Low pressure chemical vapor deposition of B-N-C-H films from triethylamine borane complex

Abstract
In this study, films consisting of B-N-C-H have been synthesized by low pressure chemical vapor deposition using the liquid precursor triethylamine borane complex (TEAB) both with and without ammonia. When no NH3 is present, the growth rate was observed to follow an Arrhenius behavior in the temperature range of 600 to 800 °C with an apparent activation energy of 11 kcal/mol. A linear dependence of growth rate is observed as a function of square root of flow rate for the TEAB range of 20 to 60 sccm, indicating that the reaction rate is controlled by the adsorption of borane. The addition of NH3 to TEAB had the effect of lowering the deposition temperature down to 300 °C and increasing the apparent activation energy to 22 kcal/mol. Above 650 °C, the carbon concentration of the deposits increased significantly, reflecting the breakup of the amine molecule. X-ray diffraction measurements indicated the films to be in all cases amorphous. Infrared spectra of the films showed absorption peaks representing the vibrational modes of B-N, B-N-B, B-H, and N-H. The index of refraction varied between 1.76 and 2.47, depending on composition of the films. Films deposited with no NH3 above 700 °C were seen to be compressive while films below that temperature were tensile. In the range of 350 to 475 °C, the addition of NH3 to TEAB resulted in films that were mildly tensile, while below 325 °C and above 550 °C, the films were found to be compressive. Both the hardness and Young's modulus of the films decreased with higher temperatures, reflecting the influence of the carbon presence.