Surface Modification of Kapton Film by Plasma Treatments

N. INAGAKI,* S. TASAKA, and K. HlBl

Laboratory of Polymer Chemistry, Shizuoka University, 3-5-1, Johoku, Hamamatsu 432, Japan

SY N0PSIS

Kapton films were treated with seven plasmas: Ar-, Nz-, Oz-, CO-, COP-,NO-, and NOz-
plasmas. Surface properties and chemical composition of the plasma-treated Kapton films
were investigated from the contact angle measurement, and the IR and XPS spectra. The
plasmas, especially NO- and NOz-plasma, made the Kapton film surface hydrophilic. The
XPS and IR spectra showed that the plasma led to the modification of the imide groups
in the Kapton film to secondary amide and carboxylate groups.
Keywords: plasma treatment Kapton surface modification hydrophilic properties
contact angle IR spectra XPS spectra

INTRODUCT10 N The generally accepted mechanisms of adhesion

Polyimides are one of the high-temperature poly-
mers widely used in the fields of microelectronic de-
vices, wire insulation, aerospace, corrosion protec-
tion, etc. One of the most widely used polyimides is
a polycondensation polymer made from pyromellitic
dianhydride and oxydianiline, and is commercially
available in the forms of film and solution of pre-
polymer.
For microelectronic devices, many investigators
have focused their attention on adhesion between
polyimide and metal. From this viewpoint, surface
modification for the adhesion between wiring metal
and polyimide film, metal-on-polyimide system, be-
comes an important issue.'-13 The surface modifi-
cation by chromium metal is one of techniques to
improve the adhesion between copper metal and po-
lyimide film.14,15 The technique involves the depo-
sition of a thin layer of chromium metal at the sur-
face of the polyimide film and the deposition of cop-
per metal a t the polyimide surface modified by
chromium metal. The adhesion between polyimide
and chromium metal which is vacuum-evaporated
at the surface of polyimide is good due to the for-
mation of charge-transfer complex in the chromium/
polyimide interface. As a result, the adhesion copper
metal is good.
* To whom all correspondenceshould be addressed.
Journal of Polymer Science: Part A Polymer Chemistry,Vol. 30,1425-1431 (1992)
0 1992 John Wiley & Sons,Inc. CCC 0&37-624X/92/071425-07$04.00
are: ( 1 ) mechanical interlocking theory, ( 2 ) theories
based on surface energy, wetting, and adsorption,
( 3 ) diffusion theory, ( 4 ) electronic or electrostatic
theory, ( 5 ) chemical bonding, and ( 6 ) weak bound-
ary layer mechanism.16 Fowkes l7 emphasized that
to obtain maximum adhesion between polymer and
metal it is best to have strong acid-base interaction
between them. Surface phenomena including adhe-
sion, adsorption, zeta potential, and dispersibility,
are interpreted from the acid-base concept." Surface
modification to form functionalities into the polymer
is of importance. From concept, the formation of
new functionalities, acid or base component, at the
polyimide surface may be a useful technique to im-
prove the adhesion. We focus on plasma treatment
as a technique to modify the polyimide film surface.
Our objectives in this study are the surface mod-
ification of polyimide film, hydrophilic modification,
whether plasma treatment is possible, and what
functionalities are formed at the surface of the
plasma-treated film. The surface of the polyimides
is investigated from contact angle, ATR FTIIR,
and XPS.
EXPERIMENTAL
Materials
The polyimide film used in this study was
poly [ (N,N'-oxydiphenylene)pyromellitimide],
Kapton" H, was kindly provided from Toray du Pont
