Cathodic and anodic pre-treated boron doped diamond with different sp2 content: Morphological, structural, and impedance spectroscopy characterizations

• Cathodic and anodic pre-treatment were made on boron doped diamond.
• The oxidation process influences the diamond acceptor concentration.
• We report the sp2 bonds influence in the BDD doping level.
• The highest doped sample was obtained with the lowest CH4 addition in the gas phase.

In this work, the influence of cathodic (Red) and anodic (Ox) pre-treatment on boron doped diamond (BDD) films grown with different sp2/sp3 ratios was systematically studied. The sp2/sp3 ratios were controlled by the addition of CH4 of 1,3,5 and 7 sccm in the gas inlet during the growth process. The electrodes were treated in 0.5 mol L−1 H2SO4 at −3 and 3 V vs Ag/AgCl, respectively, for 30 min. The electrochemical response of BDD films was investigated using electrochemical impedance spectroscopy (EIS) and Mott–Schottky Plot (MSP) measurements. Four film sample sets were produced in a hot filament chemical vapor deposition reactor. During the growth process, an additional H2 line passing through a bubbler containing the B2O3 dissolved in methanol was used to carry the boron. The scanning electron microscopy morphology showed well faced films with a small decrease in their grain size as the CH4 concentration increased. The Raman spectra depicted a pronounced sp2 band, mainly for films with 5 and 7 sccm of CH4. MSP showed a decrease in the acceptor concentration as the CH4 increased indicating the CH4 influence on the doping process for Red–BDD and Ox–BDD samples. Nonetheless, an apparent increase in the acceptor concentrations for both Ox–BDD samples was observed compared to that for Red–BDD samples, mainly attributed to the surface conductive layer (SCL) formation after this strong oxidation process. The EIS Nyquist plots for Red–BDD showed a capacitance increase for the films with higher sp2 content (5 and 7 sccm). On the other hand, the Nyquist plots for Ox–BDD can be described as semicircles near the origin, at high frequencies, where their charge transfer resistance strongly varied with the sp2 increase in such films.