PSE2014-Tut 1 5 Oehr Plasma Treatment

8/10/2019 PSE2014-Tut 1 5 Oehr Plasma Treatment

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Fraunhofer IGB

Dr. Christian Oehr

Titel_OTTI.ppt

Content IntroductionPolymers

general aspects

Plasma functionalization and polymerizationmonomers, conditions and resulting surfaces

Applicationswetting, adhesion, biomedical devices

outlook

Plasma Treatment of Polymers and Plasma

Polymerization


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Interfaces

Films/foils0,01 bis 0,12 m 2/g

roughness

Woven/non-woven0,5 bis 10 m 2/g

monofil, multifil

Membranes0,5 bis 60 m 2/g

Nanoparticles50-150 m 2/g

Nanotubes, -fibers

400-2000 m2

/gSWNT, MWNT

Chemistry and Structure

Film depositionfilm thickness sub-nm to 5 mpreparation and characterization

a) b)

a) b)

100 nm 100 nm


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Development of plasma technology

microelectronics

wear/corrosionprotection

lightening,lamps

Plasma

Coating of archi-tecture glass


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a) Scratch-resistantcoating on polymers

b) Solvent-resistantcoating onpolycarbonate

c) Hydrophobic finish ofcotton/polyester

d) Treatment of textilesubstrates for

enhanced cell growth

a) b)

c) d)

Tailored Surfaces


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Biocompatible /bioinert coatings minimizing of non-

specific proteinadsorption

blood vesselprotheses

blood compatibility implantsImmobilization ofenzymes synthesis of drugs biosensorsSubstrates forcell cultures implants specific cell adhesionSterilization

medical equipment durability ofpackaging materials

Cleaning/ activation

Organiccoatings

Medicaltechnology

Membranetechnology

Textilemodification

Metals removability of orga-

nic contaminations removability of inor-

ganic contaminations cleaning efficiency of

gap insides cleaning of

oxidation-sensitiveparts

Plastics adhesive bounding activation wetting

Anti-foggingcoatings

transparent glassesand foils

Scratch-resistantcoatings on organic glasses

Coatings of inside

surfaces vessels tubes

Powder coating new materials

Barrier layers corrosion resistance

of aluminium membranes with

permeability > 0

Gas separation oxygen enrichment

Solution diffusionmembranes alcohol enrichment

UF/MF Membranes improvement of

selectivity

antifouling hydrophilization ofthe inner surfaces ofpores

Functionalmembranes affinity membranes

chargedmembranes

bipolar membranes

Consumer textiles wettability hydrophobicity /

oleophobicity dyeability antistatic properties flame retardance

Technical textiles biological

applications medical

applications laminates composites

Plasma Technology - Application Areas


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Motivation

polymers:

+ low density+ flexibility+ ease of manufacture+ cost-effectiveness

surface properties

plasma treatment of polymers to improve surfaceproperties

(wetting, adhesion, friction, cleanness, etc.)

Increase of surfacetension


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Fields of usefor plastics


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WorldPlastics Production 1950 2013

Source: PlasticsEurope Market Research Group (PEMRG) / Consultic Marketing & IndustrieberatungGmbH

Plastics are a globalsuccess story.Continuous growthfor more than 50 years.Plastics productionramped up from1.5 Mio t in 1950 to almost300 Mio t (299 Mio t) in

2013. In 2013 globalplastics production grewby 3.9% compared to2012.Compound Annual Growth

Rate (CAGR) from 1950 to2013 is about 8.6%.

Includes Thermoplastics, Polyurethanes, Thermosets, Elastomers, Adhesives,Coatings and Sealants and PP-Fibers. Not included PET-, PA- and Polyacryl-Fibers

0

50

100

150

200

250

300

350

1950 1960 1970 1980 1990 2000 2010 2020

1950: 1.5

1977: 50

2002: 200

1989: 100

World

1950: 1.5

1977: 50

World

Mio t

1950: 1.5

1977: 50

World

1950: 1.5

1977: 50

2009: 250

2011: ~280

2013: ~299

World


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ThermoplasticsClassification 2013

amorphous structure semi-crystalline structure

StandardPlastics

EngineeringThermoplasticsTI = 100 - 150 C

High PerformancePolymersTI > 150 C

100 C

150 C

Capability by Temperature Index byUnderwriter Laboratories, USA

> 2,000 EUR/ton

> 4,000 EUR/ton

> 10,000 EUR/ton

PEEKFP

LCPPPSPPA PA 46

PET (Injection)PBTPOMPA 6 PA 66

PPHDPELDPE LLDPE

PIPAI

PEIPESPSU

PPE mod.PC

PMMAPA 11 PA 12ABS, SAN, ASA

EPS PSPET (Bottle grade) PVC

Triangle of Thermoplasticsby Structure, Capability and Price

Standard Plasticsinclude Polyolefins,

PS, EPS, PVCand PET (Bottle grade).

Engineering Plasticswith improved perfor-mance at higher costs.

High PerformancePolymerspermitting exceptionalend-use-applications,specialized nicheproducts at high costs.



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WorldPlastics Material Production 2013 by

Regions

250 Mio tw/o Other Plastics (~49 Mio t)

Asiawith the leadingcountry China (24.8%)

mean-while accountsfor 45.5% ofworldwide demand.

Europe and NAFTA

are on a similar leveleach with a share ofaround 20%.

Due to the economic

crisis, Europe lostglobal productionshares.


