ARTICLE IN PRESS

Vacuum 81 (2006) 325–328

www.elsevier.com/locate/vacuum

Plasma pre-treatment of liquid crystal polymer and subsequent

metallization by PVD
B. Wang, W. Eberhardt, H. Kück
Hahn-Schickard-Institute for Micro Assembly Technology, Breitscheidstr. 2b, 70174 Stuttgart, Germany
Received 14 July 2005; received in revised form 15 May 2006; accepted 24 May 2006

Abstract

In this paper surface modification of a liquid crystal polymer (LCP) substrate by oxygen containing plasma pre-treatment and
subsequent Cu/Cr deposition by physical vapour deposition (PVD) technique is described. By pre-treatment with oxygen containing
plasma more volatile reaction products are generated compared to argon plasma pre-treatment as is shown by the etching rate. The small
molecule fragments generated during the pre-treatment process are analyzed by mass spectrometry. After the pre-treatment metal layers
with suitable adhesion strength even after 1000 cycles of thermal shock are obtained.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Plasma; Liquid crystal polymer (LCP); Adhesion; Metallization; Physical vapour deposition (PVD)

1. Introduction modify most polymer surfaces, regardless of their substrate

Liquid crystal polymers (LCP) are important materials
for molded interconnect devices (MID) due to their
excellent properties, e.g. high temperature resistance,
chemical stability, low thermal expansion coefficient [1]
as well as excellent flow properties for the fabrication of
fine structures by molding techniques [2]. Metallization of
polymers to produce metal lines on the plastic substrates
is a key technology for MID [3–5]. Therefore electroless
plating is a common method [5]. One disadvantage of
electroless plating is the roughness of the metallized LCP
substrate surfaces depending on the adhesion strength
required. Physical vapour deposition (PVD) is another
widely used method for metallization of polymers [6–9]. A
major advantage of PVD is that there is no significant
roughening of the surface.
Over the years, several methods have been developed to
modify the surface of polymer substrates before metalliza-
tion in order to improve the adhesion between a metal layer
and polymer. Low pressure and low temperature non-
equilibrium plasma activation is a suitable method for pre-
treating the surface. The excited species of the plasma can
Corresponding author. Fax: +49 711 68583705.
E-mail address: eberhardt@hsg-imat.de (W. Eberhardt).
pattern geometry and chemical reactivity. However, the
surface modification effect strongly depends on the gas
combination used in the plasma process as well as the
substrate material [10–12].
In this work, we report on the pre-treatment of LCP
substrates in different plasma atmospheres before deposi-
tion of a Cu/Cr layer system. Argon, oxygen and a mixture
of argon and oxygen are used. The properties related to
the plasma pre-treatment are presented. The adhesion
strength between the metal layer and LCP substrate is also
evaluated.
2. Experiment
Molded tensile bars made from a commercially available
LCP containing about 40% mineral filler (Vectra E820i
from Ticona GmbH) were used as substrates. A typical
chemical structure of LCP is shown in Fig. 1. Before metal
deposition the substrate was cleaned in an aqueous
cleaning agent (Mucasol from Merz Consumer Care
GmbH, Frankfurt am Main, Germany) at 50 1C for
3 min using ultrasonic agitation and rinsed with deionized
water.

0042-207X/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2006.05.009
 ARTICLE IN PRESS
326 B. Wang et al. / Vacuum 81 (2006) 325–328

O O O

C O C O C
O O

O C O C O

Fig. 1. Typical chemical structure of liquid crystal polymer (LCP).

