plasma surface treatment and polymerization for functionalizing material surfaces jw bradley

Plasma surface treatment and polymerization for

functionalizing material surfaces

JW Bradley

Dept of Electrical Engineering and Electronics

The University of Liverpool

1) Remove material

1) Add material

1) Change chemical or physical nature of the surface

Incident particle

Sputtered particle

Atomic collisions

Plasma surface treatment of polymers

Environmental advantages over conventional processes

bullEnhanced adhesion eg automotive - car bumpers

bullEnhanced wetability

bullSurface preparation for cell support

bullBio-compatibility - lens treatment

bullTextile treatment

bullMicro-electronics

PC

Mass SpectrometerProbe

HAL EQP 1000 Mass Spectrometer

Controller

Pirani gauge

Rotary Pump

Monomer vapour inlet

Substrate

OscilloscopePulse Generator

Matching Network

RF Generator and Power Meter

Turbo Pump

Glass chamber

LOW-PRESSURE PLASMA

Cell growth and viability on patterned surfaces

MG63 cells on plasma patterned PS after 48 hours culture The gaps width 200 m

5m

10m

AFM Friction image (O+N)C = 027

With RD Short ndash Sheffield

Controlling ion energy and flux

XPS analysis of the surface modification of polystyrene

0

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0 5 10 15 20 25 30 35

Power (W)

OC

()

VUV + Neutral Treatment

VUV Treatment Only

Pulsed plasma polymerisation

bull Wide range of potential applications

ndash Barrier coatings PET films to form packaging cartons

ndash Scratch resistant transparent coatings

ndash Anti-corrosive layers

ndash Anti-adhering anti-soiling coatings - ie baking trays pans etc

ndash Biocompatibility

Production of deposits by pulsed plasma polymerisation

CH2 CH CO

OH

bull Model for film growth

bull Time evolution of plasma parameters

bull XPS (with derivatisation) functional group quantification

Plasma polymerisation (Acrylic acid NIPAAm hexane allyl aminehellip)

Plasmaa

Porous scaffold (varying lengths L)

ions neutrals radicals

Mass spec extraction electrode

L

Plasma deposition inside 3-D porous engineering scaffolds ndash Collaboration with M Alexander Nottingham

Cell (3T3 fibroblasts ) adhesive plasma deposits of allyl amine and cell repellent hexane coatings

Using Knudsen diffusion in gaps

Laboratory of Biophysics and Surface Analysis School of Pharmacy The University of Nottingham University Park Nottingham NG7 2RD UK

Tissue Engineering Group School of Pharmacy Centre for Biomolecular Sciences The University of Nottingham University Park Nottingham NG7 2RD UK

Water contact angle versus distance under the gap

Average number of cells in 02 mm increments along the steep gradient (left ppHex right ppAAm) after 1() 2() and 3() days of incubation

The sample mask interface was set at the origin of the x-axis The columns to the right are the average cell number on the uniform ppAAm samples after 1 and 2 days

Study 3T3 fibroblasts cell interactions

Average number of cells in 02 mm increments along the shallow gradient (left ppHex rightppAAm) after 1() 2() and 3() days of incubation

The columns to the right are the average cell number on the uniform ppAAm samples after 1 and 2 days

Cell number on the shallow gradient after day 1() 2() and 3() plotted against the corresponding WCA The uniform samples (larger symbols) are shown for day 1 (ppHex 1048711ppAAm 1048711) and day 2 (ppHex 1048711 ppAAm 1048711) The error bars represent SEM (gradient n=15 uniform samples n=35)

Cell density as function of the surface energy - WCA

Plasma physics- chemistry study - Acrylic acid

The orifice and end cap for detection of negative ions

Orifice at +65 V

End cap and spectrometer barrel at ground potential

Extracting ions from the plasma

Surface Analysis

Functional group retention ndash by XPS

Pulsed plasma

Time-averaged mass spectra for a pulse off-time of 10 ms

Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions

Negative ion mass spectra for pulse off times of 05 ms (a) and 10 ms (b)

