Materials and Design 30 (2009) 34283435

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Materials and Design

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Design and investigation of photo-induced super-hydrophilic materials for car mirrors

Pitak Eiamchai a,*, Pongpan Chindaudom a, Mati Horprathum a, Viyapol Patthanasettakul a, Pichet Limsuwan b
a b

National Electronics and Computer Technology Center, Pathumthani 12120, Thailand King Mongkuts University of Technology Thonburi, Bangkok 10140, Thailand

a r t i c l e

i n f o

a b s t r a c t
During the past decades, interests in various properties in titanium dioxide thin lms have been growing rapidly. There have been several reports for TiO2 thin lms prepared on various media with photocatalytic and hydrophilic properties, in order to function as self-cleaning and/or anti-fogging materials. An obvious application is usually found in side-view car mirrors in the automobile industries. In this study, a number of photocatalytic TiO2 lms are prepared on soda-lime glasses for car mirrors by an electronbeam evaporation. The designs and development of the photocatalytic TiO2 lms, based on crystallinity, deposition rate, lm thickness, lm structure, and surface roughness are discussed. In comparison to the commercialized products, a systematic investigation procedure for the super-hydrophilic properties of the light-induced TiO2 lms for car mirrors has been developed, based on super-hydrophilicity, sustainability, self-cleaning property, and degradation of the samples. In addition, physical characterization by X-ray diffraction and surface roughness are also discussed. It has been found that most commercial products attain super-hydrophilicity only after exposed to ultraviolet and solar irradiation in less than 1 h. They can also maintain hydrophilicity after rigorous cleaning process. On the other hand, our prepared TiO2 thin lms demonstrate super-hydrophilic and photocatalytic properties after exposed to ultraviolet light for more than 2 h. According to the study, their anatase crystallinity, small grain size, and surface conditions all contributes to the excellent results. However, the prepared samples do not attain sufcient retention property to maintain their hydrophilicity. Conclusively, the designs of the TiO2 lms on car mirrors prove adequate to produce super-hydrophilic materials, which still degrade over normal usage. Nevertheless, our proposed investigation methods prove useful in quality evaluation in order to differentiate the results of super-hydrophilic materials of interests. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 5 February 2009 Accepted 20 March 2009 Available online 26 March 2009 Keywords: TiO2 Thin lms Photocatalytic Hydrophilic Sustainability Degradation

1. Introduction Titanium dioxide (TiO2) thin lms have been extensively studied in research and development for a wide range of applications. The fact is due to several properties, i.e., its high optical index, refraction and transparency across visible wavelength range [1,2], innate semiconducting and electrical properties [3,4], compatibility to human body [5], and photocatalytic properties [57]. TiO2 is also recently used in gas sensors [8], protective coatings [9], optical coatings, hydrophilicity and photocatalysis because of its environmental benets. One widely active researches are photoassisted degradation of organic compounds and photocatalytic reactions of TiO2 thin lms [10,11], where fundamental understandings in physical and optical properties, surface investigations and the replacement of the chemisorbed hydroxyl groups are essential.
* Corresponding author. Tel.: +66 8 7708 7741. E-mail address: po_po_pop@hotmail.com (P. Eiamchai). 0261-3069/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.matdes.2009.03.025

In this study, we are specically interested in a light-induced super-hydrophilic property of prepared TiO2 lms coated on soda lime glasses for side-view car mirrors. In the development of the photocatalytic TiO2 lms, we propose possible methods to investigate sustainability of their hydrophilicity based on (1) hydrophilic property, (2) sustainability, (3) light-induced self-cleaning property, and (4) deterioration and degradation of the previously-mentioned properties. The prepared lm samples will be comparatively studied with commercial products, which will be accordingly referred to as the reference samples. 2. Experimental 2.1. Sample preparation A number of TiO2 samples were prepared by a production-sized electron-beam evaporator (Baalzer BAX500), which combined rotary and booster pumps for a low vacuum, and a diffusion pump for a high vacuum. The deposition process occurred in a range of

