Quasi-Equilibrium Nucleation and Growth of Diamond and Cubic Boron-Nitride

Material growth is an inherently non-equilibrium process. However, thermodynamic considerations often provide important insight into material growth, the structure of grown materials, and process control parameters. In essence, thermodynamic considerations are important when activated processes are either slow or fast on the time scale of the growth. Activated kinetic processes are important when their time scale is the same as that of growth. Realistic ab-initio calculations of material structure and dynamics can provide a microscopic understanding of both thermodynamics and the kinetics of material growth. The primary focus of this article is a recently proposed defect-assisted multiple-regrowth stabilization of cubic phases. in this theory the incorporation of vacancies at the growth face changes the relative binding energy of cubic versus hexagonal phases so that diamond and cubic boron nitride can nucleate and grow. This theory predicts that diamond nucleation and growth is enhanced under electron rich or positive ion conditions. Experimental results on growth of both diamond and cubic boron nitride that motivate and support theoretical predictions are described. Cubic boron-nitride grows under off-stoichiometric conditions. The nucleation rate of diamond is increased by many orders of magnitude when a flux of electrons impinges upon the surface. Raman line broadening and ESR measurements indicate the presence of significant concentrations of point defects. Predictions and experimental evidence for both n and p type doping will be discussed. Ab-initio calculations of key kinetic processes and thermodynamic quantities for diamond and boron nitride growth are described.