Interaction élastique de défauts ponctuels dans un cristal hexagonal semi-infini avec ou sans adsorbat

The energy of elastic interaction between a point defect and the (0001) surface of a hexagonal crystal is calculated, as well as the energy of the elastic interaction between two defects near such a surface. The defects are represented by the superposition of three mutually perpendicular double forces without moment. The calculation is done by means of a Green function method. As for an isotropic medium, the energy of a point defect presents a variation in x₃^?3 with the distance x₃ to the surface. On the other hand, the mutual interaction between two defects depends upon different geometric parameters, and not simply on an image factor. We also study the effect of a thin adlayer on these elastic interactions. This is done by showing that the presence of the adlayer is equivalent to effective boundary conditions at the surface of the substrate. We derive these conditions and then the elastic energies to the first order in the thickness h of the layer. Finally we present the mean square displacements of atoms in the presence of a clean or adsorbed surface.     

Ultraviolet-visible spectroscopic characterization of lanthanum beryllate crystals doped with Er,Nd, or Pr ions

Spectroscopic characterization of lanthanum beryllate La₂Be₂O₅ (BLO) single crystals doped with trivalent ions of Eu, Nd or Pr, was carried out in the ultraviolet-visible spectral range using synchrotron radiation spectroscopy in combination with conventional optical absorption and luminescence spectroscopy techniques. On the basis of the obtained data, the energy level diagram for these trivalent impurity ions in BLO host lattice was developed; the optical and electronic properties of the crystals were determined; the possibility of the 4f-4f, 4f-5d and charge transfer transitions was analyzed; spectroscopic properties of the lattice defects formed during the introduction of trivalent impurity ions in the BLO host lattice, were investigated. We found that the lattice defects are responsible for a wide-band photoluminescence (PL) in the energy region of 400–600 nm. The most efficient excitation of the defect photoluminescence in the energy gap of BLO occurs in broad PL excitation-bands at 270 and 240 nm. The PL intensity of defects depends on the type of impurity ion and increases in the sequence: Pr-Nd-Er.     

Energy spectrum of electron trapping centers in CuInAsS<Subscript>3</Subscript>

This paper presents the results of the investigation of the energy spectrum of electronic states due to trapping centers, the role of which in CuInAsS₃ is played by lattice defects. The results of the analysis of the thermally stimulated current curves of CuInAsS₃ demonstrate that the energy spectrum of trapping centers is localized under the bottom of the conduction band in the energy range E _C–(0.14–0.35) eV.     

Crystalline and magnetic structures of La1−x BixMnO3+δ manganites

The crystalline and magnetic structures and magnetic properties of La_1?x Bi_xMnO_3+δ (0.4 ≤ x ≤ 0.6, 0 ≤ δ ≤ 0.06) manganites have been studied. The solid solutions having the stoichiometric oxygen content are shown to be orbitally ordered A-type antiferromagnets. An increase in the oxygen content above the stoichiometric value is found to cause Mn⁴⁺ ions in the perovskite lattice, to remove the cooperative Jahn-Teller distortions, and to form a long-range ferromagnetic order. This order becomes broken as the concentration of the tetravalent manganese ions increases further. The tendency toward breaking the ferromagnetic order increases with the bismuth content. The magnetic properties are interpreted in terms of superexchange interactions on the assumption of local lattice distortions induced by anisotropy of the 6s ²(Bi³⁺)-2p ⁶(O^2?) chemical bonds.     

Luminescence of LaBr3: Ce,Hf crystals under photon excitation in the ultraviolet,vacuum ultraviolet,and X-ray ranges

This study has been carried out using synchrotron radiation, time-resolved luminescence ultraviolet and vacuum ultraviolet spectroscopy, optical absorption spectroscopy, and thermal activation spectroscopy. It has been found that, in scintillation spectrometric crystals LaBr₃: Ce,Hf characterized by a low hygroscopicity, along with Ce³⁺ centers in regular lattice sites, there are Ce³⁺ centers located in the vicinity of the defects of the crystal structure. It has also been found that the studied crystals exhibit photoluminescence (PL) of new point defects responsible for a broad band at wavelengths of 500–600 nm in the PL spectra. The minimum energy of interband transitions in LaBr₃ is estimated as E _g ～ 6.2 eV. The effect of multiplication of electronic excitations has been observed in the range of PL excitation energies higher than 13 eV (more than 2E _g ). Thermal activation studies have revealed channels of electronic excitation energy transfer to Ce³⁺ impurity centers.     

