JP2003096556A - Method and apparatus for depositing thin film of crystalline compound on sheet base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for depositing a crystalline thin film in which a step of depositing an amorphous thin film or the like and a step of changing the thin film into the crystalline thin film can be continuously performed, and each step can be easily performed at a low temperature, and an apparatus therefor. SOLUTION: The method for depositing the crystalline thin film on a base sheet comprises a first step of depositing an amorphous thin film or the like on the continuously carried base sheet under a vacuum or low gas pressure atmosphere, and a second step of irradiating the thin film with the light of the wavelength absorbed by the thin film while maintaining the base sheet at the temperature of 50-300 deg.C under the vacuum condition or under the low gas pressure. The apparatus for the method comprises a first chamber having a means of depositing the amorphous thin film or the like and a means of keeping the inside of the chamber under a vacuum or low gas pressure atmosphere, a second chamber having a means of maintaining the base sheet at the temperature of 50-300 deg.C, a light irradiating means of irradiating the light of the wavelength absorbed by the thin film, and a means of maintaining the inside of the chamber under a vacuum or gas atmosphere, and a base sheet carrying means.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a crystalline compound thin film on a sheet-shaped or roll-shaped substrate and an apparatus for producing the same. The sheet or roll type crystalline compound thin film is a basic technique for producing a functional element necessary for an electronic circuit, an optical circuit, a high-performance device and the like. In particular, the application of the sheet or roll substrate provided with this thin film is lightweight and highly functional, and it is used for various circuit boards, various display devices such as CCD cameras and liquid crystal display elements, color image sensors, etc., especially mobile phones and sheet type personal computers. It is suitable for parts of mobile terminals such as.

[0002]

2. Description of the Related Art At present, sheet-type personal computer and sheet-type display devices are being actively researched and developed for sheet-type semiconductor circuit boards. The thin film forming methods mainly studied in these researches and developments are a sputtering method, an ion plating method, a printing method, a spin coating method and a sol-gel method. However, in the thin film forming method by these methods, the obtained thin film has low crystallinity, and good electrical characteristics and optical characteristics cannot be obtained, and there are many problems in practical use. Further, the sol-gel method described later requires high-temperature heat treatment, so that the base material is severely restricted, and development to a flexible film base material cannot be obtained, and the characteristics for practical use have not been obtained.

On the other hand, in recent years, an optical semiconductor having a photocatalytic action or a photovoltaic action has attracted attention due to its unique application. For example, titanium dioxide, which is a photocatalyst film material, is oxidized due to its photocatalytic action and is contaminated with organic material substances adhering to the surface, nitrogen oxides (NOx), sulfur oxides (SOx), air pollution such as malodorous substances. It is said that substance adsorption and adherent bacteria are oxidatively decomposed. As a specific application example, a method of attaching a titanium dioxide photocatalyst to the outer wall of a building or the like to remove air pollutants under sunlight 6-315614), a method of attaching a titanium dioxide catalyst to a wall or a handrail in a hospital to kill bacteria and the like (JP-A-7-102678), dispersing titanium dioxide catalyst powder in wastewater, Many applications have been proposed, such as a method of irradiating light from an ultraviolet lamp to decompose filth in water (JP-A-5-92192).

It is also known that the surface of the photocatalyst thin film is highly hydrophilized based on its photoreaction, and it is applied to antifogging of mirrors (bathrooms, automobiles), lenses, glass windows, etc. Various thoughts have been made. For example, high voltage power lines,
When an optical semiconductor thin film is formed on the surface of train exteriors, building exterior walls, automobile glass, and window glass, hydrophobic dirt is less likely to adhere due to the hydrophilicity of the surface of the film, and even if dirt adheres, it decomposes. It is also known that the photocatalytic thin film can provide a self-cleaning action in which the dirt or the decomposed product thereof is easily washed away by rain, washing with water or the like. A compound thin film having high crystallinity is required to have good electrical properties, optical properties, photovoltaic properties, and photocatalytic properties.

A method of forming these thin films will be described by taking a titanium oxide thin film as an example. If the titanium oxide thin film is not a crystalline thin film, functions such as photoelectromotive force, photocatalytic property and superhydrophilic property cannot be obtained. In order to obtain a crystalline thin film, it is necessary to heat an amorphous or low crystalline titanium oxide thin film to 400 ° C. or higher. For example, titanium compounds such as titanium alkoxide and titanium acetate are hydrolyzed and used as a base material. After applying on the surface and drying, after sintering at 500 ℃ or more to obtain an anatase type titanium dioxide film, or after forming an amorphous titanium dioxide layer by vapor deposition method,
A method of annealing the obtained amorphous or low crystalline titanium dioxide layer at 400 ° C. or higher to form a layer containing anatase type titanium dioxide, a method of oxidizing the surface of metallic titanium at 500 ° C. or higher for crystallization, and a substrate There is known a method of obtaining an anatase type titanium dioxide film by an RF sputtering method in the state of being heated to 350 ° C. or higher.

[0006] In such a conventional method, the method of forming a highly crystalline titanium oxide thin film by firing an amorphous titanium oxide film requires heating the substrate to a high temperature for a long time, so that the process is maintained during operation. It is expensive, and it is practically impossible to form a highly crystalline titanium oxide thin film on a plastic substrate described later by this method from the viewpoint of heat resistance of the substrate. The RF sputtering method is an excellent method for obtaining anatase-type titanium oxide having a high photovoltaic power, but it requires heat resistance of the base material at 400 ° C. or higher and requires the use of an expensive device. It is difficult to produce a highly crystalline titanium oxide thin film on a plastic substrate by the method. Furthermore, although there are some plastic substrates that have a heat resistance of 350 ° C. or higher, the heat resistance is insufficient to be applied to the RF sputtering method, and further, the light transmittance and the cost are low. At present, there is no known plastic base material that is compatible with both points.

By the way, the highly crystalline titanium oxide thin film has attracted attention for its photovoltaic effect in addition to the characteristics such as antifouling, antibacterial and antifogging based on the photocatalytic reaction of the surface as described above. Photovoltaic power is obtained by immersing a substrate provided with a conductive thin film and a highly crystalline titanium oxide thin film in water or a liquid having an electrolytic action, and irradiating the thin film with ultraviolet rays, the photovoltaic power is applied to the irradiated portion. This is a phenomenon that occurs. By utilizing this phenomenon, for example, the electrodeposition film can be selectively formed on the irradiated portion. That is, the substrate is immersed in an electrodeposition liquid containing a film-forming electrodeposition substance, and a bias voltage is applied or not applied between the conductive thin film and a counter electrode provided in the liquid, When the thin film is irradiated with a pattern of ultraviolet rays, a photoelectromotive force is generated in a light pattern irradiated portion of the thin film, a photocurrent flows, and a film forming substance is electrodeposited on the portion. When the photovoltaic power of the thin film is small, it is possible to apply a bias voltage. The present inventors have previously
A method for forming an extremely fine pattern such as a color filter with high resolution using the above-mentioned photovoltaic is provided (JP-A-11-174790 and JP-A-11-13).
3224, JP-A-11-335894, etc.).

