting gap of (i) a rectangular distribution of site diagonal terms in the Hamiltonian, and (ii) vacancies distributed randomly over the lattice. The relationship of these results to experiment is briefly explored.     

Competition between ferromagnetic and anti-ferromagnetic couplings in Co doped ZnO with vacancies and Ga co-dopants

Spin-polarized first-principles electronic structure and total energy calculations have been performed to better understand the magnetic properties of Co doped ZnO (ZnO:Co) with vacancies and Ga co-dopants. The paramagnetic state of ZnO:Co, in which Co ions lose their magnetic moments, has been found to be unstable. The total energy results show that acceptor-like Zn vacancies and donor-like Ga co-dopants render the anti-ferromagnetic (AFM) and ferromagnetic (FM) states to be more favorable, respectively. With O vacancies, ZnO:Co has been found to be in the weak FM state. These magnetic properties can be understood by the calculated O- and Zn-vacancies and Ga co-dopant induced changes of the electronic structure, which suggest that AFM and FM Co-Co couplings are mediated by O 2p-Co majority (↑)-spin 3d hybridized states in the valence band of ZnO and O-vacancy-derived p states or Ga sp states in the ZnO band gap, respectively. For ZnO:Co with Zn vacancies (Ga co-dopants) the AFM (FM) coupling outweighs the FM (AFM) coupling and results in the AFM (FM) state, while for ZnO:Co with O vacancies, both the FM and AFM couplings are enhanced by similar degrees and result in the weak FM state. This study reveals a competition between FM and AFM couplings in ZnO:Co with vacancies and Ga co-dopants, the detailed balancing between which determines the magnetic properties of these materials.