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Changes in the adhesion strength

between copper thin films and
polyimide substrates after heat
treatment
a b c
Satoru Iwamori , Takehiro Miyashita , Shin Fukuda ,
d e f
Shouhei Nozaki , Kazufuyu Sudoh & Nobuhiro Fukuda
a
Central Research Institute, Mitsui Toatsu Chemicals, Inc.,
1190 Kasama-cho, Sakae-ku, Yokohama, Japan 247
b
Central Research Institute, Mitsui Toatsu Chemicals, Inc.,
1190 Kasama-cho, Sakae-ku, Yokohama, Japan 247
c
Central Research Institute, Mitsui Toatsu Chemicals, Inc.,
1190 Kasama-cho, Sakae-ku, Yokohama, Japan 247
d
Central Research Institute, Mitsui Toatsu Chemicals, Inc.,
1190 Kasama-cho, Sakae-ku, Yokohama, Japan 247
e
Central Research Institute, Mitsui Toatsu Chemicals, Inc.,
1190 Kasama-cho, Sakae-ku, Yokohama, Japan 247
f
Central Research Institute, Mitsui Toatsu Chemicals, Inc.,
1190 Kasama-cho, Sakae-ku, Yokohama, Japan 247
Published online: 02 Apr 2012.

To cite this article: Satoru Iwamori , Takehiro Miyashita , Shin Fukuda , Shouhei Nozaki ,
Kazufuyu Sudoh & Nobuhiro Fukuda (1997) Changes in the adhesion strength between
copper thin films and polyimide substrates after heat treatment, Journal of Adhesion
Science and Technology, 11:6, 783-795, DOI: 10.1163/156856197X00912

To link to this article: http://dx.doi.org/10.1163/156856197X00912

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 Changes in the adhesion strength between copper thin

films and polyimide substrates after heat treatment

SATORU IWAMORI,* TAKEHIRO MIYASHITA, SHIN FUKUDA,

Downloaded by [Michigan State University] at 11:53 07 February 2015

SHOUHEI NOZAKI, KAZUFUYU SUDOH and NOBUHIRO FUKUDA

Central Research Institute, Mitsui ToatsuChemicals,Inc.,
1190 Kasama-cho, Sakae-ku, Yokohama,Japan 247

Received in final form 16 December 1996

Abstract-The adhesion strength between a copper (Cu) thin film and a polyimide [pyromelliticdianhy-
dride-oxydianiline (PMDA-ODA)]substrate is reduced by heat treatment at 150°C in air. In this work,
we determinedthe changes in adhesion strength between Cu films and polyimide substratesusing Auger
electron spectroscopy (AES), attenuated total reflection Fourier-transforminfrared spectroscopy(FTIR),
and X-ray photoelectronspectroscopy(XPS). The analysis showed that the weak boundary layer (WBL)
shifted towards the Cu interface as the heat treatment time was increased. To confirm this shift, we
looked at two other polyimide substrates: biphenyl dianhydride-p-phenylene diamine (BPDA-PDA)and
biphenyl dianhydride-oxydianiline(BPDA-ODA).Comparingthe adhesion strength for the Cu thin film,
the adhesion strength was high for the Cu/PMDA-ODA and Cu/BPDA-ODA laminates, but very low
for the Cu/BPDA-PDA laminate. One of the possible reasons for this behavior could be that the ether
moiety between the two benzene rings in ODA is related to the adhesion between a Cu film and an
02-plasma-treatedpolyimide (PI) substrate. The relationshipbetween the adhesion strength and chemical
bonding states is also discussed. We conclude that a Cu thin film sputtered onto a PI substrate is apt to
peel at the oxidized interface, due to the heat treatment.

Keywords:Copper; polyimide; adhesion strength; weak boundary layer.

1. INTRODUCTION

Polyimides (PIs) have good thermal stability, chemical stability, and excellent me-
chanical properties such as a high modulus of elasticity. For these reasons, copper
(Cu)-deposited PI films are commonly used in printed circuit boards (PCBs). Exten-
sive studies on the relationship between Cu and PI show that Cu reacts weakly with
the ether oxygen in the oxydianiline (ODA) part of PI [1-3]. Therefore, Perstin and
Pashunin [4] reported that the chemical bonding state at the interface between Cu and
PI was due to the formation of Cu+ -0- -C linkages. Chou and Tang [2] reported

*To whom correspondenceshould be addressed.