Electronic structures and optical properties of rutile TiO2 with different point defects from DFT + U calculations

The electronic states and formation energies of four types of lattice point defects in rutile TiO₂ are studied using the first-principles calculations. The existence of oxygen vacancy leads to a deep donor defect level in the forbidden band, while the Ti interstitial forms two local states. It is predicted that oxygen vacancy prefers to combine with Ti-interstitial to form V_O–Ti_i dimer by a partial 3d electron transfer from the Ti_i to its neighboring V_O. The charge distribution between a Ti interstitial and its neighboring Ti ions partially shields the Coulomb interactions. Lastly, optical properties of these defective lattices are discussed.     

Deformation-assisted pairing in solid 3He: A conjecture

We suggest an interpretation of the magnetic transition in solid ³He at T_N = 1 mK, based on the self-consistent nature of the exchange operator. Our hypothesis is that the relevant excitations are localized magnetic pair defects trapped in a lattice deformation. The transition then appears rather similar to a metal-insulator phase transition. An activation energy of the order of a typical exchange frequency agrees semi-quantitatively with the characteristic features of the transition.     

Cooper pair and electron-hole pair instabilities in a quasi-one dimensional system

We calculate for an almost half-filled tight-binding band, the mean field ground state energy differences between the charge-density-wave (CDW) and BCS paired states for a truncated model Hamiltonian with zero-range instantaneous electron-electron interactions. The CDW pairing is found to be always unstable vis-à-vis BCS for a static lattice distortion of wave vector Q = (2k_F, π, π).     

Crystal field and microscopic spin Hamiltonians approach including spin-spin and spin-other-orbit interactions for d and d ions at low symmetry C3 symmetry sites: V in Al2O3

A new module has been developed within the CFA/MSH computer package, which is applicable for d² and d⁸ ions at sites of trigonal symmetry type I (C_3v,D₃,D_3d) and type II (C₃,C_3i), including the ‘imaginary’ CF term. For the first time the spin-spin (SS) and spin-other-orbit (SOO) interactions have also been included in the Hamiltonian. This module enables to study the contributions to the energy levels and the spin Hamiltonian parameters, i.e. zero-field splitting D and g-factors: g_∥ and g_⊥. The contributions arising from the spin-orbit (SO), SS, and SOO interaction as well as those due to the low symmetry CF effects induced by the distortion angle ?, which describes the difference between C₃ and C_3v symmetry, can be studied. As an application of the new module, calculations have been carried out for V³⁺(3d²) ions in α-Al₂O₃ crystal, taking into account for the first time the SS and SOO interactions, and the low symmetry CF effects. The results show that (i) the contributions from the SS and SOO interactions to the energy levels are larger for free V³⁺ ions than those for V³⁺ ions in α-Al₂O₃ crystal, (ii) both the contributions to the SH parameters and the energy levels arising from the SOO interaction are larger than those arising from the SS interaction, (iii) the contributions due to the low symmetry CF effects induced by the distortion angle ? are in general significant, (iv) D and g_⊥ are sensitive to the distortion angle ?, whereas g_∥ is insensitive to ?, and (v) the influence of the lattice distortions on the spectroscopic properties of V³⁺ ion in α-Al₂O₃ is pronounced. It appears important for similar ion-crystal cases to consider the lattice distortions in detailed calculations, which take into account the relevant contributions from the SO, SS and SOO interactions. A good agreement between the theoretical and experimental results has been obtained.     

