Initiated-chemical vapor deposition of organosilicon layers: Monomer adsorption, bulk growth, and process window definition

Abstract

Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers)Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Organosilicon layers have been deposited from 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V 3 D 3 ) by means of the initiated-chemical vapor deposition (i-CVD) technique in a deposition setup, ad hoc designed for the engineering of multilayer moisture permeation barriers. The application of Fourier transform infrared (FTIR) spectroscopy shows that the polymerization proceeds through the scission of the vinyl bond and allows quantifying the degree of conversion of vinyl groups, which is found to be larger than 80% for all the deposited layers. In situ real-time spectroscopic ellipsometry (SE) allows following all the i-CVD growth stages, i.e., from the initial monomer adsorption to the layer bulk growth. Finally, the combination of SE and FTIR has allowed defining the process window for the deposition of stable and highly cross-linked poly(V 3 D 3 ) layers by tuning a key process parameter, i.e. the surface monomer adsorption.

One-step vapor-phase synthesis of transparent high refractive index sulfur-containing polymers

“…The SCPs from allyl compounds, poly(sulfur- co -1,11-dodecadiene) (SDDDE) and poly(sulfur- co -1,9-decadiene) (SDDE), also showed characteristic peaks around 2900 cm −1 , representing the C─H stretching. Analogously in the FTIR spectra of polymers with organosilicon-containing monomers including 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane (V3D3), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (V4D4), and hexavinyldisiloxane (HVDS), the peak at 1260 cm −1 corresponding to the Si─C bond is observed ( 27 , 28 ), confirming the full retention of the characteristic functional groups of each monomer, regardless of the monomer species. All the SCPs prepared by sCVD had not been reported to date by other synthesis method to date, which strongly suggest that a wide variety of SCPs can further be generated directly from elemental sulfur through sCVD in expanded manner, regardless of their compatibility with sulfur in solid or liquid state.…”

On the synergistic effect of inorganic/inorganic barrier layers: An ellipsometric porosimetry investigation

“…SiO 2 layers with a thickness of 100 nm were deposited on c‐Si substrate in a home‐built rf‐driven parallel plate PE‐CVD system. Details of the system and deposition process can be found elsewhere . The deposition was carried out at 100 °C by a plasma fed with 1,3,5‐trivinyl‐1,3,5‐trimethylcyclotrisiloxane (V 3 D 3 > 95% purity, Gelest), Ar, and O 2, with flows of 0.5, 70, and 30 sccm, respectively.…”

The impact of the nano-pore filling on the performance of organosilicon-based moisture barriers

“…The monomer functional groups (namely the Si\ \CH 3 bending absorption band at 1260 cm − 1 [41,42], and the Si\ \O\ \Si asymmetric stretching band, either cyclic at 995 cm − 1 , or linear 1066 cm −1 [43]) are entirely retained in the i-CVD polymer structures, as also shown in Ref. [40], since the vinyl groups are the only units involved in and affected by the polymerization process [41,44,45]. On the contrary, the opening of the cyclotrisiloxane ring into the SiO x C y H z layer spectrum is witnessed by the broadening of the Si\ \O\ \Si asymmetric stretching band centered at 1020 cm −1 .…”

“…Table 1 reports the experimental conditions for all the processes. In the case of the poly(V 3 D 3 ) layer, the conditions were chosen according to previous studies aimed at the deposition of stable, smooth layers with a high conversion (i.e., N85%) of vinyl groups [40]. The setup is equipped with spectroscopic ellipsometry (SE)-compatible windows to study the film growth during each process.…”

“…The polymerization and polymer characteristics were investigated by following the same procedure adopted for V 3 D 3 and explained in Ref. [40]. For the TVTSO monomer, a process window was identified at P M /P sat values below 0.2.…”