Recently, the liquid crystal color display panel includes (1) a driving side substrate in which driving elements such as thin film transistors (hereinafter sometimes referred to as "TFTs") and pixel electrodes are arranged in a matrix, and a color filter. And a filter-side substrate provided with a counter electrode and facing each other while aligning with a spacer interposed therebetween, and a liquid crystal material sealed in a gap between them (2) A color filter is directly formed on the drive-side substrate In some cases, a color filter integrated drive substrate and a counter substrate provided with an electrode are simply arranged to face each other with a spacer interposed, and a liquid crystal material is sealed in a gap between them. It can be prepared by the photoelectric deposition method using the optical semiconductor thin film described in the above publications.

In the liquid crystal display panel of the above (1), an exposure mask is required when manufacturing a color filter, and an error in the alignment accuracy between the driving side and filter side substrates is likely to occur, resulting in poor display quality and yield. There is a problem of causing a decrease. On the other hand, in (2), the bias voltage can be selectively applied (addressing) by the TFT provided on the driving side substrate during photoelectric deposition.
Since the exposure mask is not required when manufacturing the color filter and the alignment of both substrates is not required, the latter one is currently drawing attention. However, in the latter method, since it is necessary to make the color filter conductive by using a through hole or the like, the cost increases.

In particular, recently, demand for small devices such as portable terminals such as mobile phones and small personal computers has rapidly increased, and various studies have been made from the viewpoint of mobile. In particular, in the case of a device intended for carrying, it is required that the device be lightweight and thin, and that portability to the outdoors and impact resistance against external force are important, and that it is unlikely to be damaged by dropping or the like. From the viewpoint of this mobile, the use of a flexible plastic substrate instead of a conventional glass substrate has recently attracted attention as a substrate that constitutes a liquid crystal color display panel. Generally, a liquid crystal flexible substrate is required to have a transparent, highly heat-resistant, plastic substrate excellent in gas barrier properties, but even polyimide materials, which are considered to have the best heat resistance at present, have no heat resistance. Since the temperature is only about 300 ° C., it is difficult to provide the crystalline optical semiconductor thin film as described above on the plastic substrate, and the polyimide material film is difficult to use because it has a polarizing property and is colored due to the stretching treatment. Forming a color filter on a substrate by the photoelectric deposition method has not been realized commercially.

At present, the liquid crystal panel using a plastic substrate is only known as the STN system which does not require a TFT drive circuit. The reason is that in order to form a polycrystalline semiconductor thin film having a high carrier concentration used for a TFT or the like, a high temperature treatment step is required, and it is impossible at present to fabricate a TFT drive circuit on a plastic substrate. Because it is. However, since the society demands high image quality, the realization of a TFT liquid crystal display element made of a plastic material is a goal that must be realized sooner or later. Then, as a method of manufacturing a color filter used for a liquid crystal panel using a plastic substrate,
(1) Inkjet method (2) Electrodeposition method is only in practical use. The inkjet method has the advantage that it does not require a photolithography process, but it is prone to color mixing and is inferior in terms of resolution and positional accuracy. Further, in the electrodeposition method, since it is necessary to form continuous electrodes corresponding to the pixels, the pattern shape is limited to the stripe type or the like.
It cannot be used for a liquid crystal panel equipped with an FT drive circuit. Therefore, in addition to the above-mentioned optical semiconductor thin film, T
It is required to efficiently manufacture a semiconductor thin film at a low temperature such as used in an FT circuit.

As a method of forming a semiconductor thin film on a sheet-shaped plastic substrate, Japanese Patent Laid-Open No. 6-11738 discloses a method of forming a semiconductive crystalline silicon film of an MIM device, which is based on an insulating silicon-based compound material. It describes a method of irradiating the surface of a thin film with an energy beam such as a laser beam to melt the surface layer, convert the surface layer into a crystalline silicon film, and leave the insulating silicon-based compound material as the underlying layer. Further, as a method of forming a semiconductor thin film on a plastic film, Japanese Patent Application Laid-Open No. 5-315361 discloses forming a non-crystalline material film and an oxide insulating film in this order on a plastic film, and applying a laser from the oxide insulating film side. Irradiating light, the amorphous material film is melted and crystallized near the interface between the amorphous material film and the oxide insulating film.
It describes a method for producing a crystallized semiconductor film without giving thermal damage to a plastic film by laser light. Further, in Japanese Unexamined Patent Publication No. 5-326402, similarly, in order to eliminate the influence of heat from laser light on the plastic film, after forming a thermal barrier layer on the plastic film, an amorphous silicon layer is formed thereon, and then, A method of irradiating a laser beam to form a polycrystalline silicon layer is described. All of the above methods are methods of crystallizing an amorphous semiconductor film by annealing with a laser beam, but heat of the laser beam (which may reach 1000 ° C.) should not affect the plastic film. To melt and crystallize only the surface of the amorphous semiconductor layer, or
This is a method of providing a thermal barrier layer. Therefore, these methods cannot crystallize the entire amorphous layer. There is a large limitation in providing heat resistance, which is a big problem in practical use, and the need for an expensive laser light irradiation device is also a big problem. Moreover, since it is necessary to scan the laser beam spot over the entire film, it is difficult to increase the area of the film, and it takes a long time to crystallize the entire film. It is a disadvantage.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and it comprises a continuous process of forming an amorphous or low crystalline thin film and a process of converting the thin film into a crystalline thin film. In addition, it is to provide a method for forming a crystalline thin film and an apparatus therefor capable of performing each of the steps at low temperature and easily.

