698 IEEE TRANSACTIONS ON INSTRUMENTATION AND MEASUREMENT, VOL. 47, NO.
3, JUNE 1998
Optical Properties of Fluorinated Silicon Oxide Films
by Liquid Phase Deposition for Optical Waveguides
Tetsuya Homma, Atsushi Satoh, Seiji Okada, Masahiro Itoh, Masaki Yamaguchi, and Hideo Takahashi
Abstract—Optical properties of fluorinated silicon oxide (SiOF)
films for optical waveguide in optoelectronic devices were inves-
tigated. The SiOF films are formed at 25  C by a liquid phase
deposition (LPD) technique using a supersaturated hydroflu-
osilicic acid (H2 SiF6 ) aqueous solution. Two main absorption
peaks corresponding to Si-O and Si-F bonds were observed at
the wavenumbers of 1090 and 930 cm01 in Fourier transform
infrared (FTIR) spectrum, respectively. The LPD-SiOF films
show very little content of water components such as Si-OH
bonds and OH group. Although the transmittance for 600-nm-
thick LPD-SiOF film gradually decreased from the wavelength
around 700 nm, the relative transmittances to quartz glass are
over 98% in the wavelength region from 350–2500 nm. The
concentration of fluorine atoms in the LPD-SiOF film was about
5%, and the calculated composition was SiO1:85 F0:15 : The cal-
culated refractive index from the polarizability for LPD-SiOF
film was 1.430, and agrees very well with the measured value
at the wavelength of 632.8 nm by ellipsometry. The dispersion
of refractive index was evaluated and fitted to a three-term
Sellmeier’s dispersion equation. The zero dispersion wavelengths
for the LPD-SiOF and thermally grown SiO2 films were 1.271
and 1.339 m, respectively.
Index Terms— Fluorinated silicon oxide (SiOF), heterodyne
interference, optical waveguide, refractive index, laser.
I. INTRODUCTION
A thin-film optical waveguide is essential for high-
performance optoelectronic integrated circuits (OEIC’s).
As core layers in the waveguide, various dielectric materials
such as silicon dioxide (SiO ) with various dopants have been
mainly used [1]–[3]. The SiOF films are one of the most
attractive core layer materials because of lower refractive
index than SiO films [4], [5]. This low refractive index is
useful for propagation characteristics of light waves. The
plasma-enhanced chemical vapor deposition (PECVD) tech-
niques have been mainly used for the SiOF film formations,
Manuscript received August 11, 1998; revised November 30, 1998. This
work was supported in part by the project research of Shibaura Institute of
Technology (SIT) and by Research Organization for Advanced Engineering,
SIT.
T. Homma is with the Department of Electronics Engineering, Faculty
of Engineering and the Research Organization for Advanced Engineering,
Shibaura Institute of Technology, 3-9-14 Shibaura, Minato-ku, Tokyo 108-
8548, Japan.
A. Satoh, S. Okada, and M. Itoh are with the Department of Electronics
Engineering, Faculty of Engineering, Shibaura Institute of Technology, 3-9-14
Shibaura, Minato-ku, Tokyo 108-8548, Japan.
M. Yamaguchi is with the Department of Electrical Engineering, Faculty
of Engineering, and the Research Organization for Advanced Engineering,
Shibaura Institute of Technology, 3-9-14 Shibaura, Minato-ku, Tokyo 108-
8548, Japan.
H. Takahashi is with the Department of Electrical Engineering, Faculty of
Engineering, 3-9-14 Shibaura, Minato-ku, Tokyo 108-8548, Japan.
Publisher Item Identifier S 0018-9456(98)09822-2.
0018–9456/98$10.00  1998 IEEE
especially in semiconductor industries [6]–[8]. As source
gases for the SiOF film deposition, tetraethylorthosilicate
TEOS, Si(OC H ) /oxygen (O /hexafluoroethane
[6], TEOS/triethoxyfluorosilane TEFS, FSi(OC H [7],
or tetrafluorosilane [8] gas system has been
used. However, it is well known that the low temperature
deposition techniques can not simultaneously achieve high
quality without residual OH components. The OH components
such as H-OH and Si-OH increase the power loss of the
propagation light [9]–[11]. On the other hand, low-temperature
deposition has been required for the waveguide in the OEIC’s.
A room-temperature deposition technique for the SiOF films
using a liquid phase deposition (LPD) is one of the most
feasible techniques, and has been stated by Nagayama et al.
to be used as passivation films for a liquid crystal display
(LCD) [12]–[16]. The basic properties of the LPD-SiO
films have already been reported [12], [17]. The features
of LPD technique and the LPD-SiOF films are; i) deposition
temperatures lower than 40 C, ii) capability of selective
deposition, and iii) high quality with low refractive index.
These features can realize damage-free fabrication and high-
performance thin-film optical waveguide. An application
of the LPD technique to selective SiOF films deposition
has been proposed for the full planarization of interlayer
dielectric films in ultra-large scale integrated circuits (ULSI’s)
[18]. However, the precise research on refractive index of
LPD-SiOF films has not yet been done. Although the film
thickness and refractive index have generally been measured
using ellipsometric systems, we have investigated heterodyne
interference techniques for this purpose [19], [20]. Since the
heterodyne interference technique utilizes a simpler system
than the ellipsometric system, this technique has the possibility
of high-resolution measurement for refractive index and film
thickness.
In this paper, we will reveal the optical properties of LPD-