Before the Cu/Cr metal layers were deposited by the 30

RF-sputter system (Leybold Z400), in situ plasma pre-
treatment was carried out using a radio frequency electric

Etching rate (µg min-1 cm-2)

25
field of 13.56 MHz. The copper and chromium targets with
a purity of 99.99% and a diameter of 75 mm were mounted 20
on a water-cooled copper plate. Before a copper layer with
a thickness of about 1.5 mm was sputtered on the substrate, 15
a thin chromium layer of less than 100 nm was deposited as
an interlayer. The deposition rate of copper and chromium 10
is about 10 and 3 mm/h, respectively. All metal layers were
prepared at a basic vacuum pressure below 3  10 3 Pa. 5
A mass spectrometer (HPQ2-S, from MKS instruments
Deutschland GmbH, Dresden, Germany) was used to 0
monitor the residual gas during the plasma pre-treatment. Ar Ar/Oxygen 1/1 Oxygen
The pull-off test was performed using a Dage series 4000 Fig. 2. Etching rate of LCP substrates depending on the process gas used.
test equipment as described in Ref. [3] in order to evaluate
the adhesion strength between the Cu/Cr metal layer and
the LCP polymer. Circles with a diameter of 2.3 mm were 12 Before pre-treatment During pre-treatment
patterned in the metal layer by laser ablation using a
Partial pressure (x10-6 mbar)

frequency tripled Nd:YAG laser at 355 nm. Metal cylinders 10

were bonded with an epoxy based resin upright onto a
metallization test pad. After curing, the cylinders were 8
pulled off from the pad at a rate of 0.7 mm/s and the force
6
was measured. The adhesion strength values were based on
25 individual measurements each.
4
Thermal shock has been carried out up to 1000 cycles in
a thermal shock chamber. One cycle means that the 2
samples were heated up to 125 1C and kept for 10 min,
cooled down to 40 1C within 10 s and kept at this 0
temperature for 10 min. The adhesion strength was 12 14 17 18 28 44
evaluated after different numbers of cycles. Mass

Fig. 3. Partial pressures of different species before and during argon

3. Result and discussion plasma pre-treatment.

In a glow discharge at low pressure, i.e., o1 mbar, and
frequency 41 MHz, heavy particles, such as gas molecules
and ions, are essential for modifying the polymer surface.
The interaction of the particles with the substrate surface
strongly depends on the kinetic energy as well as on the
species of the particles. Thereby cleaning the surface is one
of the major effects of plasma pre-treatment. Removal of
contaminants from the surface results in a weight loss of
the treated polymer. Furthermore, weakly bound layers
can also be removed from the surface. By the reaction
of atomic oxygen with the surface carbon atoms, more
volatile reaction products e.g. CO2 were formed. This
means that, by a combination of physical sputtering with
chemical and photochemical reactions of the reactive
plasma, the etching rate of oxygen-containing plasma is
higher than that of argon and tends to increase with higher
oxygen concentration. Fig. 2 shows the etching rates of the
surfaces depending on different plasma atmospheres used.
The partial pressure of typical small molecule fragments
before and during argon plasma pre-treatment is shown in
Fig. 3. The total pressure of the vacuum chamber was
9  10 3 mbar. Under these conditions, the plasma pre-
treatment provides a low temperature discharge. In the
discharge zones there are free electrons with energies of
1–10 eV, which is equivalent to a temperature of 104–105 K.
However, the temperature of the ions and molecules is
 ARTICLE IN PRESS
B. Wang et al. / Vacuum 81 (2006) 325–328 327

12 Before pre-treatment During pre-treatment

8 Argon plasma Oxygen plasma

Partial pressure (x10-6 mbar)

Partial pressure (x10-6 mbar)

10
6
8

6 4

4 2

2
0
0 2 4 6 8 10
0
12 14 17 18 28 44 Proceesing time [min]
Mass Fig. 5. Partial pressure of mass 28 during plasma pre-treatment
dependence on processing time.
Fig. 4. Partial pressures of different species before and during oxygen
plasma pre-treatment.

