WO2004101146A1 - Film mince en oxyde de titane presentant une forte activite photocatalytique sous un faible rayonnement ultraviolet - Google Patents

Film mince en oxyde de titane presentant une forte activite photocatalytique sous un faible rayonnement ultraviolet Download PDF

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Publication number
WO2004101146A1
WO2004101146A1 PCT/JP2004/002395 JP2004002395W WO2004101146A1 WO 2004101146 A1 WO2004101146 A1 WO 2004101146A1 JP 2004002395 W JP2004002395 W JP 2004002395W WO 2004101146 A1 WO2004101146 A1 WO 2004101146A1
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Prior art keywords
titanium oxide
thin film
oxide thin
film
less
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PCT/JP2004/002395
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English (en)
Japanese (ja)
Inventor
Masakazu Anpo
Takashi Kamegawa
Satoru Dohshi
Masaya Matsuoka
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Murakami Corporation
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Publication of WO2004101146A1 publication Critical patent/WO2004101146A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings

Definitions

  • the present invention provides a titanium oxide thin film exhibiting a high photocatalytic activity having a water contact angle of substantially 0 ° under irradiation of weak ultraviolet light having a light amount of 1.0 iw / cm 2 or less, a method of forming the same, and the like.
  • a titanium oxide thin film exhibiting a high photocatalytic activity having a water contact angle of substantially 0 ° under irradiation of weak ultraviolet light having a light amount of 1.0 iw / cm 2 or less, a method of forming the same, and the like.
  • Titanium oxide photocatalyst material has anti-staining properties, antibacterial properties, deodorizing properties, etc., and is a material for which applied technology is expected.
  • the titanium oxide thin film has high transparency, exhibits high photocatalytic activity when irradiated with ultraviolet light, and exhibits high hydrophilic properties such that the contact angle with water is substantially 0 °.
  • an ultraviolet intensity of at least 10 wZcm 2 or more is necessary.
  • the environment in which ultraviolet light can be irradiated is limited, and there is a demand for the development of a titanium oxide photocatalyst material that can exhibit a photocatalytic function even with visible light or weak ultraviolet light included in, for example, fluorescent light.
  • Non-Patent Document 1 Korean like, Ad v. M atter. 2 00 0, 1 2, N o. 24, pi 9 2 3.
  • the composite membrane of the c- W0 3 and T i 0 2 It has been reported that a highly hydrophilic state in which the contact angle of water is substantially 0 ° can be achieved under irradiation with a faint ultraviolet light of a light intensity of 1.0 / zwZ cm 2 .
  • an object of the present invention is to provide a titanium oxide thin film having a light intensity of 1.0 / zw / cm 2.
  • the goal is to achieve a highly hydrophilic state in which the contact angle of water is substantially 0 ° under the irradiation of weak ultraviolet light. Disclosure of the invention
  • the present inventors have conducted intensive studies and found that the contact angle of water was substantially (measured) 0 ° under irradiation of weak ultraviolet light of 1.0; w Z cm 2 with the titanium oxide thin film alone. For the first time, the present inventors succeeded in achieving a high photocatalytic activity state (claim 1).
  • the titanium oxide single film having such characteristics can be produced by controlling the conditions at the time of film formation.
  • RF output 250 to 350 W
  • substrate temperature at the time of film formation room temperature to 600 ° C
  • deposition rate 0.37 nm / min-1.47 nm / min (deposition time: 1-9 hours)
  • deposition pressure 1-3 Pa It has been found that it can be produced by RF-magnet sputtering under controlled conditions (claim 2).
  • the contact angle of water is substantially 0 ° under the irradiation of the weak ultraviolet light of 1.0 iwZ cm 2 with the titanium oxide thin film alone.
  • the titanium oxide thin film alone can be used under irradiation of ultraviolet light with a light intensity of 1.0 w / cm 2 or less by controlling the film formation conditions.
  • the contact angle of water is preferably 4 ° or less (approximately 0 ° to 4 °), more preferably 3 ° or less (approximately 0 ° to 3 °), and further preferably 2 ° or less (approximately 0 ° to 2 °).
