applied

surface science
ELSEVIER

Applied Surface Science 79/81)(1994) 332 337

UV-assisted deposition of TEOS SiO 2 films

using the spin-coating method
Koji Kinashi

a, M i c h i o N i w a n o

*'~', N o b u o

Miyamoto

~l, K o j i H o n m a

'~ Research Institute of Electrical Communication, Tohoku Unicersity, Sendai 980, Japan
t, Chemitronics ('o., Ltd., Tatsuno 2-7-3, Higashiyarnato, Tokyo 189, Japan

(Received 13 October 1993; accepted for publication I December 1993)

Abstract

We have previously proposed a method of depositing silicon dioxide films on Si from tctraethoxysilanc
S i ( O C z H s ) 4 (TEOS) using ultraviolet (UV) light from a low-pressure mercury lamp. In the method, an organic

solution which contains TEOS is spin-coated onto a Si wafer surface to form a thin organic film which is then
exposed to UV light to synthesize silicon dioxide. In this study, the photochemical reactions in the oxide formation
process have been investigated using infrared (IR) and UV absorption spectroscopy. The IR and UV absorption data
confirm that the UV light decomposes the organic compounds in the spin-coated organic film to convert the film
into a silicon dioxide film. We also demonstrate with thermal desorption spectroscopy (TDS) measurements that the
deposited film is stable with respect to substrate heating to approximately 400C.

1. Introduction

Dielectric films such as silicon dioxide are

widely used in integrated circuit (IC) technology.
Deposition of these films is commonly carried out
by means of chemical-vapor-deposition (CVD). In
general, this technique requires relatively high
substrate temperatures for film deposition; the
substrate temperature ranges from 400C to
1000C, depending on the chemical system [1].
Such high substrate temperatures are often undesirable because they may enhance the rates of
unwanted side processes such as dopant diffusion. It therefore is quite important for fabricating highly-reliable, high-density ICs to perform

* Corresponding author. Fax: (+ 81) 22 266 6295.

dielectric film deposition at lower temperatures.

One promising technique to do this is photon-induced CVD (photo-CVD). In this technique, relatively high-energy photons are utilized as the
exciting light source to decompose the source
materials. For example, in the photo-CVD of
silicon dioxide film, ultraviolet (UV) light has
been utilized to decompose source gases such as
silane (Sill4), N 2 0 and O 2 [2-5].
We have previously proposed a simple method
of depositing a silicon dioxide film on Si at low
temperature by photolysis of tetraethoxysilane
(TEOS), Si(OC2Hs) 4 [6]. This compound seems
to be a promising class of silicon sources for
silicon oxide deposition because of its atomic
composition and molecular structure. In our deposition method, a spin-coated organic film which
contains T E O S is irradiated by UV light from a

0169-4332/94/$07.00 1994 Elsevier Science B.V. All rights reserved

SSDI 0 1 6 9 - 4 3 3 2 ( 9 4 ) 0 0 0 7 3 - A

K. Kinashi et al. /Applied Surface Science 79/80 (1994) 332-337

low-pressure mercury lamp to generate silicon

oxide. The major advantage of this method is that
the oxide film formation can be accomplished at
low temperatures, that is, below 100C, and
moreover, neither a specialized reaction chamber
nor a gas doser system is necessary. Additionally,
this method makes it possible to perform selective deposition of a silicon oxide film through
projection of a photomask. In a previous paper
[6], we demonstrated that some of the physical
properties of these deposited films are comparable to those of oxide films obtained with conventional methods.
In this study, we investigate the photochemical
reactions which take place in the spin-coated
organic film when exposed to UV light, using
infrared (IR) and UV absorption spectroscopy.
Detailed knowledge of the deposition process is
inevitably necessary in order to improve and control the film quality and to develop deposition
sources. We also examine the thermal properties
of the deposited films using thermal desorption
spectroscopy (TDS).

