Solid State Ionics 172 (2004) 283 288 www.elsevier.

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Deposition mechanism of anatase TiO2 from an aqueous solution and its site-selective deposition
Yoshitake Masuda a,*, Won-Seon Seo b, Kunihito Koumoto a
a b

Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan Korea Institute of Ceramic Engineering and Technology (KICET), Nagoya University, Nagoya 464-8603, Japan Received 9 November 2003; received in revised form 18 February 2004; accepted 20 February 2004

Abstract We have developed a novel method for site-selective deposition (SSD) of anatase TiO2 thin films using a seed layer based on the knowledge obtained by the evaluation of deposition mechanism. The nucleation and initial growth of anatase TiO2 were found to be accelerated on amorphous TiO2 thin films compared with the substrates modified by silanol, amino, phenyl or octadecyl groups. Micropattern having octadecyl group regions and amorphous TiO2 regions was immersed in the aqueous solution at pH 1.5 to be used as a template for SSD. Anatase TiO2 was selectively deposited on amorphous TiO2 regions to form a micropattern of anatase TiO2 thin film in an aqueous solution. Furthermore, deposition mechanism of anatase TiO2 in an aqueous solution has been evaluated in detail. The adhesion of homogeneously nucleated particles to the amino group surface by attractive electrostatic interaction caused rapid growth of TiO2 thin films in the supersaturated solution at pH 2.8. On the other hand, TiO2 was deposited on self-assembled monolayers (SAMs) without the adhesion of TiO2 particles regardless of the type of SAM in the solution at pH 1.5 whose degree of supersaturation is low due to high concentration of H+. Additionally, the orientation of films deposited on all SAMs was shown to be improved by enlarging the reaction time regardless of the kind of SAM or pH. It is conjectured that the adsorption of anions to specific crystal planes caused c-axis orientation of anatase TiO2. D 2004 Elsevier B.V. All rights reserved.
Keywords: Titanium dioxide; Self-assembled monolayer; Liquid phase deposition; Deposition mechanism; Site-selective deposition; Seed layer; Thin film

1. Introduction Titanium dioxide (TiO2) thin films are of interest for various applications including microelectronics [1], optical cells [2], solar energy conversion [3], highly efficient catalysts [4], microorganism photolysis [5], antifogging and self-cleaning coatings [6], gratings [7], gate oxides in metal-oxide-semiconductor field effect transistor (MOSFETs) [8.9], etc. Accordingly, various attempts have been made to fabricate thin films and micropatterns of TiO2 by several methods, and in particular, to synthesize materials and devices including TiO2 thin films from an aqueous solution through an environment-friendly synthesis process, i.e., green chemistry. Micropatterning of TiO2 was attempted by a number of methods [10 14]. We realized site-selective deposition (SSD) of amorphous TiO2 to fabricate micropatterns of

* Corresponding author. Tel.: +81-52-789-3329; fax: +81-52-789-3201. E-mail address: masuda@apchem.nagoya-u.ac.jp (Y. Masuda). 0167-2738/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.ssi.2004.02.068

TiO2 thin films on self-assembled monolayers (SAMs) [12 14]. SAMs of octadecyltrichloro-silane (OTS) were formed on Si wafers, and were modified by UV irradiation using a photomask to generate octadecyl/silanol-pattern. They were used as templates to deposit TiO2 thin films by the use of titanium dichloride diethoxide (TDD). Amorphous TiO2 films were selectively deposited on silanol regions. Annealing the films at high temperatures (400 600 jC) gave rise to an anatase phase, while the resolution of a micropattern remained unchanged. However, annealing process is required to obtain patterns of anatase TiO2 thin films in this process. On the other hand, a micropattern of anatase TiO2 thin film was fabricated by the site-selective immersion [15] method using a SAM which has a pattern of both hydrophilic and hydrophobic surfaces. A solution containing Ti precursor contacted the hydrophilic surface during the experiment and briefly came in contact with the hydrophobic surface. The solution on the hydrophilic surface was replaced with fresh solution by continuous movement of bubbles. Thus, TiO2 was deposited and a thin film was grown on the hydrophilic surface selectively. However, feature edge acuity of the

