Orientation of sp(2)-bonded boron carbonitride (BCN) hybrid films has been investigated. The films were synthesized on Ni (111) and polycrystalline Ti substrates by radio frequency plasma enhanced chemical vapor deposition using tris-dimethylamino borane as a single-source molecular precursor. The deposition was performed at the radiofrequency power 400-800 W at the working pressure 2.6 Pa. Formation of sp(2)-BCN hybrids in the samples was confirmed by X-ray diffraction (XRD). In the XRD profile, the peak at 26.3 degrees revealed formation of crystalline phase in the samples in which the lattice planes are separated from each other by around 3.5 angstrom. The D band at similar to 1350 cm(-1) and the G band at similar to 1570 cm(-1) in Raman spectra also suggested presence of graphite-like sp(2)-B-C-N hybrid bonds. The films were composed of different B-N, B-C, and C-N bonds to form sp(2)-BCN atomic hybrids confirmed by X-ray photoelectron spectra. Orientation and local structures of the films were studied by near-edge X-ray absorption fine structure (NEXAFS) measurements. The dominant presence of pi* and sigma* resonance peaks of the sp(2) hybrid orbitals in B K-edge NEXAFS spectra revealed preferred formation of sp(2)-BCN atomic hybrids around B atoms like-BN3 configuration in respect to the plane of Ni (111) substrate. Different orientations were suggested on the basis of polarization dependence of B K-edge and N K-edge of the NEXAFS spectra. (C) 2010 Elsevier B.V. All rights reserved.