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WorldPlastics Materials Demand 1990 2018e


1)Fibres not included, only molding compounds

Demand in Mio tby type of pl astic

1990 2013 2018eGrowth p. a.2013 2018e

PE-LD, PE-LLD 18,8 43,6 53,3 3,9%PE-HD 11,9 38,6 45,8 3,5%PP 12,9 56,5 66,7 3,4%PVC 17,7 38,9 47 3,9%PS 7,2 11,8 13,7 2,0%EPS 1,7 6 7,8 5,3%

ABS, ASA, SAN 2,8 7,6 9,3 4,1%PA1) 1 3 3,9 4,2%PC 0,5 3,7 4,5 4,1%PET 1,7 18 22,6 5,2%

PUR 4.6 (5.0) 13.5 (16.3) 17.3 (20.6) 4,8%Other Thermoplastics 2,8 9,1 11,2 4,1%Total ~83.6 ~250 ~303 3,9%


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Polymer surface

outermost surface (~1 nm) : density profile; enhanced density of chain ends;

wettingnear-surface layer (~50 nm) : lowered entanglement reduced T gbulk (>100 nm): macroscopic properties

++ +

adsorption layer

Surface

Near-surface Layer

Bulk

surface charge

fillersadditives

crystallinity

entanglement

phasesdurability

density

surface tension

glass transition

cross-linking

roughness contaminants


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Dr. Christian Oehr

Titel_OTTI.ppt

Content Introduction

Polymersgeneral aspects



outlook


Polymerization


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Interaction ofPlasmas withSurfaces

Species generatedin a glow discharge


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Energy of Excitationand Ionization ofSpecies inGlow Discharges

Species Energy of Excitation[eV]

Energie of Ionisation[eV]

Helium 19,8 24,6

Neon 16,6 21,6Argon 11,5 / 11,7 15,8Krypton 9,9 14,0Xenon 8,3 12,1

at. Hydrogen 10,2mol. Hydrogen 15,6at. Oxygen 2,0 / 4,2mol.Oxygen 0,98 / 1,6 / 4,5 12,5

mol. Nitrogen 6,2


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Bond- und Dissociation Energies relevant for Polymertreatment

Bond Energy(eV)

CC 3.61

C=C 6.352.74 for bond

CH 4.30CN 3.17CO 3.74

C=O 7.78CF 5.35C-Cl 3.52NH 4.04OH 4.83

O-O 1.52SiC 2.50SiH 3.30

molecule Energy of DissociationThermic Electronic

H2 4.5 8.8O2 5.1 ca. 7N2 9.8 24.3F2 1.6Cl2 2.5 ca. 3.7

NO 6.5 >10


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Materials Segments example) resistant against is attacked byStandard Polymers

Polyolefine C CH H

H CH3n

Alkali,org. solvents

Oxidizing acids

Polyvinylchloride C CH H

H Cln

Acids, CFC,aromatic hydrocarbons

Strong alkali, esters, ketones

Engineering Polymers

Polyacrylnitrile C CH H

H CNn

Weak acids, alkali,aliphat. hydrocarbons

Oxidizing acids, CFC, ketones,esters

Polycarbonate

CH3

nO C O CCH 3 O

Acids, ketones, aliphat.hydrocarbons

Strong alkali,CFC, benzene

PolysulfoneCH3

C

CH3n

O S

O

O

OAlkali, acids,aliphat. hydrocarbons

hydrofluoric acid, CFC, esters,ketones

High Performance PolymersPolyvinyliden-

flourideC C

H

H n

F

F

Acids, CFC,

hydrocarbons, alcohols

DMF, DMSO, ketones, esters

Polyetherether-ketone C

O

On

O

Acids, alkali,org. solvents

almost inert

Wet-Chemical Resistance of Polymers


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substrate

plasma

pump

gas inlet

DIN A3-reactor forhomogeneous coatings

DIN A3-reactor forremote processes

Modular Plasma Reactors at IGB

pump

cold trapmonomer carrier gas

13,56 MHz

plasma

substrates

R

R RRe -

e -e -

e-

+

++ +

M*

M*M*

M*

Re-+M*

radicalselectronsionselectronically excitedparticlesUV-radiation


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Up- andDownscaling


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Ablation

CleaningEtchingSterilisationDesmearing

Modification

Generation offunctional groups

GraftingCASING

Deposition

PlasmapolymerisationProtective coating

0

20

40

60

80

100

0 200 400 600

Ar-Plasma Dauer [s]

G e w

i c h t s v e r l u s

t [ % ]

Polycarbonat

PMMA

Ethylcellulose

Polystyrol

Ishikawa et al. (1996)

Possibilities of the Plasma-Treatment of Polymers

Ar-plasma duration [s]


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Energy inputfrequencypower densitydurationCW / pulse

Material flowmonomers,carrier gasespressure, flow

(total/partial)gas background

Substratematerialdimensionmorphology

quantitytemperaturepotential

Reactorgas leading systeminner wallelectrode material

configuration temperature

type and degree ofdissoziation of thegases

live time and residencetime of active species

homo-/ heterogenousreactions

ion bombardementand radiation

Plasma

Operational Plasma Parameters

topography


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Etching of polymer surfaces

treatment of differentpolymers in Ar plasma

etching by

ions

VUV

Increased etchingwhen

an oxygenfunctionality

is present in thepolymer

backbone

0

100

200

300

400

500

0 5 10 15 20

treatment time [min]

m a s s

l o s s

[ g

/ c m

2 ]

PMMA

PETPC

PE

PP

PSC-H polymers

O-containingpolymers

Ar plasma, 0.2 mbar, 350 W


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Plasma CVDcompact(e.g. hard coating)

Pulsed plasmapolymerisationmedium cross-linked/ functionalized(e.g. membranes)

Grafting(e.g. spacer forbiochemistry)

Plasma Coating with Various Degrees of Cross-Linking


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Chem.Reaction 1796 Bondt et al .: Spark discharge in acetylene1857 Siemens, W. v .: development of the Ozonizer

Films 1930 Austin, J., Black, J . Observation of not easy-to-clean filmsunintensional 1931 Brewer, A., Kveck, R discharge tubes.intensional end of the 50th Amorphous solvent-resistent films for the

electron microscopy

1960 Goodman, J. Plasmapolymerisation of styrene for

dielectric filmsmechanisms of 1963 until Haller, I., White, D., Mayhan, K. G.Film deposition 1972 Ionic mechanisms were proposed

1969 until Denaro, A.R. et al,. Kobayashi, H., Bell, A.T. et al. end of 70thRadical-based mechanisms were proposed

1981 Yasuda, H . Concept of atomic polymerisation

History of Plasma Polymerization


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Polymerization Mechanisms, proposedMechanisms Arguments, Observationsionic

Williams, Hayes (1966) No polymer on the anode. Deposition rate directly proportional to the current densityand correlates to the adsorption rate.