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micropattern needs to be improved further in order to use anatase TiO2 micropatterns for electronic or optical devices. Investigation of the mechanism of nucleation and growth of TiO2 from the aqueous solution would produce valuable information for making desired thin films and micropatterns. In this study, we have developed a novel method for SSD of anatase TiO2 thin films using a seed layer and the knowledge obtained by the evaluation of deposition mechanism. We evaluated the surface zeta potential of SAMs and 2 TiO2 particles in a solution containing ions such as TiF6 3 and BO3 . We also investigated the TiO2 deposition rate and quantity for several kinds of SAMs and the time dependence of the crystal-axis orientation to clarify the mechanism of nucleation and growth. The nucleation and initial growth of anatase TiO2 were found to be accelerated on amorphous TiO2 thin films compared with silanol, amino, phenyl or octadecyl groups by the evaluation of deposition mechanism using a quartz crystal microbalance (QCM). In our process, amorphous TiO2 was shown to decrease the nucleation energy of anatase TiO2 and provided nucleation sites for the formation of anatase TiO2. The micropattern having amorphous TiO2 regions and OTSSAM regions was immersed in an aqueous solution containing Ti precursor to be used as a template for SSD. Anatase TiO2 was selectively deposited on amorphous TiO2 regions to form a micropattern of anatase TiO2 thin films.

2. Experimental 2.1. SAM preparation

Au-coated quartz crystal of a quartz crystal microbalance (QCM; QCA917, Seiko EG&G) in a bicyclohexyl solution containing OM, PM or AET, respectively. OM-SAM on the quartz crystal of the QCM was exposed for 2 h to UV light (184.9 nm) to assess the deposition rate of TiO2 on OH groups. OM-SAM, PM-SAM and AET-SAM were used instead of OTS-SAM, PTCS-SAM or APTS-SAM for QCM analysis. Initially deposited OTS-SAM, PTCS-SAM, APTS-SAM, OM-SAM, PM-SAM and AET-SAM showed water contact angles of 96j, 74j, 48j 96j, 76j and 53j, respectively. UV-irradiated surfaces of SAMs were, however, wetted completely (contact angle < 5j). This suggests that SAMs of OTS, PTCS, APTS, OM, PM and AET were modified to hydrophilic OH group surfaces by UV irradiation. The order of SAM hydrophobicity determined from these measurements was OTS-SAM>PTCS-SAM>APTSSAM>OH groups on silicon. Zeta potentials measured in aqueous solutions (pH = 7.0) for the surface of silicon substrate covered with OH groups, phenyl groups (PTCS) and amino groups (APTS) were measured to be 38.23, + 0.63 and + 22.0 mV [23], respectively. The order of zeta potential in the aqueous solution of our experiment is presumed to be APTS-SAM>PTCS-SAM>OH-SAM (OH groups on silicon). OTS-SAMs were exposed for 2 h to UV light through a photomask. The UV-irradiated regions became hydrophilic owing to the formation of Si-OH groups, while the nonirradiated part remained unchanged, i.e., it was composed of hydrophobic octadecyl groups, which gave rise to patterned OTS-SAM. This patterned SAM was used as a template for SSD of amorphous TiO2 thin films [12,13]. 2.2. Deposition of anatase TiO2 thin films

OTS-SAM, phenyltrichlorosilane (PTCS)-SAM and 3aminopropyltriethoxysilane (APTS)-SAM were prepared by immersing the Si substrate in toluene solutions containing OTS, PTCS, APTS, respectively [16 22]. Octadecylmercaptan (OM)-SAM, phenylmercaptan (PM)-SAM and 2-aminoethanethiol (AET)-SAM were prepared by immersing the

Ammonium hexafluorotitanate ([NH4]2TiF6) and boric acid (H3BO3) were separately dissolved in deionized water at 50 jC and kept for 12 h (Fig. 1). An appropriate amount of HCl was added to the boric acid solution to control pH, and ammonium hexafluorotitanate solution was added.

Fig. 1. Deposition quantity of anatase TiO2 on amorphous TiO2, octadecyl groups, phenyl groups, amino groups or hydroxyl groups at pH 1.5 as a function of deposition time and conceptual process for site-selective deposition of anatase TiO2 thin films using a seed layer.

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SAMs were immersed in the solution containing 0.05 M (NH4)2TiF6 and 0.15 M (H3BO3) at pH 1.5 or 2.8 and kept at 50 jC to deposit anatase TiO2. Deposition of TiO2 proceeds by the following mechanisms [24]: TiF2 2H2 OfTiO2 4H 6F 6 BO3 4F 6H ! BF 3H2 O 3 4 2.3. QCM measurement Quartz crystals covered with SAMs were placed 5 mm below the surface of the solution. The solution was kept covered to prevent the evaporation of water, and water (50 jC) was added to compensate for any evaporated water. Frequency decrease (DF (Hz)) was converted into weight increase (Dm (ng)) by the following equation: Dmng 1:068 DFHz c a b

