Epitaxy of binary compounds and alloys

The present work aims at constructing a theoretical framework within which to address the issues of morphological instabilities (one-dimensional step bunching and two-dimensional step meandering), alloying, and phase segregation in binary systems in the context of (physical or chemical) vapor deposition. The length scale of interest, although nanoscopic, is sufficiently large that the steps on a vicinal surface can be viewed as smooth curves and, correspondingly, the theory is a continuum one. In a departure from theories inaugurated by Burton, Cabrera, and Frank [The growth of crystals and the equilibrium structure of their surfaces. Phil. Trans. Roy. Soc. A 243 (1951) 299-358] the steps are endowed with a thermodynamic structure whose main ingredients are a step free-energy density and edge species chemical potentials. Moreover, crystal anisotropy, with its altering of the dynamics of steps and the associated morphological instabilities, is accounted for - in a manner consistent with the second law - both in the thermodynamic and kinetic properties of terraces and, more importantly, of steps. Additionally, in contrast with most of the literature on the subject (cf. [J. Krug, Introduction to step dynamics and step instabilities. In: A. Voigt (ed.) Multiscale Modeling in Epitaxial Growth. Birkhausser, Berlin (2005)]), adsorption-desorption along the steps, bulk atomic diffusion, and chemical reactions (both on the terraces and along the step edges) are incorporated and coupled to the other mechanisms, e.g., terrace adatom diffusion and step attachment-detachment kinetics, whose interplay governs the evolution of steps on vicinal surfaces. Importantly, aided by the concept of configurational forces for which a separate balance law is postulated (cf, e.g., [M.E. Gurtin, Configurational Forces as Basic Concepts of Continuum Physics. Springer, Berlin Heidelberg New York (2000)]), the proposed theory allows the steps to evolve away from local equilibrium thus contributing to a general treatment of the dynamics of steps. Finally, a specialization to the epitaxy of binary compounds and alloys is afforded, yielding a generalization of the classical Gibbs-Thomson relation in the former and novel evolution equations for an individual step in the latter.