[0014]

The above-mentioned object of the present invention is solved by providing the following method for forming a crystalline thin film on a sheet base material and an apparatus therefor. (1) First step of forming an amorphous or low crystalline thin film in a vacuum or low gas pressure atmosphere on a continuously conveyed sheet substrate, a thin film was formed in vacuum or in a gas atmosphere While maintaining the sheet base material at a temperature of 50 ° C. or higher and 300 ° C. or lower, the first
The method for forming a crystalline thin film on a sheet base material, which comprises the second step of irradiating the thin film formed in the step of (3) with light having a wavelength absorbed by the thin film. (2) The gas used in the gas atmosphere in the second step is one or more of hydrogen gas, oxygen gas, carbon monoxide gas, nitrogen gas, methane gas, ethylene gas, ammonia gas, silane gas, phosphine gas, and argon gas. The method for forming a crystalline thin film on a sheet base material according to (1) above, which further comprises: (3) The method of forming a crystalline thin film on a sheet base material according to (1) or (2) above, wherein the wavelength of light in the second step is 3 times or less the film thickness of the thin film. . (4) The light source in the second step is the light from the ultraviolet lamp,
The amorphous or low crystalline thin film is Si, Ge, Ga,
Zr, Ti, Zn, Bi, Ta, In, Sn, As, Al, P, Sb, Cd, Y,
Any one of the above (1) to (3), characterized in that it contains one or more of Nb, V, B, Ru, Re, Mo oxides, nitrides, carbides, and composite ceramics as a main component. A method for forming a crystalline thin film on the sheet substrate according to.

(5) The sheet base material is a polymer base material, and the maintenance temperature is in a temperature range from 50 ° C. to the heat resistant temperature of the polymer base material, (1) to (). A method for forming a crystalline thin film on the sheet substrate according to any one of 4). (6) The glass transition point of the polymer material contained in the sheet base material is in the range of 10 ° C. to 250 ° C., and the heating temperature is in the temperature range of 50 ° C. to the melting point or flow starting point of the polymer material. A method for forming a crystalline thin film on a sheet base material according to any one of (1) to (5) above. (7) The material of the sheet base material is polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone, polyether sulfone, polysulfone, polyetherimide, polyether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, epoxy resin The method for forming a crystalline thin film on a sheet base material according to any one of (1) to (6) above, which comprises at least one selected from the group consisting of :, a polyolefin, and a polyaramid.

(8) Any of the above (1) to (7), characterized in that a heat insulating and heat resistant thin film is provided between the sheet base material and the amorphous or low crystalline thin film. 2. A method for forming a crystalline thin film on the sheet substrate according to 1. (9) A crystalline thin film is formed on the sheet substrate according to any one of (1) to (8), wherein the amorphous or low crystalline thin film is a thin film containing an oxide as a main component. how to. (10) The above-mentioned (1) to (9), wherein the amorphous or low crystalline thin film is a thin film containing titanium oxide as a main component formed by a sputtering method.
A method for forming a crystalline thin film on the sheet substrate according to any one of 1.

(11) The crystalline thin film obtained after the second step is a thin film containing microcrystalline titanium oxide as a main component, or one or two of anatase titanium oxide, rutile titanium oxide and amorphous titanium oxide. A method of forming a crystalline thin film on a sheet substrate according to any one of (1) to (10) above, which is a thin film containing a mixture of at least one species as a main component. (12) The method for forming a crystalline thin film on a sheet base material according to any one of (1) to (11) above, wherein the amount of light is controlled according to the temperature of the sheet base material. (13) The method for forming a crystalline thin film on a sheet base material according to any one of (1) to (12), wherein the light irradiation is performed in a pulsed manner. (14) The sheet base material includes a light-transmissive thin film, a semiconductive thin film,
The method for forming a crystalline thin film on the sheet substrate according to any one of (1) to (13) above, wherein a conductive thin film or a patterned film is present.

(15) The method for forming a crystalline thin film on a sheet substrate according to any one of (1) to (14), wherein the sheet substrate is a continuous sheet substrate. (16) The sheet base material according to any one of (1) to (15) above, characterized in that the sheet base material is a discontinuous sheet placed on a conveying member and conveyed. Method for forming a conductive thin film. (17) The sheet base material according to any one of (1) to (16), further comprising a step of cleaning and / or degassing the sheet base material before the first step. Method for forming crystalline thin film on. (18) The sheet substrate according to any one of (1) to (17), wherein the cleaning and / or deaeration is performed by heat treatment and / or discharge treatment of the sheet substrate. Method for forming crystalline thin film.

(19) The first chamber for forming an amorphous or low crystalline thin film and the sheet substrate are 50 to 3
A second chamber for irradiating light having a wavelength absorbed by the thin film while maintaining the temperature at 00 ° C .; and a means for transporting the sheet base material in the first chamber and the second chamber in this order, The first chamber comprises means for forming an amorphous or low crystalline thin film, means for maintaining the chamber in a vacuum or low gas pressure atmosphere, and a carrying-in and carrying-out part of the sheet base material, and the second chamber is A means for maintaining the sheet base material at 50 to 300 ° C., a light irradiating means for irradiating light having a wavelength absorbed by the thin film, a means for holding the chamber in a vacuum or gas atmosphere, and a sheet base material carrying-in part. An apparatus used in the method for forming a crystalline thin film on the sheet base material according to claim 1, further comprising: (20) The apparatus according to (19), wherein the first chamber, the second chamber, and the means for conveying the sheet base material are in the same vacuum system. (21) The above-mentioned (19) or (20), further comprising means for cleaning and / or degassing the sheet base material in the same vacuum system before loading the sheet base material into the first chamber. Equipment.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The method for forming a crystalline thin film on a sheet base material of the present invention comprises at least the following two steps: A first step of forming an amorphous or low crystalline thin film (hereinafter, may be simply referred to as "amorphous thin film" including amorphous and low crystalline thin film) in a low gas pressure atmosphere, and (2) vacuum The thin film formed in the first step is absorbed by the thin film formed in the first step while maintaining the temperature of the sheet base material on which the thin film is formed at 50 ° C. or higher and 300 ° C. or lower under a gas atmosphere. It has a 2nd process of irradiating light of a wavelength and converting the said amorphous thin film into a crystalline thin film. In the present invention, a step of forming an amorphous thin film,
By continuously performing the step of converting the amorphous thin film into the crystalline thin film, various functional thin films can be easily prepared according to the use of the crystalline thin film.

Particularly, in the second step of the present invention, while maintaining the temperature of the sheet base material on which the amorphous thin film is formed in the temperature range of 50 to 300 ° C., the thin film is irradiated with light having a wavelength of a wavelength absorbed by the thin film. A highly crystalline thin film can be obtained by simply
The heating temperature may be very low as compared with the method of obtaining a crystalline thin film by annealing at a temperature close to 000 ° C. Further, it is not necessary to scan the laser beam spot, and it suffices to irradiate the specific light beam on the entire surface by the lamp type light irradiation device. Therefore, as compared with the conventional method, it is possible to manufacture a large area planar crystalline thin film in a short time without requiring a large-scale apparatus, and the manufacturing apparatus cost and manufacturing cost are significantly reduced. . Further, conventionally, a special process or apparatus was required to form a compound thin film on a plastic substrate, but the present invention provides a simple process and apparatus for forming a high-quality compound film on a plastic substrate. It has become possible to produce crystalline thin films.

