Optical Emission Imaging and Modeling Investigations of Microwave-Activated SiH4/H2 and SiH4/CH4/H2 Plasmas

Silicon is a known trace contaminant in diamond grown by chemical vapor deposition (CVD) methods. Deliberately Si-doped diamond is currently attracting great interest because of the attractive optical properties of the negatively charged silicon-vacancy (SiV–) defect. This work reports in-depth studies of microwave-activated H2 plasmas containing trace (10–100 ppm) amounts of SiH4, with and without a few % of CH4, operating at pressures and powers relevant for contemporary diamond CVD, using a combination of experiment (spatially resolved optical emission (OE) imaging) and two-dimensional plasma chemical modeling. Key features identified from analysis and modeling of the OE from electronically excited H, H2, Si, and SiH species in the dilute Si/H plasmas include the following: (i) fast H-shifting reactions ensure that Si atoms are the most abundant silicon-containing species throughout the entire reactor volume, (ii) the low ionization potentials of all SiH x (x ≤ 4) species and efficient ion conversion reactions ensure that even trace SiH4 additions cause a change in the dominant ions in the plasma volume (from H3 + to SiH x +), with consequences for electron-ion recombination rates and ambipolar diffusion coefficients, and (iii) the total silicon content in the reactor volume can be substantially perturbed by silicon deposition and H atom etching reactions at the reactor walls. The effects of adding trace amounts of SiH4 to a pre-existing C/H plasma are shown to be much less dramatic but include the following: (i) a Si substrate or fused silica components within the reactor are a ready (unintended) source of gas-phase Si-containing species, (ii) OE from electronically excited Si atoms should provide a reliable measure of the Si content in the hot plasma region, and (iii) Si atoms and/or SiC2 species are the most abundant gas-phase Si-containing species just above the growing diamond surface and thus the most likely carriers of the silicon incorporated into CVD diamond.