  • a titanium oxide single film having the above characteristics has an unprecedented characteristic of having a crystal particle diameter of 13 to 17 nm (claim 3).
  • the photocatalytic activation light of the titanium oxide thin film can be highly improved (the work function of metal and the rate of hydrophilization). (There is a correlation with the constant) (Claim 4).
  • a titanium oxide thin film (highly active By forming a titanium oxide thin film, it is possible to achieve a highly hydrophilic state in which the contact angle of water becomes substantially 0 ° under irradiation of a weak ultraviolet light of 1. 1.zw/cm 2. (Claim 5).
  • a light amount of 1.0 iwZ It has been found that a highly hydrophilic state in which the contact angle of water becomes substantially 0 ° can be stably and surely achieved under irradiation with a faint ultraviolet light of cm 2 (claims 6 to 8).
  • the metal or alloy having a small work function for example, aluminum (4.2 ev) or an aluminum alloy is preferable from the viewpoint of enhancing the photocatalytic property of the titanium oxide thin film, and has a work function equal to or less than that of aluminum. It has been found that it is preferable to use a metal that emits electrons in the presence of light (claim 9).
  • the present invention by forming a predetermined titanium oxide thin film (a highly active titanium oxide thin film) on a metal or an alloy having a small work function, the light amount 1.
  • the contact angle of water is preferably 4 ° or less (approximately 0 ° to 4 °), more preferably 3 ° or less (approximately 0 ° to 3 °), and further preferably 2 ° or less (approximately 0 ° to 2 °).
  • the angle is more preferably 1 ° or less (approximately 0 ° to 1 °), and further preferably substantially 0 ° (measured 0 °).
  • the titanium oxide thin film of the present invention preferably has an anatase type titanium oxide content of 70% or more. This makes it possible to obtain a high photocatalytic activity.
  • the titanium oxide thin film of the present invention preferably has a titanium oxide crystal particle diameter of 13 to 17 nm. Make the titanium oxide crystal particle size in the range of 13 to 17 nm. It is considered that this makes it possible to obtain high photocatalytic activity.
  • the titanium oxide crystal particle diameter is in the range of 13 to 17 nm” means, as can be seen from the SEM photograph of the titanium oxide thin film of the present invention described later, 80% or less of the titanium oxide crystal particles.
  • the above (preferably at least 85%, more preferably at least 90%, more preferably at least 95%) is intended to have a particle size within this range. This is not the purpose except for the case where crystal particles are included.
  • the titanium oxide preferably has an average crystal particle diameter of 13 to 17 nm, and preferably contains crystal particles having a particle diameter in this range in the above ratio.
  • the titanium oxide thin film of the present invention uniform gaps are formed between crystal grains of the titanium oxide film, and the crystal grains are independent of each other without contacting each other, and the crystal grains are joined together as they grow and further grow. It is preferable that the number of particles considered to be small is small, the surface area (specific surface area) is large, the shape of the crystal particles is an angular rock, and the uniformity of the crystal particle shape is high. It is thought that these characteristics make it possible to obtain high photocatalytic activity.
  • the material of the substrate on which the film is formed it is preferable to select and control the material of the substrate on which the film is formed and / or the surface roughness of the surface on which the substrate is formed. It is thought that these make it possible to obtain high photocatalytic activity.
  • the thickness of the titanium oxide layer is not particularly limited and may be appropriately selected depending on conditions such as a rate of hydrophilicity and a property of maintaining darkness (recovery of a contact angle). 0 nm.
  • a photocatalytic action can be exerted even under the irradiation of a weak ultraviolet light having a light amount of 1.0 iwZ cm 2 or less. Therefore, it has become possible to provide a sample that can exhibit photocatalysis even with a fluorescent lamp or visible light, as compared with a conventional composite material that can exhibit photocatalysis only with a relatively high amount of ultraviolet light.
