Selective photorefractive scattering in LiNbO<Subscript>3</Subscript>:Rh crystals

Photorefractive scattering occurs in rhodium-doped lithium niobate crystals irradiated by coherent light. The photorefractive scattering has both wide-angle and selective components. The results of experimental investigation of selective photorefractive scattering in LiNbO₃:Rh crystals and calculation of the spatial structure of scattering are reported. The selective scattering is regarded as a kind of a frequency-degenerate fourwave vector interaction.     

Light scattering in single crystals of nonlinear-optical photorefractive LiNbO<Subscript>3</Subscript>:Cu and LiNbO<Subscript>3</Subscript>:Zn

Comparative studies are made of the photorefractive scattering of light in nonlinear single crystals of lithium niobate with congruent compositions (LiNbO₃) doped with "photorefractive" Cu [0.015 mass %] and "nonphotorefractive" Zn [0.5 mass %] cations. For the first time it is found that single crystals doped with "photorefractive" and "nonphotorefractive" cations have different indicatrices for photorefractive light scattering. The aperture angle for photorefractive scattering reaches its steady state value more rapidly with high laser powers than with low. However, at high powers laser induced heating of the crystal is greater, and this leads to a narrowing of the scattering indicatrix. It is also found that photorefractive scattering in these single crystals depends on the region of the boule from which a sample has been cut. This indicates that there is a nonuniform distribution over the boule of the imperfections with localized electrons which determine the magnitude of the photorefractive effect.     

Electronic structure of A15-type compounds: V<Subscript>3</Subscript>Co,V<Subscript>3</Subscript>Rh,V<Subscript>3</Subscript>Ir and V<Subscript>3</Subscript>Os

Band structure and Fermi surfaces of the A₃B compounds V₃Co, V₃Rh, V₃Ir and V₃Os are calculated in FP-LAPW calculations. From V₃Co to the V₃Os compound one observes a decrease of the overlap for d-states from both V and B atoms; the center of gravity of the d-band for V moves upwards, while for the B-atom it moves toward lower energies. Hence, despite the band widening, a weakening of interactions takes place throughout this series, which leads to a lattice expansion as experimentally observed. The bonding mechanism in these compounds is found to be dominated by the lower energy d-states. Comparatively, the DOS at E_F does not change appreciably between these compounds, except for V₃Os, where a sharp peak is observed at E_F. This feature leads to the highest electronic heat-capacity coefficient γ (2.31 ) in this compound, which otherwise possesses the smallest Bulk modulus (209.05 GPa). In V₃Os, for whom no report has been found, a stronger admixture between p-states from both metals near E_F is observed, and the Os d-states form a common d-band with the V d-states between 0.4–0.6 Ry. A stronger s–s hybridization is observed for V₃Co, which is in the source of the fact that this compound has an anomalously large quadrupole interaction and exhibits a positive Knight shift.     

Structure and lattice dynamics of PrFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>: Ab initio calculation

The crystal structure and phonon spectrum of PrFe₃(BO₃)₄ are ab initio calculated in the context of the density functional theory. The ion coordinates in the unit cell of a crystal and the lattice parameters are evaluated from the calculations. The types and frequencies of the fundamental vibrations, as well as the line intensities of the IR spectrum, are determined. The elastic constants of the crystal are calculated. A “seed” frequency of the vibration strongly interacting with the electron excitation on the praseodymium ion is obtained for low-frequency A₂ mode. The calculated results are in agreement with the known experimental data.     

Specific features of the electronic structure of the CeCu<Subscript>6</Subscript>, CePd<Subscript>3</Subscript>, CeSi<Subscript>2</Subscript>, and CeF<Subscript>3</Subscript> systems

The electronic structure of cerium systems, the hybridization of 4 f and outer-shell electrons, and the influence of the position of the localized 4 f level with respect to the Fermi level E _F in the conduction band have been investigated. The CeCu₆, CePd₃, CeSi₂, and CeF₃ systems have been studied using X-ray photoelectron spectroscopy. The densities of states have been calculated by the tight-binding linearized muffin-tin orbital method within the atomic sphere approximation, which takes into account the covalent character of bonds and the nonspherical distribution of the electron density. The results obtained from the calculations of the total density of states are in good agreement with the valence band X-ray photoelectron data for the systems under investigation. It has been shown that the differences in the properties of the cerium systems are determined by the specific features of their electronic structure. A strong interatomic interaction is characteristic of heavy-fermion systems.     

