Plasma processes under lowand atmospheric pressure.

Charles University in PragueFaculty of Mathematics and Physics

O.Kylián, J. Hanuš, A. Choukourov, J. Kousal, A. Kuzminova, P. Solar, A. Shelemin, H. Biederman

• Who we are?

• What is plasma?

• How can be plasma used for surface

modification?• Plasma treatment of polymers

• Sterilization

• Thin film deposition

• Nanostructured coatings

• Nanoparticles

Charles University in Prague has more than 7,500 employees

Over 51,000 students

17 faculties

Faculty of Mathematics andPhysics

~ 1000 student of Physics

14 departments

Who we are?

5 researchers8 students (6 PhD)

Department of Macromolecular physics

• Ar + H2 ?

Bogaerts et.al. 2002

Ar H2

main: Ar, H2

10-3-10-6: H, H*, Ar*, Arm

*,Ar+, Ar2+, H+, H2

+, H3+,

ArH+, ... e-

ArH2

No thermal equilibrium!Tn 0.03eV, Ti 0.1eV, Te 1eV +fast (>10eV) ions and electrons

Classical

Plasma Advantage:Rich physics and chemistry!

Disadvantage:Rich physics and chemistry!

glow discharge

Plasma is a complex mixture of electron, ions, neutrals, radicals, excited species.

Plasma emits radiation in wide spectral range.

Plasma interacts with solid surfaces and may change their properties (chemical composition,

morphology, bioresponsive properties etc.)

DBD plasma

Low pressure plasmaAtmospheric pressure plasma

Plasma is a complex mixture of electron, ions, neutrals, radicals, excited species.

Plasma emits radiation in wide spectral range.

Surface modificationSurface cleaning

Surface sterilization

Deposition of thin filmsDeposition of nanostructured coatingsDeposition of nanocompoiste materials

Biomedical applications Biomedical applicationsPhotovoltaic, Fuel cells

Barrier and protective coatings

Possibility to process virtually any substrate materialFast, cost-effective, environmentally friendlyHigh flexibility

Advantages:

292 290 288 286 284 282 280

Binding energy [eV]

Inte

nsity [a.u

.]

C-C

5 mm

DBD plasma may change surface energy, chemical composition as well as morphology of polymers.

292 290 288 286 284 282 280

C-C

C-N

C-C

C-H

O-C=OC=O

Inte

nsity [a

.u.]

Binding energy [eV]

5 mm

DBD plasma30 W1 atm

air1” plasma treatment

SAOS

HUVEC

BeforeDBD 1“ DBD

Ostoblast-like cells

Endotel

3 days after seeding

Improved biocompatibility

296 294 292 290 288 286 284 282 280

CF3

C-OCF

CF2

Inte

nsity [

arb

. un

its]

CF3

C-C

C-H

C=C-O

O=C-N

C-C

C-H

Inte

nsity [

arb

. un

its]

C-N

C-O

C-N

C-OC=C-O

O=C-N

CF

CF2

Inte

nsity [

arb

. un

its]

Binding energy [eV]

PTFE

PTFE + DBD + BSA + SDS wash

BSA

Covalent immobilization of biomolecules

30 40 50 60 70 8010

0

101

102

103

104

105

106

107

Untreated

DBD pre-treated

Sh

ee

t re

sis

tan

ce

[

]

Deposition time [s]

Improved metallization of polymers

Non-treated

H2O

Effect on bacterial spores

Oxygen plasma

Ar/O2/N

2 20:1:1 Ar/O

2 20:2

Ar/N2 20:2Untreated

100 mm

Height [nm]

0

10,00

20,00

30,00

40,00

50,00

60,00

70,00

80,00

Effect on proteins

Effect on endotoxins

Non-treated Plasma treated

By means of plasma it is possible to sterilize/decontaminate surfaces.

O.Kylián et. al. J.Phys.D: Appl. Phys 41, 2008, Art. No 095201Kylian and Rossi . Phys. D: Appl. Phys. 42 (2009) 085207Kylian et.al. Plasma Process. Polym. 2011, 8, 1137Fumagalli et. al. J. Phys. D: Appl. Phys. 45 (2012)

Highly competitive with other

sterilization methods!!!

