You are on page 1of 6

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

b

'~ 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 400°C.

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 400°C to
1000°C, 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

Additionally. N=O. Note that nitrocellulose is sensitive to UV light. The resultant mixture was spin-coated onto a silicon wafer with a spinner.H . and C . N2. this method makes it possible to perform selective deposition of a silicon oxide film through projection of a photomask. Experiment The deposition was performed in a simple aluminum box equipped with a low-pressure mercury lamp. and 1660. below 100°C. The base pressure of the chamber was in the order of 10 -8 Torr. 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. As shown in the top of Fig. The Si substrate was heated directly with a Ta resistive heater. was used as the carrier which prevents TEOS from evaporating from the substrate when exposed to UV light. The wafer was then placed 2 cm from the UV lamp in the deposition box.H stretching vibrations. Detailed knowledge of the deposition process is inevitably necessary in order to improve and control the film quality and to develop deposition sources. under UV irradiation. Prior to UV irradiation.1 /xm as measured by a profilometer. We also examine the thermal properties of the deposited films using thermal desorption spectroscopy (TDS). and NO [7]. After exposure to UV. respectively. 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. In a previous paper [6].1. UV absorption measurements were performed using a Seya-Namioka monochromator and a deuterium discharge lamp. /Applied Surface Science 79/80 (1994) 332-337 low-pressure mercury lamp to generate silicon oxide. collodion and ethylalcohol were mixed with a volume ratio of 4 : 2 : 1 . TEOS. this material is readily decomposed into volatile products such as CO. neither a specialized reaction chamber nor a gas doser system is necessary. I R absorption Fig.N . H 2 0 . and the absorption spectra of the film were measured before and after exposure to UV light. the film prior to UV exposure exhibits five pronounced peaks at 840. collodion. Results and discussion 3. First. Si-O. as 333 measured by a thermocouple attached to the sample surface. 1280. we demonstrated that some of the physical properties of these deposited films are comparable to those of oxide films obtained with conventional methods. the sample was placed in a dry N 2 environment to record infrared absorption spectra. using infrared (IR) and UV absorption spectroscopy. the deposition box was purged of air by flowing dry N 2 gas. which can be attributed to the C . the TEOS-containing organic solution was coated onto a LiF crystal plate which is transparent above 105 nm. 3.K. and 2980 cm-~. The temperature of the wafer surface under UV irradiation was approximately 60°C. and moreover. Kinashi et al. TEOS does not contain a hydroxyl group. Since TEOS is volatile.O . The observed . The major advantage of this method is that the oxide film formation can be accomplished at low temperatures. In this study. CO 2. The deposition procedure was as follows. C . 1 shows infrared absorption spectra of the TEOS-containing organic film spin-coated on a Si wafer surface. that is. 1080. 2. Outgas species desorbing from the surface during ramped heating were detected by the QMS. we investigate the photochemical reactions which take place in the spin-coated organic film when exposed to UV light. Thermal desorption experiments were carried out using an ultra-high vacuum chamber equipped with a quadrupole mass spectrometer (QMS). 1. which is nitrocellulose dissolved in ethylalcohol and ethylether. The optical power density on the wafer surface was about 3 m W / c m 2 at 254 nm. The linear heating rate was set at 10 d e g r e e / m i n . taken for different UV exposure times. but collodion and ethylalcohol do. A broad peak at 3400 cm-~ is attributed to the stretching vibration of O . The thickness of the spin-coated film prior to UV exposure was approximately 0. For this measurement.