2. Experiment
The deposition was performed in a simple
aluminum box equipped with a low-pressure mercury lamp. Since TEOS is volatile, collodion,
which is nitrocellulose dissolved in ethylalcohol
and ethylether, was used as the carrier which
prevents TEOS from evaporating from the substrate when exposed to UV light. Note that nitrocellulose is sensitive to UV light; under UV irradiation, this material is readily decomposed into
volatile products such as CO, CO 2, H 2 0 , N2, and
NO [7]. The deposition procedure was as follows.
First, TEOS, collodion and ethylalcohol were
mixed with a volume ratio of 4 : 2 : 1 . The resultant mixture was spin-coated onto a silicon wafer
with a spinner. The wafer was then placed 2 cm
from the UV lamp in the deposition box. Prior to
UV irradiation, the deposition box was purged of
air by flowing dry N 2 gas. The optical power
density on the wafer surface was about 3 m W / c m 2
at 254 nm. The temperature of the wafer surface
under UV irradiation was approximately 60C, as

333

measured by a thermocouple attached to the

sample surface.
The initial decomposition of organic compounds in the spin-coated organic film caused by
UV irradiation was monitored by Fourier-transform infrared (FT-IR) spectroscopy. After exposure to UV, the sample was placed in a dry N 2
environment to record infrared absorption spectra. UV absorption measurements were performed using a Seya-Namioka monochromator
and a deuterium discharge lamp. For this measurement, the TEOS-containing organic solution
was coated onto a LiF crystal plate which is
transparent above 105 nm, and the absorption
spectra of the film were measured before and
after exposure to UV light. Thermal desorption
experiments were carried out using an ultra-high
vacuum chamber equipped with a quadrupole
mass spectrometer (QMS). The base pressure of
the chamber was in the order of 10 -8 Torr. The
Si substrate was heated directly with a Ta resistive heater. The substrate temperature of the
sample was monitored by an A l u m e l / C r o m e l
thermocouple which was attached to the sample
surface. The linear heating rate was set at 10
d e g r e e / m i n . Outgas species desorbing from the
surface during ramped heating were detected by
the QMS.

3. Results and discussion

3.1. I R absorption

Fig. 1 shows infrared absorption spectra of the

TEOS-containing organic film spin-coated on a Si
wafer surface, taken for different UV exposure
times. The thickness of the spin-coated film prior
to UV exposure was approximately 0.1 /xm as
measured by a profilometer. As shown in the top
of Fig. 1, the film prior to UV exposure exhibits
five pronounced peaks at 840, 1080, 1280, and
1660, and 2980 cm-~, which can be attributed to
the C - N , Si-O, C - O , N=O, and C - H stretching
vibrations, respectively. A broad peak at 3400
cm-~ is attributed to the stretching vibration of
O - H . TEOS does not contain a hydroxyl group,
but collodion and ethylalcohol do. The observed

334

K. Kinashi et aL /Applied Surface Science 7 9 / 8 0 (1994) 332 337

O - H vibration peak, therefore, is attributed to

the collodion and ethylalcohol which remained in
the spin-coated film. It is probable that hydrolysis
of T E O S partly occurred during spin coating to
produce OH-substituted oligonomers. Such O H containing products are also the origin of the
O - H vibration peak. The intense peaks at 840,
1280 and 1660 cm -~ are most probably due to
fibrous nitrocellulose.
As can be seen from Fig. 1, while the intensity
of the S i - O peak did not decrease considerably
with increasing U V exposure, those of all other
peaks did. This confirms that UV light decomposes organic compounds in the spin-coated film
to generate a silicon oxide-like film. In particular,
the peaks at 840, 1280 and 1660 c m - ~ are significantly decreased in intensity and vanish for 40
min U V exposure. This shows that nitrocellulose,
which was used as the carrier for TEOS, is readily dissociated by UV, which is consistent with the
results of a previous study [7].
U p o n close inspection of Fig. 1, we notice that
the O - H vibration peak at 3400 c m - ] initially
increases and then drops with increasing UV
exposure. Additionally, for a 5 min exposure a
new peak appears at 1740 cm ~. This peak is due

FT-IR

T E O S SiO 2
f
g
r

"~
i

I.,

i r

'b

e
JI

,
i

FT-IR
TEOS

'\

SiO 2

'

do!I

'%-__

/
/

z
LLI
I-'Z ~

t
~

LU

>
t-.

