Auger electron spectroscopic study of CO2 adsorption on Zircaloy-4 surfaces

We investigate the adsorption of CO₂ onto Zircaloy-4 (Zry-4) surfaces at 150, 300 and 600 K using Auger electron spectroscopy (AES). Following CO₂ adsorption at 150 K the graphitic form of carbon is detected, whereas upon chemisorption at 300 and 600 K we detect the carbidic phase. As the adsorption temperature is increased, the carbon Auger signal increases, whereas the oxygen signal decreases. Adsorption at all three temperatures results in a shift of the Zr Auger features, indicating surface oxidation. The effect of adsorbed CO₂ on the Zr(MVV) and Zr(MNV) transitions depends on adsorption temperature and is less pronounced at higher temperatures. On the other hand, changes in the Zr(MNN) feature are similar for all three adsorption temperatures. The changes in the Zr Auger peak shapes and positions are attributed to oxygen from dissociated CO₂, with the differences observed at various temperatures indicative of the diffusion of oxygen into the subsurface region.     

Luminescence of Ni doped CaF2

Luminescence measurements of CaF₂ : Ni are reported. Before X-irradiation an emission band at 680 nm is observed with the corresponding excitation band at 255 nm. After RT X-irradiation the emission spectrum consists of three peaks at 290, 375 and 680 nm, all of them with an excitation band at 255 nm. The same emission spectrum together with the electron-hole recombination band is obtained by X-ray excitation.A comparison with previous EPR and optical absorption measurements indicates that the emission bands are due to different kinds of Ni²⁺ centers. The emission processes are similar to those found in CaF₂ : Co and CaF₂ : Mn.     

H2 分子在Li3N(110)表面吸附的第一性原理研究

采用第一性原理方法研究了H₂分子在Li₃N(110)晶面的表面吸附. 通过研究H₂/Li₃N(110)体系的吸附位置、吸附能和电子结构发现: H₂分子吸附在N桥位要比吸附在其他位置稳定,此时在Li₃N(110)面形成两个-NH基,其吸附能为1.909 eV,属于强化学吸附;H₂与Li₃N(110)面的相互作用主要是H 1s轨道与N 关键词： 第一性原理 3N(110)')" href="#">Li₃N(110) 2')" href="#">H₂ 吸附和解离     

Tetravalent vanadium in CaF2 and SrF2 crystals: An EPR study

An EPR study of tetravalent vanadium centers created by room temperature X-irradiation in CaF₂ and SrF₂ is presented. The production efficiency of these centers is enhanced by previous annealing of the samples at 1000 K in air. The symmetry of V⁴⁺ ions is tetragonal and its EPR spectrum can be described by an axial spin Hamiltonian including a Zeeman and hyperfine term with $\text{S =}\text{1}\text{2}$ and $\text{I =}\text{7}\text{2}$ (corresponding to ⁵¹V nuclei). The following values for the spin Hamiltonian parameters are obtained g_∥ = 1.947 ± 0.002, g_⊥ = 1.935 ± 0.005, A_∥ = 500 ± 5 MHz, A_⊥ = 150 ± 10 MHz in the case of SrF₂ and g_∥ = 1.945 ± 0.002, A_∥ = 505 ± 5 MHz and A_⊥ < 200 MHz, in the case of CaF₂. A model for the center including an interstitial O^2? ion is tentatively proposed.     

Selective adsorption of He,H2 on copper surfaces

The selective adsorption of helium and molecular hydrogen has been experimentally observed on various copper surfaces characterized by a quasi one-dimensional corrugation: Cu(110), (113), (115), (117). Four bound state energy levels for the He-Cu potential and six for H₂-Cu have been measured. They are independent of the surface crystalline structure. They are well fitted by a 9-3 potential from which the well depth is deduced: D = 6.35 meV for He-Cu and D = 22 meV for H₂Cu. The Van der Waals constant C₃ is also estimated from the data. The ratio is approximately the ratio of the static polarizabilities of He and H₂. The semi-empirical formula of Hoinkes is found to agree with the present data.     

Thermoluminescence of 3d-ions doped CaF2

Thermoluminescence measurements of 80 K X-irradiated CaF₂: Me (Me: Mn, Co, Ni) are reported. The spectral distributions of the glow peaks coincide with those of the X-ray excited luminescence. It has been previously attributed to Me²⁺ emission. The temperatures, activation energies and order of the kinetics for each peak are reported. They do not depend on the dopant and are the same as those given by other authors for the glow peaks in 80 K X-irradiated CaF₂: RE. The observed emission is attributed to the de-excitation of Me²⁺ formed in an excited state by recombination of released holes with Me⁺ formed during low temperature X-irradiation. A similar mechanism has been proposed to explain the TL measurements in CaF₂: RE.     