SiOF films and study the feasibility of the LPD-SiOF films
for the thin-film optical waveguide in OEIC’s. Especially, the
dispersion of refractive index and material dispersion coeffi-
cient will be discussed, based on the Sellmeier’s dispersion
equation.
II. EXPERIMENTAL PROCEDURE
The LPD of SiOF films was carried out in a system equipped
with a Teflon vessel, a dripper for boric acid (H BO aqueous
solution, and a stirrer. The schematic diagram of LPD system
is shown in Fig. 1. The base solution for the deposition was
prepared in the same manner described in previous papers [17],
[18]. In order to maintain the saturated hydrofluosilicic acid
HOMMA et al.: OPTICAL PROPERTIES OF SiOF FILMS BY LPD
Fig. 1. Schematic diagram of LPD system.
(H SiF solution supersaturated, H BO aqueous solution
with the concentration of 0.1 mol/L was continuously added
in the saturated H SiF solution at a rate of 1 10 L/h
per 1 L of H SiF solution during the film deposition. The
supersaturated H SiF solution was stirred by a stirrer at the
spin speed of 500 rpm, in order to diffuse the H BO solution.
Silicon (Si) substrates with the surface area of 15 mm 15
mm and quartz glass substrates were used for the experiments.
The deposition rate on the Si substrates was 15 nm/h at the
deposition temperature of 25 C.
Optical properties of the LPD-SiOF films such as chemi-
cal bonding structure, transmittance, composition, refractive
index, and thickness were evaluated, where the LPD-SiOF
films were formed on Si or quartz glass substrates. The
chemical bonding structures were investigated using Fourier
transform infrared (FTIR) spectra, where about 160-nm-thick
film was used. The transmittance was evaluated using a
spectrophotometer with covering wavelength of 190–2500 nm,
where the SiOF films with thicknesses of about 200 and
600 nm, deposited on quartz glass substrates, were used. To
determine the composition of LPD-SiOF films, represented as
SiO F , the concentrations of silicon, oxygen, and fluorine
atoms were analyzed by Auger electron spectroscopy (AES),
where about 160-nm-thick film was used. The refractive index
and thickness were evaluated from the average of ten point
measurements by using a heterodyne interference technique
using various wavelengths from laser sources, as compared
to conventional ellipsometric measurement at 632.8 nm. The
schematic illustration for the heterodyne interference system
used in this experiment is shown in Fig. 2. This interferometer
has the ability to use various laser beams in the wavelength
region of 400–1400 nm by varying only the acoustic frequency
of the acoustooptic tunable filter (AOTF). The refractive
index and film thickness can be obtained by measuring the
phase difference between with sample and without sample
(Mirror), and by measuring the reflected amplitudes and
from the sample by the and polarizations [20]. The
and are parallel and perpendicular polarizations to the plane
of incidence, respectively. The and are obtained
699
Fig. 2. Schematic illustration for the heterodyne interference system used in
this experiment.
by applying the with the shutter ( polarization), and
without the shutter ( polarization). In this experiment, He–Ne
lasers with the wavelengths of 632.8 and 1150 nm were used
as light sources. For the wavelengths of 780, 830, 980, and
1310 nm, semiconductor lasers were used as light sources. The
incident angle was 70 . The dispersion of refractive index
as a function of wavelength was evaluated and fitted to the
three-term Sellmeier’s relation, represented by
(1)
where and are the refractive index, wavelength
expressed in microns, and oscillator wavelengths, respectively
[21]. The are constants related to material oscillator
strengths. The and values were calculated by a nonlinear
least-square fitting. The material dispersion coefficient
was also determined using the second
derivative of (1). The data for LPD-SiOF film were also
compared to those of an SiO film grown thermally at 900 C.
III. RESULTS AND DISCUSSION
Fig. 3 shows FTIR spectrum for the LPD-SiOF film with
thickness of about 160 nm. There are two main absorption
peaks corresponding to fundamental vibrations of Si-O and
Si-F bonds at the wavenumbers of 1090 and 930 cm ,
respectively [13], [22]. The absorption peak position for the
Si-F bond is lower than that for the Si-O bond, indicating that
this film has capability of low transmission loss at long wave-
lengths [10]. The absorption peaks for fundamental vibrations
of Si-OH bonds and OH group, which are usually observed
at the wavenumbers around 3650 and 3400 cm , were under
detection limit [13], [22]. The low contents of OH components
will reduce the first overtone of these absorption, resulting in
low transmission loss [10]. Fig. 4 shows transmittance spectra
for the LPD-SiOF films formed on quartz glass substrates with
thicknesses of 200 and 600 nm, as compared to the quartz glass
substrate only. The absorption peaks around 1300 and 2200 nm
are due to CO in ambience and to mechanical exchange of
prism, respectively. For the 200-nm-thick LPD-SiOF film, the
transmittance variation is as small as the quartz glass. Although
the transmittance for 600-nm-thick LPD-SiOF film gradually
decreased from the wavelength around 700 nm, the relative
700 IEEE TRANSACTIONS ON INSTRUMENTATION AND MEASUREMENT, VOL. 47, NO. 3, JUNE 1998

