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@article{1389319,
author = {Manakhov, Anton and Michlíček, Miroslav and Felten, Alexandre and Pireaux, JeanandJacques and Nečas, David and Zajíčková, Lenka},
article_location = {AMSTERDAM},
article_number = {February},
doi = {http://dx.doi.org/10.1016/j.apsusc.2016.10.099},
keywords = {XPS depth profiling; Surface reactions; Amine derivatization; TFBA; Plasma polymers},
language = {eng},
issn = {0169-4332},
journal = {Applied Surface Science},
title = {XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach},
url = {http://www.sciencedirect.com/science/article/pii/S0169433216322152},
volume = {394},
year = {2017}
}
TY - JOUR
ID - 1389319
AU - Manakhov, Anton - Michlíček, Miroslav - Felten, Alexandre - Pireaux, Jean-Jacques - Nečas, David - Zajíčková, Lenka
PY - 2017
TI - XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach
JF - Applied Surface Science
VL - 394
IS - February
SP - 578-585
EP - 578-585
PB - ELSEVIER SCIENCE BV
SN - 01694332
KW - XPS depth profiling
KW - Surface reactions
KW - Amine derivatization
KW - TFBA
KW - Plasma polymers
UR - http://www.sciencedirect.com/science/article/pii/S0169433216322152
L2 - http://www.sciencedirect.com/science/article/pii/S0169433216322152
N2 - The quantitative analysis of the chemistry at the surface of functional plasma polymers is highly important for the optimization of their deposition conditions and, therefore, for their subsequent applications. The chemical derivatization of amine and carboxyl-anhydride layers is a well-known technique already applied by many researchers, notwithstanding the known drawback of the derivatization procedures like side or uncomplete reactions that could lead to "unreliable" results. In this work, X-ray photoelectron spectroscopy (XPS) combined with depth profiling with argon clusters is applied for the first time to study derivatized amine and carboxyl-anhydride plasma polymer layers. It revealed an additional important parameter affecting the derivatization reliability, namely the permeation of the derivatizing molecule through the target analysed layer, i.e. the composite effect of the probe molecule size and the layer porosity. Amine-rich films prepared by RF low pressure plasma polymerization of cyclopropylamine were derivatized with trifluoromethyl benzaldehide (TFBA) and it was observed by that the XPS-determined NH2 concentration depth profile is rapidly decreasing over top ten nanometers of the layer. The anhydride-rich films prepared by atmospheric plasma co-polymerization of maleic anhydride and C2H2 have been reacted with, parafluoroaniline and trifluoroethyl amine. The decrease of the F signal in top surface layer of the anhydride films derivatized by the "large" parafluoroaniline was observed similarly as for the amine films but the derivatization with the smaller trifluoroethylamine (TFEA) led to a more homogenous depth profile. The data analysis suggests that the size of the derivatizing molecule is the main factor, showing that the very limited permeation of the TFBA molecule can lead to underestimated densities of primary amines if the XPS analysis is solely carried out at a low take-off angle. In contrast, TFEA is found to be an efficient derivatization agent of anhydride groups with high permeability through the carboxyl-anhydride layer. (C) 2016 Elsevier B.V. All rights reserved.
ER -
MANAKHOV, Anton, Miroslav MICHLÍČEK, Alexandre FELTEN, Jean-Jacques PIREAUX, David NEČAS a Lenka ZAJÍČKOVÁ. XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach. \textit{Applied Surface Science}. AMSTERDAM: ELSEVIER SCIENCE BV, 2017, roč.~394, February, s.~578-585. ISSN~0169-4332. Dostupné z: https://dx.doi.org/10.1016/j.apsusc.2016.10.099.
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