HK1028362A1 - Functional film, functional substrate, and the preparation method of titanium oxide film - Google Patents
Functional film, functional substrate, and the preparation method of titanium oxide film Download PDFInfo
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Abstract
PROBLEM TO BE SOLVED: To obtain a titanium oxide thin film having high durability and photocatalytic function. SOLUTION: Titanium oxide thin films 31 are made to exist at intervals on the surface of a barrier thin film 12, hydrophilic thin films 41 are formed between the titanium thin films to constitute a functional thin film 3. Since both parts to which the titanium oxide thin films 31 are exposed and parts to which the hydrophilic thin films 41 are exposed exist together on the surface of the functional thin film 31, functions of both the thin films can be obtained. Consequently a self cleaning effect and superhydrophilic nature are developed under an environment of irradiation with ultraviolet rays and a hydrophilicity of a certain degree is obtained even at a dark place. When a titanium oxide target in the titanium oxide thin films 31 is sputtered with a sputtering gas containing an oxygen gas, deficient oxygen in the titanium oxide thin film to be formed can be supplied with oxygen to form the titanium oxide thin films 31 having a photocatalytic function.
Description
Technical Field
The present invention relates to the technical field of functional films, and particularly to the technical field of application of functional films with photocatalytic functions.
Background
In recent years, titanium oxide (TiO) has been used as a thin film material having super-hydrophilicity and an antifouling effect2) Are of great interest.
Titanium oxide is known as one of photocatalysts, and is activated when irradiated with ultraviolet rays to generate hydroxyl radicals and peroxide anions from oxygen in the air, and since these can decompose organic pollutants adhered to the surface, it has a self-cleaning effect, and since the decomposition of pollutants exposes a clean surface, it is possible to obtain super-hydrophilicity.
In FIG. 8, reference numeral 110 denotes a mirror to which the above titanium oxide is applied. The mirror 110 has a substrate 111 made of alkali-lime glass, a reflective layer (chrome layer) 118 formed on the back surface thereof, and a barrier film 112 made of a silicon oxide film formed on the front surface thereof.
A dispersion of titanium oxide powder is thermally sprayed on the surface of the barrier thin film 112 and fired to form a titanium oxide thin film 113 (sol-gel method), and a photocatalytic thin film composed of the titanium oxide thin film 113 is formed on the surface, whereby a self-cleaning effect and super-hydrophilicity can be obtained by this titanium oxide thin film 113.
The barrier film 112 is a thin film for preventing diffusion of impurities such as sodium in the substrate 111. When the titanium oxide thin film 113 is formed by directly spraying the titanium oxide dispersion on the surface of the substrate 111 without forming the barrier thin film 112, the sodium component contained in the substrate 111 is impregnated into the titanium oxide thin film 113 in the process of firing the titanium oxide thin film, and a Ti — Na compound is generated to deactivate the titanium oxide thin film 113.
However, the crystal series of titanium oxide includes anatase type, rutile type and brookite type, and anatase type is known to exhibit the highest optical activity. However, anatase type is converted to rutile type when exposed to high temperature, and as a result, it becomes impossible to exhibit the antifouling effect and superhydrophilicity.
In general, when a thin film is formed by a sputtering method, an anatase-type titanium oxide thin film cannot be formed because the film formation energy is too large. In the case of the vapor deposition method, it is not suitable for forming a thin film on the surface of a glass substrate because it is necessary to heat the film formation object side at a high temperature to form a thin film.
On the other hand, in the sol-gel method, since an anatase-type titanium oxide powder is used and fired at a low temperature of about 800 ℃ to form a thin film, an anatase-type titanium oxide thin film can be formed without causing crystal transformation.
However, the titanium oxide thin film 113 formed by the sol-gel method has a disadvantage that it is easily peeled off because of its poor film strength.
In recent years, the titanium oxide thin film has attracted attention for its super-hydrophilic property, and when applied to mirrors, it is expected to have a high visibility even in rainy weather, and a high-performance mirror or the like having a self-cleaning function. Therefore, the demand for the production of functional thin films using titanium oxide thin films and durability is increasing.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a titanium oxide thin film having high durability and a photocatalytic function.
In order to solve the above problems, the invention according to claim 1 is a functional thin film comprising a hydrophilic thin film and a titanium oxide thin film, wherein the exposed portion of the hydrophilic thin film and the exposed portion of the titanium oxide thin film are mixed in a minute region on the surface of the functional thin film.
The invention according to claim 2 is the functional thin film according to claim 1, wherein the titanium oxide thin film is formed on the hydrophilic thin film.
