Development of TiSiN CVD process using TiCl₄/SiH₄/NH₃chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O2 diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl4, SiH4, and NH3 in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH4 partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O2. The resistivity of TiSiN films was increased by adding SiH4 to the reactant gas. With an increase in SiH4 partial pressure up to PsiH4 = 0.8 Torr, the resistivity gradually increased, but for PsiH4 = 1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O2. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.