Optical properties of Si/CaF2 superlattices

We present a first-principle theoretical study of the dielectric functions of Si/CaF₂ superlattices. In particular, we investigate how the optical response depends on the thickness of the Si layers. Our results show that for very thin Si slabs (well width less than 20 Å) optical excitation peaks are present in the visible range. These peaks are related to strong transitions between localized states. Moreover, the static dielectric costant is considerably reduced. From the comparison made with recent experimental data on similar systems we conclude that the quantum confinement, a good surface passivation and the presence of localized states are the key ingredients in order to have photoluminescence in confined silicon based systems.     

Luminescence in x-irradiated CaF2:Co

Photoluminescence of X-irradiated CaF₂:Co single crystals is reported. The emission spectrum shows four peaks at 505, 550, 640 and 685 nm, all of them with an excitation band at 275 nm. The same emission spectrum, plus a band at 280 nm, is found in X-ray excited luminescence measurements. Thermoluminescence of 80 K X-irradiated crystals gives a glow curve with five peaks at 100, 125, 145, 190 and 225 K. The spectral distribution of these glow peaks is similar to that of the X-ray excited luminescence. The 280 nm band is associated with electron—hole recombination. The other four bands are associated with electron transitions among excited states of Co²⁺ produced by recombination of holes and Co⁺-ions created by X-irradiation.     

Polarization properties of SC generated in CaF2

Polarization of SC generated by 80 fs pulses of Ti:Sapphire laser strongly depends on the orientation of CaF₂ plate with respect to the plane of polarization of the pump light. Intensity modulation of the broad blue-shifted wing of SC against crystal rotation for the polarization parallel and orthogonal to the polarization of the pump beam is observed with CaF₂ and Sapphire. Observed modulation is due to evolution of the polarization state along the propagation distance in crystal.     

Ground state and lattice dynamical study of ionic conductors CaF2, SrF2 and BaF2 using density functional theory

The present paper reports a comprehensive and complementary study on structural, electronic and phonon properties of face centered cubic fluorites, namely CaF₂, BaF₂ and SrF₂, using first principles density functional calculations within the generalized gradient approximation. The calculated lattice constants and bulk modulus are in good agreement with available experimental data. The analysis of band structure and density of states confirms the ionic character for all the three fluorides. The phonon dispersion curves and corresponding phonon density of states obtained in the present work are consistent with the available experimental and other theoretical data. The LO-TO splitting is maximum for CaF₂, which confirms that the ionicity is maximum in the case of CaF₂. The phonon properties for SrF₂ have been calculated for the first time.     

Efficient fluorescence of dissolved CaF2:Tb and CaF2:Ce, Tb nanoparticles through surface coating sensitization

Oleic acid (OA)-modified CaF₂:Tb³⁺ nanoparticles with various Tb³⁺ concentrations and CaF₂:Ce³⁺, Tb³⁺ nanoparticles were synthesized. The as-prepared nanoparticles were shown to be well dissolved in some common organic solvents, such as chloroform and toluene. The nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-Ray diffraction (XRD) and transmission electron microscopy (TEM). The investigation of fluorescence properties of CaF₂:Tb³⁺ nanoparticles showed that the Tb³⁺ ions could be sensitized efficiently by the surface coating of OA and CaF₂:Tb³⁺ nanoparticles with 10 mol% Tb³⁺ concentrations possess the highest emission intensity. The comparison of emission for CaF₂:Ce³⁺, Tb³⁺ and CaF₂:Tb³⁺ (10 mol%) nanoparticles revealed that the emission intensity of the former is about 4.5 times as strong as that of the latter.     

ESR study of europium ions in hydrolyzed CaF2: Eu crystals

Oxidation and reduction processes of europium ions in CaF₂ were studied by optical and ESR methods. Europium ions can be readily oxidized from the divalent to the trivalent states by heat-treatment above 600°C in a moist air atmosphere. The conversion can be well approximated by first order kinetics with an activation energy of 0.75 eV.

The reverse conversion from the trivalent to the divalent states can be accomplished by exposure to ionizing X-ray radiation. However, those reduced europium ions are thermally unstable and bleached completely by heating to 200°C. The decay process by low temperature annealing also follows first order kinetics with an activation energy of 0.60 eV. The conversions between the two states are explained by electron transfer.     