3. Results and discussion 3.1. Quantitative analysis of the deposition of anatase TiO2 onto an amorphous TiO2 thin film or onto SAMs Quartz crystals covered with amorphous TiO2 thin film, OM-SAM (CH3), PM-SAM (Ph), AET-SAM (NH2) or OHSAM (OH) were immersed in a solution [15] containing

2 3 0.05 M TiF6 and 0.015 M BO3 at pH 1.5 or pH 2.8 (Fig. 1). The supersaturation degree of the solution at pH 1.5 was low as the high concentration of H+ suppressed TiO2 generation, and hence the deposition reaction progresses slowly with no homogeneous nucleation occurring in the solution. We found that anatase TiO2 was deposited on an amorphous TiO2 thin film faster than on OM-, PM- AET- or OH-SAMs at pH 1.5. This shows that the deposition of anatase TiO2 was accelerated on amorphous TiO2 compared with on silanol, amino, phenyl or octadecyl groups. Amorphous TiO2 probably decreases the nucleation energy of anatase TiO2. The difference in deposition rate enables SSD to be achieved. The amorphous TiO2 thin film can be used as a seed layer to accelerate the deposition of anatase TiO2. The deposition rate at pH 2.8 was larger than that at pH 1.5 because of the high degree of supersaturation, and homogeneously nucleated particles in the solution deposited on the whole surface of the substrate, regardless of the surface functional groups. The thickness of anatase TiO2 thin film deposited on a quartz crystal covered with amorphous TiO2 at pH 1.5 for 1 h and at pH 2.8 for 30 min was estimated to be 36 and 76 nm, respectively, assuming the density of anatase type TiO2 to be 3.89 g/cm3.

3.2. SSD of anatase TiO2 using a seed layer A micropattern [12,13] having amorphous TiO2 and octadecyl groups was immersed in an aqueous solution

Fig. 2. SEM micrographs of (1-a), (1-b) a micropattern of amorphous TiO2 thin films and (2-a), (2-b) a micropattern of anatase TiO2 thin films deposited at pH = 1.5.

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[15] at pH 1.5 for 1 h (Fig. 1). Deposited thin films made it appear white compared with octadecyl group regions in SEM micrographs (Fig. 2(2-a), (2-b)) because of the difference in height. The feature edge acuity of anatase TiO2 pattern was f 2.1% variation (i.e., 0.5/23.2) and was much the same as we calculated from amorphous TiO2 pattern. This resemblance was observed from Fig. 2(1-a) and (2-a). These micrographs were taken from the same position. Variations of these patterns were much better than that of the pattern fabricated with a lift-off process and the usual 5% variation afforded by current electronics design rules. Additionally, these variations were similar to that of a TEM mesh (2.1%) we used as a photomask for Fig. 2. Therefore, variations of these patterns can be improved through the use of a high-resolution photomask. Deposited films showed weak XRD patterns of anatase type TiO2 because the films were not sufficiently thick to show strong diffraction. This finding provides evidence for the deposition of anatase TiO2 on amorphous TiO2 regions. An atomic force microscope (AFM; Nanoscope E, Digital Instruments) image showed anatase TiO2 thin films to be higher than octadecyl group regions. The center of the anatase TiO2 thin film region was 61 nm higher than the octadecyl regions, and the thickness of the anatase TiO2 thin film was estimated to be 36 nm considering the thickness of amorphous TiO2 thin film (27 nm) [12,13] and OTS molecules (2.4 nm) (Fig. 1). This result is similar to that estimated by QCM measurement (36 nm). The surface roughness (RMS) of the anatase TiO2 thin film was estimated using an AFM image. The AFM image showed the film roughness to be 3.7 nm (horizontal distance between measurement points: 6.0 Am), which is less than that of amorphous TiO2 thin film (RMS 9.7 nm, 27 nm thick, horizontal distance between measurement points: 6.0 Am) [12,13]. Additionally, the roughness of the octadecyl group regions was shown to be 0.63 nm (horizontal distance between measurement points: 1.8 Am). Amorphous TiO2 accelerated the deposition of anatase TiO2 and showed its excellent performance as a seed layer. The feature edge acuity of anatase TiO2 patterns was

Fig. 4. FE-SEM micrograph for cross-section profile of TiO2 thin film deposited at pH 2.8.

