Vol 58, No 3 (2016)

Theoretical studies of defect formation in semiconductor silicon play an important role in the creation of breakthrough ideas for next-generation technologies. A brief comparative analysis of modern theoretical approaches to the description of interaction of point defects and formation of the initial defect structure of dislocation-free silicon single crystals has been carried out. Foundations of the diffusion model of the formation of structural imperfections during the silicon growth have been presented. It has been shown that the diffusion model is based on high-temperature precipitation of impurities. The model of high-temperature precipitation of impurities describes processes of nucleation, growth, and coalescence of impurities during cooling of a crystal from 1683 to 300 K. It has been demonstrated that the diffusion model of defect formation provides a unified approach to the formation of a defect structure beginning with the crystal growth to the production of devices. The possibilities of using the diffusion model of defect formation for other semiconductor crystals and metals have been discussed. It has been shown that the diffusion model of defect formation is a platform for multifunctional solution of many key problems in modern solid state physics. Fundamentals of practical application of the diffusion model for engineering of defects in crystals with modern information technologies have been considered. An algorithm has been proposed for the calculation and analysis of a defect structure of crystals.

Evolution of the electronic structure of the NpMGa₅ (M = Fe, Co, Ni) series of neptunium compounds, whose crystal structure is similar to that of the known family of Pu115 superconductors, was studied by the LDA + U + SO method. The calculations took into account both the strong electron correlations and the spin‒orbit coupling in the 5f shell of neptunium. For the first time, the electronic structure was calculated for a hypothetical series of compounds in which gallium is replaced with indium. Parameters of the crystal structure of the given series were obtained using the relationship between the parameters of the crystal structure of the earlier-studied compounds PuCoGa₅ and PuCoIn₅. The analysis of the electronic structure and characteristics of neptunium ions calculated in the framework of the LDA + U + SO method showed that the neptunium ions in NpMIn₅ with M = Fe, Co, and Ni should have an electron configuration closer to f⁴, but a spin and magnetic characteristics close to those in NpMGa₅.

The local crystal structure of superconducting powders of iron chalcogenides FeTe_xSe_1–x (x = 0.1, 0.22, 0.49, 0.8, 0.9) prepared by dry synthesis (without mineralizer) has been studied by EXAFS spectroscopy above the K Se and K Fe absorption edges in the temperature range of 80–300 K. The dependences of Se–Fe, Fe–Te, and Fe–Fe interatomic bond lengths and degrees of their local disordering (Debye–Waller factors) on the tellurium content and temperature have been obtained. Einstein temperatures characterizing the stiffness of each bond have been determined. The correlation of the Se–Fe bond stiffness with the dependence of the critical temperature of the superconducting transition T_c on the composition of the samples under study have been established, which indicates the specific role of the Se–Fe bond in the superconducting state formation in iron chalcogenides FeTe_xSe_1–x.

In this work, we consider an alternative implementation of the band structure unfolding method within the framework of the density functional theory, which combines the advantages of the basis of localized functions and plane waves. This approach has been used to analyze the electronic structure of the ordered CuCl_xBr_1–x copper halide alloys and F⁰ center in MgO that enables us to reveal qualitatively the features remaining hidden when using the standard supercell method, because of the complex band structure of systems with defects.

The effect of codoping of hydroxyapatite (HAP) nanocrystals with average sizes of 35 ± 15 nm during “wet” synthesis by CO₃²⁻ carbonate anions and Mn²⁺ cations on relaxation characteristics (for the times of electron spin–spin relaxation) of the NO₃²⁻ nitrate radical anion has been studied. By the example of HAP, it has been demonstrated that the electron paramagnetic resonance (EPR) is an efficient method for studying anion–cation (co)doping of nanoscale particles. It has been shown experimentally and by quantummechanical calculations that simultaneous introduction of several ions can be energetically more favorable than their separate inclusion. Possible codoping models have been proposed, and their energy parameters have been calculated.

The temperature dependence of the molar heat capacity of HoMnO₃ has been measured by differential scanning calorimetry. The experimental data have been used to calculate the thermodynamic properties of the oxide compound (changes in the enthalpy H°(T)–H°(364 K), entropy S°(T)–S°(364 K), and reduced Gibbs energy Φ°(T)). The data on the heat capacity of HoMnO₃ have been generalized in the range of 40–1000 K.

A three-dimensional computer simulation of dynamic processes occurring in a domain wall moving in a soft-magnetic uniaxial film with in-plane anisotropy has been performed based on the micromagnetic approach. It has been shown that the domain wall motion is accompanied by topological transformations of the magnetization distribution, or, more specifically, by “fast” processes associated with the creation and annihilation of vortices, antivortices, and singular (Bloch) points. The method used for visualizing the topological structure of magnetization distributions is based on the numerical determination of topological charges of two types by means of the integration over the contours and surfaces with variable geometry. The obtained data indicate that the choice of the initial configuration predetermines the dynamic scenario of topological transformations.