The invention according to claim 3 is a functional substrate comprising a glass substrate, a barrier thin film formed on the glass substrate, and a titanium oxide thin film formed on the barrier thin film, wherein a part of the surface of the barrier thin film is exposed on the titanium oxide thin film.
The invention according to claim 4 is the functional substrate according to claim 3, wherein a hydrophilic thin film is disposed in the titanium oxide thin film, and the exposed portion of the titanium oxide thin film and the exposed portion of the hydrophilic thin film are mixed together in a minute region on the substrate.
The invention of claim 5 is a functional substrate comprising a glass substrate, a barrier thin film formed on the glass substrate, a titanium oxide thin film formed on the barrier thin film, and a hydrophilic thin film formed on the titanium oxide thin film, wherein exposed portions of the hydrophilic thin film and exposed portions of the titanium oxide thin film are mixed in minute domains on the glass substrate.
The invention according to claim 6 is a method for producing a titanium oxide thin film, comprising the steps of placing an object to be film-formed in a vacuum atmosphere, and sputtering a titanium oxide target with a plasma of a sputtering gas to produce a titanium oxide thin film on a surface of the object to be film-formed, wherein the sputtering gas contains 1 or 2 or more kinds of oxygen, ozone, or nitrogen dioxide as an oxygen-containing gas.
The invention according to claim 7 is the method for producing a titanium oxide thin film according to claim 6, wherein a content ratio of the oxygen-containing gas in the sputtering gas is 10 vol% or more.
The 8 th aspect of the present invention is a method for producing a titanium oxide thin film, in which a film-forming object is placed in a vacuum atmosphere, a titanium oxide target is sputtered by plasma of a sputtering gas, and a titanium oxide thin film is produced on a surface of the film-forming object, wherein the titanium oxide thin film is formed while irradiating the surface of the film-forming object with oxygen plasma.
The invention according to claim 9 is a vacuum apparatus comprising a vacuum chamber, a rotatable and vertically movable turntable disposed in the vacuum chamber, and a plurality of film forming members disposed in the vacuum chamber and a partition plate for covering between the film forming members, wherein an object to be film formed is disposed on the turntable, and the object to be film formed can be transferred between the film forming members when the turntable is rotated and vertically moved.
The invention according to claim 10 is the vacuum apparatus according to claim 9, wherein at least 1 of the plurality of film forming members is a sputtering apparatus using titanium oxide as a target.
The invention according to claim 11 is the vacuum apparatus according to claim 10, wherein at least 1 of the plurality of film formation members is a sputtering apparatus using silicon oxide as a target.
The 12 th aspect of the present invention is a sputtering apparatus including a vacuum chamber and a target disposed in the vacuum chamber, the sputtering target and a thin film forming member transferred into the vacuum chamber, wherein a mesh is disposed in the target and the film forming member, and the thin film is not formed on a shadow portion of the surface of the film forming member.
The invention according to claim 13 is a sputtering apparatus according to claim 12, characterized in that titanium oxide is used for the target.
The 14 th aspect of the present invention is the sputtering apparatus according to the 12 th aspect of the present invention, wherein silicon oxide is used for the target.
The 15 th aspect of the present invention is the sputtering apparatus according to the 12 th aspect of the present invention, wherein a positioning device for relatively aligning the film formation object and the web is provided.
The functional thin film of the present invention is configured as described above, that is, the hydrophilic thin film exposed portion and the titanium oxide thin film exposed portion are present in a mixed manner in minute domains on the surface of the functional thin film. For example, the hydrophilic thin film may be a titanium oxide thin film in which islands are dispersed. The titanium oxide thin film and the hydrophilic thin film may be arranged so as to intersect in a linear shape, may be arranged in a net shape, or may be arranged at mesh positions.
The functional thin film in which the exposed portion of the titanium oxide thin film surface and the exposed portion of the hydrophilic thin film surface are present in a mixed state can be formed on a barrier thin film formed on a glass substrate. The hydrophilic thin film may be filled and dispersed in the middle of the titanium oxide thin film, or the titanium oxide thin film may be filled and dispersed in the middle of the hydrophilic thin film. Further, island-like dispersed hydrophilic thin films, or linear or network-like hydrophilic thin films may be formed on the titanium oxide film formed on the entire surface of the barrier thin film.
It is important that the titanium oxide film surface and the hydrophilic film surface are present in a mixed manner in the minute regions of the functional film surface. When the minute area is 1 square inch, it is preferable that about 100 island-like titanium oxide thin films are dispersed thereon.
