Diffusion and compressibility of sodium on the (110) plane of tungsten

The surface diffusion parameters and the compressibility of sodium on the (110) plane of tungsten have been measured using the field emission fluctuation method for sodium coverages from 0.2 to 3 × 10¹⁴ atoms cm^?2 and for temperatures from 170 to 500 K. Two temperature regimes can be defined. In the high temperature regime (? 300 K) the diffusion is essentially normal with an activation energy ranging from 0.28 to 0.58 eV and a preexponential coefficient D₀ from 10^?8.1 to 10^?2.7 cm² s^?1. In this regime the compressibility increases with temperature indicating an effective repulsive adatoms interaction. In the low temperature regime (? 300 K) the diffusion coefficient decreases with temperature at high coverage and slowly increases with temperature at lower coverage. The transition between both regimes appears on the compressibility versus temperature curve as an inflection point. The comparison of the present results with slow electron diffraction results furnishes strong evidence that the observed transition corresponds to a continuous short-range order-disorder transition.     

Implant redistribution in high-dose ion implanted and annealed silicon

Abstract

Diffusion constants of helium in gold, silver and aluminium are determined from thermal desorption experiments, giving:

Au: D ₀ = 10^?1.0 cm²/sec, ΔH = 1.70 eV

Ag: D ₀ = 10^?1.2 cm²/sec, ΔH = 1.50 eV

Al: D ₀ = 10^+0.1 cm²/sec, ΔH = 1.35 eV

The results are compared to self-diffusion and to the diffusion of other light elements in metals. Possible diffusion mechanisms are discussed.     

Electron stimulated desorption of H− and H+ from hydrogen covered tungsten

Electron stimulated desorption from a hydrogen covered polycrystalline tungsten surface has been investigated. The H^? and H⁺ desorption current as a function of incident electron energy was measured in both the low and high energy region. Some threshold-like structures appear in the curve of the desorption current versus incident electron energy; however, no threshold structures have been observed for H^? desorption in the high energy region. The experimental results obtained and the desorption process are discussed in some detail, including initial excitation, charge transfer and ultimate desorption.     

The kinetics of hydrogen (deuterium) sorption by thin palladium layers studied with a piezoelectric quartz crystal microbalance

The kinetics of the hydrogen (deuterium) Sorption processes in the α-phase region of a thin electrodeposited Pd layer (thickness 3 × 10^?5 cm) are reported. Measurements have been performed with a piezoelectric quartz crystal microbalance using an AT-cut crystal with a resonance frequency f⁰_q = 5.27 MHz and a sensitivity of ～10¹⁰ digits g^?1, at a constant temperature 80.3 ± 0.05 °C and different pressures. Both the absorption and the desorption of H₂(D₂) on Pd layers are controlled successively by a chemisorption step (second order kinetics) in the early stage of the processes and by a surface migration step (first order kinetics), in the subsequent stage of the processes. Consistent with the reported piezoelectric quartz crystal microbalance measurements, thermal desorption and electrochemical desorption studies, a mechanism is suggested which takes into account the adsorption ofH(D) atoms on two different surface states: (a) a “pre-dissolved” state which does not depend on the surface nature; (b) and adsorption state, the density of which depends upon the structure and nature of the Pd sample. The kinetic control of the entire processes (sorption and desorption) depends on the ratio of the density of sites (a) to (b).     

Adsorption,coadsorption, and reactivity of sodium and nitric oxide on Ag(111)

The adsorption, desorption, and surface structural properties of Na and NO on Ag(111), together with their coadsorption and surface reactivity, have been studied by LEED, Auger spectroscopy, and thermal desorption. On the clean surface, non-dissociative adsorption of NO into the a-state occurs at 300 K with an initial sticking probability of ~0.1, saturation occurring at a coverage of $\text{~}\text{1}\text{20}$. Desorption occurs reversibly without decomposition and is characterised by a desorption energy of E_d ~ 103 kJ mol^?1. In the coverage regime 0 < θ_Na < 1, sodium adsorbs in registry with the Ag surface mesh and the desorption spectra show a single peak corresponding to E_d ~ 228 kJ mol^?1. For multilayer coverages (1 < θ _Na < 5) a new low temperature peak appears in the desorption spectra with E_d ~ 187 kJ mol^?1. This is identified with Na desorption from an essentially Na surface, and the desorption energy indicates that Na atoms beyond the first chemisorbed layer are significantly influenced by the presence of the Ag substrate. The LEED results show that Na multilayers grow as a (√7 × √7) R19.2° overlayer, and are interpreted in a way which is consistent with the above conclusion. Coadsorption of Na and NO leads to the appearance of a more strongly bound and reactive chemisorbed state of NO (β-NO) with E_d ~ 121 kJ mol^?1. β-NO appears to undego surface dissociation to yield adsorbed O and N atoms whose subsequent reactions lead to the formation of N₂, N₂O, and O₂ as gaseous products. The reactive behaviour of the system is complicated by the effects of Na and O diffusion into the bulk of the specimen, but certain invariant features permit us to postulate an overall reaction mechanism, and the results obtained here are compared with other relevant work.     