Fig. 5. Depth profiles of silicon, oxygen, and fluorine atoms for the
LPD-SiOF film, analyzed by AES.

Fig. 3. FTIR spectrum for the LPD-SiOF film with thickness of about 160
nm.

Fig. 6. Dispersion property of refractive index for the LPD-SiOF film, as

compared to that for thermally grown SiO2 film.

expressed as follows:
(2)
where and are electronic polarization, dielectric
constant of free space, and atomic radius, respectively. The
electronic polarization for and are
Fig. 4. Transmittance spectra for the LPD-SiOF films formed on quartz glass 1.04 10 cm and 3.88 10 cm , respectively [23].
substrates with thicknesses of 200 and 600 nm, as compared to the quartz From the data, the polarization of is 1.94 10
glass substrate only. cm . The relationship between refractive index and
dielectric constant at high frequency is represented as
transmittances to quartz glass substrate are over 98% in the . Therefore, the electronic polarization of can be
hypothesized to be proportional to . When the polarization
wavelength region from 350 to 2500 nm. This high transmit-
of is ideally corresponding to 100% of for SiO
tance property is due to low content of Si-OH bonds and OH
(1.456 measured at 632.8 nm by ellipsometry), and
group, as mentioned in the FTIR spectrum analysis results.
for the LPD-SiOF are corresponding to 7.5% and 92.5%
Fig. 5 shows AES depth profiles of silicon, oxygen and flu-
of and , respectively, where these percentages are
orine atoms across the 160-nm-thick LPD-SiOF film. Silicon, calculated from the LPD-SiOF film composition. Therefore,
oxygen, and fluorine atoms were almost uniformly distributed the and can be calculated as 0.078 10 cm and
across the film. The concentration of fluorine atoms in the 1.795 10 cm , respectively. As the calculation results,
film was about 5%. The composition calculated from the the total polarization for the LPD-SiOF film is
fluorine concentration for the LPD-SiOF film is SiO F 1.873 10 cm . The polarization ratio of 5% fluorine
The refractive index was roughly estimated from the fluorine containing LPD-SiOF film to SiO film is 0.965. Accordingly,
concentration in the LPD-SiOF films. At the frequency of the refractive index of LPD-SiOF film can be estimated as
light, the electronic polarization is dominant for the dielectric 1.430. This value agrees very well with the refractive index
polarization. The electronic polarization of ions by Poling is measured by ellipsometry for the LPD-SiOF film.
HOMMA et al.: OPTICAL PROPERTIES OF SiOF FILMS BY LPD 701

TABLE I TABLE II
SELLMEIER COEFFICIENTS FOR LPD-SiOF AND THERMALLY GROWN SiO2 FILMS SUMMARY OF MEASURED REFRACTIVE INDEXES AND THICKNESSES
FOR LPD-SiOF AND THERMALLY GROWN SiO2 FILMS