The titanium oxide thin film provided on the functional thin film or the functional substrate must have a photocatalytic function. When a titanium oxide target is formed by sputtering, oxygen-containing gas such as oxygen, ozone, or nitrogen dioxide is added to rare gas such as argon to form sputtering gas, and when the target is sputtered by plasma of the sputtering gas, oxygen atoms missing in the titanium oxide thin film can be replenished and an anatase-type titanium oxide thin film having a photocatalytic function can be obtained.
In order to obtain a titanium oxide thin film having a photocatalytic function, it is necessary to contain 10% by volume or more of a rare gas and an oxygen-containing gas as the ratio of the oxygen-containing gas is increased as much as possible. When the ratio of a rare gas such as argon is small, the sputtering rate is low, and therefore the upper limit of the oxygen-containing gas is determined by the film forming rate.
In the sputtering, since oxygen plasma may be irradiated onto the substrate surface by an ion gun or the like to replenish the deficient oxygen atoms, a titanium oxide thin film having a photocatalytic function can be formed.
Drawings
FIGS. 1(a) to (d) are explanatory views of a method for producing a functional thin film and a functional substrate according to an example of the present invention.
Fig. 2(a), (b): are illustrations of other examples.
FIG. 3 shows an example of a film forming apparatus capable of forming a functional thin film.
FIG. 4 is a view for explaining a method of forming a titanium oxide thin film.
FIG. 5 is an explanatory view of the arrangement state of the filter board.
Fig. 6 is a graph showing the contact angle.
Fig. 7 is a graph showing the relationship between the ultraviolet irradiation time and the contact angle θ.
Fig. 8 is an explanatory view of a functional film according to the prior art.
In the figure:
2 to 4 functional thin film
5 to 7 functional substrates
11 glass substrate
12 Barrier or hydrophilic films
31. 32 thin film of titanium oxide
41. 42 hydrophilic film
Detailed Description
Preferred embodiments of the invention are described below
The functional thin film and the functional substrate of the present invention will be described in detail, and the method for producing the titanium oxide thin film of the present invention will be also described.
Referring to FIG. 3, reference numeral 9 denotes an example of a film forming apparatus for forming the functional thin film of the present invention. The film forming apparatus 9 has a vacuum chamber 54. A turntable 59 is disposed on the bottom side in the vacuum chamber 54, and a feeding/discharging member 60 and the 1 st to 3 rd film forming members 51 to 53 are disposed on the top portion above the turntable.
The turntable 59 is horizontally rotatable and also vertically movable, and a substrate to be film-formed is fed into a feeding member 60 from a feeding inlet not shown and placed on the turntable 59, and the substrate is sequentially fed to the lower sides of the 1 st to 3 rd film forming members 51 to 53 when the turntable 59 is rotated, and the substrate placed on the turntable 59 is fed into the 1 st to 3 rd film forming members 51 to 53 when the turntable 59 is vertically moved.
Reference numeral 11 in FIGS. 1(a) to (d) denotes a substrate made of alkali-lime glass. A reflective film 18 is formed in advance on the back surface of the glass substrate 11.
When the functional thin film is formed by using the film forming apparatus 9, the substrate 11 is fed into the carrying-in unit 50 while a vacuum atmosphere is maintained in the vacuum chamber 54 by a vacuum pump not shown. The turntable 59 is restarted to feed the substrate 11 into the 1 st film forming unit 51.
The 1 st film forming means 51 is a sputtering apparatus, and is configured to dispose a target made of silicon oxide, sputter the target, and form a barrier thin film 12 (fig. 1(b)) made of silicon oxide on the entire surface of the substrate 11.
Subsequently, the turntable 59 is started to move the substrate 11 to the 2 nd film forming unit 52. The 2 nd deposition part 52 is also a sputtering apparatus, and its model configuration is shown in FIG. 4.
The film forming member 52 has a separator 71, a cathode 72 is disposed on the top side, and a target 73 made of titanium oxide is disposed on the bottom side of the cathode 72. The substrate 11 is placed in the spacer 71 with the barrier film 12 on the surface facing the target 73.
In the partition plate 71, a filter plate 75 is disposed between the target 73 and the substrate 11. Their mutual position is shown in fig. 5.
The filter plate 75 is a 100-mesh (a mesh made of metal having 100 meshes in 1 square inch) screen, and is composed of a shielding part 76 of a mesh part and a passing part 77 forming a mesh.
After the substrate 11 was loaded, the atmosphere in the 2 nd film forming part 52 was separated from the atmosphere in the vacuum chamber 54, and argon gas and oxygen gas were introduced at a predetermined ratio (here, 1: 1, that is, the ratio of oxygen gas was 50 vol%) to stabilize the pressure at 3.0X 10-2A voltage is applied to the cathode 72 at torr (1 torr is about 133 pa).
