Raman and conductivity studies of boron-doped microcrystalline diamond, facetted nanocrystalline diamond and cauliflower diamond films

We present a large amount of data showing how the electrical conductivity and Raman spectra of boron-doped CVD diamond films vary as a function of both B content and film type -- in particular, diamond crystallite size. Three types of film have been investigated: microcrystalline diamond (MCD), faceted nanocrystalline diamond (f-NCD) and [`]cauliflower' diamond (c-NCD). For the same B content (measured by SIMS), the conductance of MCD films was much higher than those for the two types of smaller grained films. Multi-wavelength laser Raman spectroscopy showed that Fano interference effects were much reduced for the smaller grain-sized material. The position of the Lorentzian contribution to the 500 cm- 1 Raman feature was used to estimate the B content in each type of film, and compared to the value measured using SIMS. We found that the Raman method overestimated the concentration of B by a factor of ~ 5 for the f-NCD and c-NCD films, although it remains reasonably accurate for MCD films. The shortfall may be explained if only a small fraction of the B found in the small-grained films is being incorporated into substitutional sites. We conclude that in diamond films with a high concentration of grain boundaries, the majority of the B (80% in some cases) must be present at sites that do not contribute to the continuum of electronic states that give rise to metallic conductivity and the Fano effects. Such sites may include (a) interstitials, (b) the surface of the crystallites, or (c) bonded within the non-diamond carbon impurities present at the grain boundaries. This suggests that heavy doping of nanograined diamond films will give rise to a material with many different conducting regions, and possibly different conducting pathways and mechanisms.