Energy disposal via electron-hole pair excitation in atom recombination on metal surfaces: Electron distribution function and detailed balancing

The energy disposal via electron-hole (e-h) pair formation in the highly exoergic recombination of gas atoms on metal surfaces, has been studied. The impact of this excitation process on the energy spectrum of the metal electrons has been investigated at steady state. The energy distribution function of the electrons is shown to be non-thermal to an extent that depends on the reaction rate, probability distribution function for e-h pair creation and physical parameters of the material. The model has been applied to compute the electron spectra of metal surfaces, using kinetic data on H atom recombination that are available from the literature. The number of electrons made available for detection as chemicurrent has been derived and compared to experimental data on the H/Cu system. The interplay between the electron distribution function and the reaction kinetics is analysed by means of the principle of detailed balance. The detailed balancing analysis shows that, depending on the e-h excitation energy, the rate constant of energy transfer from the bath to the adlayer can be orders of magnitude larger than that proper for equilibrium conditions.     

Role of electron-hole pair excitations in the dissociative adsorption of diatomic molecules on metal surfaces

We quantitatively evaluate the contribution of electron-hole pair excitations to the reactive dynamics of H2 on Cu(110) and N2 on W(110), including the six dimensionality of the process in the entire calculation. The interaction energy between molecule and surface is represented by an ab initio six-dimensional potential energy surface. Electron friction coefficients are calculated with density functional theory in a local density approximation. Contrary to previous claims, only minor differences between the adiabatic and nonadiabatic results for dissociative adsorption are found. Our calculations demonstrate the validity of the adiabatic approximation to analyze adsorption dynamics in these two representative systems.     

The possible role of intermediate NH species in oscillations of the NO+H2 reaction on noble metal surfaces

A comparative study of the thermodynamic properties of adsorbed NH_n species (n = 0, 1, 2, 3) on transition metal surfaces is performed by using the semi-empirical method of interacting bonds. The principal difference between single crystal surfaces exhibiting oscillatory behavior in the NO+H₂ reaction, and those surfaces which do not show such a behavior is that the combination reaction of NH species can easily proceed in the former case, whereas it is substantially endothermic on the latter surfaces.A trigger-like route for the oscillatory behavior is considered where the combination reaction of NH species operates as a temporary reaction pathway. This pathway practically does not contribute to the N₂ formation until the nitrogen coverage reaches some critical value, which ensures a sufficiently close distance between adjacent NH particles. The trigger pathway starts upon reaching that stage initiating the surface wave propagation, and stops immediately when the wave propagation is completed. The surface becomes then nearly clean and ready for the next oscillatory cycle. In this way, the feedback mechanism and the critical point of the regular wave initiation can be understood without any further assumptions. An alternative key reaction is also considered.     

The role of electron-hole pair excitations in the optical absorption of metals,particularly metal spheres

It is shown that electron-hole pair excitations can dominate the optical absorption of a small metal sphere over the entire frequency range up to the bulk plasma frequency. The limited size has the effect of giving more surface to volume, thereby giving a larger relative weight to the single particle excitations, predominantly produced in the surface region, as compared to the planar case where they make up for a smaller part of the total absorptance.     

On the flow of thermal defects from the bulk to surfaces

This paper treats flow of defects between bulk and surface sites, as a crystal passes towards equilibrium, for some practical cases. These include the realistic but quite elaborate example in which vacancy flow from the bulk is coupled to surface step edges, acting as sinks, by reaction with adatoms that are believed to dominate transport on metal surfaces. It is shown how surface processes modify the defect flow from the bulk only at short times. Lacking accurate parameters (such as concentrations) for surface defects, a crude modeling of the theoretical results is offered in order to explore likely generic behavior. The model employs a recently described approximate universality of behavior, scaled to the melting temperature, relevant mainly to fcc (1 1 1) surfaces. Under a range of conditions it is the reaction of advacancies with adatoms that provides the important channel for bulk vacancy flow. Adatom flow onto the terraces from surface step edge sinks is the bottleneck to flow above a crossover temperature (depending on step spacing) and equilibrium recombination is the bottleneck below the crossover.     

Application of the statistical rate theory of interfacial transport to investigate the kinetics of divalent metal ion adsorption onto the energetically heterogeneous surfaces of oxides and activated carbons

Divalent metal cation adsorption from solution onto oxides or activated carbons can be described by the Surface Complexation Model (SCM). We assumed that the adsorbent surface is strongly energetically heterogeneous and derived the adsorption isotherm using rectangular distribution of adsorption energy and condensation approximation for the local isotherm equation. Assuming additionally that the bulk concentration of divalent metal ion is low and does not change considerably during the adsorption process and next applying the Statistical Rate Theory of Interfacial Transport (SRT) we derived the Elovich equation—the experimental formula describing adsorption kinetics.     