Viscosity at small scales in polymer melts

Flows around small colloidal particles of diameter b, or in thin films, capillaries, etc., cannot always be described in terms of the macroscopic polymer viscosity. We discuss these features for entangled polymer melts, where two distinct regimes can be found: (a) the thin regime where b is smaller than the coil radius R₀, but larger than the diameter of the Edwards tube; (b) the ultrathin regime, where . We consider (i) non adsorbing particles, where slippage may occur between the melt and the solid surface; (ii) “hairy” particles, which carry some bound polymer chains. We obtain scaling predictions for mobilities of spheres, of needles, and of clusters of particles. We also discuss translational and rotational diffusion of needles. Received 19 April 1999     

A molecular-beam investigation of the reaction H2 + 12O2 → H2O on Pd(111)

Using molecular-beam relaxation techniques and isotopic exchange experiments, the water-formation reaction on Pd(111) has been shown to proceed via a Langmuir-Hinshelwood mechanism. The reaction product H₂O is emitted from the surface with a cosine distribution. The rate-determining step is the formation of OH_ad in the reaction O_ad + H_ad → OH_ad. The activation energy for this step is 7 kcal/mole with a pre-exponential factor, v, of 4 × 10^?8 cm² atom^?1 sec^?1. This value for v lies well below that observed for simple second-order desorption of dissociatively adsorbed diatomic gases, but is roughly of the order of that obtained for the oxidation of CO on Pd(111). The formation of H₂O proceeds differently under conditions of excess O₂ or H₂. In an excess of H₂, the kinetics is dominated by the transport of atomic hydrogen between the bulk and the surface as was found for the H?D exchange reaction on Pd(111). In an excess of O₂, diffusion of hydrogen into the bulk is blocked by adsorbed oxygen and the hydrogen reservoir available for reaction at the surface is decreased by several orders of magnitude. This results in a drastic reduction of the reaction rate which can be reversed by increasing the partial pressure of H₂.     

Periodic structures and scaling Laws in a magnetic colloid

Summary Phase separation was found in an eicosane-based ferrofluid in zero applied field. Upon applying a magnetic field, the condensed phase breaks up to form a lattice of periodic columns. The periodicity λ scales with the layer thicknessL. Two scaling regimes were found. When thickness is small, where no branching is observed, λ ∞L ^1/2. In the large-thickness regime, a tree type of structure develops at the tail of each column, and the columns are separated by side bands while the scaling relation crosses over to λ ∞L ^2/3. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994. this work is in collaboration with Hao Wang, Yun Zhu, C. Boyd, A. Cebers and R. E. Rosensweig.     

Hydrogen-plasma etching of hydrogenated amorphous silicon: a study by a combination of spectroscopic ellipsometry and trap-limited diffusion model

The kinetics of etching hydrogenated amorphous silicon by a hydrogen plasma has been studied by in-situ spectroscopic ellipsometry measurements. The formation of a hydrogen-rich sublayer is clearly emphasized. Its thickness increases from 7 to 27?nm when the temperature during the hydrogen-plasma treatment is raised from 100 to 250°C. This effect is interpreted by solving the differential equation for trap-limited hydrogen diffusion through a mobile surface. By assigning the thickness of this sublayer to the mean diffusion distance of hydrogen we determined values of the effective diffusion coefficient of hydrogen higher than 10^?14?cm²s^?1 with an activation energy of 0.22?eV. The density of hydrogen traps is found to decrease from 7.3 × 10¹⁸ to 4.5 × 10¹⁷?cm^?3 as the temperature of the hydrogen treatment increases from 100 to 250°C with an activation energy of 0.43?eV. This effect is interpreted by a thermal equilibrium involving hydrogen transitions between shallow states and hydrogen-trapping sites.     

