Microstructural and electrochemical properties of sulfur ion implanted nanocrystalline diamond films

Abstract

Nanocrystalline diamond (NCD) films have a composite structure composed of diamond grains and amorphous carbon grain boundaries. Compared with microcrystalline diamond (MCD) films, the NCD film grain boundaries are rich in a large number of π bonds, thus providing conductive channels. Its conductivity is 3−7 orders of magnitude higher than that of MCD, and the surface of NCD film is uniform and dense, and the roughness is lower, so the NCD film is a promising electrode material. In our previous study, microwave plasma chemical vapor deposition was successfully used to prepare n-type sulfur-doped diamond films with good electrical properties. However, the electrochemical properties of sulfur-doped nanocrystalline diamond films have not been studied till now. In the present work, the nanocrystalline diamond films are prepared by the hot-wire chemical vapor deposition. The films are subjected to ion implantation and vacuum annealing. The effects of annealing temperature on the microstructure and electrochemical properties of the films are investigated. The results show that the sulfur ion implantation is beneficial to the improvement of the electrochemical reversibility of the film. When annealed at 800 °C and below, the amorphous carbon phase at the grain boundary in the film gradually changes into the trans-acetylene phase, resulting in a gradual deterioration of electrochemical performance. When the annealing temperature rises to 900 °C, Raman spectrum and TEM results show that the film has more diamond phase content and better lattice quality, and the trans-polyacetylene in the grain boundary is cracked; XPS results indicate that the CO bond at this time, C=O bond, and π—π* content increase significantly; Hall test shows that the film mobility and carrier concentration are significantly higher than those of unannealed film. The redox peak in the electrolyte is highly symmetrical, the peak potential difference is reduced to 0.20 V, the electrochemical active area is increased to 0.64 mC/cm<sup>2</sup>, and the electrochemical reversibility is much better thanthose of samples annealed at 600 °C, 700 °C, and 800 °C, respectively.