Investigation of electrical and optical properties of ZnO thin films grown with O<Subscript>2</Subscript>/O<Subscript>3</Subscript> gas mixture

The electrical and optical properties of ZnO thin films grown with an O₂/O₃ gas mixture are compared with samples grown with pure oxygen gas. The ZnO films were grown on sapphire(0001) by pulsed laser deposition. The residual background carrier concentration is reduced by using an O₂/O₃ gas mixture as compared to pure molecular oxygen. In particular, a one order of magnitude reduction in residual background carrier density (6.15×10¹⁶ cm^-3) is achieved by using an O₂/O₃ gas mixture. The lower donor defect density is attributed to the generation of acceptor defects compensating for the residual donor defects. Photoluminescence results show that the deep level emission increased and the band edge emission decreased for the ZnO films grown with ozone, as compared to the samples grown with pure oxygen gas. PACS 73.61.Ga; 78.55Et; 81.05 Dz; 81.15.Fg     

Luminescence and scintillation properties of Y<Subscript>3</Subscript>A<Subscript>l5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

Luminescence and scintillation properties of Y₃A_l5O₁₂:Ce single crystals grown from the melt by the Czochralski and horizontal directed crystallization methods in various gas media and Y₃A_l5O₁₂:Ce single-crystal films grown by liquid-phase epitaxy from a melt solution based on a PbO-B₂O₃ flux have been comparatively analyzed. The strong dependence of scintillation properties of Y₃A_l5O₁₂:Ce single crystals on their growth conditions and concentrations of Y_Al antisite defects and vacancy defects has been established. Vacancy defects are involved in Ce³⁺ ion emission excitation as the centers of intrinsic UV luminescence and trapping centers. It has been shown that Y₃A_l5O₁₂:Ce single-crystal films are characterized by faster scintillation decay kinetics than single crystals and a lower content of slow components in Ce³⁺ ion luminescence decay during high-energy excitation due to the absence of Y_Al antisite defects in them and low concentration of vacancy defects. At the same time, the light yield of Y₃A_l5O₁₂:Ce single-crystal films is comparable to that of single crystals grown by directed crystallization due to the quenching effect of the Pb²⁺ ion impurity as a flux component and is slightly lower (∼25%) than the light yield of single crystals grown by the Czochralski method.     

Manifestations of Phase Transitions and the Thermooptical-Memory Effect in the Absorption Spectra of (N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>)<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> Crystals

The manifestations of phase transitions and the spatial modulation of the structure of the (N(CH₃)₄)₂CuCl₄ crystal in its absorption spectra have been investigated. It has been established that the thermooptical-memory effect manifesting itself in the absorption spectra of this crystal entirely corresponds to the model of ordering of defects and impurities in a sample with a modulated structure. It is shown that, as a result of stabilization of the crystal studied in the incommensurate phase, its symmetry and the symmetry of the metal-halogen complex in it lower depending on the defect wave. This manifests itself as a marked shift of the intraionic-absorption bands and an increase in their intensity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 386–390, May–June, 2005.     

Atomic and Electronic Structures of Intrinsic Defects in Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>: Ab Initio Simulation

The atomic and electronic structure of intrinsic point defects in orthorhombic tantalum oxide has been studied by numerical simulation within the density functional theory. It has been shown that all defects responsible for metal enrichment of Ta₂O₅ serve as electron and hole traps. Under conditions of strong oxygen depletion and at a metal–insulator interface, which are characteristic of resistive memory elements, interstitial tantalum atoms compete with an oxygen vacancy in the formation of a conducting filament. Interstitial oxygen atoms are not involved in charge transport. Tantalum substituting oxygen can be considered as a combination of the oxygen vacancy and interstitial tantalum. The analysis of the calculated thermal and optical energies of trap ionization shows that the oxygen vacancy is a key defect for charge transport in Ta₂O₅.     

