Nature of the stable oxide layer formed on an aluminum surface by work function measurements

The interaction of oxygen with clean aluminum results in formation of a stable oxide layer on the surface of the metal. This stable layer has a lower work function than that of clean aluminum. The nature of this stable layer is studied by measurement of work function changes. Heating of the stable layer, formed at room temperature and low oxygen pressures' (~10^?8 torr), in ultra-high vacuum resulted in a further decrease in the work function. The extent of this additional decrease was a function of temperature and the changes in work function caused by heating were irreversible in nature. At high oxygen pressures (p_O2 > 10^?2 torr) the effect of growth of incorporated oxide on the net limiting work function change appears to be small and the reversible changes in the work function are mainly a result of the variation in the amount of surface oxide. At 250°C, the contribution of incorporated oxide to net limiting work function change was dependent on oxygen pressure when it was formed at low oxygen pressures (P < 10^?7 torr). However, when the incorporated oxide was formed at oxygen pressures above 10^?7 torr, its contribution to the limiting work function change and, perhaps, the structure of the incorporated oxide itself were nearly independent of oxygen pressure. The difference in limiting work function change at various oxygen pressures was mainly because of the difference in the limiting amounts of surface oxide. Similar behavior is expected at room temperature.     

Molecular beam surface ionization detection: II. Field reversal and surface ionization study of Na on Re with adsorbed oxygen

The desorption and surface ionization of Na on a polycrystalline Re surface with various amounts of adsorbed oxygen have been studied by field reversal, surface ionization and thermoelectronic emission methods. In this work the unique properties of the field reversal method are taken advantage of, i.e. that both neutral and ionic desorption rate constants can be determined simultaneously. Absolute ionization coefficients have been measured by field reversal and have been compared with values found by the “oxygen coverage” method and by static surface ionization. The application to beam flux density determinations is discussed. The simultaneous variation of the neutral and ionic desorption rate constants during oxygen adsorption and the temperature dependence of them have been studied. The Re surface in 2 × 10^?8 Torr of oxygen and at 1300–1500 K is shown to be very stable and to behave differently than in studies at higher temperatures. The very rapid change in both desorption rate constants at an effective work function Φ^e = 5.35 V is here correlated with the results of LEED experiments (Gorodetskii and Knysh) and is proposed to indicate a change from a stable Re oxide surface at low Φ^e (and oxygen coverage) to a different surface structure at higher Φ^e. Desorption energies have been determined at various values of Φ^e. The neutral desorption energy at low oxygen pressure is 2.70 ± 0.06 eV, which agress well with earlier, here corrected modulated beam results. The energy (Schottky) cycle for surface ionization is shown to be closed at low Φ^e, which has been difficult to show with other methods in any other case.     

Measurement of the Hydrodynamic Efficiency of Laser Plasma at the “Kanal-2” Installation using Aluminum and Copper Targets

The results of experimental measurements of the hydrodynamic efficiency of laser plasma for aluminum and copper targets are presented. The studies were performed on the “Kanal-2” laser setup system using the ballistic pendulum method. The pressure in the interaction chamber was 10^?4 Torr, the pendulum length was 145 mm, the mass of the pendulum with a target was 7.2 g. At the half-height pulse duration of 2.5 ns, the power density on the target surface was ～10¹³ W/cm². In the case of aluminum target, the hydrodynamic efficiency coefficient increased from 1.5% to 4.5% with increasing laser pulse energy from 5 J to 10 J, whereas it remained at the level of 5% for the copper target.     

Electron gas compression and Coulomb explosion in the surface layer of a conductor heated by femtosecond laser pulse

The hypothesis is put forward on the basis of experimental data that strong inhomogeneous heating of the skin layer of conducting materials by a femtosecond pulse gives rise to a double electrical layer that is formed of a “surface” layer of positive ions and a thin (about 1 nm) “subsurface” layer of a superdense (10²³–10²⁵ cm^?3) degenerate electron gas. The double layer breaks within one picosecond through the Coulomb explosion.     

Adsorption of oxygen on W(110): II. The high coverage range

The structure and composition of the interaction layer between oxygen and a W(110) surface for oxygen coverages θ above 0.5 monolayers is studied with LEED, AES, thermal desorption and work function change measurements. Oxygen is adsorbed by depositing WO₂ followed by annealing. The results are interpreted in terms of a topmost layer consisting only of oxygen atoms followed by the formation of isolated three-dimensional WO₃ crystals after saturation of the two-dimensional oxidation layer at 15 × 10¹⁴ O atoms cm^?2. All available experimental evidence is compatible with this interpretation.     

