Surface diffusion of K on Pd{111}: Coverage dependence of the diffusion coefficient determined with the Boltzmann–Matano method

The surface diffusion of potassium on Pd{111} has been studied with photoelectron emission microscopy (PEEM) for coverages up to one monolayer. The coverage dependence of the chemical diffusion coefficient is determined by analysis of the concentration profiles obtained from the PEEM images with the Boltzmann–Matano method. The diffusion coefficient, D, decreases with increasing coverage but a local maximum is found at a coverage of Θ≈0.5 ML. The values of D at low coverages (Θ<0.3 ML) agree well with those obtained in a previous investigation for Θ≈0.12 ML. The maximum in D is interpreted in terms of an order–disorder phase transition in the adsorbed layer

Surface diffusion of Au on Si(111): A microscopic study

The direct evolution of submonolayer two-dimensional Au phases on the Si(111)-(7x7) surface was studied in real time using the spectroscopic photoemission and low energy electron microscope located at the synchrotron radiation source ELETTRA. A finite area covered by 1 monolayer (ML) of gold with a steplike transition zone was prepared by evaporation in situ. Subsequent annealing resulted in the spread of the Au layer and the formation of laterally extended Si(111)-(5x1)-Au and Si(111)-(√3x √3)R30°-Au surface reconstructions. At a temperature around 970 K, the boundary of the gold-covered region propagates on the clean Si(111)-(7x7) and exhibits a nonlinear dependence on time. The ordered Si(111)-(5x1)-Au plateau develops a separated front moving with constant velocity. Two values of the Au diffusion coefficients were estimated at a temperature of about 985 K: (1) D7x7=5,2x10-8 cm2 s-1 as the average diffusion coefficient for Au on a clean Si(111)-(7x7) surface in the concentration range from 0.4 ML up to 0.66 ML and (2) D5x1=1.2x10-7 cm2 s-1 as the lower limit for the diffusion of single Au atoms on the Si(111)-(5x1)-Au ordered phase

Thermodynamics of adatoms diffusing on a surface with two different sites: a new type of phase transition

The chemical surface diffusion coefficient D has been determined for a lattice-gas model where diffusion proceeds through two non-equivalent lattice sites with different activation energies, E1 and E2. By calculating the thermodynamic factor as well as jump diffusion rate we obtain the coverage dependence of D as a function of the energy difference E1-E2. No lateral interactions are considered. Depending on the sign of E1-E2, the diffusion coefficient shows either a maximum or a step-like increase at a particular coverage, both of which develop into discontinuities in the limits of either E1-E2 → ± ∞. In the case of the step-like behaviour of D, the variation of D can be classified as being due to a kind of diffuse phase transition between a low and a high diffusivity state, which in the limits is shown to be of first order

Connection between thermodynamic properties and diffusion coefficient for a system of non-interacting particles on a lattice with two non-equivalent sites

By calculating the jump diffusion rate (Г) and the thermodynamical factor (Kd) for a layer of non-interacting particles on a lattice with the non-equivalent bond sites we show that the diffusion coefficient D=ГKd exhibits specific features as a function of coverage, such as steps or maxima at critical coverages, which correspond to phase transformations in the adlayer. The chemical potential of the adlayer is derived analytically from the free energy. The difference of binding energy between the two kinds of sites is described by a parameter k and it is shown that the chemical potential (or the thermodynamic factor) at the critical coverage indicates the existence of a diffuse phase transition which develops for k → 0 into a first-order point phase transition

Analysis of the Arrhenius shape of adatom diffusion coefficient in a surface model with two energy barriers

The effective energy barrier for diffusion, Ea, has been previously determined as a function of coverage and temperature within a two-barrier model of diffusion, assuming an Arrhenius form of chemical diffusion coefficient. To determine the diffusion coefficient at a given temperature and coverage, we used previously published results based on the lattice gas model of non-interacting adatoms. The presence of two non-equivalent sites for adsorption and diffusion of atoms on a surface (with energy barriers E1, E2) results in substantial changes to Ea within coverage Θ, with a step-like shape having a value close to Θ=1/3. The temperature dependence of Ea shows a slight minimum, and the Arrhenius shape (with constant Ea) seems to be good approximation of the relatively small differences in energy barriers E1, E2. We obtain considerable deviation from such an Arrhenius behaviour of diffusion when there is a large difference in the energy barriers

Surface diffusion on a lattice with two non-equivalent adsorption sites: repulsive interactions

We calculated the surface diffusion coefficient D as a function of coverage in the quasi-chemical approximation of a system of particles on a square lattice with two non-equivalent binding sites characterized by different activation energies E1 and E2 for diffusion. A short-range repulsive interaction between particles in the nearest neighbour non-equivalent sites is considered, resulting in the modification of these energies by δE. The thermodynamic and kinetic parts of D have been calculated separately, in order to estimate their contribution to the diffusivity at different concentrations. It has been found that D exhibits a step-like increase at a critical coverage Θc which varies from Θc=0.33 for δE=0 to Θc=0.5 for E1=E2. The origin of the concentration dependence of D is discussed in terms of the repulsion strength between particles and their jump-rate through the sites existing on the surface

Recrystallization of InSb Surfaces Induced by Pulsed Lasers

Pulsed laser processing of InSb wafers for the application in designing high speed infrared detectors is studied both theoretically and experimentally. The recrystallization of InSb surfaces resulting in restoration of the implanted region to a single crystal state is presented as a reasonable alternative to the conventional thermal heating. In the theoretical part, thermal equilibrium and nonequilibrium models of melting, recrystallization and evaporation are formulated to describe transport phenomena in the material induced by laser irradiation. In the experimental part, InSb samples irradiated by the ruby (694 nm, 80ns FWHM), and ArF (193 nm, 10 ns FWHM) lasers are studied using time resolved reflectivity, Auger electron spectroscopy and low energy electron diffraction methods to analyze surface modifications. A comparison of the experimental data with the numerical predictions shows that while for the ruby laser a reasonable agreement in surface melt duration is achieved, the results for the ArF laser differ quite a lot. As a main reason for these differences, the amorphization of the surface is identified

Electronic Structure of Diluted Semimagnetic Semiconductor (Cd,Co)Se

The electronic structure of a new semimagnetic semiconductor (Cd,Co)Se is studied by UPS and calculated by a tight-binding version of the disordered-local-moment theory. The theory accounts for the chemical disorder and for electron interactions within the Co 3d$\text{}^{7}$ shells. Both theory and experiment show Co 3d states deep in the valence band and also at the band edge. The last state seem to be responsible for unique properties of the Co-based semimagnetic semiconductors

Surface diffusion of oxygen on a Ge{100}(2 × 1) surface studied by laser-induced thermal desorption (LITD)

The capability of the laser-induced thermal desorption technique (LITD) to detect the migration of adsorbed oxygen on a semiconductor surface is demonstrated. The surface diffusion coefficient of oxygen on Ge{100}(2 × 1) has been measured for a constant initial coverage in a wide temperature range (220–650 K). The experimental results show that after an initial stage of fast refilling of the depleted area the diffusion process strongly slows down. In the first stage the data can be fitted by the solution of Fick's second law. Within this approximation of a constant diffusion coefficient, an extremely low activation energy (∼ 0.04 eV) is obtained. The observations suggest that the second stage in the refilling process is connected with an irreversible chemical reaction between adsorbate and substrate