As a result, a sputtering gas plasma composed of argon gas and oxygen gas is generated in the vicinity of the surface of the target 73, and the target 73 can be sputtered.
When the sputtering particles (titanium oxide) emitted from the surface of the target 73 reach the surface of the barrier thin film 12 of the substrate 11, a titanium oxide thin film is formed thereon.
When a titanium oxide thin film is formed by a sputtering method, if an oxygen-containing gas is contained in a sputtering gas, the formed titanium oxide thin film is anatase-type. In addition, the pressure of the sputtering atmosphere has a close relationship with the crystal form.
The following table shows the pressure of the sputtering environment when the titanium oxide thin film was formed and the properties of the formed titanium thin film.
TABLE 1 TiO2Sputtering conditions
Contact of pressure (torr) after ultraviolet irradiation for 18 hours at the time of film formation
(Ar∶O21: 1) angle theta (·)
3.0×10-3 ×
1.0×10-2 △
2.0×10-2 ○
3.0×10-2 ○
O: less than 10 DEG
And (delta): 10 to 20 DEG
X: over 20 degrees
The contact angle θ is an angle formed between the glass substrate and the surface of the water droplet when the surface of the titanium oxide thin film formed on the entire surface of the glass substrate is irradiated with ultraviolet light for a predetermined time and the water droplet is carried. The contact angle θ is shown in fig. 6, where 60 is a glass substrate and 61 is a water droplet.
As can be seen from Table 1, the ratio was 2.0X 10-2When the contact angle θ formed at a pressure of torr or higher is 10 ° or less, the resulting film is considered to have super-hydrophilicity. Therefore, at 2.0X 10-2Under the above pressure, an anatase-type titanium oxide thin film can be formed.
FIG. 7 is a graph showing the relationship between the UV irradiation time and the contact angle θ when the super-hydrophilicity was obtained. As can be seen, the super-hydrophilicity can be obtained after the irradiation for about 40 to 60 minutes.
However, at 1.0X 10-2The contact angle of the titanium oxide film obtained at the Torr pressure was sufficient for practical use, and it was considered that it was 5.0X 10-3A titanium oxide film formed at a pressure of torr or more can be used. The upper limit is a pressure at which arc discharge does not occur during sputtering, and is 5.0X 10-2About torr.
However, in the above-described 3 rd film forming section 53, since the filter plate 75 is disposed between the target 73 and the substrate 11, when the sputtered particles emitted from the target 73 pass through the filter plate 75, a part of the sputtered particles adhere to the shielding member 76, and only the sputtered particles passing through the mesh 76 reach the surface of the barrier film 12. Therefore, the titanium oxide thin film formed on the surface of the barrier membrane 12 using the filter plate 75 is mesh-like. The reference numeral 31 in FIG. 1(c) denotes the mesh-like titanium oxide thin film, which is regularly dispersed on the surface of the barrier thin film 12.
After the formation of the mesh-like titanium oxide thin film 31, when the substrate 11 is taken out from the film forming apparatus 9 to produce a sight glass, the surface is cleaned by the self-cleaning function of the titanium oxide thin film 31 under an environment where ultraviolet rays are irradiated onto the surface of the titanium oxide thin film 31, and a super-hydrophilic effect is observed. In this state, even if a water film is spread on the surface, water droplets are not generated.
Since the surface of the hydrophilic barrier film 12 is exposed in the titanium oxide thin film 31, a certain degree of hydrophilicity can be secured even in an environment where ultraviolet rays are not irradiated.
Therefore, the functional thin film 2 composed of the mesh-like titanium oxide thin film 31 and the barrier thin film 12 has hydrophilicity regardless of the presence or absence of ultraviolet irradiation. Reference numeral 5 denotes a functional substrate having the functional thin film 2.
Here, the substrate 11 may be further carried into the 3 rd deposition part 53 without being taken out of the deposition apparatus 9.
The film forming unit 53 is a sputtering apparatus, and a target made of silicon oxide and a filter plate made of the metal mesh are provided inside the sputtering apparatus.
The substrate 11 fed into the film forming section 53 is arranged behind the filter plate, the positions of the filter plate and the substrate 11 are positioned in a relative matching position, and the mesh of the filter plate is positioned on the barrier film 12 exposed in the titanium oxide film 31. When sputtering is performed in this state, a hydrophilic film 41 composed of silicon oxide can be formed on the exposed surface of the barrier film 12 (fig. 1 (d)).
