Unusual Dependence of the Diamond Growth Rate on the Methane Concentration in the Hot Filament Chemical Vapor Deposition Process

Although the growth rate of diamond increased with increasing methane concentration at the filament temperature of 2100 °C during a hot filament chemical vapor deposition (HFCVD), it decreased with increasing methane concentration from 1% CH4 –99% H2 to 3% CH4 –97% H2 at 1900 °C. We investigated this unusual dependence of the growth rate on the methane concentration, which might give insight into the growth mechanism of a diamond. One possibility would be that the high methane concentration increases the non-diamond phase, which is then etched faster by atomic hydrogen, resulting in a decrease in the growth rate with increasing methane concentration. At 3% CH4 –97% H2, the graphite was coated on the hot filament both at 1900 °C and 2100 °C. The graphite coating on the filament decreased the number of electrons emitted from the hot filament. The electron emission at 3% CH4 –97% H2 was 13 times less than that at 1% CH4 –99% H2 at the filament temperature of 1900 °C. The lower number of electrons at 3% CH4 –97% H2 was attributed to the formation of the non-diamond phase, which etched faster than diamond, resulting in a lower growth rate.

Phase Transformation of Nanocrystalline Diamond Films: Effect of Methane Concentration

Ultra-nanocrystalline diamond films were prepared by a microwave plasma-enhanced chemical vapor deposition reactor using CH4/H2 gas mixture with a power as low as 650 W. The effects of CH4 concentration on nanostructure of the films and gas-phase species in plasma were investigated. The CH4 concentrations of 1.5%, 3.0%, 3.5%, and 4.0% were used and balanced with H2 to a total flow rate of 200 sccm. Morphology and composition of the films were characterized by SEM, Raman spectroscopy and Auger spectroscopy. The gas-phase species and electron density in the plasma were explored by optical emission spectroscopy and plasma-impedance measurement. The increasing CH4 concentration from 1.5% to 4.0% increased C2Hx species and decreased electron density. Phase of the film transform from nano- into ultranano- diamond phase but the growth rate revealingly decreased from 300 to 210 nm/h. Raman spectra indicate the higher CH4 concentration promted phase of the film transiton from NCD to UNCD. While Auger spectra revealed that UNCD film deposited with 4.0%CH4 was composed of 90.52% diamond phase but only 9.48% of graphite phase. The relation between phase transformation of the films and growth mechnism controlled by gas-phase species in the plasma will be dissused.

Зарождение алмаза из активируемой газовой фазы

The thermodynamically metastable diamond nucleation in the volume of activated vapor phase and on nondiamond materials surfaces, as well, have been considered. Basic factors influencing for emerging diamond phase surface energy reducing and for the activation energy for addition to a building blocks nucleus lowering are considered. The importance of experimentally revealed regularities for instance for nanocrystalline submicrometerr diamond film synthesis was stressed.