Combinatorial Measurements of Polymer Adhesion

Combinatorial Measurements of
Polymer Adhesion
Rui Song, Alfred Crosby, Alamgir Karim and Eric J Amis
Polymers Division, NIST

Gaithersburg, MD 20899
NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Introduction
although adhesion is omnipresent, our current understanding

of the fundamental mechanism of polymer adhesion is far from
complete

Motivation
Industrial
Many applications involved - such as electronic packaging,
biomedical devices and implants, composites, .
Product design and quality control, .
Many variables control adhesion and varied existing techniques
for measuring adhesion
Scientific issues
Interface strength/stability between polymer and non-polymer,
including metal, ceramics,
Molecular chain diffusion, bond generation, .

Objective
Develop & test methodologies for quantitative high-throughput

measurement of adhesive strength of polymer interface

Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems
Stress gradient on PMMA adhesion
Temperature effects on adhesion (Tg, Gradient)
Surface energy gradient on PMMA adhesion
Gradient UV-exposure on PMMA stability
Casting-solvent effect on PMMA adhesion
Material aspects (different tapes, metals)
Tape adhesion on surface energy gradient

Why select PMMA
Widely used in industries such as microelectronics

Easily prepared into uniform solution
Relatively stable upon heating & without
crystallization
Wide visible- and UV-absorbance range

Gradient Methods Used
Thermal gradient
Temperature increase
Contact angle gradient
UV exposure gradient

Peel-off Test (mini-Instron)
Control:
Peel-off Rate
Measure:
Force (Peel-off Position)

Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems
Temperature effects on adhesion

Simultaneous Thickness & Surface
Energy Gradient on PMMA adhesion
Create 2-D Orthogonal Gradients
Thickness Gradient (Induces PMMA/Si Thermal

Expansion Mismatch Stress Gradient):
Flow coater gradient
Contact Angle Gradient (Affects Adhesion):

SAM layer irradiated by UV

Orthogonal Gradients - Contact
Angle and Thickness of PMMA Film
13
70
12
Contact angle, degree

60
11 50
10 40
Thickness, micron
30
9
20
8 0 10 20 30 40 50
Distance, mm
7
3
0 5 10 15 20 25 30
Distance, mm

Combinatorial Measurement
of Polymer Adhesion
Hydrophilicity increase (
After peel-off test
180o Peel Test on Combinatorial Libraries
70
-
30
degree)
After thermal cooling

Thickness increase (Liquid
Liquid Nitrogen for 5 sec.)
( 3-
3-11 micron )

Critical Thickness and Contact
Angle for PMMA Thin Film
20
2.2
h CA
8.113 27.28
2.0
30 7.743
7.35
28.88
30.85
6.908 33.89
6.456 37.59
5.974 40.86
5.532 45.21
5.041 49.55
40 4.525 54.12 1.8
4.034 58.91
0
3.566 63.26
/
50
1.6
60
1.4
70
3 4 5 6 7 8 9 10 1.2
25 30 35 40 45 50 55 60 65 70
Thickness, micron
( Martin Chiang)

PMMA Films with Single Gradient
( After Annealed Below or Above its Tg )
Thickness gradient
Contact angle gradient
70 C for 64 h, spin coating 140 C for 20 h, spin 70 C for 64 h 140 C for 20 h

PMMA layer, ca. 240 nm coating PMMA layer

PMMA Film with Orthogonal Contact
Angle and Thickness Gradients
(Annealed Below or Above its Tg )
70C for 64 h, 70C for 64 h, 140C for 20 h, 140C for 20 h,

cut before cut after cut before cut after

=> Conclusion
Above T g annealing is more effective to enhance

the adhesion
No obvious thickness dependence on adhesion

Samples for Combi Peel off Test
Spin coating film (5wt.% chloroform solution)

Floated off on water surface
Transferred on to the substrates Si (Al, Cu, Au, etc)
PMMA film thickness: 100-120 nm

Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems

Adhesion of PMMA on Si
( Annealed on Thermal Gradient, then Peeled Off )
200
28
(83 -170C) (83 -170C)
(88 -180C)
24 190 (88 -180C)
Critical temperature (Tc),C

