Vous êtes sur la page 1sur 5

@

.

ELSEVIER

Nuclear Instruments and Methods in Physics

Research

B 105 (1995)

245-249

NINI

B

Beam Interactions with Materials 6 Atoms

Processing

of polymer

surfaces

by laser radiation

E.W. Kreutz

*, H. Frerichs,

J. Stricker,

D.A. Wesner

E.W. Kreutz *, H. Frerichs, J. Stricker, D.A. Wesner Abstract of operation) and processing variables (repetition

Abstract

of

operation) and processing variables (repetition rate, pulse number). Polymers under investigation are polyamide, polymethyl- methacrylate, polypropylene, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile

copolymer, polybutadiene terephtalate, and polyoxymethylene, which are studied in air within different processing regimes such as modification of surface properties for subsequent metallization and removal of material for structuring of surface geometry. The metallization of polymers, which are pretreated by laser irradiation, wet chemical etching or plasma etching, is performed via electroplating and physical vapour deposition as a function of surface properties. The removal of polymers including non-thermal and thermal processes is done by direct processing techniques in the demagnification mode within one processing step. The diagnosis and the modelling of physical processes involved in tailoring the surface properties of polymers with laser radiation have to be implied to improve any application of these materials.

The processing

of polymer

surfaces

by laser

radiation

is investigated

as a function

of laser

parameters

(fluence,

mode

as a function of laser parameters (fluence, mode Lehrstuhl fiir Lasertechnik der Rheinisch-Wesfdlischen

Lehrstuhlfiir Lasertechnik

der Rheinisch-Wesfdlischen

Technischen

Hochschule

Aachen,

SteinbachstraPe

15. D-52074

Aachen.

Germany

1. Introduction

interlevel

dielectric,

on

the

other

hand,

it

is

essential

to

 

have

a

low

dielectric

constant

to

reduce

signal

delays.

Microsystems

with

dimensions

ranging

from

the

nm to

Polymers

have

dielectric

constants

considerably

below

the mm scale depending

on the application

play a vital role

those

of ceramics

and

glass-ceramics.

Polyimides,

in par-

during

the

1990s

and

beyond

in

combining

mechanical,

 

ticular,

have

been

widely

explored

for

such

applications

optical

and

electrical

components.

The

development

of

because

they

have

low

dielectric

constants,

are thermally

microsystem

technology

is characterized

by

specific

fea-

stable,

and are photodefinable

for ease of patterning.

How-

tures

such

as the

high

density

of integration

of the single

ever,

they tend to absorb

water

with consequent

changes

in

elements,

3D

integration

of

the

elements

in

the

hybrid

dielectric

properties.

Also, they are difficult to planarize.

system,

the

use

of

new

materials

having

specific

proper-

another

important

feature

for multilevel

structures.

ties,

ing

and the overall

miniaturization

increase

in

levels

of

integration

as well.

and

The continu-

operational

in

During

the

high-precision

past

few

years

also

a

tendency

towards

processing of surfaces is observed [3]. Parti-

speeds

within

microsystems

will

demand

more

compact

cle

and photon

beams

have

begun

to take

over

important

and higher

density

packaging

and interconnection

schemes,

roles

in

the

fabrication

of

microsystems

[4,5].

This

is

i.e. the overall

trend

is towards

integrated

packages

of the

natural,

because

as the demands

of microfabrication

esca-

functional

components.

This

trend

poses

a

challenge

to

late,

the

need

for

greater

spatial

and

temporal

control

of

develop

new

materials

and processing

techniques

[l].

the processing

environment

increases: i.e. by directed pro-

Fiberglass-reinforced

polymer-matrix

composites,

due

cessing

in

a

manner

not

possible

by

immersion

of

a

to

their

good

combination

of

mechanical

 

and

chemical

material

in a conventional

isotropic liquid or plasma. Pro-

properties

and

cost,

and

polymers,

due,

for

example,

to

cessing

of

materials

with

directed

energy

beams

can

be

their

resistance

to

irradiation,

 

to

mechanical

deformation

used

to

generate

spatially

confined,

anisotropic

features.

and

to

solvents,

are

candidates

to

be

considered

in

the

Especially,

the

use

of

chemically

specific

energy

beams

design

of

multi-layer

thin-film

interconnecting

networks

within

microelectronic

and

optoelectronic

application

has

for

high-density

packaging

 

of

components.

