Adsorption dynamics of CO2 on Cu(1 1 0): A molecular beam study

Molecular beam scattering measurements have been conducted to examine the adsorption dynamics of CO₂ on Cu(1 1 0). The initial adsorption probability, S₀, decreases exponentially from 0.43 ± 0.03 to a value close to the detection limit (∼0.03) within the impact energy range of E_i = (0.12-1.30) eV. S₀ is independent of the adsorption temperature, T_s, and the impact angle, α_i, i.e., the adsorption is non-activated and total energy scaling is obeyed. The coverage, Θ, dependent adsorption probability, S(Θ), agrees with precursor-assisted adsorption dynamics (Kisliuk type) above T_s ∼ 91 K. However, below that temperature adsorbate-assisted adsorption (S increases with Θ) has been observed. That effect is most distinct at large E_i and low T_s. The S(Θ) data have been modeled by Monte Carlo simulations. No indications of CO₂ dissociation were obtained from Auger Electron Spectroscopy or the molecular beam scattering data.     

CO2 adsorption on Cr(1 1 0) and Cr2O3(0 0 0 1)/Cr(1 1 0)

We attempt to correlate qualitatively the surface structure with the chemical activity for a metal surface, Cr(1 1 0), and one of its surface oxides, Cr₂O₃(0 0 0 1)/Cr(1 1 0). The kinetics and dynamics of CO₂ adsorption have been studied by low energy electron diffraction (LEED), Aug er electron spectroscopy (AES), and thermal desorption spectroscopy (TDS), as well as adsorption probability measurements conducted for impact energies of E_i = 0.1-1.1 eV and adsorption temperatures of T_s = 92-135 K. The Cr(1 1 0) surface is characterized by a square shaped LEED pattern, contamination free Cr AES, and a single dominant TDS peak (binding energy E_d = 33.3 kJ/mol, first order pre-exponential 1 × 10¹³ s⁻¹). The oxide exhibits a hexagonal shaped LEED pattern, Cr AES with an additional O-line, and two TDS peaks (E_d = 39.5 and 30.5 kJ/mol). The initial adsorption probability, S₀, is independent of T_s for both systems and decreases exponentially from 0.69 to 0.22 for Cr(1 1 0) with increasing E_i, with S₀ smaller by ∼0.15 for the surface oxide. The coverage dependence of the adsorption probability, S(Θ), at low E_i is approx. independent of coverage (Kisliuk-shape) and increases initially at large E_i with coverage (adsorbate-assisted adsorption). CO₂ physisorbs on both systems and the adsorption is non-activated and precursor mediated. Monte Carlo simulations (MCS) have been used to parameterize the beam scattering data. The coverage dependence of E_d has been obtained by means of a Redhead analysis of the TDS curves.     

Dynamics of interaction of H2 and D2 with Ni(110) and Ni(110) surfaces

Elastic and direct-inelastic scattering as well as dissociative adsorption and associative desorption of H₂ and D₂ on Ni(110) and Ni(111) surfaces were studied by molecular beam techniques. Inelastic scattering at the molecular potential is dominated by phonon interactions. With Ni(110), dissociative adsorption occurs with nearly unity sticking probability s₀, irrespective of surface temperature T_s and mean kinetic energy normal to the surface 〈 E_⊥ 〉. The desorbing molecules exhibit a cos θ_e angular distribution indicating full thermal accommodation of their translation energy. With Ni(111), on the other hand, s₀ is only about 0.05 if both the gas and the surface are at room temperature. s₀ is again independent of T_s, but increases continuously with 〈 E⊥ 〉 up to a value of ～0.4 for 〈 E⊥ 〉 = 0.12 eV. The cos⁵θ_e angular distribution of desorbing molecules indicates that in this case they carry off excess translational energy. The results are qualitatively rationalized in terms of a two-dimensional potential diagram with an activation barrier in the entrance channel. While the height of this barrier seems to be negligible for Ni(110), it is about 0.1 eV for Ni(111) and can be overcome through high enough translational energy by direct collision. The results show no evidence for intermediate trapping in a molecular “precursor” state on the clean surfaces, but this effect may play a role at finite coverages.     