Volume properties and compressibility of the graphite-potassium-mercury compounds

Abstract

The volume properties of graphite intercalation compounds (GIGS) C4KHg and of the initial intermetallic compounds KHg and KHg₂ have been investigated in the piston-cylinder apparatus, using the direct volumetric technique, under pressures up to 25 kbar. The compounds, average compressibility K₊, was determined to be 3.8×10^?3 kbar^?1 for C₄KHg, 3.0×10^?3 kbar-^?1 for C₈KHg, 4.8×10^?1 kbar^?1 for KHg, and 4.0 ×10^?1 kbar^?1 for KHg₂ at pressures of 0-20 kbar. The compressibility of the “two-dimensional” KHg layer in the GIC under various pressure conditions has been estimated. These estimates permit comparison of KHg properties in the “three dimensional” and “quasi-two dimensional” states. It was concluded that the influence of the graphite matrix on the intercalant is insignificant for this type ternary GIC.     

Investigation of the interaction of oxygen with an Al(100) surface by work function methods

The change in work function (Δφ) of an Al(100) surface due to oxygen adsorption at different pressures (10⁻⁶– 10⁻⁵ Torr) and different crystal temperatures (115–600 K) has been investigated. The data show an initially positive Δφ at low temperatures and negative Δφ values for temperatures above 160 K. The results are pressure independent during the first 500 L oxygen exposure but become pressure dependent at higher exposures. Measurements of Δφ in vacuum after exposure to 1040 L O₂ show a nearly exponential decrease of Δφ with time. The time constants of this exponential behaviour are temperature dependent and vary between 1.5 min for 370 K and 33 min at 115 K. These time dependent effects are believed to be related to the movement of adsorbed oxygen to sites below the aluminum surface.     

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.     

Helium scattering and work function investigation of co adsorption on Pt(111) and vicinal surfaces

CO adsorption on Pt(111) and vicinal Pt(111) surfaces has been studied by means of work function variation and He scattering measurements. AES and LEED were used mainly for correlations with other work. Special attention has been paid to the low coverage regime (θ_co < 0.1) with emphasis on surface structural dependencies. The minimum of the work function versus CO exposure curve occurs at a coverage less than 11% on “kink-free” surfaces. This is much lower than the hitherto commonly accepted value of 33%, and does not relate to any observed LEED superstructure. The value of Δφ_min depends strongly on the surface structure. For an “ideal” Pt(111) surface with a step density less than 10^?3 at a temperature of 300 K, Δφ_min = ?240 meV. The scattering cross section Σ of CO adsorbed on Pt(111) for 63 meV He is typically > 250 Ų, i.e. much larger than expected from the Van der Waals radii of He and CO. For two nominal Pt(111) surfaces with step densities of 10^?2 and less than 10^?3, respectively, the measured Σ values varied by a factor of three. This can be explained by preferential CO occupation of defect sites, which are already not “seen” by thermal helium. By comparing results on a stepped (997) and a kinked (12 11 9) Pt surface with similar defect densities, the kinks are proven to play a decisive role. They probably form saddles in the recently proposed activation barrier for migration between terrace and step sites.     

Auger spectroscopy of the electron-stimulated absorption of oxygen on surfaces of polycrystalline aluminum

Electron spectroscopic analysis of oxygen absorption on aluminum is performed at a partial oxygen pressure of ～10^?6 mm Hg, with and without external impact (electron bombardment). It is shown that under these conditions, an aluminum surface oxidizes in the time required for the content of an oxide film affected by Al radiation with electrons having an energy of 800 eV to stabilize.     

Structural and electronic model of negative electron affinity on the Si/Cs/O surface

Structural and electronic models are proposed which correlate Goldstein's LEED, Auger, photo-emission, plasmon, and desorption data for negative electron affinity (NEA) on Si(100) surfaces. In the structural model, the surface Si atoms group into adjacent rows of surface “pedestals” and surface “caves”. Their density is 3.4 × 10¹⁴ cm^?2 each, as inferred from the LEED 2 × 2 reconstruction pattern and other data. Adsorbed Cs resides in fourfold coordination with Si atop the pedestals. Adsorbed oxygen is completely submerged in the caves of aperture 2.98Å to give a Cs-O dipole length of 2.9Å. Similar structural arguments show why Cs must be adsorbed before O₂, and why Si(111) does not exhibit NEA. In the electronic model, the surface dielectric constant, 5.3. obtained from the surface plasmon energy, 7 eV, is used to compute the dipole length from the final work function, 0.9 eV. It is 2.8Å in excellent agreement with the dipole length computed from the above structural model. Some properties of the “induced” surface states in the presence of Cs and O are also described.     