Further, before, in order to perform antifogging treatment, antifouling treatment, hydrophilization treatment, etc., in which a photocatalytic thin film is provided on the surface of a mirror, glass, etc., an amorphous thin film of titanium oxide is first applied to the surface of the mirror, glass, etc. After the formation, it was necessary to calcine this at 400 ° C. or higher to control the crystallinity, which was a method involving a complicated and highly accurate control means because of high temperature treatment. By the manufacturing method of the present invention, a substrate in which a highly crystalline thin film is provided on a low heat resistant plastic substrate can be easily obtained, and a desired highly crystalline compound film can be easily obtained.

In particular, T is formed on a sheet-like plastic substrate.
It has become possible to fabricate an FT drive circuit or to form a color filter film by a photoelectric deposition method using an electrodeposition substrate having a highly crystalline thin film for photovoltaic generation provided thereon. In the case of a color filter, the substrate is required to have a light-transmitting property, but at present, the only heat-resistant plastic substrate that has a non-polarizing property is a heat-resistant temperature of around 200 ° C. Because there is no, 20
Photoelectric conversion efficiency (photovoltaic) by heat treatment at around 0 ℃
It was impossible to form a highly crystalline thin film with
This is made possible by the present invention. Therefore, it is expected to be applied to portable liquid crystal display panels, which are required to be further reduced in weight and improved in impact resistance.

First, the first step of the present invention will be described. Examples of the material of the sheet base material used in the method of the present invention include glass, plastics, glass epoxy substrates, various ceramics, and single crystal substrates such as Si, GaN, GaAs, and GaP. Since the sheet base material needs to be capable of being continuously conveyed, the sheet base material is a continuous sheet base material composed of a flexible film, sheet or plate, or is flexible. It does not have to be provided as long as it has a shape and a size such that it can be continuously carried by being placed on a carrying means, for example, a carrying belt. Examples of the plastic material include polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone, polyether sulfone, polysulfone, polyetherimide, polyether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate,
Examples thereof include polyaramid and norbornene resin (manufactured by JSR, trade name: Arton). Among the above resins, the norbornene resin has recently been attracting attention as a resin having a high light transmittance in a wide wavelength range and an excellent heat resistance (monthly "Chemical Economy", December 1997, Supplement).

The sheet base material used in the present invention is preferably a light transmissive material in the sense of expanding various uses of the crystalline thin film-forming sheet base material to be produced.
Furthermore, in order to form a semiconductor thin film with high photoelectric conversion efficiency used in the photoelectric deposition method, it is preferable to use a relatively high heating temperature. Therefore, when a plastic substrate is used as the substrate, a plastic substrate having higher heat resistance is used. You need wood. Polyimide is a typical material for a plastic base material having high heat resistance, but transparency is required when it is used in a liquid crystal display device. In this case, polycarbonate (PC), polyether sulfone ( PES),
Polysulfone (PS) or the like is used. In particular, heat-resistant PC and PES are highly transparent, can obtain heat resistance up to about 230 degrees, and have little optical anisotropy. Therefore, they are optimal as thin film deposition base materials for liquid crystal parts. is there.
The heat resistance of plastics can be expressed by the glass transition point, and the glass transition point of the plastic material used for the sheet base material of the present invention can be about 10 to 250 ° C.

When a continuous plastic sheet base material is used as the sheet base material, the thickness is such that the thin film formed by the stable transportability and handling of the sheet base material and the rigidity of the sheet base material itself can be stably maintained. 7 etc.
Approximately 500 μm is suitable, and a thickness of 75 to 260 μm is more preferable. Further, even when the discontinuous plastic sheet base material is conveyed by a conveying means such as a conveyor belt, it is preferable to use the sheet base material having the above-mentioned thickness in view of handling.
In order to increase the thermal stability of the sheet base material, an extremely thin heat insulating or heat resistant thin film can be formed on the side of the sheet base material on which the crystalline thin film is provided. This thin film has a heat resistance of 180 ° C. or higher, preferably 300 ° C. or higher, and a thermal conductivity of 0.02 cal / sec · ° C. · cm ³ or lower, preferably 0.00
It can be formed from a material having a low thermal conductivity of 8 cal / sec · ° C · cm ³ or less, and a film thickness of 0.01 to 50 μm, preferably 0.1.
About 07 to 1.9 μm is suitable. As such a thin film, ceramics such as silicon oxide, silicon nitride, zirconia oxide, and aluminum oxide are used.

The crystalline semiconductor thin film of the present invention can be formed by using a sheet base material further provided with a light-transmissive conductive thin film such as ITO. When a color filter is produced by the photoelectric deposition method using the sheet base material on which the resulting light-transmitting conductive thin film and crystalline semiconductor thin film are formed, the sheet base material also needs to be light-transmitting. is there. The conductive thin film such as ITO can be formed by the method of the present invention as described later. Also,
Depending on the function and application of the crystalline thin film obtained, a light transmissive thin film such as silicon oxide, zirconia, and silicon nitride, a semiconductive thin film such as silicone, silicon carbide, and gallium nitride, and a light such as ITO can be used for the sheet base material. Transparent conductive thin film, patterned film,
A film provided with a light antireflection film such as zirconium oxide (ZrO ₂ ) or a gas barrier film such as silicon oxide or silicon nitride can also be used for forming the crystalline thin film of the present invention.

The amorphous thin film formed in the first step of the present invention is Si, Ge, Ga, Zr, Ti, Zn, Bi, Ta, In, Sn, A.
s, Al, P, Sb, Cd, Y, Nb, V, B, Ru, Re, Mo oxides, nitrides, carbides, and composite ceramics as a main component. What is the composite ceramics?
It means a compound such as oxynitride or carbonitride of the above elements. Specifically, SiC, SiO ₂ , GaN, ZrO ₂ ,
ZnO, PbO, BaTiO ₃ , Bi ₂ Ti ₄ O ₁₁ , Bi ₄
Ti ₃ O ₁₂ , ITO, Y ₂ O ₃ · Al ₂ O ₃ , YAlO ₃ , S
tTiO ₂ , TiO ₂ , ZnO, NaNbO ₃ , NaV
O ₃ , V ₂ O ₃ , VO, BeO.AlO ₃ , RuO ₂ , Zr
_{C, TiC, TaC, B 4} C, BN, Mo 1-x N x, and the like. Among them, TiO ₂ , ZnO and the like, when crystallized (metal oxide semiconductor), have a large band gap and are transparent, and have excellent light irradiation efficiency (photovoltaic efficiency). In particular, TiO ₂ has excellent stability when immersed in an electrodeposition liquid, has an absorption of 400 nm or less, and is light transmissive.
It can be used as it is as an optical semiconductor thin film for producing a color filter, and it is also preferably applied to the above-mentioned anti-fogging or anti-fouling applications.

