Photolysis of M(NEt2)4 in the gas phase produces diatomic MN molecules (M = Ti, Zr, Hf). TiN and ZrN molecules were identified in the gas phase under CVD conditions by emission spectroscopy and time-of-flight mass spectroscopy. Nanostructured deposits of TiN were formed on quartz substrates by irradiating Ti(NEt2)4 gas at 355 nm. These studies demonstrate the gas phase formation of diatomic molecules having the same stoichiometry as that of the desired solid-phase deposit.