for a 5 min exposure a new peak appears at 1740 cm ~. 2. the peaks at 840. We discuss the time evolution of the O . 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 [8.334 K. those of all other peaks did. 1 are plotted as a function of exposure time. that is. we determine that some photochemical reactions proceed through an intermediate chemical state. i FT-IR TEOS '\ SiO 2 j ' do!I '%-__° \ 1 e i / / z LLI I-'Z ~ t ~ _ b LU > t-.. 5 + H20 f HsC20--Si--OH J + C2HsOH. Such O H containing products are also the origin of the O . As can be seen from Fig.H vibration peak. The figure attached to each spectrum is the exposure time in minutes. Kinashi et aL /Applied Surface Science 7 9 / 8 0 (1994) 332 337 O . 5LLI n" 0 0 10 20 30 40 0 10 20 30 40 EXPOSURE TIME (min) Fig. in which the intensities of the peaks observed in the spectra of Fig. 1. This peak is due p I d FT-IR I T E O S SiO 2 f g r "~ i o r I. It is probable that hydrolysis of T E O S partly occurred during spin coating to produce OH-substituted oligonomers. which is consistent with the results of a previous study [7]. ( e ) 1740cm i.H peak intensity.9]. c i r 'b ] e JI L / E z . In particular. Upon further exposure to UV this peak also decreases in intensity.H vibration peak. These trends can be clearly seen in Fig. 2. Intensities of the infrared absorption peaks as a function of the UV exposure time. C=O. U p o n close inspection of Fig.] initially increases and then drops with increasing UV exposure. (b) 1080 cm l. This confirms that UV light decomposes organic compounds in the spin-coated film to generate a silicon oxide-like film.I (d) 1660cm t . This shows that nitrocellulose. t HsC20--Si--OC2H I 4000 3000 2000 1000 WAVENUMBER (cm -1) Fig. The intense peaks at 840. Additionally. 1. therefore. 1280 and 1660 cm -~ are most probably due to fibrous nitrocellulose. (1) The origin of the water consumed in this reaction process would be water present in air or ethylal- .O peak did not decrease considerably with increasing U V exposure. is attributed to the collodion and ethylalcohol which remained in the spin-coated film. (a) 840 cm I. 1280 and 1660 c m . is readily dissociated by UV. which was used as the carrier for TEOS.~ are significantly decreased in intensity and vanish for 40 min U V exposure.(f) 298/) cm I and (g) 3400 cm t to the stretching vibration of the carbonyl group. we notice that the O . 1. Infrared absorption spectra of the TEOS-containing organic film taken for different U V exposure times.H vibration peak at 3400 c m . The hydrolysis and condensation of T E O S is known to be a reaction route to the production of glasses [8]. From these observations.(c) 1 2 8 0 c m . while the intensity of the S i .

3.. Water and ethylalcohoi are released by the condensation. important for oxide formation. However. that is. . U V absorption spectra of the TEOS-containing organic film before and after U V exposure. . water and ethylalcohol are increasingly generated.O . . Note that ethylalcohol is decomposed by UV to generate water and volatile hydrocarbons [10]. These decomposition processes can explain the observed evolution of the C=O peak intensity. the C=O peak at 1740 I . (2) I 5 + HO--Si--OC2H I 5 I I I I [ H5C20-.C . .2.O . Indeed. occur in the film is (3) These processes can be referred to as condensation or polymerization. leading to an increase in the O H peak intensity. . I . hydroxyl-containing compounds such as OH-substituted monomers. These radicals will promote the hydrolysis reaction.. /Applied Surface Science 79/80 (1994) 332-337 cohol incorporated in the film.. 3 we show the absorption spectra of the spin-coated film before and after 40 min UV exposure. 3.S i . Fig. We can therefore say that at the early stages of polymerization. I UV absorption TEOS SiO 2 == . . / 150 200 WAVELENGTH (nm) . . . 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 . 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. One possible process which produces the carbonyl group is the decomposition of the nitro group in nitrocellulose. I d ..{5 Before UV exposure aJ z ~ m n" 0 r/? < re b Quartz c ~ I 100 . leading to a decrease in the intensity of the O . we observed that when a thin collodion film formed on Si is exposed to UV.S i bridging bond: I HsC20--Si--OH I + HO--Si--OC2H I 5 I I I I I -~ H s C 2 0 . The carbonyl groups thus generated would be decomposed upon further exposure to UV. In Fig.. 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. This indicates that UV irradiation converts the spin-coated organic film into an inorganic silicon oxide film.H vibration peak.N O . . This is consistent with the observation that upon UV exposure the N=O peak at 1660 cm -1 is reduced in intensity. For comparison. 5 335 cm -] appears accompanied with a decrease in intensity of the N=O peak at 1660 cm -1.C = O + NO T. Water is also decomposed by UV light to produce hydrogen and O H radicals [10]. such hydroxylcontaining compounds will be gradually consumed through repeated cycles of hydrolysis and polymerization.I~ Kinashi et al. . as well as of synthetic quartz. we also show the absorption spectrum of synthetic quartz in Fig. The extent to which photochemical reactions.Si--O--Si--OC2H + C2HsOH.O C 2 H I HsCzO--Si--OC2H 5 + H20. . B . 3.