As the amorphous thin film in the present invention,
Although oxides such as Sn, In, and Zn are transparent conductive materials, the crystallinity of the oxide thin film can be improved by subjecting the oxide thin film having low crystallinity to the second step of the present invention. Is higher and the conductivity is improved. Therefore, even if the film thickness of the thin film is reduced in order to increase the light transmittance, it becomes possible to secure the necessary conductivity. As the amorphous thin film to which the second step of the present invention is applied, in addition to the above oxide,
Further, SnO ₂ added with Sb, Zn, or an oxide thereof, F, or the like, In ₂ O ₃ added with Sb, Z
n, Sn, Si, Ge, or oxides thereof, or F added, ZnO Al, Ga, In, G
e, or those containing these oxides, InGa
O ₂ , MgIn ₂ O ₄ , CdO, CdSnO ₄ , CdGaO
₄ , inorganic transparent conductive materials such as Cd ₂ SnO _{4 and the} like.

The "amorphous" of the amorphous thin film in the present invention does not mean only a completely amorphous thin film, but a mixture of an amorphous portion and a crystalline portion is also included in the category of the "amorphous".
It has been confirmed that even with a thin film containing a slight amount of an amorphous part, the crystallinity is increased and the photocatalytic effect and photoelectric conversion effect are increased by the treatment of the present invention. Further, the “crystallinity” of the crystalline thin film of the present invention includes both polycrystalline and single crystal.

In the method of the present invention, as the method for forming the amorphous thin film, vacuum vapor deposition method, sputtering method, R
An F sputtering method, an EB vapor deposition method, an ion plating method or the like is used. These thin film forming methods are performed in a vacuum or in a low gas pressure atmosphere, and the conditions are appropriately selected from known conditions depending on the thin film forming methods. For example, in the case of the vacuum evaporation method, 1.33 × 10 ⁻³ Pa (10
^-5 Torr) The thin film is formed in the vacuum range below.
In the case of the sputtering method, the degree of vacuum with an inert gas introduced is 1.33 × 10 ⁻³ Pa to 1.33 × 10 ⁻¹ Pa (10 ⁻⁵
Performing film formation in an atmosphere in the range of 10- ³ Torr) from. The film thickness of the amorphous thin film in the present invention is appropriately selected according to the application, and is, for example, about 170 to 370 nm in the case of an optical semiconductor thin film such as titanium dioxide used for photoelectric deposition, and that of an oxide conductive thin film such as ITO. In some cases 170
It is about 350 nm. When an amorphous thin film or a low crystalline thin film is formed on a plastic substrate, it is relatively low temperature, for example, not more than the heat resistant temperature of what is currently known as plastics having good transparency (23
A sputtering method or an RF sputtering method, which can form a film even at 0 ° C. or less) and has little damage to the substrate, is preferably used. At that time, by providing a cooling mechanism on the back surface of the sheet base material that allows cooling water or a refrigerant to pass through,
It is also possible to prevent the temperature of the sheet base material from rising too high.

In the first step, different 2
It is also possible to provide an amorphous thin film having more than one layer by laminating it on a sheet base material. For example, a transparent conductive film having low crystallinity is first formed on a sheet base material, and then an amorphous semiconductor thin film is formed thereon. The photo-annealing in the second step converts both the conductive film and the semiconductor thin film into a thin film having higher crystallinity.

Next, the second step of the method of the present invention will be described. In the second step, the sheet base material on which the thin film is formed is heated to 50 ° C. under vacuum or gas atmosphere.
The amorphous thin film is converted to a crystalline thin film by irradiating the thin film formed in the first step with light having a wavelength absorbed by the thin film while maintaining the temperature at 300 ° C. or lower. (Hereinafter, the second step in the present invention may be referred to as a “photo-annealing step”, and the treatment of this step may be referred to as a “photo-annealing step”.) The maintenance temperature is the temperature of the sheet base material. Since the amorphous thin film formed on the substrate is a very thin film, the substrate temperature is 50 to 30
When controlled to be 0 ° C., the temperature of the amorphous thin film becomes extremely close to this temperature.

In the method of the present invention, if the temperature of the substrate having the amorphous thin film is set to 50 ° C. or higher, the amorphous state can be sufficiently changed to the crystalline or polycrystalline state. The sheet substrate is usually heated to maintain this temperature. The upper limit temperature of heating is not particularly limited, but is 300 ° C. or less from the viewpoint of heat resistance of the sheet base material, selection of heating method, control of heating temperature, energy loss, and the like. From the viewpoint of producing a thin film with high crystallinity (for example, high photoelectric conversion efficiency), a higher temperature is preferable in the above temperature range, but it is also necessary to consider the heat resistant temperature of the sheet base material, and the heating temperature is It is preferable not to exceed the heat resistant temperature of the sheet base material, and it is particularly preferable to heat to at least 10 ° C. or lower than the heat resistant temperature of the sheet base material. When the material of the sheet base material is a plastic material, it is preferable to apply a glass transition temperature, a melting point, or a temperature below the flow starting point of the plastic material. Although the temperature of the amorphous thin film rises due to the irradiation of light, which will be described later, if the temperature rise is such that the sheet base material is damaged, the temperature of the sheet base material can be adjusted appropriately by using a cooling means.

