JP4083036B2 - Titania nanocrystallite film, article having this pattern, and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The invention of this application relates to a titania nano-microcrystalline film, an article provided with this pattern, and a method for producing the same.
[0002]
[Prior art]
Conventionally, titania's characteristics such as photocatalytic activity and superhydrophilicity have attracted attention. Along with a thin film made of titania itself, a titania dispersion film (SiO2) mainly composed of silica and titania.₂-TiO₂Development of articles having various functions such as purification, antibacterial, and antifouling using a thin film containing titania such as a system film) has been promoted and put into practical use.
[0003]
The inventors of this application pay attention to the excellent properties of the titania thin film as described above and the possibility of its wide application, and already have a high photocatalytic activity and a superhydrophilic transparency made of a titania anatase microcrystalline film. A thin film has been developed and presented as a practical technology.
[0004]
Although the inventors have been striving to further develop this technology, the titania anatase microcrystalline thin film presented by the inventors has high photocatalytic activity, but has no reaction selectivity for photocatalytic reaction, and is in contact with it. Most organic substances that are present are decomposed, and organic substances that are used to impart functionality such as water repellency to the substrate are also photodegraded.
[0005]
When applying this photocatalytic function, it is possible to pattern a field having a function such as a photocatalytic function and a field of an organic substance having other functions that are not photodegraded in any part and shape on the substrate. This is what is desired.
[0006]
Therefore, the inventors conducted photoirradiation on the composite metal oxide gel film obtained from silicon alkoxide, titanium alkoxide, and β-diketone through a photomask, and the irradiated portion of the photoactive titania anatase microcrystalline thin film pattern forming technology. After curing, a method for etching the non-irradiated part and then treating with hot water to deposit titania microcrystals on the surface of the non-irradiated part has been newly developed and proposed (Patent Application 1).
[0007]
However, in this new titania microcrystalline film, it is desirable that the etching process is indispensable in practice, and it is easy to add various functions to the titania thin film. There was room for further ingenuity.
[0008]
[Patent application]
Japanese Patent Application No. 2002-237606
[0009]
[Problems to be solved by the invention]
Therefore, the invention of this application has been studied to further develop the titania microcrystalline film and the manufacturing method proposed by the inventors, and is simple as a practical manufacturing process without requiring an etching process. Therefore, it is an object of the present invention to provide a new titania film and a method for manufacturing the same that are highly possible in terms of imparting various functions.
[0010]
[Means for Solving the Problems]
The invention of this application is characterized in that, in order to solve the above-mentioned problems, first, the substrate surface has a portion of the titania nano-microcrystalline film together with a portion of the organosilsesquioxane-titania film. A titania nano microcrystal film is provided, and secondly, a titania nano microcrystal film characterized in that portions of the titania nano microcrystal film are arranged in a predetermined plane arrangement pattern, and third, an organosil Sesquioxane-titania has the following formula:
[RSiO_3/2]_x[TiO₂]_y
(R represents a hydrocarbon group which may have a substituent, x and y represent a composition ratio, and 0 <x <100, 0 <y <100, and x + y = 100. )
A titania nanocrystallite film characterized by the following is provided:
[0011]
And, the invention of this application is, fourthly, a titania nano microcrystal film characterized in that the organosilsesquioxane-titania film on the substrate is irradiated with light and then treated with warm water to precipitate titania nano crystallites. Fifth, a method for producing a patterned titania nanocrystallite film characterized in that site-selective light irradiation is performed and titania nanocrystallites are deposited as a predetermined planar arrangement pattern. Sixth, a method for producing a titania nano-microcrystalline film that uses a photomask, laser light irradiation or site-selective light irradiation by optical condensing prescription, and seventh, an organotrialkoxysilane and β -An organosilsesquioxane-titania film is formed by sol-gel reaction with titanium alkoxide modified with diketone. That titania manufacturing method of a microcrystalline film, the eighth, in the above manufacturing method, organosilsesquioxane - titania, its composition, the following formula
[RSiO_3/2]_x[TiO₂]_y
(R represents a hydrocarbon group which may have a substituent, x and y represent a composition ratio, and 0 <x <100, 0 <y <100, and x + y = 100. )
The manufacturing method of the titania nano microcrystal film | membrane characterized by these is provided.
