Journal of the Korean Physical Society, Vol. 50, No. 6, June 2007, pp.

18541857
Characterization of Organic Polymer Thin Films Deposited
Using the PECVD Method
I.-S. Bae, C. K. Jung, S.-J. Cho, Y.-H. Song and J.-H. Boo

Department of Chemistry and Center for Advanced Plasma Surface Technology,

Sungkyunkwan University, Suwon 440-746
(Received 5 September 2006)
Polymer-like cyclohexene thin lms have been deposited on glass and silicon substrates at room
temperature and 100

C for analysis of their various properties using the plasma enhanced chemical
vapor deposition (PECVD) method. Cyclohexene monomer was utilized as an organic precursor,
and hydrogen and Ar were used as bubbler and carrier gases, respectively. In order to compare the
inuence of the electrical and the optical properties of the plasma-polymerized organic thin lms
with the deposition condition such as the RF power and deposition temperature. We analyzed the
as-grown plasma-polymerized thin lms using Fourier-transform infrared and ultraviolet-visible
spectroscopy, and I-V and C-V curves. As the plasma power was increased, the ellipsometry and
the ultraviolet-visible spectroscopy measurements should that the refractive index of thin lms
increased and the transmittance decreased. The minimum dielectric constant and the best leakage
current were 2.43 and 7 10
12
A/cm
2
, respectively. The contact angles also increased with
increasing RF power.
PACS numbers: 77.55.+f, 72.80.Sk, 73.90.+f
Keywords: Plasma polymerization, PECVD, C-V and I-V propertie
I. INTRODUCTION
As the integration level and speed of semiconduc-
tor devices increase, the reduction of the resistance-
capacitance (RC) delays in the metallization is becoming
more important than before. The problems are propaga-
tion delay, cross-talk noise, and power dissipation due to
RC coupling, which becomes signicant due to increased
wiring capacitance, especially the interline capacitance
between the metal lines on the same metal level [1, 2].
Whereas the resistance is aected by conducting mate-
rials, the capacitance is mainly determined by dielectric
materials [3]. Therefore, thin lms with relative low di-
electric constants (k < 3.0) are under intense study due
to their application as interlayer dielectrics for multilevel
metallization of ultra-large-scale integrated (ULSI) semi-
conductor devices [4]. A low-k value is one of the most
important requirements for interlayer dielectrics.
Polymer thin lms are considered as possible candi-
dates for low-k materials due to their low k values [5].
However, poor adhesions with Si substrates and produc-
tion diculties have hindered their use in microelectron-
ics. On the other hand, plasma enhanced chemical va-
por deposition (PECVD) of polymer lms (plasma poly-

E-mail: jhboo@skku.edu; Fax: +82-31-290-7075

merization) has many advantages that help to overcome
these problems. PECVD uses a glow discharge to cre-
ate activated species, such as radicals and ions, from the
original monomer, and the polymer lms are deposited
through various gas phases and surface reactions of these
active species, including ablation of the deposited lm.
In this study, we report our results of the growth for
polymer-like thin lms on Si (100) and glass substrates
at room temperature and 100

C by using a cyclohexene
precursor and the PECVD method for low dielectric con-
stant device applications. In addition, the eects of de-
position of the plasma power on the dielectric constants
were mainly studied.
II. EXPERIMENTS
The experiment was carried out in a homemade
stainless-steel PECVD system. The Si(100) cleaned and
etched using acetone, isopropyl alcohol, HF solution, and
DI water, sequentially, was used as a substrate. Glass
was cleaned by the same method, but without the HF
solution. After the samples had been cleaned, the pre-
cleaned substrates were in situ pre-treated with a Ar
plasma to make an oxygen-free surface and/or a buer
layer to enhance lm adhesion. The deposition lasted
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Characterization of Organic Polymer Thin Films Deposited I.-S. Bae et al. -1855-
for 2 5 min, depending on the RF power. The general
deposition pressure and temperature were 2 4 10
1
Torr and room temperature, respectively. The typical
conditions of the PECVD process used in this study for
lm deposition were 20 50 W of RF power, 50 sccm
of Ar carrier gas, and 50 sccm of H
2
bubbler gas. Cyclo-
hexene (C
6
H
10
) was used as an organic precursor. Due
to the high vapor pressure of the precursor itself, it was
not necessary to heat the source during deposition.
The as-grown plasma polymerized thin lms were ex
situ characterized with using Fourir-transaction infrared
(FT-IR), UV-Visible, and contact angle measurements.
For the electrical analysis, the hetero junctions, includ-
ing the back contact, were made by using thermal evap-
oration of an Al lm with a thickness of 150 nm on cy-
clohexene. Also, the Al contact dots were prepared us-
ing a conventional lithographic process, and the area of
the contacts was 2.4 10
4
cm
2
. An impedance an-
alyzer was utilized to determine the I-V curve for the
leakage current density and the C-V curve for dielectric
constants. C-V characteristics were measured using a
Boonton 7200 capacitance meter. The electrical mea-
surements were carried out in the dark using a metal-
insulator-semiconductor (MIS) sandwich structure.
III. RESULT AND DISCUSSION
Figure 1(a) shows the FT-IR spectra of plasma-
polymerized cyclohexene lms grown on Si(100) sub-
strates for various RF powers. We can see two strong ab-
sorption peaks around 2940 and 1713 cm
1
. The absorp-
tion peaks at 2940 cm
1
and 1713 cm
1
can be assigned
to the aliphatic CHx stretching made and the C=O bond.
The methyl group can also be used to assign the absorp-
tion peak at 2910 cm
1
to the C-H stretching mode.
The C-H stretching peak of thin lms decreases with in-
creasing RF power, as shown in Figure 1(a). This result
indicates that the cyclohexene molecule is ionized by the
plasma because the peaks can not be shown two iso-
mers of cyclohexene molecules. Also, cyclohexene lms
have a higher degree of cross-linking because cyclohex-
ene molecules produce more radical with increasing RF
power.
Figure 1(b) shows UV-Vis transmittance spectra of
the plasma polymerized thin lms that grown at RT un-
der Ar : H
2
= 1 : 1 with dierent RF powers. From
Figure 1(b), the remarkable facts are that the transmit-
tance of lms has a decreasing tendency with increasing
RF power. Moreover, The curve in Figure 1(b) decrease
with increasing RF powers due to relatively high num-
ber of C=O bonds in the lm layers. From the results
of the FT-IR and the UV-Visible spectra, we conclude
that increasing the RF power can increase the C=O bond
content due to high cross-linking between radicals of cy-
clohexene monomer molecules.
Figures 2(a) and 2(b) show the dielectric constants
Fig. 1. (a) FT-IR spectra of cyclohexene monomer and
as-grown thin lms. (b) UV-visible transmittance spectra
obtained from the cyclohexene thin lms that grown on glass
at R.T. and various RF powers.
and the leakage current densities obtained from polymer-
ized thin lms grown at 100