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1.33 1071.33 108 Pa at 350 C and at a deposition rate of 1.1 /s. The oxygen gas was supplied into the chamber close to the substrate xture such that TiO2 evaporants were easily oxidized during the deposition. The TiO2-target tablets were located near the bottom and the substrates were located near the top of the evaporation chamber at 90 cm distance. The substrate xture was in a parabolic dome shape in order to promote lm uniformity due to the symmetric lobe-shape vapor cloud of the TiO2 evaporants. For each batch of prepared samples, silicon (1 0 0) wafers and soda-lime car mirrors were used as substrates such that the identical TiO2 lms were obtained and appropriately characterized by several characterization instruments. 2.2. Design and characterization The design and preparation of the samples were conducted in parallel with lm characterization and analysis from several instruments. A variable-angle spectroscopic ellipsometer (VASE; J.A. Woollam) was used to determine lm thickness, lm homogeneity and optical constants. The results from VASE analysis were used extensively for the lm designs. The modeling process for TiO2 lms with suitable optical functions is extensively discussed elsewhere [12]. An X-ray diffractometer (XRD; Bruker) was used to examine lm crystallinity. Moreover, measurements from an atomic force microscope (AFM; Seiko) also helped understanding surface topology and surface roughness of the samples. During the lm design and development, all the samples were mainly measured and characterized by a contact angle goniometer (ram-hart) from which we could determine hydrophilicity of the lms. The nal design of lm-coated mirrors was to be comparatively and systematically examined with the commercial photocatalytic car mirrors. 2.3. Investigations of hydrophilicity and sustainability During the development of light-induced photocatalytic TiO2 lms, all samples had been prepared and kept in normal laboratory environments, i.e., without proper covers and without exposing to a direct sunlight for several days. On each sample, ve consecutive contact angle measurements, as well as advancing and receding steps, were conducted such that its average hydrophilic angle was obtained. A series of investigation methods were applied to the prepared samples and the reference samples in order to investigate the following properties. (1) Super-hydrophilicity: super-hydrophilic property of the samples was examined by exposing UV-A with a UV black-light bulb (1.2 mW/cm2) to the as-deposited samples, prior to the contact angle measurements. This procedure helps assure that the freshly prepared samples hold a hydrophilic property within the time limit compared to the reference samples. The samples with excellent hydrophilic conditions are considered at the water contact angle less then 10. According to Table 1, we categorized the effectiveness of the hydrophilic property of the samples to t our experimentation. (2) Sustainability: sustainability or water retention of the samples hydrophilicity was examined immediately right after method (1) under the assumption that the samples attained their best hydrophilic conditions after UV exposure. The sustainability was carefully examined by applying a singlepassed gentle stroke, using Kimwipes papers, at a constant pressure on the surface of the sample before the next contact angle measurement. This procedure was alternatively repeated until the contact angle of the samples was worse than that of a blank glass substrate (30). This method imitates a normal usage of side-view car mirrors where users

Table 1 Legends classifying effectiveness of water contact angle results in terms of hydrophilicity are explained. Since oat glass substrates have water contact angle at 30, those angles higher than 30 will be categorized as of poor quality. Symbol d s x Implication Excellent Good Moderate Poor quality Contact-angle range 0 6 h 6 10 10 < h 6 20 20 < h 6 30 h > 30 Remarks Super-hydrophilic Hydrophilic Worse than glass

clean up occasionally. We regard the samples in excellent conditions at more than 30 times during the wipe-cleaning process. (3) Self-cleaning property: after method (2), all the samples were again kept in the laboratory environments for 7 days. Selfcleaning property was now examined by exposing solar irradiation (2.02.4 mW/cm2 in a clear-sky day), to the samples prior to the contact angle measurements. This method is to imitate a normal usage in order to ensure how all samples, after sustainability test, can recharge and/or reactivate their hydrophilic property in outdoor environments. We expect the samples in excellent conditions at less than 1 h of photo-induced recharge for a threshold of super-hydrophilic contact angles. (4) Degradation: after method (3), all the samples were kept in a dark storage for 4 months. Degradation and/or deterioration of the previously-mentioned properties were re-examined by the contact angle measurements on the samples after exposed in UV-A. This method helps verify the degradation of the photocatalytic property of the TiO2 lms after a long-time storage. Good samples must still be usable more than 6 months of normal storage.

