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The effect of the gas-phase reaction on the deposition rate and the properties of TiN films from metallorganic chemical vapor deposition with tetrakis(dimethylamido)titanium was investigated. In situ Fourier transform infrared spectrometry was used to study the gas-phase reaction mechanism, and the deposition of TiN films was carried out in a low pressure, cold-wall chemical vapor deposition reactor at a deposition temperature from 200 to 400°C. It was observed that tetrakis(dimethylamido)titanium in the gas phase was dissociated into dimethylamine above 280°C, and, in this case, the deposition rate was decreased and a Ti-rich film was formed. It was shown that the gas-phase reaction has a significant effect not only on the deposition rate but also on the film properties.

For the metalorganic chemical vapor deposition (MOCVD) of copper, (hfac)Cu(VTMS) (hfac = hexafluoroacetylacetonate, VTMS = vinyltrimethylsilane) and (hfac)Cu(ATMS) (ATMS = allyltrimethylsilane) were compared, and the effect of L ligand in (hfac)Cu–L was examined. It was found by 1H-NMR (nuclear magnetic resonance) that the thermal stability of (hfac)Cu(VTMS) was better than that of (hfac)Cu(ATMS) due to the relatively weak Cu–ATMS bond. From in situ Fourier transform infrared spectroscopy (FTIR) experiments, the formation of Cu(hfac)2, the product of disproportion reaction of Cu(hfac), was observed in the gas phase and (hfac)Cu(ATMS) was found to be more reactive to form Cu(hfac)2. The minimum temperature for the deposition of copper films from (hfac)Cu(ATMS) was as low as 60 °C, which was about 70 °C lower than from (hfac)Cu(VTMS). The grain size of the film deposited with (hfac)Cu(ATMS) was substantially larger than that with (hfac)Cu(VTMS), which showed that the chemical reactivity of the precursor had an influence on the microstructure along with the deposition temperature.