Investigation of the dielectric,optical and photorefractive properties of Sb-doped Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> crystals

In this work we report results on electro-physical, optical and photorefractive investigations for Sb-doped Sn₂P₂S₆ crystals. The crystals are obtained by two methods: the vapour-transport technique and the Bridgman technique using stoichiometric Sn₂P₂S₆ composition with different amounts of antimony in the initial compound. The good optical quality of the crystals obtained with the Bridgman technique is underlined. The dependences of the photorefractive two-beam coupling coefficient and the grating build-up time are investigated at the wavelength of 633 nm. It is found that the sample doped with 1.5% of Sb is characterized by an optimal combination of the main photorefractive parameters exhibiting a fairly high two-beam coupling coefficient (up to 20 cm⁻¹) and a short response time (1.3 ms) that is the shortest among all the previously studied Sn₂P₂S₆ crystals in the red spectral region.     

Modification of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surface by high-energy bismuth ions

This paper reports on an atomic-force microscopy study of the surface of α-Al₂O₃ single crystals irradiated by Bi ions with energies of 710, 557, 269, and 151 MeV. The shape of the radiation defects produced by single ions was established to depend on the ionization energy loss. The threshold ionization density above which the surface topography is observed to change lies in the 27–35 keV/nm interval. Possible mechanisms of defect formation in the thermal-spike model, namely, a phase transition and the creation of thermoelastic stresses in the high-energy ion track, are considered.     

Computer calculations for thermal behavior of Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Li<Subscript>2</Subscript>CO<Subscript>3</Subscript> melt

The thermal behavior of Na₂CO₃+Li₂CO₃ melt is studied by the method of thermodynamic simulation. The equilibrium compositions of the gas and salt phases are calculated at different temperatures in the initial argon atmosphere. Basic trends of the variation in the compositions of the melts and the gas phase above the melts in the presence of carbon are determined. The obtained results characterizing the stability of carbonate components in the melt are analyzed.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

Elastic,electronic structure,and optical properties of orthorhombic Na<Subscript>3</Subscript>AlF<Subscript>6</Subscript>: a first-principles study

First-principles investigation of elastic, electronic, and optical properties of orthorhombic Na₃AlF₆ has been carried out by DFT using plane-wave pseudo-potentials within the LDA and GGA. Calculated lattice parameters agree well with experimental results. From calculated elastic constants, Na₃AlF₆ is a mechanically stable anisotropic and behaves in a ductile manner. Electronic structure analysis indicates that Na₃AlF₆ behaves as an insulator with a direct band gap of 6.065 eV in LDA and 5.868–5.949 eV in GGA. DOS, population analysis, and charge densities difference indicate that Al-F bonds are mainly ionic as well as partially covalent due to the hybridization of F-2p and Al-3s (3p) states. Moreover, the imaginary part of calculated dielectric function ε₂(ω) shows three prominent peaks due to the inter band transitions F 2p states→Na 3s states. From calculated ε (ω), other optical properties such as reflectivity and refractive index are also obtained up to the photon energy range of 40 eV.     

Geometries and electronic structures of Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>, Ga<Subscript>3</Subscript>Se<Subscript>2</Subscript> and their anions. Theoretical insights

We hereby report a theoretical study on the equilibrium geometries, electronic structures and harmonic vibrational frequencies of Ga₂Se₃, Ga₃Se₂ and their anions. The ground and low-lying excited states of Ga₂Se₃⁻, Ga₂Se₃, Ga₃Se₂⁻ and Ga₃Se₂ are studied at the B3LYP and/or MP2 and CCSD(T) levels in conjunction with 6-311+G(d) and 6-311+G(2df) one particle basis sets. Ga₂Se₂⁻ adopts the C_2v kite geometry while Ga₂Se₃ has a ‘V’ geometry. Ga₃Se₂⁻ has a three-dimensional ‘D_3h ’ geometry and Ga₃Se₂ prefers the three-dimensional ‘C_2v ’ structure. Electron detachment energies from the ground electronic states of the anions to several neutral states are reported and discussed. At CCSD(T)//MP2 level, the adiabatic electron affinity (AEA) of Ga₂Se₃ is calculated to be 3.23 eV when using the 6-311+G(2df) basis set and that of Ga₃Se₂ is 2.77 eV with the 6-311+G(d) basis set. The findings of this research are analyzed and compared with gallium oxide and sulfide analogues.     