3. Results and discussion 3.1. Investigations of the commercial products

(1) Super-hydrophilicity: several commercial products of photocatalytic side-view mirrors were obtained from three different manufacturers and had been kept in normal environments for more than 6 months. They were examined for hydrophilic properties by contact angle measurements after UV black-light exposure at 1.2 mW/cm2. Fig. 1 illustrates the results of water contact angles on the reference samples. Notice that, as the samples taken right out of storage were full of dusts, they had as high the contact angle as 6090. After UV irradiation, the contact angles decreased gradually as exposure time increased. It is also noted that, although during the rst 2 h each samples resulted differently, after 4-h exposure, the nal results do not differ too differently. The reference sample of interested is the sample with the lowest contact angle at 4 at the rate faster than other manufacturing products. The reference sample with the most efcient hydrophilic property is the sample that had been kept in normal lab conditions for several months. Prior to the experiments, we could easily observe dust and oily stains on its surface. Without prior cleaning on the surface, UV-A exposure dramatically reduced the water contact angle to 4. This is the self-cleaning process from UV exposure which results in excellent super-hydrophilicity. (2) Sustainability: immediately after the hydrophilicity investigation, we began contact angle measurements in alternation to a gentle cleaning on the surface. The number of wipe-

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100 90 80 Contact Angle (degrees) 70 60 50 40 30 20 10 0 Ref1#1 Ref1#2 Ref1#3 Ref1#4 Ref2#1 Ref2#2 Ref3#1 Ref3#2 Glass

100 90 80 70 60 50 40 30 20 10 0 0 1 2 3 Solar Irradiation Time (hours)

Contact Angle (degrees)

Ref1#1 Ref1#2 Ref1#3 Ref1#4 Ref2#1 Ref2#2 Glass

Fig. 3. Evolution of water contact angles for the commercial side-view car mirrors after solar irradiation.

2 3 UV Irradiation Time (hours)

4
thus results in faster discharge when kept in the storage. However, its charging capability is still as effective as the rest when exposed to irradiation up to 2 h. From previous three investigations, it is sufcient to distinguish the most efcient product sample from a certain manufacturer (Ref1). This sample will then be used as a reference sample in the following studies. Therefore, we decide to omit the degradation investigation at this time, but will be eventually be included in the next discussion.

Fig. 1. Evolution of water contact angles for the commercial side-view car mirrors after UV irradiation. The samples were obtained from three different manufacturers with two or three different batches. The contact angle of a blank glass substrate is also included.

cleaning and corresponding water contact angles were carefully recorded and illustrated in Fig. 2. The graph obviously shows that all samples begin at similar lowest water contact angles at 4. The wipe-cleaning process eventually causes the lost of their hydrophilic properties, although at different rates. It is very important to note that, the samples with the most effective results in previous investigation also show their most sustainable results in this investigation, with the water contact angle at 20 after 70 times of the wipecleaning. (3) Self-cleaning property: after method (2), the samples were kept in the laboratory environments for several days before the next investigation. Fig. 3 shows the results from selfcleaning properties of the reference samples after solar irradiation. Although the samples are very effective after 1 h of solar irradiation, their quality is distinguished by the rate at which the water contact angle decrease during the rst hour of irradiation. Notice that a certain sample has starting water contact angle as high as 90, but can be photocatalyzed by solar irradiation to 12 within 2 h. We believed that this sample has been out of production line longer than the rest,

3.2. Designs and preparations of photocatalytic TiO2 lms for sideview mirrors There are several factors that must be considered in our designs and preparations of photocatalytic TiO2 lms for car mirrors. The lm preparation and characterization results, according to the design and deposition process, are summarized in Tables 2 and 3. (1) Crystallinity: TiO2 lm layer is important for photocatalytic behaviors on hydrophilic side-view mirrors and self-cleaning glasses. It has been found that suitable TiO2 crystallinity must be in anatase phase [1315] due to its advantages in high-density porosity and smaller grain size [7,16]. In our experiments, a number of lm preparations had been conducted where the substrate temperature at 350 C helped promote anatase-phase crystallinity of TiO2 lm. In this

100 90 Contact Angle (degrees) 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 Number of Wipe-Cleaning 60 70 Ref1#1 Ref1#2 Ref1#3 Ref1#4 Ref2#1 Ref2#2 Ref3#1 Ref3#2

Fig. 2. Illustration of contact angle measurements for the commercial side-view car mirrors during the wipe-cleaning process. The degrees of contact angles are directly affected by the number of wipe-cleaning.