Co. and received in 508 mm wide and 25 pm thick.
1425
1426 INAGAKI, TASAKA, AND HIBI
Plasma Treatment
The polyimide film was mounted on the sample stage
shown in Figure 1 and was plasma-treated using a
home-made reactor which was a capacitively coupled
system at a 20 kHz frequency. It consisted of a bell-
jar (400 mm &am, 470 mm height) with a monomer
inlet, a pair of parallel electrodes ( 150 X 150 mm) ,
a substrate stage, a pressure gauge, and a vacuum
system. A scheme of the reaction system is shown
in Figure 1.
The experimental procedures for the plasma
treatment were essentially the same as reported
elsewhere." The reaction system was evacuated to
approximately 0.13 Pa, and then the given gas, either
of argon, ( Ar ) ,nitrogen ( N2),oxygen ( O2) ,carbon
monoxide (CO) , carbon dioxide ( C 0 2 ), nitrogen
monoxide ( N O ) , or nitrogen dioxide ( NO2),whose
flow rate was adjusted at 10 cm3 (STP)/min by a
mass flow controller was introduced into the reaction
chamber. The plasma treatment was performed at
a discharge current of 150 mA at 20 kHz frequency
a t a system pressure of 13.3 Pa for 3 min.
Contact Angle of Water and Surface Energy
The advancing contact angles of water, glycerol,
formamide, diiodomethane, and tricresyl phosphate
on the treated polyimide film surfaces were measured
a t 20°C using an Erma contact angle meter with a
goniometer, model G-1. The advancing contact angle
was determined from an average of 10 specimens.
The receding contact angle of water was measured
according to the bubble method. The polyimide film
was immersed in water at 25"C, and a constant vol-
ume ( 1pL) of air bubble was introduced at the lower
surface of the polyimide films using a microsyringe.
The contact angle of the air bubble against the poly-
imide surface was measured using the Erma contact
PlasmaGas 11
I DC Amdfier I
Figure 1. Schematic of reaction chamber.
GCPower supply
Figure 2. Electric circuit diagram for electron temper-
ature measurement.
angle meter. The receding contact angle was deter-
mined from an average of 10 specimens.
The surface energy of the plasma-treated poly-
imide film surface was estimated from the data of
the advancing contact angles of the five liquids ac-
cording to the Kaelble's method."
Infrared and X-Ray Photoelectron Spectra
The plasma-treated polyimide film was supplied as
a specimen for IR and XPS measurements. The at-
tenuated total reflection ( ATR) IR spectra for the
surface of the polyimide film were recorded on a
Nihon Bunko Fourier transform spectrometer FT/
IR-3. The crystal of germanium was used for ATR
measurement, and the incidence angle of infrared
light was 45". The sampling depth in the ranges of
2000 to 400 cm-' is estimated to be about 0.66 to 3.3
pm. The spectral resolution was 2 cm-', and 500
scans were recorded on each sample.
The XPS spectra of the surface of the polyimide
were obtained on an Ulvac-Phi spectrometer 5300
using AlK, photon source. The anode voltage was
15 kV, the wattage 400 W, and the background pres-
sure in the analytical chamber 1X lop7Pa. The C1,
spectra were decomposed by fitting Gaussian func-
tions to experimental curve using a nonlinear, least-
squares curve-fitting program supplied by Ulvac-
Phi. The sensitivity factor (S) for core levels was
S(C,,) = 1.00, S(N,,) = 1.61, and S(Ol,) = 2.40.
Electron Temperature in Plasma Zone
The double probe method which was proposed by
Dotez1was applied for the measurement of the elec-
tron temperature ( T,)in the plasma zone. The elec-
 SURFACE MODIFICATION OF KAPTON FILM 1427