The wavelength of light absorbed by the amorphous thin film varies depending on the chemical composition of the thin film, but is, for example, 170 to 370 nm in the case of titanium oxide, and IT
In the case of O, it is 170 to 350 nm. A light source that emits light having an absorption wavelength is appropriately used as a means for irradiating light having a wavelength that the amorphous thin film has absorption. When a lamp-shaped light source is used to increase the light irradiation efficiency, it is possible to uniformly irradiate a large area in a short time. For the light wavelength range of the light source,
In the short wavelength region, particularly in the wavelength region of 400 nm or less, the energy density is high and the heating efficiency at the light absorption site is high due to the energy selectivity, which is more preferable. For example, in the case of irradiating with ultraviolet rays, it is sufficient to use a commercially available high-pressure mercury lamp as a light source and an ultraviolet irradiating device having a peak wavelength taken out, but an excimer lamp is preferably used among them. Further, if the wavelength of the light is set to 3 times or less the film thickness of the amorphous thin film, and more preferably 2 times or less of the thin film thickness, it is possible to specify only the inside of the thin film and rapidly raise the temperature. Therefore, the temperature rise of the sheet base material is suppressed,
Moreover, since the light absorption efficiency is increased, the light annealing efficiency is also increased. Further, the wavelength band of the irradiation light is preferably a narrow wavelength range centered on the central absorption wavelength because heating of other portions is not required. The light irradiation amount is the thickness of the compound thin film to be produced,
Depending on the type of material that penetrates, for example, 0.1 to 1
A light amount in the range of 000 W · sec, preferably 20 to 300 W · sec is suitable. The light irradiation can be pulsed irradiation as well as continuous irradiation. By adjusting the pulse interval appropriately, it is possible to finely control the light irradiation amount, so that the heat dissipation of the sheet base material etc. can be performed while the light is not irradiated, and the temperature rise of the substrate can be suppressed. Further, when it is difficult to control the temperature of the sheet base material, it becomes possible to perform highly accurate temperature control by controlling the number of pulses.

The atmosphere in the second step of the present invention is preferably vacuum or gas atmosphere. The above-mentioned "vacuum" generally refers to a degree of vacuum of about 10 ^-2 Pa or less, but can be appropriately determined by considering other conditions. The type of gas is appropriately selected depending on whether the compound thin film to be produced is a carbide type, a nitride type, or the like. For example, hydrogen gas, oxygen gas, nitrogen gas, methane gas, ethylene gas, carbon monoxide gas, One or more kinds of silane gas, phosphine gas, ammonia gas, argon gas and the like are used. These gases act as a reaction gas or an active gas, and the amorphous thin film reacts at high temperature under the irradiation of light, and is oxidized or reduced, or the compound is modified by another reaction (and at that time). , The inside of the film is heated to a considerably high temperature, which causes a change in crystallinity. The pressure of the gas atmosphere is 1.33 × 10 ⁻³ Pa
(10 ⁻⁵ Torr) to 133000 Pa (10 ³ Torr), preferably 1.33 × 10 ⁻² Pa (10 ⁻⁴ Torr) to 13.3 Pa
It is a (10- ¹ Torr) about.

In the case of an oxide semiconductor such as titanium dioxide, for example, 2 to 5% of hydrogen (below the explosion limit), an inert gas of high purity (eg, nitrogen gas, argon gas, helium gas, etc.) are used. Annealing treatment under light irradiation is performed in a reducing gas atmosphere mixed with (for example, when using a device having an internal capacity of 1 l, the flow rate is 0.5 to 2 l / min and the gas pressure is about atmospheric pressure). In the case of an oxide semiconductor thin film, since the heating temperature can be lowered by lowering the oxygen partial pressure, it is preferable to vacuum-treat the atmosphere in advance to lower the oxygen partial pressure. When annealing is performed while irradiating light in the atmosphere as described above, the amorphous thin film of titanium oxide is polycrystallized, and the lattice defect of oxygen is generated to increase the carrier concentration of the semiconductor, so that the photocurrent characteristic of the semiconductor is improved. Greatly improved.
The crystal structure of the titanium oxide thin film after annealing is one kind or a mixture of two or more kinds of microcrystalline titanium oxide, anatase type titanium oxide, rutile type titanium oxide and amorphous type titanium oxide, for example, anatase type crystal, anatase type titanium oxide. And a rutile type mixed crystal, or an amorphous and anatase type mixed crystal.

Further, in order to reduce the resistance of the light-transmissive oxide conductive film such as ITO, the photo-annealing process is performed in the same atmosphere as titanium oxide. Also in this case, the heating temperature of the transparent conductive oxide film can be lowered by lowering the oxygen partial pressure.

The physical properties of the crystalline thin film obtained by the method of the present invention can be controlled by variously changing the light irradiation time, light intensity, kind of atmospheric gas, atmospheric pressure, sheet substrate heating temperature and the like. Is.

Before the first step, it is preferable to further provide a step of washing and / or degassing the sheet base material. In particular, the plastic sheet base material has dirt on its surface, adsorption of gas and moisture, etc., and if an amorphous thin film is formed while holding these on the surface, the adhesiveness of the film becomes poor or a high-purity thin film is formed. Formation is hindered.
In the cleaning process, ultrasonic cleaning is performed while the sheet base material is being passed through a washing bath, and cleaning is performed by passing it through a bath of an organic solvent such as acetone, followed by drying to remove water and organic solvent. It can be done by doing. Also,
The degassing step is performed by heat treatment on the surface of the sheet base material, for example, heat treatment by electric heating, or discharge treatment with or without heating. Degassing can also be performed by simply rewinding the roll-shaped sheet base material several times under vacuum. These washing and / or degassing steps are preferably performed in a vacuum atmosphere. The degree of vacuum is 1.33 × 10 ^-8 Pa (10 ^-10 Torr) to 1.3
A range on the order of 3 × 10 ⁻¹ (10 ⁻³ Torr) applies.

Next, the conveyance of the sheet base material in the method of the present invention will be described. Hereinafter, a continuous sheet base material will be described, but the same applies to a discontinuous sheet base material. The manner in which the sheet base material is conveyed includes the time for completing the first step and the second step, the size of the region in which the first and second steps are performed, the first step and the second step.
It can be appropriately determined in consideration of the degree of vacuum in the process. For example, the sheet base material is conveyed at a certain speed to the first step (including all steps when the first step has two or more different amorphous thin films) and the execution area of the second step. In this case, if it is possible to complete those steps within a time range of passing through each area, those areas may be continuously moved at a constant speed. Also, when transported at a constant speed,
For example, when the second step is not completed, the speed of passing through the execution area of the second step is reduced, an area for storing the sheet base material is provided before the second step, and the first step and the second step are performed. It suffices to absorb the difference in transport speed. Furthermore, the first
In the area for performing the step and / or the second step,
It is also possible to set the transport speed to zero. In this case,
Means for storing the sheet base material may be provided in front of the process area where the transport speed is set to zero. At this time, it is necessary not to apply an extra load to the transportation of the sheet base material. In the above aspect, a known storage means is used as the storage means for absorbing the speed difference. 3 (A) and (B)
An example is shown in. As shown in FIG. 3A, the transfer speeds V _A and V _B in the chamber A and the chamber B are V _A
When there is a speed difference such as> V _B , it is of a type in which the sheet base material from the chamber A is accumulated (loosened) in the looper section by using a multistage roll mechanism. Also, FIG.
The one shown in (B) uses a dancer roll mechanism shown in R ₁₁ to R ₁₄ that uses vertically movable rolls (dancer rolls), and the transport speed in both chambers is such that V _A > V _B. R ₁₁ and R
Raises ₁₂ dancer rolls, while R ₁₃ and R ₁₄
Is a type in which the sheet base material is accumulated in the looper portion by lowering the dancer roll.