Westwood (1971) Deposition rate corresponds to the bias potential of substrate support.Deposition at neg. bias (pos. Ions relevant).

Thompson, Mayhan Radical scavenger do not decrease the polymerization rate.(1972)

radicalic Denaro (1969) High concentration of radicals in plasma polymers detectable. A model is developed for

radical based styrene plasma polymerization.

Kobayashi (1974) Less energy is necessary for radical production than for ionization. Average energy at 2-5eV. Radicals concentration in the discharge two orders of magnitude higher than that ofions.No correlation between ionization potential and deposition rate. High amount ofradicals in polymers, up to 10 19 spins/g.The high deposition rate in DC-discharges on cathodes may be due to the nearbynegative glow (there proceeds the main material conversion).


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Observation The composition of the plasma polymer is mainly related to the power and theposition in the reactor. Inert gas molecules in contrast to conventionalPolymerization are incorporated.

Supposition Monomers are highly fragmented, these reactive particles are in the gas phase aswell as at surfaces reorganized, and are building blocks for film deposition. Thus,the film structures are very different compared with the structure of the precursormolecules.Main parameters for film deposition are: Power, monomer flow and molecularweight of the monomer.

Yasuda factor The so-called Yasuda-Factor is the ratio of power input (W) to monomer flow (F)and molecular weight (M):

Yasuda factor = W/FM [J/kg]

(J/kg = W/FM) 1.3410 9 with W in Watts, F in sccm, M in gram/Mol). At smallYasuda-factors more monomer is flowing through the reactor than can beconverted due to a power deficit. Thus the fragmentation is incomplete. Biggerstructure elements from the monomer will be retained. At elevated Yasuda factorsalmost complete fragmentation down to atomic units will proceed.(atomicpolymerization)

Yasudas Concept


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up scaling Difference to sputtering-

Plasma Processes for Thin Film Techniques


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To minimizefragmentation of themonomer precursor

in the plasma processand to control thecross-linking of adeposited film severalmeans have beenempolyed

use of low power input (pulsed, low Yasuda factors,working at higher pressures

avoiding ionic bombardementsubstrate cooling

working down-streamplasma grafting

indirect:

direct:

Retention of Monomer Structure


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Oligomerisation of Methane in the Gas Phase

Mass spectrum ofIons from themethane plasma

Ion mass


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Dependence of needed discharge powerto obtain a comparable level of glowdischarge polymerization on the flow ratesof starting materials. The neededdischarge power is greatly dependent onthe molecular weight of the startingmaterials.

Yasuda and Hirotsu (1978).

Influence of Monomers on depositionrate


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Dependence of needed dischargepower to obtain a comparable level

of glow discharge polymerization onthe flow rates of hydrocarbonprecursors containing six carbonatoms. The needed discharge poweris dependent on the structures of thestarting materials.

Yasuda and Hirotsu (1978).

Influence of molecular structure ondeposition rate


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Defined wettability siloxane-based plasma layers

Siloxane-based plasmacoatings cover the wholerange between quartz(SiO2) and PDMS(SiOC2:H) of contactangle against water.

Wetting propertiesdepend on the residualcarbon content.

Defined wettingproperties

0

10

20

30

40

50

60

7080

90

100

110

120

0 10 20 30 40 50

rel. carbon concentration [at%]

a d v .

c o n

t a c

t a n g

l e [ ]

PDMS

quartz

SiO xCy films


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0

20

40

60

80

100

120

-50 -25 0 25 50 75 100 125 150 175 200

film thickness [nm]

r e l . c o n c .

[ a t % ]

O2/HMDSO

PC interphase gradient

O

Si

C

continuously varyingdeposition conditions

gradually reducedcarbon content

designed to uniformlyadapt film properties topolymer

Chemical composition ofthe gradient layer (byXPS)

Improvement of adhesion gradientlayers


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IR-Spectra from polysiloxane films


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SIMS-Spectrum of plasma-polymerized HMDSO (section)


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The fragments areproposed on the baseof IR- and SIMS-Spectra

pp-HMDSO-Structure


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Carboxylgruppen CO

OH

Primre Amine NH

H

Thiole S H

Alkohole C OH

Epoxy-Verbindungen CH

O

CH2

Carboxyl

Primary amine

Thiol

Alcohol

Epoxy

Functional Groups


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Composition by ESCA[at%]

substrate Activation with CF 2 COOH COH

COC

CH2 O N F

poly-propylene

untreated

H2O grafted

N2 grafted

4.4

7.3

7.2


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RF plasma (13.56 MHz, 0.3 mbar)By using moderate plasma power the monomerstructure of acrylic acid is preserved

Peak No.

EB(eV)

5288.1

4286.8

3289.4

2

285.5

1285.0

chem. composition in at%

40 W 5.5 26.1 27.3 41.1100 W 5.1 11.6 4.7 33.5 45.0

( CH CH )2

C=O

OH

2

3

n1

1

2

2nd

Approach: Retention of MonomerStructureCoating with Acrylic Acid

2nd Approach: Retention of Monomer


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rf pulse plasma (40 W, 0.3 mbar)

off-time variation

Peak No.EB(eV)

5287.6

4286.8

3289.4

2285.5

1285.0

chem. composition in at%

1ms/2ms 4.1 24.5 28.8 42.5

1ms/5ms 2.5 26.8 28.5 42.1

1ms/10ms 8.2 17.4 19.5 18.5 36.3

2nd Approach: Retention of MonomerStructure 1ms/10ms

1ms/5ms

1ms/2ms

Binding Energy (eV)292 290 288 286 284

( CH CH )2

C=O

OH

2

3

n1

1

2

Acrylic Acid on Si Wafer and KBr


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Acrylic Acid on Si-Wafer and KBr

treatment(on/off times)

[W]

pressure[mbar]

flow[sccm]

Yasudafactor

[MJ/kg]

