Nuclear Instruments and Methods in Physics Research B 105 (1995) 245-249

__. NINI B
Beam Interactions
@ with Materials 6 Atoms

ELSEVIER

Processing of polymer surfaces by laser radiation

E.W. Kreutz *, H. Frerichs, J. Stricker, D.A. Wesner
Lehrstuhlfiir Lasertechnik der Rheinisch-Wesfdlischen Technischen Hochschule Aachen, SteinbachstraPe 15. D-52074 Aachen. Germany

Abstract
The processing of polymer surfaces by laser radiation is investigated as a function of laser parameters (fluence, mode 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.

1. Introduction interlevel dielectric, on the other hand, it is essential to

Microsystems with dimensions ranging from the nm to
the mm scale depending on the application play a vital role
during the 1990s and beyond in combining mechanical,
optical and electrical components. The development of
microsystem technology is characterized by specific fea-
tures such as the high density of integration of the single
elements, 3D integration of the elements in the hybrid
system, the use of new materials having specific proper-
ties, and the overall miniaturization as well. The continu-
ing increase in levels of integration and in operational
speeds within microsystems will demand more compact
and higher density packaging and interconnection schemes,
i.e. the overall trend is towards integrated packages of the
functional components. This trend poses a challenge to
develop new materials and processing techniques [l].
Fiberglass-reinforced polymer-matrix composites, due
to their good combination of mechanical and chemical
properties and cost, and polymers, due, for example, to
their resistance to irradiation, to mechanical deformation
and to solvents, are candidates to be considered in the
design of multi-layer thin-film interconnecting networks
for high-density packaging of components. Research and
development of new fibers and polymers continues, and
the potential for significant improvements - and even
technological breaktroughs - seem boundless [2]. For the
* Corresponding author. Tel. + 49 241 8906 0 or 8906 146. fax
+49 241 8906 121, e-mail postmaster@llt:rwth-aachen.de.
have a low dielectric constant to reduce signal delays.
Polymers have dielectric constants considerably below
those of ceramics and glass-ceramics. Polyimides, in par-
ticular, have been widely explored for such applications
because they have low dielectric constants, are thermally
stable, and are photodefinable for ease of patterning. How-
ever, they tend to absorb water with consequent changes in
dielectric properties. Also, they are difficult to planarize.
another important feature for multilevel structures.
During the past few years also a tendency towards
high-precision processing of surfaces is observed [3]. Parti-
cle and photon beams have begun to take over important
roles in the fabrication of microsystems [4,5]. This is
natural, because as the demands of microfabrication esca-
late, the need for greater spatial and temporal control of
the processing environment increases: i.e. by directed pro-
cessing in a manner not possible by immersion of a
material in a conventional isotropic liquid or plasma. Pro-
cessing of materials with directed energy beams can be
used to generate spatially confined, anisotropic features.
Especially, the use of chemically specific energy beams
within microelectronic and optoelectronic application has
matured significantly within the last years.
The recent advances of surface processing with Ex-
timer laser radiation [6] are illustrated for the modification
of polymer surfaces for metallization and the removal of
polymers for structuring by direct processing techniques
[7]. The excitation mechanisms involved in processing of
polymers can be classified into photothermal, photophysi-
cal, and photochemical [8,9]. The investigations of poly-

0168-583X/95/$09.50 0 1995 Elsevier Science B.V. All rights reserved

SSDI 0168-583X(95)00539-0 III. ADVANCED MATERlALS
246 E. W. Kreutz et al. / Nucl. In&r. and Meth. in Phys. Rex B 105 (1995) 245-249

I I
mers via modification and removal are addressed to the
&PC
influence of material properties, laser parameters, and pro-
-PA
cessing variables on surface morphology, processing ge- -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)
t I I
molecular groups such as polyamide (PA), polypropylene
IO2 IO3
(PP), polyoxymethylene (POM), and polymethylmethacry-
late (PMMA) in order to study the influence of chemical fluence F [mJ/cm*]
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 roughness ratio RJR, is plotted the properties of the metal films deposited onto the poly-
versus fluence. For non-irradiated surfaces the roughness mer surfaces [lo]. For ABS laser pretreatment, wet chemi-
R, is in the range l-4 pm, for irradiated surfaces the 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) 245-249 247

0.5

/
Exp. Data: i
a PC i
,
0 PBT I
/
0.4 0 ABS
n PS .’
m SAN
/

Linear Fit:
g i
~~ PC
1 0.3
,a -PBT
E
1 ~~- ABS
N PS
5
a
$
s 0.2
‘Z
m
%

0.1

0.0 -J

IO2 IO3
fluence F [mJlcm2]
Fig. 3. Ablation depth per pulse (average values for 10’ pulses)
versus fluence for different polymers (repetition rate 1 s- ’ ).

