Interaction of cesium and oxygen on W(110): I. Cesium adsorption on oxygenated and oxidized W(110)

Cesium adsorption on oxygenated and oxidized W(110) is studied by Auger electron spectroscopy, LEED, thermal desorption and work function measurements. For oxygen coverages up to 1.5 × 10¹⁵ cm^?2 (oxygenated surface), preadsorbed oxygen lowers the cesiated work function minimum, the lowest (～1 eV) being obtained on a two-dimensional oxide structure with 1.4 × 10¹⁵ oxygen atoms per cm². Thermal desorption spectra of neutral cesium show that the oxygen adlayer increases the cesium desorption energy in the limit of small cesium coverages, by the same amount as it increases the substrate work function. Cesium adsorption destroys the p(2 × 1) and p(2 × 2) oxygen structures, but the 2D-oxide structure is left nearly unchanged. Beyond 1.5 × 10¹⁵ cm^?2 (oxidized surface), the work function minimum rises very rapidly with the oxygen coverage, as tungsten oxides begin to form. On bulk tungsten oxide layers, cesium appears to diffuse into the oxide, possibly forming a cesium tungsten bronze, characterized by a new desorption state. The thermal stability of the 2D-oxide structure on W(110) and the facetting of less dense tungsten planes suggest a way to achieve stable low work functions of interest in thermionic energy conversion applications.     

Adsorption-desorption properties,coadsorption, and surface structural chemistry of chlorine and oxygen on Ag(331)

At 300 K oxygen chemisorbs on Ag(331) with a low sticking probability, and the surface eventually facets to form a (110)?(2 × 1) O structure with ΔΦ = +0.7 eV. This facetting is completely reversible upon O₂ desorption at ~570 K. The electron impact properties of the adlayer, together with the LEED and desorption data, suggest that the transition from the (110) facetted surface to the (331) surface occurs at an oxygen coverage of about two-thirds the saturation value. Chemisorbed oxygen reacts rapidly with gaseous CO at 300 K, the reaction probability per impinging CO molecule being ~0.1. At 300 K chlorine adsorbs via a mobile precursor state and with a sticking probability of unity. The surface saturates to form a (6 × 1) structure with ΔΦ = +1.6 eV. This is interpreted in terms of a buckled close-packed layer of Cl atoms whose interatomic spacing is similar to those for Cl overlayers on Ag(111) and Ag(100). Desorption occurs exclusively as Cl atoms with E_d ~ 213 kJ mol^?1; a comparison of the Auger, ΔΦ, and desorption data suggests that the Cl adlayer undergoes significant depolarisation at high coverages. The interaction of chlorine with the oxygen predosed surface, and the converse oxygen-chlorine reaction are examined.     

Chemisorption of H2 on W(100): Absolute sticking probability,coverage, and electron stimulated desorption

Measurements of both the absolute sticking probability near normal incidence and the coverage of H₂ adsorbed on W(100) at ~ 300K have been made using a precision gas dosing system; a known fraction of the molecules entering the vacuum chamber struck the sample crystal before reaching a mass spectrometer detector. The initial sticking probability S₀ for H₂/W(100) is 0.51 ± 0.03; the hydrogen coverage extrapolated to S = 0 is 2.0 × 10¹⁵ atoms cm^?2. The initial sticking probability S₀ for D₂/W(100) is 0.57 ± 0.03; the isotope effect for sticking probability is smaller than previously reported. Electron stimulated desorption (ESD) studies reveal that the low coverage β₂ hydrogen state on W(100) yields H⁺ ions upon bombardment by 100 eV electrons; the ion desorption cross section is ~ 1.8 × 10^?23 cm². The H⁺ ion cross section at saturation hydrogen coverage when the β₁ state is fully populated is ? 10^?25 cm². An isotope effect in electron stimulated desorption of H⁺ and D⁺ has been found. The H⁺ ion yield is ? 100 × greater than the D⁺ ion yield, in agreement with theory.     

