Journal of Sol-Gel Science and Technology 24, 95103, 2002 c 2002 Kluwer Academic Publishers. Manufactured in The Netherlands.

The Effect of SiO2 Addition on the Grain Size and Photocatalytic Activity of TiO2 Thin Films
JIAGUO YU AND JIMMY C. YU Department of Chemistry and Materials Science & Technology Research Centre, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, Peoples Republic of China
yujiaguo@public.wh.hb.cn

XIUJIAN ZHAO State Key Lab of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, Peoples Republic of China Received April 3, 2001; Accepted October 16, 2001

Abstract. The uniform transparent TiO2 /SiO2 nanometer composite thin lms were prepared via sol-gel method on the soda lime glass substrates, and were characterized by X-ray photoelectron spectroscopy (XPS), FTIR spectroscopy, UV-VIS spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and BET surface areas. It was found that the addition of SiO2 to TiO2 thin lms could suppress the grain growth of TiO2 crystal and increase the hydroxyl content of the surface of TiO2 lms. The photocatalytic activity of the as-prepared TiO2 /SiO2 composite thin lms increases for SiO2 content of less than 5 mol%. Keywords: sol-gel method, TiO2 /SiO2 , thin lms, grain size, photocatalytic activity

1.

Introduction

Titanium dioxide has been investigated as a semiconductor photocatalyst for its application in solar energy conversion and environmental purication since Fujishima and Honda discovered the photocatalytic splitting of water on TiO2 electrodes in 1972 [1]. Environmental purication using TiO2 photocatalysts has attracted a great deal of attention with the increasing number of recent environmental problems in society. Recently, the application has been focused on purication and treatment of water and air, which is important for the protection of the environment, such as nature and life space [24]. However, the use of conventional powder catalysts results in the disadvantages of requiring stirring during the reaction and also of requiring separation after the reaction. Preparation of the catalysts coated as thin lms will overcome these

disadvantages and extend the industrial applications, such as their use as antibacterial ceramic tiles and selfcleaning glass and so on. Therefore, many researchers have begun to work on TiO2 thin lm photocatalyst [513]. The use of binary metal oxides (TiO2 /SiO2 ) as photocatalysts for photocatalytic degradation of organic contaminants is not entirely new. As early as 1986, it has been reported that the photocatalytic activity of TiO2 in titanium-silicon oxides can be enhanced [14]. Recently, Anderson and Bard [15, 16] demonstrated that a mixed oxide of TiO2 and SiO2 produced by a sol-gel method was a more efcient photocatalyst for the photocatalytic decomposition of rhodamine6G than TiO2 alone. Very recently, Xu et al. [17] also reported the dispersing effect of SiO2 and the enhancement of photocatalytic activity. However, few studies have been carried out on photocatalysis over

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TiO2 /SiO2 composite nanometer thin lms. In the present work, the transparent uniform TiO2 /SiO2 composite nanometer thin lms were prepared via the solgel method on soda-lime glass, and characterized by X-ray photoelectron spectroscopy (XPS), FTIR spectroscopy, UV-VIS spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and BET surface areas. The photocatalytic activity of TiO2 /SiO2 composite thin lms was evaluated for the photocatalytic decolorization of aqueous methyl orange. The effects of SiO2 addition on the crystalline phase, grain size, surface hydroxyl content, transmittance and photocatalytic activity of nanometer TiO2 thin lms were discussed. 2. 2.1. Experimental Procedure Preparation

