XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach

Anton Manakhov, Miroslav Michlíček, Alexandre Felten, Jean-Jacques Pireaux, David Nečas, Lenka Zajíčková

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)578-585
Number of pages8
JournalApplied Surface Science
Volume394
DOIs
Publication statusPublished - 1 Feb 2017

Fingerprint

Depth profiling
Anhydrides
Amines
Polymers
X ray photoelectron spectroscopy
Plasmas
Molecules
Permeation
Maleic Anhydrides
Plasma polymerization
Argon
Takeoff
Maleic anhydride
Copolymerization
Porosity
Composite materials
Chemical analysis

Keywords

  • Amine derivatization
  • Plasma polymers
  • Surface reactions
  • TFBA
  • XPS depth profiling

Cite this

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title = "XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach",
abstract = "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.",
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XPS depth profiling of derivatized amine and anhydride plasma polymers : Evidence of limitations of the derivatization approach. / Manakhov, Anton; Michlíček, Miroslav; Felten, Alexandre; Pireaux, Jean-Jacques; Nečas, David; Zajíčková, Lenka.

In: Applied Surface Science, Vol. 394, 01.02.2017, p. 578-585.

Research output: Contribution to journalArticle

TY - JOUR

T1 - XPS depth profiling of derivatized amine and anhydride plasma polymers

T2 - Evidence of limitations of the derivatization approach

AU - Manakhov, Anton

AU - Michlíček, Miroslav

AU - Felten, Alexandre

AU - Pireaux, Jean-Jacques

AU - Nečas, David

AU - Zajíčková, Lenka

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AB - 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.

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