Nonequilibrium energy of Rayleigh waves in half-limited crystals with hot electrons close to the defect surface

Nonequilibrium energies of surface (Rayleigh) lattice oscillations in half-limited crystals with static defects and a two-dimensional layer of hot Fermi and Boltzmann electrons close to the stress free surface were calculated. Substances with electrons heated by an external field retaining their intrinsic temperature for a certain time, T _e ? T, where T is the temperature of the lattice, were considered. As shown earlier, the thermodynamic characteristics of thin films can then be determined by nonequilibrium energy of Rayleigh waves (R-phonons) caused by their interaction with hot electrons. This energy decreases as the widths of the energy spectrum of R-phonons increase. In this work, the earlier calculated spectrum widths are used. These widths are caused by the scattering of R-phonons by electrons and static defects close to the surface (point and extended surface defects, edge dislocations perpendicular to the surface and emerging to it, and random lattice grooves in the lattice plane). In all the calculations, the Keldysh diagram technique transformed for half-limited media was used.     

Lattice dynamics of LaMnO3: Coupling of the lattice and orbital degrees of freedom

The lattice dynamics of regular LaMnO₃ is calculated within a shell model with pairwise interionic interaction potentials and with a Jahn-Teller (JT) contribution included into the energy and dynamic matrix of the crystal. A correlation is made between Raman spectral lines and lattice vibrations. The positions of some lines in the Raman spectrum are found to depend heavily on the linear JT coupling constant V _e . The effect of the JT coupling on the phonon density of states of LaMnO₃ is investigated.     

New approach to treating the energetics of activation processes in the lattice of superionic conductors with intrinsic structural disorder

Using LaF₃-type superionic trifluorides as an example, it is shown that the intrinsic thermal structural disorder not affecting the symmetry of the lattice is embodied in light inelastic scattering spectra. Tools for analyzing the Arrhenius-like temperature dependence of the activation energy of disordering in the superionic conductor lattice are discussed. It is found that activation energy ΔEa found from the temperature dependence of the Raman line width is many times lower than energy Ea responsible for LaF₃ lattice disordering.     

Highly efficient cooperative energy transfer from Ho3+ and Tm3+ ions to Ce3+ ions in crystals

A phenomenon of highly efficient cooperative energy transfer from Ho³⁺ and Tm³⁺ ions to two-particle (2Ce³⁺) cooperative acceptors in crystals of solid solutions of La_1?x Ce _x F₃ is revealed. The rates of cooperative energy transfer in Ho³⁺→2Ce³⁺, Tm³⁺→2Ce³⁺, and Tb³⁺→ 2Yb³⁺ systems are measured, as well as their dependence on the magnitude of the matrix elements of donor transition.     

Chemical trends for deep antisite defect levels in III –V compounds

Chemical trends for all deep antisite defect levels which are expected to lie within or close to the main energy gap are presented for nine III-V compounds. We use a previously presented rescaled defect-molecule model to select the relevant levels and calculate their position by extrapolating from available experimental data in GaAs. Charge-state effects as well as symmetry-conserving lattice distortions are included qualitatively. Anion antisite defects are fourd to produce deep A₁ levels within the main energy gap and T₂ levels close to the conduction band edge. For most of the investigated compounds we find that cation antisite defects induce deep T₂ levels which lie within the forbidden energy gap. No other deep sp³-type levels are expected to lie within or close to the main energy gap. Both the prediction and the calculated positions of these levels are in good agreement with previous calculations and the few experimental data available. The predicted chemical trends agree well with those obtained previously by tight-binding models, where available. This is quite remarkable because our model is mainly based on a simple rescaling assumption similar to that of tight-binding models, but does not require a detailed information on the band structure of the host.     

Ionic conduction in KBr-KI mixed crystals

Ionic conductivity of KBr_1?xI_x (0 ? x ? 0.5) mixed crystals has been studied as a function of temperature in the range of 2 ionic conductivity and lowers the activation energy appreciably which is consistent with our earlier results on AgBr-AgI mixed crystals, and proposal that the purely elastic displacements (lattice strain) caused by the very “wrong size” of the substituent ions is primarily responsible for the behavior. The strain thus produced is expected to cause “lattice loosening” and hence lowering of the melting points (T_m) or the enthalpy of formation of the Schottky defects (H_s). A semiquantitative calculation shows this to be the case.     

