DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Interaction of long‐lived reactive species from cold atmospheric pressure plasma with polymers: Role of macromolecular structure and deep modification of aromatic polymers

Abstract

We report (a) the deep modification of polymers by long‐lived reactive species generated in atmospheric pressure plasma and (b) the dependence of plasma–polymer interaction on the macromolecular structure. Styrene‐based polymers show significant thickness expansion whereas polymers with methyl, alcohol, and ether side groups show low‐rate etching. The characterization of polystyrene (PS) by X‐ray photoelectron spectroscopy and attenuated total reflectance–Fourier transform infrared shows that plasma treatment destroys aromatic rings and produces ether, ester, and surface organic nitrate groups. These modifications can happen at tens of nanometers below the surface, which we attribute to the reaction–diffusion of plasma species. Comparing three styrene‐based polymers namely PS, poly(4‐methyl styrene), and poly(α‐methyl styrene), we find that long‐lived species primarily attack the C–H bond on the carbon site where the aromatic ring connects.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Department of Materials Science and Engineering, Institute for Research in Electronics and Applied Physics University of Maryland College Park Maryland
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1557881
Grant/Contract Number:  
DE‐SC0001939
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Plasma Processes and Polymers
Additional Journal Information:
Journal Name: Plasma Processes and Polymers Journal Volume: 16 Journal Issue: 11; Journal ID: ISSN 1612-8850
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Luan, Pingshan, and Oehrlein, Gottlieb S. Interaction of long‐lived reactive species from cold atmospheric pressure plasma with polymers: Role of macromolecular structure and deep modification of aromatic polymers. Germany: N. p., 2019. Web. doi:10.1002/ppap.201900053.
Luan, Pingshan, & Oehrlein, Gottlieb S. Interaction of long‐lived reactive species from cold atmospheric pressure plasma with polymers: Role of macromolecular structure and deep modification of aromatic polymers. Germany. https://doi.org/10.1002/ppap.201900053
Luan, Pingshan, and Oehrlein, Gottlieb S. Mon . "Interaction of long‐lived reactive species from cold atmospheric pressure plasma with polymers: Role of macromolecular structure and deep modification of aromatic polymers". Germany. https://doi.org/10.1002/ppap.201900053.
@article{osti_1557881,
title = {Interaction of long‐lived reactive species from cold atmospheric pressure plasma with polymers: Role of macromolecular structure and deep modification of aromatic polymers},
author = {Luan, Pingshan and Oehrlein, Gottlieb S.},
abstractNote = {We report (a) the deep modification of polymers by long‐lived reactive species generated in atmospheric pressure plasma and (b) the dependence of plasma–polymer interaction on the macromolecular structure. Styrene‐based polymers show significant thickness expansion whereas polymers with methyl, alcohol, and ether side groups show low‐rate etching. The characterization of polystyrene (PS) by X‐ray photoelectron spectroscopy and attenuated total reflectance–Fourier transform infrared shows that plasma treatment destroys aromatic rings and produces ether, ester, and surface organic nitrate groups. These modifications can happen at tens of nanometers below the surface, which we attribute to the reaction–diffusion of plasma species. Comparing three styrene‐based polymers namely PS, poly(4‐methyl styrene), and poly(α‐methyl styrene), we find that long‐lived species primarily attack the C–H bond on the carbon site where the aromatic ring connects.},
doi = {10.1002/ppap.201900053},
journal = {Plasma Processes and Polymers},
number = 11,
volume = 16,
place = {Germany},
year = {Mon Aug 12 00:00:00 EDT 2019},
month = {Mon Aug 12 00:00:00 EDT 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/ppap.201900053

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Surface Modification of Polypropylene (PP) by Argon Ions and UV Photons: Surface Modification of Polypropylene (PP) by Argon Ions and UV Photons
journal, October 2013

  • Große-Kreul, Simon; Corbella, Carles; von Keudell, Achim
  • Plasma Processes and Polymers, Vol. 10, Issue 12
  • DOI: 10.1002/ppap.201300078

Infrared absorption cross sections for N2O5
journal, July 1988

  • Cantrell, Chris A.; Davidson, James A.; McDaniel, Anthony H.
  • Chemical Physics Letters, Vol. 148, Issue 4
  • DOI: 10.1016/0009-2614(88)87288-9