Amorphous GaP produced by ion implantation

Two types of non-crystalline states (“disordered” and “amorphous”) of GaP were produced by using ion implantation and post annealing. A structural-phase-transition-like annealing behaviour from the “disordered” state to the “amorphous” state was observed.The ion dose dependence and the annealing behaviour of the atomic structure of GaP implanted with 200 keV ? N⁺ ions were studied by using electron diffraction, backscattering and volume change measurements. The electronic structure was also investigated by measuring optical absorption and electrical conductivity.The implanted layer gradually loses the crystalline order with the increase of the nitrogen dose.The optical absorption coefficient α and electric conductivity σ of GaP crystals implanted with 200 keV?N⁺ ions of 1 × 10¹⁶ cm^?2 were expressed as αhν = C(hν ? E₀)ⁿ and log $\text{σ = A ? BT}{}^{\mathrm{<mtext>-</mtext><mtext>1</mtext><mtext>4</mtext>}}$, respectively. Moreover, the volume of the implanted layer increased about three percent and the electron diffraction pattern was diffused halo whose intensity monotonically decreases along the radial direction. These results indicate that the as-implanted layer has neither a long range order nor a short range order (“disordered state”).In the sample implanted at 1 × 10¹⁶ cm^?2, a structural phase-transition-like annealing stage was observed at around 400°C. That is, the optical absorption coefficient α abruptly fell off from 6 × 10⁴ to 7 × 10³ cm^?1 and the volume of the implanted layer decreased about 2% within an increase of less than 10 degrees in the anneal temperature. Moreover, the short range order of the lattice structure appeared in the electron diffraction pattern. According to the backscattering experiment, the heavily implanted GaP was still in the non-crystalline state even after annealing.These facts lead us to believe that heavily implanted GaP, followed by annealing at around 400°C, is in the “amorphous” state, although as-implanted Gap is not in the “amorphous” state but in the “disordered” state.     

A “comb” structure measurement of a micrometer displacement in laser plasma propulsion

A “comb” structure of beam intensity distribution is achieved to measure target displacements at the micrometer level in laser plasma propulsion experiments. Compared with single-beam and double-beam detection, the “comb” structure is more suitable for a thin film targets with a velocity lower than 10^?2 m/s. Combined with a light-electric monitor, the “comb” structure can be used to measure a velocity range from 10^?3 to 1 m/s. Using this “comb” structure, the coupling coefficient of aluminum ablated by nanosecond pulse laser in air is determined and compared. The results indicate that this “comb” structure is an effective experimental approach.     

Characterization of clean and oxidized (100)LaB6

We have studied clean and oxidized (100)LaB₆ grown from aluminum melts by making Auger, LEED, evaporation and work function measurements on well-defined surfaces. The clean surface shows no La enrichment when initially heated as high as 1700°C. Its LEED pattern is 1 × 1, indicating no surface reconstruction. Langmuir evaporation studies up to temperatures of 1700°C show only La and B evaporating non-congruently, and LaO. The activation energy for B evaporation from LaB₆ (and from CeB₆ and EuB₆ also) is abot 5.5 eV, very close to that from elemental B. The rare-earth activation energies, however, vary, being highest for the rare-earth whose pure metal vapor pressure is lowest. Oxidation was carried out at room temperature using O₂ pressures up to 10^?7 Torr and at 1000°C using O₂ pressures up to 10^?4 Torr. At room temperature oxygen adsorption proceeeds to a saturated value indicated from LEED behavior to be about one monolayer. It produces a monotonic work function increase, which also saturates (at 1.40 V), varying linearly with the oxygen uptake. Oxidation at 1000°C is much more extensive than at room temperature, involving at least several monolayers, and results in a work function increase of 2.42 V. Results are discussed in terms of a terminal plane composed of La atoms, and adsorbed oxygen which, when given sufficient mobility, prefers bonding to La atoms at sites atop the B octahedra.     

