Angular and energy dependences of the surface excitation parameter for semiconducting III-V compounds

Sum-rule-constrained extended Drude dielectric functions were used to study surface excitations generated by energetic electrons moving across surfaces of semiconducting III-V compounds. Parameters in the dielectric functions were determined from fits to experimental optical data and electron energy-loss spectra. Electron inelastic mean free paths (IMFPs) in GaN, GaP, GaAs, GaSb, InAs and InSb were calculated for electron energies between 200 and 2000 eV, and the results were found to follow the simple formula, i.e., λ = kE^p, where λ is the IMFP and E is the electron energy. Surface excitation parameters (SEPs), which describe the total probability of surface excitations by electrons crossing the surface and travelling in vacuum, were also calculated for different electron energies and crossing angles. The SEP was found to follow the simple formula, i.e., , where P_s is the SEP and α is the crossing angle relative to the surface normal.     

Trinal Nature of the Excitation of Bulk Plasmons by a Fast Charged Particle at Grazing Incidence on the Interface between Vacuum and a Metal with Strong Spatial Dispersion

The excitation and propagation of bulk and surface (surface waves of transition radiation of plasmons at frequencies above the plasma frequency) plasma waves by incident electrons moving both in vacuum toward the surface of a metal and inside the metal whose boundary elastically and spectacularly reflects internal nonequilibrium electrons have been analyzed. In contrast to work [B. N. Libenson, J. Exp. Theor. Phys. 113, 553 (2011)], attention in this work is focused on the influence of surface effects on bulk-plasmon excitation by incident electrons. The probabilities and spectra of single characteristic energy loss of an intermediate- energy electron (50–500 eV) moving at an angle to the surface of the medium in three regions: in vacuum, in the medium, and again in vacuum after the electron leaves the medium are calculated. The kinetic approximation is used for the dielectric function, where the entire range of the plasmon spectrum is taken into account correctly for the problem under consideration. In the indicated energy range of incident electrons, surface effects, on the one hand, significantly reduces the probability of excitation of bulk plasma waves in the medium with strong spatial dispersion, in particular, as compared to the results obtained in [B.N. Libenson, J. Exp. Theor. Phys. 113, 553 (2011)], where surface effects were disregarded and the probability of bulkplasmon excitation by a 200-eV electron incident and emitted perpendicularly to the boundary is about one third of that in the unbounded medium. On the other hand, at grazing incidence from vacuum, the probability of transition radiation of bulk plasmons increases significantly and can lead to a change in the character of the angular dependence of the intensity of bulk plasma energy loss. Thus, the main result of this work is that a decrease in the glancing angle of the fast electron with respect to the vacuum–metal interface is accompanied both by an increase in the contribution from the transition mechanism to the probability of bulk-plasmon excitation in the vacuum region and by a decrease in the contribution from Cherenkov and bremsstrahlung mechanisms of excitation in the medium. The probability of bulk-plasmon excitation in the vacuum region exceeds the probability of excitation at the further motion of the electron in metallic aluminum at angles of incidence larger than 65°, 70°, and 75° at the energies E = 200, 350, and 500 eV, respectively.     

Anisotropy analysis of the surface stress and surface energy in Cu surfaces with the modified embedded atom method

Taking Cu as an example, the surface stress and surface energy in three low index surfaces and two families of representative surfaces and belong to [0 0 1]- and -rotating axis respectively, have been calculated using MEAM. For the three low index surfaces, the decrease in the surface energy is small after relaxation, while the surface stresses in the surface planes τ_xx and τ_yy show opposite changes (decreasing and increasing) for inward and outward relaxations. The resulting relaxation direction is related to the normal stress τ_zz before relaxation. For the surfaces of the and families, with the increasing angle α (between the and (1 0 0) planes, and between and (0 0 1) planes, respectively), the surface stress and surface energy go through an oscillatory change. The surface stress and surface energy are symmetric about the planes (1 0 0), (1 1 0) and (0 1 0) at α=0^°, 45^° and 90^°, and about the planes (0 0 1) and (1 1 0) at α=0^° and 90^° respectively, due to crystal symmetry.     