  • the present invention it is possible to have a photocatalytic effect under irradiation of ultraviolet light having a light amount of 1.0 wZ cm 2 or less. Therefore, in the present invention, by irradiating the surface of the titanium oxide layer, which is a photocatalyst layer, with light, the photocatalyst is excited even under the irradiation of weak light having a light amount of 1.0 O / x wZ cm 2 or less, thereby preventing the dyeing. It can exhibit photocatalytic action such as antibacterial property, antibacterial property and deodorizing property.
  • the present invention can be effectively applied not only to conventional uses but also to various uses under irradiation of weak light, for example, an outer mirror and an inner mirror for a vehicle, and a mirror for a bathroom.
  • FIG. 1 is a cross-sectional view showing a sample manufactured in the example.
  • FIG. 2 is a diagram showing characteristics of a fluorescent lamp (18 W) as a light source used in the example.
  • FIG. 3 is a diagram illustrating characteristics of the light quantity measuring device used in the example.
  • FIG. 4 is a diagram showing the results of an RF output dependency test measurement of a sample using a quartz substrate as the substrate.
  • FIG. 5 is a diagram showing a measurement result of an RF output dependency test of a sample using a quartz substrate as the substrate.
  • FIG. 6 is a view showing an electron microscope (SEM) photograph of each sample in which a titanium oxide film is formed on a quartz substrate by changing the RF output.
  • SEM electron microscope
  • FIG. 7 is a diagram showing a measurement result of a film forming temperature dependence test of a sample using a quartz substrate as a substrate.
  • FIG. 8 is a view showing an electron microscope (SEM) photograph of each sample in which a titanium oxide film was formed on a quartz substrate by changing the substrate temperature during film formation.
  • Figure 9 shows for each sample by changing the deposition when the substrate temperature was deposited titanium oxide film on a quartz substrate, a 5 0 0 ⁇ ultraviolet light irradiation time of cm 2, the relationship between the contact angle of water FIG.
  • FIG. 10 is a view showing a measurement result of a film thickness dependency test of a sample using a quartz substrate as a substrate.
  • FIG. 11 is a view showing an electron microscope (SEM) photograph of each sample in which a titanium oxide film was formed on a quartz substrate by changing the film formation time and the film thickness.
  • FIG. 12 is a diagram showing a measurement result of a film forming pressure dependency test of a sample using a quartz substrate as the substrate.
  • FIG. 13 is a view showing an electron microscope (SEM) photograph of each sample in which a titanium oxide film was formed on a quartz substrate by changing the film forming pressure and the film forming time.
  • FIG. 14 is a diagram showing the measurement results of the light amount dependency test of a sample using a quartz substrate as the substrate.
  • FIG. 15 is a diagram showing the measurement results of the light intensity dependence test of a sample using a quartz substrate as the substrate.
  • FIG. 16 is a view showing the results of a measurement of a sample using a quartz base material as a base material, which was maintained in place.
  • FIG. 17 is a diagram showing an ultraviolet-visible light absorption measurement result of a sample using a quartz substrate as the substrate.
  • FIG. 18 is a diagram showing the results of X-ray diffraction measurement of a sample using a quartz substrate as the substrate.
  • FIG. 19 is a diagram showing the results of an RF output dependency test measurement of a sample using an A1 plate as a base material.
  • FIG. 20 is a diagram showing a measurement result of an RF output dependency test of a sample using an A1 plate as a base material.
  • FIG. 21 is a diagram showing a measurement result of a film forming temperature dependency test of a sample using an A1 plate as a base material.
  • FIG. 22 is a diagram showing a measurement result of a film thickness dependency test of a sample using an A1 plate as a substrate.
  • FIG. 23 is a diagram showing a measurement result of a film forming pressure dependency test of a sample using an A1 plate as a base material.
  • FIG. 24 is a view showing the measurement results of the light amount dependency test of the sample using the A1 plate as the base material.
  • FIG. 25 is a diagram showing the measurement results of a light amount dependency test of a sample using an A1 plate as a base material.