Research

and

matured

significantly

within

the last years.

development

of

new

fibers

and

polymers

continues,

and

The

recent

advances

of

surface

processing

with

Ex-

the

potential

for

significant

 

improvements

-

and even

timer

laser radiation

[6] are illustrated

for the modification

technological

breaktroughs

-

seem

boundless

[2]. For the

of polymer

surfaces

for

metallization

and

the

removal

of

 

polymers

for

structuring

by

direct

processing

techniques

[7]. The

excitation

mechanisms

involved

in processing

of

* Corresponding author. Tel. + 49 241 8906 0 or 8906 146. fax

+49

polymers

can be classified

into

photothermal,

photophysi-

241 8906 121, e-mail postmaster@llt:rwth-aachen.de.

cal,

and

photochemical

[8,9].

The

investigations

of

poly-

[8,9]. The investigations of poly- 0168-583X/95/$09.50 0 1995 Elsevier Science B.V. All rights

0168-583X/95/$09.50

0

1995

Elsevier

Science

B.V.

All

rights

reserved

SSDI

0168-583X(95)00539-0

III. ADVANCED

MATERlALS

2 4 6 E.W. Kreutz et al. / Nucl. In&r. and Meth. in Phys. Rex

246

E.W. Kreutz et al. / Nucl. In&r. and Meth. in Phys. Rex B 105 (1995) 245-249

 

mers via modification

and

removal

are

addressed

to the

 

I

I

 

&PC

influence of material properties, laser parameters, and pro-

cessing variables on surface morphology, processing ge-

-PA

-a-

PBT

ometry, processing quality, and mechanisms of processing.

--c

ABS

-o-

SAN

-A-

POM

2.

Experimental

details

The

processing

is performed

in

ambient

air

at

atmo-

 

spheric

pressure.

The

KrF

Excimer

laser

radiation

source

(248

nm)

emits

pulsed

(pulse

energy

< 400

mJ,

fluence

< 30 J/cm21

laser radiation

of

25 ns

pulse

length

with

an

average

power

of

up

to

<

70

W

at a maximum

repetition

rate

of 400

Hz.

The

laser

beam

was

focussed

 

by

a tele-

 

scope

and a field

lens

to beam

cross-sections

 

yielding

the

power

density

(intensity)

or the energy density (fluence)

required

for

modification

or structuring with the position

of the optics

optically

and mechanically

controlled.

 
 

The

polymers

studied

are classified

into

those

contain-

 

ing

cyclic

benzene

or

styrene

molecular

groups

such

as

polystyrene

(PS),

acrylonitrile-butadiene-styrene

 

copoly-

mer

CABS),

styrene-acrylonitrile-copolymer

 

(SAN),

polybutadien

terephtalate

(PBT),

and

polycarbonate

(PC),

 

and

those

with

linear

C-C

and/or

C-R

(R

=

H,

N,

0)

molecular

groups

such

as polyamide

(PA),

polypropylene

 

t

I

(PP),

polyoxymethylene

(POM),

and polymethylmethacry-

IO2

IO3

late

(PMMA)

in order

to study

the

influence

of chemical

fluence F [mJ/cm*]

I

properties

via optical

properties

on the surface

processing.

Fig.

1. Roughness

ratio

versus

fluence

for different

polymers.

The thickness

of all the polymers

under

investigation

was

in

the

range

l-3

mm.

The

metallization

methods

are

physical

vapour

deposition

(PVD)

for

titanium

and

alu-

ness ratio after processing,

which

for low fluences

is

in

the

minum

and

electroplating

for

Ni

and

Ni/Cu

deposition,

range

of 1.3, increases

to values

in the range

4-9

for high

respectively.

The

pretreatment

processes

in

the

case

of

fluences depending

on the type

of polymer.

 

PVD

were

plasma

etching

and

laser

surface

modification.

 

SEM

(Fig.

2) exhibits

also

different

surface

morpholo-

For

the

electroplating

a

wet

chemical

pretreatment

and

gies of polymer surfaces during processing.