* R, Residuals * Measured by ellipsometry

Fig. 6 shows the dispersion property of refractive index

calculated by the nonlinear least-square fitting for the LPD-
SiOF film, as compared to that for the thermally grown SiO
film. In this calculation, the data for SiO disclosed by Tatian
were used for initial values of the fitting [24]. The calculated
and values are listed in Table I. The obtained values
are similar to those calculated by Fleming for 1% fluorine-
doped SiO [1]. Table II summarizes the measured refractive
indexes and thicknesses for LPD-SiOF and thermally grown
SiO films. The measured refractive index for LPD-SiOF film
by the heterodyne interferometer at the wavelength of 632.8
nm is a little bit higher than that measured by ellipsometry.
The refractive indexes for the LPD-SiOF film were lower than
those for thermally grown SiO films. Using the LPD-SiOF
films as core layers, high propagation capacity, as well as
high-speed propagation of light waves will easily be achieved. Fig. 7. Material dispersion coefficient for the LPD-SiOF film, as compared
Fig. 7 shows the material dispersion coefficient for LPD- to that for thermally grown SiO2 film.
SiOF film, as compared to that for thermally grown SiO
film. The zero dispersion wavelengths for the LPD-SiOF These analysis results suggest that the LPD-SiOF films have
and thermally grown SiO films are 1.271 and 1.339 m, high performance potential as optical waveguides.
respectively. The refractive index analysis results suggest that
ACKNOWLEDGMENT
the LPD-SiOF films have high performance potential as optical
waveguides. The authors would like to thank Dr. T. Nagatomo for his
encouragement. They also thank Y. Ariyama, Y. Suzuki, T.
IV. CONCLUSIONS Oana and S. Kanegae for their assistance in experiments.
Optical properties of the LPD-SiOF films for optical wave-
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Tetsuya Homma was born in Niigata, Japan, on
March 23, 1959. He received the B.E. degree in
electronics engineering and the M.E. degree in elec-
trical engineering from Shibaura Institute of Tech-
nology (SIT), Tokyo, Japan, in 1981 and 1983,
respectively, and the Ph.D. degree in physical elec-
tronics engineering from Tokyo Institute of Tech-
nology, Tokyo, Japan, in 1994.
He worked for NEC Corporation, Kanagawa,
Japan, from 1983 to 1996. He moved to SIT in 1996
and is now an Associate Professor in Department of
Electronics Engineering. He joined the Research Organization for Advanced
Engineering, SIT, in 1997. He has now been working on optoelectronic
devices, optoelectronic integrated circuits (OEIC’s), and related materials.
Dr. Homma is a member of the Japan Society of Applied Physics (JSAP)
and The Institute of Electronics, Information, and Communication Engineers
(IEICE), Japan.
Atsushi Satoh was born in Tokyo, Japan, on June
12, 1972. He received the B.E. degree in electron-
ics engineering and the M.E. degree in electrical
engineering from Shibaura Institute of Technology
(SIT), Tokyo, Japan, in 1996 and 1998, respectively.
He joined Toshiba Corp., Tokyo, Japan, in 1998.
He is now working on planning and coordinating
for industrial systems in the Industrial Systems
Division.
Seiji Okada was born in Saitama, Japan, on Feb-
ruary 2, 1974. He received the B.E. degree in elec-
tronics engineering and the M.E. degree in electrical
engineering from Shibaura Institute of Technology
(SIT), Tokyo, Japan, in 1996 and 1998, respectively.
He joined Kenwood Corp., Tokyo, Japan, in 1998.
He is now working on circuits and software design
in the Communication Division.
Masahiro Itoh was born in Saitama, Japan, on April
5, 1974. He received the B.E. degree in electronics
engineering from Shibaura Institute of Technology
(SIT), Tokyo, Japan, in 1997.
He is now working on thin-film optical waveg-
uides.
Masaki Yamaguchi was born in Chiba, Japan, on
January 25, 1970. He received the B.E. degree in
electronics engineering, the M.E. degree in electrical
engineering, and the Ph.D. degree in functional
control systems from Shibaura Institute of Technol-
ogy (SIT), Tokyo, Japan, in 1993, 1995, and 1998,
respectively.
He joined SIT as a Lecturer in Department of
Electrical Engineering in 1998. He is also a member
of the Research Organization for Advanced Engi-
neering at SIT. He has been engaged in the research
on electronic materials and devices in general, with special interests in the
functional oxide thin films.
Dr. Yamaguchi is a member of the Japan Society of Applied Physics (JSAP),
and the Institute of Electronics, Information, and Communication Engineers
(IEICE), Japan.
Hideo Takahashi was born in Sendai, Japan, on
May 10, 1939. He received the B.S. and M.S.
degrees in electrical engineering from Shibaura In-
stitute of Technology (SIT), Tokyo, Japan, in 1963
and 1965, respectively, and the Ph.D. degree in
communication engineering from Osaka University,
Osaka, Japan, in 1986.
From 1965 to 1967, he worked for SIT as a
Research Assistant. From 1967 to 1981 he worked
for SIT as a Lecturer of Electronic Engineering.
From 1981 to 1988 he worked for SIT as an
Assistant Professor of Electrical Engineering. Since 1988 he has worked at
SIT as a Professor of Electrical Engineering. In recent years, he has been
engaged in research in acoustooptic devices and their applications.
Dr. Takahashi is a member of the Optical Society of America, the Japan So-
ciety of Applied Physics (JSAP) and The Institute of Electronics, Information,
and Communication Engineers (IEICE), Japan.