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Highly conformal amorphous W-Si-N thin films by plasma-enhanced atomic layer deposition as a diffusion barrier for Cu metallization

Highly conformal amorphous W-Si-N thin films by plasma-enhanced atomic layer deposition as a diffusion barrier for Cu metallization
Hong, T.E.[Hong, Tae Run]Jung, J.-H.[Jung, Jae Hun]Yeo, S.[Yeo, Seung Min]Cheon, T.[Cheon, Tae Hoon]Bae, S.I.[Bae, Soik]Kim, S.-H.[Kim, Soo Hyun]Yeo, S.J.[Yeo, So Jeong]Kim, H.-S.[Kim, Hyo Suk]Chung, T.-M.[Chung, Taek Mo]Park, B.K.[Park, Bo Keun]Kim, C.G.[Kim, Chang Gyoun]Lee, D.-J.[Lee, Do Joong]
DGIST Authors
Cheon, T.[Cheon, Tae Hoon]
Issue Date
Journal of Physical Chemistry C, 119(3), 1548-1556
Article Type
Amorphous FilmsAmorphous SiliconAnnealingAspect RatioAtomic Layer DepositionBond Strength (Chemical)Chemical AnalysisCopperCu MetallizationDepositionFilm GrowthHigh Growth RateHigh TemperatureLinear DependencyMetallic FilmsMetathesis ReactionsOrganometallicsPlasma-Enhanced Atomic Layer DepositionRutherford Back-Scattering SpectrometrySiliconSilicon NitrideSilicon OxidesSubstrate TemperatureThin-FilmsTungstenTungsten CompoundsX Ray Photoelectron Spectroscopy
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(NtBu)2{N(SiMe3)2}2], and H2 plasma at a substrate temperature of 300 °C. Here, W(NtBu)2{N(SiMe3)2}2 was prepared through a metathesis reaction of W(NtBu)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. © 2014 American Chemical Society.
American Chemical Society
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