estimated to be approximately 2.1% using the same method as used for a micropattern fabricated by the lift-off process [24] and was the same as that of amorphous TiO2 [12,13]. The feature edge acuity could be improved by using a higher feature edge acuity photomask since this variance is similar to that of the TEM mesh (2.1%). XRD measurements for the thin film deposited for 1 h did not show any peaks since the deposited quantity was not sufficient to show any diffraction, however, the thin film deposited for 7 h was composed of anatase TiO2. Anatase TiO2 thin films were not peeled off by sonication in ethanol for 10 min and showed strong adhesion to the amorphous TiO2 layer. This suggests that strong chemical bonds were formed between anatase TiO2 and amorphous TiO2. 3.3. Crystal-axis orientation of TiO2 thin film The growth process of TiO2 thin films and the crystal-axis orientation changes were investigated using an X-ray diffractometer (XRD; RAD-C, Rigaku) with CuKa radiation (40 kV, 30 mA) and Ni filter. Deposited films on all SAMs showed XRD patterns of anatase TiO2 after 24 h at pH 1.5 or after 4 h at pH 2.8. XRD patterns showed the same tendency regardless of the type of SAM, and intensities of (004) and (105) peaks on all SAMs increased with deposition time faster than other peaks. The degree of crystal-axis orientation ( f ) was evaluated using the Lotgering method [25] taking into account the following diffraction peaks: (101) = 25.3, (004) = 37.8j, (200) = 48.0j, (105) = 53.9j, (204) = 62.7j, (116) = 68.8j, (215) = 75.0j (Fig. 5). f P P0 1 P0 d

P I00l PP Ihkl
Fig. 3. Intensities of peaks as a function of reaction time (at pH 1.5, on OH groups).

P, calculated for the oriented sample; P0, P for nonoriented sample (JCPDS card).

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other particles whose c-axis was far from perpendicular to the substrate, thus lowering the diffraction intensities of crystal planes such as (101) and (200).

4. Conclusions We utilized the knowledge obtained by the evaluation of deposition mechanism for SSD of anatase TiO2 thin films. The deposition of anatase TiO2 was shown to be accelerated on amorphous TiO2 thin films compared with on octadecyl, phenyl, amino or hydroxyl groups. A micropattern having amorphous TiO2 regions and octadecyl regions to be used as a template was prepared and immersed in the aqueous solution. Anatase TiO2 was successfully deposited on amorphous TiO2 regions, and amorphous TiO2 thin film was shown to act effectively as a seed layer to accelerate the nucleation and initial growth of anatase TiO2. Consequently, SSD was achieved and a micropattern of anatase TiO2 was fabricated in the aqueous solution using a seed layer.

Fig. 5. TEM micrograph and electron diffraction pattern for cross-section profile of TiO2 thin film deposited at pH 2.8 (an arrow shows growth direction of thin film).

Acknowledgements This work was supported in part by the 21st Century COE Program Nature-Guided Materials Processing of the Ministry of Education, Culture, Sports, Science and Technology. This work was partly supported by a Grantin-Aid for Scientific Research (Grant-in-Aid for Young Scientists No. 14703025, Exploratory Research No. 14655239) from the Ministry of Education, Culture, Sports, Science and Technology granted to Y. Masuda.

The c-axis (00l) orientation of the film was enhanced by increasing the reaction time for all the kinds of SAMs and pH. This result suggests that the orientation of the film is determined not at the initial nucleation or deposition stage but at the film growth stage. The intensity of the (004) peak quickly increased but that of (105) increased only gradually with reaction time, and the intensities of the (101) and (200) peaks decreased after reaching their maxima regardless of the type of SAM or pH condition (Fig. 3). Furthermore, the orientation of thin film deposited at pH 2.8 for 4 h was evaluated by a field emission scanning electron microscope (FE-SEM; JSM-6700F, point-to-point resolution 1 nm, JEOL) and a transmission electron microscope (TEM; JEM4010, 400 kV, point-to-point resolution 0.15 nm, JEOL). The cross-section profile of TiO2 thin films showed columnar morphology (Fig. 4). However, the columns were not clearly identified compared with the needlelike morphology of TiO2 thin films reported recently [26,27]. This columnar morphology is consistent with XRD measurement which showed weak c-axis orientation. Fig. 5 shows a TEM micrograph and electron diffraction pattern for the cross-section profile of a TiO2 thin film. Many small crystals of anatase TiO2 were observed throughout the thin film. These observations firmly indicate that TiO2 particles whose c-axes were perpendicular to the substrate surface may have grown faster than other crystals. Hence, the diffraction intensities of crystal planes almost perpendicular to the c-axis such as (004) and (105) increased with deposition time (Fig. 3). These particles then consumed

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