Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)

Abstract Poly(para‐xylylene)s (PPXs), or so‐called parylenes, have become a well‐established polymer class in the conformal coating industry. Due to their transparent nature, low electrical conductivity, and high biocompatibility, they are ideal candidates for coating medical devices and other delic...

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Main Authors: Lukas Bichlmaier, Tetsuhiko F. Teshima, Arseni Kostenko, George Al Boustani, Rebecca Wilhelm, Sebastian Stigler, Shuma Tanaka, Hiroaki Onoe, Bernhard Wolfrum, Shigeyoshi Inoue
Format: Article
Language:English
Published: Wiley-VCH 2025-03-01
Series:Advanced Materials Interfaces
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Online Access:https://doi.org/10.1002/admi.202400701
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author Lukas Bichlmaier
Tetsuhiko F. Teshima
Arseni Kostenko
George Al Boustani
Rebecca Wilhelm
Sebastian Stigler
Shuma Tanaka
Hiroaki Onoe
Bernhard Wolfrum
Shigeyoshi Inoue
author_facet Lukas Bichlmaier
Tetsuhiko F. Teshima
Arseni Kostenko
George Al Boustani
Rebecca Wilhelm
Sebastian Stigler
Shuma Tanaka
Hiroaki Onoe
Bernhard Wolfrum
Shigeyoshi Inoue
author_sort Lukas Bichlmaier
collection DOAJ
description Abstract Poly(para‐xylylene)s (PPXs), or so‐called parylenes, have become a well‐established polymer class in the conformal coating industry. Due to their transparent nature, low electrical conductivity, and high biocompatibility, they are ideal candidates for coating medical devices and other delicate electronics. However, the crosslinking of PPXs to enhance their durability is still challenging today. Expensive setups need to be used to obtain crosslinked PPXs. Furthermore, the possibility of functionalization post‐polymerization is limited. In this work, we present the synthesis of a hydrosilane functionalized [2.2]paracyclophane, which is used to obtain the corresponding hydrosilane functionalized poly(para‐xylylene) (PPX‐SiH). Through the formation of siloxane bonds during the low‐pressure chemical vapor deposition (LP‐CVD), which increases internal bonding, PPX‐SiH is obtained as a flexible and durable polymer film. The siloxane formation during the LP‐CVD is investigated through X‐ray photoelectron spectroscopy (XPS), nuclear magnetic resonance spectroscopy (NMR), and Fourier‐transform infrared spectroscopy (FTIR). Additionally, mechanistic insights into the formation of siloxane bonds are given through quantum chemical calculation. The Si‐H bonds in the polymer allow for oxidation to form bridging siloxane moieties which enhances stretchability while also increasing the resistance to organic solvents. Through the passivation of the surface during oxygen plasma treatment, PPX‐SiH becomes practically plasma‐etch‐resistant.
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spelling doaj-art-cc96d6d1e48a4b25880d68a90a4ac0f32025-08-20T02:52:08ZengWiley-VCHAdvanced Materials Interfaces2196-73502025-03-01126n/an/a10.1002/admi.202400701Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)Lukas Bichlmaier0Tetsuhiko F. Teshima1Arseni Kostenko2George Al Boustani3Rebecca Wilhelm4Sebastian Stigler5Shuma Tanaka6Hiroaki Onoe7Bernhard Wolfrum8Shigeyoshi Inoue9TUM School of Natural Sciences Department of Chemistry and Catalysis Research Center Institute of Silicon Chemistry Technical University of Munich (TUM) Lichtenbergstraße 4 85748 Garching GermanyMedical & Health Informatics Laboratories NTT Research Incorporated 940 Stewart Dr. Sunnyvale CA 94085 USATUM School of Natural Sciences Department of Chemistry and Catalysis Research Center Institute of Silicon Chemistry Technical University of Munich (TUM) Lichtenbergstraße 4 85748 Garching GermanyMedical & Health Informatics Laboratories NTT Research Incorporated 940 Stewart Dr. Sunnyvale CA 94085 USATUM School of Natural Sciences Department of Chemistry and Catalysis Research Center Chair of Technical Electrochemistry Technical University of Munich (TUM) Lichtenbergstraße 4 85748 Garching GermanyTUM School of Natural Sciences Department of Chemistry and Catalysis Research Center Institute of Silicon Chemistry Technical University of Munich (TUM) Lichtenbergstraße 4 85748 Garching GermanyFaculty of Science and Technology Department of Mechanical Engineering Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama‐shi Kanagawa 223‐8522 JapanFaculty of Science and Technology Department of Mechanical Engineering Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama‐shi Kanagawa 223‐8522 JapanMedical & Health Informatics Laboratories NTT Research Incorporated 940 Stewart Dr. Sunnyvale CA 94085 USATUM School of Natural Sciences Department of Chemistry and Catalysis Research Center Institute of Silicon Chemistry Technical University of Munich (TUM) Lichtenbergstraße 4 85748 Garching GermanyAbstract Poly(para‐xylylene)s (PPXs), or so‐called parylenes, have become a well‐established polymer class in the conformal coating industry. Due to their transparent nature, low electrical conductivity, and high biocompatibility, they are ideal candidates for coating medical devices and other delicate electronics. However, the crosslinking of PPXs to enhance their durability is still challenging today. Expensive setups need to be used to obtain crosslinked PPXs. Furthermore, the possibility of functionalization post‐polymerization is limited. In this work, we present the synthesis of a hydrosilane functionalized [2.2]paracyclophane, which is used to obtain the corresponding hydrosilane functionalized poly(para‐xylylene) (PPX‐SiH). Through the formation of siloxane bonds during the low‐pressure chemical vapor deposition (LP‐CVD), which increases internal bonding, PPX‐SiH is obtained as a flexible and durable polymer film. The siloxane formation during the LP‐CVD is investigated through X‐ray photoelectron spectroscopy (XPS), nuclear magnetic resonance spectroscopy (NMR), and Fourier‐transform infrared spectroscopy (FTIR). Additionally, mechanistic insights into the formation of siloxane bonds are given through quantum chemical calculation. The Si‐H bonds in the polymer allow for oxidation to form bridging siloxane moieties which enhances stretchability while also increasing the resistance to organic solvents. Through the passivation of the surface during oxygen plasma treatment, PPX‐SiH becomes practically plasma‐etch‐resistant.https://doi.org/10.1002/admi.202400701functionalizationhydrosilaneparylenepoly(para‐xylylene)post‐modification
spellingShingle Lukas Bichlmaier
Tetsuhiko F. Teshima
Arseni Kostenko
George Al Boustani
Rebecca Wilhelm
Sebastian Stigler
Shuma Tanaka
Hiroaki Onoe
Bernhard Wolfrum
Shigeyoshi Inoue
Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)
Advanced Materials Interfaces
functionalization
hydrosilane
parylene
poly(para‐xylylene)
post‐modification
title Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)
title_full Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)
title_fullStr Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)
title_full_unstemmed Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)
title_short Hydrosilane‐Functionalized [2.2]Paracyclophane for Plasma‐Etch‐Resistant and Post‐Modifiable Poly(Para‐Xylylene)
title_sort hydrosilane functionalized 2 2 paracyclophane for plasma etch resistant and post modifiable poly para xylylene
topic functionalization
hydrosilane
parylene
poly(para‐xylylene)
post‐modification
url https://doi.org/10.1002/admi.202400701
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