Strengthening TiN diffusion barriers for Cu metallization by lightly doping Al

Thin films of Ti1-x Alx N were deposited on (100) Si by ultrahigh-vacuum dual-target reactive sputtering, and the impact of lightly doping Al of x as small as 0.09 on altering the films's microstructure upon thermal annealing, and hence the performance of the films (40 nm thick) as diffusion barriers for Cu metallization was evaluated. The results of transmission electron microscopy, Rutherford backscattering spectroscopy, and grazing-incidence x-ray diffraction show that the TiN barrier layer gives the commonly observed voided, columnar grains composed of 5 nm sized subgrains. Upon annealing, the subgrains tend to coalesce into 20 nm sized equiaxed grains full of crystalline defects, initiating an inward penetration of Cu and a partial dissociation of TiN, transforming themselves, respectively, into pyramidal (or columnar) Cu3 Si precipitates and a dendritic Ti5 Si3 layer just after 550 °C, 10 min annealing. However, the lightly doped Al not only overrides the tendency to form intercolumnar voids inherent in sputter deposition by self-shadowing and statistical roughening, but also substantially enhances the microstructural and thermochemical stability, hence significantly improving barrier property, as evidenced from an annealing test at an elevated temperature (600 °C) for a prolonged period of 30 min.