Precursor solutions for TiO2 /SiO2 composite nanometer thin lms were prepared according to the literature [18, 19]. Tetraethylorthosilicate [TEOS] and tetrabutylorthotitanate [TBOT] were both obtained commercially at 99.0% purity. Both were dissolved in an equal volume of ethanol, and an additional hydrochloric acid catalyst was added to the TEOS precursor to take the mixture to a water:alkoxide ratio of 1. This mixture was then hydrolyzed by reuxing at 70 C for 2 h. The TEOS and TBOT precursors were then mixed together to give the required silica:titania ratio. Further quantities of ethanol and the hydrochloric acid catalyst were then added to take the water:alkoxide ratio to R = 2, and the mixture was aged, typically for 24 h. A nal dilution of ethanol (typically 1.5 parts ethanol to 1 part sol-gel by volume) was made to achieve the required viscosity before use. Slide glass plates (75 mm 25 mm 1.5 mm) were used as the support substrates. The TiO2 /SiO2 composite thin lms were prepared by a dip-coating method [9, 10]. The withdrawal speed was 2 mm s1 . Gel coating lms were dried at 100 C for 5 min and then carefully heat treated at 500 C for 1 h in air. The thickness of the TiO2 /SiO2 composite thin lms was adjusted by repeating the cycles from withdrawing to heat treatment. Powder samples were prepared apart from the abovedescribed glass samples. Titanium dioxide sol or mixed-solution of TiO2 SiO2 sol of the same composition as the glass samples were dried at 100 C in an air bath, ground by agate mortar and then heat-

The crystallinity of the powder samples was identied by X-ray diffraction (XRD) with a diffractometer (type HZG4-PC) employing Cu K radiation. The accelerating voltage and the applied current were 35 kV and 20 mA, respectively. The average grain size of TiO2 was calculated using X-ray line broadening methods based on the Scherrer formula. The morphology and grain size of TiO2 /SiO2 composite powders were observed using transmission electron microscopy (TEM) (Jcol Co., 1200EX, Japan). The thickness of the TiO2 /SiO2 composite thin lms were observed using scanning electron microscopy (SEM) (type SX-40) with an accelerating voltage of 20 kV and surface proler (Alphastep 500). Spectroscopic analyses of the TiO2 /SiO2 composite thin lms were obtained using a UV-visible spectrophotometer (type UV160A, wavelength range 200800 nm). The BET surface areas of the composite powders were determined by using nitrogen adsorption data at 77 K obtained with a Micromeritics GEMINI2360 apparatus. The TiO2 /SiO2 composite thin lms were analyzed by X-ray photoelectron spectroscopy (XPS), using a VG Scientic ESCALAB Mark II spectrometer equipped with two ultrahigh-vacuum (UHV) chambers. The pressure in the chambers during the experiments was about 107 Pa. A Mg K X-ray source was used. The analyzer was operated at 20 eV pass energy for high-resolution spectra and 50 eV for survey spectra. The X-ray photoelectron spectra were referenced to the C1s peak ( E b = 284.80 eV) resulting from the adventitious hydrocarbon (i.e. from the XPS instrument itself) present on the sample surface. 2.3. Photocatalytic Activity

The photocatalytic activity of TiO2 /SiO2 composite nanometer thin lms was evaluated by using methyl orange degradation decolorization [9, 20]. Experiment details were as follows: TiO2 /SiO2 thin lms were settled in aqueous methyl orange solution with a concentration of 0.03 mM in a quartz cell (10 mm 10 mm 30 mm). A high-pressure mercury lamp (125 W) was used as the light source. One face (10 mm 30 mm) of the TiO2 /SiO2 thin lms was irradiated along the normal direction. Integrated UV intensity in the range

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310400 nm was measured by a UV radiometer (UV-A, Photoelectric Instrument Factory Of Beijing Normal University, Beijing, China). The averaged intensity of UV radiation was 6.8 mW/cm2 . The solution was bubbled with air during irradiation. The concentration of methyl orange, which was decolorized, was determined by a UV-visible spectrophotometer.

3. 3.1.

Results and Discussion Thin Film Thickness

Figure 2. UV-VIS spectra of the TiO2 /SiO2 (1:1) composite lms prepared by repeating (a) 1, (b) 2 and (c) 5 coating cycles and heattreated at 500 C, respectively.