In the present invention, the above-mentioned first step and
The second step is both performed in a vacuum or low gas pressure atmosphere.
Since it often happens, the first step and the second step are carried out.
Performing the area and further cleaning and / or degassing steps
The areas are preferably arranged in a common vacuum system. Both
The degree of vacuum in the general vacuum system is 1.33 × 10^-8Pa (10
^-TenTorr) to 1.33 x 10^-1Pa (10-³ Torr)
It is adjusted every time.

Next, an apparatus used in the method for forming a crystalline thin film on the sheet base material of the present invention will be described. This device is used for forming a first amorphous or low crystalline thin film.
And a second chamber for irradiating light having a wavelength absorbed by the thin film while maintaining the sheet base material at 50 to 300 ° C., and the sheet base material in the first chamber and the second chamber. A means for transporting in this order is provided, and the first
The chamber of (1) comprises means for forming an amorphous or low crystalline thin film, means for maintaining the inside of the chamber in a vacuum or low gas pressure atmosphere, and a carry-in part and a carry-out part for the sheet base material. 50 to 30 sheets of base material
It is provided with means for maintaining the temperature at 0 ° C., light irradiating means for irradiating light having a wavelength absorbed by the thin film, means for maintaining the inside of the chamber in a vacuum or gas atmosphere, and a loading and unloading part for the sheet base material. .

The first chamber, the second chamber, and the means for transporting the sheet base material should be in the same vacuum system so that the vacuum atmosphere or the low gas in the first chamber and the second chamber is low. It is preferable from the viewpoint of maintaining a pressure atmosphere.

Further, it is advantageous that the apparatus is provided with means for cleaning and / or degassing the sheet base material before carrying it into the first chamber in the same vacuum system.
Examples of the cleaning means include ultrasonic cleaning means in a water bath and cleaning means using an organic solvent cleaning bath, and examples of the degassing means include heating means and / or discharge treatment means. Further, in the method of forming a crystalline thin film on the sheet base material of the present invention, when a plurality of different amorphous thin films are laminated in the first step, the first chamber is formed according to the type of amorphous thin film to be formed. It consists of multiple chambers.

Further, in order to make the sheet base material conveyance speed different in the first and second chambers, means for independently controlling the conveyance speed in each chamber is required. Further, as the storage means for absorbing the speed difference, the other-stage roll mechanism or the dancer roll mechanism as described above is appropriately used.

A conceptual diagram showing an example of the apparatus of the present invention is shown with reference to the drawings. FIG. 1 shows two thin film forming chambers 1 for sequentially stacking two different amorphous thin films.
0 and 20, a conceptual diagram of an apparatus in which an optical annealing chamber 30 for performing an optical annealing process is arranged in a common vacuum system 40. The thin film forming chamber 10 is provided with an amorphous thin film forming means 12, a sheet base material temperature control means (usually a heating means, and optionally a cooling means) 14,
The thin film forming chamber 20 is provided with an amorphous thin film forming means 22 and a sheet base material temperature control means (usually a heating means, and optionally a cooling means) 24.
Although not shown, the thin film forming chambers 10 and 20 include a sheet base material temperature detecting means, a vacuum exhausting means,
Atmosphere gas introduction and discharge means and the like are provided. The optical annealing chamber 30 includes means 32 for irradiating light having a wavelength absorbed by the amorphous thin film and 50 to 300 sheets for the substrate.
Means 34 for maintaining the temperature at 0 ° C. (usually heating means, and optionally cooling means in addition to this) are provided, and further sheet base material temperature detecting means, vacuum exhausting means, atmospheric gas introducing and exhausting means, etc. are provided. The cooling means is used when the temperature of the sheet base material deviates from the maintenance temperature range of the present invention due to light irradiation.

Reference numeral 50 is a roll for feeding the sheet base material wound in a roll shape, and 52 is a roll for winding the sheet base material, which is driven by a driving means (not shown). Also, 60
Indicates an electric discharge treatment means for degassing the sheet base material. As the temperature maintaining means used in the chambers 10, 20 and 30, in the case of heating, for example, a heater that electrically heats is used, and in the case of cooling, a cooling means such as cooling water or a refrigerant is used. Further, as the light irradiation means used in the chamber 30, for example, an excimer lamp is used.

Next, using a device as shown in FIG. 1, thin films of ITO having a high electric resistance and titanium oxide having a low crystallinity are sequentially formed on a plastic sheet substrate, and then an optical annealing treatment is carried out. A method of converting the ITO thin film and the titanium oxide thin film into a thin film having high crystallinity will be described. In this case, the lengths of the chambers 10, 20 and 30 in the sheet substrate transport direction are such that when the sheet substrate is continuously transported at a specific constant speed, formation of an amorphous thin film and optical annealing treatment can be sufficiently achieved. It has a sufficient length. First, a roll-shaped plastic sheet substrate A is shown in FIG.
And the vacuum degree of the common vacuum system 40 in which the chambers 10, 20 and 30 are arranged is adjusted. In addition, the chamber 10 is previously vacuum-treated (10 ^-2 Pa
After removing oxygen for about 2 hours, the atmosphere is adjusted to a high-purity nitrogen gas atmosphere containing hydrogen gas or an argon gas atmosphere, and the chamber 20 is similarly vacuum-treated to adjust the atmosphere. The sheet base material is conveyed by roll driving means (not shown). First, the surface of the plastic sheet base material is treated by the electric discharge treatment means 60, then the sheet base material is conveyed into the chamber 10, and the temperature control means adjusts the temperature of the sheet base material to a temperature suitable for thin film formation, and RF sputtering. ITO is formed on the sheet substrate by a thin film forming means such as an apparatus.
Form a thin film. The sheet base material on which the ITO thin film is formed is sent to the chamber 20 and similarly a low crystalline titanium oxide film is formed. Then, the sheet base material is conveyed to the chamber 30, and is irradiated with light by a light irradiation means such as an excimer lamp while maintaining the temperature of the sheet base material in the temperature range of 50 to 300 ° C. The sheet base material after the optical annealing treatment is wound up on the roll 52.