5LLI
n"

10

20

30

40

10

20

30

40

EXPOSURE TIME (min)

Fig. 2, Intensities of the infrared absorption peaks as a
function of the UV exposure time. (a) 840 cm I, (b) 1080
cm l,(c) 1 2 8 0 c m - I (d) 1660cm t , ( e ) 1740cm i,(f) 298/)
cm I and (g) 3400 cm t

to the stretching vibration of the carbonyl group,

C=O. Upon further exposure to UV this peak
also decreases in intensity. These trends can be
clearly seen in Fig. 2, in which the intensities of
the peaks observed in the spectra of Fig. 1 are
plotted as a function of exposure time. From
these observations, we determine that some photochemical reactions proceed through an intermediate chemical state.
We discuss the time evolution of the O - H
peak intensity. The hydrolysis and condensation
of T E O S is known to be a reaction route to the
production of glasses [8]. It therefore is most
probable that initially a hydrolysis reaction takes
place in which O C 2 H 5 groups in T E O S are replaced with a hydroxyl group to generate O H substituted monomers [8,9]; that is,

t
HsC20--Si--OC2H

4000

3000
2000
1000
WAVENUMBER (cm -1)
Fig. 1. Infrared absorption spectra of the TEOS-containing
organic film taken for different U V exposure times. The
figure attached to each spectrum is the exposure time in
minutes,

5 + H20

f
HsC20--Si--OH

+ C2HsOH.

(1)

The origin of the water consumed in this reaction

process would be water present in air or ethylal-

I~ Kinashi et al. /Applied Surface Science 79/80 (1994) 332-337

cohol incorporated in the film. Note that ethylalcohol is decomposed by UV to generate water
and volatile hydrocarbons [10]. Water is also decomposed by UV light to produce hydrogen and
O H radicals [10]. These radicals will promote the
hydrolysis reaction. The OH-substituted monomers generated by the hydrolysis then react with
each other or with T E O S to generate oligoethoxysilanes such as Si20(OC2H5) 6 which
contain the S i - O - S i bridging bond:

HsC20--Si--OH

+ HO--Si--OC2H

I
I

-~ H s C 2 0 - - S i - - O - - S i - - O C 2 H

HsCzO--Si--OC2H

5 + H20,

(2)
I

5 + HO--Si--OC2H

I
I

H5C20-- Si--O--Si--OC2H
+ C2HsOH.

335

cm -] appears accompanied with a decrease in

intensity of the N=O peak at 1660 cm -1. The
carbonyl groups thus generated would be decomposed upon further exposure to UV. These decomposition processes can explain the observed
evolution of the C=O peak intensity.

3.2. UV absorption
In order to examine the photosensitivity of the
spin-coated film in the UV region, we have performed optical-absorption measurements in the
wavelength region 100-220 nm. In Fig. 3 we show
the absorption spectra of the spin-coated film
before and after 40 min UV exposure. For comparison, we also show the absorption spectrum of
synthetic quartz in Fig. 3. We can see that upon
UV exposure the absorbance of the film is enhanced in the vicinity of 150 nm and the spectrum of the UV exposed film shows a close resemblance to that of synthetic quartz. This indicates that UV irradiation converts the spin-coated
organic film into an inorganic silicon oxide film.
The extent to which photochemical reactions,
important for oxide formation, occur in the film is

(3)

These processes can be referred to as condensation or polymerization. Water and ethylalcohoi

are released by the condensation. We can therefore say that at the early stages of polymerization,
hydroxyl-containing compounds such as OH-substituted monomers, water and ethylalcohol are
increasingly generated, leading to an increase in
the O H peak intensity. However, such hydroxylcontaining compounds will be gradually consumed through repeated cycles of hydrolysis and
polymerization, leading to a decrease in the intensity of the O - H vibration peak.
One possible process which produces the carbonyl group is the decomposition of the nitro
group in nitrocellulose; that is, - C - O - N O - ,
- C = O + NO T. This is consistent with the observation that upon UV exposure the N=O peak at
1660 cm -1 is reduced in intensity. Indeed, we
observed that when a thin collodion film formed
on Si is exposed to UV, the C=O peak at 1740

UV absorption
TEOS SiO 2

==
.{5

Before UV exposure
aJ

z
~
m
n"
0
r/?
<

re
b

Quartz

~
I

100

150
200
WAVELENGTH (nm)

Fig. 3. U V absorption spectra of the TEOS-containing organic

film before and after U V exposure, as well as of synthetic
quartz.