The nitrate radical: Physics, chemistry, and the atmosphere
journal, January 1991


Role of the dense amorphous carbon layer in photoresist etching
journal, March 2018

  • Pranda, Adam; Gutierrez Razo, Sandra A.; Tomova, Zuleykhan
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 36, Issue 2
  • DOI: 10.1116/1.5009640

Subsurface chemistry in the plasma treatment of polymers
journal, September 1999


Applications of cold plasma technology for microbiological safety in meat industry
journal, June 2017


A comparative study of biomolecule and polymer surface modifications by a surface microdischarge
journal, February 2016

  • Bartis, Elliot A. J.; Luan, Pingshan; Knoll, Andrew J.
  • The European Physical Journal D, Vol. 70, Issue 2
  • DOI: 10.1140/epjd/e2015-60446-3

Plasma–surface interaction at atmospheric pressure: A case study of polystyrene etching and surface modification by Ar/O 2 plasma jet
journal, September 2017

  • Luan, Pingshan; Knoll, Andrew J.; Bruggeman, Peter J.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 5
  • DOI: 10.1116/1.5000691

Why Can’t We See Hydrogen in X-ray Photoelectron Spectroscopy?
journal, July 2012

  • Stojilovic, Nenad
  • Journal of Chemical Education, Vol. 89, Issue 10
  • DOI: 10.1021/ed300057j

Precision Trace Gas Analysis by FT-IR Spectroscopy. 1. Simultaneous Analysis of CO 2 , CH 4 , N 2 O, and CO in Air
journal, January 2000

  • Esler, Michael B.; Griffith, David W. T.; Wilson, Stephen R.
  • Analytical Chemistry, Vol. 72, Issue 1
  • DOI: 10.1021/ac9905625

Plasma diagnostics for surface modification of polymers
journal, January 1998


Study of ion and vacuum ultraviolet-induced effects on styrene- and ester-based polymers exposed to argon plasma
journal, January 2009

  • Bruce, R. L.; Engelmann, S.; Lin, T.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 27, Issue 3
  • DOI: 10.1116/1.3136864

Fluorocarbon assisted atomic layer etching of SiO 2 and Si using cyclic Ar/C 4 F 8 and Ar/CHF 3 plasma
journal, January 2016

  • Metzler, Dominik; Li, Chen; Engelmann, Sebastian
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 34, Issue 1
  • DOI: 10.1116/1.4935462

Oxygen plasma etching for resist stripping and multilayer lithography
journal, January 1989

  • Hartney, M. A.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 7, Issue 1
  • DOI: 10.1116/1.584440

Polymer etching by atmospheric-pressure plasma jet and surface micro-discharge sources: Activation energy analysis and etching directionality
journal, March 2018

  • Knoll, Andrew J.; Luan, Pingshan; Pranda, Adam
  • Plasma Processes and Polymers, Vol. 15, Issue 5
  • DOI: 10.1002/ppap.201700217

Biodeactivation of Lipopolysaccharide Correlates with Surface-Bound NO 3 After Cold Atmospheric Plasma Treatment : Biodeactivation of Lipopolysaccharide Correlates …
journal, November 2015

  • Bartis, Elliot A. J.; Luan, Pingshan; Knoll, Andrew J.
  • Plasma Processes and Polymers, Vol. 13, Issue 4
  • DOI: 10.1002/ppap.201500072

Inactivation mechanisms of non-thermal plasma on microbes: A review
journal, May 2017


Atmospheric pressure plasmas: A review
journal, January 2006

  • Tendero, Claire; Tixier, Christelle; Tristant, Pascal
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 61, Issue 1
  • DOI: 10.1016/j.sab.2005.10.003

Dry Etch Resistance of Organic Materials
journal, January 1983

  • Gokan, H.
  • Journal of The Electrochemical Society, Vol. 130, Issue 1
  • DOI: 10.1149/1.2119642

The photochemistry of the nitrate radical and the kinetics of the nitrogen pentoxide-ozone system
journal, February 1978

  • Graham, Richard A.; Johnston, Harold S.
  • The Journal of Physical Chemistry, Vol. 82, Issue 3
  • DOI: 10.1021/j100492a002