Morphology-controlled PANI nanowire electrode by using deposition scan rate in H<Subscript>2</Subscript>SO<Subscript>4</Subscript>/PVA polymer electrolyte for electrochemical capacitor

Polyaniline (PANI) nanowire electrode was successfully prepared using electrodeposition method. The morphology, thickness, and electrochemical performance of PANI electrode can be controlled by varying the deposition scan rates. Lower deposition scan rate results in compact and aggregates of PANI nanowire morphology. The uniform nanowire of PANI was obtained at the applied scan rate of 100 mV s^?1, and it was used as symmetric electrode coupled with H₂SO₄/polyvinyl alcohol (PVA) gel electrolyte. The different concentrations of H₂SO₄ acid in polymer electrolyte have influenced the electrochemical performance as well. The optimum specific capacitance and energy density of P100 PANI electrode in 3 M H₂SO₄/PVA gel polymer electrolyte was 377 F g^?1 and 95.4 Wh kg^?1 at the scan rate of 1 mV s^?1. The good stability of the electrode in this system is applicable to many wearable electronics applications.     

Adsorption of hydrogen on evaporated cobalt films

Hydrogen adsorption on evaporated Co films has been studied by means of measurements of the surface potential changes that occur during this process, and analysis of the desorption spectrum of hydrogen. It has been observed that hydrogen adsorbed at 78 K on Co films exists in three forms with essentially different electrical properties: atomic, electronegatively polarized β^? form; atomic, electropositively polarized β⁺ form and reversibly adsorbed, molecular, positively polarized α form. The β^? form is not homogeneous from the point of view of the bond energy with the metal surface and consists of the states β_s^? and β^? characterized by activation energy of desorption 10.0 and 18.8 kcal/mol H₂ correspondingly. The Activation energy of desorption of the β⁺ form is low, i.e. 2.1 $\text{kcal}\text{mol}$ H₂.     

X-ray induced electron stimulated desorption versus photon stimulated desorption: NH3 on Ni(110)

The X-ray induced desorption of H⁺ ions from NH₃ layers adsorbed at T = 90 K on Ni(110) has been compared to the corresponding total electron yield (TY) in the photon energy range 390 to 900 eV. The H⁺ yield exhibits a jump at the N K-edge and the Ni L-edge which inversely varies with the NH₃ layer thickness. The H⁺ Ni L-edge jump is closely correlated to the TY jump. Both vanish for the saturated NH₃ multilayer, indicating that the observed Ni L-edge jump in the H⁺ yield is exclusively due to X-ray induced electron stimulated desorption (XESD). At the N K-edge, the near edge absorption fine structure of the H⁺ yield and TY of the saturated NH₃ multilayer are distinctly different. This is interpreted as the H ⁺ yield being the superposition of direct photon stimulated ion desorption (PSID) and XESD. Based on the observed variation of the H⁺ yield near edge fine structure with varying NH₃ layer thickness, a deconvolution of the PSID and XESD contributions is used to derive the relative contribution of PSID versus XESD to be 40% versus 60%, respectively. The relevance of this result for future PSID-SEXAFS studies is discussed. For monolayer NH₃ on Ni(110) the polarization dependence of the N K-edge fine structure in the N(KVV) Auger yield indicates that the symmetry axis of NH₃, is perpendicular to the surface.     

The interference of an electron beam with the surface reaction between oxygen and germanium

Electron beam assisted adsorption and desorption of oxygen was studied by Auger electron spectroscopy (AES). Beam assisted adsorption was observed on clean as well as on oxidized surfaces. After an oxygen exposure of 1000 × 10^?7 Torr min and continuous irradiation with beam voltage of 1.5 kV and beam current density 2 microA mm^?2, the oxygen 510 eV signal amplitude from the point of beam impact was 2.5 times greater than the signal from the non-irradiated region. The Ge 89 eV signal showed a corresponding decrease. Enhanced adsorption occurred at beam energies as low as 16.5 eV. After irradiation, the oxidized surface was not carbon contaminated. Following an oxygen exposure of 30 min at 0.1 Torr and 550°C and subsequent additional beam assisted exposure of 1000 × 10^?7 Torr min, the maximum oxide thickness was about 18 Å. Beam assisted desorption did not occur from thin oxygen layers (0–510 eV signal strength less than 5 units, calculated oxide thickness about 6 Å), but occurred from thick oxides and stopped after the signal amplitude had decreased to 5 units. Based on these results, a model for the structure of the oxygen layer covering the Ge(111) surface is proposed. Mechanisms for adsorption and desorption are discussed. The implications of beam assisted adsorption and desorption on electron beam operated surface measurements (LEED, AES, ELS, APS etc.) are stressed.     