[0012]
The invention of this application is characterized in that the ninth and tenth are provided with any one of the above-mentioned titania nano-microcrystalline films, or the titania nano-microcrystalline film produced by any one of the above-described production methods. Provided is an article characterized by comprising.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The invention of this application has the features as described above, and an embodiment thereof will be described below.
[0014]
The invention of this application is an organosilsesquioxane-titania (RSiO) obtained by the sol-gel method from an organotrialkoxysilane obtained by the inventors and a titanium alkoxide previously chemically modified with β-diketone._3/2・ TiO₂) The film was first discovered to be a titania anatase microcrystalline film by UV irradiation to this, and further treated with warm water, and this showed photocatalytic activity, and further UV irradiation via a photomask or the like. However, it has been completed based on the knowledge that the titania anatase microcrystalline thin film can be patterned by hot water treatment.
[0015]
Compared to the technology for which the inventors previously applied for a patent, the characteristic feature is that the non-irradiated part has RSiO._3/2-TiO₂The film remains, and this R (various substituents) can provide various functions, and further has excellent features such as the need for an etching operation and simplified process. It is to have.
[0016]
The technology of the present invention provides a multifunctional thin film having both a photocatalytic activity function and other organic functions, such as being capable of finely patterning a photocatalytic activity part and, for example, a water-repellent part, and effectively utilizing both functions. This is a significant technology for future application development of photocatalytically active thin films.
[0017]
The production method of the invention of this application will be described. As shown in FIG. 1, the outline is as follows: organosilsesquioxane-titania (RSiO_3/2-TiO₂The thin film is abbreviated to light and then treated with warm water such as boiling water to precipitate titania nanocrystallites in the irradiated region. This forms titania nanocrystallites.
[0018]
In this method, the organosilsesquioxane-titania has the composition as described above.
[RSiO_3/2]_x[TiO₂]_y
It can be expressed as Of course, it goes without saying that inevitable impurities such as those derived from raw materials are allowed to be mixed into this composition.
[0019]
The symbol R in the above formula is a hydrocarbon group which may have a substituent. In this case, the hydrocarbon group may be either a chain or a ring, and may be either saturated or unsaturated. Good. Specifically, examples of the hydrocarbon include alkyl groups such as methyl group, ethyl group, and propyl group, alkenyl groups such as vinyl group, and aryl groups such as phenyl group and tolyl group. Moreover, as a substituent, you may be various accept | permitted things including a halogen atom. For example, as R, C_nF_{2n + 1}Perfluoroalkyl group and the like.
[0020]
Depending on what kind of organic group is used as the symbol R, the thin film produced may be provided with various functions other than those derived from titania, or synergistically enhancing the functions derived from titania. It becomes possible.
[0021]
For the organosilsesquioxane-titania film, for example, organotrialkoxysilane: RSi (OR¹)_Three(R represents the above, R¹Are the same or different hydrocarbon groups) and a titanium alkoxide modified with β-diketone: Ti (OR²)_Four(R²Can be produced on a substrate by a sol-gel reaction with the same or different hydrocarbon groups. In this case, the β-diketone may be selected from various types, for example, ethyl acetoacetate and the like are shown as representative ones. This modification with β-diketone is made possible by mixing with titanium alkoxide.
[0022]
For the sol-gel reaction, for example, organotrialkoxysilane: RSi (OR¹)_ThreeOf alcoholic acid water, and then titanium alkoxide: Ti (OR²)_FourAnd an alcohol mixture of β-diketone can be added.
[0023]
The molar ratio of the solution at this time is RSi (OR¹)_Three: Ti (OR²)_Four: H₂O (acidic) = 1: 0.5 to 1.5: 2 to 6, Ti (OR²): Β-diketone = 1: 0.5-2.
[0024]
After the reaction, it is preferable to dry at room temperature (15 to 25 ° C.) and then heat-treat at a temperature of about 80 to 110 ° C. for about 0.5 to 1.5 hours.