IR modesC=O/C-H

depostion[nm/min]

rate[nm/J]

AAc plasma CW 100 0.3 20 92.9 1.25 150 0.03

AAc plasma CW 40 0.3 20 37.2 7.0 200 0.08

AAc pulsed (1ms/1ms)AAc pulsed (1ms/2ms) AAcpulsed (1ms/4ms) AAcpulsed (1ms/5ms)

AAc pulsed (1ms/10ms)

2013.3

86.7

3.6

0.30.30.30.3

0.3

20202020

20

(18.6)(12.4)(7.4)(6.1)

(3.3

9.512.510.59.8

8.2

250160180170

40

0.210.200.380.42

0.19

AAc + KBr 13.5

Acrylic Acid(AAc)

M2 = 72.06

O

OH

Epoxy Functionalisation of Polypropylene


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Comparison of pulse plasmaand CW-plasma depositionwith glycidylmethacrylate

CH3

( CH C )2

C=O

O

O

1

2

3

3

4 4

5n

1

1

2

( CH C )2

CH CH CH2 2

Peak No. 5 4 3 2 1EB (eV) 288.6 286.4 286.2 285.0 284.5

Composition in Atom%Theory 14.3 28.5 14.3 14.3 28.5Pulse 15.3 25.1 18.0 17.5 23.8

CW 14.4 25.2 12.3 14.2 29.8

I n t

e n s

i t y

( a r

b .

u n

i t s

)

292 290 288 286 284 282Binding Energy (eV)

Pulse-Plasma

1

23

4

5 I n t

e n s

i t y

( a r

b .

u n

i t s

)

Binding Energy (eV)292 290 288 286 284 282

CW-Plasma

1

23

4

5

Erh_Mono_PP_Epoxy1(e).ppt

Epoxy-Functionalisation of Polypropylene

Glycidyl Methacrylate


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FTIR-Spektra

rf pulse plasma 40 W

glycidyl methacrylate

0.4 mbar, 30 sccm

Wave number [cm -1]

Glycidyl-Methacrylate

Glycidyl Methacrylate on Polypropylene and KBr


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treatment time

pressure flow thickness IR modes IR modes

[min] [W] [mbar] [sccm] [nm] Epoxy/C-H C=O/C-H

GM plasma CW 5 40 0.4 30 900 0.85 5.15

GM pulse plasma1 ms/1 ms on/off

5 20 0.4 30 850 1.15 7.1


5 13.3 0.4 30 800 1.3 7.2


5 8 0.4 30 750 1.15 7.1

GM + KBr 1.65 7.65

Mr=142.16

(CH) = 2930 cm -1

(epoxy group) = 910 cm -1

(C=O) = 1720 cm -1

O

H2C=CCOCH2CHCH2CH3

Glycidyl Methacrylate on Polypropylene and KBr

Glycidyl-Methacrylate(GM)

O


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1 Of five bonds in the ring, the two onesvicinal to the ketone group are weakerand thus may be preferentially brokendue to electron impact, resulting in abiradical.

2 (or 3) Termination of one of the radicalpositions by hydrogen results in analdehyde group

3 (or 2) The radical grafts onto the substrate

HCOO

electronimpact

C

O

+ H

CH

O

+ substrate

3rd Approach: Opening of cyclic molecules by

plasma

Cyclopentanon

eas precursor


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NH2

HN

plasma

OHO

plasma

SHS

plasma

primary amine frompyrrolidine

hydroxyl fromtetrahydrofurane

Thiol groups fromtetrahydrothiophene

3rd Approach: Opening of cyclic molecules by plasma


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Wet chemical quantification of amino groups on surfaces using Sulfo-SDTB

Sulfo-SDTBSulfo-succinimidyl-4-O-(4,4-dimethoxytrityl)-butyrateMW 605.6 (Pierce Inc.)

+ H2NH2N

H2N

OCH3

C O (CH2)3 CO

O N

SO3Na

OCH3 OCH3

C O (CH2)3 C

O

OCH3

O N

H

OCH3

CH

OCH3

perchloricacid solution

1 2

Amino modifiedsurface

+

e = 70.000 M -1 cm -1

weak alkalinesolution

HO (CH2)3 C

O

N

H


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A thin layer (5-50 nm) ofplasma polymer or parylenedeposited onto a glas

substrate (coverslip).Derivatisation with asuitable spin label(maleimide-PROXYL forthiol, amine-TEMPO foraldehyde).As a control, the sameplasma polymer treatedwith the same solution butwithout spin label, or withspin label with aninappropriate function(e.g. carboxy-TEMPO) isused.

water

SH S

+

NO

N

O

O

NO

N

O

O

water

HCO

H2C

HNN

NH 2

O

+

N O NaCNBH 3

carbodiimide+

NH2N

O

OOH

HN

N OO

Quantitative detection of surface functionalities via spin labelling


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For tetrahydrothiopheneplasma polymer, density ofaccessible thiol groups of0.1 to 0.15 nm -2 is measured.

For cyclopentanone plasmapolymer, the density ofaccessible aldehyde groupsis 0.15 to 0.3 nm -2.

The functional groupsdetection limit depends onthe number of plasmaproduced radicals in thesample and is estimated to


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Working frequency

13.56MHz RF in pulsedmode

Symmetrical, ccp chamber

Process gas4sccm CHF3+25sccm ArProcess pressure 0.8mbar

Experimental Setup / Plasma Parameters

Contact AngleM


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Measurements

advancing and receding contact angles

(water, benzyl alcohol, 1-

bromonaphtaline )

Hysteresis:

Information oninhomogenities

Owens-Wendt: polar and dispersesurface energies

sdisps polldisp

l pol

ldisp

ltot ,,,

,

,,

2

)cos1(

SurfaceE


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Energy

Surface tensions determinedwith linear regression fromOwens-Wendt;Fitted curves:

exponential decay

200ms off 5ms on


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X-ray Photo-electron Spectra

200ms off 5ms on

Development of integral

peaks

(a) shows steeper increase

in fluorine content -> faster

film growth

KRATOS AXIS ULTRA


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with increasing duty-cycle

CF-structure CF 3 already present at low

dc Peak shift with increasing

dc due to enhancedcrosslinking

200ms off 5ms on

ESCA-Spectrafrom domains towards closed film



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Dr. Christian Oehr

Titel_OTTI.ppt


general aspects



outlook

Polymerization

Fields of Application I


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Protective coatingsagainst mechanical stress scratch and wear resistance,hardnessagainst chemical attack corrosion and solvent resistance

Coatings with specified transport propertiesOptical transport lenses, mirrors, waveguidesetcElectrical transport conductive and dielectric layersetcMaterial transportMaterial specific permeation separation membranespermeation 0 barrier layers

Material transport out of layer- systemsDefined release (medicament) dosage systems

Fields of Application IThin films (micro...)