Adhesion strength without pretreatment

close to that of the environment. This means that the
Adhesion strength increase
temperature of electrons is higher by a factor of 10–100
than that of ions and molecules. In such a non-equilibrium 6
Adhesion strength [N/mm2]

plasma environment, elastic electron–molecule collisions

occur causing ionization, excitation and dissociation
reactions. During the argon plasma pre-treatment process,
physisorbed contaminants are removed by interaction of
the plasma. As observed in Fig. 3 the partial pressure of
OH (mass 17) and H2O (mass 18) is slightly increased
during the pre-treatment process. The partial pressure
of mass 28 (N2, C2H4, CO) and mass 44 (C3H8, CO2) is
also increased due to the generation of volatile reaction
products. Argon plasma usually generates free radicals on
the substrate surface, therefore it is difficult to convert the
molecules to volatile compounds. Predominantly polymer-
ization or recombination are probable processes. However,
in an oxygen-containing plasma surface carbon atoms react
with atomic oxygen and generate more volatile reaction
products such as CO (mass 28) and CO2 (mass 44).
Therefore, the increase of the partial pressure of the former
species in an oxygen plasma atmosphere is higher than that
in an argon plasma atmosphere (Fig. 4).
In Fig. 5 the partial pressure of mass 28 during the
plasma pre-treatment is shown for two different gases
depending on the processing time. It was observed that the
partial pressure was relatively high during the first minute
before dropping off significantly. When the plasma was
switched off after 8 min the partial pressure of the observed
species decreased further. As mentioned above, volatile
reaction products are generated during ion bombardment
until the pre-treatment process is stopped.
Fig. 6 shows the adhesion strength of Cu/Cr PVD layers
on an LCP substrate pre-treated with oxygen plasma at
different pressures. As expected, the adhesion strength
between Cu/Cr layer and LCP with plasma pre-treatment
was better than that of untreated samples. In oxygen-
containing plasma, besides a cleaning process two mod-
ification processes occur simultaneously. First the polymer
4
2
0
3.5 5.0 9.0 10
Oxygen pressure [10-3 mbar]
Fig. 6. Adhesion strength of Cu/Cr PVD layers on LCP substrates after
oxygen pre-treatment with different pressure.
surface is etched by the reactions of atomic oxygen with the
surface carbon atoms giving volatile reaction products, e.g.
CO2. Furthermore an increase in the pressure of oxygen
gives a higher etching rate. In addition oxygen-containing
functional groups at the polymer surface are formed by
reactions between the active species from the plasma and
the surface atoms. The concentration of active species in
the plasma increases with high oxygen content accelerating
the formation of oxygen-containing functional groups.
Therefore, the adhesion strength is improved with increas-
ing oxygen pressure during plasma pre-treatment. How-
ever, with too high oxygen concentration above ca.
12  10 3 mbar only the etching rate is enhanced but the
formation of additional functional groups on the polymer
surface is saturated, therefore no further adhesion im-
provement was observed.
The adhesion strength between the Cu/Cr layer and LCP
after thermal shock is given in Fig. 7. It is shown that the
 ARTICLE IN PRESS
328 B. Wang et al. / Vacuum 81 (2006) 325–328

0 cycle 200 cycles 500 cycles 1000 cycles 4. Conclusion

6 Pre-treatment of LCP substrates with an oxygen-

containing plasma increases the etching rate of the
substrates. Mass spectrometry during the pre-treatment
Adhesion strength [N/mm2]

process shows the formation of small molecules indicating

the modification of the plastic surface. Best adhesion of a
4 sputtered Cu/Cr layer on LCP is achieved with a pre-
treatment in a pure oxygen plasma atmosphere. The
adhesion strength of Cu/Cr on LCP pre-treated with
oxygen plasma is not reduced significantly after 1000 cycles
of thermal shock.
2

References

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Fig. 7. Adhesion strength of PVD Cu/Cr layers on LCP substrates before
and after thermal shock.
pre-treatment with oxygen plasma improves the adhesion
of the Cu/Cr layer compared to that for the other samples.
For the untreated samples, as well as for the samples pre-
treated with argon plasma, no decrease of the adhesion was
observed with increasing number of temperature cycles.
The adhesion strength of the oxygen pre-treated samples
dropped slightly after 1000 temperature cycles but is still
higher than that of the samples mentioned above. After
1000 temperature cycles still 5.0 N/mm2 are achieved.
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