  • FIG. 26 is a diagram showing the results of a dark place maintenance test measurement of a sample using the A1 plate as the base material.
  • FIG. 28 is a diagram showing the amount of hydrophilic constant of each sample in which a titanium oxide film was formed on the A1 substrate and the QZ substrate under the same conditions.
  • FIG. 29 is a diagram showing electron microscope (SEM) photographs of each sample in which a titanium oxide film was formed on the A1 substrate and the QZ substrate under the same conditions.
  • SEM electron microscope
  • a fluorescent lamp (18 W) having the characteristics shown in FIG. 2 (vertical axis: intensity, horizontal axis: wavelength (nm)) was used as a light source. As is evident from Fig. 2, the amount of ultraviolet light in this light source is very small and its intensity is extremely low.
  • the light intensity was measured by mounting UD-36 to UVR-2 manufactured by TOP COM. As shown in Fig. 3 (vertical axis: relative sensitivity, horizontal axis: wavelength (nm)), UD-36 can measure light in the wavelength range of 310 to 400 nm. The amount of light was adjusted by adjusting the distance between the substrate and the light source.
  • a titanium oxide sintered body was used as an evening get.
  • the RF output was set to 250 W (1 Pa, 600 hours, 4.5 hours), 300 W (l Pa, 600 ° C).
  • the titanium oxide layer was formed on a quartz substrate under each RF output condition of, 3.0 hours) and 350 W (1 Pa, 60 O, 2.75 hours).
  • W a low water contact angle and a high hydrophilization rate constant were obtained. Therefore, it can be seen that in the present invention, it is preferable to set the RF output to about 300 W. It is also found that by controlling the film forming conditions and the like, a titanium oxide film exhibiting a high photocatalytic activity with a water contact angle of 5 ° or less can be formed.
  • the crystal grains are independent of each other without contact, the surface area (specific surface area) is large, and the shape of the crystal grains is angular. It can be seen that it is rocky.
  • Example 1 the film formation rate was 0.37 nm / min to 1.47 nm
  • the substrate temperature during film formation was set to (a) room temperature (RT), (b) 200 ° C, and (c) 400 °. C, (d) Electron microscope (SEM) photographs (X100K, 5.K) of each sample in which a titanium oxide film was formed on a quartz substrate by RF magnet sputtering by changing the temperature to 600 ° C.
  • the substrate temperature during film formation was set to (a) room temperature (RT), (b) 200 ° C, and (c) 400 ° C. (D) 600.
  • RT room temperature
  • D 600.
  • each sample on which a titanium oxide film was formed on a quartz substrate by RF magnet sputtering by means of RF magnet sputtering was irradiated with 500 / xwZcm 2 of ultraviolet light (light source: SHL-10
  • FIG. 9 shows the contact angle of water (°)
  • the horizontal axis shows the irradiation time (unit: minute) of 500 / iwZcm 2 ultraviolet light. From FIG. 9, it can be seen that the higher the film formation temperature, the shorter the time required for the water contact angle to become 5 ° or less.
  • Example 2 the film formation rate was 0.37 nmZmin to l.47 nmZm
  • the film thickness is 200 nm (1.0 Pa, 3 hours, 600 W, 300 W), 400 nm (1.0 Pa, 6 hours, 6001 :, 300 W)
  • a titanium oxide layer was formed on a quartz substrate under various film thickness conditions (deposition time conditions) of 700 nm (1.0 Pa, 9 hours, 600 ° C., 300 W). It can be seen that the higher the film thickness, the higher the hydrophilicity.
  • Titanium oxide deposited under the condition of 700 nm (1.0 Pa, 9 hours, 600 ° C, 300 W) was irradiated with ultraviolet light with a light intensity of 1.0 tw / cm 2 or less. Below, for the first time, it was confirmed that after 72 hours, it exhibited a high degree of hydrophilicity with a water contact angle of substantially 0 °. It is also found that a titanium oxide film exhibiting a high photocatalytic activity with a water contact angle of 5 ° or less can be formed by controlling the film forming conditions and the like.