ABS

shows

a

laser

surface

modification

were

used.

uniformly

rough

surface

without

holes.

For

PA

a

pitted

The

processed

surfaces

are analyzed

using

optical

mi-

surface with isolated holes is observed at high fluences,

croscopy,

scanning

electron

microscopy

@EM),

and

opti-

probably caused by the outgassing

of

volatile

species

to

cal profilometry.

The geometric

properties

of the structur-

yield CO or CO,. At lower fluences

isolated

holes

are not

ized

surfaces,

especially,

the

surface

roughness,

the

re-

observed, that the processing

probably

occurs

without

moval

rates

and

depths,

have

been

derived

from

scanning

outgassing. In comparison,

POM

shows

a crinkled

surface

profilometty.

 

structure

with

some

isolated

holes

and cracks,

giving

evi-

 

dence for a thermal contribution

to the

surface

modifica-

tion and changes

in surface

morphology.

3.

Results

 
 

3.2. Metallization

 

3.1. Surface

modification

 
 

The

methods

of pretreatment

and

metallization

govern

In Fig.

1 the surface

For

roughness

non-irradiated

versus

fluence.

ratio

RJR,

surfaces

the

is plotted

roughness

the properties

of the metal

[lo].

For ABS

films

laser

deposited

pretreatment,

onto the poly- wet chemi-

R,

is

in

the

range

l-4

pm,

for

irradiated

surfaces

the

mer surfaces cal and plasma

etching

result

in the same

film

properties.

roughness

R,

generally

increases

as a function

of fluence

For

PA

the

laser

pretreatment

gives

comparable

or

even

with

the

magnitude

and

the

functional

behaviour

of

the

better

film

properties

than the pretreatment

by wet chemi-

changes

depending

on

fluence

of

the

laser

radiation,

on

cal

or

plasma

etching.

For

PBT

the

laser

pretreatment

optical

properties

of

the

polymers,

and

on

physical

pro-

offers

better

adhesion

for

Ti-films

and crack free deposi-

cesses

of interaction

(Section

4). For

example,

the rough-

tion

for

Al-films.

For

the

electroplated

Ni-films

no

im-

E. W. Kreutz et al. /Mucl. Instr. and Meth. in Phys. Res. B 105 (1995)

E. W. Kreutz et al. /Mucl.

Instr. and Meth. in Phys. Res. B 105 (1995) 245-249

247

0.5

/ Exp. Data: i i a PC , I 0 PBT / 0 ABS 0.4
/
Exp. Data:
i
i
a
PC
,
I
0
PBT
/
0
ABS
0.4
PS
n
.’ /
m
SAN
Linear Fit:
i
g
~~
PC
1
0.3
,a
-PBT
E
~~-
ABS
1
N
PS
5
a
$
s
0.2
‘Z
m
%
0.1
0.0
IO2
fluence F [mJlcm2]
Fig.
3. Ablation
depth
per
pulse
(average
values
for
10’
versus fluence for different
polymers
(repetition
rate
1 s-
3.3.
Structuring

The

Fig. 3 shows

a plot of ablation

depth

ablation

depth

generally

increases

z versus

linearly

as

-J

IO3

pulses)

’ ).

fluence.

a func-

tion of fluence

with

the

magnitude

depending

on fluence

of the laser radiation,

on

optical

properties

of

polymers,

and on physical

processes

of interaction

(Section

4).

and on physical processes of interaction (Section 4). Fig. 2. SEM micrographs of polymer surfaces (top
and on physical processes of interaction (Section 4). Fig. 2. SEM micrographs of polymer surfaces (top

Fig. 2. SEM micrographs

of polymer

surfaces

(top

ADS,

middle

PA, bottom

POM)

after

laser

irradiation

(fluence

3 J/cm’,

repeti-

tion

rate

1 s-l,

pulse

number

10).

repeti- tion rate 1 s-l, pulse number 10). provement is to be observed. adhesion with the

provement

is to be observed.

adhesion

with the roughness

The Al-films

properties.

ratio, which

on PC are crack

in

has only slightly

Thus,

with laser

For

ratios

is

<

free but show

agreement

changed

no improvement

radiation

higher roughness

improved

during

bad

PC and

The

results

are

for

[lo]

PBT

during

laser

pretreatment.

pretreated

in any

of adhesion

is observed

ratios

the

for

film

laser

pretreatment

on areas

roughness

adhesion

[lo].