Plasma may be used for deposition of thin films of metals, metal-oxides as well as plasma polymers.

WSh

M

c

PS

PS

c P

Non-fouling PEO-like thin films

290 288 286 284 282290 288 286 284 282290 288 286 284 282290 288 286 284 282

Binding energy, eV

e) 200W

d) 120W

c) 10W

a) evaporated

without plasma

b) 1W

O-C=OC=O

C-O

C-C, C-H

PEO PEO + UV

PEO + autoclave PEO + dry heat

It is possible to fabricate non-fouling PEO-like coatings that withstand UV light

sterilization.

A. Choukourov et al. Plasma Process. Polym. 2012, 9, 48A. Artemenko et. al. Thin Solid Films 2012, 520, 7115

Amino-rich thin films

TiAlV

TiAlV + Nylon sputtered in Ar

TiAlV + Nylon sputtered in mixture nitrogen-hydrogen

O. Kylian et al. J. Phys. D. Appl. Phys. 2009, 42, 142001A. Artemenko et. al. Surf. Coat. Tech. 2011, 205, S529

It is possible to fabricate coatings that promote cells

growth.

Barrier a-C:H coatings

0 20 40 60 80 100 120

1

10

100

Barr

ier

impro

vem

ent fa

cto

rs

-400 V

-200 V

Thickness [nm]

100x better barrier properties of PET !!

Thin a-C:H films may significantly improve barrier properties of polymeric foils.

O. Polonskyi et al. Thin Solid Films 2013, 540, 65

a

Substrate

Magnetron

Ag columns(Bio)sensing

SERS spectra of three free-base porphyrinsConcentrations <10-6

M. Subr et al. J. Nanomat. in press.

Pt Ti Al C:H C:H:NCu Ag Au

Solar et al. Surface Coat. Technol. 2011, 205, S42 Drabik et al., Plasma Proces Polym, 2011, 7, 544Kylian et al., Material Letters 2012, 79, 229Polonskyi et al., J. Phys D. Appl. Phys. 2012, 45, 495301Kylian et al. Thin Solid Films 2014, 550, 46Solar et al. Vacuum 2015, 111, 124…..

Power

Gas inlet

~100 Pa

<1 Pa

Power

Gas inlet

Power

Gas inlet

Overcoating nanoparticles by plasma polymer

Step 1 Step 2

As a source of the overcoat material may be used PECVD or magnetron sputtering.

Ti C:H NPs + Ti

It is possible to control independently surface roughness and surface chemical composition.

We can prepare nanorough surfaces e.g. for faster osseo-integration or water

repellent character

• dielectric barrier discharge (typical):• 20 W, 23 kHz, 15 kVPP, substrate(glass) -electrode gap 1.5 mm

• monomer: titanium tetraisopropoxide (TTIP), 0.5 mass% in gas (N2, air)

• gas flow: 0.7-2.5 slm

• A. Shelemin, A. Choukourov, J. Kousal, D. Slavinska, H. Biederman: Nitrogen-Doped TiO2 Nanoparticles and Their Composites withPlasma Polymer as Deposited by Atmospheric Pressure DBD, PLASMA PROCESSES AND POLYMERS 11, 9 (2014) 864-877

SEM images of the films deposited in N2 at various Yasuda parameter -a) 11 W/slm (8W, 0.7slm) b) 14 W/slm (20W, 1.4slm) c) 8 W/slm (20W, 2.5slm) d) 43 W/slm (30W, 0.7slm)

a)

d)c)

b)

8 W/slm 43 W/slm

14 W/slm11 W/slm

b) - cross section

Plasma is versatile tool for surface modification and for deposition of thin functional coatings.

By means of plasma it is possible to tailor surface properties of solid objects.

Possible applications include:Biomedical applications(Bio)sensorsBarrier coatingsSurfaces with controllable wettabilityetc.

Thank you for your attention.