Direct-inelastic and trapping-desorption scattering of N2 and CH4 from Pt(111)

Angle and velocity distributions for supersonic chopped beams of N₂ and CH₄ scattered from clean close-packed Pt(111) surfaces are reported. For specular direct-inelastic scattering N₂ and CH₄ velocity distributions can be characterized by empirical relationships used for Ar scattering. For instance, for specular scattering the following relation is found for Ar, N₂ and CH₄: 〈KE_f〉 = A(KE_i) + B(2kT_s), where 〈KE_f〉 is the average final kinetic energy, KE_i is the incident kinetic energy and T_s is the surface temperature. The beam and surface temperature independent coefficients A and B are, respectively: Ar 0.87, 0.17; N₂ 0.79, 0.19 and CH₄ 0.84, 0.25. Unlike Ar, N₂ desorbs from Pt with a Maxwell-Boltzmann velocity distribution near the surface temperature. Qualitatively the trapping probabilities for these molecules on Pt(111) are ordered: Xe > N₂ > CH₄> Ar.     

Study of cross sections for the loss of outer 1s, 2s, and 2p electrons by fast ions and atoms of light elements

In the case of light-element ions propagating with velocities V = 1.83 and 3.65 au in H₂, He, N₂, Ne, and Ar, the loss cross sections σ_{i, i+m} for m electrons (m = 1, 2, 3) are considered. The partial loss cross sections σ_i(nl) for one of the outer 1s, 2s, or 2p electrons are determined using the obtained data. It is shown that the experimental cross sections for the loss of the 1s and 2s electrons by positive ions qualitatively agree with the theoretical values calculated in the Born approximation. In the case of the ion velocity V = 1.83 au, the cross sections σ_i for 2p electrons are greater than the cross sections σ_i (1s) and σ_i (2s) by a factor of 1.2–3 for the same binding energies of electrons in the ion (I _nl > 20 eV). It is found experimentally that, at V = 1.83 au, the cross sections σ_i (2p) for I _nl ～ 10–20 eV are less than the cross sections σ_i (1s) by a factor of 2–3, which is probably caused by a decrease in the screening parameter (θ_2p < 1) of the outer shell of atoms.     

Molecular beam scattering of linear and branched butane on graphite (HOPG)

The adsorption of n-butane and iso-butane on HOPG (highly-oriented pyrolitic graphite) has been studied by molecular beam scattering. The initial adsorption probability, S₀, decreases with impact energy, E_i, and is independent of surface temperature, T_s, i.e., molecular adsorption is present. The adsorption probability, S, increases with coverage, Θ, which is most distinct at large E_i and low T_s. Thus, precursor mediated adsorption is concluded. Whereas S₀ of the linear alkane is larger than the one of the branched alkane, consistent with their molecular structure, the shapes of S(Θ) curves are approximately identical. The rotational excitation of the molecules appears to affect S₀ for n-butane but not for iso-butane. Monte Carlo simulations (MCS) have been conducted to extract dynamics parameters from the S(Θ) curves.     

Focused scattering of low energy Li+ from Mo(001): Experimental and computer simulation results

The azimuthal dependence of the energy distribution of Li⁺, specularly scattered from Mo(001), has been obtained for several incident energies E_i. The energy distributions exhibit one or two peaks, which always lie below the kinematical single scattering energy and which have intensity and energy that depend upon the azimuth. Due to trajectory focusing, the intensity is strongly peaked along the [100] azimuth for E_i ? 500 eV, but at higher E_i the intensity enhancement is shifted toward the [310] azimuth. Results of computer simulation give reasonable agreement with experimental observations. Analysis of the simulated trajectories allows identification of the scattering mechanisms which contribute to each portion of the spectrum.     

Adsorption of gold on oxidized tungsten

The kinetics of adsorption and desorption of gold atoms from the surface of a thin (<2 nm) oxide film grown on a textured W ribbon with the preferred emergence of the (100) face is studied using termal desorption spectrometry in a wide range of coatings. A single desorption phase is observed in the spectra of termal desorption of Au atoms from oxidized W. The activation energy of desorption of Au atoms from tungsten oxides is lower than the gold sublimation heat (it amounts to E = 3.1 eV for the concentration of adsorbate atoms on the surface corresponding to coverage θ _s = 2.38). The gold film on oxidized tungsten at room temperature grows in the form of 3D islands. The sticking coefficient for gold atoms at T = 300 K is close to unity in the coverage range 0.5 < θ _s < 2.5.     

