Titanium nitride was deposited from the reactant gases H2, N2, and TIC14 at atmospheric pressure. The weight change of the sample was noted by means of a thermobalance. Stainless steel was used as the substrate. It has been found that the deposited film is TiN by the use of x-ray diffraction. Under experimental conditions of minimal influence by mass-transport control, the deposition rate was in proportion to the square root of the partial pressures of hydrogen and nitrogen, respectively. The deposition rate decreased with increasing partial pressure of TIC14 under the experimental conditions employed in this study. By comparing these results with Langmuir-Hinshelwood--type equations, it has been suggested that the probable rate-controlling step is the reaction of hydrogen atoms with nitrogen atoms on the reaction surface or the adsorption of hydrogen molecules and that of nitrogen molecules on the surface. The extent of surface coverage by these atoms is considered to have been reduced when the partial pressure of TIC14 is increased, due to competitive adsorption.

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For the purpose of clarifying the process of the CVD of normalTiN , the chemisorption of TiCl4 , H2 , and N2 on normalTiN has been investigated by the use of a thermal conductivity detector at 900 and 950 K. It has been found that the equilibrium constant of the chemisorption and the adsorption heat of TiCl4 molecules are larger than those of hydrogen atoms and nitrogen atoms.

We have investigated a mechanism for increasing the contact resistance (R c) of the ruthenium (Ru) and the titanium nitride (TiN) barrier during the tantalum oxide (Ta2O5) oxidation annealing in the metal–insulator–metal (MIM) capacitors. It has been found that controlling the atomic ratio of Ti to N (Ti/N ratio) is a key to keeping the contact resistance low. Controlling the Ti/N ratio is easy for the sp-TiN, while it is difficult for the chemical-vapor-deposited TiN. On the basis of this result, we have proposed a novel Ru/TiN contact with a stacked-barrier structure fabricated by using the point-cusp magnetron (PCM) sputtering method. We have applied this structure to the MIM-Ru/Ta2O5/Ru capacitor in a gigabit DRAM with 0.10 µm design. In this capacitor, we have obtained the contact resistance of 10 kΩ·bit and the capacitor leakage current of 10-17 A/bit in the range of -1 to +1 V.

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