Mechanism and kinetics of thin zirconium and hafnium oxide film growth in an ALD reactor

A mechanism of HfO₂ and ZrO₂ film growth in an ALD reactor from metal chlorides and water vapor is proposed to explain the experimentally observed features of the process: the formation of less than one monolayer per cycle and the dependence of the film growth rate (mass or thickness increment per cycle) and the residual chorine concentration on the process temperature. Energy parameters of the relevant gas-surface reactions are estimated from quantum-chemical density functional theory calculations. The rate constants of the elementary reactions are calculated using RRKM theory. ALD process simulations, based on the proposed mechanism and a transient plug-flow reactor model, are consistent with the available experimental data, indicating a decrease in deposition rate with increasing temperature. The reduction in deposition rate is attributed to the increased dehydroxylation of the film surface as the temperature is increased. The H₂O adsorption energy was found to increase with increasing dehydroxylation from 33 to 53 kcal/mol for ZrO₂ and from 35 to 51 kcal/mol for HfO₂. A kinetic Monte Carlo model of film growth, based on the proposed mechanism, describes the observed temperature dependence of the residual chlorine concentration in the film in terms of the steric repulsion between chemisorbed surface groups and adsorbed MCl₄ molecules (M=Zr, Hf).     

Impact of surface science on the understanding of kinetics of heterogeneous catalytic reactions

The kinetics of chemical reactions in gas and liquid phases are usually described by employing the conventional mass-action law equations. The laws governing the kinetics of heterogeneous catalytic reactions are as a rule much more complex due to adsorbate–adsorbate lateral interactions, surface heterogeneity, spontaneous and adsorbate-induced changes in a surface, and/or limited mobility of reactants. The importance of these factors was recognized by the heterogeneous catalysis community far before the surface-science era. Only with the development of surface science, however, has it become possible to study in detail the non-ideality of rate processes on solid surfaces. In the present paper, we survey the main conceptual results currently available in this field and illustrate the impact of surface science on its development. Specifically, we outline the approaches used to describe elementary reaction steps and the whole reaction kinetics near and far from equilibrium, including such topics as kinetic phase transitions, pattern formation, kinetic oscillations and chaos, and pressure- and structure-gap problems. All these phenomena and problems are demonstrated to provide promising opportunities for further experimental and theoretical studies.     

Characterization of protein-conjugating kinetics based on localized surface plasmon resonance of the gold nanoparticle

The gold nanoparticle exhibits optical property of localized surface plasmon resonance (LSPR), which dynamically alters as the surface adsorbs new ligands. We carried out a semi-quantitative analysis with the method of multivariate curve resolution, observing that the adsorption of serum albumin on gold nanoparticle was best deciphered as two-mode competitive kinetics. Interestingly, for human serum albumin, the slower mode contributed considerably to the LSPR response of protein-conjugated surfaces, while in the case of bovine serum albumin the faster mode overwhelmed the slower one at high protein concentrations. The kinetic patterns were rationalized with diversity of biomolecular orientations on the nanoparticle surface. The simple but efficient protocol supports semi-quantitative analysis combining UV-vis spectroscopy with chemometrics method for distinguishing conjugation kinetics of different types of proteins on the surface of nanoparticles at nanomolar concentration.     

Local bond breaking via STM-induced excitations: the role of temperature

We discuss the influence of temperature on local bond breaking through multiple vibrational excitations induced by inelastic tunneling in the STM. We focus on hydrogen desorption from the H---Si(111) and H---Si(100) systems, but the results are general. The substrate temperature affects the desorption yield in two important ways: first, lowering the temperature increases the H---Si vibrational energy relaxation time, resulting in a higher effective adsorbate temperature and an increased desorption yield. Second, lowering the substrate temperature decreases the dephasing rate of the H---Si modes (manifested by a decrease of the infrared absorption linewidth), which then reduces the rate of incoherent (Förster) vibrational energy transfer away from the Stark-shifted H---Si mode under the tip. This increases the localization of the vibrational energy and enhances the probability for multiple vibrational excitation and desorption. Finally, we discuss the possible implications of our findings on the mechanism of MOS device degradation by hot electrons.     

The role of reconstruction in self-assembly of alkylthiolate monolayers on coinage metal surfaces

Through a combination of standard laboratory-based surface science methods, together with synchrotron radiation-based normal incidence X-ray standing wave (NIXSW) experiments, the interface structure of simple alkylthiolate ‘self-assembled monolayers’ on Cu(1 1 1), Ag(1 1 1) and Au(1 1 1) has been investigated over the last ∼15 years. A key conclusion is that in all cases the adsorbate produces a substantial, density-lowering, reconstruction of the outermost metal layer, although the nature of these reconstructions is quite different on the three metals. The main results of these investigations are briefly reviewed and contrasted.     

Surface kinetics of GaN evaporation and growth by molecular-beam epitaxy

The kinetics of surface processes during the growth of GaN by molecular-beam epitaxy (MBE) with ammonia as the source of reactive nitrogen is studied theoretically and experimentally. A model of surface processes is developed taking into account specific effects of the blocking of NH₃ adsorption sites by Group III and Group V surface species. Parameters of the model (respective kinetic rate constants) are determined from comparison with experimental data. It is shown that the evaporation rate of GaN in ammonia atmosphere is much lower than that in vacuum. Kinetics of GaN growth under gallium-rich and nitrogen-rich conditions are compared. Under nitrogen-rich conditions the GaN surface is predicted to be enriched by NH_x surface radicals, in contrast to the case of growth under gallium-rich conditions or of free evaporation in vacuum. It is shown that use of the nitrogen-rich conditions allows one to increase the growth temperature by 80–90°C compared with the case of gallium-rich conditions or plasma-activated MBE. The increased growth temperature is favorable in improving the optical and electrical properties of the material grown.     

