Optical emission study of a doped diamond deposition process by plasma enhanced chemical vapor deposition

Abstract

Standard H2∕CH4∕B2H6 plasmas (99% of H2 and 1% of CH4, with 0–100ppm of B2H6 added) used for doped diamond film growth are studied by optical emission spectroscopy in order to gain a better understanding of the influence of boron species on the gas phase chemistry. Only two boron species are detected under our experimental conditions (9∕15∕23Wcm−3 average microwave power density values), and the emission spectra used for studies reported here are B(S1∕22−P1∕2,3∕202) and BH[AΠ1-XΣ+1(0,0)]. Variations of their respective emission intensities as a function of the ratio B∕C, the boron to carbon ratio in the gas mixture, are reported. We confirmed that the plasma parameters (Tg, Te, and ne) are not affected by the introduction of diborane, and the number densities of B atoms and BH radical species were estimated from experimental measurements. The results are compared to those obtained from a zero-dimensional chemical kinetic model where two groups of reactions are considered: (1) BHx+H↔BHx−1+H2 (x=1–3) by analogy with the well-known equilibrium CHx+H set of reactions, which occurs, in particular, in diamond deposition reactors; and (2) from conventional organic chemistry, the set of reactions involving boron species: BHx+C2H2 (x=0–1). The results clearly show that the model based on hydrogen and boron hydrides reactions alone is not consistent with the experimental results, while it is so when taking into account both sets of reactions. Once an upper limit for the boron species number densities has been estimated, axial profiles are calculated on the basis of the plasma model results obtained previously in Laboratoire d’Ingénierie des Matériaux et des Hautes Pressions, and significant differences in trends for different boron species are found. At the plasma-to-substrate boundary, [BH] and [B] drop off in contrast to [BH2], which shows little decrease, and [BH3], which shows little increase, in this region.