2.

case

Fig.

projection

4.

Patterning

technique.

of

PMMA

surface

(fluence

3

J/cm’)

by

[lo]. 2. case Fig. projection 4. Patterning technique. of PMMA surface (fluence 3 J/cm’) by 111.ADVANCED

111.ADVANCED

MATERIALS

Fig. 4 gives an example of patterning PMMA with laser radiation considering a lithographic technique
Fig. 4 gives an example of patterning PMMA with laser radiation considering a lithographic technique

Fig. 4 gives an example of patterning PMMA with laser radiation considering a lithographic technique with a pro- jection mask showing a 2D structure typical for replica

techniques, which develops to a 3D structure with increas-

exhibits

lateral contours according to the exactness of the manufac- tured geometry of the projection mask. The edge steepness depends on the processing variables, especially processing fluence compared to threshold fluence of material removal (Section 4) and divergence of the beam homogenizer.

ing number of laser pulses. The 3D structure

4. Discussion

The excitation mechanisms during processing with laser radiation can be classified into photothermal, photophysi- cal, and photochemical [8,9] processes, depending on the laser parameters, processing variables, as well as proper- ties of the matter involved. Photothermal excitation is based on laser-induced heating with possibly subsequent phase transformation like melting and vaporization. Photo- physical excitation via phonons and carriers influences the corresponding density of states with possibly activation of matter, e.g. involving incubation. Photochemical excitation results e.g. in ionization, formation of radicals, in breaking of bonds with removal or matter, etc. In this regime of excitation processes [7], the maximum thickness of the layer processed within the interaction time (equals the pulse length t,) could be of the order of the thermal (D is thermal diffusivity) penetration depth

ablation depth per

pulse as seen from Fig. 3 for PC, PBT,

and ABS. For PP and POM without strong UV-absorbing

molecular groups low absorption coefficients and large

optical

energy

large ablation depth per pulse (Fig. 3).

of

UV photons leads to electronic and/or vibrational excita-

tions of chromophoric groups within organic polymers [ 1l-131. The transport of absorbed optical energy is deter- mined by the life time and density of excited states and the electronic coupling of different excited states. Depending on the laser parameters the processing variables, and the polymer properties three different excitation mechanisms

accordingly have

changes in chemistry and structure below the fluence threshold for material removal Fchcmica,, ii) photochemical and/or photothermal changes in geometry above the flu-

ence threshold for material

changes in structure and geometry above the fluence threshold for material changes Ftherma, [11,13]. For i) the removal rates are insignificant and polymer surfaces suffer from photochemical changes in chemical composition, molecular structure, surface energy, reactivity and electri- cal potential of the surface [ll,lS--191 implying a modified surface morphology and/or surface microstructure. Signif- icant removal occurs above the threshold fluence, where the ablation depth per pulse

in

penetration depths are observed [lo]. The optical

is

confined

more

to

the photon-matter

the

bulk

interaction

region

yielding

the absorption

During

to be considered: i) photochemical

removal Fchemica,, iii) thermal

2 = d14F/Fchemid

>

248

E. W. Kreutz

et al./Nucl.

Instr.

and Meth.

in Phys.

Rex

B IO5 (1995) 245-249

zth = (4Dt,)

l’*,

 

(1)

 

varies

logarithmically

with

laser

fluence

[ll-131

 

assuming

or

the

optical

(a

is

absorption

coefficient)

penetration

a critical

density

of

excited

states

for

material

removal.

depth

The

driving

force

for

the

material

removal

is

the

large

Iopt = a-1,

(2)

increase

in specific

volume

of the fragments

compared

to

 

the

volume

of the

original

polymer.

For

large

irradiation

depending

on

which

is

larger.