X-ray initiated molecular photochemistry of Cl-containing adsorbates on a Si(1 0 0) surface using synchrotron radiation

X-ray initiated molecular photochemistry for SiCl₄ and CCl₄ adsorbed on Si(1 0 0) at ∼90 K following Cl 2p core-level excitation is investigated by photon stimulated ion desorption and ion kinetic energy distribution measurements. The Cl excitation of solid SiCl₄ induces the significant enhancement (∼900%) of the Cl⁺ yield, while the Cl excitation of condensed CCl₄ leads to a moderate enhancement (∼500%) of the Cl⁺ yield. The enhancement of Cl⁺ yield at the specific core-excited states is strongly correlated to the ion escaped energy. Upon X-ray exposure for CCl₄ adsorbed on Si(1 0 0) (20-L exposure), the Cl⁺ yields at resonances decrease and new structures at higher photon energies are observed. Cl⁺ yields at these new resonances are significantly enhanced compared to those at other resonances. These changes are the results of desorption and surface reaction of the CCl₄-Si surface complex due to X-ray irradiation. We have demonstrated that state-specific enhancement of ion desorption can be successfully applied to characterize the reaction dynamics of adsorbates adsorbed on surfaces by X-ray irradiation.     

Experimental and theoretical studies on X-ray induced secondary electron yields in Ti and TiO2

Generation of X-ray induced secondary electrons in Ti and TiO₂ was studied from both experimental and theoretical approaches, using X-ray photoelectron spectroscopy (XPS) attached to a synchrotron radiation facility and Monte Carlo simulation, respectively.The experiment revealed that the yields of secondary electrons induced by X-rays (electrons/photon) at photon energies to 4950 and 5000 eV for Ti and TiO₂ are δ_Ti(4950 eV) = 0.002 and δ_Ti(5000 eV) = 0.014 while those for TiO₂ are δTiO₂(4950 eV)=0.003 and δTiO₂(5000 eV)=0.018.A novel approach to obtain the escape depth of secondary electrons has been proposed and applied to Ti and TiO₂. The approach agreed very well with the experimental data reported so far. The Monte Carlo simulation predicted; and while and .An experimental examination on the contribution of X-ray induced secondary electrons to photocatalysis in TiO₂ has also been proposed.     

Surface defect states of CdTexS1 − x quantum dots

Properties of surface defect states of CdTe_xS_1 − x quantum dots with an average diameter of 7 nm are investigated experimentally. The stoichiometric ratio is found to be for by use of the energy dispersive analysis of x-ray. The photoluminescence spectrum, the photoluminescence excitation spectrum, and the surface passivation are adopted to characterize the properties of surface defect states. The energy levels of surface defect states of CdTe_xS_1 − x quantum dots are also determined.     

Photocatalytic reduction of oxygen molecules at the (1 0 0) TiO2 anatase surface

The adsorption, photoreduction and chemical activity of oxygen molecules on the (1 0 0) anatase surface have been investigated here together with the effects that surface oxygen vacancies (V_O) can have on these O₂-related processes. We use an original approach by treating molecules on the TiO₂ surface like surface defects in the same framework successfully used for defects in semiconductors. The achieved results: (i) give the first theoretical evidence of an acceptor behaviour of an adsorbed O₂ molecule, which is at the origin of its photoreduction; (ii) show that the V_O donor character is strongly affected by the interaction with O₂; and (iii) suggest that the release of radicals as well as the formation of O₂-related radicals may be favoured by photogenerated electrons in presence of surface V_O’s.     

Electron-phonon interaction in magnesium: From the monolayer to the Mg(0 0 0 1) surface

We report ab initio study of the electron-phonon coupling in a free standing magnesium monolayer and at the Mg(0 0 0 1) surface. The calculations were carried out using a linear-response approach in the plane-wave pseudopotential representation. Eliashberg spectral function α²F(ω) averaged over electron states at the Fermi surface is presented for the monolayer while for the Mg(0 0 0 1) surface, we compute the electron-phonon spectral function α²F_k,i(ω) for surface states at the and points.     

