Diffusion barrier property of TiN and TiN/Al/TiN films deposited with FMCVD for Cu interconnection in ULSI

Abstract

Flow modulation chemical vapor deposition (FMCVD) with titanium tetrachloride (TiCl4) and ammonia (NH3) is effective for depositing titanium nitride (TiN) films with conformal morphology, good step coverage, low electrical resistivity, and low chlorine residual contamination. It means that FMCVD TiN film is a good candidate of diffusion barriers for copper interconnection technology in ULSI. But the diffusion barrier property of FMCVD TiN film against Cu diffusion has not been confirmed. So, firstly, we deposited Cu (100 nm)/FMCVD TiN (25 nm)/Si multilayer films and investigated the thermal stability of Cu/TiN/Si structure. Vacuum annealing was done at 400, 500, 550 and 600 °C. For films annealed for 30 min at 400 °C, Cu diffused through the TiN layer and formed copper silicides on the surface of Si substrates. Therefore, FMCVD films formed under such conditions are unsatisfactory diffusion barriers. To enhance the diffusion barrier property of FMCVD TiN films, we used sequential deposition to introduce a monolayer of Al atoms between two TiN films. Etch-pit tests showed that for TiN films with Al interlayer, Cu diffusion through the barrier occurred at 500 °C and that is 100 °C higher than TiN film without Al interlayer. Al atoms formed AlOx with oxygen atoms present in the TiN films as impurities, and fill up the grain boundaries of TiN film, thereby blocking the diffusion of Cu atoms.