[0025]
And the titania nano microcrystal film | membrane of invention of this application can make a titania nano microcrystal precipitate in the predetermined plane arrangement pattern after a hot water process by performing site | part selective light irradiation. In the site-selective light irradiation in this case, patterning can be performed by using a photomask, laser light irradiation, optical condensing prescription or the like. FIG. 2 illustrates the case where a photomask is used.
[0026]
In the invention of this application, RSiO_3/2-TiO₂Even if the film (R = vinyl, methyl, ethyl, phenyl group, etc.) is treated with warm water as it is, titania crystals hardly precipitate, but when irradiated with ultraviolet light, some SiO2₂-TiO₂Anatase nanocrystallites are deposited by forming a membrane and further performing hot water treatment.
[0027]
As shown in FIG. 2, if the ultraviolet light is irradiated through a mask, RSiO_3/2-TiO₂Anatase microcrystals can be selectively deposited at desired locations on the membrane.
[0028]
Moreover, if an external stimulus such as vibration is given during the hot water treatment, titania nanosheet microcrystals can also be deposited.
[0029]
The obtained substrate with titania nanocrystal pattern is RSiO._3/2By the effect of the organic functional group R, it has functions such as water repellency and functions such as super hydrophilicity and photocatalytic activity by titania microcrystals.
[0030]
For the hot water treatment, hot water of 80 ° C. or higher is preferably used, but treatment with boiling water is more preferable. In this treatment, various means such as immersion in warm water, spraying of warm water, and flowing down of warm water can be employed.
[0031]
Then, an Example is shown below and invention of this application is demonstrated in detail. Of course, the invention is not limited by the following examples.
[0032]
【Example】
<1>(100-x) RSiO _3/2 ・ XTiO ₂ Sol preparation and sample preparation method
FIG. 3 shows (100-x) RSiO._3/2・ XTiO₂The preparation method of sol and coating film was shown.
[0033]
As the organic functional group R, a methyl group (R = Me), an ethyl group (R = Et), or a vinyl group (R = Vi) is selected, and a raw material organotrialkoxysilane (RSi (OR¹)_Three) As MeSi (OEt)_Three, EtSi (OEt)_Three, ViSi (OEt)_Three(Shin-Etsu Chemical Co., Ltd.) was used. A predetermined amount of this organotriethoxysilane: RSi (OEt)_ThreeAfter mixing with ethanol: EtOH and stirring for 5 minutes, 0.1 wt% dilute hydrochloric acid (Wako Pure Chemical) was added, and after hydrolysis and polycondensation for 1 hour, ethyl acetoacetate (CH_ThreeCH₂COCH₂COCH_ThreeManufactured by Kishida Chemical Co., Ltd., hereinafter abbreviated as EAcAc) and titanium tetranormal butoxide (Ti (O-nBu)) stirred with EtOH for 1 hour._Four(100-x) RSiO by adding a solution and stirring for 1 hour._3/2・ XTiO₂A sol was prepared. Solution composition is molar ratio [RSi (OEt)_Three+ Ti (O-nBu)_Four]: H₂O (in HCl solution): EtOH = 1: 4: 1, Ti (O-nBu)_Four: EAcAc = 1: 1. Using this sol, dip coating is performed on quartz glass or silicon substrate, and (100-x) RSiO_3/2・ XTiO₂A film was prepared, dried at room temperature for 40 minutes, and then heat-treated at various temperatures for 1 hour. Thereafter, ultraviolet light irradiation was performed for various times using an ultrahigh pressure mercury lamp. Furthermore, after preparing pure water in a beaker and heating to about 100 ° C., a sample was obtained by immersing the coating film for a predetermined time.
<2>Hot water treatment method
The sample was immersed in about 500 ml of warm water (about 100 ° C.) placed in a 500 ml beaker and treated with warm water while stirring with a stirrer.
