Monolithic TiB2 films and double layer and composite TiCN-TiB2 films were deposited on Si wafers from a mixture of titanium tetra-ethoxide and boron tri-ethoxide solutions at a 1:2 mole ratio at 800 degrees C for 20 min by chemical vapor deposition in a thermal N-2/H-2 plasma. The TiB2 films were deposited without N-2, while the double layer and composite TiCN-TiB2 films of various compositions were deposited by varying N-2 flow rates in N-2/H-2 plasma. The surfaces and cross-sections of the films were observed by SEM, exhibiting the microstructures and thickness of the films. The relative atomic percentages of Ti, N, B, bonded and free C, and O in the films were determined semi-quantitatively from their XPS peak areas. Microstructures of the composite films with the composition 3TiC(0.5)N(0.5)/2TiB(2) formed at N-2 = 50 mL min(-1) were observed by TEM, revealing the sizes and orientations of the particles with the distribution of Ti and B elements in the film. (C) 2007 Elsevier B.V. All rights reserved.