Interplay of adsorption and surface mobility in tracer diffusion in porous media.

We model the diffusion of a tracer that interacts with the internal surface of a porous medium formed by a packing of solid spheres. The tracer executes a lattice random walk in which hops from surface to bulk sites and hops on the surface have small probabilities compared to hops from bulk sites; those probabilities are related to bulk and surface diffusion coefficients and to a desorption rate. A scaling approach distinguishes three regimes of steady state diffusion, which are confirmed by numerical simulations. If the product of desorption rate and sphere diameter is large, dominant bulk residence is observed and the diffusion coefficient is close to the bulk value. If that product is small and the surface mobility is low, the tracers are adsorbed most of the time but most hops are executed in the bulk. However, for high surface mobility, there is a nontrivial regime of dominant surface displacement, since the connectivity of solid walls allows the tracers to migrate to long distances while they are adsorbed. In this regime, we observe rounded tracer paths on the sphere walls, which are qualitatively similar to those of a recent experiment on polystyrene particle diffusion. The calculated average residence times are proportional to the bulk and surface densities of an equilibrium ensemble of noninteracting tracers, and the relation between those densities sets the adsorption isotherm. Simulations performed with initially uniform (nonequilibrium) distribution of tracers in the pores show other nontrivial results in cases of dominant surface residence: slow increase of the mean-square displacement at short times, since the tracer has not explored a homogeneous medium, and a remarkable slowdown between the first encounter with a solid wall and the first hop from that point. Relations between our results and other models of diffusion and adsorption in porous media are discussed.

Crossover from compact to branched films in electrodeposition with surface diffusion.

We study a model for thin film electrodeposition in which instability development by preferential adsorption and reduction of cations at surface peaks competes with surface relaxation by diffusion of the adsorbates. The model considers cations moving in a supported electrolyte, adsorption and reduction when they reach the film surface, and consequent production of mobile particles that execute activated surface diffusion, which is represented by a sequence of random hops to neighboring lattice sites with a maximum of G hop attempts (G≫1), a detachment probability ε<1 per neighboring particle, and a no-desorption condition. Computer simulations show the formation of a compact wetting layer followed by the growth of branched deposits. The maximal thickness z_{c} of that layer increases with G but is weakly affected by ε. A scaling approach describes the crossover from smooth film growth to unstable growth and predicts z_{c}∼G^{γ}, with γ=1/[2(1-ν)]≈0.43, where ν≈0.30 is the inverse of the dynamical exponent of the Villain-Lai-Das Sarma equation that describes the initial roughening. Using previous results for related deposition models, the thickness z_{c} can be predicted as a function of an activation energy for terrace surface diffusion and the temperature, and the small effects of the parameter ε are justified. These predictions are confirmed by the numerical results with good accuracy. We discuss possible applications, with a particular focus on the growth of multifuncional structures with stacking layers of different porosity.

Effects of film growth kinetics on grain coarsening and grain shape.

We study models of grain nucleation and coarsening during the deposition of a thin film using numerical simulations and scaling approaches. The incorporation of new particles in the film is determined by lattice growth models in three different universality classes, with no effect of the grain structure. The first model of grain coarsening is similar to that proposed by Saito and Omura [Phys. Rev. E 84, 021601 (2011)PLEEE81539-375510.1103/PhysRevE.84.021601], in which nucleation occurs only at the substrate, and the grain boundary evolution at the film surface is determined by a probabilistic competition of neighboring grains. The surface grain density has a power-law decay, with an exponent related to the dynamical exponent of the underlying growth kinetics, and the average radius of gyration scales with the film thickness with the same exponent. This model is extended by allowing nucleation of new grains during the deposition, with constant but small rates. The surface grain density crosses over from the initial power law decay to a saturation; at the crossover, the time, grain mass, and surface grain density are estimated as a function of the nucleation rate. The distributions of grain mass, height, and radius of gyration show remarkable power law decays, similar to other systems with coarsening and particle injection, with exponents also related to the dynamical exponent. The scaling of the radius of gyration with the height h relative to the base of the grain show clearly different exponents in growth dominated by surface tension and growth dominated by surface diffusion; thus it may be interesting for investigating the effects of kinetic roughening on grain morphology. In growth dominated by surface diffusion, the increase of grain size with temperature is observed.