Statistical mechanics of cation ordering in PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

A model Hamiltonian for B cation ordering (Sc-Nb(Ta)) in PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃ solid solutions is constructed. The parameters of the model Hamiltonian are determined from the ab initio calculation within the ionic crystal model with allowance made for the deformability and the dipole and quadrupole polarizabilities of the ions. The temperatures of the phase transition due to the ordering of the B cations are calculated by the Monte Carlo method in the mean-field and cluster approximations. The phase transition temperatures calculated by the Monte Carlo method (1920 K for PbSc_1/2Ta_1/2O₃ and 1810 K for PbSc_1/2Nb_1/2O₃) are consistent with the experimental data (1770 and 1450 K, respectively). The thermodynamic properties of the cation ordering are investigated using the Monte Carlo method.     

Thermal sensors based on Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> and (Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>70</Subscript>(Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>30</Subscript> thin films

Thin films of Sb₂Te₃ and (Sb₂Te₃)₇₀(Bi₂Te₃)₃₀ alloy and have been deposited on precleaned glass substrate by thermal evaporation technique in a vacuum of 2?×?10^?6 Torr. The structural study was carried out by X-ray diffractometer, which shows that the films are polycrystalline in nature. The grain size, microstrain and dislocation density were determined. The Seebeck coefficient was determined as the ratio of the potential difference across the films to the temperature difference. The power factor for the (Sb₂Te₃)₇₀ (Bi₂Te₃)₃₀ and (Sb₂Te₃) is found to be 19.602 and 1.066 of the film of thickness 1,500 Å, respectively. The Van der-Pauw technique was used to measure the Hall coefficient at room temperature. The carrier concentration was calculated and the results were discussed.     

Magnetic properties of DyFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The magnetic properties of an easy-axis trigonal DyFe₃(BO₃)₄ antiferromagnetic crystal have been theoretically studied. On this basis, recent experimental data [1] on the field and temperature dependences of magnetization and the temperature dependence of the initial magnetic susceptibility for three crystallographic directions in this antiferromagnet have been interpreted. The characteristics of the trigonal crystal field for the rare earth ion and the parameters of the Fe-Fe and Fe-Dy exchange interactions are determined. Limitations imposed by features of the magnetic characteristics (anisotropic magnetization in the three crystallographic directions, Schottky-type anomalies in the magnetic susceptibility, etc.) on the possible splitting of the ground-state multiplet in the crystal field and the splitting of the lowest doublet due to the f-d interaction for Dy³⁺ ions are established.     

Low-frequency relaxation processes in Pb<Subscript>5</Subscript>Ge<Subscript>3</Subscript>O<Subscript>11</Subscript> ferroelectric crystals

Measurements and analysis of the temperature and frequency dependences of permittivity and losses and of the electrical resistivity of Pb₅Ge₃O₁₁ ferroelectric crystals at temperatures of 100 to 600 K and frequencies of 0.1 to 100 kHz are reported. The dielectric characteristics of the crystals exhibit, in addition to clearly pronounced anomalies near the Curie point T_C=450 K, less distinct anomalous features of the relaxation character in the range 230–260 K. The data obtained on the effect of various factors (degree of crystal polarization, crystal annealing at different temperatures and in different environments, etc.) on the low-temperature anomalies serve as a basis for discussing the possible mechanisms responsible for these anomalies. It is concluded that the low-temperature dielectric anomalies originate from thermal carrier localization in defect levels in the band gap, which entail the formation of local polarized states.     

Coherent semilinear oscillator with Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript>:Sb crystals

We present experimental results for the semilinear oscillator geometry based on Sn₂P₂S₆:Sb photorefractive crystals. The samples with strong two-wave mixing gain demonstrate degenerate oscillation regime. A mirrorless oscillation is also observed.