Thermal desorption and surface lifetimes of bromine and iodine adsorbed on an ionizer of LaB6

Thermal desorption of bromine and iodine from an ionizer surface made of cold pressed and sintered LaB₆ powder has been studien in the temperature interval 800–1300°C. A new technique, where the extraction field is accelerating only during short intervals, has been developed to monitor separately the neutral desorption of readily ionized elements. The technique has been combined with the modulated beam and the modulated voltage methods for measurements of residence times and ionization efficiencies. It has also been combined with the temperature programmed desorption method used for determination of the Arrhenius parameters of desorption. The following values were obtained for l_? and l₀, the activation energies of ionic and neutral desorption, and for the corresponding pre-exponential factors C and D (D = 4C) for halogens): Bromine: l_? = 3.8 eV, l₀ = 4.3 eV, C = 2.0 × 10¹³ s^?1; Iodine: l_? = 3.4 eV, l₀ = 3.7 eV, C = 1.1 × 10¹³ s^?1. The ionization efficiencies measured at 1100°C, 0.95 for bromine and 0.7 for iodine, correspond well to what is given by the Saha-Langmuie equation using a work function of 2.7 eV. All measurements were performed with the number of adsorbed particles well below 10¹⁷ atoms/m². For higher coverages l_? was found to increase linearly by about 0.15 eV for an adsorption of 10¹⁸ atoms/m².     

Electron stimulated desorption of oxygen from nickel

Electron Stimulated Desorption (ESD) of O⁺ ions from oxygen-covered Ni(100) has been investigated at 390 K and 500 eV primary energy. The ion energy distribution is found to peak at 7.5 eV and to extend to 11 eV, over our whole exposure range (0–1000 L). The 7.5 eV peak height as a function of exposure shows that desorption takes place both in the chemisorption and the oxidation region. Emission of O⁺ occurs preferentially along the surface normal, with a base width of ≈ 60°. No azimuthal structure is observed. Additional electron energy dependent measurements clearly show a threshold near the oxygen 2s level.     

Entrapment of inert gas ions near molybdenum surface

The thermal desorption spectra of inert gas ions (neon, argon and krypton) injected with various energies (430–1950 eV) into a polycrystalline molybdenum target with various dosages (6.4×10¹²−3.9×10¹⁴ ions/cm²) are reported. At least four different states of binding of the trapped atoms corresponding to the activation energies for desorption have been observed from the spectra. The activation energies are found to be relatively insensitive to the species of the bombarding ion, incident ion energy and the dosage. The shapes of the spectra are strongly influenced by the depth of penetration of the ions into the solid. The activation energies deduced are in good agreement with those reported for the migration of atoms and defects in molybdenum.     

The GaP(001) surface and the adsorption of Cs

GaP(001) cleaned by argon-ion bombardment and annealed at 500°C showed the Ga-stabilized GaP(001)(4 × 2) structure. Only treatment in 10^?5 Torr PH₃ at 500°C gave the P-stabilized GaP(001)(1 × 2) structure. The AES peak ratio $\text{P}\text{Ga}$ is 2 for the (4 × 2) and 3.5 for the (1 × 2) structure. Cs adsorbs with a sticking probability of unity up to 5 × 10¹⁴ Cs atoms cm^?2 and a lower one at higher coverages. The photoemission measured with uv light of 3660 Å showed a maximum at the coverage of 5 × 10¹⁴ atoms cm^?2. Cs adsorbs amorphously at room temperature, but heat treatment gives ordered structures, which are thought to be reconstructed GaP(001) structures induced by Cs. The LEED patterns showed the GaP(001)(1 × 2) Cs structure formed at 180°C for 10 h with a Cs coverage of 5 × 10¹⁴ atoms cm^?2, the GaP(001)(1 × 4) Cs formed at 210°C for 10 hours with a Cs coverage of 2.7 × 10¹⁴ atoms cm^?2, the GaP(001)(7 × 1) and the high temperature GaP(001)(1 × 4), the latter two with very low Cs content. Desorption measurements show three stability regions: (a) between 25–150°C for coverages greater than 5 × 10¹⁴ atoms cm^?2, and an activation energy of 1.2 eV; (b) between 180–200°C with a coverage of 5 × 10¹⁴ atoms cm^?2, and an activation energy of 1.8 eV; (c) between 210–400°C with a coverage of 2.7 × 10¹⁴ atoms cm^?2, and an activation energy of 2.5 eV.     

