Step bunching during the epitaxial growth of a generic binary-compound thin film

A discrete-continuum theory for the step-flow growth by chemical beam or metalorganic vapor-phase epitaxy of a generic binary-compound thin film is developed from basic considerations of continuum physics in accordance with the second law of thermodynamics. Our theory accounts for dissipation, chemical and otherwise; allows for departures from equilibrium; and generalizes the classical, variationally derived Gibbs–Thomson relation along the steps. In contrast to existing models, the diffusing species are coupled through a chemical reaction whereby bulk molecules are crystallized from adatoms attaching to the step edges. The linear stability analysis of the resulting free-boundary problem for a periodic train of rectilinear steps yields pairing in the presence of the normal Ehrlich–Schwoebel barrier for both species, counter to the predictions of standard Burton–Cabrera–Frank models for single-species growth. In particular, we show that the onset of step bunching occurs as long as the adatom equilibrium coverage of either species is sufficiently high, a condition met, e.g., during the epitaxy of gallium arsenide. The physical origin of this instability is to be found in the dependence of the step chemical potential on the jump in the adatom grand canonical potential, a term that couples adjacent terraces and—counter to elastic, entropic, or electrostatic interactions between steps—is attractive.