0.21 and 0.067, respectively, that are slightly lower

Figure 3. Schematic diagram of current-voltage char-
acteristics.
tric circuit diagram used for the double probe method
is shown in Figure 2. The probe is a cylinder of nickel
and the dimension of the probe is 1 mm diam and
10 mm long. The two probes which were separated
at a distance of 15 mm from each other were posi-
tioned in the plasma zone, and were connected to
the choking coil and the capacitor for reducing the
high frequency noise. A dc field from -15 to 15 V
was applied between the probes, and the current of
the circuit was measured as a function of the dc
field. From the data of the current-voltage charac-
teristics (Fig. 3 ) , the net positive ion current ( C I,),
slope ( d I d / d v d ) at the inflection point of the cur-
rent-voltage curve, and the slope (S)at the positive
ion saturation were estimated, and then the electron
temperature ( T,)was estimated by eq. ( 1) , where
k and e are the Boltzman’s constant and the charge
of electron, respectively. The theoretical back-
grounds for the measurement of the electron tem-
perature has been described in the literature.22
than those calculated from the repeating unit struc-
ture, C22H10N205, O / C = 0.227 and N / C = 0.091.
This difference, similarly reported by Pertsin and
Pashunin, 23 may be due to carbonaceous contami-
nation or a heterogeneous structure of the outermost
layer. For the plasma-treated Kapton films, the O /
C atomic ratio is 0.380-0.469-that is 1.9-2.3 times
higher than that of the untreated Kapton film, and
the N / C atomic ratio is 0.04-0.79-that 0.6-1.2
times higher than that of the untreated Kapton film.
The origin of the oxygen, when the Kapton films
were exposed to Ar- and N2-plasmas, may be due to
post reactions of radical sites created during the
plasma treatment. This comparison indicates that
the plasma treatment is effective in introduction of
oxygen atom into the Kapton surface but ineffective
in that of nitrogen atom. Therefore we could con-
clude that the surface modification of Kapton film
by the plasma treatment results in incorporating
oxygen atoms rather than nitrogen atoms.
Contact Angle of Water and Surface Energy of
Plasma-Treated Kapton Film
Figure 4 shows a typical surface modification of the
Kapton film by the NO2-plasma treatment. The
surface modification is evaluated by the advancing
and receding contact angle of water against the
Kapton films as a function of the NO2-plasma ex-
posure time. The ordinate in the figure is graduated
in the cosine function of these contact angles. A
rapid decrease in the advancing contact angle occurs
Table I. Elemental Composition of Kapton Film
Treated with Plasmas