3.3. Structuring

Fig. 3 shows a plot of ablation depth z versus fluence.

The ablation depth generally increases linearly as 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).

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).

provement is to be observed. The Al-films on PC are crack

free but show bad adhesion properties. The results are in
agreement with the roughness ratio, which has only slightly
changed for PC and PBT during laser pretreatment. Thus,
no improvement of adhesion on areas pretreated with laser
radiation [lo] is observed for roughness ratios < 2. For
higher roughness ratios the film adhesion in any case is Fig. 4. Patterning of PMMA surface (fluence 3 J/cm’) by
improved during laser pretreatment [lo]. projection technique.

111.ADVANCED MATERIALS
248 E. W. Kreutz et al./Nucl. Instr. and Meth. in Phys. Rex B IO5 (1995) 245-249
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-
ing number of laser pulses. The 3D structure 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.
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
zth = (4Dt,) l’*,
or the optical (a is absorption coefficient) penetration
depth
Iopt = a-1,
depending on which is larger. Though the density, heat
capacity and thermal conductivity are different, the result-
ing thermal diffusivity for all the investigated polymers is
in the range 0.13-0.15 X lop6 m*/s for the present ex-
perimental conditions. Following Eq. (1) the thermal pene-
tration depth, thus, is about 0.11 p.rn for all the investi-
gated polymers. This indicates, that thermal influences due
to heat conduction are nearly equal for all the investigated
polymers and their optical properties mainly determine the
processing characteristics. The dissipation of energy be-
yond the volume, which is influenced during photon-matter
interaction, is suppressed.
Following the outline above the absorbed optical en-
ergy is confined to a small surface region, which is
determined by the optical penetration depth (Eq. (2)). The
polymers containing styrene or benzene exhibit a small
optical penetration depth [lo], which is due to strong
absorption at 248 nm [14]. The absorbed optical energy is
confined to the surface region, which leads to a small
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 penetration depths are observed [lo]. The optical
energy is confined more to the bulk region yielding in
large ablation depth per pulse (Fig. 3).
During the photon-matter interaction the absorption of
UV photons leads to electronic and/or vibrational excita-
tions of chromophoric groups within organic polymers
[ 1 l-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 to be considered: i) photochemical
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 removal Fchemica,, iii) thermal
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
2= d14 F/Fchemid >
(1)
varies logarithmically with laser fluence [ll-131 assuming
a critical density of excited states for material removal.
The driving force for the material removal is the large
increase in specific volume of the fragments compared to
(2)
the volume of the original polymer. For large irradiation
doses or high numbers of pulses polymers show thermal
degradation with the surface morphology turning from
rough to smooth due to cumulative heating and transient
melting.
Due to their similar optical properties [lo] SAN and
ABS should exhibit the same roughness ratios after laser
pretreatment. As obviously seen from Fig. 1 SAN shows a
stronger increase of roughness ratio with fluence. A contri-
bution of thermal removal is assumed to originate in the
additional increase of the roughness ratio, because the
threshold for thermal degradation is observed at 0.3 J/cm*,
and for fluences just below the degradation threshold
thermal removal is the dominant process [l&12]. A quali-
tatively similar characteristic is observed for POM with a
thermal degradation threshold of 3 J/cm* and a removal
threshold of 1.1 J/cm2 both determined by SEM (Fig. 2).
At fluences above 1 J/cm* the roughness ratios for PC
and PBT behave similarly in agreement with their similar
optical properties [lo]. In comparison, ABS shows a satu-
 E. W. Kreutz et al. /Nucl. Instr. and Meth. in Phys. Res. B 105 (1995) 245-249
ration of roughness ratio at high fluences, probably caused
by melting of the surface.
The optical penetration depth of PBT is nearly two
times that of PC [lo], because PC contains two and PBT
one benzene group per monomer. The optical penetration
depth of ABS and SAN is the same [lo], since both
contain one styrene group per monomer. This indicates
that the density of the chromophores in the polymers
affects the removal of polymers and the modification of
polymer surfaces [ 131. For PA the optical penetration depth
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’,
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
249
by the absorbing group of the chromophores. Polymers
with similar molecular structure show the same absorption
process, those with similar optical properties the same
processing properties. Irradiation with laser radiation is a
suitable pretreatment for metallization of polymer surfaces
in those cases, where the original surface roughness can be
increased by a factor of 2. The properties of the metallic
films on polymers are comparable or even better than for
the pretreatments plasma etching and wet chemical etch-
ing.
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III. ADVANCED MATERIALS