Improvement of adhesion gradient layers


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Adaption of mechanicalproperties of SiO x filmson polycarbonate:

Graded transition ofinternal stress andhardness improvesadhesion to polymers.

(Measurements wereperformed on individuallayers.)

-140

-120

-100

-80

-60

-40

-20

0-50 -25 0 25 50 75 100 125 150 175 200

film thickness [nm]

i n t e r n a

l s t r e s s

[ M P a ] .

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

h a r d n e s s

[ G P a ]

PC after N 2 gradient layer pre-treatment

O2/HMDSO

Improvement of adhesion aging


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0

1

2

3

4

5

6

7

8

9

0 2 4 6 8 10 12 14

aging [months]

p e e

l s

t r e n g

t h [ N / c m

]

measurement limit

measurement limit

0

1

2

3

4

5

6

7

8

9

0 2 4 6 8 10 12 14

aging [months]

p e e

l s

t r e n g

t h [ N / c m

]

1.5 m SiO x on PC (without gradient)

measurement limit

measurement limit

The adhesion of quartz-likefilms on PC is subject toaging due to waterdiffusion into the interface.

(peel strength was measuredusing an adhesive tape peeltest)

0

1

2

3

4

5

6

7

8

9

0 2 4 6 8 10 12 14

aging [months]

p e e

l s

t r e n g

t h [ N / c m

]

1.5 m SiO x on PC


measurement limit

measurement limit

0

1

2

3

4

5

6

7

8

9

0 2 4 6 8 10 12 14

aging [months]

p e e

l s

t r e n g

t h [ N / c m

]

1.5 m SiO x on PC

250 nm SiO x on PC


measurement limit

measurement limit

0

1

2

3

4

5

6

7

8

9

0 2 4 6 8 10 12 14

aging [months]

p e e

l s

t r e n g

t h [ N / c m

]

1.5 m SiO x on PC/ABS

1.5 m SiO x on PC

250 nm SiO x on PC


measurement limit

measurement limit

0

1

2

3

4

5

6

7

8

9

0 2 4 6 8 10 12 14

aging [months]

p e e

l s

t r e n g

t h [ N / c m

]

1.5 m SiO x on PC/ABS

1.5 m SiO x on PC

250 nm SiO x on PC


250 nm SiO x on PC (stored in water)

measurement limit

measurement limit

aging depends on:

adaption of mechanicalproperties

film thickness (int. stresses)storage conditions

(air or water)

Functions determining the Membrane Characteristics


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J =-Ddc d x

c = Sp J = DS p /

P = DS = J / p

AB =P AP B

DADB

S AS B

=

J = flux [ cm 3 gas/cm 2s]

D = difusion constant [cm 2/s]

c = concentration

S = solubility coefficient [cm 3 gas /

(cm3

polym cmHg)]p = pressure difference over the

membrane [ cmHg]

d = membrane thickness [cm]

P = permeability

= selectivity A,B= components

Yasuda Factor and Membrane Properties I


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p6

4

2

0

E t O

H

3015

51

W/FM [kJ/g]Einflu von W/FM auf ETOH und Q. Beschichtungsdauer: 60 min

Q [ k g / ( m

2 h ) ]

2

1

3

50 100 150 20000

Matsuyama et al. (1994)

50 100 150 20000

Influence of W/FM on ETOH and Q, deposition time: 60 min

Matsuyama et al 1994

Yasuda Factor and Membrane Properties II


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p

E t O H

[ -

]

0

W/FM [kJ/g]20 40 60

5,0

4,5

5,5

E t O H

[ -

]

6

4

2

0100 110 120 130

E t O H

[ -

]

00

6

4

2

6

4

2

020 40 60

Beschichtungsdauer [min]

Q [ k g

/ ( m 2 h ) ]

30 W15 W

5 W1 W

Matsuyama et al. (199

Correlation between ETOH and low valuesof W/FM

Influence of durationof deposition

W/FM= 36kJ/g, W=5 W

Correlation between ETOH and contact angleW/FM> 30kJ/g

Yasuda Factor and Membrane Properties III DMTSO


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p

6

4

2

0

E t O H

[ - ]

50 100 150 20

Q [ k g

/ ( m

2 h ) ]

0

2

1

3

0

W/FM [kJ/g]

OMTSOHMDSO

Einflu von W/FM auf ETOH und Q.15 W. Beschich tungsdauer: 60 m

Matsuyama et al. (1994)

Influence of W/FM on ETOH and Q, deposition time: 60 min

Plasmadeposited multilayer barriers


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Permeability (plasma only):WVTR: 10 -2 -10 -3 g/m 2d plasOTR: 10 -2 -10 -3 cm 3 /m 2dbar

Production with combination of vacuum andliquid phase process about 2 orders ofmagnitude better

Competition: Pilot Production of Ultrabarrier

Substrate for Flexible Displays (Vitex Systems,mixed process)

Fields of Application II


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Tailored surface energy (wettability waterrepellency) (solid-liquid-gaseous)

Tailored contact between polymers and other phasesstatic: solid-solid, (Adhesion)dynamic: solid-(liquid)-solid (Tribology)

Interaction with biological systems

(binding and adsorption of biomolecules,biocompatible or bioactive surfaces)

Separation membranes and ion-exchange materials

Basic research and analytical methods

Fields of Application IIUltra-thin films (nano...)

