Elimination of O2 plasma damage of low-k methyl silsesquioxane film by As implantation

Wang, C.Y.; Zheng, Jingjing; Shen, Zexiang; Lin, Yih-Chuan; Wee, Andrew Thye Shen

doi:10.1016/s0040-6090(01)01401-8

Cited by 20 publications

(11 citation statements)

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“…Interestingly, a change of the bonding configuration due to physical bombardment of heavy atoms/molecules can also contribute to the chemical shift, such as the 0.5 eV increase observed after Ar plasma treatment. In a previous study, when physical bombardment induced amorphous or unbonded carbon atoms in the film, a shift of ~1 eV of the Cls peak was observed [20].…”

Section: Resultsmentioning

confidence: 80%

Mechanistic Study of Plasma Damage of Low k Dielectric Surfaces

Bao

Shi

Liu

et al. 2007

AIP Conference Proceedings

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Abstract. Plasma damage to low k dielectric materials was investigated from a mechanistic point of view. Low k dielectric films were treated by plasma Ar, O2, N2/H2, N2 and H2 in a standard RIE chamber and the damage was characterized by Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS), X-Ray Reflectivity (XRR), Fourier Transform Infrared Spectroscopy (FTIR) and Contact Angle measurements. Both carbon depletion and surface densification were observed on the top surface of damaged low k materials while the bulk remained largely unaffected. Plasma damage was found to be a complicated phenomenon involving both chemical and physical effects, depending on chemical reactivity and the energy and mass of the plasma species. A downstream hybrid plasma source with separate ions and atomic radicals was employed to study their respective roles in the plasma damage process. Ions were found to play a more important role in the plasma damage process. The dielectric constant of low k materials can increase up to 20% due to plasma damage and we attributed this to the removal of the methyl group making the low k surface hydrophilic. Annealing was generally effective in mitigating moisture uptake to restore the k value but the recovery was less complete for higher energy plasmas. Quantum chemistry calculation confirmed that physisorbed water in low k materials induces the largest increase of dipole moments in comparison with changes of surface bonding configurations, and is primarily responsible for the dielectric constant increase.

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Section: Resultsmentioning

confidence: 80%

Mechanistic Study of Plasma Damage of Low k Dielectric Surfaces

Bao

Shi

Liu

et al. 2007

AIP Conference Proceedings

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“…Other possible assignments include the symmetric Si–O–Si stretching of oxide film . Branching was unlikely because the dichlorosilanes only have two active sites. , The other bands at 1086 cm –1 and 1029 cm –1 were probably the vibrational modes of linear siloxanes, reported at 1080 cm –1 and 1020 cm –1 , supporting the formation of Si x –O–Si cs chains. Subscript x refers to an unspecified silicon atom, originating from either a dichlorosilane (cs) or a substrate silicon atom (s).…”

Section: Resultsmentioning

confidence: 94%

Surface Modification of Porous Silicon-Based Films Using Dichlorosilanes Dissolved in Supercritical Carbon Dioxide

Vyhmeister

Valdés-González

Muscat

et al. 2013

Ind. Eng. Chem. Res.

