grown by chemical vapor deposition

We present a calculational method to predict terminations of growing or as-deposited surfaces as a function of the deposition conditions. Such characterizations are valuable for understanding catalysis and growth phe-nomena. The method combines ab initio density-functional-theory calculations and experimental thermody-namical data with a rate-equations description of partial pressures in the reaction chamber. The use of rate equations enables a complete description of a complex gas environment in terms of a few, experimentally accessible parameters. The predictions are based on comparisons between free energies of reaction associated with the formation of surfaces with different terminations. The method has an intrinsic nonequilibrium char-acter. In the limit of dynamic equilibrium with equal chemical potential in the surface and the gas phase we find that the predictions of the method coincide with those of standard ab initio based equilibrium thermody-namics. We illustrate the method for chemical vapor deposition of TiC111 and TiN111, and find that the emerging termination can be controlled both by the environment and the growth rate. DOI: 10.1103/PhysRevB.82.045415 PACS numbers: 68.55.A, 81.15.z, 68.35.Md, 05.70.Ln I