Effect of electron cyclotron resonance H+, Ne+, Ar+, and Xe+ plasma precleaning on titanium silicide formation

A vacuum integrated cluster tool process incorporating electron cyclotron resonance plasma cleaning, Ti sputter deposition, and rapid thermal annealing in N₂ is used to form a TiN_x<1/TiSi_y bilayer on (100) Si where the film composition is controlled by the preclean chemistry. Chemical cleaning with nominal 10 eV H⁺ completely removes native Si oxide resulting in a hydrogen terminated surface that promotes silicidation compared to one cleaned with buffered-oxide-etching (BOE). If the native oxide is only partially reduced, viz., SiO_x<2 surface, for example by shortening the H⁺ exposure time, then silicidation is largely inhibited and a thicker nitride layer is formed. Sputter cleaning with 50 to 250 eV Ar⁺ results in a bilayer that is roughly equivalent to that formed with BOE, whereas 50 to 150 eV Xe⁺ bombardment favors nitridation. Precleaning with >150 eV Ne⁺ promotes silicidation, thereby minimizing nitride thickness. The effects of precleaning are significant as the activation energy for TiSi_y formation is reduced from 1.8 eV characteristic of a BOE cleaned surface to 1.2 eV on Si etched with 250 eV Ne⁺. Mechanistically, the silicide kinetics are shown to be inhibited by the presence of a thin amorphous layer that is formed only when cleaning Si with Ar⁺ and Xe⁺ with the effect that both knock-on oxygen atoms and implanted noble gas atoms trapped within the amorphous layer retard the requisite solid-phase epitaxial regrowth kinetics. Recrystallizing the amorphous Si surface prior to metallization appears to restore the near-normal silicide kinetics that is characteristic of Ne⁺ cleaning