X-ray photoelectron diffraction from adsorbate core levels in the energy range 500–10000 ev and with polarized radiation: a theoretical study

X-ray photoelectron diffraction (XPD) from adsorbate core levels shows considerable promise as a surface-structural probe, especially since a simple single-scattering theory appears capable of describing such photoelectron diffraction. In the past, several types of XPD structural investigations have been made using conventional Al Kα radiation, including determinations of bond orientations for diatomic molecular adsorption and of vertical bond distances for atomic adsorption. In this work, a theoretical investigation has been made within the single-scattering cluster model to determine the possible advantages and disadvantages of using different photon energies over a broad range from 500 to 10000 eV and/or a polarized radiation source in such structure determinations. Two test cases, of intramolecular scattering in C 1s polar scans above vertically adsorbed CO and of interatomic scattering in O 1s azimuthal scans for c (2 × 2) O on Cu(100), are considered in detail. In general, precision in determining bond orientations can be unproved by using higher energies and/or polarized radiation, although it may be more difficult to obtain the data owing to lower percent effects and lower total intensities. In azimuthal scans, going to higher energy yields narrower features, but requires much lower takeoff angles and concomitantly lower intensities. Other aspects of using variable energy and polarization in XPD are also considered.     

Solid electrochemical modification of semiconductors

It is shown that the properties of semiconductors can be modified by solid electrochemical cells. These cells can be used as dopant sources for introduction of impurities into the semiconductor lattice. The solid electrolyte is so chosen that the ionic conducting species are the desired dopants. The controllability of the doping operation is very sensitive and either a constant concentration or a specified concentration profile can be achieved. These cells can also be used to modify the semiconductor surfaces such that only limited penetration of impurities is achieved.     

Thermoluminescence of rare earth activated CdSO4, SrSO4 and BaSO4

The thermoluminescence (TL) of rare earth (RE) activated sulfates of Cd, Sr and Ba was studied above room temperature. Many of the phosphors prepared exhibit an extremely bright TL following X-irradiation (most notably with Sm, Eu, Tb, Dy and Tm dopants), having an efficiency comparable to that of the highest sensitivity phosphors available for TL dosimetry, and exhibiting activator-induced glow peaks between 405 and 480°K. In a given lattice, the RE³⁺ ions produce a characteristic glow peak at the same temperature (independent of the particular RE ion), whereas Eu²⁺ produces a single glow peak at a different temperature. A decrease in glow peak temperature with increasing interatomic spacing was observed in the homologous SrSO₄-BaSO₄ system - this shift being most pronounced in the Eu²⁺ -doped materials. TL emission spectra were obtained for trivalent Sm, Tb, Dy and Tm and for divalent Eu in these sulfates (and also in CaSO₄).     

Small polaron electron transport in reduced CeO2 single crystals

An investigation of the electrical properties of reduced ceria, CeO_2?x, carried out on single crystals, shows that CeO_2?x provides one of the clearest examples of hopping conduction and the small polaron mechanism. Included are conductivity and Seebeck coefficient measurements at constant x, obtained by sealing off the specimen chamber after reduction. The Seebeck coefficient is independent of temperature, suggesting that the number of carriers is constant. On the other hand, the mobility is activated, with activation energy E_h = 0.40 eV at small x and increasing to 0.52 eV at x = 0.25. The results for the mobility preexponential are consistent with the adiabatic theory of small polaron behavior. A puzzling feature of the Seebeck data as a function of x is that, for low x, the data fit the well-known Heikes formula, without a degeneracy factor of 2 for spin. Nevertheless, these data are interpreted to show that the proportion of mobile carriers decreases as x increases, presumably because of the presence of short-range ordered configurations which immobilize some carriers.     

Temperature dependence of the reflectance spectrum of (TMTSF)2ClO4

The near-infrared and visible reflectance spectrum was measured on (TMTSF)₂ClO₄ single crystal at various temperatures in the range of 30K–290K. The reflectance spectrum polarized parallel to the stacking axis was analyzed by Drude model, giving the results that the band width 4t is about 1 eV and m¹_p/m is about 1.3. The band parameters obtained here were almost the same as those of (TMTSF)₂PF₆ reported by Jacobsen et al.     

Spin-density-wave and superconducting states in thermally quenched (TMTSF)2ClO4

Successive transitions from metal to the spin-density-wave (SDW) state and the three-dimensional superconducting (3D-SC) state were found in thermally quenched bis-tetramethyltetraselenafulvalenium perchlorate, (TMTSF)₂ClO₄. The SDW state was suppressed after the sample was warmed above ～25 K and cooled slowly. The appearance of the SDW state in addition to the 3D-SC state in the quenched sample is interpreted by the decrease in interchain coupling which could result from the thermal quenching of a high temperature configuration with disordered (ClO₄)-anions. The effect of thermal quenching on quantum oscillations in transverse magnetoresistance was also studied.     

Surface composition of Fe-Al2O3 granular thin films by X-ray photoemission spectroscopy

X-ray photoemission Spectroscopy (XPS) results are presented which have given a direct insight into the surface composition of Fe-Al₂ O₃ “granular” thin films consisting of fine iron particles (φ ~ 40–150 Å) dispersed in an insulating alumina matrix. The data are mainly discussed in relation to: (i) the bulk iron content in the sample, (ii) the sample preparation procedure (e.g., by rotation of the sample target) and (iii) the mean iron particle size.At the surface, the iron is in a fully oxidized 3⁺ state within an alumina-rich partly hydrated region. Depth analysis, achieved by an Ar⁺ etching procedure, provides evidence of metallic iron and iron aluminate forms. In general, the metallic iron percentage increases with depth and with increasing iron bulk content.Good agreement is found between X-ray photoemission spectroscopy and Mössbauer Spectroscopy data. Fe²⁺ aluminate forms, which indicate an interaction between the metal particle and the alumina matrix, show increasing percentages with decreasing mean particle sizes.Particular attention is paid to evaluating the accuracy of XPS quantitative results, obtained by use of a first-principles model, and to assessing the importance of the artefacts associated with the Ar⁺ etching procedure.     

Linear and nonlinear optical properties of Ca3(VO4)2

Single crystals of Ca₃ (VO₄)₂ have been grown by the Czochralski method. The refractive indices show that the crystals are phasematchable between 1.72 μm and 2.94 μm with favourable values for acceptance angle and spectral width of the incident laser beam in the entire phasematching range. The nonlinear optical coefficients have been measured by the Maker fringe method at a fundamental wavelength of 1.064 μm. They are comparable to those of KDP. Thus the crystals are potentially useful for frequency conversion of broadband or tunable laser sources as semiconductor and F-center lasers. They may also be installed in high f-number IR image converters.     

Tunneling spectroscopic study on the superconductivity of (TMTSF)2ClO4 crystals

We observed the energy gap spectra for (TMTSF)₂ClO₄-Al₂O₃-Au junctions at 1.5 K by measuring their tunneling current characteristics. The superconducting gap was estimated to be less than 2 meV (T_c<6 K) which is much smaller than the previously reported value, 8 meV.     

Thermally stimulated luminescence and infrared studies of CaS : Bi,Tm phosphors

Calcium sulphide phosphors doped with bismuth and thulium are prepared from Indian minerals. The glow curves are recorded in the temperature range of 96–320 °K. The activation energies are determined by analyzing the glow peaks after thermal cleaning, using different methods. The results show that, in these phosphors, the electron traps responsible for thermoluminescence are present prior to irradiation. The infrared absorption spectra are recorded in the range of 4000-250 cm^-1. It is concluded that the traps are due to host lattice defects which may arise from S^-2 ion vacancies, created during phosphor preparation.     

Perturbation calculations of the c(2×2) sodium overlayer structure on Al(001)

The chemisorption bond-length and binding location of the c(2×2) sodium overlayer on Al(001) surface are determined by a convergent perturbation calculation of the dynamical LEED approach. The use of convergent perturbation calculation allows accurate surface structures to be determined with very economical amounts of computation effort. Efficiency features specific to our computation method are outlined. Using a set of simple dynamical inputs, we determine that the sodium atom sits in a 4-fold coordinated binding site with a NaAl chemisorption bond-length of 2.08 ± 0.12 Å.     