A lattice model of nearest-neighbor hopping conduction and its application to neutron-doped Ge: Ga

A model of hopping conduction between nearest neighbors is developed in which the majority and compensating dopant atoms are assumed to form a unified simple cubic lattice in a crystalline matrix. The hopping of carriers occurs when thermally activated “equalization” of majority impurity levels takes place, while the compensating impurities block the corresponding sites. The range of relatively high temperatures is considered in which the interactions giving rise to a Coulomb gap can be neglected and the density of states of the majority impurity band is Gaussian. The concentration dependences of the activation energy for hopping conductivity ? ₃ (nonmonotonic and having a maximum) and the preexponential factor σ₃ are found. The results are compared with experimental data obtained by different authors for neutron-doped Ge: Ga.     

Characterization of 1T-TiSe2 surface by means of STM and XPD experiments and model calculations

Scanning tunneling microscopy (STM) and X-ray photoelectron diffraction (XPD) are applied to study the surface of layered dichalcogenide 1T-TiSe₂. XPD pattern simulation for the 1T-TiSe₂ surface is performed in the approach of electron multiple scattering within the EDAC code: considered are models of structural defects in the 1T-TiSe₂ lattice, relaxation contraction (expansion) of surface layers and van der Waals gap, and deviation of the 1T-TiSe₂ surface geometry from the basal plane (001). The atomic structure of 1T-TiSe₂ surface layers is reconstructed from the XPD pattern on Se(LMM) and Ti2p core level using the photoelectron holography scattering pattern extraction algorithm with maximum entropy method (SPEA-MEM). The results of the 3D reconstruction are in agreement with the XPD pattern simulation data. In both cases, the TiSe₂ surface corresponds to 1T polytype; an increase is observed in the parameter a₀ and in the van der Waals gap between two surface slabs. It is assumed that similar structural distortions of the 1T-TiSe₂ lattice lead to the formation of an energy gap between the valence band and the conduction band of titanium diselenide, which was observed earlier by photoemission spectroscopy and follows from the theoretical calculations.     

Comparative computations of the lattice energy of sodium chlorate and bromate using explicit minimisation procedures

Two methods are described to evaluate the lattice energies of salts containing polyatomic ions by means of a minimisation procedure. A multipole expansion is used for the electrostatic part of the lattice energy, and the repulsion energy is described within either the simple Born-Mayer scheme or the Huggins and Mayer scheme. The minimum condition for the lattice energy determines the repulsion parameter, whereas the repulsion exponent ρ is either calculated using the experimental compressibility (Method A) or is given a constant value (Method B). Both methods are applied to cubic NaClO₃ and NaBrO₃, where the lattice energies are obtained as a function of the charge of the oxygen atom. The results are very similar indeed suggesting that either approach is satisfactory.     

Electronic theory for impurity segregation at lattice defects in metals

A tight-binding type electronic theory is used to study the impurity segregation at lattice defects in metals. It is shown that the heat of segregation E_segr results from a simple physical origin: It is roughly proportional to the difference in the diagonal matrix elements (V_i-V₀) of impurity potentials, where V_i (V₀) is determined for atomic sites in the vicinity of lattice defects (for a perfect lattice site). Applications to impurity segregation at cleaved surfaces, screw dislocations and tilt grain boundaries are discussed.     

Dynamical Arrest,Tracer Diffusion and Kinetically Constrained Lattice Gases

We analyze the tagged particle diffusion for kinetically constrained models for glassy systems. We present a method, focusing on the Kob–Andersen model as an example, which allows to prove lower and upper bounds for the self-diffusion coefficient D _S. This method leads to the exact density dependence of D _S, at high density, for models with finite defects and to prove diffusivity, D _S > 0, at any finite density for highly cooperative models. A more general outcome is that under very general assumptions one can exclude that a dynamical transition, like the one predicted by the Mode-Coupling-Theory of glasses, takes place at a finite temperature/chemical potential for systems of interacting particle on a lattice.