XAFS studies of the local structure and charge state of the Pr impurity in SrTiO3

Solid solutions of (Sr_{1 ? x} Pr _x )TiO₃ have been studied using X-ray methods. It has been shown that, with an increase in the praseodymium concentration, the temperature of the structural phase transition to the phase with space group I4/mcm increases and, at x ?? 0.15, the structure at 300 K is tetragonal. X-ray absorption fine structure (XAFS) spectroscopy studies have revealed that Pr ions are predominantly in the charge state 3+ and occupy the Sr sites. No indications of the off-centering of Pr atoms at the Sr sites have been revealed. The local environment of Pr atoms is characterized by a strong relaxation of the oxygen atoms, the value of which corresponds to the difference between the ionic radii of Pr³⁺ and Sr²⁺. It has been found that, in the second shell, there occurs a significant repulsion of the Pr³⁺ and Ti⁴⁺ ions, which is responsible for the weak dependence of the lattice parameter in the solid solution on the praseodymium concentration.     

High-pressure phases in the GaSb-Mn system

The effect of high pressure (6 GPa) on the formation of new phases in a polycrystalline mixture GaSb: Mn = 1: 1 upon heating was studied. Sphalerite-type solid solutions with a small amount of Mn form at temperatures below 520–600 K. At higher temperatures, new crystalline GaSbMn phases are synthesized: a phase with a simple cubic structure with a lattice parameter a = 2.946 ± 0.001 Å (at 620–670 K) and a phase with a tetragonal CuAl₂-type structure (space group I4/mcm) with lattice parameters a = 6.426 ± 0.004 Å and c = 5.349 ± 0.004 Å (at 690–870 K). These new phases are metastable under normal conditions and have magnetic properties. The structure, conductivity, and thermal stability of the synthesized phases are investigated, and the products of decomposition of these new phases upon annealing are analyzed.     

Vibrational modes and phase transition of Si-Ge solid solution

We present the simplified treatment where the lattice vibrations of Si or Ge atoms in the Si-Ge solid solution are replaced with that of pure Si or Ge crystal at lattice constants of the alloy. Considering the volume effect on the force constants of the pure constituent, we obtain the phonon dispersion curves of the local and band modes for Si_0.91Ge_0.09 and Si_0.11Ge_0.89 systems and the concentration x-dependence of the local and band modes frequencies in the Si_1?xGe_x solid solutions. Then, from the calculation of the effective mode Grüneisen parameter γ_i for the average phonon modes in the Si_1?xGe_x systems, we obtain the predominant correlation between TA mode Grüneisen parameter γ^X_TA at the point X and the phase transition pressure P_t, and the softening of TA modes is related to the pressure-induced phase transition of the Si-Ge solid solution.     

Met-Cars: a unique class of molecular clusters

Currently there is extensive interest in systems of finite size as they often give rise to unique properties that differ from those of an extended solid or the individual molecular constituents of which they are comprised. Particularly interesting are systems whose composition can be selectively chosen, and ones whose individual characteristics may be retained, thus allowing them to serve as the building blocks for nanostructured/cluster-assembled materials. In 1992 we discovered a new class of molecular clusters termed metallocarbohedrenes, or Met-Cars for short, which involve bonding between early transition metals and carbon with a stoichiometry of M₈C₁₂. Calculations, as well as recent experimental findings, suggest that these species exhibit considerable free electron behavior which becomes manifested through observations of changing electronic energy levels with the nature of the metal. Indications that it is possible to produce Met-Cars with various endohedral atoms, as well as the finding that other metals and non-metal atoms may also be substituted in the cage lattice, suggest that these cluster materials are valuable in the context of unraveling the properties of condensed matter of finite size. This also opens an avenue for exploring the prospect that they may provide building blocks for new materials. Their discovery, formation, and ionization dynamics are reviewed herein. To cite this article: B.D. Leskiw, A.W. Castleman, C. R. Physique 3 (2002) 251–272.     

Lattice parameter of sodium close to the melting point

We report high precision lattice parameter measurements (Δa/a < 10^?6) of high purity sodium single crystals close to the melting transition. Data were taken by a neutron-double crystal-back-scattering device. Just below the melting point a decrease in the lattice parameter is observed. This effect is discussed in terms of the defect structure and the limit of stability in the crystalline solid state.     