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study, we nd that the nominal temperature during the deposition is a dominant factor to the desired crystallinity, while the deposition rate is not. (2) Deposition rate: according to Table 2 (G2), nominal lm thickness had been set at 180 nm. The TiO2 lms were deposited at several deposition rates, i.e., 0.9, 1.1, 1.3, 1.5, and 1.7 /s. The rates of 0.9 and 1.1 /s give samples with good hydrophilicity. We discovered that the physically possible, homogeneously structured TiO2 lms were achieved at 1.1 /s deposition rate. (3) Film thickness: from Table 2 (G3), when the deposition rate was xed at 1.1 /s, the lm nominal thickness was congured at 180, 200, and 220 nm. All samples still demonstrated anatase-phase crystallinity. It is important to note that the intensity of the preferred orientation of XRD peak is higher when the thickness increases, thus proving that the lm thickness actually affects the lm crystallinity. (4) Multi-layer lm structure: (a) A single layer lm structure is proposed as TiO2/substrate in Table 2 (G3). Experimental results from Table 3 show that, after a week and 4 months of storage, super-hydrophilic property still holds. However, all prepared samples of the single TiO2 layer do not sustain their hydrophilicity even though no lm peeling is observed. That is, immediately after a wiping-off, the samples cannot hold their hydrophilic property and their water contact angles increase dramatically. This is because they cannot endure a slight surface changes from even a single-passed cleaning. It can be conveniently concluded that, the single-layer structured samples have good super-hydrophilic property, but do not hold a good sustainability test. (b) A double layer lm structure is proposed as SiO2/TiO2/ substrate in Table 2 (G4). The SiO2 layer has been rst introduced on top of TiO2 layer [17] where this combination promises practical uses in automobiles side view mirrors [18]. In this study, the SiO2 layer had been added on top of the previously prepared samples in order to act as a protective layer. In addition, SiO2 is chosen because SiO2 lm usually possesses hydrophilic property. Hence, SiO2-coated TiO2 samples are expected to sustain their hydrophilicity longer than that from single-layer structured samples. Experimental results show that, contact angle measurement results do not satisfy our qualication standard. Moreover, after less than 10 wiping-offs, although no lm peeling is observed, the samples eventually lose their hydrophilicity. Nevertheless, the proposed double layer lm structure is a good start to preparing hydrophilic multi-layer structured lms. (c) A triple layer lm structure is proposed as SiO2/TiO2/ SiO2/substrate in Table 2 (G5). For manufacturing propose, the triple layer structured lms best suits the simpler, the better model concept such that the multi-layer lm structure with the least highest number of lm layers could maintain super-hydrophilic properties and can be conveniently prepared in manufacturing environments. In this study, an additional SiO2 layer is added as an inter-layer between substrates and TiO2 lm layers in order to act as a buffer in order to protect the above layers from Na diffusion from soda-lime glass substrate. From Table 2, the sample S31 holds its super-hydrophilicity and maintains its property of interests, thus is suitable as a reference sample in the next experimental group (Table 2 (G6)) in order to verify repeatability in production

environments. This group of experiment will make sure that the deposition conditions were most effective and repeatable in preparation. (5) Surface roughness: there have been several reports claiming that smaller TiO2 grain size on the surface helps promote hydrophilic behaviors. This is because smaller grain size results in higher surface area that could effectively inuence photocatalytic activities [16,19]. This could actually affect the surface roughness of the lm samples, and can be explained by two factors: TiO2 layer thickness and SiO2 layer thickness.When TiO2 evaporants deposit and condensate on the substrate, they form molecular island-lm formation into a columnar-grain structure normal to the substrate itself [20]. As lm thickness increases, columnar structure is increased, thus directly results in a larger grain size. Although the TiO2 layer is easily photo-induced, it is prone to photo-activity which could contaminate or damage the lm surface itself. Therefore, the SiO2 top layer is considered as a hard-coating layer. The thickness of the SiO2 will always directly affect the surface roughness and the surface grain size.

