Applied Surface Science 243 (2005) 125128 www.elsevier.

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Conversion of a solid surface from super-hydrophobic to super-hydrophilic by photocatalytic remote oxidation and photocatalytic lithography
Wakana Kubo, Tetsu Tatsuma*
Institute of Industrial Science, University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan Received 5 July 2004; accepted 9 September 2004 Available online 18 November 2004

Abstract A super-hydrophobic surface, of which contact angle was 1518, was obtained by modifying a SiO2 microparticle lm-coated glass plate with octadecyltriethoxysilane (ODS). The super-hydrophobic surface was converted to super-hydrophilic by remote oxidation using a TiO2 photocatalyst for 40 min, due to oxidative decomposition of the ODS monolayer. The increase in the wettability of the super-hydrophobic surface with water was faster than that of a normal hydrophobic surface. Patterning of the super-hydrophobic surface was also possible by means of photocatalytic lithography based on the remote oxidation using a photomask. It was possible to entrap water in the oxidized regions. # 2004 Elsevier B.V. All rights reserved.
Keywords: Super-hydrophobic; Super-hydrophilic; Photocatalytic lithography; Remote oxidation; TiO2 photocatalyst

1. Introduction Wettability with a liquid is one of the important properties of solid surfaces. In particular, superhydrophobic surfaces (with water contact angle lager than 1508) and super-hydrophilic surfaces (with water contact angle less than 58) have collected great attention for their industrial signicance [13]. If it is possible to convert surfaces from super-hydrophobic
* Corresponding author. Tel.: +81 3 5452 6336; fax: +81 3 5452 6338. E-mail address: tatsuma@iis.u-tokyo.ac.jp (T. Tatsuma).

to super-hydrophilic and to pattern them, the technique would be applied to fabrication of various devices including biochips, lab-on-a-chip devices, sensor arrays and display devises. Feng et al. [4] have reported that nanostructured ZnO surfaces were changed from super-hydrophobic to super-hydrophilic reversibly by UV irradiation. Although this is a very interesting phenomenon that might enable surface patterning, it may not necessarily be suitable to the above-mentioned applications because the surface returns to super-hydrophobic in a week, and organic compounds on the surface would be decomposed by photocatalytic reactions.

0169-4332/$ see front matter # 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2004.09.102

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Fig. 1. Experimental setup for the photocatalytic lithography.

We have reported surface patterning by means of photocatalytic lithography [5,6] based on remote oxidation by TiO2 photocatalysts [7,8]. In this method, a solid surface is faced with a TiO2-coated photomask (Fig. 1), and photo-irradiated areas of the solid surface are oxidized and decomposed. Since the surface to be patterned is not required to be in contact with the TiO2 lm, the surface is not damaged easily. The patterning is possible in a dry process, without a photoresist. A simple light source is the only equipment required. The irradiation time is much shorter than the conventional UV-based non-photocatalytic patterning. With this method, hydrophobic/hydrophilic patterns could be obtained easily [5,6]. Other research groups [9,10] have also applied our technique to surface patterning. In our previous studies of photocatalytic lithography, however, water contact angle changed from about 908 to 08 in the case of octadecyltriethoxysilane (ODS)-coated glass surfaces. Therefore, when an aqueous solution was cast on a patterned surface, the solution sometimes overowed into hydrophobic areas, depending on the sort of solution, treatment time and dimension of the pattern. To solve this problem, the glass substrate was coated with a SiO2 microparticle lm prior to the modication with ODS so as to obtain a super-hydrophobic surface. The photocatalytic lithography treatment of the surface resulted in faster patterning and greater contrast in hydrophilicity.

plate by spin-coating at 1000 rpm for 10 s. The lm was calcined at 500 8C for 60 min. The obtained substrate was soaked in a 17 vol.% ethanol solution of ODS for 60 min, then rinsed thoroughly with ethanol, and dried for overnight. A TiO2 coating was prepared as follows. A TiO2 aqueous sol STS-01 (Ishihara Sangyo, Japan) was diluted with ethanol (30 vol.%), sonicated for 1 h, and coated on a clean nonalkaline glass plate or a photomask (Dai Nippon Printing Company) by spin-coating at 1500 rpm for 15 s. The TiO2-coated glass plate was calcined at 400 8C for 60 min. The resulting TiO2 coating was irradiated with a blacklight-type lamp overnight to clean the surface. In a remote oxidation experiment, a TiO2 coating and a substrate was faced with a small intervening gap (12.5 mm) and irradiated with a HgXe lamp (Luminar Ace 300UV, Hayashi, Tokei; UV intensity, 100 mW cm2) from the backside of the TiO2coating. After the irradiation, the water contact angle was measured with a contact angle meter (CA-X, Kyowa, Japan).