Figure 1 shows a linear relationship between the TiO2 /SiO2 composite thin lm thickness and the number of coating cycles. However, the line does not go through the origin. This is considered to be simply due to the fact that the coating lms from the second coating onwards are coated on the material formed just before, while the rst one is coated directly on a glass substrate [10, 20]. The average lm thickness per coating cycle is estimated to be about 0.10 m at the pulling speed of 2 mm s1 from the second coating onwards, while the rst coating lm thickness is about 0.18 m. The lm thickness was measured through SEM observation of the cross section of the lms and surface proler.

3.2.

UV-VIS Spectra

Figure 2 shows the UV-VIS spectra of the TiO2 /SiO2 composite thin lm deposited on soda lime glass by

Figure 1. Relationship between the lm thickness and the coating cycle times at a pulling speed of 2 mm s1 .

repeating (a) 1, (b) 2 and (c) 5 coating cycles in the wavelength range 200800 nm. The absorption edge of the TiO2 /SiO2 composite thin lms prepared by 1 and 2 coating cycles (as shown in Fig. 2(a) and (b)) is observed to be at a shorter wavelength range than that of the TiO2 /SiO2 composite thin lms prepared by 5 cycles (as shown in Fig. 2(c)). The shift is ascribed to the difference in crystallite size. The thin coating lms which underwent a short-term heat treatment, contained relatively small crystallites and showed a pseudo-blue shift [10]. The bands due to the interference color of the lms appeared in the wavelength range 350800 nm. The transmittance of TiO2 /SiO2 thin lms decreased with increasing cycle times. The absorption edge shifts towards shorter wavelengths for the TiO2 /SiO2 composite thin lm prepared by 1 or 2 cycles and clearly indicates an increase in the bandgap of TiO2 . To have an estimate of the bandgap energies, the absorption coefcient ( ) of the lms, near the absorption edge, were calculated from the transmittance (T ) and reectance ( R ) data using the simplied relation T = (1 R )2 ed /(1 R 2 e2d ), where d is the thickness of the lms [21, 22]. The intercept of the tangent to the ( )1/2 versus photon energy (h ), will give an estimate of the bandgap energies for indirect bandgap materials such as TiO2 . Plots of ( )1/2 versus photon energy (h ) are drawn for the TiO2 /SiO2 (1:1) composite lms deposited on soda lime glass by repeating (1) 1 and (2) 5 coating cycles and are shown in Fig. 3. The bandgap energies estimated from the intercept of the tangents to the plots are 3.68 and 3.76 eV for TiO2 /SiO2 (1:1) lms deposited by (1) 1 and (2) 5 coating cycles, respectively. These values are approaching the values reported by literature [23].

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Figure 3. Plots of ( )1/2 versus photon energy (h ) for the TiO2 /SiO2 (1:1) composite lms deposited on soda lime glass by repeating (1) 1 and (2) 5 coating cycles.

soda lime glass coated (d) TiO2 lm is about 350 nm. In fact, the band gap of TiO2 is 3.2 eV, its absorption edge should be 387.5 nm. However, the crystallite size of TiO2 thin lms prepared by the sol-gel method is smaller, owing to quantum size effects. The band gap of TiO2 become larger, therefore its absorption edge shows a pseudo-blue shift. The extrapolated optical absorption bandgap of the TiO2 lm deposited on soda lime glass by 2 coating cycles was found to be 3.5 eV, larger than the bandgap energy (3.2 eV) of bulk TiO2 . Furthermore, by comparing soda lime glass coated with TiO2 /SiO2 (1:1) lms (as shown in Fig. 4(c)) and TiO2 lms (as shown in Fig. 4(d)) , it can be found that although the number of coating cycles and heat-treatment time are the same, the adsorption edge of soda lime glass coated with TiO2 /SiO2 (1:1) lm shows a greater pseudo-blue shift and its bandgap energy is 3.70 eV, estimated by the extrapolated optical absorption method [21, 22]. This is probably attributable to the fact that the TiO2 crystallite size in TiO2 /SiO2 (1:1) thin lms is smaller than that in TiO2 thin lms. This shows that the grain growth of TiO2 crystal is suppressed by addition of SiO2 to TiO2 thin lms. 3.3. XRD, TEM and BET Surface Areas Study

Figure 4. UV-VIS spectra of (a) optical silica glass and soda lime glass coated (b) SiO2 lm, (c) TiO2 /SiO2 (1:1) lms and (d) TiO2 lms by repeating 2 coating cycles and heat-treated at 500 C, respectively.