3.3. Investigations of the nal-design photocatalytic TiO2 lms In previous section, a number of samples was prepared and examined for effective photocatalytic lm structures for side-view car mirrors. We found that the most effective lm samples were the triple layer lm system of SiO2(40 nm)/TiO2(220 nm)/ SiO2(20 nm)/substrate with the anatase phase TiO2 prepared at 350 C. In this section, the investigation of the prepared samples will be conducted and examined in comparison to the reference samples. (1) Super-hydrophilicity and sustainability investigation: (a) Super-hydrophilicity: several freshly prepared prototypes (of 1-week storage) were examines for water contact angles, as shown in Fig. 4, after exposed to UV-A in normal environments. We noticed that, even before the UV-A exposure, their hydrophilicity were already in a good condition. With the UV-A exposure, they all exhibit an excellent super-hydrophilicity with water contact angle as low as 5 within an hour of black light exposure. Note that the sample S32 is the only sample prepared without proper cleaning of the evaporation chamber prior to the lm preparation. Its good hydrophilicity but poor quality than the rest of the group can be simply explained as contamination and several other factors in the chamber and vacuum systems. It must be noted that these prototypes in the investigation are of 1-week old, which is greatly different from the reference commercial products of 6-month storage. Therefore, results from the commercial products will not be compared in the gure due to very different controlled conditions. (b) Sustainability: Table 4 shows the results of contact angle measurements of prototype samples compared to those of the reference. It is observed that the most effective sample could sustain the wipe-cleaning process at as many as 25 times, which also proves that it can endure normal usages. Notice that a certain sample shows lower result as it loses hydrophilicity at ve times of wipe-cleaning. This is the only sample that had been prepared without proper chamber cleaning prior to the thin lm deposition process. Poor results can be deductively explained as contamination in the system.In comparison, results of the products from the same manufacturers are also shown. It is obvious that the

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Table 2 A summary of categorized experimentation for photocatalytic lm systems under different conditions is shown. The results from contact angle, VASE, and AFM measurements for water contact angles after UV exposure, lm thickness, and surface roughness, respectively, are shown. The investigation goals of sub-experiments are also given. Group Samples Materials Contact angle (1 Week) G1 S01 S02 S03 S04 S05 S06 S07 S08 S09 S10 S11 S12 S13 S14 S15 S16 S17 S18 S19 S20 S21 S22 S23 S24 S25 S26 S27 S28 S29 S30 S31 S32 S33 S34 SiO2 SiO2 SiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 d d d d d d d d d (4 Months) d x d d s s s s d d 66 35 36 170 160 165 180 155 200 180 145 210 221 217 28/220 11/167 28/176 10/170 23/130 22/182 28/233 29/240 25/200 33/221 34/215 31/217 30/218 10/122/22 28/230/47 16/220/41 0.71 2.27 2.79 2.18 1.66 1.53 2.68 1.48 2.47 1.28 3.61 2.45 2.69 2.57 2.54 2.52 1.56 2.07 2.38 2.4 2.17 2.5 2.6 1.58 2.01 2.6 11 11 11 0.9 1.1 1.3 1.5 1.7 1.1 1.1 1.1 1.1 1.1 1.1 1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1 11/1.1/11 11/1.1/11 11/1.1/11 11/1.1/11 11/1.1/11 11/1.1/11 System Calibration Thickness (nm) SRough (nm) Rate (/s) Investigation goals

G2

Deposition Rate

G3

Film Thickness

G4

Double Layer Films

s s s d s s s d d s

G5

Triple Layer Films Repeat1 Repeat2 Repeat3

G6

d d

d = Excellent (0 < h 6 10);

= good (10 < h 6 20); s = moderate (20 < h 6 30); x = poor quality (h > 30).

reference samples hold longer quality in sustainability investigation, where the most efcient sample can sustain the wipe-cleaning process at as many as 50 times.

