We have grown nickel doped boron-carbon alloy films by the technique of plasma enhanced chemical vapor deposition. The source gas closo-1,2-dicarbadodecaborane (orthocarborane) was used to grow the boron-carbon alloy, while nickelocene [Ni(C5H5)(2)] was used as the dopant source for nickel. With sufficient levels of Ni doping, diodes with characteristic tunnel diode behavior can be fabricated. The doping of nickel transformed a B5C p-type material, relative to lightly doped n-type silicon, to a strongly n-type material. In order to gain insight into the shift of the Fermi level of the Ni-doped material, we have examined the changes in the electronic structure of sodium doped films of the precursor molecule orthocarborane which has an icosahedral structure similar to that of boron-carbon materials. The establishment of unoccupied states at the Fermi level with Na doping of the orthocarborane films is consistent with the transformation of the p-type B5C to an n-type material with Ni doping.