Optical Emission from Microwave Activated C/H/O Gas Mixtures for Diamond Chemical Vapor Deposition

The spatial distributions and relative abundances of electronically excited H atoms, OH, CH, C-2 and C-3 radicals, and CO molecules in microwave (MW) activated CH4/CO2/H-2 and CO/H-2 gas mixtures operating under conditions appropriate for diamond growth by MW plasma enhanced chemical vapor deposition (CVD) have been investigated by optical emission spectroscopy (OES) as a function of process conditions (gas mixing ratio, incident MW power, and pressure) and rationalized by reference to extensive 2-dimensional plasma modeling. The OES measurements clearly reveal the switch in plasma chemistry and composition that occurs upon changing from oxygen-rich to carbon-rich source gas mixtures, complementing spatially resolved absorption measurements under identical plasma conditions (Kelly et al., companion article). Interpretation of OES data typically assumes that electron impact excitation (Em) is the dominant route to forming the emitting species of interest. The present study identifies a number of factors that complicate the use of OES for monitoring C/H/O plasmas. The OH* emission from EIE of ground state OH(X) radicals can be enhanced by excitation energy transfer from metastable CO(a(3)Pi) molecules. The CH* and C-2* emissions can be boosted by chemiluminescent reactions between, for example, C2H radicals and 0 atoms, or C atoms and CH radicals. Additionally, the EIE efficiency of each of these radical species is sensitively dependent on any spatial mismatch between the regions of maximal radical and electron density, which itself is a sensitive function of elemental C/O ratio in the process gas mixture (particularly when close to 1:1, as required for diamond growth) and the H-2 mole fraction.