<3>ViSiO _3/2 -TiO ₂ About membrane
RSiO_3/2-TiO₂By irradiating the system film with ultraviolet light, amorphous TiO₂The photocatalytic reaction occurs due to, and the organic functional group R is eliminated. That is, the trifunctional Si and the tetrafunctional Si bonded to the organic functional group exist in the gel film after the ultraviolet light irradiation. On the other hand, the inventors already have SiO.₂-TiO₂The anatase nanocrystallites have been successfully deposited by treating the system membrane with warm water._3/2-TiO₂In the hot water treatment of the system membrane, almost no titania nanocrystallites are generated. By this, RSiO irradiated with ultraviolet light_3/2-TiO₂In the system film, the structure of the film is partially SiO 2₂-TiO₂TiO 2 on the film surface by hot water treatment₂It is thought that nanocrystallites precipitate.
[0034]
That is, SiO₂-TiO₂When the system film is treated with warm water, the Si—O—Ti bond in the film is hydrolyzed to generate Ti—OH groups. Thereafter, the generated chemical species having Ti—OH groups diffuse to the film surface while being dissolved in water. TiO dissolved₂The seed concentration reaches supersaturation and TiO₂It is thought that seed reprecipitation occurs and anatase nanocrystallites are formed.
[0035]
Further, if an ultraviolet ray is irradiated through a mask or selectively irradiated with an ultraviolet laser, anatase nanocrystallites can be selectively deposited at a desired location on the film surface.
[0036]
Actually, 80RSiO with and without UV irradiation_3/2・ 20TiO₂The structural change in warm water was examined by measuring the IR spectrum of the membrane by hot water treatment.
[0037]
FIG. 4A shows 80 ViSiO irradiated with ultraviolet light for 1 hour._3/2・ 20TiO₂FIG. 4 (b) shows an unirradiated 80 ViSiO film._3/2・ 20TiO₂The IR spectrum in the various warm water processing time of a film | membrane is shown.
[0038]
From Fig.4 (a), it is 900 cm with the increase in hot water treatment time.^-1The peak intensity attributed to the nearby Si—O—Ti bond has decreased, and SiO₂It can be seen that the Si—O—Ti bond is hydrolyzed and cleaved, similar to the —TiO 2 film. 1100cm^-1The peak intensity attributed to the nearby Si—O—Si bond also decreases. This is considered to be because the silica component eluted into water after the Si—O—Ti bond was hydrolyzed. These structural changes were almost completed after 4 hours of hot water treatment, and no significant change was observed in the IR spectrum after 4 hours.
[0039]
On the other hand, in FIG. 4B as well, the peak intensity attributed to the Si—O—Ti bond and the Si—O—Si bond is similarly decreased, indicating that hydrolysis has occurred. In this spectrum, the peak intensity attributed to the Si—O—Ti bond decreased after 4 hours. Here, when FIG. 4A is compared with FIG. 4B, the band intensity attributed to the OH group near 3400 cm −1 is 80 ViSiO irradiated with ultraviolet light._3/2・ 20TiO₂It can be seen that the film is strong. Already in the stage before the hot water treatment, it is stronger than the unirradiated film and further increases with the hot water treatment. 80ViSiO_3/2・ 20TiO₂In the film, it is known that the contact angle with water greatly decreases because the Si—OH group increases on the film surface by ultraviolet light irradiation. For this reason, it is considered that by performing further hot water treatment, the gel film irradiated with ultraviolet light having a low contact angle is easily hydrolyzed, and Si—OH groups and Ti—OH groups are easily generated on the film surface and inside the film.
[0040]
FIG. 5 shows 80 ViSiO when ultraviolet light is not irradiated and when irradiated for 1 hour._3/2・ 20TiO₂The film | membrane surface FE-SEM observation image in the various warm water processing time of the film | membrane was shown.
[0041]
As the observation of the FE-SEM, the surface and the cross section of the gel film were observed using a field emission scanning electron microscope (S4500 Hitachi, hereinafter referred to as FE-SEM). The sample was divided together with the Si substrate using a diamond cutter to obtain a surface and a fracture surface. The sample was attached to a sample stage using a silver paste, vacuum-dried in a vacuum desiccator for about 30 minutes, and then subjected to platinum sputtering using a quick coater (ULVAC VPS-020).