ESCA applied to polymers. XV. RF Glow-discharge modification of polymers, studied by means of ESCA in terms of a direct and radiative energy-transfer model
journal, October 1977

  • Clark, D. T.; Dilks, A.
  • Journal of Polymer Science: Polymer Chemistry Edition, Vol. 15, Issue 10
  • DOI: 10.1002/pol.1977.170151004

Synthetic Calibration and Quantitative Analysis of Gas-Phase FT-IR Spectra
journal, January 1996


Handbook of Ellipsometry
book, January 2005


Gas-Phase Databases for Quantitative Infrared Spectroscopy
journal, December 2004

  • Sharpe, Steven W.; Johnson, Timothy J.; Sams, Robert L.
  • Applied Spectroscopy, Vol. 58, Issue 12
  • DOI: 10.1366/0003702042641281

Cold Atmospheric Pressure Plasma VUV Interactions With Surfaces: Effect of Local Gas Environment and Source Design: Cold Atmospheric Pressure Plasma VUV Interactions…
journal, August 2016

  • Knoll, Andrew J.; Luan, Pingshan; Bartis, Elliot A. J.
  • Plasma Processes and Polymers, Vol. 13, Issue 11
  • DOI: 10.1002/ppap.201600043

Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV
journal, January 1976


Effective Thickness of Bulk Materials and of Thin Films for Internal Reflection Spectroscopy
journal, January 1966


Nitric Oxide Radical Trapping Analysis on Vacuum-Ultraviolet Treated Polymers
journal, November 1998

  • Wilken, R.; Holländer, A.; Behnisch, J.
  • Macromolecules, Vol. 31, Issue 22
  • DOI: 10.1021/ma9802071

Model polymer etching and surface modification by a time modulated RF plasma jet: role of atomic oxygen and water vapor
journal, December 2016

  • Luan, P.; Knoll, A. J.; Wang, H.
  • Journal of Physics D: Applied Physics, Vol. 50, Issue 3
  • DOI: 10.1088/1361-6463/aa4e97

Ion and Vacuum Ultraviolet Photon Beam Effects in 193 nm Photoresist Surface Roughening: The Role of the Adamantyl Pendant Group
journal, August 2011

  • Chung, Ting-Ying; Graves, David B.; Weilnboeck, Florian
  • Plasma Processes and Polymers, Vol. 8, Issue 11
  • DOI: 10.1002/ppap.201100071

Plasmas for medicine
journal, September 2013


Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis
journal, January 1995


Plasma chemistry model of surface microdischarge in humid air and dynamics of reactive neutral species
journal, October 2012


Stages of polymer transformation during remote plasma oxidation (RPO) at atmospheric pressure
journal, March 2018


On the absence of post-plasma etch surface and line edge roughness in vinylpyridine resists
journal, July 2011

  • Bruce, R. L.; Weilnboeck, F.; Lin, T.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 29, Issue 4
  • DOI: 10.1116/1.3607604

Application of EPR Spectroscopy to Oxidative Removal of Organic Materials
journal, January 1983

  • Cook, J. M.
  • Journal of The Electrochemical Society, Vol. 130, Issue 12
  • DOI: 10.1149/1.2119613

On the Interaction of Cold Atmospheric Pressure Plasma with Surfaces of Bio-molecules and Model Polymers
journal, October 2015

  • Bartis, E. A. J.; Knoll, A. J.; Luan, P.
  • Plasma Chemistry and Plasma Processing, Vol. 36, Issue 1
  • DOI: 10.1007/s11090-015-9673-2

Comparison of FTIR and Particle Mass Spectrometry for the Measurement of Particulate Organic Nitrates
journal, February 2010

  • Bruns, Emily A.; Perraud, Véronique; Zelenyuk, Alla
  • Environmental Science & Technology, Vol. 44, Issue 3
  • DOI: 10.1021/es9029864

Characterization of Ultrathin Polymer Films Using p-Polarized ATR-FTIR and Its Comparison with XPS
journal, February 2019


Anhydrous nitric acid integrated absorption cross sections: 820–
journal, November 2003

  • Chackerian, Charles; W. Sharpe, Steven; A. Blake, Thomas
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 82, Issue 1-4
  • DOI: 10.1016/S0022-4073(03)00168-7

Hydrophobicity recovery of polydimethylsiloxane after exposure to corona discharges
journal, May 1998