Plasma gas temperatures were measured via in situ optical emission spectroscopy in a microwave CH4–H2 plasma under carbon nanotube (CNT) growth conditions. Gas temperature is an important parameter in controlling and optimizing CNT growth. The temperature has a significant impact on chemical kinetic rates, species concentrations and CNT growth rates on the substrate. H2 rotational temperatures were determined from the Q-branch spectrum of the (0) transition. N2 rotational and vibrational temperatures were measured by fitting rovibrational bands from the N2 emission spectrum of the C 3Πu → B 3Πg transition. The N2 rotational temperature, which is assumed to be approximately equal to the translational gas temperature, increases with an increase in input microwave plasma power and substrate temperature. The measured H2 rotational temperatures were not in agreement with the measured N2 rotational temperatures under the CNT growth conditions in this study. The measured N2 rotational temperatures compared with the H2 rotational temperatures suggest the partial equilibration of upper excited state due to higher, 10 Torr, operating pressure. Methane addition in the hydrogen plasma increases the gas temperature slightly for methane concentrations higher than 10% in the feed gas.

Wavelength and spatially resolved imaging and 2D plasma chemical modeling methods have been used to study the emission from electronically excited C2 radicals in microwave-activated dilute methane/hydrogen gas mixtures under processing conditions relevant to the chemical vapor deposition (CVD) of diamond. Obvious differences in the spatial distributions of the much-studied C2(d3Πg–a3Πu) Swan band emission and the little-studied, higher-energy C2(C1Πg–A1Πu) emission are rationalized by invoking a chemiluminescent (CL) reactive source, most probably involving collisions between H atoms and C2H radicals, that acts in tandem with the widely recognized electron impact excitation source term. The CL source is relatively much more important for forming C2(d) state radicals and is deduced to account for >40% of C2(d) production in the hot plasma core under base operating conditions, which should encourage caution when estimating electron or gas temperatures from C2 Swan band emission measurements. Studies at higher pressures (p ≈ 400 Torr) offer new insights into the plasma constriction that hampers efforts to achieve higher diamond CVD rates by using higher processing pressures. Plasma constriction is proposed as being inevitable in regions where the local electron density (n e) exceeds some critical value (n ec) and electron–electron collisions enhance the rates of H2 dissociation, H-atom excitation, and related associative ionization processes relative to those prevailing in the neighboring nonconstricted plasma region. The 2D modeling identifies a further challenge to high-p operation. The radial uniformities of the CH3 radical and H-atom concentrations above the growing diamond surface both decline with increasing p, which are likely to manifest as less spatially uniform diamond growth (in terms of both rate and quality).