  • Example 3 the film formation rate was 0.37 nmZmin: 1.47 nmZmin.
  • the film forming pressure and film forming time are (a) l Pa, 3 hours (300 w, 6 ⁇ 0), (b) 2 Pa, 6 hours (300 w, 600 ⁇ ), (c ) 3 Pa, 9 hours (300 w, 600 ° C) with RF magnet sputtering.
  • the titanium oxide film of l to 2Pa has a large crystal grain size, and more uniform gaps between the crystal particles than in Figs. 11 (a) to (c). Are formed, the crystal grain shape is highly uniform, and there are few particles that are considered to have joined together with the growth of the crystal grains and to have grown further.
  • Example 4 the film formation rate was 0.37 nmZmin to l.47 nm / min.
  • FIG 1 4 (a) it is understood that capable of expressing (b) as shown in, 1. O ⁇ contact angle of water in weak light quantity of WZcm 2 becomes 5 ° or less advanced photocatalytic activity.
  • the vertical axis in Fig. 14 (a) shows the contact angle of water (°), and the horizontal axis shows the irradiation time (unit: time) of each amount of ultraviolet light.
  • the irradiation angle of water at 500 cm 2 was substantially 0 ° immediately after irradiation with UV light, and 20 wZcm
  • the contact angle of water becomes substantially 0 ° in the time after irradiation
  • the contact angle of water becomes substantially 0 in 24 hours after irradiation. °, it turns out.
  • the vertical axis in FIG. 15 shows the contact angle (°) of water, and the horizontal axis shows the irradiation time (unit: time) of the ultraviolet light of each light amount.
  • the film formation time was changed to (a) 3 hours, (b) 6 hours, and (c) 9 hours, and by RF magnet sputtering.
  • a titanium oxide film with a thickness of (a) 200 nm, (b) 400 nm, and (c) 700 nm was formed on a quartz substrate, and a UV light of 1.0 iwZc m 2 or less was formed.
  • the cells were stored in a dark place, and the relationship between the contact angle of water and time was examined. The results are shown in FIG. From Fig.
  • the vertical axis is the contact angle of water (°), and the horizontal axis is the elapsed time from the end of UV light irradiation (unit: days)]
  • the recovery of the contact angle is slow as the film thickness increases. It turns out that the dark place maintenance is high.
  • a sample was prepared by forming a titanium oxide film on a quartz substrate by RF magnet sputtering under the respective film forming conditions of 0 Pa, 9 hours, 600 ° C., and 300 W.
  • the film thicknesses were (a) 200 nm, (b) 400 nm, and (c) 700 nm, respectively.
  • Figure 17 shows the results of ultraviolet-visible light absorption measurement of these samples. As shown in Fig.
  • each sample had an anatase content of 70% or more and a particle size of 13 nm to 17 ⁇ m.
  • the crystallinity and orientation of each sample were very good.
  • samples were produced in the same manner as in the above examples except that the substrate was A1 plate (commercially available aluminum plate; manufactured by Nicola Corporation: 0131461 aluminum plate), and photocatalytic properties were obtained. And examined the relationship.
  • FIG. 19 (a) indicates the contact angle of water (°), and the horizontal axis indicates the irradiation time (unit: time) of 1.0 iw / cm 2 ultraviolet light (Fig. 20 (a) described later). The same applies to FIG. 23 (a)).
  • FIG. 19 (b) shows the hydrophilization rate constant (the same applies to FIGS. 20 (b) to 23 (b) described later).
  • the sample formed with the RF power of 300 W showed very good photocatalysis.
  • the photocatalytically active light of the titanium oxide thin film can be improved to a high degree, and the contact angle of water is substantially reduced under the irradiation of weak UV light with a light intensity of 1.0 / wZ cm 2. It has been found that a high degree of hydrophilicity of 0 ° can be achieved.
  • the RF output was set to 250W (lPa, 600 ° C, 4.5 hours), 300W (lPa, 60h). 0, 3.0 hours) and 350 W (lPa, 600 ° C., 2.75 hours) under a RF output condition, a titanium oxide layer was formed on an aluminum substrate.