C and various RF powers
with Ar : H
2
= 1 : 1. Figure 2(a) shows the variation
of the dielectric constant obtained from experimentally
observed C-V curves by using the MIS structure as a
function of RF power. With increasing RF power, the
obtained dielectric constant decreased from 2.90 to 2.43.
This result was aected by the degree of crystallinity of
the as-grown lms. This can be explained by the degree
of cross-linking of the polymerized thin lms. From Fig-
ure 3(b), we observed the insulating properties of plasma
polymerized thin lms by measuring the leakage current
density (J) at dierent applied elds (F). As the plasma
power was increased from 20 W to 50 W, the leakage
current density decreased, and breakdown did not ap-
pear below 1 MV. This indicates that our lms had a
compact structure with high density and pin-hole free
layers that are well known to have a lower leakage cur-
rent density and a higher breakdown eld. The best
leakage current density was obtained at an RF power of
50 W and was about 10
12
A/cm
2
at 1 MV/cm, sug-
-1856- Journal of the Korean Physical Society, Vol. 50, No. 6, June 2007
Fig. 2. Electrical properties as functions of the RF powers.
(a) dielectric constant of cyclohexene and (b) leakage current
density of cyclohexene.
gesting that this polymer thin lm could be applied as
an insulating material in semiconductor devices.
Figure 3(a) shows the lms growth rate as a function
of the RF power at dierent temperatures. When the
RF power increased, the deposition rate was increased
at room temperature and 100

C. With increasing RF
power and deposition temperature, the number of re-
active fragments and atoms increased to form a ran-
domly structured plasma polymer. This can be simply
explained in terms of an increase in the plasma density
with an adequate amount of energy that can be used
for plasma polymerization of the cyclohexene precursor.
The maximum growth rate was 62 nm/min at 100

C
and 50 W.
Figure 3(b) presents the contact angles of silicon sub-
strates covered with cyclohexene lms as a function of
the RF power at room temperature and 100

C. With in-
creasing RF power and temperature, the value of contact
angle increased. This indicates that the plasma polymer-
ized cyclohexene lms will have high hydrophobicity and
low surface energy with increasing RF power and tem-
perature.
Fig. 3. (a) Growth rate of cyclohexene lms as a function
of RF power for two deposition temperatures. (b) Contact
angle of cyclohexene lms as a function of RF power for two
deposition temperatures.
IV. CONCLUSIONS
Polymer-like organic thin lms were deposited at tem-
peratures in the range of room temperature and 100

C
by using the PECVD method with organic precursors
such as cyclohexene monomers. The electrical and the
optical properties of the organic thin lms and the eects
of the RF plasma power and deposition temperature were
investigated in this study. The dielectric constant ob-
tained from the as-grown polymerized lm deposited at
100

C and various RF powers changed from 2.90 to 2.43.
However, the leakage current density measured by using
the I-V characteristic curves were always below 10
12
A/cm
2
at an applied eld of 1 MV/cm for all deposited
lms, suggesting a possibility of low-dielectric constant
device applications.
From our study, we realized that a relatively high den-
sity cyclohexene lm with high hydrophobicity could be
obtained with increasing RF power and temperature.
FT-IR and UV-visible also results show that the as-
grown transparent organic lms had high degree cross-
linking density with high transmittance.
Characterization of Organic Polymer Thin Films Deposited I.-S. Bae et al. -1857-
ACKNOWLEDGMENTS
Support of this research by the Korea-Germany
Plasma Center Project through the Ministry of Com-
merce, Industry, and Energy in Korea is gratefully ac-
knowledged. This work was also supported by the BK21
project of the Ministry of Education, Korea, and by
the Center for Advanced Plasma Surface Technology at
Sungkyunkwan University.
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