 784

that chromium (Cr) and nickel (Ni) reacted with the pendent oxygen in a PI substrate,
whereas Cu and silver did not. Pappas et al. [5] reported that the adhesion strength be-
tween Cu and PI was improved by 0+ ion treatment. Chambers and Chakravorty [6]
reported that Cu atoms in contact with a PI overlayer were completely oxidized to
CuO after being exposed to air for several days.
A serious problem in Cu-deposited PI films is that the adhesion strength between
Cu and PI is reduced after heat treatment at 150°C in air. Shih et al. [7] reported that
Cu catalyzed the oxidation of PI films after heat treatment at 350°C for 1 h in air.
Burrell et al. [8] also reported that Cu catalyzed the oxidation of PI film in air. Cham-
bers et al. [9] reported that for Cu/PI laminates, metal oxidation was accompanied
by Cu out-diffusion and PI decomposition after being exposed to high humidity (85%
relative humidity) air at 85 °C. Despite extensive research on Cu/PI films, there is lit-
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tle available on the relationship between the adhesion strength and chemical bonding
of Cu to PI, especially the relationship between the adhesion strength and the weak
boundary layer (WBL), which is the layer in which peeling occurs. In this work, we
therefore studied this relationship by measuring the peel strength and evaluating the
chemical bonding states at the peeled surfaces of Cu-deposited films and PI substrates
for three different substrates, different heat treatment times (at 150°C), and with and
without 02-plasma treatment.

2. MATERIALS AND METHODS

The PI substrates used were Kapton-V (PMDA-ODA, TORAY-du Pont Chemical),

Upilex-R (BPDA-ODA, Ubekousan), and Upilex-S (BPDA-PDA, Ubekousan). Fig-
ure 1 shows the structural formulae of these substrates. Figure 2 is a schematic
diagram of the sputtering system (HSM-521, Shimazu Co., Ltd.) used to deposit
Cu on the PI substrates. Table 1 lists the conditions for the 02-plasma treatment and
Cu sputtering. PI substrates were treated with the 02 plasma before the Cu sputtering.
Except for the measurement of the adhesion strength as a function of the 02-plasma
treatment time, the 02-plasma treatment time was normally 5 min. A 0.03-mm-thick
layer of Cu was plated up on the Cu-sputtered thin film. This Cu layer was then pat-
terned using 2-mm-wide IC tapes as resists and a FeCl3 solution. After the patterning,
the Cu thin film was heat-treated at 150°C in air for 24, 48, or 72 h.

Table 1.
Experimentalconditionsfor 02-plasma treatment and copper deposition
 785
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Figure 1. Structural formulae of the polyimides used as substrates in copper/polyimide laminates.

(a) Kapton-V(PMDA-ODA);(b) Upilex-R (BPDA-ODA);(c) Upilex-S (BPDA-PDA).

Figure 2. Schematic diagram of the sputtering apparatus used to deposit copper (Cu) on polyimide
(PI) substrates.
 786

The peel strength of each laminate was measured using the 180° peel test described
previously [10]. The composition of the peeled surfaces of the Cu side was determined
using Auger electron spectroscopy (AES) in which an MH93-4001 Auger Spectro-
meter (Perkin-Elmer) was installed in the UHV chamber (2 x 10-g Pa). Depth profiles
were obtained by sputtering the sample surfaces with Ar ions that had an energy level
of 3 keV To minimize contamination, the peeled surface was prepared just before
the laminate was introduced into the load-lock vacuum chamber. The depth profile
of the peeled surfaces was determined using Ar-sputter AES at a sputtering pressure
of 6.7 x 10-5 Pa. Changes in the chemical bonding state at the peeled surface of
the PI were determined using attenuated total reflection Fourier-transform infrared
spectroscopy (ATR-FTIR) [ 11 and X-ray photoelectron spectroscopy (XPS).
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3. RESULTS AND DISCUSSION

Figure 3 shows the measured adhesion strength for the three PI substrates as a function
of the 02-plasma treatment time. The figure shows that without this plasma treatment,
Cu adhered weakly (adhesion strength less than 10 N/m) to the PI substrates, implying
that 02-plasma treatment is effective for improving the adhesion strength. Despite
this improvement, the adhesion strength was reduced by the heat treatment (Fig. 4).
Figure 4 shows the measured adhesion strength of the Cu/PMDA-ODA laminate
treated at 150 °C in air as a function of the heat treatment time. Up to a heat treatment
time of 24 h, the strength decreased sharply, after which it decreased only slightly.
On the other hand, the adhesion strength of the Cu/PMDA-ODA laminate hardly
decreased (adhesion strength more than 70 mN/m) even after the heat treatment at
150°C in a vacuum of 1.3 Pa for 100 h. This result clearly shows that the adhesion
strength deterioration is due to oxygen and moisture in air. Figures 5a-5c show the

Figure 3. Peel strength of copper/polyimide (Cu/PI) laminates versus the 02-plasma treatment time.
 787
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Figure 4. Peel strength of the Cu/PMDA-ODAlaminate versus the heat treatment time.

