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Title: Polymer etching by atmospheric-pressure plasma jet and surface micro-discharge sources: Activation energy analysis and etching directionality

Journal Article · · Plasma Processes and Polymers

Treatments of polymer films using either a MHz atmospheric pressure plasma jet (APPJ) or an atmospheric pressure surface micro-discharge (SMD) plasma are investigated. While the typical approach to determine relevant reactive species is to correlate surface effects with gas phase species measurement, this does not capture potential synergistic or other complex effects that may be occurring. Activation energy and directionality of the etching process can characterize what is occurring at the surface for these processes in more detail. The APPJ source shows an apparent activation energy of ~0.18 eV at 8 mm distance and up to ~0.34 eV at 16mmdistance for a temperature range of 20–80 °C tested with thin polymer films. The APPJ source shows directional etching at 8 mm distance with less anisotropy the more distance is increased. The SMD source has an apparent activation energy of ~0.8–0.9 eV at a distance of 3 mm. The SMD also only shows isotropic etching behavior. However the SMD surface chemistry changes significantly to less oxidation with increased temperature while the APPJ source induced modifications remain very similar with temperature change. The lower apparent activation energy of the APPJ induced etching reactions as compared with low pressure work (0.5 eV) and observation of line-of-sight contribution to etching suggests the involvement of a directional species at closer distances facilitating the etching which falls off with increasing distance. The high activation energy of the SMD suggests that species with less capability for etching is responsible compared to the APPJ and low pressure plasma. In conclusion, the high surface oxidation from low temperature SMD treatments shows that the surface is being oxidized but not sufficiently to reach the desorption step of the etching process.

Research Organization:
Univ. of Maryland, College Park, MD (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Fusion Energy Sciences (FES); National Science Foundation (NSF)
Grant/Contract Number:
SC0001939; PHY-1415353
OSTI ID:
1660376
Alternate ID(s):
OSTI ID: 1423710
Journal Information:
Plasma Processes and Polymers, Vol. 15, Issue 5; ISSN 1612-8850
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

References (61)