W tt bilit i


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Wettability isrelevant for:

Wetting

Adhesion

Gluing Contamination

Printing

Varnishing

Coating

Cleanabilityeasy-to-clean

LaminationProtein-Adsorptionfouling, biocompatibility

Water transportcapillarity, goretex , sympatex

Microfluidicsdiagnostics

Soldering


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Aramid Textileright: hydrophilic row materialleft: hydrophobized in a flourcarbonplasma

Oleophobic Finish on Cotton/PET


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Material:Cotton/Polyester-Mixture

Evaluation:3M-Oiltest

Method:Plasmagrafting of aflourcarbon monomer

The finish was washed at60 C

Defined wettability aging


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Polymers can berendered eitherhydrophobic orhydrophilic.

To minimize agingeffects ,a stable and well-adherent ultrathin

plasma layer is superiorto a plasma treatment.

Moreover, active sites inthe plasma layers should

be avoided.

(samples were stored in air)

0

20

40

60

80

100

120

0 2 4 6 8 10 12 14

aging [months]

w a t e r c o n

t a c

t a n g

l e [ ]

PC untreated

siloxane on PC

fluorocarbon on PC

N2 plasma treated PC

SiOx on PC

hydrophobicplasma treatment

hydrophilicplasma treatment

Enhanced


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Adhesive PVD direct metallization

Polymers after a plasma treatment Epoxid Urethane Cyan-acrylate

Copper

FEP (Polytetrafluorethylene- co-hexafluorpropylene)

>15 (film rupture)

10-15 *

PTFE (Polytetrafluorethylene) 7 10-15 *

PFA (Hyflon MFA) Poly(perfluoralkoxy)

5

F l u o r p o

l y m e r s

PVDF (Polyvinylidendifluoride) 20-25 *

PI (Polyimide) 10-15

PP (Polypropylene) >15 ** 10-15 *

P o

l y -

o l e f i n s

PE (Polyethylene) >15 ** 10-15 * >10-15

PE (primer DP8005 from 3M) 5,2

* (cohesion failure in the adhesive)** (film rupture)

Adhesion

The effectivity ofadhesives isenhanced by thinfunctional films

Requirements regarding Surface Properties of Polymeric


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have to be well defined with respect to their

topographysurface tension

density and distribution of chemical groups

density and distribution of surface charges

The polymericsurfaces

Materials for biomedical use

Thin Plasma Films deposited for


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Diagnostics and Therapy

Thin Plasma Films deposited for

Replacement of Glassin Medicine and Pharmacy

Interface between Technical Materials and Biology


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Interface between Technical Materials and Biology

Interface and... enhanced Interaction decreased Interaction

Proteins andother biologicalactive molecules

Specific binding of bio-molecule >> diagnosticse.g. new pyrogene test,heterogeneous bio-catalysis, specific scavengers

Decreased proteinadsorption>> minimized fouling

Microbes Immobilized Microbes/plasma sterilization

bacteriophobic,bacteriostatic, bacteriozidicsurfaces

Mammaliancells

Growing and proliferationof cells for artificial organsand test-kits

minimizing problems withtemporary Implants,minimized restenosis etc.

Minimisation of Unspecific Protein Adsorption (IgG) with


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Minim_Proteinads.ppt

Different Surface Modifications

Type of Surface Modification

P r o

t e i n a

d s o r p

t i o n

g

/ c m 2 2

Plasma grafting (O 2)Vinylpyrrolidon

Plasma fixation of (PEO-PPO-PEO) 80

using Ar

N2-Plasma grafting Allyl-PEO (1100)

unmodified O2-plasma graftingVinyllimidazole

Plasma grafting (O 2)Ethoxide

Plasma fixation(PEO-PPO-PEO) 250

Plasma grafting (N 2)(Allyl-PEO) 350

N2-Plasma graftingHEMA

The measurements were doneafter stability testing using1 M NaOH, 1 h, 50 C

Type of surface modification

Specific Biofunctionalisation of Textile Substrates


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NH

OON

O

O

O

NaO3S

S

HN NH

O

NHS-LC-Biotin-immobilisation

plasmaaminofunctionalisation

NH2

NH2

NH2 NH Biotin

NH Biotin

NH2

Streptavidin

NH2

OregonGreen

textile substrate

PumpeKhlfalle

Monomer Trgergas

13,56 MHz

Plasmabrennraum

Substrate

RR RRe -

e -e -

e -++

+ +

M*M*

M*

M*

substrate with IGF-1

NH Biotin

NH Biotin Biotin

Biotin

Microporous Membranes as alternative Carrier Material for


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Microporous membrane Pore size ~ 0.5 m) with selective functionalization ofpores

Affinity Adsorption from Blood

New approach: Chemical regioselective Aim:Inner pore surface is widely functionalised,


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surface modification

Convective flowof plasma through

the pores of the membraneBlood plasmaon permeate

side

Laminar flow of whole blood in the lumen

[ m ]20

0

[ -NH2 ]

Inner pore surface is widely functionalised,but not the blood compatible lumen surfaceGreen line: ideal distribution

Parameters:In vitro Apheresis:LPS removal from donated human blood


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Membrane module:A(fiber lumen) = 200 cm, n(fiber) =140, l eff = 10 cm

Blood from healthy donors,V=70ml , T=37

LPS: E. coli, 3 EU/ml,45 min prior perfusion

270 min recirculation

g = 600s -1 (QB=8ml/min),QF=1ml/min, TMP


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LPS retention duringplasma permeation acrossthe membrane

LPS reduction in the bloodreservoir

0%

25%

50%

75%

non-modif.membrane

polycationicmembrane

L P S r e

d u c

t i o

[ 1 - c f i l t r a

t e / c

f e e d

0

1

2

3

4

5

0 50 100 150 200 250 300

t [min]

C L P S

[ E U / m

l ]

non-modif. membrane

polycationic membrane

theor

Penetration of active species into the wall of a hollow fiber


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Plasma functionalization with amino groups,XPS spot measurement on cross-section of hollow fiber: ~15 m resolution