Desorption kinetics and directional dependence of the surface diffusion of potassium on stepped W(100) surfaces

Using a surface ionisation ion microscope the desorption parameters and the diffusion constant of potassium were measured on stepped W(100) surfaces. The activation energy of ionic desorption as well as the corresponding prefactor do not depend on the step density; the mean adsorption lifetime τ can be expressed as τ=1.6×10^?14s exp(2.44 eV/kT).Whereas the surface diffusion of potassium on “flat” W(100) and on W(S)-[9(100)×(110)] was found to be isotropic, on W(S)- [5(100)×(110)] and W(S)-[3(100)×(110)] it occurs preferentially parallel to the step direction. The diffusion constant D_∥ for this direction has roughly the same value for all investigated surfaces: D_∥=7.8×10^?2 cm²s^?1 exp(?0.42 eV/kT). For the direction perpendicular to the steps D⊥ depends on the step density, whereby the activation energy as well as the prefactor increase with increasing step density.     

Adsorption-desorption properties and surface structural chemistry of chlorine on Cu(111) and Ag(111)

The adsorption, desorption, and structural properties of chlorine adlayers on Cu(111) and Ag(111) have been studied by LEED, Auger, Δ?, and thermal desorption measurements. Ancillary experiments were also carried out on cuprous chloride for purposes of comparison with the Cu(111)-Cl data. Chlorine adsorption is rapid on both metals and follows precursor kinetics, the absolute initial sticking probabilities being ~1.0 (Cu) and ~0.5 (Ag). Δ? results suggest that significant depolarisation of the chemisorption bond occurs at high coverages, the maximum values being + 1.2 eV (Cu) and + 1.8 eV (Ag). On Cu(111), adsorption leads to the formation of a sequence of well-ordered phases; in order of increasing coverage, these are as follows: (√3 × √3)R30°, (12√3 × 12√3)R30°, (4√7 × 4√7)R19.2°, and (6√3 × 6√3)R30°. On Ag(111) (√3 × √3)R30°, and (10 × 10) structures are observed. All six structures are susceptible to a straightforward interpretation in terms of coincidence lattices resulting from the progressive uniform compression of a hexagonal layer of Cl atoms. This interpretation is consistent with all the experimental results, and gives values for the nearest-neighbour ClCl spacing on both Cu(111) and Ag(111) which are in good agreement with other work on other surfaces. Chlorine desorbs exclusively as atoms from both metals with first-order desorption kinetics, and apparent desorption energies of 236 (Cu) and 209 (Ag) kJ mol^?1. These values, which depend on an assumed pre-exponential factor of 10¹³ s^?1, are shown to be inconsistent with the thermochemical constraints on the system necessitated by the complete absence of Cl₂ desorption. Lower limits for the pre-exponential factors are then deduced, and the values are found to be consistent with the differences between the CuCl and AgCl systems.     

TDS and LEED studies of H2O adsorption on GaAs(110)

The UHV cleaved (110) face has been exposed to water in the range from 10 L to 2 × 10⁴ L. The main TDS peak in H₂O desorption appears at 350 K, independent of coverage. The low desorption energy of 0.7 eV (16 kcal/mol) is reasonable for oxygen atoms bound via the lone pair orbital to As as was earlier derived from UPS measurements. A broad spur between 450 and 600 K may be related to O-Ga bonds. The sticking probability shows values below 10^-4; only near 4.8 × 10³ L (6 × 10¹⁵ cm^-2 s^-1 H₂O molecules for 300 s) corresponding to a coverage of about 0.4 monolayes a steep maximum appears. At about one monolayer saturation is observed. Exposures to more than 10⁴ L of water quench the intensity of the (10) LEED spot considerably stronger than the intensity of the (11) spot. A comparison of the I(E) curves with existing model calculations suggests that the observed behaviour of the LEED spots is caused by a change in surface structure towards the unrelaxed configuration. The higher sticking coefficient observed near 0.4 monolayers may be connected with this rearrangement of surface atoms.     