When the substrate 11 is removed from the film forming apparatus 9 and a mirror is manufactured, the titanium oxide thin film 31 and the hydrophilic thin film 41 are exposed on the surface, and thus a self-cleaning mirror having super-hydrophilicity is obtained.
When the surface of the barrier thin film 12 is covered with the titanium oxide thin film 31 or the hydrophilic thin film 41, the barrier thin film 12 may not be hydrophilic, and the impurities in the substrate 11 may be prevented from diffusing into the titanium oxide thin film 31. Therefore, the titanium oxide thin film 31 and the hydrophilic thin film 41 can constitute the functional thin film 3 having hydrophilicity. Reference numeral 6 denotes a functional substrate having the functional thin film 3.
As shown in fig. 2 a, a titanium oxide thin film 32 is formed on the entire surface of the barrier thin film 12 of the substrate 11 (about 500 to 3000 * thick), and a hydrophilic thin film 42 such as an island-like dispersed silicon oxide thin film (about 500 to 3000 * thick) may be formed on the surface. The titanium oxide thin film 32 exposed on the bottom surface of the hydrophilic thin film 42 can obtain a self-cleaning function and super-hydrophilicity in this portion. Therefore, the functional thin film 4 can be constituted by the titanium oxide thin film 32 and the hydrophilic thin film 42. Reference numeral 7 denotes a functional substrate having the functional thin film 4.
In this case, the barrier thin film 12 may be any film that can effectively prevent impurities such as sodium in the substrate 11 from penetrating into the titanium oxide thin film 32, and may have no hydrophilicity.
Since a titanium oxide thin film can be formed by a sputtering method, a functional thin film having toughness can be obtained.
Since the titanium oxide thin film has a hydrophilic thin film surface, hydrophilicity can be obtained even in an environment where ultraviolet rays are not irradiated. Since the surface of the titanium oxide film and the surface of the hydrophilic film are mixed in the minute region, it is difficult to form water droplets.
Claims (8)
1. A method for producing a functional thin film having a hydrophilic thin film and a titanium oxide thin film, characterized in that the titanium oxide thin film is formed by a sputtering method, and the exposed portion of the hydrophilic thin film and the exposed portion of the titanium oxide thin film are present in a mixture in a minute region on the surface of the functional thin film, wherein the sputtering gas contains 1 or 2 or more kinds of oxygen, ozone, or nitrogen dioxide as an oxygen-containing gas in a vacuum atmosphere, and the ratio of the oxygen-containing gas in the sputtering gas is 10 vol% or more.
2. The method of producing a functional film according to claim 1, wherein the titanium oxide thin film is formed on the hydrophilic thin film.
3. The method of producing a functional thin film according to claim 1, wherein a vacuum apparatus is used, the vacuum apparatus having a vacuum chamber, a rotatable and liftable turntable provided in the vacuum chamber, and a plurality of film forming members disposed in the vacuum chamber and a partition plate for shielding spaces between the film forming members, and wherein the film forming objects are disposed on the turntable, and wherein the film forming objects can be transported between the film forming members when the turntable is rotated and lifted, and wherein at least 1 of the plurality of film forming members is a sputtering apparatus for targeting titanium oxide.
4. The method of producing a functional thin film according to claim 3, wherein at least 1 of the plurality of film formation members is a sputtering apparatus using a silicon oxide as a target.
5. The method of producing a functional thin film according to claim 1, wherein a sputtering apparatus is used, the sputtering apparatus having a vacuum chamber and a target disposed in the vacuum chamber, and the target is sputtered to form a thin film on a surface of a film formation object fed into the vacuum chamber, wherein a mesh is disposed on the target and the film formation object, and the thin film is not formed on a shadow portion on the surface of the film formation object.
6. The method of claim 5, wherein titanium oxide is used as the target.
7. The method of claim 5, wherein silicon oxide is used as the target.
8. The method of producing a functional film according to claim 5, wherein a positioning device for aligning the relative positions of the object to be film-formed and the web is provided.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11003916A JP2000203885A (en) | 1999-01-11 | 1999-01-11 | Functional thin film, functional substrate and production of titanium oxide thin film |
| JP3916/1999 | 1999-01-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1028362A1 true HK1028362A1 (en) | 2001-02-16 |
| HK1028362B HK1028362B (en) | 2005-05-13 |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1165366C (en) | 2004-09-08 |
| CN1260232A (en) | 2000-07-19 |
| JP2000203885A (en) | 2000-07-25 |
| CN100340696C (en) | 2007-10-03 |
| CN1528946A (en) | 2004-09-15 |
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Effective date: 20150111 |