Though

the

density,

heat

doses

or high

numbers

of pulses

polymers

show

thermal

capacity

and thermal

conductivity

are different, the result-

degradation

with

the

surface

morphology

turning

from

ing thermal

diffusivity

for all the investigated

polymers

is

rough

to smooth

due

to cumulative

heating

and

transient

in the

range

0.13-0.15

X lop6

m*/s

for

the

present

ex-

melting.

 

perimental

conditions.

Following

Eq. (1) the thermal

pene-

 

Due

to their

similar

optical

properties

[lo]

SAN

and

tration

depth,

thus,

is about

0.11

p.rn for

all the

investi-

ABS

should

exhibit

the

same

roughness

ratios

after

laser

gated

polymers.

This

indicates,

that thermal

influences

due

pretreatment.

As obviously

seen

from

Fig.

1 SAN

shows

a

to heat conduction

are nearly

equal

for all the investigated

stronger

increase

of roughness

ratio with fluence. A contri-

polymers

and their

optical

properties

mainly

determine

the

bution

of

thermal

removal

is assumed

to originate

in the

processing

characteristics.

The

dissipation

of

energy

be-

additional

increase

of

the

roughness

ratio,

because

the

yond the volume,

which

is influenced

during

photon-matter

threshold

for thermal

degradation

is observed

at 0.3 J/cm*,

interaction,

is suppressed.

and

for

fluences

just

below

the

degradation

threshold

Following

the

outline

above

the

absorbed

optical

en-

thermal

removal

is the dominant

process

[l&12]. A quali-

ergy

is

confined

to

a

small

surface

region,

which

is

tatively

similar

characteristic

is observed

for POM

with

a

determined

by the optical

penetration

depth

(Eq.

(2)).

The

thermal

degradation

threshold

of

3 J/cm*

and

a removal

polymers containing

styrene

or

benzene

exhibit

a

small

threshold

of 1.1 J/cm2

both

determined

by SEM

(Fig.

2).

optical penetration

depth

[lo],

which

is

due

to

strong

At

fluences

above

1 J/cm*

the

roughness

ratios

for

PC

absorption

at 248 nm [14]. The absorbed

optical

energy

is

and

PBT

behave

properties

similarly

in agreement

[lo].

In comparison,

with their similar

confined

to

the

surface

region,

which

leads

to

a

small

optical

ABS shows a satu-

ration of roughness ratio at high fluences, probably caused by the absorbing group of the
ration of roughness ratio at high fluences, probably caused by the absorbing group of the

ration

of roughness

ratio at high fluences,

probably

caused

by

the

absorbing

group

of

the

chromophores.

Polymers

E. W. Kreutz

et al. /Nucl.

Instr.

and Meth.

in Phys.

Res. B 105 (1995) 245-249

249

by melting

of the surface.

 

with similar molecular structure show the same absorption

 
 

The

optical

penetration

depth

of

PBT

is

nearly

two

process,

those

with

similar

optical

properties

the

same

times

that

of PC

[lo],

because

PC contains

two

and

PBT

processing properties.

Irradiation

with

laser

radiation

is

a

one

benzene

group

per

monomer.

The

optical

penetration

suitable pretreatment

for metallization

of polymer surfaces

depth

of

ABS

and

SAN

is

the

same

[lo],

since

both

in those

cases,

where

the original

surface

roughness

can be

contain

one

styrene

group

per

monomer.

This

indicates

increased

by

a factor

of

2. The

properties

of the

metallic

that

the

density

of

the

chromophores

in

the

polymers

films

on polymers

are comparable

or even

better

than

for

affects

the

removal

of

polymers

and

the

modification

of

the pretreatments

plasma

etching

and

wet

chemical

etch-

polymer

surfaces

[ 131. For PA the optical

penetration

depth

ing.

is less

than for the other

linear

polymers,

probably because

 

of the additional

absorption

of the CO group

[14]. For PA

 

we

observe

significant

removal

for

fluences

>

1 J/cm’,

References

though

the

threshold

fluence

amounts

0.18

J/cm’,

which

gives

indication

for an incubation effect [20]. These results

confirm

the main

influence

of the optical

properties

on the

removal

of polymers

by laser

radiation,

which is of photo-

chemical

nature

in

the

range

of

fluences

investigated

as

also

supported

by

the

logarithmic

dependence

of ablation

depth

on fluence

(Fig.

