Transcript Impact of Reactor Design on Plasma Polymerization

AVS Tampa 2012 PsThA8
Impact of Reactor Design on Plasma
Polymerization Processes - An
International Round-Robin Study
J.D.Whittle, A.Michelmore, D.A.Steele, R.D.Short
www.liquipel.com
www.myskin-info.com/
www.hi-tec.com/infinity/uk/liquid-mountaineering/
www.youtube.com/watch?v=Oe3St1GgoHQ
www.bdbiosciences.com/purecoat
Biomaterials Surfaces
A method for the deposition of controllable chemical gradients.
J.D.Whittle, D.Barton, M.R.Alexander, R.D.Short.
Chemical Communications pp1766-1767 (2003)
COOR Component of C1s
region at 0.5mm intervals
Protocols
• Argon Plasma Treatment
– 2 samples – spin-cast polystyrene
– Treatment at 5W for 20 seconds at 2sccm argon
• Acrylic Acid plasma polymer deposition
– 3 runs
– 2 samples per run
– All at 2sccm for 20 minutes, at 2, 5 and 20W continuous wave rf
power
Run
Samples
Process Gas
Flow Rate
Power
Duration
1
2x PS film on glass coverslip
Argon
2sccm
5W
30 seconds
2
3x Si wafer
Acrylic Acid
2sccm
2W
20 mins
3
3x Si wafer
Acrylic Acid
2sccm
5W
20 mins
4
3x Si wafer
Acrylic Acid
2sccm
20W
20 mins
Responses
• Samples from 16 different reactors at 11
different labs
• Study requirements are fairly arbitrary and
not well suited to some plasma set-ups –
samples which did not meet the
requirements are not used in the analysis
- e.g. Some were unable to measure flow-rate
online for AA, so calculate post-plasma.
Reactor Types
Steel Barrel (2)
• non-coaxial geometry
• Internal Electrodes
Steel Cylinder (3)
• Axial Symmetry
• Internal Electrodes
Glass Cylinder (2)
• Substrates perpendicular to flow
• Insulating walls, Internal Electrodes
Glass Barrel (7)
• Substrates parallel to flow
• External Electrodes
• Band (5) or Coil (2) Electrodes
Glass Cross-piece (2)
• Substrates parallel to flow
• External Coil electrodes
Argon Plasma Treatment
Operator variability
Treatment
Measure
Average SD
Add XPS and Deposition rate data here for the 6 runs in
(n=6)
warwick. Plus quickie description.
Argon Plasma
O/C ratio
0.08
0.01
Acrylic Acid Plasma
Polymerisation 2W
Acrylic Acid Plasma
Polymerisation 5W
Acrylic Acid Plasma
Polymerisation 20W
O/C ratio
0.38
0.02
%COOR
13.8
1.1
Deposition Rate(nm/min)
0.96
0.16
O/C ratio
0.35
0.01
%COOR
12.3
0.7
Deposition Rate(nm/min)
1.17
0.17
O/C ratio
0.32
0.01
%COOR
9.5
0.4
Deposition Rate (nm/min)
1.42
0.2
Argon Plasma Treatment
• Oxygen ranged from 6 - 15%
• Nitrogen ranged from 0.1 –
2.4%
• No correlation between
incorporation of N and O
A
B
C
D
E
F
G
H
I
J
M
N
• Oxygen ranged from 6 - 15%
• Nitrogen ranged from 0.1 –
2.4%
• No correlation between
incorporation of N and O
• Oxygen ranged from 6 - 15%
• Nitrogen ranged from 0.1 –
2.4%
B
D
G
M
I
Argon Plasma Treatment
• No correlation between N and O incorporation
• No correlation between reactor base pressure and
N or O incorporation
Acrylic Acid Deposition
Comparison – Typical Low and High Power
Acrylic Acid Deposition
Acrylic Acid Deposition
Acrylic Acid Deposition
Acrylic Acid Deposition
Processing Correlations
Conclusions
•
W/F provides insufficient information for us to use it to compare treatments
between systems
•
Within-system variation is very low and processes can be very well
controlled
•
There appear to be no simple correlation between pressure, flow, power,
residence time, number of molecules etc.
•
For some reactors this exercise was outside the normal operating regime,
which leads to non-representative treatments
•
We would like to add more data points – [email protected]
Future Work
• Trying to link internal measures with outcome
• Example: Ion flux (Andrew Michelmore presented earlier
in week)
Acknowledgements
Prof. Morgan Alexander, Dr. Andrew Hook,
University of Nottingham, UK
Prof. Hynek Biederman, Dr. Anton Serov,
Charles University, Prague, CZ.
Dr. Francois Rossi, Dr. Giacomo Ceccone, Dr. Jan Hanus,
European Commission Joint Research Centre, IT.
Prof. Renate Förch, Dr. Juan-Carlos Ruiz, Max
Plank Institute for Polymer Research, Mainz, DE
Prof. Gary Kinsel, Kristopher Kirmess, Stephanie
Eastwood, Southern Illinois University, US
Prof. Sally McArthur, Dr. Thomas Ameringer,
Swinburne University of Technology, AU
Dr. Toby Jenkins, Dr. David Jamieson,
University of Bath, UK.
Dr. Dirk Hegemann, Dr Enrico Körner, Swiss
Federal Laboratory for Materials Testing, CH
Prof. David Castner, Dr. Winston Ciridon,
University of Washington, Seattle, US
Prof. James Bradley, Dr. Faiq Jan,
University of Liverpool, UK
Dr. Sue Low, Dr. Karyn Jarvis, Dr. Louise Smith, Dr. David Robinson, Carla Daunton, Agnieska Zuber,
Emily Mitchell, Shima, Taheri, Akash Bachhuka, Mawson Institute, University of South Australia, AU