It has been shown that the magnetostatic interaction in an inhomogeneous medium leads to the removal of the chiral degeneracy of magnetic distributions. Noncollinear states of two magnetic dipoles and a helical cycloid placed over a superconducting half-space have been considered as examples. The influence of a finite penetration depth of the magnetic field on the efficiency of removal of the chiral degeneracy has been studied in the framework of the London approximation.

It has been found that temperature dependences of the saturation magnetization of sintered hard magnetic (Pr,Dy,M)₂(Fe,Co)₁₄B (M = Gd, Sm, Nd) alloys demonstrate an increase at a temperature lower than a critical temperature (150 K for Sm and Nd and 70 K for Gd). An additive of copper does not influence the critical temperature. It has been assumed that there is a low-temperature phase in which cobalt is replaced with boron that diffuses from the (Pr,Dy,Gd)(Fe,Co)₄B phase to the near-surface region of grains of the main magnetic (Pr,Dy,Gd)₂(Fe,Co)₁₄B phase.

Magnetic nanoparticles of magnetite Fe₃O₄ and Fe synthesized by physical vapor deposition with a fast highly effective method using a solar energy have been studied. Targets have been prepared from tablets pressed from Fe₃O₄ or Fe powders. Relationships between the structure of nanoparticles and their magnetic properties have been investigated in order to understand principles of the control of the parameters of magnetic nanoparticles. Mössbauer investigations have revealed that the nanoparticles synthesized from tablets of both pure iron and Fe₃O₄ consist of two phases: pure iron and iron oxides (γ-Fe₂O₃ and Fe₃O₄). The high iron oxidability suggests that the synthesized nanoparticles have a core/shell structure, where the core is pure iron and the shell is an oxidized iron layer. Magnetite nanoparticles synthesized at a pressure of 80 Torr have the best parameters for hyperthermia due to their core/shell structure and core-to-shell volume ratio.

A qualitative assessment of axial vector Γ_z in invariant P_z(McurlM)Γ_z proposed earlier for the description of the thermodynamic potential of a CaMn₇O₁₂ multiferroic material with electric polarization P_z along the z axis of the helix of magnetic moments M has been performed based on the fan-shaped structure of the atomic cell of the crystal. The dependence of Γ_z on the permanent dipole moment of MnO₆ octahedra (rhombohedra), which are inevitably distorted in the paraelectric phase due to the structural transformation, on the mechanical stiffness of the crystal lattice, and on the projected area of the cross section of rhombohedra with bevels undergoing a shift has been determined from dimensional considerations. It has been demonstrated how these factors contribute to the twist of rhombohedra.

Microdeformations of the crystal lattices in the phombohedral and tetragonal regions of the PbZr_1–xTi_xO₃ phase diagram have been calculated and their dependences on the titanium concentration have been constructed. Based on an analysis of these dependences, it has been concluded that tetragonal-phase clusters form in the range 0.11< x < 0.12 and rhombohedral-phase clusters form in the range 0.725 < x < 0.750.

The polarization and depolarization processes in a LiF crystal during indentation after exposure to a dc magnetic field (B = 0.9 T, t = 30 min) have been studied. It has been shown that the potential difference appearing due to movement of charged dislocations in the exposed crystal increases more than two-fold as compared to the initial sample, and the subsequent charge equilibrium in the samples is established approximately 1.5 times faster. These developments demonstrate significant increase in the concentration of free cation vacancies due to action of a magnetic field.

A new micromechanism of nucleating deformation twins in nanocrystalline and ultrafine-grained materials under action of severe mechanical stresses has been proposed and theoretically described. The mechanism is a subsequent splitting of grain-boundary dislocations into lattice partial and sessile grain-boundary dislocations. Ensembles of gliding partial dislocation forms deformation twins. The energy characteristics of this process are calculated. The nucleation of the twins is shown to be energetically profitable and can be athermic (without an energy barrier) under conditions of severe mechanical stress. The dependence of a critical stress at which the barrier-less nucleation of twins took place on the widths of these twins is calculated.