[0042]
According to the above FE-SEM observation, the film surface before the hot water treatment is smooth and no precipitates are observed, but the precipitates are slightly confirmed on the film surface by the hot water treatment for 1 hour. . It can be seen that even when the hot water treatment time is increased, the amount of the precipitate is hardly changed. On the other hand, 80ViSiO irradiated with ultraviolet light for 1 hour_3/2・ 20TiO₂It can be seen that the anatase nanocrystallites as precipitates can be confirmed on the entire surface of the membrane by warm water treatment for 1 hour, and further increased by warm water treatment for 4 hours or more. Compared with the film not irradiated with ultraviolet light, the shape of the precipitate is granular, and it can be seen that each one grows greatly.
[0043]
80ViSiO irradiated with ultraviolet light_3/2・ 20TiO₂Since it was confirmed that a large amount of anatase nanocrystallites were deposited on the membrane surface by treating the membrane with warm water, changes in the properties of the gel membrane accompanying the deposition of anatase nanocrystallites were investigated.
[0044]
First, FIG. 6 shows that 80 ViSiO irradiated without ultraviolet light and irradiated for 1 hour._3/2・ 20TiO₂The hardness change with the warm water treatment time of the film was shown. It can be seen that with the increase of the hot water treatment time, a large increase in hardness occurs only in the irradiated gel film. This is because anatase nanocrystallites were deposited on the film surface. At first, the amount of precipitation was small and the increase in hardness was small, but it was thought that the amount increased significantly because the amount of precipitation gradually increased. On the other hand, in the gel film which was not irradiated, since the precipitation amount was very small, the hardness increase hardly occurred.
[0045]
FIG. 7 shows 80 ViSiO irradiated with ultraviolet light for 1 hour._3/2・ 20TiO₂The UV-VIS transmission spectra at various warm water treatment times of the membrane were shown. It can be seen that even the gel film subjected to the hot water treatment has a high light transmittance. Moreover, it can confirm that the absorption edge has shifted to the long wavelength side with warm water treatment. This is due to the precipitation of anatase nanocrystallites.
[0046]
The organic functional group (R) other than the vinyl group (Vi) was also examined. The results are shown in FIGS. In the case of the methyl (Me) group and the ethyl (Et) group, similarly to the case of the vinyl (Vi) group, the Si—C bond is cleaved by irradiation with ultraviolet light, and the anatase nanocrystallites are formed by hot water treatment after irradiation. It turns out that it precipitates.
[0047]
FIG. 10 shows the time-dependent changes in the photodecomposition reaction of methylene blue: MB, showing the evaluation results of the photocatalytic activity of the anatase nanocrystallites deposited on the Me-based film, Et-based film, and Vi-based film. In evaluating this catalytic activity, methylene blue tetrahydrate (C₁₆H₁₈N_ThreeS ・ C₁₄・ H₂1 × 10 using O, manufactured by Wako Pure Chemical Industries, Ltd.^-FiveAn MB aqueous solution of M was prepared, put in a certain amount (2.0 g) in a Pyrex (registered trademark) glass cell, and an alkali-free substrate coated with a film on one side was inserted. Coating area is 1.0cm²Unified. Next, using a colored glass filter (UV-33, manufactured by Toshiba Glass Co., Ltd.), ultraviolet light from which light of 300 nm or less is cut is irradiated from the back side of the substrate, and the concentration change of the MB aqueous solution at that time is ultraviolet-visible absorbed. The photocatalytic activity was evaluated from the spectrum.
[0048]
The target composition is 80RSiO_3/2・ 20TiO₂80SiO₂・ 20TiO₂The membrane results are also shown. The deposition conditions of anatase nanocrystallites were the same, ultraviolet light irradiation was 1 hour, and hot water treatment time was 4 hours. The film thickness after the hot water treatment was about 0.7 μm for the Me-based film, about 0.65 μm for the Et-based film, and about 0.8 μm for the Vi-based film. 80SiO₂・ 20TiO₂The film was warmed for 2 hours and the film thickness was 150 nm. From the results of FIG. 10, it can be seen that almost no adsorption occurs in any system film. Of the three types of films, the Vi-based film has the highest photocatalytic activity, and SiO₂-TiO₂Although the values were almost the same as those of the system film, it was found that the Et system film and the Me system film were slightly lower than the Vi system film. This is considered to be due to the precipitation of anatase nanocrystallites most frequently in the Vi-based film under the conditions of 1 hour ultraviolet light irradiation and 4 hours of hot water treatment, and less likely to precipitate in the Me-based film, and the amount of precipitation is small. It is done.
