Novel hard, tough HfAlSiN multilayers, defined by alternating Si bond structure, deposited using modulated high-flux, low-energy ion irradiation of the growing film
Hf{sub 1−x−y}Al{sub x}Si{sub y}N (0 ≤ x ≤ 0.14, 0 ≤ y ≤ 0.12) single layer and multilayer films are grown on Si(001) at 250 °C using ultrahigh vacuum magnetically unbalanced reactive magnetron sputtering from a single Hf{sub 0.6}Al{sub 0.2}Si{sub 0.2} target in mixed 5%-N{sub 2}/Ar atmospheres at a total pressure of 20 mTorr (2.67 Pa). The composition and nanostructure of Hf{sub 1−x−y}Al{sub x}Si{sub y}N films are controlled by varying the energy E{sub i} of the ions incident at the film growth surface while maintaining the ion-to-metal flux ratio constant at eight. Switching E{sub i} between 10 and 40 eV allows the growth of Hf{sub 0.78}Al{sub 0.10}Si{sub 0.12}N/Hf{sub 0.78}Al{sub 0.14}Si{sub 0.08}N multilayers with similar layer compositions, but in which the Si bonding state changes from predominantly Si–Si/Si–Hf for films grown with E{sub i} = 10 eV, to primarily Si–N with E{sub i} = 40 eV. Multilayer hardness values, which vary inversely with bilayer period Λ, range from 20 GPa with Λ = 20 nm to 27 GPa with Λ = 2 nm, while fracture toughness increases directly with Λ. Multilayers with Λ = 10 nm combine relatively high hardness, H ∼ 24 GPa, with good fracture toughness.