  • a RF power of 300 W a low water contact angle and a high hydrophilization rate constant were obtained. Therefore, in the present invention, the RF output is set to about 300 W is preferable.
  • the photocatalytically active light of the titanium oxide thin film can be improved to a high degree, and the contact angle of water is 5 ° under the irradiation of a faint ultraviolet light of 1.0 z ⁇ wZcm 2 .
  • the contact angle of water is 5 ° under the irradiation of a faint ultraviolet light of 1.0 z ⁇ wZcm 2 .
  • Example 9 the film formation rate was 0.37 nm / min to l.47 nmZmin.
  • the photocatalytically active light of the titanium oxide thin film can be improved to a high degree, and the contact angle of water is 5 ° or less under the weak ultraviolet light of 1.0 / iwZcm 2 , In particular, it has been found that a highly hydrophilic state of substantially 0 ° can be stably and surely achieved.
  • the contact angle of water is 5 ° or less (approximately 0 ° to 5 °) under irradiation of ultraviolet light with a light intensity of 1.OiwZcm 2 or less.
  • Example 10 the deposition rate was 0.37 nm / min to 1.47 nm / min.
  • the film thickness is 200 nm (1. OP a, 3 hours, 600 ° C, 300 W), 400 nm (1. OP a , 6 hours, 600 ° C, 300 W), 700 nm (1 OPa, 9 hours, 600, 300 W)
  • the layer was formed on an aluminum substrate, It turns out that it shows high hydrophilicity.
  • a titanium oxide thin film can be improved photocatalytic activity light with high degree of light intensity 1.
  • 0 / iw / cm 2 water contact angle of substantially under irradiation of weak ultraviolet light that It has been found that a high degree of hydrophilicity of 0 ° can be achieved stably and reliably.
  • iwZc m 2 or less of ultraviolet light water contact angle of 5 ° or less (approximately 0 ° ⁇ 5 °), 4 ° or less (approximately 0 ° to 4 °), 3 ° or less (approximately 0 ° to 3 °), 2 ° or less (approximately 0 ° to 2 °), 1 ° or less (approximately 0 ° to 1 °), substantial It has been found that a state showing a high photocatalytic activity of 0 ° (0 ° in measurement) can be achieved.
  • Example 11 the film formation rate was 0.37 nm / min to .47 nm / mi ⁇ .
  • the deposition pressure l Pa 300 W, 600 ° C, 3 hours
  • 2 Pa 300 W, 600 ° C
  • 3 Pa 300 W, 600 ° C., 3 hours
  • the photocatalytic activation light of titanium thin film can be improved to a high degree, and a highly hydrophilic state in which the contact angle of water becomes substantially 0 ° under the irradiation of a faint ultraviolet light of 1.0 wZ cm 2 is stably and reliably achieved. Have achieved what they can achieve.
  • the contact angle of water is 5 ° or less (approximately 0 ° to 5 °) and 4 ° under irradiation of ultraviolet light with a light amount of 1.0 cm 2 or less. Less than (approximately 0 ° to 4 °), less than 3 ° (approximately 0 ° to 3 °), less than 2 ° (approximately 0 ° to 2 °), less than 1 ° (approximately 0 ° to: 1 °), substantially It has been found that a state showing a high photocatalytic activity of 0 ° (0 ° on measurement) can be achieved.
  • Example 12 the film formation rate was 0.37 nm / min to 1.47 nm / min.
  • the vertical axis indicates the contact angle of water (°), and the horizontal axis indicates the irradiation time (unit: time) of the ultraviolet light of each light amount.
  • FIG. 27 shows the results. From Fig. 27 [The vertical axis indicates the contact angle of water (°) and the horizontal axis indicates the irradiation time of ultraviolet light (unit: hours)], the sample with the titanium oxide film formed on the A1 substrate is virtually zero. It can be seen that a high degree of photocatalytic activity can be expressed and the time required for the water contact angle to become 5 ° or less is short (that is, the hydrophilization constant is large). Figure 28 shows the hydration constants of these samples.