Unbroken length l(o), mm
(93 -193C) (93 -193C)

20 180
16
170
12
160
8
150
4
140
0
130
0 2 4 6 8 10 12 14 0 5 10 15 20
Annealing time, h Annealing time, h
l0
Tc
l0: unbroken length
Tc: critical temp.
L
Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems

Adhesion of PMMA on Substrate
with Contact Angle Gradient
90
90.0
80
Water Contact Angle ( Degrees)

80.0
Water contact angle,
70 Debonded
70.0
60
60.0
50 Bonded
annealing @ 180C
50.0 T = 140 C
40 annealing @ 160C
annealing @ 140C
T = 160 C
T = 180 C
30 40.0
0 200 400 600 800 1000 10 1 10 2 10 3 10 4
a *Time (min)
Annealing time, min t

Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems

PMMA after UV Exposure Gradient
- Contact Angle and Peel off Force
600
PMMA thin film subject to UV exposure
80 PMMA thin film from 5 wt.% chloroform
500
70
Average Peel off force, g

Contact angle,
60 400 (totally degraded)
50
300
40
30 200
20
100
10
0
0 (highly cured)
-10 0 10 20 30 40 50 60 70 -10 0 10 20 30 40 50 60 70
UV exposure time, min UV exposure time, min

Effect of UV Exposure
Time on PMMA Thin Film
0 min 2 min 4 min
8 min 16 min 32 min 64 min

UV Effect of Exposure Time
on PMMA Thin Film Surface
2 min 16 min
4 min 32 min
8 min 64 min

Roughness of PMMA film after
UV Exposure
UV-O time, min RMS, nm Ra, nm
0 3.52 2.78
2 9.83 6.50
4 5.73 4.13
8 6.90 5.44
16 10.49 7.82
32 5.13 3.86
64 4.14 3.27

C=O / C-O-CH3 Ratios
C=O
1.2
0 min, 0.636
2 min, 1.138
4 min, 1.403
8 min, 1.812
16 min, 2.636
0.8
Absorbance
32 min
64 min
C-O-CH3
0.4
0.0
1800 1740 1680 1300 1200 1100
-1
Wavenumbers (cm )
(N. Eidelman)
C=O / C-O-CH3 FTIR Map
+
Min
0 64 32 16 min 8 4 2
3
C
o
n Adhesion Good
cm
2 t Failure Zone Adhesion

r
o
1 l
1 3 cm 5
(N. Eidelman)
Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems

Effect of Casting Solvent
on PMMA Thin Film Adhesion
Chloroform Toluene
180
80C (78-158C) 160 77C (78-158C)
Critical temperature, C
87C (83-170C) 82C (82-164C)
170 92C (88-180C) 150 91C (85-176C)
100C (93-193C) 100C (88-188C)
140
160
130
150 120
110
140
100
130 90
PMMA film from 5wt.% chloroform solution 80 PMMA film from 5wt.% toluene solution
120
0 5 10 15 20 25 0 5 10 15 20 25
Annealing time, h Annealing time, h

Solubility Parameter:
PMMA: 22.7 MPa1/2; Toluene: 18.2 MPa1/2 ; Chloroform: 19.0 MPa1/2.
Polymer Handbook, 4th edition, 1999, J. Brandrup; et.al

Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems

Tapes Used for Peel off Test

Different Tapes on the Highly
Cured PMMA Thin Film
280
240 2
200 GIC, (g/cm)

Peel off force, g
160
120 Tape 1: 43.92

3
80
40 Tape 2: 192.5
1
0
-40 Tape 3: 94.2

0 20 40 60 80
Displacement, mm

Peel-off with 3 Different Tapes
(PMMA thin film annealed @85-178 C for different time)
Critical temperature, C 180 Tape-1

Tape-2
Tape-3
170
160
150
140
130
120
0 5 10 15 20 25
Annealing time, h
Adhesion Behavior for PMMA on
Different Metals - Al, Cr, Cu and Au
180 Annealing temperature gradient is from 85 to 180C