Desorption kinetics and surface diffusion of potassium,rubidium and cesium on a silicon(111)7 × 7-surface

Using pulsed atomic beam technique and a surface ionization ion microscope, the desorption kinetics and the surface diffusion of the alkalis potassium, rubidium and cesium were investigated on a Si(111)7 × 7-surface at extremely low alkali coverages. In the temperature range 1120 … 800 K, the mean adsorption lifetime τ(T) = τ₀ · exp(E_desⁱ/kT) and the mean diffusion length x(T) - defined in the equilibrium between adsorption, diffusion and desorption - were measured. From these data the diffusion constant D(T) = D₀ · exp(-E_diff/kT) was obtained as D = x^?2/τ. For temperatures T ? 750 K, the diffusion constant was calculated from nonstationary alkali concentration profiles using the Boltzmann-Matano method. From the temperature dependence of these quantities the parameters of desorption (E_des,ⁱ τ₀) and surface diffusion (E_diff, D₀) for K, Rb and Cs on Si(111) were obtained. The values of E_diff and D₀ are comparably high and may be interpreted by non-localized diffusion according to a model proposed by Bonzel (Surf. Sci. 21 (1970) 45).     

Wetting and Phase Separation in Polymer Blend Films: Identification of Four Thickness Regimes with Distinct Morphological Pathways

Using forward recoil spectrometry and atomic force microscopy, the phase evolution of a critical blend thin film of deuterated poly(methyl methacrylate) (dPMMA) and poly(styrene-ran-acrylonitrile) (SAN) is found to depend on film thickness. Four regimes are identified as film thickness l ₀ decreases from semi-infinite to below the radius of gyration, R _g. In the semi-infinite limit or regime IV (l ₀ R _g), surface directed spinodal decomposition is observed and found to agree with cell dynamic simulations. In regime III (10 R _g < l ₀ < 150 R _g), three stages of evolution are observed. During the early stage, wetting dominates and produces a dPMMA-rich/SAN-rich/dPMMA-rich structure. During the intermediate stage, the surface phase flows back into the middle layer inducing lateral phase coarsening. During the late stage, capillary fluctuations rupture the middle layer by spinodal dewetting, resulting in a final morphology with SAN-rich droplets encapsulated by dPMMA-rich wetting layers. Although regime II (R _g < l ₀ < 10 R _g) films also exhibit a tri-layer early stage, correlated holes in the middle layer spontaneously grow suggesting that this layer is too thin to support fully developed capillary fluctuations. Three stages of roughening are observed with a final morphology similar to regime III. In regime I (l ₀ < R _g), films roughen almost immediately after annealing in contrast to the other regimes. Initially, the surface roughness increases logarithmically with time before reaching a constant value of 2 R _g. The final average droplet height, 29.5 nm, is in good agreement with a simple interfacial energy model. Whereas the final morphology for regimes I, II and III are identical, the pathways by which films roughen are distinct suggesting that erroneous conclusions can be made by simply analyzing the final morphology.     

Identification of non-thermal and thermal processes in femtosecond laser-ablated aluminum

Non-thermal and thermal processes due to femtosecond laser ablation of aluminum (Al) at low, moderate, and high-fluence regimes are identified by Atomic Force Microscope (AFM) surface topography investigations. For this purpose, surface modifications of Al by employing 25 fs Ti: sapphire laser pulses at the central wavelength of 800 nm have been performed to explore different nano- and microscale features such as hillocks, bumps, pores, and craters. The mechanism for the formation of these diverse kinds of structures is discussed in the scenario of three ablation regimes. Ultrafast electronic and non-thermal processes are dominant in the lower fluence regime, whereas slow thermal processes are dominant at the higher fluence regime. Therefore, by starting from the ablation threshold three different fluence regimes have been chosen: a lower fluence regime (0.06–0.5 J cm^?2 single-shot irradiation under ultrahigh vacuum condition and 0.25–2.5 J cm^?2 single-shot irradiation in ambient condition), a moderate-fluence regime (0.25–1.5 J cm^?2 multiple-shot irradiation), and a high-fluence regime 2.5–3.5 J cm^?2 multiple-shot irradiation. For the lower fluence (gentle ablation) regime, around the ablation threshold, the unique appearance of individual, localized Nano hillocks typically a few nanometers in height and less than 100 nm in diameter are identified. These Nano hillock-like features can be regarded as a nonthermal, electronically induced phase transition process due to localized energy deposition as a result of Coulomb explosion or field ion emission by surface optical rectification. At a moderate-fluence regime, slightly higher than ablation threshold multiple-pulse irradiation produces bump-formation and is attributed to ultrafast melting (plasma formation). The high-fluence regime results in greater rates of material removal with highly disturbed and chaotic surface of Al with an appearance of larger protrusions at laser fluence well above the ablation threshold. These nonsymmetrical shapes due to inhomogeneous nucleation, cluster formation, and resolidification of a metallic surface after melting are attributable to slow thermal processes (ps time scale).     