Critical phenomena in the β-(2×4) → α-(2×4) reconstruction transition on the (001) GaAs surface

The critical exponents of the β-(2×4) → α-(2×4) reconstruction phase transition on the (001) GaAs surface are determined experimentally. It is found that the phase transition is analogous to a van der Waals transition. The critical parameters T _c , P _c , and Θ_c have been measured experimentally. The mean field theory is applied, and three-parameter isotherms are obtained that agree with the experimental results at the following values of the parameters: E_st = 0.36 eV, ΔE = 0.18 eV, and E _i = 0.134 eV. Precision measurements of the critical exponents β and δ are carried out. Their values β = 1/8 and δ = 15 indicate that the phase transition is truly two-dimensional.     

Investigation of crystal structure and new ellipsometric properties of hexagonal CdS epilayers

High quality hexagonal CdS epilayer was grown on GaAs (1 1 1) substrates by the hot-wall epitaxy method. The crystal structure of the grown CdS epilayers was confirmed to be the hexagonal structure by X-ray diffraction pattern and scanning electron microscopy image. The optical properties of the hexagonal CdS epilayers were investigated in a wide photon energy range between 2.0 and 8.5 eV using spectroscopic ellipsometry (SE) at room temperature. The data obtained by SE were analyzed to find the critical points of the pseudodielectric function spectra, 〈?(E)〉 = 〈?₁(E)〉 + i〈?₂(E)〉, such as E₀, E_1A, E_1B, E^0′, F₁, and two E₂ structures. In addition, the second derivative spectra, d²?(E)/dE², of the pseudodielectric function of hexagonal CdS epilayers were numerically calculated to determine the critical structures. Four structures, such as E^0′F₁, and two E₂ structures, from 6.0 eV to 8.0 eV were observed, for the first time, at 300 K by ellipsometric measurements for the hexagonal CdS epilayers.     

Green function theory of Curie and order—order transitions in ferromagnetic systems

Dipolar critical temperatures in ferromagnetic systems with isotropic bilinear and biquadratic exchange are investigated by means of the Green function technique. Expressions are found for both the familiar Curie temperature, T_c, and the less well known order-order transition temperature, T_o, at which, under appropriate conditions, the magnetic ordering undergoes a change between fully aligned and canted ferromagnetism. At T = 0, a fully aligned state has <s_i^z = s for spin s and all lattice sites i, while a canted state has 〈s_i^z〉<s. It is shown independently of the Green function analysis that the T = 0 ground state is fully aligned if α, the ratio of biquadratic to bilinear exchange integrals, obeys ?[2s(s?1)]^?1<α< [2s²?2s+1]^?1. The region below the lower limit is identified as the range in which canted ferromagnetism can occur and is a range that does not appear to have been considered previously via the Green function formalism.The temperature dependence of the magnetic ordering is investigated by means of the double-time temperature-dependent Green function formalism. A new decoupling scheme is derived and used to reduce higher order Green functions to lowest order. It is found that a canted state, occuring at low temperatures, undergoes a transition to a fully aligned state at a temperature T₀ and subsequently becomes disordered at temperature T_c. Transitions to paramagnetism are found to be second order for α<α_c and first order for α?α_c where α_c is a critical value that depends on the atomic spin and weakly on the lattice structure. A phase diagram is given to illustrate the results, and a comparison is made with the corresponding results found in mean field theory.     

Temperaturen in Ionenlaserplasmen

Plasma temperatures of the wall-stabilized low pressure Ar-arc, which has been optimized for maximum inversion density of the Ar II 4p- 4s laser transitions (i.e.kT _e?4 eV), have been determined experimentally and compared with literature data. Ion temperature is obtained from the Doppler linewidths of Ar II transitions, which have been measured both spectroscopically and indirectly by measuring the gain of the 4880 å laser line. Neutral temperature is obtained from the Doppler linewidths of Ar-I-transitions and by relating fill pressure and calculated values of the corresponding gas density. Ion- and neutral temperature are reported to reach values ofT _i? 30000 K andT _a? 25 000 K, respectively. In the range under present concern (kT _e?4 eV, 15≦jR [A cm^?1]≦150)T _i as well asT _a is a function of the characteristic parameterjR alone (j=current density,R=tube radius).     

