Hexagonal boron carbonitride (h-BCN) hybrid films have been synthesized on highly oriented pyrolytic graphite by radiofrequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane as a single-source molecular precursor. The films were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopic measurements. XPS measurement showed that the B atoms were bonded to C and N atoms to form the sp(2)-B-C-N atomic hybrid chemical environment. The atomic composition estimated from the XPS of the typical sample was found to be almost B(1)C(1)N(1). NEXAFS spectra of the B K-edge and the N K-edge had the peaks due to the pi* and sigma* resonances of sp(2) hybrid orbitals implying the existence of the sp(2) hybrid configurations of h-BCN around the B atoms. The G band at 1592 and D band at 1352 cm(-1) in the Raman spectra also suggested the presence of the graphite-like sp(2)-B-C-N atomic hybrid bonds. The films consisted of micrometer scale crystalline structure of around 10 mu m thick has been confirmed by the field emission scanning electron microscopy. (C) 2009 Elsevier B.V. All rights reserved.