Elemental
Composition
RESULTS AND DISCUSSION (Atomic Ratio)

Elemental Composition of Plasma-Treated Kapton

Film Surface
Non 0.201 0.067
The survey by the XPS measurement showed that Ar-plasma 0.390 0.053
the plasma treatment led to changes in elemental Nz-plasma 0.380 0.070
composition for the surface of the Kapton film. Ta- 02-plasma 0.419 0.064
ble I compares the O/C and N / C atomic ratios for CO-plasma 0.382 0.040
the Kapton films treated for 3 min with the seven COZ-plasma 0.469 0.064
plasmas, Ar-, N2-, 02-, CO-, C02-, NO-, and NO2- NO-plasma 0.430 0.071
plasmas. The O/C and N / C atomic ratios deter- NOz-plasma 0.464 0.079
Calculated from repeating unit 0.227 0.091
mined by XPS for the untreated Kapton film are
1428 INAGAKI, TASAKA, A N D HIBI

oxygen functionalities were formed by exposure to

the plasmas. This assumption is based on the ex-
perimental evidence that plasma exposure, as de-
scribed in a previous section, makes the Kapton film
surface rich in the oxygen content.
% 0.8
wa2xL
Kap(0n Rlm
0

o.6
0.4

O.*?
1 Oxygen Functionalities Generated at Kapton Film
Surface by Plasma Treatment
Figure 5 shows typical XPS (Cis) spectra of the
Kapton films treated with the plasmas. The line-
ob ; 1 A ;'lb;03b1 shape of the C1, spectrum for the Kapton film is
Plasma ExposureTime (rnin) decomposed into three components whose the peaks
appear at 285.4, 286.3, and 289.2 eV, respectively.
Figure 4. Advancing and receding contact angle against
NO-plasma-treatedKapton film as a function of plasma The decomposition is consistent with the results re-
exposure time. ported by investigators. Pertsin and P a ~ h u r i re-
n~~
ported that the C1, spectrum of the Kapton film was
comprised of three components: the C, component
within 10 s when exposed to the NO2-plasma. At an a t 285.3 eV (46% in relative peak area) originated
exposure time of 10 s the advancing contact angle from carbon atoms not bound to oxygen and nitro-
of water is changed from 74.7 k 0.3' for the un- gen atoms, the C2 component at 286.3 eV (39%)
*
treated Kapton film to 27.3 0.7", thereafter, the from ether and amine carbon atoms of the oxydi-
advancing contact angle gradually decreases, and aniline (ODA) unit, and the C3component at 289.2
then, levels off at an exposure time of about 2 min. eV (13% ) from carbonyl carbon atom of the pyro-
The advancing contact angle at an exposure time of mellitic dianhydride (PMDA) unit. The T-T* sat-
2 min is 8.4 k 0.8'. Similarly, the receding contact ellite appears at 291.9 eV. While, all the plasma-
angle decreases a t an initial stage of the plasma ex- treated Kapton films (although the Nz-, CO-, and
posure time up to 2 min, and thereafter reaches NO-plasma-treated Kapton films are not repre-
equilibration. Changes in both advancing and re- sented in Figure 4 for the sake of brevity) show
ceding contact angles reveal that the NO2-plasma broadening C1, spectra. The line-shape of these C1,
exposure makes the Kapton film surface hydrophilic, spectra is decomposed into four components whose
and that the hydrophilic modification is attained the peaks appear at 285.3-285.7, 286.6-286.9, 288.8-
within 2 min of the NO2-plasma exposure. 289.1, and 290.0-290.7 eV. The former three com-
Table I1 shows the advancing contact angle of ponents correspond to the C, ,C2,and C3component
water and the surface energy for the Kapton film for the untreated Kapton film. The latter component
surface that were treated for 3 min with the seven (C,) a t 290.0-290.7 eV is a new one generated by
plasmas: Ar-, N2-, 02-, CO-, C02-, NO-, and NO2-
plasmas. The Kapton film surface is hydrophilic and
the surface energy is estimated to be 37.2 mJ/m2 Table 11. Advancing Contact Angle of Water against
Plasma-Treated Kapton Films and Surface Energy
from the contact angle data. All the Kapton films
as a Function of Plasmas
treated with the plasmas show smaller contact angle
of 7.6-11.6 degrees and their surface energy is in the Contact Surface Energy
range of 65.4-68.8 mJ/m2, indicating the capability Angle of (mJ/m2)
of the seven plasmas to make the Kapton film hy- Water
drophilic. From comparison of the advancing contact Plasma (degrees) YS Yds YB
angle and the surface energy, NO- and NO2-plasmas
may be more effective in hydrophilic modification Non 74.7 k 0.3 37.2 29.1 8.1
than the others. This enlargement of the surface Ar-plasma 11.4 f 0.9 66.6 20.2 46.4
energy by the plasma exposure is attributed mainly Nz-plasma 11.6 k 0.5 65.4 19.4 46.0
by the polar contribution rather than the dispersive 0,-plasma 9.6 f 0.5 66.9 20.2 46.7
contribution which are composed of the surface en- CO-plasma 10.5 f 0.7 66.7 19.8 46.9
ergy and which are temporarily estimated from the COz-plasma 8.4 t 0.7 67.1 19.7 47.4
NO-plasma 7.6 f 0.9 68.5 19.7 47.8
contact angle data by Kaelble's method. From the NOz-plasma 8.0 t 0.8 68.8 19.7 49.1
heavy polar contribution we could assume that new
 SURFACE MODIFICATION OF KAPTON FILM 1429

IR spectrum between the NO2-plasma-treatedKap-

ton film and the untreated is shown in Figure 6. The
difference spectrum is referred to the absorption
peak a t 1368 cm-'. We detect absorption peaks at
1680 and 1655 cm-' ,and 1560 and 1545 cm-' in the
difference spectrum (spectrum C in Fig. 6 ) . The
former two absorption peaks are assigned secondary
amides ( - CO -NHR -) and the latter two peaks
are assigned amide I1 ( 8 N - H in secondary amide) .25
Furthermore, the Kapton film that was treated with
the NO2plasma and that was treated with 1N KOH
aqueous solution a t room temperature showed an
IR absorption peak due to carboxylate group (spec-
trum D in Fig. 6 ) . These changes in the IR spectra
suggest that the imide groups of the Kapton film
were cleaved by the plasma treatment and that as a
result, secondary amide and carboxyl group were
formed. This prediction is consistent with the results
from XPS measurement. The secondary amide and
carboxyl group may be main hydrophilic components
111111111111 generated by the plasma treatment.
290 285
Binding Energy (eV) 0 0

Figure 5. XPS (CIS)spectra of Kapton films as a func-

tion of plasma: ( A ) untreated, ( B ) 0,-plasma-treated, ( C )
C0,-plasma-treated, ( D ) NO2-plasma-treated.

