We have succeeded in the fabrication of a boron–carbide/boron diode on an aluminum substrate, and a boron–carbide/boron junction field effect transistor. Our results suggest that with respect to the approximately 2 eV band gap pure boron material, 0.9 eV band gap boron–carbide (B5C) acts as a p-type material. Both boron and boron–carbide (B5C) thin films were fabricated from single source borane cage molecules using plasma enhanced chemical vapor deposition (PECVD). Epitaxial growth does not appear to be a requirement.