Adatom lifetime in film growth at solid surfaces in the framework of the Johnson–Mehl–Avrami–Kolmogorov model

On the basis of the quasi-static approximation and for simultaneous nucleation the adatom lifetime, τ, during film growth at solid surfaces has been computed by Monte Carlo (MC) simulation. The quantity DN₀τ, N₀ and D being respectively the cluster density and the adatom diffusion coefficient, is found to depend upon the portion of surface covered by clusters and, very weakly, on N₀. Moreover, a stochastic approach based on the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory has been developed to obtain the analytical expression of the MC curve. The collision factor of the mean island has been calculated and compared with those previously obtained from the uniform depletion approximation and the lattice approximation.     

On the adsorption and desorption of H2 at metal surfaces

Recent technological developments have made possible measurements of the distribution of internal levels of molecules desorbing from a hot surface. Such measurements provide new information concerning the desorption process and the potential energy surface (PES) that governs it. Associative, or re-combinative desorption is of particular interest because the distributions of internal levels reflect the manner in which the molecular bond is formed as the desorbing species leaves the surface. As the simplest associative desorption systems, H₂ and D₂ adsorbing on and desorbing from metal surfaces deserve special attention and serve as prototypes for systems with a more complex chemistry. In this note I review briefly from the theoretical point of view some features of the interaction of H₂ with metals and their relevance to associative adsorption and dissociative sticking.     

Deposition of latex particles encapsulated in polyelectrolyte shells at heterogeneous metal surfaces modified by multilayer films

We used an oblique impinging jet (OIJ) cell to determine the initial deposition rate for the microcapsules deposited on the heterogeneous metal surfaces bare or modified by polyelectrolyte (PE) films. The dependence of reduced particle flux on the Reynolds number of the flow in the OIJ cell was determined by direct counting of particles deposited on the studied surfaces. We used fluorescently labelled latex particles and microcapsules built on these fluorescent cores and the use of fluorescent microscope allowed us to observe “in situ” the deposition processes of particles on rough, highly reflective surfaces. We demonstrated that modification of metallic surfaces of various materials and heterogeneity by the multilayer PE films result in the formation of uniformly charged film of nanometers thickness. The formation of such a film leads to the increase of deposition efficiency and its initial rate is governed by the charge of the film covered surface and the outermost layer of the capsule shell being in agreement with the prediction of the convective-diffusion theory.     

The role of the surface depression of the pair potential on the Josephson and quasi-particle tunnelling in high-T c superconductors

Summary We discuss the influence of the intrinsic surface depression of the order parameter on the temperature dependence of the Josephson critical currentI _c(T) and, tentatively, on the quasi-particle tunnelling conductance in a superconductor with a very short coherence length. The comparison with the experiments shows that the presence of a surface-depressed pair potential can explain the large deviations of theI _c(T) from the ideal BCS behaviour that we recently observed in Bi₂Sr₂CaCu₂O_8+x Josephson break junctions and could mimic the presence of a broadening in the Superconductor-Insulator-Normal tunnelling conductance of the same high-T _c superconductor. Paper presented at the ?VII Congresso SATT?, Torino, 4–7 October 1994.     

The kinetics of an atom diffusing in one dimension: Hydrogen in quartz

Abstract

The time dependence of frequency recovery at 306 K of pulse-irradiated quartz is analyzed and shown to be inconsistent with the diffusion of a specie in three dimensions, but follows well diffusion in one dimension. The main feature which distinguishes these cases is a t ^?1/2 time dependence of the recovery. No extended region for a t ^?1/2 dependence is possible in three-dimensional diffusion. An extensive t ^?1/2 dependence is predicted in one-dimensional diffusion, paralleling the observation that this holds for some three decades in time and over 80% of the recovery.

Having established one-dimensional diffusion in frequency recovery, it is shown that acoustic relaxation found at 115 K and a long time component of conductivity recovery found near 300 K, as well as the frequency recovery, all appear to originate in a common mechanism—the diffusion of H⁺ in one dimension with an activation of approximately ¼ electron volt.     

On the theory of surface diffusion: kinetic versus lattice gas approach

The present paper extends the results of a recent analytic kinetic theory of particle-on-substrate diffusion. The approach treats explicitly the molecule–surface interaction and takes into account inter-molecular interaction within the hard particle approximation. The physics influencing the diffusion pre-exponential factor and mechanisms determining the density dependence of collective diffusivity are discussed. The kinetic results are compared with those of the traditional lattice gas hopping models. Analytical expressions for jump rates in the low density limit are derived, and the density dependence of effective jump rates at finite occupancy is discussed. It is shown how the traditional hopping model oversimplifies the picture of diffusion by neglecting the collision part of the hopping process.