X-ray diffraction patterns obtained from powders of the same composition as the thin lms of glass samples are shown in Fig. 5. It can be seen that the XRD patterns of

Figure 4 shows the UV-VIS spectra of (a) optical silica glass and soda lime glass coated (b) SiO2 lm, (c) TiO2 /SiO2 (1:1) lms and (d) TiO2 lms by repeating 2 coating cycles and heat-treated at 500 C, respectively. As can be seen from Fig. 4(a), the transmittance of optical silica glass is the highest, and there is also no adsorption in near-ultraviolet wavelengths, which is attributed to the fact that optical silica glass is a kind of insulator, its band gap between the valence band and the conduction band is larger (about 11.7 eV) than that of semiconductors, such as TiO2 . The energy of the near-ultraviolet light is not large enough to excite an electron from the valence band across the band gap of SiO2 ( E g = 11.7 eV) to the conduction band [24]. Figure 4(b) shows that the absorption edge of soda lime glass coated (b) SiO2 lm is about 300 nm. This is caused by the adsorption of soda lime glass, because SiO2 lm has no adsorption near 300 nm. Figure 4(d) shows that the absorption edge of

Figure 5. X-ray diffraction patterns of TiO2 SiO2 composite powders heat-treated at 500 C for 2 h. SiO2 content: (a) 0 mol%, (b) 5 mol%, (c) 10 mol%, (d) 33 mol%, (e) 50 mol%.

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Table 1. The crystallinity, grain size, surface areas and hydroxyl content of TiO2 /SiO2 thin lms. SiO2 content/mol% Phase structure Grain size/nm (XRD) Grain size/nm (TEM) Surface area/m2 g1 Hydroxyl content/% 0 A 17.5 1520 51 13.10 5 A 6.7 67 195 19.78 10 A 6.7 67 226 24.26 15 A 6.4 67 231 25.32 20 A 6.1 67 247 26.50 33 A 6.3 67 264 26.30 67 92 26.90 50 Am.

A: anatase, Am: amorphous.

powder samples show obvious peaks of anatase when the amount of SiO2 addition is smaller than 33 mol%, and almost no peaks of anatase when the amount of SiO2 addition is up to 50 mol%. At the same time, the average grain size of TiO2 was detected by using line broadening methods and the equation proposed by Scherrer. The results are shown in Table 1. As can be seen from Table 1, as a small amount of SiO2 (such as 5 mol%) is added to TiO2 thin lms, the average grain size of TiO2 drastically decreases (from 17.5 nm to 6.7 nm), and with the an increase in the amount of SiO2 , the average grain size shows almost no change, remaining in the 67 nm range. In order to further conrm the effect of SiO2 addition on grain size of TiO2 in the TiO2 /SiO2 composite thin lms, the grain size of TiO2 in the TiO2 /SiO2 composite powders and TiO2 powder was observed using TEM. Figure 6 shows TEM photographs of TiO2 /SiO2 (1:0.05) composite powder (a) and TiO2 powder (b) heat-treated at 500 C for 2 h. It can be seen that the grain size in TiO2 /SiO2 (1:0.05) composite powder is about 67 nm, however, the grain size in TiO2 powder is about 1520 nm. TEM results also show that the grain sizes in the various TiO2 /SiO2 composite powders are all about 67 nm when the