Determination of the effective surface region thickness and of Begrenzungs effect

The thickness, x_s, of the effective surface region, defined as the region in which an electron travelling inside a material experiences surface excitations, as well as Begrenzungs effect, i.e. the variation of the bulk inelastic cross section in the surface region are theoretically determined for aluminium and silicon using the QUEELS-ε(k,ω)-REELS software. This software allows to determine the energy-differential inelastic electron scattering cross sections for reflection-electron-energy-loss spectroscopy (REELS) within the dielectric response theory. This study has been carried out for electron energies between 300 eV and 5000 eV. We find that the bulk inelastic cross section decreases exponentially with the distance to the surface, that x_s is practically independent of electron incidence and exit angles and that x_s=[2(v_B)^0.4/ω_s]v^0.6, where ω_s is the surface plasmon frequency, v the electron velocity and v_B the Bohr velocity ().     

A computational study on the adsorption and ring cleavage of para-chlorophenol on anatase TiO2 surface

In this work, a computational technique based on semiempirical SCF MO method MSINDO, has been used for investigation of the adsorption and photocleavage of para-chlorophenol (p-CP) molecule on the anatase TiO₂ (0 0 1) and (1 0 0) surfaces. The surfaces have been modeled with two saturated clusters Ti₂₁O₅₈H₃₂ and Ti₃₆O₉₀H₃₆. The optimization of the perpendicular conformation of p-CP molecule relative to the anatase TiO₂ (1 0 0) surface, has resulted in a linkage of the molecule to the surface titanium atom via phenolic oxygen atom. We studied the aromatic ring cleavage by singlet oxygen (¹O₂) and superoxide radical anion () and accordingly, relevant mechanisms are suggested. The results reveal that the ring opening path of p-CP molecule on TiO₂ (1 0 0) surface, following the single electron transfer/ mechanism, is energetically more favourable than the ¹O₂/dioxetane mechanism.     

Measurements of insulator band parameters using combination of single-electron and two-electron spectroscopy

We describe the application of low energy time-of-flight coincidence (e,2e) spectroscopy for measurements of the energy band parameters of a dielectric. The (e,2e) spectrometer can operate also in a single-electron mode by switching off coincidence conditions, and can be used for recording electron energy loss spectra (EELS). Thus, the combination of (e,2e) and EELS allows the measurement of energy gap E_g, valence bandwidth ΔE_val, electron affinity χ and excitonic levels position E_ex of a dielectric. The energy band parameters of LiF film deposited on Si(001) surface are measured: ΔE_val=      

The transition from surface to bulk oxide growth on Pt(1 0 0): Precursor-mediated kinetics

We investigated the kinetics governing the transition from surface (2D) to bulk (3D) oxide growth on Pt(1 0 0) in ultrahigh vacuum as a function of the surface temperature and the incident flux of an oxygen atom beam. For the incident fluxes examined, the bulk oxide formation rate increases linearly with incident flux (Φ_O) as the oxygen coverage increases to about 1.7 ML (monolayer) and depends only weakly on the surface temperature in the limit of low surface temperature (T_S < 475 K). In contrast, in the high temperature limit (T_S > 525 K), the bulk oxide formation rate increases with for oxygen coverages as high as 1.6 ML, and decreases with increasing surface temperature. We show that the measured kinetics is quantitatively reproduced by a model which assumes that O atoms adsorb on top of the 2D oxide, and that this species acts as a precursor that can either associatively desorb or react with the 2D oxide to form a 3D oxide particle. According to the model, the observed change in the flux and surface temperature dependence of the oxidation rate is due to a change in the rate-controlling steps for bulk oxide formation from reaction at low temperature to precursor desorption at high temperature. From analysis of flux-dependent uptake data, we estimate that the formation rate of a bulk oxide nucleus has a fourth-order dependence on the precursor coverage, which implies a critical configuration for oxide nucleus formation requiring four precursor O atoms. Considering the similarities in the development of surface oxides on various transition metals, the precursor-mediated transition to bulk oxide growth reported here may be a general feature in the oxidation of late transition metal surfaces.     