(c) Self-cleaning property: Fig. 5 illustrates the results of water contact angles due to self-cleaning process by solar exposure in a clear-sky day. Two of prototype samples fall into the

Table 3 A summary of contact angle measurements of the selected samples after 4-h UV-A exposure. The measured contact angles are taken from samples of 1-week and 4-month storage in normal environments. The samples with 4-month storage are also examined for sustainability in hydrophilic properties by a number of single-passed wipe-cleaning. Samples Materials Contact angle (1 Week) S04 S05 S07 S09 S11 S12 S13 S16 S17 S21 S26 S30 S31 S32 S33 S34 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 SiO2/TiO2/SiO2 d d (4 Months) d x d d d s s s d d d s Number of wipe-cleaning 13 x x x x x x x s s x x x d s s 48 x x x x x x x s s x x x s s s 912 x x x x x x x x s x x x s x s s 1350 x x x x x x x x

s d d

d d

d = Excellent (0 < h 6 10);

= Good (10 < h 6 20); s = Moderate (20 < h 6 30); x = Poor Quality (h > 30).

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60 Contact Angle (degrees) 50 40 30 20 10 0 0 1 2 3 UV Irradiation Time (hours)

Contact Angle (degrees)

S31 S32 S33 S34 Glass

60 50 40 30 20 10 0 4 0 1 2 3 Solar Irradiation Time (hours) 4 S31 S32 S33 S34 Glass Ref1

Fig. 4. Evolution of water contact angles for the nal-designed prepared samples, exposed to UV-A black light.

Fig. 5. Evolution of water contact angles of the nal-designed prepared samples, exposed to solar irradiation. The results of the most efcient reference sample are also included.

same curve range of the reference sample, with a lower contact angle at 5 after 4 h. It can be said that these samples are stable and behave similarly to the reference samples.It is important, however, to note that, other prepared samples of the same sub-experiment take longer to reach a hydrophilic state. Moreover, one sample (S32) does not show satisfying results to meet the threshold at 30 from a blank substrate, because, as previously discussed, it was the sample prepared in the contaminated system. (d) Degradation: It is rst important to note that the prototype samples were freshly prepared in our laboratory environments and kept in normal storage for at most 4 months. Our reference samples however had been previously manufactured, and were obtained and kept in our normal storage for 6 months. However, their exact time for manufacturing the references prior to the date of receipt is unknown. Therefore, our previous rigorous hydrophilicity and sustainability investigations also aim toward reducing several advantages in our freshly-prepared prototypes before conducting the degradation investigation. Fig. 6 compares the water contact angles of the stable prototype (S31, S34), and the reference. With the UV irradiation, the sample of 1-week storage demonstrates excellent hydrophilicity across all exposure time. After 4-month storage, however, it has higher starting contact angle and cannot retain its hydrophilicity at all regardless to the exposure time as long as 3 h. With the solar irradiation, the 1-week stored sample still shows higher starting contact angle, but proves its hydrophilicity after 2 h of exposure. The same sample stored for 4 months has even higher starting contact angle, but decreases gradually as the exposure time increases. Recall that the solar exposure during daytime has higher light intensity than that of the black-light bulb, therefore the results are as expected. It is obvious that, the longer the storage time, the higher

100 90 Contact Angle (degrees) 80 70 60 50 40 30 20 10 0

S31(1Week)_UV S31(4Month)_UV S31(1Week)_Solar S31(4Month)_Solar S34(1Month)_Solar Ref(6Month+)_Solar Glass

2 3 Irradiation Time (hours)

Fig. 6. Evolution of water contact angles of the nal-designed prepared samples, exposed to different sources of irradiation, after 1-week and 4-month storage in normal laboratory conditions. The results of the reference sample are also included.

the starting contact angle and the longer it needs for the light irradiation in order to obtain similar results. From Fig. 6, notice that the reference sample, after 6 months of storage, has a very high starting contact angle more than 90. However, within 2 h of solar exposure, it quickly responds to photocatalytic recharges and decreases its contact angle to 12. Moreover, it also demonstrates better hydrophilic results, in terms of water contact angles, than those from our prepared samples. (2) X-ray diffraction investigation: In the design and preparation of TiO2 lms, we focused on its photocatalytic property. It has previously been discussed that, for hydrophilic TiO2 lms, anatase structure is preferred due to its high electron

Table 4 Sustainability investigation results of the nal-designed prepared samples after 1-week storage prior to UV-A irradiation. The reference commercial product sample had been in storage for 6 months. The contact angle measurements are conducted in alternation with the wipe-cleaning process. #Wipes Ref 1#1 Ref 1#2 Ref 1#3 Ref 1#4 S31 S32 S33 S34 12 35 s 610 s s x s s x s s 1115 x s x s x x x s 1620 x s x s x x x s 2125 x s x s x x x s 2630 x s x s x x x x 3140 x s x s x x x x 4150 x x x s x x x x

s s

s s s

= good (10 < h 6 20); s = moderate (20 < h 6 30); x = poor quality (h > 30).