SiO2 content is in the range of 550 mol% (as shown in Table 1). The above results show that if the lm consists of only TiO2 , because of sintering and grain growth progress, many comparatively large particles with roundness are observed. As for the sample with SiO2 addition, contact between TiO2 particles is barred by SiO2 or Ti O Si bonds [25, 26], the grain growth of TiO2 crystals is suppressed and particle size is maintained at original state. It can also be seen from Table 1 that the larger the amount of added SiO2 , the larger the surface areas of composite powders. The higher BET surface areas of TiO2 /SiO2 composite powders are due to the presence of SiO2 or Ti O Si bonds in the TiO2 grain boundary, which inhibits crystallite growth of TiO2 . However, when the amount of SiO2 reaches 50 mol%, the surface area of composite powders obviously drops. This is probably due to reduction of porosity in composite powders. 3.4. FTIR

Figure 7 shows FTIR spectra of TiO2 /SiO2 (1:1) gel powders which were heat-treated at different temperatures for 1 h and then placed in air for 2 days.

Figure 6.

TEM photographs of TiO2 /SiO2 (1:0.05) composite powder (a) and TiO2 powder (b) heat-treated at 500 C for 2 h.

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Figure 7. FTIR spectra of TiO2 /SiO2 (1:1) gel which was heattreated at different temperatures for 1 h and then placed in air for 2 days.

A broad absorption peak is seen at 30003800 cm1 wavelength range, which is assigned to the stretching modes of O H bonds and related to free water (capillary pore water and surface absorbed water). The peak at 1637 cm1 is due to the bending vibration of O H bonds, which is assigned to the chemisorbed water. In all samples, bands at 10001250 cm1 wavelength range are clearly visible, which is attributable to the asymmetric stretching vibrations of Si O Si band. The absorption peaks at 775 and 440 cm1 are due to the symmetric stretching vibrations of Si O Si band. The Si O Ti linkage stretching band and Si OH band appear at about 935 cm1 . The peaks related to CH3 and CH2 groups are observed at 1367, 1532, 1590 and 2950 cm1 . As can be seen in Fig. 7, with an increase in the heat-treatment temperature, the peaks related to CH3 and CH2 groups gradually disappear, at 400 C, the peaks related to CH3 and CH2 groups completely disappear. However, at 700 C, the peaks related to the chemically and physically absorbed H2 O do not disappear. The intensities of the absorption peaks at 30003800 cm1 and 1637 cm1 also increase, which is due to the fact that, rstly, with an increase in heat-treatment temperature, the residual carbon in the thin lms decompose and evaporate more easily. Secondly, SiO2 has the capability to absorb water in air. When TiO2 contains SiO2 , grain growth is suppressed and the surface area is kept larger, and in this case, the capability to hold absorbed water of SiO2 becomes larger. Up to now, we can analyze whether SiO2 is distributed in TiO2 /SiO2 composite thin lms uniformly or heterogeneously. According to preparation processing of the lms and characterization results of XRD, IR and BET results, it can be concluded that SiO2 is

uniformly distributed in TiO2 /SiO2 composite lms in nanometer scale, because the following causes: Firstly, TiO2 and SiO2 formed an even and transparent sol solution during coating process. At this stage, TiO2 and SiO2 could uniformly be mixed at atomic or molecular scale, this resulted in a high homogeneity retained in the derived gel lms. Secondly, when the gel lms were heat-treated at 500 C, some chemical reactions and phase transformations occurred. At higher TiO2 ratios (such as TiO2 content higher than 67 mol%), the TiO2 and SiO2 phases tended to segregate, producing mixed phases (anatase phase TiO2 and amorphous SiO2 ). On the other hand, at lower TiO2 ratios (such as TiO2 content lower than 67 mol%), the Ti was incorporated into the SiO2 matrix, producing amorphous TiO2 and SiO2 [15]. Therefore, SiO2 should be uniformly distributed in the nal TiO2 /SiO2 composite lms at least in nanometer scale.

3.5.

