Study of Atomic Hydrogen Concentration in Grain Boundaries of Polycrystalline Diamond Thin Films

This paper describes research focused on investigating the effect of hydrogen (H) atom insertion into the grain boundaries of polycrystalline diamond (PCD) films. This is required in order to understand the key morphological, chemical, physical, and electronic properties of the films. The PCD films were grown using the hot filament chemical vapor deposition (HFCVD) process, with flowing Ar gas mixed with CH4 and H2 gases to control film growth into microcrystalline diamond (MCD, 0.5–3 µm grain sizes), nanocrystalline diamond (NCD, 10–500 nm grain sizes), and ultrananocrystalline diamond (UNCD, 2–5 nm grain sizes) films depending on the Ar/CH4/H2 flow ratios. This study focused on measuring the H atom concentration of the PCD films to determine the effect on the properties indicated above. A simple model is presented, including a hypothesis that the two dangling bonds per unit cell of C atoms serve as the site of hydrogen incorporation. This correlates well with the observed concentration of H atoms in the films. Dangling bonds which are not passivated by hydrogen are postulated to form surface structures which include C double bonds. The Raman peak from these surface structures are the same as observed for transpolyacetyline (TPA). The data reveal that the concentration of H atoms at the grain boundaries is around 1.5 × 1015 atoms/cm2 regardless of grain size. Electrical current measurements, using a conductive atomic force microscopy (CAFM) technique, were performed using an MCD film, showing that the current is concentrated at the grain boundaries. Ultraviolet photo electron spectroscopy (UPS) confirmed that all the PCD films exhibited a metallic behavior. This is to be expected if the nature of grain boundaries is the same regardless of grain size.