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

Abstract

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.