Power dissipation, gas temperatures and electron densities of cold atmospheric pressure helium and argon RF plasma jets journal November 2011
A model for plasma modification of polypropylene using atmospheric pressure discharges journal February 2003
Temporally resolved ozone distribution of a time modulated RF atmospheric pressure argon plasma jet: flow, chemical reaction, and transient vortex journal July 2015
Contact-free cold atmospheric plasma treatment of Deinococcus radiodurans journal May 2012
Plasma-Surface Interactions in Plasma Catalysis journal October 2015
Dependence of photoresist surface modifications during plasma-based pattern transfer on choice of feedgas composition: Comparison of C[sub 4]F[sub 8]- and CF[sub 4]-based discharges
  • Engelmann, S.; Bruce, R. L.; Weilnboeck, F.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 27, Issue 3 https://doi.org/10.1116/1.3137012
journal January 2009
Influence of C4F8/Ar-based etching and H2-based remote plasma ashing processes on ultralow k materials modifications
  • Kuo, Ming-Shu; Hua, Xuefeng; Oehrlein, G. S.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 28, Issue 2 https://doi.org/10.1116/1.3308623
journal March 2010
Real-time measurements of plasma photoresist modifications: The role of plasma vacuum ultraviolet radiation and ions
  • Weilnboeck, F.; Kumar, N.; Oehrlein, G. S.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 30, Issue 3 https://doi.org/10.1116/1.3697752
journal May 2012
Etching materials with an atmospheric-pressure plasma jet journal August 1998
Nonthermal Plasma Technology as a Versatile Strategy for Polymeric Biomaterials Surface Modification: A Review journal August 2009
Atmospheric plasmas for thin film deposition: A critical review journal April 2012
Atomic oxygen in a cold argon plasma jet: TALIF spectroscopy in ambient air with modelling and measurements of ambient species diffusion journal April 2012
Reaction Chemistry in the Afterglow of an Oxygen−Helium, Atmospheric-Pressure Plasma journal August 2000
Nitric oxide density distributions in the effluent of an RF argon APPJ: effect of gas flow rate and substrate journal December 2014
Plasma etching—A discussion of mechanisms journal March 1979
Model polymer etching and surface modification by a time modulated RF plasma jet: role of atomic oxygen and water vapor journal December 2016
Cold Atmospheric Plasma for Surface Disinfection journal December 2011
Plasmas for medicine journal September 2013
Electrohydraulic Discharge and Nonthermal Plasma for Water Treatment journal February 2006
Cold atmospheric plasma for the ablative treatment of neuroblastoma journal January 2013
Focus on Plasma Medicine journal November 2009
Separation of VUV/UV photons and reactive particles in the effluent of a He/O 2 atmospheric pressure plasma jet journal June 2011
Surface conductivity dependent dynamic behaviour of an ultrafine atmospheric pressure plasma jet for microscale surface processing journal December 2016
In situ absolute air, O 3 and NO densities in the effluent of a cold RF argon atmospheric pressure plasma jet obtained by molecular beam mass spectrometry journal May 2014
On the Interaction of Cold Atmospheric Pressure Plasma with Surfaces of Bio-molecules and Model Polymers journal October 2015
Additive Nitrogen Effects on Oxygen Plasma Downstream Ashing journal October 1990
Spatially resolved ozone densities and gas temperatures in a time modulated RF driven atmospheric pressure plasma jet: an analysis of the production and destruction mechanisms journal May 2013
Oxidative Removal of Photoresist by Oxygen/Freon® 116 Discharge Products journal January 1984
Photoresist modifications by plasma vacuum ultraviolet radiation: The role of polymer structure and plasma chemistry
  • Weilnboeck, F.; Bruce, R. L.; Engelmann, S.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 28, Issue 5 https://doi.org/10.1116/1.3484249
journal September 2010
The atmospheric-pressure plasma jet: a review and comparison to other plasma sources journal January 1998
Plasma-polymer interactions: A review of progress in understanding polymer resist mask durability during plasma etching for nanoscale fabrication
  • Oehrlein, Gottlieb S.; Phaneuf, Raymond J.; Graves, David B.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 29, Issue 1 https://doi.org/10.1116/1.3532949
journal January 2011
Investigations of surface reactions during C2F6 plasma etching of SiO2 with equipment and feature scale models journal March 2001
The emerging role of reactive oxygen and nitrogen species in redox biology and some implications for plasma applications to medicine and biology journal June 2012
Real time characterization of polymer surface modifications by an atmospheric-pressure plasma jet: Electrically coupled versus remote mode journal October 2014
Large Etch Rate Enhancement by NO-Induced Surface Chemical Reaction during Chemical Dry Etching of Silicon Oxide in F[sub 2] Remote Plasmas journal January 2007
Propagation mechanisms of guided streamers in plasma jets: the influence of electronegativity of the surrounding gas journal May 2015
Plasma–surface interaction at atmospheric pressure: A case study of polystyrene etching and surface modification by Ar/O 2 plasma jet
  • Luan, Pingshan; Knoll, Andrew J.; Bruggeman, Peter J.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 5 https://doi.org/10.1116/1.5000691
journal September 2017
Identification of the biologically active liquid chemistry induced by a nonthermal atmospheric pressure plasma jet journal June 2015
Investigation of Surface Etching of Poly(Ether Ether Ketone) by Atmospheric-Pressure Plasmas journal November 2012
Etching polyimide with a nonequilibrium atmospheric-pressure plasma jet
  • Jeong, J. Y.; Babayan, S. E.; Schütze, A.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 17, Issue 5 https://doi.org/10.1116/1.581999
journal September 1999
Test for bacterial resistance build-up against plasma treatment journal July 2012
Biodeactivation of Lipopolysaccharide Correlates with Surface-Bound NO 3 After Cold Atmospheric Plasma Treatment : Biodeactivation of Lipopolysaccharide Correlates … journal November 2015
Electric field measurements in a kHz-driven He jet—the influence of the gas flow speed journal November 2016
Numerical analysis of the NO and O generation mechanism in a needle-type plasma jet journal June 2014
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
Plasma-surface interactions of model polymers for advanced photoresists using C[sub 4]F[sub 8]∕Ar discharges and energetic ion beams
  • Engelmann, S.; Bruce, R. L.; Kwon, T.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 25, Issue 4 https://doi.org/10.1116/1.2759935
journal January 2007
Cold Plasma Decontamination of Foods journal April 2012
Transitions Between and Control of Guided and Branching Streamers in DC Nanosecond Pulsed Excited Plasma Jets journal November 2012
Breakdown simulation of electronegative gases in non-uniform field journal March 1985
Gas flow characteristics of a time modulated APPJ: the effect of gas heating on flow dynamics journal December 2014
Surface etching mechanism of silicon nitride in fluorine and nitric oxide containing plasmas
  • Kastenmeier, B. E. E.; Matsuo, P. J.; Oehrlein, G. S.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 19, Issue 1 https://doi.org/10.1116/1.1329118
journal January 2001
A Review of the Properties and Applications of Poly (Methyl Methacrylate) (PMMA) journal June 2015
Plasma chemistry model of surface microdischarge in humid air and dynamics of reactive neutral species journal October 2012
Unexpected O and O 3 production in the effluent of He/O 2 microplasma jets emanating into ambient air journal May 2012
The Role of VUV Radiation in the Inactivation of Bacteria with an Atmospheric Pressure Plasma Jet journal December 2011
Electron spectroscopic analysis of the human lipid skin barrier: cold atmospheric plasma-induced changes in lipid composition journal November 2012
Plasma-modified polymer surfaces: Characterization using XPS journal May 2010
Measurement of hydroxyl radical (OH) concentration in an argon RF plasma jet by laser-induced fluorescence journal March 2013
Separation of VUV/UV photons and reactive particles in the effluent of a He/O 2 atmospheric pressure plasma jet journal August 2011
Plasmaätzen dünner Schichten organischer Polymere. Teil IX: Temperaturabhängigkeiten der Ätzrate von Polymeren verschiedener Struktur journal June 1991
A review of the molecular diffusivities of H2O, CO2, CH4, CO, O3, SO2, NH3, N2O, NO, and NO2 in air, O2 and N2 near STP journal March 1998

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Study on atmospheric air glow discharge plasma generation based on multiple potentials and aramid fabric surface modification journal August 2019
Interaction of long‐lived reactive species from cold atmospheric pressure plasma with polymers: Role of macromolecular structure and deep modification of aromatic polymers journal August 2019
Turbulence and entrainment in an atmospheric pressure dielectric barrier plasma jet journal December 2019

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