XPS Studies

Figure 8 shows the XPS survey spectrum for the surface of a TiO2 /SiO2 (1:1) composite thin lm deposited on soda lime glass by 1 coating cycle. The XPS survey spectra for other TiO2 /SiO2 composite thin lms are similar. The photoelectron peak for Ti2p appears clearly at a binding energy, E b , of 458 eV, however, Si2p is at E b = 103.0 eV, O1s at E b = 531 eV and C1s at E b = 284 eV. The Na kll photoelectron peaks are at binding energy 269 eV. The XPS peak for Na was observed in the spectrum, implying that some chemical reactions occur on the interface between the thin lm and the glass substrates and sodium migrates from the glass substrates into the thin lm. The element C in the thin lms is attributed to the residual carbon and

Figure 8. XPS survey spectrum for the surface of a TiO2 / SiO2 (1:1) lm deposited on soda lime glass by 1 coating cycle.

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Figure 9. The high-resolution XPS spectrum of O1s region on the surface of a TiO2 /SiO2 (1:1) lm deposited on soda lime glass by 1 coating cycle.

reactions that are a part of the closed photocatalytic cycle. In the presence of aqueous phase, the illuminated surface is widely regarded as a producer of hydroxyl radicals (e.g., h+ + OH OH), and these and other highly oxidizing initial products of this indirect photochemical reaction go on to attack oxidizable contaminants [10, 25]. Therefore, with the increase of the absorbed OH content on the surface of composite thin lms, photocatalytic activity of TiO2 thin lms will increase. The C O bonds in the thin lms are attributed to the organic residues such as alcohol, unhydrolyzed alkoxide groups and CO2 3 [26].

3.6. adventitious hydrocarbon (i.e. from the XPS instrument itself). Compared to XPS studies of TiO2 thin lms [27]. Ca element has not appeared in XPS survey spectrum. This is probably ascribed to the fact that CaO and SiO2 react to produce CaSiO3 , which is a kind of covalence compound. Therefore, Ca ions cannot move freely in TiO2 /SiO2 composite thin lm [24]. Figure 9 shows the high-resolution XPS spectrum of the O1s region, taken on the surface of the as-prepared TiO2 /SiO2 (1:1) composite thin lm. The O1s region is decomposed into four contributions. The main contributions are attributed to Ti O and Si O bonds, the other two kinds of oxygen contributions can be counted by the hydroxyl groups ( OH) and the C O bonds. The hydroxyl content of the TiO2 /SiO2 lms obtained from XPS study is listed in Table 1. As seen in Table 1, the hydroxyl content in the TiO2 /SiO2 composite thin lm is greater than that in the TiO2 thin lm, and the larger the amount of the added SiO2 , the larger the hydroxyl content in the TiO2 /SiO2 composite thin lms. The difference in the hydroxyl content among the composite thin lms can be ascribed to the difference in SiO2 content among them. Therefore, it can be concluded that the larger the amount of added SiO2 , the smaller the grain size in the lms, the larger the surface area of composite thin lms. The composite lms with larger surface area are more easily attacked by the water vapor to produce more hydroxyl groups. Hydroxyl groups existing in the composite lms are attributed to the chemically and physically adsorbed H2 O. Generally, heterogeneous photocatalysis is a process in which the illumination of an oxide semiconductor, usually the anatase form of titanium dioxide, produces photogenerated electrons (e ) and holes (h+ ). These can migrate to the oxide surface and participate in half-cell

Photocatalytic Activity

It is well known that the photocatalytic activity of TiO2 is greatly inuenced by its crystallinity, grain size, surface areas and surface hydroxyl content [2, 4, 9, 10]. When SiO2 is introduced to TiO2 thin lms, the composite thin lms formed may be different from TiO2 thin lm in both physical and chemical characteristics, such as the phase constitution, surface areas, surface hydroxyl groups, grain size, and chemical compositions. We will discuss the effects of these physical and chemical changes on the photocatalytic activities of the composite thin lms. Figure 10 shows the effect of SiO2 addition on the photocatalytic activity of TiO2 thin lms prepared by sol-gel processing and repeating 1 coating cycle. It was found that the photocatalytic activity of the as-prepared TiO2 /SiO2 composite thin lms slightly increases when the amount of SiO2 amount is less than 5 mol%. However, when the amount of SiO2 is

Figure 10. Effects of SiO2 addition on the degradation rate of TiO2 thin lms (degradation rate of methyl orange after photo-degradation reaction for 1 h).