Low masses detected

Higher masses detected

Positive ion flux ndash time resolved

The time-resolved IEDF ion fluxes (a) and (b) - 48 sccm 50 W (c) and (d) - 15 sccm 50W Zero time point corresponds to the beginning of the on-pulse

217217 145

73

55

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287 amu

215

143

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Negative ions ndash time resolved fluxes

Negative ion structural assignments and potential production mechanisms

0

02

04

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08

1

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2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn

Langmuir probe measurements of the negative and positive ion densities

Acrylic acid ndash pulsed RF 40ms Off time ndash 10 mTorr

Atmospheric pressure plasmas

Uses Killing bacteria sterilize medical equipment food - decontaminate biological weapons deposition treatment polymerisation

M Laroussi Old Dominion University in Virginia

E Stoffels et al - TU Eindhoven

100k to 1M colony-forming units of E coli killed after 10 seconds Plasma powers lt 150 mW

Cold Plasma

ldquoPlasma NeedlerdquoNon-thermal atmospheric pressure plasmas

Uses Dentistry and Surgery

Conclusions

Low-pressure plasma treatmentpolymerization is useful

Applications in many areas ndash Bio-surfaces flexible electronics etc

High-pressure and Atmospheric pressure plasma being developed

Activity in technological plasma research is relevant and timely

The synergy between plasma physics engineering chemistry surface science and bio-science will provide unique opportunities

Micro-plasmas

Microplasma used for

1 UV radiation source ndash He Xe

2 Light sources- flat panel displays micro-lasers

3 Plasma-reactors

4 Surface modification ndash source of radical ands ions

5 Deposition - HMDSO

6 flow reactors maskless etching of Si

7 Analytical spectroscopy- liquid and gases

8 Photo detectors

J G Eden et al J Phys D Appl Phys 36 (2003)

University of IllinoisLaboratory for Optical Physics and Engineering

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Conclusions

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1) Remove material

1) Add material

1) Change chemical or physical nature of the surface

Incident particle

Sputtered particle

Atomic collisions









PC



Controller

Pirani gauge

Rotary Pump


Substrate


Matching Network


Turbo Pump

Glass chamber

LOW-PRESSURE PLASMA



5m

10m





0

3

6

9

12

15

18

0 5 10 15 20 25 30 35

Power (W)

OC

()


VUV Treatment Only









CH2 CH CO

OH





Plasmaa




L
















Orifice at +65 V



Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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PC



Controller

Pirani gauge

Rotary Pump


Substrate


Matching Network


Turbo Pump

Glass chamber

LOW-PRESSURE PLASMA



5m

10m





0

3

6

9

12

15

18

0 5 10 15 20 25 30 35

Power (W)

OC

()


VUV Treatment Only









CH2 CH CO

OH





Plasmaa




L
















Orifice at +65 V



Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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5m

10m





0

3

6

9

12

15

18

0 5 10 15 20 25 30 35

Power (W)

OC

()


VUV Treatment Only









CH2 CH CO

OH





Plasmaa




L
















Orifice at +65 V



Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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0

3

6

9

12

15

18

0 5 10 15 20 25 30 35

Power (W)

OC

()


VUV Treatment Only









CH2 CH CO

OH





Plasmaa




L
















Orifice at +65 V



Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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CH2 CH CO

OH





Plasmaa




L
















Orifice at +65 V



Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Plasmaa




L
















Orifice at +65 V



Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Orifice at +65 V



Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Surface Analysis


Pulsed plasma


Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Series [nM+H]+ mz= 73 145 217

Series [nM-H]- mz = 71143215 287

Neutrals

Negative ions

Positive ions


Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Low masses detected




217217 145

73

55

21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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217217 145

73

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21755

287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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287 amu

215

143

71



0

02

04

06

08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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0

02

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08

1

12

14

16

18

2

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000

t (s)

nn

np (

10

15 m

-3)

np nn








Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Cold Plasma



Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Conclusions






Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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Micro-plasmas




3 Plasma-reactors





8 Photo detectors



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Conclusions

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plasma surface treatment and polymerization for functionalizing material surfaces jw bradley

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