4. ]/ k TEMPERATURE . TDS data showed that the deposited film is stable with respect to substrate heating to about 400°C. plotted as a function of the substrate temperature. we can say that the UV light used here is suited to the conversion of the TEOS-containing organic film into silicon oxide film. 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... Hence. . . As mentioned above. This means that the UV light may pass through the film.3. 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. 184 and 254 nm. proximately 400°C. Mass fragments of m / e = 12 and 14 are due to carbon and hydrocarbon CH 2. 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 400°C. 4 shows the intensities of mass fragments desorbing from the spin-coated film before and after U V exposure. respectively. 6 4 0 . and N 2.\.~ 28 / E . I_.. It should be noted that while the unexposed film exhibits an intense desorption peak around 170°C. C O . IR and U V absorption data confirmed that the spin-coated organic film is converted by UV irradiation to inorganic silicon oxide. On the other hand. are out of the region where the absorbance of the film is high. ~-~ 1/40 . After UV exposure "'. hUensitics of mass fragments desorbing from the TEOS-containing organic film before and after UV exposure as a function of the substrate temperature. if absorption of UV light were quite weak. 200 . 3. UV-induced reactions would not occur enough to convert the organic film into an inorganic silicon oxide film. As can be seen from Fig. if otherwise.. the film following 40 min UV exposure shows no desorption peak below ap- TEOS SiO 2 ' x Before UV exposure ~" M/e= 18 . This enhancement was interpreted as a result of oxide formation. 3.. We note that the emission lines from the lamp lie outside this wavelength region.. x 1/2 LL! Iz L 0 . m / e = 30 is most likely due to NO. and those of r n / e = 28 originate from C 2 H 4 .. UV light would not penetrate the film so that UV-induced reactions occur only in the vicinity of the film surface.-./ i.. upon UV irradiation the absorbance of the film was enhanced around 150 nm... a weak absorption band is visible around 190 nm. _ _ ~. TDS Fig. In the method.336 1( Kinashi et al. I R data also demonstrated that some organic compounds in the spin-coated film are decomposed through photochemical intermediates.. . 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. L • • 600 (°C) Fig. The U V absorption spectra of Fig.... /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. 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.. 3 demonstrate that the wavelengths of the emission lines from a low-pressure mercury lamp. 4.

Calvert and J. Serra. B. Okuyama and Y.i n . [7] T. References [1] For example. [9] C. J. Pitts.M. Toyoda. Hamakawa. M.N. Phys.J. 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 . 233. New York. Hamakawa. J.K. Damen. 28 (1989) L1310. M. [2] K. J. 1966). Gonzalez. Suemitsu. Phys. 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 . Pou. Miehimori.M.G. 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 . M. [8] C. Photochemistry (Wiley.A. 26 (1987) 835. Non-Cryst. J. K. Marks and R. Thin Solid Films 218 (1992) 170. Ed. Non-Cryst. Phys. Lett. M. Niwano. M. Franklin.J.C. J. Appl. . 54 (1983) 7201. 52 (1988) 810. Jpn. Miyamoto. Fernandez. New York. Garcia. Perez-Amor. Appl. Turner and K. Leon and M. 337 [3] Y. [6] M. Phys. K. J..W. Solids 91 (1987) 402. [4] J. J. Okuyama and Y. J. Solids 93 (1987) 169. Sze (McGraw-Hill. Honma and N. 26 (1987) 805. Inoue. Hirano. [5] P. S. Jr.A. in: VLSI Technology. E. Jpn. A. Robertson.W.E. Deutsch and M. Appl. Geis.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 . [10] J.M. 1988) p.F. S. Jpn. Science and Culture of Japan. D. Inoue. Appl. Appl. Phys. Adams. Mulder and A. Y a n a g i h a r a a n d A .