the plasma treatment. The C , component is ascribed

to carboxyl carbon atom and its concentration is
4.8-7.6% of the total carbon atoms.
The plasma treatment led to changes in the N1,
core level spectra: the N1, spectra broadened in the
direction of low binding energy region, and the full
width at half-maximum increased from 1.7 eV for
the untreated Kapton film to 2.0-2.5 eV for the
plasma-treated. This broadening indicates the im-
plication of at least two nitrogen functionalities. We
speculate that the nitrogen functionalities may be
imide and amine nitrogen atoms although we aban-
doned the line-shape decomposition of the N1, spec-
tra because of the low signal-to-noise ratio.
ATR IR spectra give other information about
chemical changes for the Kapton films by the plasma
treatment. Figure 6 shows comparison between the
untreated Kapton film and the plasma-treated films.
The Kapton film shows strong, characteristic ab-
sorption peaks a t 1780 ( V C = O in-phase), 1700 ( Y C = ~
out-of-phase), 1500 ( V1,4-C6H4), 1378 ( Y C N ) , 1245
( Y C - O - C ) , 1100 ( h i d e III), 815 ( ~ 1 , 2 , 4 , 5 - ~ ~ Hand
~), 2Ooo 1500 lo00 500
720 cm-' (imide IV) (spectrum A in Fig. 5) .24 The Wave Number (cm-1)
plasma-treated Kapton films also shows similar IR Figure 6. IR spectra of Kapton film and NO-plasma-
spectra but are slightly different from the untreated treated Kapton film; ( A ) untreated; ( B ) N02-plasma-
Kapton film (spectrum B in Fig. 6 ) . The difference treated, ( C ) difference spectra ( B - A ) .
1430 INAGAKI, TASAKA, A N D HIBI
Table 111. Electron Temperature in Plasma Zone
Electron Temperature
Plasma (K)
Ar-plasma 3.1 x lo4
N2-plasma 7.2
8.0
Oz-plasma
CO-plasma 6.9
COz-plasma 8.2
NO-plasma 6.1
NO2-plasma 7.3
From the results obtained from the XPS and IR
measurement we predict the modification of the
Kapton film by the plasma treatment. The imide
groups are cleaved by the plasma treatment, and as
a result, the secondary amide and carboxyl groups
are formed. The cleavage of the imide groups is pos-
sible in two processes, electron bombardment by the
plasma and photodegradation by the plasma.
Galuska" reported that the electron bombardment
a t 3 keV led to the cleavage of imide groups in Kap-
ton films, and to the formation of graphitic carbon,
ether, and amino groups. Hiraoka and Lazare' re-
ported that the UV irradiation at 254 nm brought
about the cleavage of the imide groups and made
the Kapton films hydrophilic.
Table I11 shows the electron temperature in the
plasmas which were used in this study for the plasma
treatment of the Kapton film. The electron tem-
perature except for the argon plasma is in the range
of 6.1 X 10 to 8.2 X 10 K that corresponds to 5.3-
7.1 eV. The electrons in the plasma zone are ener-
getic enough to cleave the imide groups because the
bond strength of N -C bonds is about 3 eV. The
plasmas also emit strong UV light as well as visible
light. The NO2-plasma that emits the UV light at
249.1 nm26 has a capability to cleave the imide
groups. Therefore both the electrons and photons
existing in the plasma zone may be able to break
down the imide rings in the Kapton film. Either of
the species that initiate the modification of the
Kapton film is not clear a t the presence time. More
investigation from electro- and photo-chemical
viewpoints should be done to make this issue clear;
the issue will be dealt with in the near future.
CONCLUSION
Kapton films were treated with seven plasmas: Ar-,
Nz-, 02-,CO-, C02-, NO-, and N02-plasmas. Surface
properties and chemical composition of the plasma-
treated Kapton films were investigated from contact
angle measurement, and the IR and XPS spectra.
The results are summarized as follows:
1. The plasmas, especially NO- and NO2-
plasma, made the Kapton film surface hy-
drophilic. The surface energy was increased
from 37.2 mJ/m2 for the untreated Kapton
film to 65.4-68.8 mJ/m2 for the plasma-
treated film. The formation of the polar com-
ponent attributed to the enlargement of the
surface energy.
2. The plasma treatment led to incorporation
of oxygen atoms rather than nitrogen atom.
The O/C atomic ratio of the plasma-treated
Kapton film surface was 1.9-2.3 times higher
than that of the untreated film.
3. The XPS (CIS,Nls) spectra showed the for-
mation of carboxyl carbon atom and broad-
ening the N1, spectrum in the direction of
low binding energy region when the Kapton
film was plasma-treated.
4. IR spectra showed the formation of secondary
amide groups and carboxylate groups for the
plasma-treated Kapton films.
5. Some of imide groups in the Kapton film were
cleaved by the plasma treatment, and as a
result, secondary amide groups were formed.
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Received June 10, 1991
Accepted August 25, 1991