Phenomenology of two-dimensional stably stratified turbulence under large-scale forcing

In this paper, we characterise the scaling of energy spectra, and the interscale transfer of energy and enstrophy, for strongly, moderately and weakly stably stratified two-dimensional (2D) turbulence, restricted in a vertical plane, under large-scale random forcing. In the strongly stratified case, a large-scale vertically sheared horizontal flow (VSHF) coexists with small scale turbulence. The VSHF consists of internal gravity waves and the turbulent flow has a kinetic energy (KE) spectrum that follows an approximate k^?3 scaling with zero KE flux and a robust positive enstrophy flux. The spectrum of the turbulent potential energy (PE) also approximately follows a k^?3 power-law and its flux is directed to small scales. For moderate stratification, there is no VSHF and the KE of the turbulent flow exhibits Bolgiano–Obukhov scaling that transitions from a shallow k^?11/5 form at large scales, to a steeper approximate k^?3 scaling at small scales. The entire range of scales shows a strong forward enstrophy flux, and interestingly, large (small) scales show an inverse (forward) KE flux. The PE flux in this regime is directed to small scales, and the PE spectrum is characterised by an approximate k^?1.64 scaling. Finally, for weak stratification, KE is transferred upscale and its spectrum closely follows a k^?2.5 scaling, while PE exhibits a forward transfer and its spectrum shows an approximate k^?1.6 power-law. For all stratification strengths, the total energy always flows from large to small scales and almost all the spectral indicies are well explained by accounting for the scale-dependent nature of the corresponding flux.     

Crystal Growth of Isotactic Polystyrene in Ultrathin Films: Thickness and Temperature Dependence

The growth rate and morphology of isotactic polystyrene crystals grown in ultrathin films have been examined experimentally in terms of the dependences both on the film thickness and on the crystallization temperature. We have found that the thickness dependence of growth rate, G, shows a crossover change when the film thickness becomes comparable with the lamellar thickness of the polymer crystals, irrespective of the temperatures. The morphology of crystals grown in ultrathin films shows a branching typical of dendrites, the growth of which is supposed to be controlled by a diffusion field. The change in the tip width of the dendrites with crystallization temperature follows the expected dependence of the Mullins–Sekerka stability length, ?_MS ∝ (D/G)^1/2, determined by the diffusion coefficient, D, and the growth rate. The results confirm that a diffusion field plays an essential role in the evolution of the structure.     

Superficial migration of tritium physisorbed on monocrystalline nickel (111)

The aim of this study is the measurement of superficial migration coefficient of tritium physisorbed on monocrystalline nickel without chemisorbed sublayer. The chosen crystalline orientation was (111) because it offers the greatest concentration of adsorption sites per square centimeter. A clean surface sample is obtained by mechanical polishing, chemical etching and finally ionic bombardment by high purity argon gas. The pressure in the experimental vessel is maintained below 10^?9 torr, by liquid helium cryopumping after zeolite sorption pumping.A little spot of adsorbed tritium is produced by introduction of a finite amount of tritium gas on the clean surface of the nickel sample through a stainless steel tube. Temperatures of nickel and of the gas introduction tube are respectively regulated at 5 K and 35 K. Tritium is used as a radioactive marker and its 10 keV β-radiation is measured by a channeltron type detector which permits the localization of the deposit without acting on the surface. We observed that tritium sorbed at 5 K is quite immobile (at the time scale of our experiment). After heating up to a fixed temperature T chosen between 10 K and 20 K, the deposite profile variation in function of time is observed to determine the superficial diffusion coefficient D. For the values of T from 13 K to 20 K, D varies from 10×10^?6 to 150×10^?6 cm² sec^?1. A diffusion activation energy of 200 cal mole^?1 is deduced from the exponential increase of the curve. A vibrational frequency can be evaluated to 3×10¹² sec^?1. The rate of desorption permits the evaluation of sorption energy at about 1800 cal mole^?1 in good agreement with usual results concerning physorption of H₂ on metals.