Carbon segregation on a tungsten surface

New measurements are performed and a comprehensive analysis of experimental data is made on the dependence of equilibrium carbon coverage θ on a tungsten surface on its temperature and the degree of carbon loading. It is shown that if the volume is free of carbon, the variation of θ for T≥1400 K can be approximately described by the balance between the carbon flows through the boundary with the activation energy for transition into the bulk E₁=4.6 eV and the segregation energy ΔE=1.7 eV. For tungsten loaded preliminarily with carbon to a content of ≈10^?2 at. %, the θ(T) relation cannot be described in terms of the equilibrium conditions with constant E₁ and ΔE, because these quantities depend on the degree of carbon loading; E₁ grows from 4.6 to 6.8 eV and ΔE grows from 1.7 to 2.3 eV with an increase in carbon content from 0 to 10^?2 at. %. These variations are attributed to the bonds becoming stronger in carbon-loaded tungsten with increasing carbon content.     

Morphology of Cn thin films (50 ⩽ n < 60) on graphite: Inference of energy dissipation during hyperthermal deposition

Low energy cluster beam deposition, LECBD, under UHV conditions has been used to generate thin films comprising monodispersed non-IPR fullerenes, C_n, 50 ? n < 60, on pyrolithic graphite surfaces (HOPG). The morphology of the resulting C_n deposits has subsequently been studied by ex situ atomic force microscopy. Deposition experiments were carried out under nominally normal incidence and at hyperthermal incident kinetic energies, E₀, varied between 1 and 40 eV. Surface temperatures during deposition, T_s, were varied from 300 K to the desorption onset of ～700 K. Initial sticking of C_n cages is governed by the lateral density of step edges, which act as pinning and nucleation centres for migrating cages. Consequently in the early deposition stages, the surface exhibits large areas of empty terraces, while the step edges themselves are well-decorated. The terraces in turn become decorated by dendritic C_n islands in later deposition stages. Both, the mean size of these 2D islands and the mean distance between nearest islands, δ, scale with the size of the terraces. When increasing the primary kinetic energy, the fractal-like islands become smaller and less dendritic in shape. The mean initial sticking coefficient decays exponentially with increasing E₀. The island topography has also been found to depend sensitively on the deposition temperature. Instead of the dendritic/fractal islands generated at room temperature, densely packed islands terminated by smooth rims are observed upon deposition at elevated temperatures. We rationalize our findings in terms of a three step deposition process involving: (i) conversion of perpendicular E₀ into hyperthermal surface parallel gliding/sliding motion, (ii) friction–dissipation of this surface-parallel kinetic energy within an (unexpectedly large) mean free path Λ followed by (iii) thermal diffusion. Λ, is observed to scale with E₀ and T_s.     

Work function measurements on germanium by thermionic emission

In the present paper, we report the results of experiments carried out to determine the effect of surface states on the work function of intrinsic, germanium crystals. This investigation is realised by using the Thermionic Emission Theory at the intrinsic temperature range T (from 900 to 1050 K). The “apparent work function” φ¹, obtained from the experimental ln(i_sT²) versus 1/T curves, is found different from the Richardson-Dushman equation one: “the true work fucntion” φ. This difference is mainly due to the work function and electron reflection coefficient dependence on temperature. φ is deduced from φ¹ and from RD modified equation taking into account the semiconductor case. The value of φ varies with T: from 3.97 to 4.16 eV. These results are compared with those obtained, by several authors, using other techniques. We present an analysis of these results taking into consideration the effect of surface states shifts on the surface barrier height, and on the work function consequently.     

Anisotropy of the repulsive intermolecular potential from rotationally inelastic scattering

Structure is observed in recoil velocity distributions of potassium atoms scattered inelastically from N₂ and CO molecules at CMS angles?>π/2 and collision energies 0.34≦E≦1.24 eV. It is caused by rotational excitation mainly. Individual rotational transitions are not resolved. The quasi-continuous recoil velocity distributions extend between well defined bounds, the upper corresponding to elastic scattering, the lower marking a largest amount of energy transferred into molecular rotation at given? andE. This maximal transfer increases with angle and — forE?0.64 eV — in near proportion toE. At all? andE it is larger for CO than forN ₂, amounting to about 0.42E forN ₂ and 0.64E for CO at?=150°. At or very close to each of their bounds the distributions exhibit pronounced maxima. A third intermediate maximum is present for CO, but missing for N₂. The scattering in these experiments is dominated by the repulsive core of the interaction potential. On the basis of classical scattering from a rigid, ellipsoidal, initially nonrotating potential shell, the observations can be qualitatively understood as follows: The recoil velocity dependence of the orientation averaged cross section at fixed observation angle will exhibit classical, integrable singularities at extremal amounts of rotational energy transfer. If the center of symmetry of the shell coincides with the center of mass of the molecule, there will be two such extremal transfers,ΔE=0 and a largest transfer possible at the chosen angle. If the centers do not coincide, the singularity at the largest transfer will split into two, one corresponding to the short, the other to the long “lever arm” of the shell. K + N₂ is an example of the centrical, K+CO of the excentrical case. The finite energy losses, at which the singularities occur, are — at each angle — strongly dependent on the anisotropy and excentricity of the shell.     