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Dimethyldichlorosilane (DMDCS), diethyldichlorosilane (DEDCS), and dibutyldichlorosilane (DBDCS) were dissolved in supercritical CO 2 at two concentration levels to modify hydrolyzed porous surfaces via silylation reactions. Plasmadamaged methylsilsesquioxane samples were loaded in a batch reactor with the chlorosilanes; when introduced, the low-viscosity supercritical CO 2 dissolved and transported the chlorosilanes to the porous surface. Samples were characterized using Fourier transform infrared spectroscopy (FTIR), ellipsometry, goniometry, and electrical measurements, and compared against untreated samples. Reactions between the chlorosilanes and substrate hydroxyls were strongly dependent on the length of the alkyl group on the chlorosilane, but independent of concentration. FTIR analyses showed a decreased intensity for infrared (IR)-isolated/ geminal OH vibrations (100%, 93.9% ± 5.4%, and 95.4% ± 4.3% for DMDCS, DEDCS, and DBDCS, respectively), but DEDCS and DBDCS resulted in 3.9% ± 5.0% and 20.9% ± 8.7% increases in hydrogen bonding, respectively. DMDCS was more successful, showing a 14.4% ± 9.8% reduction in hydrogen bonding. Goniometry measured hydrophobic contact angles that were consistently greater than 81°, irrespective of the chemistry used. Ellipsometry showed a strong dependence between the thickness of the deposited layers and the chlorosilane alkyl group (19.0 nm ± 1.6 nm, 31.3 nm ± 4.8 nm, and 74.2 nm ± 4.7 nm for DMDCS, DEDCS, and DBDCS, respectively). Electrical measurements indicated improved hydroxyl group elimination with shorter alkyl groups (dielectric constant decreased from 3.5 for plasma-ashed methylsilsesquioxane samples to 2.59, 2.97, and 3.4 for DMDCS, DEDCS, and DBDCS, respectively). DMDCS was found to participate in intramolecular and intermolecular reactions while the surface-modifying agents with longer hydrocarbon chains underwent predominantly intermolecular reactions, resulting in the thicker deposited layers.

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“…This increased the wettability of the coating surface. − Figure b shows the FT-IR spectra of the colloidal siloxane and colloidal siloxane layers cured by EB at a dose of 500 kGy. The following peaks were observed: the peak at approximately 1730 cm –1 was derived from the CO group, and the peaks at 1640 and 1400 cm –1 were due to CC stretching. , The intensity of the CC peak was reduced significantly after EB curing, owing to oxidation. In addition, the Si–O–Si peak (1000–1200 cm –1 ), Si–OH peak (880–980 cm –1 ), Si–O–C peak (700–950 cm –1 ), and CH n peak (740 cm –1 ) are also marked.…”

Section: Results and Discussionmentioning

confidence: 96%

“…The following peaks were observed: the peak at approximately 1730 cm −1 was derived from the CO group, 33 and the peaks at 1640 and 1400 cm −1 were due to CC stretching. 34,35 The intensity of the CC peak was reduced significantly after EB curing, owing to oxidation. In addition, the Si−O−Si peak (1000−1200 cm −1 ), Si−OH peak (880−980 cm −1 ), 36 Si−O−C peak (700−950 cm −1 ), 37 51 and O−CO (533.9 eV).…”

Section: Fourier Transform Infrared and Raman Spectramentioning

confidence: 99%

Enhanced Polymerization and Surface Hardness of Colloidal Siloxane Films via Electron Beam Irradiation

Kim

Na³

et al. 2021

ACS Omega

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Electron beam (EB) curing is a foldable hard coating process and has attracted significant research attention in the field of flexible electronic devices. In this study, we report a method for enhancing material surface hardness with low-energy EB curing in a short time. The low-energy EB improved the coating hardness of films by inducing cross-linking polymerization of the silicon-containing monomer. The hardness of the cured coating layer was measured as 3 H using a pencil hardness tester, and the transparency of the coating was higher than 90%. Owing to a series of cross-linking reactions between Si–O–C and Si–OH groups under EB curing and the formation of Si–Si bonds, the cured layer exhibited remarkable durability in the 100000-flexible cycle test. Additionally, the natural oxidation of the C–O groups on the surface of the coating formed carboxyl groups that improved the hydrophilic properties of the coating layer. To the best of our knowledge, this is the first study to propose that the hardness of polyethylene terephthalate films can be improved using low-energy EBs to rapidly cure silicon-containing coatings. Our results provide a novel and commercially viable approach for improving the hardness of touch screens and foldable displays.

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Elimination of O2 plasma damage of low-k methyl silsesquioxane film by As implantation

Cited by 20 publications

References 1 publication

Mechanistic Study of Plasma Damage of Low k Dielectric Surfaces

Mechanistic Study of Plasma Damage of Low k Dielectric Surfaces

Surface Modification of Porous Silicon-Based Films Using Dichlorosilanes Dissolved in Supercritical Carbon Dioxide

Enhanced Polymerization and Surface Hardness of Colloidal Siloxane Films via Electron Beam Irradiation

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