Temperature dependent water adsorption on Bi2Sr2CaCu2O8 single crystal

Temperature dependent infrared study of water adsorption on the bc-plane of a Bi₂Sr₂CaCu₂O₈ (Bi2212) single crystal reveals that water is molecularly physisorbed, and forms hydrogen-bonded clusters in the temperature range of 85-150 K. Although dissociative adsorption is expected on surfaces terminated with Ca-O and Cu-O groups, no dissociated species is detected. The main absorption bands occur between 3200 and 3500 cm⁻¹ and are assigned to the O-H stretching and the overtone of O-H bending. For exposures higher than 1.0 L, the sticking coefficients are similar for different temperatures. The features in the O-H stretch region for water clusters red-shift as a function of temperature between 85 and 140 K. Water clusters have an amorphous structure between 85 and 140 K, and form a crystalline structure at 150 K.     

Charge conversion of uranium ions in CaF2

Single crystals of CaF₂ doped with uranium ions exhibiting a light red colour have been grown in an inert atmosphere. ESR spectra belonging to U³⁺ centers unstable at room temperature could be observed only after UV-irradiation at liquid nitrogen temperature. The formation and annealing of these centers as well as the optical absorption date indicate that a new charge conversion mechanism is effective in such crystals.     

Free induction decay in single crystal CaF2

The free induction decay in CaF₂ has been calculated with the help of the simple model. The method allows to clarify the physical nature and to compute some parameters of the nuclear magnetic resonance spectra.     

A study of SO2 adsorption on CaO (100) surfaces using X-ray photoelectron spectroscopy

The adsorption of SO₂ on CaO (100) at 300 K has been studied using X-ray photoelectron spectroscopy. Under ultrahigh-vacuum conditions, the surface was exposed to 0–500 Langmuirs of SO₂. The resulting adsorption yields a single SO surface species with an S 2p peak at 168.2 eV and an O 1s_{$\text{sol1}\text{2}$} peak at 531.7 eV. Subsequent heating of the exposed surface to 673 K indicated no desorption or changes in the binding energies of the S 2p and O 1s_{$\text{1}\text{2}$} peaks. On the basis of these data and binding-energy data for standard compounds, the adsorbed species is identified as SO₄^2?. The surface coverage due to the SO₄^2? species was also measured as a function of SO₂ exposure. From these data, the initial adsorption is found to be first-order in surface coverage, and the initial sticking probability is found to have a value of 0.4.     

Optical properties of Sm-doped CaF2 bismuth borate glasses

Sm³⁺-doped calcium fluoride bismuth borate glasses were prepared and characterized optically and the oscillator strengths and Judd–Ofelt parameters for the glass containing 1.5 mol% of Sm₂O₃ were calculated. Density and optical absorption, transmission and the emission spectra were measured. The values of Judd–Ofelt parameters suggested an increase in the degree of asymmetry the local ligand field at Sm³⁺ sites. The optical band gap energy, band tailing parameter and Urbach's energy were calculated for all glass samples. It was found that with increasing the concentration of Sm₂O₃ content the values of the optical band gap energy decrease whereas Urbach's energy increases. Absorption and excitation spectra indicate that commercial UV and blue laser diodes, blue and bluish-green LEDs and Ar⁺ optical laser are powerful excitation sources for Sm³⁺ visible fluorescence in the glass.     

Excitation spectra and fluorescent lifetime measurements of Mn2+ in CaF2 and CdF2

The excitation spectrum of the Mn²⁺ emission has been measured in CaF₂ and CdF₂. The observed excitation bands have been assigned to transitions of the Mn²⁺ ions in a cubic environment. The calculated values for the crystal field (Dq) and Racah parameters (B,C) are Dq = 425 cm^-1 for CaF₂, Dq = 500 cm^-1 for CdF₂ and, B = 770 cm^-1 and C / B = 4.48 for both compounds. The lifetime of the fluorescent level ⁴T_1g(⁴G) has been measured in both compounds at different temperatures in the range from 10 to 500 K. The lifetime thermal dependence is explained taking into account different mechanisms (purely radiative, phonon assisted, and radiationless transitions) for the decay of excited Mn²⁺ ions.     

Synthesis and luminescence behavior of Eu-doped CaF2 nanoparticles

Luminescent Ca_1−xF_2+x:Eu_x nanoparticles were synthesized by a chemical co-precipitation method in an ethanol solution. The Ca_1−xF_2+x:Eu_x nanoparticles exhibit a sphere-like morphology with particle diameter of about 15-20 nm. With increasing concentration of Eu³⁺ ion the intensity of XRD diffraction peaks decreased significantly and full width at half-maximum of the peaks increased gradually, which indicated that more Eu³⁺ ions resulted in the increase of structural defects. The emission spectrum of Ca_1−xF_2+x:Eu_x nanoparticles consisted of a few narrow, sharp lines corresponding to Eu³⁺ ions. The luminescence intensity of Ca_1−xF_2+x:Eu_x nanoparticles increased with increasing concentration of Eu³⁺ ion and reached a maximum at approximately 15 mol%.