Pressure and temperature effects on the kinetics and quality of diamond films

Abstract

Quantitative measurements of the effects of pressure on the kinetics and quality of diamond films grown with hot-filament chemical-vapor deposition are reported. Pressure affects growth kinetics largely because it affects transport of precursors to the growing surface. H and CH3 concentrations at the growth surfaces are determined with a recombination enthalpy technique combined with appropriate transport analyses. The growth rate rises and then falls with increasing pressure, although the concentrations of CH3 and atomic hydrogen at the surface are nearly constant. Both the rise and the fall in growth rate at higher pressure are explained with a chemical kinetics model as due in large part to an increase in substrate temperature at higher pressures. The fall at higher pressure (temperature) is due to the rate of thermal desorption of the CH3 precursor increasing more rapidly with temperature than the competing rate of its incorporation: Once these rates become comparable, higher substrate temperatures lower the incorporation rates, and the growth rate decreases. Previously measured Arrhenius plots for diamond-growth kinetics are explained quantitatively. The quality of the diamond, as determined using Raman and scanning electron micrograph data, falls with increasing pressure and substrate temperature. For the first time, this decline in quality is correlated with experimental temperature, H:CH3 ratio, and C2H2 concentration measurements.