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Type: Journal article
Title: Hyperthermal intact molecular ions play key role in retention of ATRP surface initiation capability of plasma polymer films from ethyl α-bromoisobutyrate
Other Titles: Hyperthermal intact molecular ions play key role in retention of ATRP surface initiation capability of plasma polymer films from ethyl alpha-bromoisobutyrate
Author: Saboohi, S.
Coad, B.
Michelmore, A.
Short, R.
Griesser, H.
Citation: ACS Applied Materials and Interfaces, 2016; 8(25):16493-16502
Publisher: American Chemical Society
Issue Date: 2016
ISSN: 1944-8244
Statement of
Solmaz Saboohi, Bryan R. Coad, Andrew Michelmore, Robert D. Short, and Hans J. Griesser
Abstract: We report a systematic study of the plasma polymerization of ethyl α-bromoisobutyrate (EBIB) to produce thin film coatings capable of serving as ATRP initiation surfaces, for which they must contain α-bromoisobutyryl functional groups. In the deposition of polymeric coatings by plasma polymerization there generally occurs considerable fragmentation of precursor (“monomer”) molecules in the plasma; and the retention of larger structural elements is challenging, particularly when they are inherently chemically labile. Empirical principles such as low plasma power and low pressure are usually utilized. However, we show that the α-bromoisobutyryl structural moiety is labile in a plasma gas phase and in low pressure plasma conditions, below the collisional threshold, there is little retention. At higher pressure, in contrast, fragmentation of this structural motif appears to be reduced substantially, and coatings useful for ATRP initiation were obtained. Mass spectrometry analysis of the composition of the plasma phase revealed that the desired structural moiety can be retained through the plasma, if the plasma conditions are steered toward ions of the precursor molecule. Whereas at low pressure the plasma polymer assembles mainly from various neutral (radical) fragments, at higher pressure the deposition occurs from hyperthermal ions, among which the protonated intact molecular ion is the most abundant. At higher pressure, a substantial population of ions has low kinetic energy, leading to “soft landing” and thus less fragmentation. This study demonstrates that relatively complex structural motifs in precursor molecules can be retained in plasma polymerization if the chemical and physical processes occurring in the plasma phase are elucidated and controlled such that desirable larger structural elements play a key role in the film deposition.
Keywords: Hyperthermal polyatomic ions; molecular ion; plasma polymerization; ATRP; surface grafting; ethyl α-bromoisobutyrate; plasma analysis
Description: Published: June 15, 2016
Rights: © 2016 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
DOI: 10.1021/acsami.6b04477
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