The plasma-treated membrane was derivatized wet-chemically with pentafluorphenylalanine priorto XPS.

scan through

cross-section

g f e d c b a

0.2

0.2

00

0.4

0.4

0

1

scan width [mm]

s c a n w

i d t h [ m m

]

0

0.5

1

1.5

2

2.5

g f e d c b a

analysis spot

F 1 s c o n c e n

t r a

t i o n [ a

t % ]

fluorine conc.(corrected)

fluorine conc.(not corrected)

Scalable in-line air to air low pressure plasmamodification unit


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Plasma chamber

Rotary pump 1

Rotary pump 3

Rotary pump 2

Hf-Excitation

Aminoprecursor

N2-liqu. trap

Ventilation

Tnzerwelle

+ Feed through: 0.5 mm * Feed through: 0.7 mm

Hoolow fiber membrane feed

Drying chamber

N2-Addition

Transport velocity variation: 5 - 100 m/min

Plasma exposure time: 4 s 200 ms

+ * * * * +

Rotary pump 4

* *

1 2 3 4 5 6 7

Enhanced Cell Growth by Surface Treatment


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ECTFE untreated

ECTFE modified

Keratinocytes Cornea cells

Human rhabdomyosarcoma cells: dyed with ethidium bromide (red) and calcein(green)


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Rat insulinoma cells (Pankreas): dyed with ethidium bromide (red) andFDA (green)


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hydrophobic/hydrophilicpatterning done byplasma deposition

D Ch i ti O h

Plasma Treatment of Polymers


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Dr. Christian Oehr

Titel_OTTI.ppt


general aspects

Plasma functionalization and polymerisationmonomers, conditions and resulting surfaces


outlook

The need for simplified manageability makes

k i i i l t i t d t


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T. Vaahs, KU Kunststoffe 90/ 10 (2000) 242

Evolution

Driver

Results

Intelligent packaging more complex dosage systems Chip-Integration etc.

Differentiationincreasingly bymanageability;less by activeagent

Inhaler systems

Needleless Injection

Increasingly simplifiedmedication

+ Information (date)

Prefilled syringes

Glass bottles

Blister packaging

+ in dosage system

Insulin PENs

protective function

+ individual dosage

packaging increasingly turn into dosage systems

Structured coatings via plasma based mask techniques


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Strukturierte_Beschichtung.ppt

water droplets onhydrophilized areas(plasma treatment withmask technique).

Volume of droplets:approx. 50 nl

Fluorpolymere stainless steel / TitaniumPolycarbonate

chemically patterned substratesStained with thioninacetate.

Functionalisisation with Carboxyl-Groups.

Dotsize: 100 m 2mm

1 cm cm

AFM-Investigation of microstructured AAc-coated Si-wafer


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ESCA-Investigations of microstructured AAc-Coating

225007000

CH-Image Si-Image

on Silicon wafer


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200m 200m5000 0

on Silicon wafer

on Polypropylene

200m 200m

10000

1500

32000

9000

COOH-Image O1s-Image

Energy-dispersive x-ray microanalysis of mask structureElement mapping of mask structure


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SEM-Figure 5KV

C-K

O-K

Si-K

C-K O-K

Si-K

Line-scan measurement:

high C- and O-rate, dark areashigh Si-rate, light areas

Element mapping:

C- and O-contrast in meshesSi-contrast on tissue threads

Deposition rate related to the position in a plasma


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D e p o s i

t i o n r a

t e [ n m

/ m i n ]

Substrate position between electrodes[mm]

from diploma thesisJ. Matheis,

Stuttgart 2004

Highest deposition ratesome mm apart from theelectrode at the edgebetween bulk plasma tothe plasma sheath

Plasma treatment of trenches parallel to the applied fieldDeposition of SiO x films on polycarbonate parts.


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Deposition of SiO x films on polycarbonate parts.

Film thickness on the inside depends on pressure and plasma sheatheffects.

plane width/depth 1.5/3 mm electrodew/d 1/2 mm w/d 6/30 mmw/d 3/6 mm

sheath2.6 2.6 2.6

2.0

3.0

50 Pa

film thickness in mat top and bottom

50 Pa

30 Pa50 Pa

20 Pa

20 Pa 20 Pa

bulk plasma

0.36 0.74 1.1 0.212.92.9

1.20.65

0.8

0.025E

Plasma treatment of trenches parallel to the appliedfield

Film thickness on the inside higher than expected from an isotropic model:


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g p p

for a sticking coefficient = 1 and width/depth = 0.5 d bottom /d top = 0.06[*]

d bottom /d top 20 Pa 30 Pa 50 Pa

3 mm 0.22 0.41

4 mm 0.14 0.29 0.428 mm 0.11

pressure

Heigth

ofsample

increase of electric field (non-isotropic)

increase of pressure(collisions)

enhanced surfacediffusion

[*] M.A. Lieberman, A.J. Lichtenberg, Principles of Plasma Discharges and Materials Processing, Wiley, 1994.

Plasma treatment of trenches parallel to the appliedfield

Pressure effects are1 5 fil t f th t h


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present fortrenches >100 m(mean free pathlength).

Deposition of SiO xon smaller trenches.

d bottom /d top = 0.4

15 m

75 m

600 nm

1.5 m film on top of the trench

250 nm

Light-optical microscope and AFM results

Plasma treatment (30


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(min. treatment time) ofsilicon wafers through afinely woven tissue

Carboxylbehandlung.ppt

Result: Plasma coating through a finely woven tissue results in astrong layer thickness reduction.

Light-optical microscope photo ofa wafer, coated with one-layertissure

AFM-picture of a wafer, coated with one-layer tissueLayer thicknss valley: 50-80nmLayer thickness mountain: 150-190 nm

Coating with double-layer tissueLayer thicknessvalley: 30nm

Coating with double-layer tissue (45)Layer thicknessvalley: 10nm

Coating with three-layer tissueLayer thicknessvalley : 5nm

Coating with four-layer tissueLayer thicknessvalley :


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SEM Scanning Electron Microscopy

High Resolution Digital Microscopy

AFM Atomic Force Microscopy

Ellipsometry

Contact Angle Measurements

ESCA / XPS X-Ray Photoelectron Spectr.