Applications of the master equation of a two-level atom in a narrow-bandwidth squeezed vacuum

In this paper, we derive the time-dependent solution of the effective master equation for the reduced density matrix operator of a two-level atom driven by a coherent laser field and damped by a finite-bandwidth squeezed vacuum. The master equation has the standard form known from the broadband squeezing approaches but with new effective squeezing parameters and and new rate coefficients. There are also new terms, proportional to β, which are essentially narrow-bandwidth modifications determined by the parameters γ_n, δ_n and the shifts δ_N and δ_M. These parameters become zero when the squeezing bandwidth tends to infinity. The effects of the detuning parameter Δ of the driving laser field frequency ω_L from the atomic resonance ω_A and the squeezing parameters and on the atomic inversion, the von Neumann entropy and the resonance fluorescence spectrum are discussed.     

Relationships between surface compositions and properties of surfaces of mixed fumed oxides

Fumed oxides SiO₂/Al₂O₃ (SA), SiO₂/TiO₂ (ST) and Al₂O₃/SiO₂/TiO₂ (AST) at different content of alumina and titania were investigated by one-pass temperature-programmed desorption (OPTPD) time-of-flight mass-spectrometry (TOFMS), Auger electron spectroscopy (AES), NMR, FTIR, thermally stimulated depolarization current (TSDC), microcalorimetry, adsorption of nitrogen, water, (dimethylamino)azobenzene (DMAAB) and metal ions (Pb(II) and Ni(II)). It was shown that all the studied adsorption/desorption and energetic properties of mixed fumed oxides depend strongly on the surface content of alumina (shown as a surface content of aluminum, ) in SA and AST and titania (shown as a surface content of titanium, ) in ST and AST. Many of these properties demonstrate clear correlations with the and values over the total range of alumina and titania content in the materials.     

Stretch-bend combination polyads in the ÃAu state of acetylene, C2H2

Rotational analyses are reported for a number of newly-discovered vibrational levels of the S₁-trans (ùA_u) state of C₂H₂. These levels are combinations where the Franck-Condon active and vibrational modes are excited together with the low-lying bending vibrations, and . The structures of the bands are complicated by strong a- and b-axis Coriolis coupling, as well as Darling-Dennison resonance for those bands that involve overtones of the bending vibrations. The most interesting result is the strong anharmonicity in the combinations of (trans bend, a_g) and (in-plane cis bend, b_u). This anharmonicity presumably represents the approach of the molecule to the trans-cis isomerization barrier, where ab initio results have predicted the transition state to be half-linear, corresponding to simultaneous excitation of and . The anharmonicity also causes difficulty in the least squares fitting of some of the polyads, because the simple model of Coriolis coupling and Darling-Dennison resonance starts to break down. The effective Darling-Dennison parameter, K₄₄₆₆, is found to increase rapidly with excitation of , while many small centrifugal distortion terms have had to be included in the least squares fits in order to reproduce the rotational structure correctly. Fermi resonances become important where the K-structures of different polyads overlap, as happens with the 2¹3¹B¹ and 3¹B³ polyads (B = 4 or 6). The aim of this work is to establish the detailed vibrational level structure of the S₁-trans state in order to search for possible S₁-cis (¹A₂) levels. This work, along with results from other workers, identifies at least one K sub-level of every single vibrational level expected up to a vibrational energy of 3500 cm⁻¹.     