Surface reconstruction of Cu (111) upon oxygen adsorption

Low-energy He⁺ ion scattering (IS) in combination with AES, LEED and work function measurements has been applied for the determination of surface reconstruction of Cu(111) upon oxygen adsorption. IS data clearly indicate that oxygen is not significant incorporated into the bulk at room temperature adsorption, however the surface shows reconstruction by displacement of Cu atoms by 0.3 Å. The disappearance of structure of both Cu_IS and O_IS in the “?_in pattern” demonstrate the development of a disordered layer of reconstruction centres. At saturation coverage, a rough and dis-ordered oxygen-copper surface layer is present.     

Interaction of O2 with Pt(100): I. Equilibrium measurements

Two newly discovered phases on the Pt(100) surface produced by the adsorption of oxygen have been investigated using Rutherford baekscattering (RBS), nuclear microanalysis (NMA), work function changes (Δφ) and LEED. One phase is associated with the oxygensaturated surface (0.63 ± 0.03 monolayers0.81 × 10¹⁵ O atoms cm^?2), where a very complex LEED pattern is observed; the other is observed at an average coverage of 0.44 ± 0.05 monolayers and gives rise to a (3 × 1) LEED pattern (when observed at room temperature). For both surfaces, RBS measurements indicate large (? 0.025 nm) Pt atom displacements. Also discussed is a new method for preparing the “clean” (1 × 1)-Pt(100) surface without the need for NO adsorption/decomposition.     

Field emission studies of oxygen on silver tips

Clean [111] oriented silver field emitting tips have been exposed to oxygen at 10^?3 Torr for 1 min at temperatures ranging from ? 170 to 200°C. From 50 to 200°C, an adsorption structure is formed that is stable in oxygen. The structure is characterized by intensely emitting regions on either side of enlarged {110}, {210} and {310} faces and a dark region in the (111)-{100} zone line directions. For adsorption from ? 170 to 200°C, the structure of the patterns depends distinctly on the adsorption temperature because the coverages are different and adsorption is activated. Oxygen adsorption at 10^?3 Torr for 1 min at 0°C causes an increase in the average work function of 1.15 eV. At 0°C, silver was exposed increasingly at 10^?6 Torr until 6100 L was reached. The work function increased progressively by 0.61 eV for this exposure. The {111}, {100}, {311}, {211} and {533} faces are attacked first. Then, the {110} faces are attacked followed by the {210} {310} and {320}. Heating of the adsorption layer formed at 0°C produced no changes in pattern and work function up to 100°C. Between 100 and 200°C, a strong decrease in work function and changes in the pattern result from oxygen penetration into the bulk.     

Calculations of the Overtone Transitions Of Sh− Pairs In KCl

In this work all vibration transitions up to the second overtone of pair SH^? molecules in KCl were calculated. The interaction of the identical molecules, which are characterized by “exact” resonance (equal pairs “SH^?—”SH^?, n = 32,33,34,36) were researched. The unequal molecular ions—“inexact” interaction (unequal pairs, “SH^?—^kSH^?, n≠ k, n, k = 32,33,34,36) were also considered. In both cases the problem was to find the eigenvalues of the matrix of dipole—dipole interaction that conforms to the solution of a secular equation. The elements of the dipole—dipole matrix were calculated in terms of the mechanical anharmonicity. It was supposed that the function of the dipole moment has linear dependence on the vibrational coordinate. The conditions of “exact” resonance and the conditions of “inexact” resonance diverged considerably. In the case of the “exact” resonance we used the orthogonal transformation of the dipole-dipole matrix and obtained a precise solution. In case of the “inexact” resonance we used the method of successive diagonalization. The intensities of the pair lines were calculated as well.     

The oxidation of aluminum studied by sims at low energies

The adsorption of oxygen by aluminum was studied using secondary ion mass spectrometry at low primary ion energies (? 500 eV) and low primary ion fluxes (? 5 × 10¹⁰ions/cm²/sec) in an ultrahigh vacuum system. The SIMS characteristics of a cleaned aluminum surface were measured and yield changes of positive and negative ions were measured as a function of oxygen exposure. The results strongly support a model of oxygen uptake in two stages, the first monolayer equivalent being mostly incorporated into the aluminum, probably in the second layer and the next half-monolayer equivalent being superficially chemisorbed. Selection of the correct model is important in calculations of the resonances in the electronic (valence band) structure of free-electron-like metals caused by oxygen adsorption.     

Untersuchungen an dünnen Alkalimetallschichten V

At 10^?8 mm Hg thin potassium films are evaporated on a quartz target by means of a potassium atomic beam in a reproducible manner. The big change of the optical absorption and of the electrical conductivity of such films on targets which are either “unbekernt” or “bekernt” is measured as a function of target temperature and film thickness.