Langmuir probe and optical emission spectroscopy studies for RF magnetron sputtering during TiON thin film deposition

Low-pressure plasma of gas mixture of Ar, O₂ and N₂ generated by RF magnetron sputtering was characterized by Langmuir probe and optical emission spectroscopy (OES). The electron temperature (T_e), ion density (n_i) and electron energy distribution function (EEDF) in Ar-O₂-N₂ plasma atmosphere were calculated from I-V characteristic of Langmuir probe. Boltzmann plot method was applied for calculating the vibrational temperature (T_vib) of the second positive system of N₂ (N₂SPS) in Ar-O₂-N₂ plasma. The T_e, n_i, EEDF and T_vib in Ar-O₂-N₂ plasma were studied as a function of O₂ percentages. It was found, the T_vib increased from 0.47 eV to 0.55 eV as the oxygen percentage in Ar-N₂-O₂ plasma increased from 10% to 40%. Further, the T_e increased from 1.6 eV to 3 eV as the O₂ concentration increased from 10% to 40%.     

Effect of series resistance on the performance of silicon Schottky diode in the presence of tin oxide layer

The current–voltage (I–V) characteristics of Al/SnO₂/p-Si (MIS) Schottky diodes prepared by means of spray deposition method have been measured at 80, 295 and 350 K. In order to interpret the experimentally observed non-ideal Al/SnO₂/p-Si Schottky diode parameters such as, the series resistance R_s, barrier height Φ_B and ideality factor n, a novel calculation method has been reported by taking into account the applied voltage drop across interfacial oxide layer V_i and ideality factor n in the current transport mechanism. The values obtained for V_i were subtracted from the applied voltage values V and then the values of R_s were recalculated. The parameters obtained by accounting for the voltage drop V_i have been compared with those obtained without considering the above voltage drop. It is shown that the values of R_s estimated from Cheung’s method were strongly temperature-dependent and decreased with increasing temperature. It is shown that the voltage drop across the interfacial layer will increase the ideality factor and the voltage dependence of the I–V characteristics. The interface state density N_ss of the diodes has an exponential growth with bias towards the top of the valance band for each temperature; for example, from 2.37 × 10¹³ eV⁻¹ cm⁻² in 0.70−E_v eV to 7.47 × 10¹³ eV⁻¹ cm⁻² in 0.62−E_v eV for 295 K. The mean N_ss estimated from the I–V measurements decreased with increasing the temperature from 8.29 × 10¹³ to 2.20 × 10¹³ eV⁻¹ cm⁻².     

Adsorption of iso-butane on ZnO(0 0 0 1)-Zn

Presented are thermal desorption spectroscopy (TDS) and adsorption probability measurements of iso-butane on the Zn-terminated surface of ZnO. The initial adsorption probability, S₀, decreases linearly from 0.57 to 0.22 (±0.02) with impact energy, E_i = 0.74-1.92 eV, and is independent of adsorption temperature, T_s = 91-114 K (±5 K), indicating non-activated molecular adsorption. The coverage, Θ, dependent adsorption probabilities, S(Θ), show a cross-over from adsorbate-assisted adsorption (S increases with Θ) to Kisliuk-like dynamics at about the desorption temperature of iso-butane bi-layers (∼110 K). Thus, the adsorption dynamics are precursor-mediated. The enhanced (gas-surface) mass-match, caused by forming a second layer of the alkane, leads to adsorbate-assisted adsorption. A direct fitting procedure of the TDS data yields a pre-exponential factor of 2.5 × 10¹³/s and a coverage dependent heat of adsorption of E_d(Θ) = 39 − 6 ∗ Θ + 2.5 ∗ exp(−Θ/0.07) kJ/mol.