3).

The requirements

necessary

for processing

of polymers

with

laser

radiation

are given

according

to the applications

of the structured

polymers

which

claim

for special

proper-

ties

such

as temperature

stability, hardness, or inertness.

The material

removal

of polyurethane

with

soot,

for exam-

ple,

exhibits

a deposit

of fused

material

at the

machined

edge

zone

[3] resulting

from

a coalescence

between

the

filler

material

and

the

base

material.

Therefore,

these

surfaces

developing

during

manufacturing

of structures

are

changing

continuously

their

properties,

so

the

surface

is

not suitable

for the further

processing

via removal.

On the

other

hand,

PMMA

(Fig.

4) exhibits

high

edge

steepness

and

flat processed

surfaces

with

minor

deposits

of vapor-

ized material,

so this material

meets

all processing

require-

ments

for microstructuring

of polymers.

5. Conclusion

The

modification

of polymers

by Excimer

laser

radia-

tion

is investigated

giving

information

on the

roughening

of the surfaces

and the thresholds

of removal.

The optical

properties

of the polymers

affect

the processing

properties

[l]

G.Y.

Shin, Adv.

Mater.

Processes

137 (1990)

47.

 

[2]

T.J.

Reinhart,

Adv.

Mater.

Processes

137 (1990)

33.

[3]

H.K.

Tlinshoff

and

J. Mommsen,

NATO

ASI

Ser.

E: Appl.

Sci.

265 (1994)

221,

and references

therein.

 

[4]

D.I. Flamm,

Solid

State

Technol.

36 (1993)

49.

[5]

D.J.

Ehrlich,

NATO

ASI

Ser.

E: Appl.

Sci.

265

(1994)

307.

and references

therein.

[6]

A. Gasser,

E.W.

Kreutz

and K. Wissenbach,

Proc.

SPIE

1020

(1988)

70.

 

[7]

E.W.

Kreutz,

H.

Frerichs,

M.

Mertin.

M.

Wesner

and

W.

Pfleging,

Appl.

Surf.

Sci. in press.

 

[8]

T.J.

Chuang,

Surf.

Sci.

Rep.

3 (1983)

1.

[9]

D.J.

Ehrlich

and

T.Y.

Tsao

(eds.),

Laser

Microfabrication:

 

Thin

Film

Processes

and

 

Lithography

(Academic

Press,

Boston,

MA,

1989).

[lo]

H. Frerichs,

J. Stricker,

D.A.

Wesner

and E.W.

Kreutz,

Appl.

Surf.

Sci.,

in press.

 

[ll]

R. Srinivasan

and

B. Braren,

J. Polym.

Sci.

22 (1984)

2601.

[12]

R. Srinivasan,

M.A.

Smrtic

and S.V.

Babu,

J. Appl.

Phys.

59

(1986)

3861.

 

[13]

G.H.

Pettit

and

R. Sauerbrey,

Appl.

Phys.

A 56 (1993)

51.

[14]

M.

Hesse,

H.

Meier

and

B.

Zeeh,

in:

Spektroskopische

Methoden

in

der

organischen

Chemie

(Thieme.

Stuttgart.

1987).

 

[15]

Y.S.

Liu and

H.S.

Cole,

Chemtronics

4 (1989)

209.

 

[16]

H. Niino

and A. Yabe,

Appl.

Phys.

Lett.

60 (1992)

2697.

[17]

N.J.

Chou

and

C.H.

Tang,

J. Vat.

Sci.

Technol.

A 2 (1984)

751.

[18]

E. Ochiello

and F. Garbassi,

 

J. Mat.

Sci.

24 (1989)

569.

 

[19]

J.T.C.

Yeh,

J. Vat.

Sci. Technol.

A 4 (1986)

653.

[20]

M.

Stuke,

Y.

Zangh

and

S.

Kiiper,

Mat.

Res.

Sot.

Symp.

Proc.

101 (1989)

139.

 
and S. Kiiper, Mat. Res. Sot. Symp. Proc. 101 (1989) 139.   III. ADVANCED MATERIALS

III. ADVANCED

MATERIALS