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greater than 10 mol%, the photocatalytic activity of the as-prepared TiO2 /SiO2 composite thin lms begins to decrease. Also, when the amount of SiO2 is over 33 mol%, the photocatalytic activity of the as-prepared TiO2 /SiO2 composite thin lms greatly decreases. The increased photocatalytic activity can be attributed to the following factors. Firstly, when a small amount of SiO2 is added to TiO2 thin lms, the grain size of TiO2 drastically decreases (from 17.5 to 6.7 nm) and specic surface areas obviously increase (from 51 to 195 m2 g1 ). The decrease in the crystallite size probably results in a larger driving force for charge transfer existing in a quantum-sized TiO2 in the composite thin lms [2, 4]. The increase in surface area probably causes a higher adsorptivity toward organic contaminants [1517]. Of course, the increase in surface hydroxyl content will trap more holes in the valence band and thus prevent electron-hole recombination [10]. These factors will all enhance the photocatalytic activity of TiO2 . Therefore, though TiO2 /SiO2 composite thin lms contain a small amount of SiO2 (SiO2 is a kind of insulator and has no photocatalytic activity), the photocatalytic activities of the composite thin lms are still higher than that of the pure TiO2 . It can be concluded that a small amount of SiO2 in the composite thin lms does not play a signicant role in determining their photocatalytic activity. The decreased photocatalytic activity can be attributed to the following two factors: based on the results of FTIR and XPS measurements, most silicon atoms exist as SiO2 particles mixed evenly with TiO2 . It is known that the band gap energy of SiO2 (11.7 eV) is much larger than that of anatase TiO2 (3.2 eV). Therefore, the presence of SiO2 in the composite thin lms can only decrease their quantum yield. This may explain why the samples have relatively poor photoactivity when the amount of added SiO2 is over 10 mol%. According to XRD results, with an increasing amount of added SiO2 in TiO2 /SiO2 composite powders, the peak intensity of anatase decreases and this shows that the amount of amorphous TiO2 increases, when the amount of SiO2 reaches 50 mol%, TiO2 exists mainly in the amorphous phase. We have shown recently that amorphous TiO2 has a lower photocatalytic activity compared to crystalline TiO2 [20, 24]. Therefore, the photocatalytic activity of the as-prepared TiO2 /SiO2 composite thin lms (50 mol% SiO2 ) signicantly decreases. Also, the excess amounts of SiO2 in the sample (50 mol%) may shield the photocatalyst, resulting poor photocatalytic activity.

4.

Conclusions

The TiO2 /SiO2 composite thin lms were prepared from precursor solutions with different amounts of SiO2 . The crystal phase, grain size, light transmission, surface hydroxyl content and photocatalytic activity of the lms were studied. It was shown that the larger the amount of added SiO2 , the smaller the grain size in the resultant TiO2 /SiO2 composite thin lms, and the larger the surface hydroxyl content on the surface of the lms. It was found that besides Ti, Si and O elements, there is a certain amount of residual carbon from the starting organic components and a small amount of sodium ions diffused from the glass substrates. The photocatalytic activity of the as-prepared TiO2 /SiO2 composite thin lms increases when the amount of SiO2 is less than 5 mol%. However, when the amount of SiO2 is greater than 10 mol%, the photocatalytic activity of the as-prepared TiO2 /SiO2 composite thin lms begins to decrease. Acknowledgment The work described in this paper was partially supported by a grant from the National Natural Science Foundation of China and Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. N CUHK433/00). This work was also nancially supported by the Foundation for University Key Teachers of the Ministry of Education, the National Natural Science Foundation of China (50072016). References
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