Figure 5. Depth profiles of the peeled Cu surface of a Cu/PMDA-ODAlaminate for (a) carbon, (b) oxy-
gen, and (c) Cu.

depth profiles for carbon, oxygen, and Cu, respectively, of the peeled Cu surface of
this laminate treated at 150°C in air for 24 h. (These profiles are the distribution
of atoms as a function of the etching time by the AES.) The carbon was below the
detection limit after an etching time of 1800 s for the unheated sample, after 1200 s
for the 24-h heat-treated sample, after 450 s for the 48-h heat-treated sample, and after
120 s for the 72-h heat-treated sample. For Cu, the depth profile becomes shallower
with increasing heat treatment time. These results show that the position of the WBL,
where peeling occurs [12], between Cu and PI is a function of the heat treatment
 788
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Figure 5. (Continued).

Table 2.
Adhesion strengths (mN/m) of the copper/polyimide laminates
 789

time: the longer the heat treatment time, the closer the WBL to the interface side in
the PI. Figure 5b shows that the amount of oxygen near the peeled Cu surface was
increased by the heat treatment. The peeled Cu surface was found to be oxidized by
the heat treatment at 150 °C in air for 24 h, but the amount of oxygen near the peeled
Cu surface decreased with increasing heat treatment time.
To confirm this relationship between the adhesion strength and the WBL, we mea-
sured the adhesion strength and depth profiles of Cu/BPDA-PDA and Cu/BPDA-
ODA laminates. Table 2 shows the measured adhesion strengths for unheated and
24-h heat-treated samples of all three laminates. For all three laminates, the adhesion
strength was reduced by the heat treatment, although only slightly for the Cu/BPDA-
PDA laminate. These results show the possibility that the ether moiety between the
two benzene rings in the ODA is related to the strong adhesion between Cu and
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02 plasma-treated PI. Chenite et al. [13] reported the adhesion mechanism of Cr/PIs
and Ti/PIs laminates as follows: the diamine portions, PDA and ODA, could affect
the adhesion strength, probably by modifying the PI chain conformation. In PMDA-
ODA, the PI chain is flexible and could rotate around the ether oxygen, while in the
BPDA-PDA the conjugation effect is more important and makes the macromolecules
more rigid. This is most probably the way in which PDA and ODA segments could
influence the adhesion performance of PI. This mechanism seems to be applicable to
the Cu/PI laminate, in which the ether moiety between the two benzene rings in the
ODA would play an important role for the strong adhesion between Cu and PI.
Figures 6a-6c show the depth profiles of nitrogen at the peeled Cu surface of
the heat-treated Cu/PMDA-ODA, Cu/BPDA-ODA, and Cu/BPDA-PDA laminates,
respectively. For all three laminates, the detection limit of nitrogen for the 24-h
heat-treated samples was lower than that for the unheated samples. These results
coincide with those shown in Fig. 5, thus confirming that the heat treatment causes

Figure 6. Depth profiles for nitrogen (N) of the peeled Cu surface of (a) the Cu/PMDA-ODAlaminate,
(b) the Cu/BPDA-ODAlaminate, and (c) the Cu/BPDA-PDA laminate.
 790
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Figure 6. (Continued).

the WBL to shift towards the interface side. Figure 7 shows the relationship between
the depth profiles of the nitrogen detection limit at the peeled Cu surface and the
adhesion strength. The nitrogen detection limit, which shows the existence of the
adhered PI material to the peeled Cu surface, is apt to be shallower with decreasing
adhesion strength. This result means that the WBL shifted to the interface side in the
PI as the adhesion strength decreased.
Changes in the chemical bonding state at the peeled surfaces of the unheated and
heat-treated PMDA-ODA laminates were analyzed with ATR-FTIR and are shown
in Figs 8a and 8b, respectively. The absorption peak around 1720 cm-1 indicates
the C=O bond in the PI structure; 1500 cm-1, the benzene ring; 1380 cm-1, the
C-N bond; 1100 cm-1, the C-O bond; and between 880 and 830 cm-1, the
 791
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Figure 7. Relationshipbetween the depth profiles of the nitrogen (N) detection limits and the adhesion
strength of Cu/PI films.

