Plasma Interactions on Organosilicate Glass Dielectric Films and Emerging Amorphous Materials- Approach to Pore Sealing and Chemical Modifications

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In-situ x-ray photoemission (XPS) and ex-situ FTIR studies of nanoporous organosilicate glass (OSG) films point to the separate roles of radicals vs. VUV photons in the carbon abstraction. The studies indicate that reaction with O2 in presence of VUV photons (~123 nm) result in significant carbon abstraction within the bulk and that the kinetics of this process is diffusion-limited. In contrast, OSG exposed to atomic O (no VUV) results in Si-C bond scission and Si-O bond formation, but this process is self-limiting after formation of ~1 nm thick SiO2 surface layer that inhibits further diffusion. Therefore, the diffusion-dominated kinetics of ... continued below

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xiv, 120 pages : illustrations (some color)

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Kazi, Haseeb May 2015.

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In-situ x-ray photoemission (XPS) and ex-situ FTIR studies of nanoporous organosilicate glass (OSG) films point to the separate roles of radicals vs. VUV photons in the carbon abstraction. The studies indicate that reaction with O2 in presence of VUV photons (~123 nm) result in significant carbon abstraction within the bulk and that the kinetics of this process is diffusion-limited. In contrast, OSG exposed to atomic O (no VUV) results in Si-C bond scission and Si-O bond formation, but this process is self-limiting after formation of ~1 nm thick SiO2 surface layer that inhibits further diffusion. Therefore, the diffusion-dominated kinetics of carbon abstraction observed for OSG exposed to O2 plasma is definitively attributed to the diffusion of O2 down OSG nanopores, reacting at photo-activated sites, rather than to the diffusion of atomic O. Pretreatment of OSG by 900 eV Ar+ ion bombardment also results in formation of 1 nm thick SiO2-like surface overlayer that inhibits O2 diffusion, inhibiting VUV+O2 and O2 plasma-induced reactions, and that the effectiveness of this treatment increases with ion kinetic energy. On the contrary, organosilicate glass (OSG) films with backbone carbon (-Si-R-Si-) exhibit significantly enhanced resistance to carbon loss upon exposure to O2 plasma, radicals and VUV+O2 compared to films with terminal methyl groups (Si-CH3). Films incorporating backbone carbon chains (-Si-R-Si-) were deposited from 1,2 bis (triethoxysilyl) ethane (BTESE) precursor by ebeam or plasma cross-linking. The radical effects on BTESE film indicates negligible carbon loss or Si oxidation, combined with C-O bond formation, under conditions where OSG films with terminal methyl groups exhibit > 80% carbon loss within the surface region of the film. C-O bond formation is never observed for terminal CH3 groups. Further, backbone carbon (-Si-R-Si-) films exposed to VUV+O2 exhibit self-limiting, minimal net carbon loss. This indicates that plasma-induced Si-C bond rupture still occurs in the linking unit, but with a low probability of simultaneous rupture of both Si-C bonds required for abstraction of an in-line methylene bridging group. The data thus demonstrate that OSG films containing backbone carbon groups exhibit greatly reduced rates of carbon loss in the presence of O2 plasma, radicals or VUV+O2 compared to films with terminal carbon groups due to fundamentally different patterns of Si-C bond scission. The results demonstrate the potential of backbone carbon low-k films to resist plasma induced damage.

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xiv, 120 pages : illustrations (some color)

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  • May 2015

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  • Feb. 9, 2016, 4:37 p.m.

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Kazi, Haseeb. Plasma Interactions on Organosilicate Glass Dielectric Films and Emerging Amorphous Materials- Approach to Pore Sealing and Chemical Modifications, dissertation, May 2015; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc801876/: accessed September 22, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .