금속-폴리머 접착력 증진을 위한

플라즈마 표면처리

KISTAdvanced Metals Research Center

Seunghee Han

◆ 1 eV = 10,000 K

◆ Ti ,Tn << Te

◆ h<1 %

◆ Radical species

Plasma Properties

(eV)log10 eT

⊗

HighPressure

arcs

Shocktubes Theta

pinch

FocusLaser

plasma

FusionReactor

Flames

Solarcorona

InterplanatarySolarwind

Fusionexperiments

n34 <π

10-2 10-1 1 10 102 103 104 105

05

1015

20

전형적인 산업적응용 저온 플라즈마

⊗

HighPressure

arcs

Shocktubes Theta

pinch

FocusLaser

plasma

FusionReactor

Alkalimetal

plasmas

Solid Si

Lowpressure

glowdischargesFlames

Solarcorona

InterplanatarySolarwind

Fusionexperiments

10-2 10-1 1 10 102 103 104 105

05

1015

20

산업적 응용저온 플라즈마

Earth’s ionosphere

)(c

mn

log

-310

)(c

mn

log

-310

)(c

mn

log

-310

e

e

e

e

e

e

e

e

e

e

e

e

e

ee

Plasma Sheath

+

+

+

+-V

DC RF MWCCP

ICPDC-Magnetron

ECRDC

◆ Helicon, SW, Laser,Arc, etc

Plasma Generation

Ion Implantation

Injection of high energy ions into materials surface

%

Z

Advantages of ion implantation

Selective improvement of surface regionNo sharp interfaceNo dimensional change or distortionHigh-energy / non-equilibrium processEasy process control

Ion-beam ion implantation

Ext. & Acc. Rastering

Ion BeamMask Target

3-Axis TargetManipulator

Plasma Source Ion Implantation (PSII, PIII)

HV Pulser

Advantages of PSIIUniform implantation over 3-D & large targetSimple and economicHigh dose rateImplantation capability on insulatorsModular design

Plasma

Plas

ma

Phys

ics

High Voltage

Pulse Eng.

MaterialScience

PSIISemiconductor Polymer

Ceramic

Metal

Plasma Source Ion Implantation - Principle

-HV

Target

Vacuum chamber wall

Child-Langmuir Sheath

Dynamic Sheath

Debye Sheath

Plasma

Expanding sheathIncoming ions

Ion Matrix Sheath

HV Pulser0

CW Plasma + HV pulseor

Pulsed Plasma + DC biasor

Pulsed Plasma + HV pulse

PSII Modes

0 2 4 6 8 10 12 14 16 18 200

2

4

6

8

10

12

pulse bias -40 k Vpulse bias -30 k Vpulse bias -20 k V

Shea

th p

ositi

on (c

m)

Sheath propagation time (usec) μ

Advantages of Pulsed Plasma

Pulsed plasma has been widely used in many processes because it has several advantages over continuous (CW) plasma.

Ion species can be varied.

Discharge chemistry is changed.

Charging damage is low.

Film quality is improved in deposition.

Etch and deposition rate increase.

Very well suited for pulsed-process nature of PSII.

Amplifier RF-Deck

13.56 MHz, 50 kW peak, 3 kW avg.4CX5000A RF TetrodePi-tank matching network to 50 Ω(2 vacuum caps / roller inductor)L-R anode parasitic suppression Forward / reflected RF powermonitored using 1-5/8” rigid LS and Bird RF elementsMicroprocessor-controlled powermeasurement and SWR protection Easy and safe tuning with stepperMotors

4CX5000A

CTCL

LCB

RFC

Line S.Anode S.

Amp CTRL / Display

Time-resolved Plasma Parameters

Peak RF power : 10 kW, RF pulse width : 1ms, pulse repetition frequency : 25 Hz

At early stage, the electron density is low and electron temperature and plasma potential is high.

During the RF pulse on time, plasma parameters reach the steady state after about 500 μs.

Plasma parameters are similar to continuous wave (CW) operation from about 500 μs to the end of the RF pulse except the electron density.

After the RF pulse is turned off, plasma parameters decrease gradually.

0 500 1000 1500 20000

10

20

30

40

50(c)

peak 10 kW CW 2 kW CW 1 kW

Time (μs)

Vp

(V)

0 500 1000 1500 20000

2

4

6

8

10(b)

peak 10 kW CW 2 kW CW 1 kWT e (

eV)

0 500 1000 1500 20000

1

2

3(a)

n e (

1011

cm-3

)

peak 10 kW CW 2 kW CW 1 kW

Schematic Diagram of PSII Equipment

2

3

10

9

128

13

4

1916

15

6

7

111415

17

18

1. Vac. chamber 2. Antenna3. RF generator 4. Matching box5. Plasma 6. Target stage 7. Target 8. Vac. Pump9. Ion gauge 10. Langmuir probe11. MFC 12. Working gas13. HV pulse gen. 14. CT15. HV divider 16. Oscilloscope17. Magnets 18. Lead shield19. Chamber ground

PSII Equipments

PSII - I (100L, 100kV, 10A) PSII - II (60L, 10kV, 2A)

Internal ICP Antenna

New PSII Facility for Large Sample Implantation

Ceramic-insulated, internal antenna (water-cooled)Protected by inner-liners Oil-cooled sample stageOil-insulated HVFT

RF Antenna

Sample Stage

Matching Box 1m x 1m x 1mNd-Fe-B magnet cuspsWater-cooled walls2000 L/s turbo-pumpedLead-shielded (6 mm T)Sliding-door type

CTRL / PS

PSII - III (1000L, 100kV, 30A)

RF Antenna / Matching Box

Standard-type matching networkTwo vacuum capacitors and oneceramic capacitorStepper-motor driven from remotecontroller

Antenna

Ceramic Support

Machinable Ceramic

Stepper Motors

Vacuum Caps.

Circuit Diagram of HV Pulse Generator

in

out

Internal View of HV Pulse Modulator

• Dual-mode hard tube type high voltage pulse generator.

• Using high voltage tetrode(TH-5188) and capacitor bank.• 100 kV, 10 A, 10~60 μsec, 10~10000 Hz.

-1 0 0 -5 0 0-7 0

-6 0

-5 0

-4 0

-3 0

-2 0

-1 0

0

-6 0 k V P u ls e B ia s

Bia

s V

olta

ge (k

V)

- 1 0 0 -5 0 0-2

0

2

4

6

8

Impl

anta

tion

Cur

rent

(A)

T im e (u s e c )

Implantation voltage and current

High Voltage Pulse Modulator

Hard-tube type using CB and TH-5188’s2 x TH5188 - MOSFET cascode circuit 100 kV, 30 A HV pulseDC-mode possible for sputter cleaningRC Voltage divider for Vi monitoring(10000 : 1) Immersed in oil tank Will be upgraded using IGBT stack

TH-5188 x 2

Cap. Bank

R / D Array

Mod. CTRL

Un-implanted N2-10 min N2-20 min N2-40 min0

50

100

150

Wea

r D

epth

(nm

)

0 5 10 15 200

20

40

60

80

100

60 kV, 25 usec

150 Hz, 10 min.

Φ = 1017/cm2

Sputter Rate : 130 A SiO2/min

O C

N W

Co

Ato

mic

%

Sputter Time (min.)

PSII N2-implantation on Co-cemented WC

PSII N2-implantation on Cr-plated SKD61

20 um Hard-Cr plating on polished SKD61

N ion implantation(N2, 60 kV, 25 usec, 30 min.)

Pin-on-disc wear tester(100 g, 200 rpm, 10000 rev. 3 mm-Dia. Ruby ball)

α-step Measurement of wear-track

U n -im planted

1 m Torr 200 W R F

100 Hz

1 m Torr 200 W R F

200 Hz

0.5 m Torr 100 W R F

200 Hz

0.5 m Torr 100 W R F

100 Hz

1059 nm 56 nm 101 nm 106 nm 56 nm

PSII N2-implantation on Nimonic (Cr-Ni, Al, Ti….)

Polished Nimonic

N ion implantation(N2, 60 kV, 30 usec, 1 hr & 2 hr, RT & HT)

Knoop Hardness Test, SEM, Auger

Un -implanted

RT 1 hr.

RT 2 hr.

HT 1 hr.

HT 2 hr.

350 HK 396 HK 405 HK 1129 HK 1246 HK

Polymer Surface Modification

고분자 고분자

ChemicalFlameCorona (UV, Laser)

플라즈마 ( 이온빔 )중간층 (Tie-layer)

고분자

금속박막

Polymer Surface Modification using PSII

0 5 10 15 200

10

20

30

40

50

60

70

80

N2 Plasma Ar Plasma O2 Plasma N2 PSII Ar PSII O2 PSII Untreated

Cont

act a

ngle

(deg

)

Aging time (day)

Water contact angles of PS as a function of aging time

Improvement of Cu-PI adhesion using PSII

0 200 400 600 800 1000 1200 14000

50

100

150

200

250

300

350

400

1500 Å Cu pre-deposition on PIPSII-IBM (20 kV, 20 us, 500 Hz)3000 Å Cu deposition

gf/c

m

Implantation Time (sec)

Un-measurable

Polymer Surface Modification using PSII

0 2 4 6 8 10 12 14 16106

107

108

109

1010

1011

1012

1013

1014

1015

1016

Ar 100W 1mTorr -30kV 20μs 100Hz -50kV 20μs 100Hz

Surfa

ce re

sistiv

ity (

Ω/sq

.)

Implantation time (min.)

Surface resistivity of MPPO as a function of ion energy

Epon’s PSII chamber for IC-tray implantation

Plas

ma

Phys

ics

High Voltage

Pulse Eng.

MaterialScience

PSII

Metal

금속 소재

PolymerSemiconductor

Ceramic

Plasma / PSII is a very promising tool for materials surface modification !!

Conclusion