160
Au Cu
140
Al
Cr
120
100
0 5 10 15 20 25
Annealing time, h

Outline
Methods
Polymer Debonding
Peel-off Test
Test Systems

Adhesion Dependence on Surface
Energy of Substrate Materials
Al
peel off rate = 0.2 mm/sec
300
250
Peel off force, g
Glass
200
PMMA
PTFE Si
150
100
50
0
Tape 1 Tape 2 Tape 3

Details of Some Substances
H2O CH2I2 sp sd Polarity
PTFE 135.2 83.99 1.81 18.68 20.49 0.088
PMMA 79.88 52.23 6.27 28.47 34.74 0.180
Al 59.06 34.52 15.43 33.61 49.03 0.315
Glass 11.42 60.52 58.06 14.31 72.37 0.802
Silicon 0 45.01 50.98 21.82 72.80 0.700
Note: Al was baked at 450C 8-12 h; the CA for newly prepared Al was ca. 47;
PMMA was spin coating on Si wafer from 5 wt.% chloroform solution, 1500 rpm;
Glass was sonicated in toluene for 10 min;
Silicon was UV burned for 20 min, then rinsed by DI water and dried with N 2.

Peel off on Surface Energy
Gradient Surface
600
Tape 2, 0.2 mm/sec, at RT

500
400
Peel off force, g
300
200
100
-10 0 10 20 30 40 50 60
Displacement, mm
30 50
Surface Energy( mN/m)

Adhesion Dependence on Surface
Energy of Substrate Materials
700 peel off rate: 2 mm/sec

Tape 2, 2 mm/sec, at RT 500
600
PMMA
400
Peel off force, g
500 Al Si
Glass
Peel off force, g

400 300
300
200
PTFE
200
100
100
0 10 20 30 40 50 60 70 80 90 0
Tape 1 Tape 2 Tape 3
Displacement, mm

Peel off Force vs. Surface Energy
400
300 PMMA
Peel off force, g
Al
200
Glass
Si
100
PTFE
0
10 20 30 40 50 60 70 80
Surface energy, mN/m

Future directions
Investigate substrate roughness effects
Investigate adhesion of photo-resists before /after cure
and rinse cycle
Investigate multi variable behavior in one experiment
Microlens experiments to quantify the adhesion and relaxation
Correlate Peel-tests with Microlens tests
Measure temperature gradients effects on-line in Peel Tests

Acknowledgements
Archie P. Smith
Martin Chiang
Karen M. Ashley

Combinatorial Measurements of Polymer Adhesion

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Combinatorial Measurements of

Polymers Division, NIST

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

although adhesion is omnipresent, our current understanding

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Develop & test methodologies for quantitative high-throughput

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Widely used in industries such as microelectronics

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Contact angle gradient

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Create 2-D Orthogonal Gradients

Thickness Gradient (Induces PMMA/Si Thermal

Contact Angle Gradient (Affects Adhesion):

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Contact angle, degree

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

After peel-off test

180o Peel Test on Combinatorial Libraries

After thermal cooling

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

70 C for 64 h, spin coating 140 C for 20 h, spin 70 C for 64 h 140 C for 20 h

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

70C for 64 h, 70C for 64 h, 140C for 20 h, 140C for 20 h,

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Above T g annealing is more effective to enhance

No obvious thickness dependence on adhesion

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Spin coating film (5wt.% chloroform solution)

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Critical temperature (Tc),C

(93 -193C) (93 -193C)

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Water Contact Angle ( Degrees)

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

Average Peel off force, g

60 400 (totally degraded)

UV exposure time, min UV exposure time, min

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

0 min 2 min 4 min

8 min 16 min 32 min 64 min

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

2 t Failure Zone Adhesion

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

87C (83-170C) 82C (82-164C)

Annealing time, h Annealing time, h

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002

200 GIC, (g/cm)

120 Tape 1: 43.92

-40 Tape 3: 94.2

NIST Combinatorial Method Center Meeting-2, October 7-8th, 2002