336

1( Kinashi et al. /Applied SurJace Science 7 9 / 8 0 (1994) 332-337

determined from a compromise between the absorption of UV light by the film and the strength
of the interaction of UV light with the film. The
U V absorption spectra of Fig. 3 demonstrate that
the wavelengths of the emission lines from a
low-pressure mercury lamp, 184 and 254 nm, are
out of the region where the absorbance of the
film is high. This means that the UV light may
pass through the film; if otherwise, UV light
would not penetrate the film so that UV-induced
reactions occur only in the vicinity of the film
surface. On the other hand, if absorption of UV
light were quite weak, UV-induced reactions
would not occur enough to convert the organic
film into an inorganic silicon oxide film. As can
be seen from Fig. 3, a weak absorption band is
visible around 190 nm. We therefore speculate
that the 184 nm light from a low-pressure mercury lamp predominantly interacts with the
TEOS-containing organic film to generate silicon
oxide. As mentioned above, upon UV irradiation
the absorbance of the film was enhanced around
150 nm. This enhancement was interpreted as a
result of oxide formation. We note that the emission lines from the lamp lie outside this wavelength region. This means that the silicon oxide
generated by UV irradiation does not absorb the
UV light significantly so that UV-induced reactions proceed efficiently in the entire portion of
the film. Hence, we can say that the UV light
used here is suited to the conversion of the
TEOS-containing organic film into silicon oxide
film.

3.3. TDS

Fig. 4 shows the intensities of mass fragments

desorbing from the spin-coated film before and
after U V exposure, plotted as a function of the
substrate temperature. Mass fragments of m / e =
12 and 14 are due to carbon and hydrocarbon
CH 2, respectively, and those of r n / e = 28 originate from C 2 H 4 , C O , and N 2. m / e = 30 is most
likely due to NO. It should be noted that while
the unexposed film exhibits an intense desorption
peak around 170C, the film following 40 min UV
exposure shows no desorption peak below ap-

TEOS SiO 2
'

Before UV exposure
~"

M/e= 18

....

~-~

1/40

_ _ ~;-- .....
After UV exposure

"',

x 1/2

LL!

Iz

.~

28

........

I_.

200

]/

TEMPERATURE

,/ i,
,\.

4 0

600

(C)

Fig. 4. hUensitics of mass fragments desorbing from the

TEOS-containing organic film before and after UV exposure
as a function of the substrate temperature.

proximately 400C. This indicates that due to UV

exposure the spin-coated organic film is converted to the inorganic oxide film which is thermally stable up to at least 400C.

4. Summary
We have investigated the method of depositing
a silicon dioxide film on Si from tetraethoxysilane
Si(OC2Hs) 4 (TEOS) using UV light from a lowpressure mercury lamp. In the method, an organic solution which contains T E O S and nitrocellulose is spin-coated onto a Si wafer surface to
form an organic film which is then exposed to UV
light to generate an inorganic silicon oxide film.
IR and U V absorption data confirmed that the
spin-coated organic film is converted by UV irradiation to inorganic silicon oxide. I R data also
demonstrated that some organic compounds in
the spin-coated film are decomposed through
photochemical intermediates. TDS data showed
that the deposited film is stable with respect to
substrate heating to about 400C.

K. Kinashi et aL /Applied Surface Science 79/80 (1994) 332-337

Acknowledgments
T h e a u t h o r s w i s h to t h a n k D r . M. Y a n a g i h a r a
a n d A . A r a i for t h e i r a s s i s t a n c e in t h e U V abs o r p t i o n m e a s u r e m e n t s . P a r t o f this w o r k w a s
s u p p o r t e d by a G r a n t - i n - A i d for G e n e r a l P r o j e c t
R e s e a r c h f r o m t h e M i n i s t r y o f E d u c a t i o n , Science and Culture of Japan.

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