约化场强对氮-氧混合气放电等离子体演化特性的影响

采用零维等离子体动力学模型,计算了不同约化场强条件下N₂/O₂放电等离子体的演化特性.结果表明,平均电子能量与约化场强有着近似的线性关系,在约化场强为100 Td时,平均电子能量约为2.6 eV、最大电子能量达35 eV;约化场强是影响电子能量函数分布的主要因素.气体放电过程结束后,振动激发态氮分子的粒子数浓度不再变化,电子激发态的氮分子、原子和氧原子的粒子数浓度达到一峰值后开始降低;放电结束后的氧原子通过复合反应生成臭氧.约化场强升高,由于低能电子减少的影响,振动激发态氮分子的粒子数浓度降低,当约化场强由50 Td增加75 Td,100 Td时,粒子数浓度由3.83×10¹¹ cm^-3降至1.98×10¹¹ cm^-3和1.77×10¹¹ cm^-3,其他粒子浓度则相应增大. 关键词： 等离子体 约化场强 粒子演化 数值模拟     

Ag离子注入非晶SiO2的光学吸收、拉曼谱和透射电镜研究

能量为200keV的Ag离子，以1×10¹⁶，5×10¹⁶，1×10¹⁷ cm^-2的剂量分别注入到非晶SiO₂玻璃，光学吸收谱显示：注入剂量为1×10¹⁶ cm^-2的样品的光吸收谱为洛伦兹曲线，与Mie理论模拟的曲线形状一致；注入剂量较大的5×10¹⁶，1×10¹⁷ cm^-2的谱线共振吸收增强，峰位红移并出现伴峰. 透射电镜观察分析表明，注入剂量不同的样品中形成的纳米颗粒的大小、形状、分布都不同，注入剂量较大的还会产生明显的表面溅射效应，这些因素都会影响共振吸收的峰形、峰位和峰强. 当注入剂量达到1×10¹⁷ cm^-2时，Ag纳米颗粒内部可能还形成了杂质团簇. 关键词： 离子注入 纳米颗粒 共振吸收 红移     

Electron stimulated desorption of O+ ions: Energy dependence of the desorption efficiency from adsorbed oxygen on metal surfaces and its bearing on the mechanism

Measurements of the structure in the curve of desorption yield versus electron energy for ESD of O⁺ from β₁-oxygen on polycrystalline W and W(100), and from oxidized V are reported. They show definite structure around the core ionization thresholds of the metal atoms. This may be taken as evidence for the existence of Auger mechanisms of ESD, e.g. that proposed recently by Knotek and Feibelman for oxidic oxygen.     

A radiotracer study of slow electron interaction with co on polycrystalline Mo

The interaction of slow (50–300 eV) electrons with CO chemisorbed on a polycrystalline Mo ribbon was investigated. A radiotracer was employed to monitor C concentration on the surface and desorbed ions were collected. From the time variation of the ion current, total electron induced desorption cross sections of 3.7 × 10^?17 to 1.6 × 10^?16 cm² were obtained. The desorption cross section for C containing species was found to be less than 1.4 × 10^?19 cm². In addition, the sticking coefficient for CO on Mo was found to be 0.13–0.16. These results are discussed in terms of the states of chemisorbed CO and the conclusions of other investigations of this systems.     

Surface diffusion of lead on tungsten

Field electron microscopy is used to study the surface diffusion of lead on tungsten. A simple method to measure rough values of the diffusion coefficient and its dependence on sub-monolayer coverage is described and tested. In the region around (001) the displacement energy found is about 1.30 eV/atom up to 10¹⁵ atoms/cm² where it decreases to 0.78 eV/atom. In the residual region except (110) this energy at 1.5×10¹⁴ atoms/cm² is 1.22 eV/atom, it decreases at 4 × 10¹⁴ atoms/cm² to 0.61 eV/atom and increases at 10¹⁵ atoms/cm² to 0.78 eV/atom. Corresponding values of the diffusion coefficient D and of the preexponential D₀ are given. The dependence of D on submonolayer coverage is discussed.     

