Ozone-Based Atomic Layer Deposition of HfO 2 and Hf x Si 1-x O 2 and Film Characterization

New ALD processes for hafnium silicate films have been developed at Aviza Technology by co-injection of tetrakis(ethylmethylamino)hafnium and tetrakis(ethylmethylamino)silicon precursors. Alternating pulses of the Hf/Si precursor vapor mixture and ozone allow process temperatures below 400°C to grow HfxSi1-xO2 films. Film characterization, including film density, crystallinity, and thermal anneal effect, was performed on five 20 nm thick HfxSi1-xO2 films where x = 0.2, 0.4, 0.6, 0.8, 1.0. X-ray measurements revealed the film densities and thicknesses for the as-deposited and 1000°C annealed samples. The densification with anneals seen in the optical measurements were confirmed. The as-deposited amorphous HfO2 and Hf0.8Si0.2O2 were crystallized after a 600°C anneal. The HfO2 formed the well known monoclinic phase while the silicate formed a face-centered-cubic (fcc) structure. This fcc phase has only recently been mentioned in the literature [1].