Magnetocaloric effect in the ferromagnetic Kondo lattice model

The Kondo lattice model describes a lattice of localized spins S_i interacting with the conduction electrons via a local exchange coupling J. Assuming a ferromagnetic Hund's rule coupling J>0, the model can be used to describe some itinerant magnetocaloric materials such as Gd(Si_xGe_1-x)₄, La(Fe_1-xSi_x)₁₃, and LaCa_1-xMn_xO₃, which are important for magnetic refrigeration near room temperature. The localized magnetic moments are described in the model Hamiltonian by spin operators, and the conduction electrons by fermionic operators. To study the magnetocaloric effect, a uniform external magnetic field is added through a Zeeman term. By averaging the fermionic degrees of freedom, one obtains an indirect exchange coupling between spins at sites i and j, which corresponds to the RKKY interaction. The self-consistent mean value is evaluated in the effective Heisenberg Hamiltonian within the random phase approximation (RPA). The conduction electron magnetization for a given value of is obtained from the corresponding Green's functions through the equation of motion method. The pressure and doping dependence of the Curie temperature are taken into account in the evaluation of . The magnetocaloric effect is characterized by the isothermal entropy change ΔS and the adiabatic temperature change ΔT_ad upon magnetic field variations in the neighborhood of the ferromagnetic phase transition. The results are obtained for and compared to measurements with Gd compounds.     

Ab initio calculations of generalized-stacking-fault energy surfaces and surface energies for FCC metals

The ab initio calculations have been used to study the generalized-stacking-fault energy (GSFE) surfaces and surface energies for the closed-packed (1 1 1) plane in FCC metals Cu, Ag, Au, Ni, Al, Rh, Ir, Pd, Pt, and Pb. The GSFE curves along (1 1 1) direction and (1 1 1) direction, and surface energies have been calculated from first principles. Based on the translational symmetry of the GSFE surfaces, the fitted expressions have been obtained from the Fourier series. Our results of the GSFEs and surface energies agree better with experimental results. The metals Al, Pd, and Pt have low γ_us/γ_I value, so full dislocation will be observed easily; while Cu, Ag, Au, and Ni have large γ_us/γ_I value, so it is preferred to create partial dislocation. From the calculations of surface energies, it is confirmed that the VIII column elements Ni, Rh, Ir, Pd, and Pt have higher surface energies than other metals.     

Inactivation of Escherichia coli and properties of medical poly(vinyl chloride) in remote-oxygen plasma

This paper reports the germicidal effect (GE) of Escherichia coli on the surface of medical poly(vinyl chloride) (PVC) in remote-oxygen plasma. The concentration of active species in plasma is determined by means of double Langmuir electron probe and electron-spin resonance (ESR) diagnosis. Moreover, surface properties of sterilized PVC are characterized by the water contact angle measurement, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The distribution of electrons, ions, and radicals in plasma reactor is different. High-purity radicals are obtained at 40 cm from the induction coil which is called remote-plasma zone. By remote-oxygen-plasma sterilization, GE value reach 4.12 under the conditions of treatment time of 60 s, plasma RF power of 100 W and oxygen flux of 60 cm³/min. Compared with direct-oxygen-plasma sterilization, remote plasma can enhance the hydrophilic property and limit the degradation of the PVC surface. After remote-plasma sterilization, PVC surface energy is increased more than twice, which mainly resulted from the increase of surface polar force , and hydrogen bonding force . Moreover, remote-plasma sterilization can increase oxygenated functional groups on PVC surface. Experimental results show that remote plasma can inactivate E. coli on the medical PVC substrate effectively. Furthermore, it can optimize the surface properties.     

Sub-Doppler high-resolution excitation spectroscopy of the S1 ← S0 transition of dibenzofuran

Rotationally resolved ultrahigh-resolution fluorescence excitation spectra of the S₁ ← S₀ transition of dibenzofuran have been observed using the technique of crossing a collimated molecular beam and the single-mode UV laser beam. 3291 rotational lines of the band and 3047 rotational lines of the band have been assigned. The band has been found to be a b-type transition, in which the transition moment is along the twofold symmetry axis of this molecule, and only the ΔK_a = ± 1 transitions were observed. The excited state is identified to be the S₁¹A₁(ππ^∗) state. In contrast with this, the band has been found to be an a-type transition in which the transition moment is along the long axis in plane. It indicates that the intensity of this vibronic band arises from vibronic coupling with the S₂¹B₂(ππ^∗) state. We determined the accurate rotational constants and the molecule have been shown to be planar both in the ground and excited states.