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Sample

Reference

Quantitatively, the prepared sample has RMS and mean diameter at 3.00 nm and 4.50 nm, respectively, while the reference sample has RMS and mean diameter at 2.29 nm and 4.72 nm, respectively. The difference in the RMS values could have contributed to the varying results in sustainability and degradation tests for both samples, although their hydrophilicity investigation shows similar results. Nevertheless, we want small grain size on the sample surface which offers better hydrophilic property [19]. This speculation involves larger surface area, when the surface contains smaller grain size, in order to be easily induced by photocatalytic-driven light source.

Intensity (a.u.) 20

30

40 2Theta (degrees)

50

60
4. Conclusions This study focuses on the development of hydrophilic and photocatalytic car mirrors prepared by TiO2 thin lms. The study aims toward properties of hydrophilicity, sustainability, self-cleaning and degradation of the samples prepared by the electron-beam evaporation with the appropriate designs as previously mentioned above. The samples prepared by evaporation also demonstrate excellent properties in hydrophilicity and photocatalysis due to desirable conditions in anatase-phase crystallinity, small grain size, and desirable surface conditions similar to those in the reference samples. However, our prototypes fail to maintain good quality of water retention after the wipe-cleaning test which causes a few samples to lose all photocatalytic properties indenitely. In addition, after long storage, the prepared samples apparently degrade overtime. That is, they cannot exhibit their hydrophilic property as fast as the reference and need longer time to recharge photocatalytic capability. The reference samples however demonstrate excellent properties in hydrophilicity and photocatalysis. They also maintain excellent retention condition after long storage in the unattended environments up to 6 months. In other words, the commercial products prove to be excellent in all hydrophilicity and sustainability investigation methods. This comparative study shows that the TiO2 thin lms prepared by electron-beam evaporation can achieve good photocatalytic lms and mirrors. However, in order to maintain its prolonged properties, further considerations in designs and preparation are still needed. Nevertheless, our focus on the investigation methods for hydrophilicity and sustainability of the materials prove to be

Fig. 7. X-ray diffraction patterns of the nal-designed prepared sample and the reference sample.

mobility, low dielectric constant and low density [14,15]. XRD patterns, as shown in Fig. 7, demonstrate similar condition for TiO2 lm containing only anatase structure without rutile crystallinity. This is because the lm with anatase crystallinity has an advantage in porosity and small grain size compared to those of other crystal phases [7,16]. The reference sample shows a very tiny peak of anatase at 2h = 25.6. Nevertheless, the measurements were conducted on mirror-glass substrates which may have caused too much background noise. Note that the results of anatase phase from XRD agrees with optical constants obtained from VASE analysis (n550 nm = 2.54) which strictly correspond to anatase crystallinity. As already mentioned, the complete VASE modelling process has been discussed elsewhere [12]. (3) Surface roughness investigation: In order to achieve similar hydrophilic properties, we assumed that surface roughness on both the reference and the prepared samples are similar and small in size [19]. The measurements by atomic force microscopy (AFM) in dynamic mode conrm the assumption, as shown in Fig. 8. The 2D illustrations of AFM topology show similar grain shape and size on the surface. However, we observe that the reference sample illustrates the surface topology in a perfect order on the xy plane, while our prepared sample is full of holes and wells (the dark areas) on its surface.

Fig. 8. AFM topology in 2D on the surfaces of (a) the nal-designed prepared sample with the SiO2 lm atop (S34), and (b) the reference sample.

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considerably useful to evaluate the quality of the self-cleaning properties in materials of interests. Acknowledgments This study was nancially and technically supported by National Electronics and Computer Technology Center (NECTEC), a member of National Science and Technology Development Agency (NSTDA), Thailand. References
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