The structure, IR absorption spectra, morphology, and spectral characteristics of compounds Lu_{1 – x – y}Ce_xTb_yBO₃ have been investigated. It has been shown that the Tb³⁺ luminescence excitation spectrum of the Lu_{1 – x – y}Ce_xTb_yBO₃ compounds is dominated by a broad band coinciding with the excitation band of Ce³⁺ ions, which clearly indicates energy transfer from the Ce³⁺ ions to the Tb³⁺ ions. The spectral position of this band depends on the structural state of the sample: in the structures of calcite and vaterite, the band has maxima at ~339 and ~367 nm, respectively. By varying the ratio between the calcite and vaterite phases in the sample, it is possible to purposefully change the Tb³⁺ luminescence excitation spectrum, which is important for the optimization of the spectral characteristics of Lu_{1 – x – y}Ce_xTb_yBO₃ when it is used in light-emitting diode sources. An estimate has been obtained for the maximum distance between Ce³⁺ and Tb³⁺ ions, which corresponds to electronic excitation energy transfer. It has been shown that the high intensity of Tb³⁺ luminescence in these compounds is due to the high efficiency of electronic excitation energy transfer from the Ce³⁺ ions to the Tb³⁺ ions as a result of the dipole–dipole interaction.

Halloysite nanotube composites covered by silver nanoparticles with the average diameters of 5 nm and 9 nm have been studied by methods of optical spectroscopy of reflectance/transmittance and Raman spectroscopy. It has been established that silver significantly increases the light absorption by nanocomposites in the range of 300 to 700 nm with a maximum near 400 nm, especially for the samples with the nanoparticle size of 9 nm, which is explained by plasmonic effects. The optical absorption increases also in the long-wavelength spectral range, which seems to be due to the localized electronic states in an alumosilicate halloysite matrix after deposition of nanoparticles. Raman spectra of nanocomposites reveal intense scattering peaks at the local phonons, whose intensities are maxima for the samples with the silver nanoparticle sizes of 9 nm, which can be caused by plasmonic enhancement of the light scattering efficiency. The results show the ability to use halloysite nanotube nanocomposites in photonics and biomedicine.

The electrical conductivity of V_{1 – x}Nb_xO₂ single crystals have been investigated over a wide temperature range covering regions of the existence of the metallic and insulating phases. It has been shown that, with an increase in the niobium concentration, the electrical conductivity of the metallic phase becomes below the Mott limit for the minimum metallic conductivity. Immediately after the metal–insulator transition, the electrical conductivity is determined by a large amount of free electrons that gradually localized with a decrease in the temperature. The temperature dependence of the electrical conductivity in the insulating phase of V_{1 – x}Nb_xO₂ has been explained in the framework of the hopping conductivity model that takes into account the effect of thermal vibrations of atoms on the resonance integral.

The steady-state energy distribution of thermal vibrations at a given ambient temperature has been investigated based on a simple mathematical model that takes into account central and noncentral interactions between carbon atoms in a one-dimensional carbyne chain. The investigation has been performed using standard asymptotic methods of nonlinear dynamics in terms of the classical mechanics. In the first-order nonlinear approximation, there have been revealed resonant wave triads that are formed at a typical nonlinearity of the system under phase matching conditions. Each resonant triad consists of one longitudinal and two transverse vibration modes. In the general case, the chain is characterized by a superposition of similar resonant triplets of different spectral scales. It has been found that the energy equipartition of nonlinear stationary waves in the carbyne chain at a given temperature completely obeys the standard Rayleigh–Jeans law due to the proportional amplitude dispersion. The possibility of spontaneous formation of three-frequency envelope solitons in carbyne has been demonstrated. Heat in the form of such solitons can propagate in a chain of carbon atoms without diffusion, like localized waves.

Temperature dependences of the galvanomagnetic properties of films of bismuth and Bi_{100 – x}Sb_x (x ≤ 12) on substrates with different temperature expansion coefficients were studied in the temperature range of 77–300 K. The block films were prepared through thermal deposition, and single-crystal Bi_{100 – x}Sb_x were grown by zone recrystallization under a coating. It was found that the temperature expansion coefficient of a substrate substantially influenced the galvanomagnetic properties of Bi and Bi_{100 – x}Sb_x films. Using the experimental data, the change in the charge-carrier concentration in the Bi and Bi_{100 – x}Sb_x films on different substrates at 77 K was estimated.

The methods of the density functional theory were used for the first time for the simulation of discrete breathers in graphene. It is demonstrated that breathers can exist with frequencies lying in the gap of the phonon spectrum, induced by uniaxial tension of a monolayer graphene sheet in the “zigzag” direction (axis X), polarized in the “armchair” direction (axis Y). The found gap breathers are highly localized dynamic objects, the core of which is formed by two adjacent carbon atoms located on the Y axis. The atoms surrounding the core vibrate at much lower amplitudes along both the axes (X and Y). The dependence of the frequency of these breathers on amplitude is found, which shows a soft type of nonlinearity. No breathers of this type were detected in the gap induced by stretching along the Y axis. It is shown that the breather vibrations may be approximated by the Morse oscillators, the parameters of which are determined from ab initio calculations. The results are of fundamental importance, as molecular dynamics calculations based on empirical potentials cannot serve as a reliable proof of the existence of breathers in crystals.