Low frequency lattice vibrations of LaF3 by neutron scattering

The phonon modes having frequencies less than 3 THz in the high symmetry directions of LaF₃ are reported. These are compared to the results of previous optical studies. A previously unobserved branch of low group velocity is found near 1.2 THz polarized both parallel and perpendicular to the basal plane. Its significance for the lifetimes of zone boundary acoustic phonons is discussed.     

Preparation and Mössbauer spectra of CoV2O4 spinel doped with Fe2+ on tetrahedral sites

Co²⁺_0.98Fe²⁺_0.02Fe³⁺_?V³⁺_2-? 04 (?? 0.001) was obtained from a sample containing the iron dope mainly in the trivalent state, by reducing it at 910°C in a CO₂/CO atmosphere. Mössbauer spectra of ⁵⁷Fe at the tetrahedral site were taken between 5 and 300 K. Below the Curie temperature (143 K) there is a magnetically induced electric field gradient eQV_zz and a reduction of the hyperfine field H_hf. Values at 5 K are H_hf=141 kG and eQV_zz=5.74 mm/s. The effective splitting of the Fe²⁺⁵E ground-state doublet, as estimated from the temperature dependence of eQV_zz and H_hf, is $\text{2q}\text{δ}\text{/k = 28 K}$. It is derived that in these oxides the coupling of the electronic ⁵E states to local Jahn-Teller active E-modes of vibration is stronger than in comparable sulphides.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

High field ESR measurements of spin gap system MCu2(PO4)2

Submillimeter and millimeter wave ESR measurements of spin gap systems SrCu₂(PO₄)₂ and PbCu₂(PO₄)₂, which have four kinds of dimers, have been performed to investigate the magnetic properties of spin gap systems using the pulsed magnetic field up to 35T. The observed ESR spectra of powder sample SrCu₂(PO₄)₂ show sharp and single peak in the temperature range from 4.2 to 80 K. The anisotropy of the g-values turned out to be very small compared to the usual anisotropic powder spectra of copper compounds. The dynamical properties will be discussed from the temperature dependence measurements.     

In situ pressure-induced solid-state amorphization in Sm2(MoO4)3, Eu2(MoO4)3 and Gd2(MoO4)3 crystals: chemical decomposition scenario

The effect of pressure on the phase transformations in Sm₂(MoO₄)₃, Gd₂(MoO₄)₃ and Eu₂(MoO₄)₃ crystals has been studied in situ using synchrotron radiation. All three isostructural compounds undergo a structural phase transition at 2.2-2.8 GPa to a new phase, which is interpreted as a possible precursor of amorphization. Amorphization in these crystals occurs irreversibly over a wide pressure range, and its mechanism, interpreted as a chemical decomposition, is found to be weakly affected by the degree of hydrostaticity.     

On the power-law behavior of the AC conductivity of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

A power law used to describe the AC conductivity from 299 to 393 K of the mixed crystal (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 led to fractional exponent values ranging from 1.08 to 0.91, depending on structural changes induced on temperature variation [B. Louati, M. Gargouri, K. Guidara and T. Mhiri, J. Phys. Chem. Solids 66 (2005) 762]. In the present note, we suggest that the fractional law exhibits features of lattice relaxation. Despite the structural changes, the parameters of the power law are mutually interconnected to yield a temperature independent phenomenon. Such behavior is probably of general validity and characterizes the universal fractional dispersion of the AC conductivity, as it was also observed in glasses of different composition.     

Experimental investigation of positron self-trapping near the vapour-liquid critical point of hellium-4

Positron self-trapping in helium near the vapor-liquid critical point is investigated using the positron annihilation lifetime technique. A 13% decrease in the slowing-down time for positrons to reach the self-trapped state is observed at the critical temperature 5.190 K relative to the slowing-down time at 5.200 K.