Trap characterization for Bi4Ti3O12 thin films by thermally stimulated currents

Thermally stimulated current (TSC) measurements performed in the 100 K–400 K temperature range on Bi₄Ti₃O₁₂ (BiT) thin films annealed at 550 °C and 700 °C had revealed two trapping levels having activation energies of 0.55 eV and 0.6 eV. The total trap concentration was estimated at 10¹⁵ cm⁻³ for the samples annealed at 550 °C and 3×10¹⁵ cm⁻³ for a 700 °C annealing and the trap capture cross-section was estimated about 10⁻¹⁸ cm². From the temperature dependence of the dark current in the temperature range 20 °C–120 °C the conduction mechanism activation energy was found to be about 0.956–0.978 eV. The electrical conductivity depends not only on the sample annealing temperature but also whether the measurement is performed in vacuum or air. The results on the dark conductivity are discussed considering the influence of oxygen atoms and oxygen vacancies. Received: 28 January 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

Study of lithium adsorption on the TiO2 surface by electron-stimulated desorption

This paper reports on a study of electron-stimulated desorption (ESD) of O⁺ and Li⁺ ions from titanium dioxide as a function of the preheating temperature T and of the concentration of lithium adsorbed at 300 K, which was carried out with a static magnetic mass spectrometer combined with a retarding-field energy analyzer. For T>1500 K, the TiO₂ surface undergoes irreversible rearrangement. At temperatures from 300 to 900 K and at lithium coverages Θ<1, the ESD cross sections of the O⁺ and Li⁺ ions vary in a reversible manner with temperature, while for lithium coverages Θ>1, the changes in the Li⁺ and O⁺ ESD cross sections become irreversible. For θ<1, the appearance threshold of the Li⁺ and O⁺ ions is 25 eV, whereas for θ>1, the ESD threshold of Li⁺ ions shifts to 37 eV.     

Polycrystalline GaSb films prepared by the coevaporation technique

Gallium antimonide (GaSb) films were deposited onto fused silica and n-Si (100) substrates by coevaporating Ga and Sb from appropriate evaporation sources. The films were polycrystalline in nature. The size and the shape of the grains varied with the change in the substrate temperature during deposition. The average surface roughness of the films was estimated to be 10 nm. Grain boundary trap states varied between 2×10¹² and 2.2×10¹² cm^?2 while barrier height at the grain boundaries varied between 0.09 eV and 0.10 eV for films deposited at higher temperatures. Stress in the films decreased for films deposited at higher temperatures. XPS studies indicated two strong peaks located at ～543 eV and ～1121 eV for Sb 3d_3/2 and Ga 2p_3/2 core-level spectra, respectively. The PL spectra measured at 300 K was dominated by a strong peak located ～0.55 eV followed by two low intensity peaks ～0.63 eV and 0.67 eV. A typical n-Si/GaSb photovoltaic cell fabricated here indicated V _oc～311 mV and J～29.45 mA/cm², the density of donors (N _d)～3.87×10¹⁵ cm^?3, built in potential (V _bi)～0.48 V and carrier life time (τ)～28.5 ms. Impedance spectroscopy measurements indicated a dielectric relaxation time ～100 μs.     

Electron beam interactions with CO on W {100} studied by Auger electron spectroscopy

The interaction of 2500 eV electrons with carbon monoxide chemisorbed on tungsten {100} was investigated by rapid-scan Auger electron spectroscopy. When no α state was present the O and C signals from the β state of CO were invariant during electron bombardment, giving an upper limit estimate for the electron stimulated desorption cross section, Q_β of 2 × 10^?21 cm². With the crystal at room temperature and saturated with CO, however, electron-beam induced accumulation of carbon was observed and characterised, the rate of the process being independent of CO pressure at pressures above 2 × 10^?8 Torr. At 450 K the rate was found to be pressure dependent up to at least 6 × 10^?7 Torr. A model is proposed for the accumulation process, which is based on electron beam dissociation of α₂-CO to form adsorbed carbon and gaseous O and the creation of new sites for further α₂-CO adsorption; it is in quantitative agreement with the results and yields a cross section for ESD of α₂-CO (Q_α2 = 1.55×10^?18cm²) in close agreement with direct measurements.