  • FIGS. 29 (a) and (b) Electron microscope (SEM) photographs (X100K, 5.OK) of each of these samples are shown in Figs. 29 (a) and (b). From FIGS. 29 (a) and (b), in the sample in which the titanium oxide film was formed on the A1 substrate, uniform gaps were formed between the crystal particles of the titanium oxide film, and the crystal particles were in contact with each other. It is preferable because they are independent from each other, have a large surface area (specific surface area), and have a crystal particle shape of angular rock. As described above, the present invention has the following excellent effects.
  • a titanium oxide thin film alone achieves a high level of photocatalytic activity in which the contact angle of water becomes substantially 0 ° under irradiation of a faint ultraviolet light of 1.0 ⁇ wZ cm 2.
  • Successful (Claim 1).
  • the titanium oxide thin film alone exhibits a high photocatalytic activity with a water contact angle of 5 ° or less (approximately 0 ° to 5 °) under irradiation of ultraviolet light of 1.O ⁇ iwcm 2 or less. The state can be achieved (Claim 1).
  • the titanium oxide single film having such characteristics can be produced by controlling the conditions at the time of film formation (claim 2), and has an unprecedented characteristic that the crystal particle diameter is 13 to 17 nm. (Claim 3).
  • a titanium oxide thin film (highly active By forming a titanium oxide thin film, a high level of photocatalytic activity with a contact angle of water of 5 ° or less to substantially 0 ° is achieved under irradiation with a faint UV light of 1.0 ⁇ wcm 2 It is possible (claim 5).
  • the light amount is 1.0 ⁇ . It is possible to stably and surely achieve a high photocatalytic activity state in which the contact angle of water is 5 ° or less to substantially 0 ° under irradiation of a weak ultraviolet light of wZcm 2 (claims 6 to 8).

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Cette invention concerne un mince film d'oxyde de titane capable de déployer une forte activité photocatalytique à telle enseigne que sous un faible rayonnement ultraviolet d'une intensité lumineuse de 1,0 νw/cm2, ledit film ait indépendamment un angle de contact avec l'eau de 5° ou moins (sensiblement zéro). Le film mince d'oxyde de titane (couche (2)) se caractérise par une activité photocatalytique telle que sous un rayonnement ultraviolet d'une intensité lumineuse de 1,0 νw/cm2, il ait indépendamment un angle de contact avec l'eau de 5° ou moins (sensiblement zéro). On obtient ce film en agissant notamment sur ses conditions de formation et sur la diamètre des grains de cristal.
PCT/JP2004/002395 2003-05-16 2004-02-27 Film mince en oxyde de titane presentant une forte activite photocatalytique sous un faible rayonnement ultraviolet WO2004101146A1 (fr)

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JP2003138977A JP2004339021A (ja) 2003-05-16 2003-05-16 微弱紫外光下で高度な光触媒活性を示す酸化チタン薄膜
JP2003-138977 2003-05-16

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WO2004101146A1 true WO2004101146A1 (fr) 2004-11-25

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US20070104922A1 (en) * 2005-11-08 2007-05-10 Lei Zhai Superhydrophilic coatings
JP2007253148A (ja) * 2006-02-24 2007-10-04 Osaka Prefecture Univ 光触媒、光触媒の製造方法、水の電気分解方法、水素の製造方法、電気分解装置および水素製造用装置
JP2009066497A (ja) * 2007-09-12 2009-04-02 Bridgestone Corp 光触媒酸化チタン薄膜及びその製造方法

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JP2000345320A (ja) * 1999-06-02 2000-12-12 Toyota Central Res & Dev Lab Inc 薄膜構造体及びその製造方法
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EP1304366A1 (fr) * 1995-03-20 2003-04-23 Toto Ltd. Procédé photocatalytique pour rendre une surface pour rendre une surface superhydrophile, un substrat avec une surface superhydrophile photocatalytique et procédé de préparation
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