Anomalous states of the crystal structure of (Rb0.1(NH4)0.9)2SO4 solid solutions in the temperature range 4.2–300 K

Crystals of (Rb_0.1(NH₄)_0.9)₂SO₄ solid solutions are studied using x-ray diffractometry. It is revealed that the temperature dependence of the lattice parameter a exhibits an anomalous behavior, namely, the “invar effect” at temperatures above the ferroelectric phase transition point T _c and an anomalous increase in the temperature range from T _c to the liquid-helium temperature. An anomalous increase in the lattice parameter a and an increase in the intensity of Bragg reflections with a decrease in the temperature are interpreted within the model of the coexistence of two sublattices hypothetically responsible for the ferroelectric phase transition. A series of superstructure reflections observed along the basis axes corresponds to a sublattice formed in the matrix of the host structure. Analysis of the ratio between the lattice parameters of these structures allows the inference that, in the temperature range 4.2–300 K, the structure of the crystal under investigation can be considered an incommensurate single-crystal composite.     

Neutron diffraction study of phase transitions in highly concentrated hydrogen solid solutions ZrV2Dx (4 < x < 5)

Structural phase transitions in highly concentrated hydrogen solid solutions ZrV₂D_x (4 < x < 5) were studied in the wide temperature range 1.5–310 K. Phase transitions associated with hydrogen ordering in the lattice were found to occur in the concentration range 4.0 < x < 4.5. Contrary to the previously studied low-concentrated solid solutions (with x < 4), ordering of hydrogen atoms in this case is accompanied by a variation in their coordination during the formation of a superstructure. It is established that this effect is due to the short-range interaction between hydrogen atoms. A new type of hydride superstructure with stoichiometric composition ZrV₂D₅ was found. Solid solutions with x > 4.5 were established to decompose at low temperatures. The phase diagram is constructed.     

Concerning the structural mechanism of oxygen inclusion into the lattice of titanium carbide

Variations in the unit cell occupancy of TiC_xO_y phase are considered in terms of successive oxygen inclusion into the lattice of defect carbides TiC_0.5 ? TiC_0.9. A classification of TiC_xO_y solid solutions formed and the concentration limits of their existence are presented. Three types of cubic ternary solid solutions are shown to occur in the system TiCO: solid solutions of interstitial oxygen inclusion into the initial carbide; solid solutions of oxygen inclusion—carbon and metal exclusion; and solid solutions of oxygen inclusion—oxygen substitution for carbon-carbon and metal exclusion.Specific points (inflection and breaks) on the plots where n_i is the number of atoms per unit cell, n_i = f(y) for TiC_xO_y, are accounted for by both variations in the type of solid solution and the possibility of atomic arrangement in the vicinity of these points. On the basis of the above scheme some experimental peculiarities of Ti carbide phase oxydation are explained.     

Effect of ion nitriding on the crystal structure of 3 mol% Y2O3-doped ZrO2 thin-films prepared by the sol-gel method

We investigated the effect of ion nitriding on the crystal structure of 3 mol% Y₂O₃-doped ZrO₂ (3YSZ) thin-films prepared by the sol-gel method. For this purpose, we used X-ray diffractometry to determine the crystalline phases, the lattice parameters, the crystal sizes, and the lattice microstrains, and glow discharge-optical emission spectroscopy to obtain the depth profiles of the elemental chemical composition. We found that nitrogen atoms substitute oxygen atoms in the 3YSZ crystal, thus leading to the formation of unsaturated-substitutional solid solutions with reduced lattice parameters and Zr_0.94Y_0.06O_1.72N_0.17 stoichiometric formula. We also found that ion nitriding does not affect the grain size, but does generate lattice microstrains due to the increase in point defects in the crystalline lattice.     

Thermodynamics of ternary Fe-Ni-N-austenites

Measurements, in the range 1140–1548 K, of the temperature variation of the solubility of nitrogen at constant pressure (1.04 × 10⁵ Pa) in Fe-Ni fee solid solutions in equilibrium with N₂ gas, show that the partial molar enthalpy $\text{H}$_i of the nitrogen atoms is invariant to the nickel concentration up to 15 atm % Ni. In the same temperature range the partial molar excess entropy $\text{S}$^xs_i exhibits a slight decrease with increasing nickel concentration.The thermodynamic data are consistent with the cell model for ternary solid solutions in which the nickel atoms create shallow trapping sites for N-atoms, deeper by only 4.9 kJ/mol than interstitial sites in binary Fe-N solutions.The variation in H_i with nickel content due to the distribution of N atoms in energetically differing cells is of about the same size, but opposite in sign, to the contribution to $\text{H}$_i ascribable to the change in specific density of the substitutional lattice with varying Ni content.     