Smoothening in thin-film deposition on rough substrates.

The evolution of the surface roughness W of a thin film deposited on a rough substrate is studied with a model of temperature-activated adatom diffusion, irreversible lateral aggregation, and no step energy barrier, in which the main parameter is the ratio R of diffusion and deposition rates. At sufficiently low temperatures (R≲10), the average number of adatom steps after adsorption is very small, thus W monotonically increases with time t due to an approximately uncorrelated deposition at short times. If the temperature is not very low (R∼10(3) or larger), smoothening occurs at short times and the Villain-Lai-Das Sarma (VLDS) growth equation governs the long time roughening, which is attained after a crossover time t(c) that increases with the correlation length ξ(i) of the substrate. Scaling arguments predict the dependence of t(c) on temperature and on the substrate production time and the scaling relation for the difference between the roughness of films deposited on rough and flat substrates, in good agreement with numerical results. The effect of temperature is not a direct extension of previous results on flat substrates because the short wavelength fluctuations delay the formation of terraces. For this reason, the effective energy obtained from the dependence of t(c) on R is 40% of the energy of activated adatom diffusion. A scaling law for the initial smoothening is proposed as W/W(i)=Ψ(t/t(c1)), with a crossover time t(c1)≡R(-θ)ξ(i)(z), where W(i) is the substrate roughness, θ≈0.4, and z is the VLDS dynamical exponent. It provides good data collapse if W is not very small and is suggested to be tested experimentally.

Kinetic roughening and porosity scaling in film growth with subsurface lateral aggregation.

We study surface and bulk properties of porous films produced by a model in which particles incide perpendicularly to a substrate, interact with deposited neighbors in its trajectory, and aggregate laterally with probability of order a at each position. The model generalizes ballisticlike models by allowing attachment to particles below the outer surface. For small values of a, a crossover from uncorrelated deposition (UD) to correlated growth is observed. Simulations are performed in 1+1 and 2+1 dimensions. Extrapolation of effective exponents and comparison of roughness distributions confirm Kardar-Parisi-Zhang roughening of the outer surface for a>0. A scaling approach for small a predicts crossover times as a(-2/3) and local height fluctuations as a(-1/3) at the crossover, independent of substrate dimension. These relations are different from all previously studied models with crossovers from UD to correlated growth due to subsurface aggregation, which reduces scaling exponents. The same approach predicts the porosity and average pore height scaling as a(1/3) and a(-1/3), respectively, in good agreement with simulation results in 1+1 and 2+1 dimensions. These results may be useful for modeling samples with desired porosity and long pores.

Universality in two-dimensional Kardar-Parisi-Zhang growth.

We analyze simulation results of a model proposed for etching of a crystalline solid and results of other discrete models in the (2+1)-dimensional Kardar-Parisi-Zhang (KPZ) class. In the steady states, the moments W(n) of orders n=2,3,4 of the height distribution are estimated. Results for the etching model, the ballistic deposition model, and the temperature-dependent body-centered restricted solid-on-solid model suggest the universality of the absolute value of the skewness S identical with W(3)/W(3/2)(2) and of the value of the kurtosis Q identical with W(4)/W(2)(2)-3. The sign of the skewness is the same as of the parameter lambda of the KPZ equation which represents the process in the continuum limit. The best numerical estimates, obtained from the etching model, are absolute value of S=0.26+/-0.01 and Q=0.134+/-0.015. For this model, the roughness exponent alpha=0.383+/-0.008 is obtained, accounting for a constant correction term (intrinsic width) in the scaling of the squared interface width. This value is slightly below previous estimates of extensive simulations and rules out the proposal of the exact value alpha=2/5. The conclusion is supported by results for the ballistic deposition model. Independent estimates of the dynamical exponent and of the growth exponent are 1.605< or =z< or =1.64 and beta=0.229+/-0.005, respectively, which are consistent with the relations alpha+z=2 and z=alpha/beta.