EDX Energy Dispersive. X-Ray Spectr.

AES Auger Electron SpectroscopyConfocal Raman & FluorescenceSpectr. (optional: Raman-AFM)

UV-Vis & IR-Spectroscopy

ChemicalCharacterization

Contact Angle & TensiometerMeasurements

BET specific Surface Area

ESR Electron Spin Resonance Analysis

OES Optical Emission Spectroscopy

LIF Laser Induced Fluorescence

Microwave Interferometer

MS Plasma Mass Spectroscopy

Plasma Temperature Measurem

FE-SEM AFM Ellipsometry Conctact AngleLMEDX ESCA / XPS AES FT-IRRaman-AFMBET Conctact Angle ESRMW-Interf.LIF MSOES

Pl a . u . ]

acrylic acidplasma polymer (x10)

fluorocarbonplasma polymer

ethylene plasma polymer

ESR-Spectrum

1.5

2.0 Spin Density exponential fit

3 (

x 1 0 2 0 )

0.1 h12 h24 h

Electron-Spin-Resonance:estimation of the radical density


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Substrat

Plasma-Polymer + dangling bonds

UVe - und Ionen-bombardment

Plasma

Radikale

330 340 350

I n t e n s i

t y [ a

B-Field [mT]

Precursor PlasmaPower[W/cm 2]

SpinDensity[1/cm 3]

c-C4F8 0,17 1,2 x10 20

c-C4F8 + H2 0,17 0,6 x10 20

AAc CH2=CHCOOH +H2

0,07 1,5 x10 18

Ethylene H 2C=CH2

(1)

0,63 6,0 x10 20

Ethylene H 2C=CH2 + H2(2)

0,63 4,9 x10 20

0 10 20 30 40 500.0

0.5

1.0

S p

i n D e n s i

t y / c m

Standing Time [hrs.]

Kinetics

Probe

percentage ofC-Radicals oftotal C-content

pp-C 4F8 0,939%

a-CH (1) 1,553%

a-CH (2) 1,792%

AAc 0,004%

CoronaIrradiation

e beam crosslinking

Coating techniques usedfor surface tailoring


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Polymercoating

Coronahydrophilicity

Sputter coatingradiopacity

Ozonisationactivation for grafting

Silanizationcoupling to metals

Texturing photoresist, screeningor printing techniques

Parylene barrier, lubricity

Dip coatingLbL,SAM ,nanocytes

Photocouplinggrafting,

Plasma(-CVD,-Polym.)regioselective deposition,

e-beam, crosslinking

Electroless depositionmetallic layers

Competitive surface treatment methods


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Von G. Decher

Ressource efficiencySurface treatment by:

Liquid based methods Gasphase based methods Gasphase based methods


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Liquid based methods p(atmos. pressure plasma)

Gasphase based methods(low pressure plasma)

solvent: e.g. H 2O3,3 10 22 molecules cm -3

solvent: air, N 2,Ar,He2,7 10 19 molecules cm -3

solvent: vacuum, carrier gas2,7 10 15 molecules cm -3( working pressure: 0.1 mbar)

Some characteristics of liquid phase and gas phase with respect

to surface treatment


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Gas phase

10 6 less material consuming

Conc. of reactive species:10 -5-50%(in-situ produced)

Diff. coeff. ca. 10 -1 to 1 cm 2 /sat atm. press.)(prop. to mean free path)Geometric restrictions prop. tomean free path (relat. to pressure)

Liquid phase

Material consuming

Conc. of reactive species:10 -2 -20%

Diff. coeff. ca. 10 -5 cm2 /s(e.g. Albumin 6*10 -7 cm2 /s)

Geometric restrictions (e.g. due tocapillary depression)

Replacement of chromic sulfuric acid

Example: tailored wettability of ink guiding systems


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X

X

Categories of plasma treated peaces

A.


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B.

C.

Costs of surface treatment by low pressure plasma

category Peaces per Year[ illi ]

Cost per peace[ ]

energy costs[f i ]

Materials


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[millions] [cent] [fraction] costs[fraction]

A. Goods inbulk(treatment bytumbling)

6-33 0,08-0,98 1-8 % 0,04-0,5%

B. smallpeaces

0,6-2,7 0,3(a)-9,77(b)


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Energy input

frequencypower densitydurationCW / pulse

o o e s,carrier gasespressure, flow (total/partial)

gas background

materialdimensionmorphologyquantity

temperaturepotential

Reactorgas leading systeminner wallelectrode material configuration

temperature

type and degree ofdissoziation of the

gases

live time and residencetime of active species

homo-/ heterogenousreactions

ion bombardementand radiation

Plasmatopography

To the Co-Workers:

Plasma Experiments and Analytics:

Acknowledgements I


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p yJ.Barz, B. Elkin, M. Haupt, E. Kurz, H. Malthaner,J. Mayer, M. Mller (Mr.), M. Riedl, V. Sciarratta,U. Vohrer,

Surface Tension, Contact AngleM. Mller (Ms.), M. Schmidt

Cell BiologyH. Walles, U. Burger-Kentischer, M. Kaufmann

MicrobiologyI. Trick, S. Schmidt

for financial support

to the German Federal Ministry for Education and Research BMBF

Acknowledgements II


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to the German Federal Ministry for Education and Research BMBFand the project coordination centers PTJ and VDI for supportingand funding this research

Thank you for your attention

Acknowledgments toDr. Hilgers, IBM,Germany, (Nanofunctionalization)Dr. Storr, Gambro GmbH, (production, wet chemical treatment and testingof hollow fiber membranes)

C ti I f ti


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Continuous Informationon the Topic:

Polymer Treatment andDeposition by Plasmas

will be released in theJournal

contemporary impactfactor (ISI): ~2,96

PSE2014-Tut 1 5 Oehr Plasma Treatment

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