Magnetostriction domain structure in a periodic system of magnetoelastic and elastic nonmagnetic layers

The spectrum of magnetoelastic waves in a periodic structure of alternating ferromagnetic and nonmagnetic layers was studied. In the case of ferromagnetic layers with easy magnetization axes parallel to the layer surfaces, an orientational phase transition induced by an external tangential magnetic field H_e was considered. The formation of an inhomogeneous phase with a spatially modulated order parameter, which is caused by the magnetization being coupled through magnetostriction to lattice strains near the interfaces separating the magnetoelastic from elastic media, is predicted. It is shown that at a certain critical field in excess of the orientational phase transition field in the system without magnetostriction, a magnetoelastic wave propagating in a direction parallel to the in-plane magnetization vector M becomes unstable at finite values of the wave vector and condenses into a magnetostriction domain structure. A phase diagram in the (L, T, H_e) coordinates is constructed, and the regions of existence of thermodynamically equilibrium collinear, canted, and domain phases are established (L and T are the thicknesses of the ferromagnetic and nonmagnetic layers, respectively).     

Lattice vibrations and local order in substitutional solid solutions. I

Expressions are derived for the effective mean square amplitudes of the thermal vibrations of atoms and the Debye characteristic temperatures for the case of binary, substitutional, metallic solid solutions. Both solid solutions with random distribution of atoms and also those with a partially ordered distribution of atoms are investigated. The calculations respect the change in the vibrational state of atoms on solid solution formation. The parameterα, characterizing this change, can be determined from X-ray diffraction experiments or from the concentration dependence of the melting temperature and lattice constant. The results are applied to a solid solution of Ag in Al. A comparison with the experimental values measured by M. Simerská (Czech. J. Phys.B 13 (1963), 737) shows good agreement.     

A theory of order-disorder transition during crystallization of binary systems2

A theory is presented describing the order-disorder transition in binary crystals growing on the condition of supersaturation from nonsolid phases. The theory applies to systems that crystallize with an almost perfectly ordered structure if exposed to conditions close to thermodynamic equilibrium. Based on a model that assumes incorporation and detachment of single atoms to occur at the kink sites of mono-atomic steps existing at an otherwise smooth crystal surface a kinetic master equation for the time dependence of configuration probabilities has been formulated. Several simplifying assumptions have been employed. Any solution for the steady-state conditions depends on a roughness parameter λ, the far-order parameter η, the incorporation frequency ω₊ and a parameter q, related to the atomic interaction energies. The solutions are discussed for conditions prevailing near equilibrium with η 1 and within the range of order-disorder transition with η 0. The analysis reveals that for different incorporation frequencies different critical values of the parameter q exist for which a transition from an ordered to a disordered phase is predicted to occur. Each of these critical values of q corresponds to a critical transition temperature T_t.     

Correlation between structural and superconducting properties of nano-granular disordered Nb thin films

We report on low temperature transport measurements on nano-granular Nb thin films deposited on Si (1 0 0) substrates using DC magnetron sputtering. The superconducting transition temperature (T_c) is found to decrease monotonically with the increase of the lattice parameter (a) irrespective of its thickness and grain size. The superconducting transition temperature is found to depend only on the lattice parameter whereas the normal state resistivity depends both on lattice parameter and the details of the sample morphology. We have modeled this T_c variation with lattice expansion in terms of Debye temperature reduction using Morse potential as the interatomic potential in Nb.     