Table 3.
Change in the area of each peak with respect to the peak area of 1500cm-1 (benzene)
(in the case of the PMDA-ODAsubstrate)

C-H bond. From these patterns, we calculated the change in the area of each peak
with respect to the unheated samples. We used the absorption peak of the benzene ring
as the reference (1500 cm-1) because the benzene ring was assumed to be the most
stable moiety in the PI structure. Table 3 lists the calculated results for these changes
and shows that the absorption peaks representing the C=O and C-O bonds increased
due to the heat treatment, whereas that representing the C-N bond decreased. The
results in Table 3 indicate that due to the heat treatment, not only oxygen but also
water may participate in the chemical bonding of Cu to PI.
To confirm the changes in bonding state revealed by ATR-FTIR, we evaluated the
peeled surfaces of the Cu/PMDA-ODA laminates. We did this by measuring the
C Is spectra of unheated samples and samples heated at 150°C for 24 h in air
(Figs 9a and 9b, respectively). The separation of these spectra was followed by other
methods [14, 15]. Although only the three peaks representing -C-, -C-N- or
- C-O-, and -N-C=O bonds could be detected at the peeled surface of the
 792
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Figure 8. ATR-FTIRspectra of the PMDA-ODAsubstrate for (a) an unheated sample and (b) a sample
heat-treated at 150°C for 24 h in air.

unheated sample, peaks representing -O-C-O- or =C=O, -(C=O)-O, and

- O-(C=O)-O- bonds appeared in addition to those three peaks at the peeled
surface of the heat-treated sample. This result coincides with that revealed by ATR-
FTIR, where the peak representing the C-O bond increased after the heat treatment.
Furthermore, the increase in peak intensity representing the -N-C=O bond also
supports the ATR-FTIR result in which the peak intensity of the C=O bond increased
after the heat treatment. We therefore conclude that a Cu thin film sputtered onto a
PI substrate is apt to peel at the oxidized interface due to the heat treatment.
 793
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Figure 9. C Is spectra of the PMDA-ODAsubstrate for (a) an unheated sample and (b) a sample heat-
treated at 150°C for 24 h in air.
 794

Table 4.
Change in the area of each peak with respect to the peak area of 1500cm-1 (benzene)
(in the case of the BPDA-ODAsubstrate)
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Table 5.
Change in the area of each peak with respect to the peak area of 1500cm- (benzene)
(in the case of the BPDA-PDAsubstrate)

Tables 4 and 5 show the changes in the chemical bonding state (represented by the
change in the absorption peak area in ATR-FTIR results) at the peeled surfaces of
unheated and heat-treated samples of the Cu/BPDA-ODA and Cu/BPDA-PDA lami-
nates, respectively. Again, as seen for the PMDA-ODA substrate (Table 3), the C=O,
C-O, and C-H bonds increased and the C-N bond decreased after the heat treat-
ment. These changes confirm the results seen for the PMDA-ODA substrate, that the
peeled surfaces are located in the oxidized interface caused by the heat treatment. The
chemical bonding states of the PMDA-ODA, BPDA-ODA, and BPDA-PDA substrates
just after exposure to 02 plasma are also shown in Tables 3, 4, and 5, respectively.
The results show that the chemical bonding states of the peeled surfaces after the heat
treatment are similar to those of 02 plasma-treated surfaces.

4. CONCLUSIONS

Our analysis of the adhesion strength between a Cu thin film and a PI substrate shows
the following:
(1) oxygen plasma treatment is effective for improving the adhesion strength between
a Cu thin film and certain PI substrates;
(2) a Cu thin film sputtered onto an 02 plasma-treated PI substrate is apt to peel at
the oxidized interface, due to heat treatment;
 795

(3) heat treatment causes the WBL to shift closer to the interface side. The amount
of this shift is related to the adhesion strength between the Cu film and the
02 plasma-treated PI substrate;
(4) one of the possibilities is that the ether moiety between the two benzene rings
in the ODA is related to the adhesion between Cu and an 02 plasma-treated
PI substrate.

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