3. Results and discussion 3.1. Conversion of a solid surface from superhydrophobic to super-hydrophilic The water contact angle of the prepared SiO2 microparticle lm was (0.88 0.38) (mean S.E., n = 5). The roughness factor of the surface measured by atomic force microscopy (AFM, Seiko Instrument Inc., SPI3800N) was 2.1 (scanned region, 10 mm 10 mm), while that of the bare glass surface was 1.0. Intrinsic roughness factor of the former should be much larger than the obtained value, since the surface area in the pores cannot be measured by AFM. After the superhydrophilic lm was modied with ODS, a superhydrophobic lm of which water contact angle was (150.68 1.88) (n = 5) was obtained as shown in Fig. 2(a and b). Then, the lm was faced with the TiO2 coating, and irradiated with UV light (100 mW cm2). The water contact angle gradually decreased to (1.88 1.18) (n = 5) in 40 min (Fig. 3(a)) to be super-hydrophilic (Fig. 2(c and d)). In contrast, no signicant changes in the water contact angle of the SiO2 microparticle lm was observed for 40 min

2. Experimental The coating suspension was prepared as follows. SiO2 particle (0.510 mm, $80% between 1 and 5 mm, Sigma) was suspended in an alkoxysilane solution (NDH-500A, Nippon Soda). The suspension (15 wt.%) was coated twice on a clean Pyrex glass

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Fig. 2. Photographs of water dropped on the ODS-modied SiO2 microparticle lm surface (a and b) before and (c and d) after remote oxidation (40 min, see text for detail).

Fig. 3. Time courses of the water contact angle of (a) the ODSmodied SiO2 microparticle lm surface and (b) the ODS-modied Pyrex glass surface during the remote oxidation experiment.

(decrement < 58), when the TiO2-coated glass plate was mounted upside down or the plate was not mounted, indicating the essential role of TiO2. Incidentally, the initial contact angle of an ODScoated Pyrex glass plate (without microparticles) was about 1008, then gradually decreased to <58 in 35 min in the remote oxidation experiment (Fig. 3(b)). We have proposed that H2O2 diffusing from a TiO2 photocatalyst to air (Eqs. (1)(6)) [11] is decomposed  to OH by UV light (Eq. (7)), which oxidizes and decomposes the alkyl chain of ODS [6]. TiO2 !TiO2 e h 2H2 O 4h ! O2 4H H2 O h ! OH H 2 OH ! H2 O2 O 2 e ! O 2
UV
  

UV

(1) (2) (3) (4) (5)

due to the roughness. Nonetheless, average decrease rates in the water contact angle (030 min) were ca. 4.58 min1 for the roughened surface and 2.58 min1 for the smooth surface. The acceleration by the roughening may be reasonable because both hydrophobicity and hydrophilicity are enhanced by introducing roughness to the surface [13]. The super-hydrophobicity of the surface was maintained at least for 10 days (water contact angle >1508). After the remote oxidation, the superhydrophilicity of the surface was also preserved in pure water at least for 10 days (water contact angle <38). In contrast to the photo-induced super-hydrophilicity of the nanostructured ZnO surface [4], which reverts to super-hydrophobic in a week, the superhydrophilicity of the present surface induced by the remote oxidation was irreversible and stable. 3.2. Patterning of the super-hydrophobic surface by photocatalytic lithography The super-hydrophobic surface was patterned by using a TiO2-coated photomask shown in Fig. 4(a).

O2 2H 2e ! H2 O2 H2 O2 !2 OH

(6) (7)

The decomposition rate on the roughened surface should be the same as that on the smooth surface, or the former is even lower for a greater ODS coverage

Fig. 4. Diagram of (a) the TiO2-coated photomask used and (b and c) photographs of the ODS-modied SiO2 microparticle lm surface patterned by photocatalytic lithography with the photomask (5 min irradiation) and water dropped on the irradiated and non-irradiated regions.

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4. Conclusions Conversion of a super-hydrophobic surface to a super-hydrophilic surface was possible by means of photocatalytic remote oxidation. Patterning of the super-hydrophobic surface by photocatalytic lithography provides faster patterning and clearer contrast in hydrophilicity than the patterning of normal hydrophobic surfaces. This is a promising patterning technique, which is potentially applicable to fabrication of various chemical, biochemical and optical devices.

Fig. 5. Photographs of (a) the TiO2-coated photomask used (stripe width, 500 mm) and (b) the ODS-modied SiO2 microparticle lm surface patterned by photocatalytic lithography with the photomask (20 min irradiation, the pattern was visualized with water).

The photomask has square windows, so that the corresponding regions on the surface undergo a decrease in hydrophobicity during the UV irradiation. After irradiation for 5 min, water was dropped on irradiated and non-irradiated regions with a cylinge. It was found that the non-irradiated region repelled the water, and the water was entrapped in the irradiated region (Fig. 4(b and c)). Thus, the irradiated area could be distinguished from the non-irradiated area clearly, and the pattern could be visualized. A striped photomask (stripe width was 500 mm) (Fig. 5(a)) was also used. After irradiation for 20 min, water droplets were placed on the irradiated regions. Then water spread over the irradiated regions quickly as shown in Fig. 5(b). Water did not overow into the hydrophobic areas. In this way, it is possible to control uid channels, suggesting that the present technique is potentially applicable to lab-on-a-chip technologies. Although we used here the microstructured SiO2 coatings scattering lights, if we use more transparent nanostructured super-hydrophobic lms, such as those reported by Xu et al. [12], the patterning by means of photocatalytic lithography would be applicable to optical devices including color lters. The irradiation time necessary for patterning is 540 min, depending on the expected difference of wettability. If a silane-coupling agent having an alkyl chain with appropriate length or a uoroalkyl chain was used, it would be possible to increase the hydrophobicity or to shorten the patterning time. Actually, water contact angle of 1658 was obtained when ODS was replaced with heptadecauorodecytriethoxysilane.

Acknowledgements The authors are grateful to Dai Nippon Printing Company for the preparation of the photomask. This work was supported in part by a Grant-Aid for Scientic Research on Priority Areas (Area No. 417, Research No. 14050028) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

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