Density Functional Theory Study of Mn+1AXn Phases: A Review

M_n+1AX_n phases (MAX phases for short with M: transition metal, A: A group elements, X: C or N, and n = 1–3) have attracted considerable attention due to the unique combination of the ceramic- and metal-like properties. The density functional theory (DFT) has emerged as a powerful theoretical approach that complements experimental testing and serves as a predictive tool in the identification and characterization of MAX phases. After the beginning with a brief introduction of the MAX phase and DFT, we review the DFT study on this class of materials, including crystal structure, electronic structure, point defects, lattice dynamics, and related properties, phase stability, compressibility, and elastic properties. Comparison between the theoretical values and available experimental ones shows that they are in decent agreement for most part, especially in the lattice constants, elastic properties, and compressibility. This article is concluded with an outlook of future research on DFT study of MAX phases, major challenges to be met and possible solutions in some cases.     

CrI_3高压相变及其光学性质理论研究

利用第一性原理计算方法,探讨了体相CrI_3在低温斜方六面体结构(■,BiI_3-type)及高压单斜结构(C2/m,AlCl_3-type)的相变、电子结构和光学性质.计算结果显示,半导体CrI_3当压强增加到26.1GPa时,高压导致的晶格畸变致使CrI_3从相■变化到相C2/m;原子之间的错位位移,使导带处的能带发生下移,价带处的能带发生了一定程度的上移,导致带隙减小.两种相的光学性质进一步验证了这些特性.     

A Mössbauer effect study of the magnetic ordering in the Y6(FexMn1−x)23 solid solutions

The ternary alloys, Y₆ (Fe_xMn_1–2)₂₃, exhibit interesting magnetic behavior over a range of solid solutions of iron and manganese. The transition metal atoms occupy four crystallographically different sites. For x less than ca. 0.27, the transition metal atoms couple ferromagnetically, whereas for greater values of x they couple antiferromagnetically. By using the iron populations for each site, obtained from neutron diffraction studies, it is possible to determine the Mössbauer effect hyperfine parameter fields for each site. As x increases, the ordering temperature decreases dramatically. At 1.3K in Y₆Fe₂₃, the four hyperfine fields range from 372kOe to 250kOe, whereas in Y₆(Fe_0.52Mn_0.48)₂₃ they decrease to values between 100kOe and 10kOe. This decrease apparently results from the increasing frustration of the ferromagnetic iron-iron coupling as additional manganese, which would prefer antiferromagnetic coupling, is introduced into the alloys.     

Dependence of the superconducting transition temperature on electron per atom ratio and lattice deformation in noble metal alloys

Superconducting transition temperature measurements of the α-phase alloys CuSi, CuGe, AgGe, AgAl, AuGe, and AuZn are reported. It is found that for alloys with the same electron per atom ratio, T_c values are highest when the pure metal lattice is deformed the least by the solute.     

Defects-driven appearance of half-metallic ferrimagnetism in Co-Mn-based Heusler alloys

Half-metallic ferromagnetic full-Heusler alloys containing Co and Mn, having the formula Co₂MnZ where Z is a sp element, are among the most studied Heusler alloys due to their stable ferromagnetism and the high Curie temperatures which they present. Using state-of-the-art electronic structure calculations we show that when Mn atoms migrate to sites occupied in the perfect alloys by Co, these Mn atoms have spin moments antiparallel to the other transition metal atoms. The ferrimagnetic compounds, which result from this procedure, keep the half-metallic character of the parent compounds and the large exchange-splitting of the Mn impurities atoms only marginally affects the width of the gap in the minority-spin band. The case of [Co_1−xMn_x]₂MnSi is of particular interest since Mn₃Si is known to crystallize in the Heusler L2₁ lattice structure of Co₂MnZ compounds. Robust half-metallic ferrimagnets are highly desirable for realistic applications since they lead to smaller energy losses due to the lower external magnetic fields created with respect to their ferromagnetic counterparts.     

Local atomic structure of niobates and titanates from X-ray absorption spectroscopic data

The local atomic structure of PbTiO₃, BaTiO₃, and KNbO₃ perovskite-type crystals and K _x Na_{1 ? x} NbO₃ solid solutions in different phases is investigated using the angular dependence of the pre-edge structure of the Ti and Nb K X-ray absorption spectra and the EXAFS data. In noncubic phases, a considerable deviation of the local structure from the structure determined from diffraction data is observed only for the tetragonal phase of the BaTiO₃ crystal. It is revealed that, in the cubic phase of niobates, the niobium atoms are characterized by significant displacements from the centrosymmetric positions along the threefold axes, so that they are close in the magnitude and the direction to the displacements in the low-temperatures rhombohedral phases.