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

doi:10.1016/j.apsusc.2016.10.099

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

Physique de la matière et du rayonnement

Résultats de recherche: Contribution à un journal/une revue › Article

Résumé

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.

langue originale	Anglais
Pages (de - à)	578-585
Nombre de pages	8
journal	Applied Surface Science
Volume	394
Les DOIs	https://doi.org/10.1016/j.apsusc.2016.10.099
état	Publié - 1 févr. 2017

Empreinte digitale

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

Citer ceci

Manakhov, A., Michlíček, M., Felten, A., Pireaux, J-J., Nečas, D., & Zajíčková, L. (2017). XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach. Applied Surface Science, 394, 578-585. https://doi.org/10.1016/j.apsusc.2016.10.099

Manakhov, Anton ; Michlíček, Miroslav ; Felten, Alexandre ; Pireaux, Jean-Jacques ; Nečas, David ; Zajíčková, Lenka. / XPS depth profiling of derivatized amine and anhydride plasma polymers : Evidence of limitations of the derivatization approach. Dans: Applied Surface Science. 2017 ; Vol 394. p. 578-585.

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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.",

keywords = "Amine derivatization, Plasma polymers, Surface reactions, TFBA, XPS depth profiling",

author = "Anton Manakhov and Miroslav Michl{\'i}ček and Alexandre Felten and Jean-Jacques Pireaux and David Nečas and Lenka Zaj{\'i}čkov{\'a}",

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Manakhov, A, Michlíček, M, Felten, A , Pireaux, J-J, Nečas, D & Zajíčková, L 2017, 'XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach', Applied Surface Science, VOL. 394, p. 578-585. https://doi.org/10.1016/j.apsusc.2016.10.099

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.

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

Résultats de recherche: Contribution à un journal/une revue › Article

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

PY - 2017/2/1

Y1 - 2017/2/1

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.

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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KW - Plasma polymers

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KW - TFBA

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