[0049]
Further, in FIGS. 11 and 12, 80 ViSiO which has been subjected to hot water treatment for 4 hours after being irradiated with ultraviolet light for 1 hour._3/2・ 20TiO₂The TEM observation image of the film was shown. From the FE-SEM observation image of the cross section of the film, precipitation of microcrystals can be confirmed only on the surface of the film by hot water treatment for 1 hour, but not in the film. From the high-resolution photograph (FIG. 12), it was found that the lattice spacing was 0.35 nm, and the precipitate on the film surface was anatase nanocrystallites. It was also confirmed that the anatase nanocrystallites were deposited only on the film surface, and the inside of the film was in a homogeneous amorphous state. From this result, 80ViSiO_3/2・ 20TiO₂ViSiO which was judged that the deposit by the warm water treatment of the film was anatase nanocrystallites and was irradiated with ultraviolet light_3/2-TiO₂It was confirmed that a large amount of anatase nanocrystallites can be produced by treating the system membrane with warm water.
<4>Fabrication of micro patterns
From the results so far, RSiO not irradiated with ultraviolet light_3/2-TiO₂Only a small amount of anatase nanocrystallites is deposited even when the system film is treated with warm water, but by treating with warm water after irradiation with ultraviolet light, Si-OH groups on the film surface increase and a large amount of anatase nanocrystallites are deposited. I understood.
[0050]
Therefore, after heat treatment at 300 ° C., 80 MeSiO irradiated with ultraviolet light through a photomask for 2 hours._3/2・ 20TiO₂Looking at the three-dimensional surface roughness of the film, the opening of the photomask is 40 × 40 μm and the pitch is 140 μm. It was found that the ultraviolet light irradiated portion had a densified network structure and decreased by about 60 nm with respect to a film thickness of about 0.6 μm.
[0051]
Also, after heat treatment at 300 ° C., 80 MeSiO was irradiated with ultraviolet light for 2 hours through a photomask and further subjected to hot water treatment for 2 hours._3/2・ 20TiO₂According to the FE-SEM observation images of the ultraviolet light irradiated part and the non-irradiated part of the film, it can be seen that the anatase nanocrystallites are uniformly dispersed in the ultraviolet light irradiated part.
[0052]
In FIG. 13, (a) one hour irradiated with ultraviolet light through a photomask, (b) 80 MeSiO treated with hot water for four hours thereafter._3/2・ 20TiO₂The results of AFM observation of the film are shown. After UV irradiation, the light irradiated portion is recessed by contracting about 35 nm due to the breakage of the Si—C bond. On the other hand, after 4 hours of the hot water treatment, the light irradiation part is about 180 nm higher than the surroundings. This is considered to be because anatase was precipitated and the unirradiated part was slightly dissolved during the hot water treatment. From the above results, it was found that by performing ultraviolet light irradiation through a photomask, it is possible to perform patterning in which the amount of deposited anatase nanocrystallites is greatly different on the surface of the gel film after the hot water treatment.
[0053]
In the produced pattern, the amount of precipitation of anatase nanocrystallites differs greatly between the irradiated part and the unirradiated part, so that a difference in characteristics occurs. 80MeSiO with and without UV irradiation for 2 hours after heat treatment at 300 ° C_3/2・ 20TiO₂Looking at the change in the contact angle of water with the warm water treatment time of the membrane, the contact angle is reduced by about 20 ° due to ultraviolet light irradiation after 300 ° C. heat treatment, and methyl groups are eliminated and Si—OH groups are generated. You can confirm that Further, after 2 hours of hot water treatment, the film irradiated with ultraviolet light is reduced to 32 ° and the film not irradiated with ultraviolet light is lowered to 88 °, and the contact angle difference between the irradiated part and the non-irradiated part is 56 °. It is determined that a micropattern can be formed.
