Highly Conformal Amorphous W–Si–N Thin Films by Plasma-Enhanced Atomic Layer Deposition as a Diffusion Barrier for Cu Metallization

Ternary and amorphous tungsten silicon nitride (W–Si–N) thin films were grown by atomic layer deposition (ALD) using a sequential supply of a new fluorine-free, silylamide-based W metallorganic precursor, bis­(tert-butylimido)­bis­(bis­(trimethylsilylamido))­tungsten­(VI) [W­(N t Bu)2{N­(SiMe3)2}2], and H2 plasma at a substrate temperature of 300 °C. Here, W­(N t Bu)2{N­(SiMe3)2}2 was prepared through a metathesis reaction of W­(N t Bu)2Cl2(py)2 (py = pyridine) with 2 equiv of LiN­(SiMe3)2 [Li­(btsa)]. The newly proposed ALD system exhibited typical ALD characteristics, such as self-limited film growth and linear dependency of the film growth on the number of ALD cycles, and showed a high growth rate of 0.072 nm/cycle on a thermally grown SiO2 substrate with a nearly zero incubation cycle. Such ideal ALD growth characteristics enabled excellent step coverage of ALD-grown W–Si–N film, ∼100%, onto nanotrenches with a width of 25 nm and an aspect ratio ∼4.5. Rutherford backscattering spectrometry and X-ray photoelectron spectroscopy analysis confirmed that the incorporated Si and W were mostly bonded to N, as in Si–N and W–N chemical bonds. The film kept its amorphous nature until annealing at 800 °C, and crystallization happened at local areas after annealing at a very high temperature of 900 °C. An ultrathin (only ∼4 nm thick) ALD-grown W–Si–N film effectively prevented diffusion of Cu into Si after annealing at a temperature up to 600 °C.