Sub-valent molybdenum, tungsten, and chromium amides as sources for thermal chemical vapor deposition of metal-containing films

A thermal CVD process for forming a selected refractory metal-containing film onto a substrate comprising the steps of: (a) introducing a subvalent refractory metal amide as a reactant gas capable of forming said metal-containing film into a CVD reaction zone containing said substrate on which said metal-containing film is to be formed; said subvalent metal amide having formula (I): [M[NRR']x]y (I) wherein M is molybdenum, tungsten, or chromium; wherein R and R' are individually selected from hydrogen and lower alkyl groups having 1-4 carbon atoms, with the proviso that at least one of R or R' must be a lower alkyl group; wherein x is selected from 2, 3, 4, or 5; and wherein y is selected from 1 or 2. (b) maintaining the temperature of said zone and said substrate at about 200 DEG C. to about 1,000 DEG C.; (c) maintaining the pressure in said zone at about 0.001 torr to about 100 torr; and (d) passing said reacting gas or gases by said heated substrate for a period of time sufficient to form said metal-containing film thereon.