[0054]
In this pattern, the amount of precipitation in the irradiated part is large, and the amount of precipitation in the non-irradiated part is small. Therefore, a pattern that selectively suppresses photocatalytic activity is possible, and the contact angle differs greatly between the irradiated part and the non-irradiated part. It is considered that the present invention can also be applied to the production of micropatterns using wettability.
[0055]
【The invention's effect】
As described above in detail, the invention of this application has been studied to further develop the titania microcrystalline film and the manufacturing method that the inventors have already proposed, and a practical manufacturing process without requiring an etching process. Thus, it is possible to provide a new titania film and a method for producing the same that are simple and have great possibilities in terms of imparting various functions.
[Brief description of the drawings]
FIG. 1 is a process diagram showing an outline of a manufacturing method of this application.
FIG. 2 is a process diagram showing an outline of patterning using a photomask.
FIG. 3 is a diagram showing a process procedure as an example.
FIG. 4 is a diagram illustrating an IR spectrum for each warm water treatment time with and without ultraviolet irradiation (a) and without (b).
FIG. 5 is a diagram illustrating an FE-SEM observation image for each hot water treatment time with or without ultraviolet irradiation.
FIG. 6 is a diagram exemplifying hardness for each hot water treatment time with or without ultraviolet irradiation.
FIG. 7 is a diagram illustrating a transmission spectrum for each boiling water treatment time of ultraviolet light irradiation for 1 hour.
FIG. 8 is a diagram illustrating peak intensities attributed to Si—C bonds at various UV irradiation times.
FIG. 9 is a diagram illustrating an FE-SEM observation image for each hot water treatment time after UV irradiation for 1 hour.
FIG. 10 is a diagram exemplifying a concentration change due to UV irradiation of an MB solution in which a film after UV irradiation for 1 hour is immersed.
FIG. 11 is a diagram exemplifying a TEM observation image of the entire film after 1 hour of UV irradiation and 2 hours of hot water treatment (precipitate: anatase is observed only on the film surface).
FIG. 12 is a diagram illustrating a high-resolution TEM observation image of precipitates on the film surface (an anatase 0.35 nm lattice is observed).
FIG. 13 is a diagram illustrating an AFM observation result when (a) UV irradiation is performed through a mask for 1 hour and (b) hot water treatment is performed for 4 hours thereafter.

Claims (10)

A titania nano-microcrystalline film having a portion of an organosilsesquioxane-titania film and a portion of a titania nano-microcrystalline film on a substrate surface. 2. The titania nano microcrystalline film according to claim 1, wherein portions of the titania nano microcrystalline film are arranged in a predetermined plane arrangement pattern. Organosilsesquioxane-titania has the following formula: [RSiO _3/2 ] _x [TiO ₂ ] _y
(R represents a hydrocarbon group which may have a substituent, x and y represent a composition ratio, and 0 <x <100, 0 <y <100, and x + y = 100. )
The titania nanocrystallite film according to claim 1 or 2, which is represented by: A method for producing a titania nanocrystallite film, characterized by depositing titania nanocrystallites by irradiating an organosilsesquioxane-titania film on a substrate with light, followed by hot water treatment. 5. The method of manufacturing a patterned titania nanocrystal film according to claim 4, wherein site-selective light irradiation is performed to deposit titania nanocrystallites as a predetermined planar arrangement pattern. The method for producing a titania nano-microcrystalline film according to claim 5, wherein site-selective light irradiation is performed by using a photomask, laser light irradiation, or optical condensing. 7. The titania nanocrystallite according to claim 4, wherein an organosilsesquioxane-titania film is formed by a sol-gel reaction between an organotrialkoxysilane and a titanium alkoxide modified with a β-diketone. A method for producing a membrane. 8. The method according to claim 4, wherein the organosilsesquioxane-titania has the following formula [RSiO _3/2 ] _x [TiO ₂ ] _y.
(R represents a hydrocarbon group which may have a substituent, x and y represent a composition ratio, and 0 <x <100, 0 <y <100, and x + y = 100. )
A method for producing a titania nanocrystallite film characterized by the following: An article comprising the titania nanocrystallite film according to any one of claims 1 to 3. An article comprising the titania nanocrystallite film produced by the production method according to claim 4.

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