Some examples of application of the sheet base material on which the crystalline thin film is formed by the above steps will be described. FIG. 2A shows an example of an electrodeposition substrate used for photoelectric deposition described later, and 100 is a PES film (100 μm) 1
Gas barrier film consisting of 00a and silicon dioxide (100
0Å) 100b sheet base material, 102 is I
A conductive thin film of a TO film (800 Å), 104 represents a crystalline titanium oxide thin film (2000 Å). FIG. 2 (B) shows an example of an antifouling sheet provided with a hydrophilic photocatalytic film used for antifouling of the surface. Reference numeral 200 denotes a polycarbonate film (150 μm) 200a and a gas barrier film 200b (800Å) made of silicon nitride. A sheet base material is constituted, 202 is an antireflection film (1200Å) made of zirconium oxide (ZrO ₂ ), and 204 is a crystalline titanium oxide thin film (1000Å). FIG. 2C shows another example of the antifouling sheet, 300 is a sheet base material made of a polyimide film (75 μm), and 302 is an adhesive layer (25 μm) for sticking the antifouling sheet on the other surface. , 304 represents a crystalline titanium oxide thin film (500 Å).

Next, as shown in FIG. 2A, a method of producing a color filter using a photoelectric deposition substrate having a light-transmitting conductive film and an optical semiconductor thin film provided on a plastic sheet substrate. Will be described. When the thickness of the plastic sheet base material in the photo-electrodeposition substrate is 0.4 mm or less, preferably 0.07 mm to 0.2 mm, more preferably 0.12 mm to 0.18 mm, the influence of light diffraction can be reduced. Therefore, it is not necessary to use an apparatus provided with an exposure apparatus having an imaging optical system and a mirror reflection optical system in the photoelectric deposition apparatus, and the film can be deposited by the apparatus described below.

An example of the electrodeposition device used in the present invention is
A conceptual diagram is shown in FIG. The electrodeposition device shown in FIG.
As described above, the apparatus is suitable for performing electrodeposition on a substrate using a thin base material (plastic base material or the like) that does not cause light diffraction, and includes a photomask 71 and an electrodeposition solution containing an electrodeposition solution. Tank 80, means 90 for applying voltage such as potentiostat, counter electrode 91 such as platinum black, reference electrode 92 such as saturated calomel electrode and Hg-X.
The uniform irradiation light source 73 of e is provided. Photo mask 71
Is used in close contact with the plastic substrate 12.

Another example of the electrodeposition apparatus is shown in FIG. The color filter manufacturing apparatus shown in FIG. 5 includes a projection type exposure apparatus, and includes a light source (not shown) for irradiating ultraviolet rays, a first imaging optical lens 72, and
An image forming optical system having a second image forming optical lens 73, a photomask 71 inserted between the first image forming optical lens and the second image forming optical lens, an electrodeposition tank 80 containing an electrodeposition liquid, It is provided with means 90 for applying a voltage such as a potentiostat, a counter electrode 91, and a reference electrode 92 such as a saturated calomel electrode. Further, it is possible to use a mirror reflection optical system instead of the image forming optical system in the color filter manufacturing apparatus. At the time of electrodeposition, as shown in FIG. 5, the substrate is placed in the electrodeposition apparatus so that the semiconductor thin film of the substrate comes into contact with the electrodeposition liquid in the electrodeposition tank, and the light from the exposure device is bound to the surface of the semiconductor thin film. Adjust to image. It is preferable from the viewpoint of handling that the distance between the imaging optical lens of the imaging optical system and the light-transmitting substrate surface is 1 mm to 50 cm, and the depth of focus of the imaging optical system is ± 10 to ± 100 μm.
From the viewpoints of accuracy and handling, the range is preferable.

Regarding the electrodeposition liquid, JP-A-11-1
All of the techniques disclosed in paragraphs 0017 to 0041 of Japanese Patent No. 74790 can be used. Further, as the electrodepositable polymer material, a material into which a crosslinkable group is introduced can be used, and heat treatment after forming the colored film can improve the heat resistance and solvent resistance of the color filter film. An electrodeposition liquid using an electrodeposition polymer material having a crosslinkable group introduced is disclosed in Japanese Patent Application No. 2000-
The electrodeposition liquid described in paragraphs 0037 to 0050 of 227721 can be used.

When the photo-semiconductor thin film is selectively irradiated with ultraviolet rays using a photomask as shown in FIG. 4 or FIG. 5, a photoelectromotive force is generated in the selected region, and the electrodeposition material in the electrodeposition solution is exposed to light. It is deposited on the semiconductor thin film. At this time, if the generated electromotive force is large enough to cause electrodeposition, it is not necessary to apply a bias voltage by the voltage applying device, but if it is insufficient, a bias of about several V is applied by the voltage applying device. Apply voltage. It should be noted that although the electrodeposited substrate has been described as an example using a plastic base material, it is a matter of course that a base material such as a glass base material can be used instead of the plastic base material.

The color filter manufacturing method described above is a method of depositing a film by a photoelectric deposition method, but it is also possible to deposit a film by a photocatalytic method. The photocatalytic method utilizes the photocatalytic action of an optical semiconductor and uses a film-forming substrate having a light-transmissive substrate, a conductive film (which may be light-transmissive), and a light-transmissive semiconductor thin film. When a selected area of the semiconductor thin film is irradiated with light, an internal circuit is formed between the semiconductor thin film / conductive film / electrolyte solution, electrolysis occurs in the electrolytic solution in contact with the semiconductor thin film, and the electrolytic solution near the semiconductor thin film is generated. The hydrogen ion concentration can be changed. By changing the hydrogen ion concentration, it becomes possible to precipitate the material from the electrolytic solution, that is, to deposit the film, as in the photoelectric deposition method. As the electrolytic solution, an aqueous solution having the same composition as the electrodeposition solution used in the photoelectric deposition method can be used. Also,
In the case of the photocatalytic method, it is necessary that the conductive film conducts to the electrolytic solution and that the semiconductor thin film and the conductive film are in contact with each other, but on the other hand, the counter electrode becomes unnecessary. The photocatalytic method is described in Japanese Patent Application No. 11-322507 and No. 11-322508.
Issue is described in detail.

[0057]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
"%" In the examples represents "mass%" except for the case of gas. Example 1 A chamber for performing the first step (first chamber) and a second chamber
An apparatus in which a chamber (second chamber) for carrying out the process and an electric discharge treatment apparatus were arranged in a common vacuum system was used. 85
A roll-shaped polyethersulfone film with a thickness of μm is used for a common vacuum system (vacuum degree: 1.33 × 10 ⁻¹ P
a (10 ^-3 Torr)) and rewind the film surface to 1
Linear velocity of 10 m while heating at 50 ° C and performing discharge treatment
The roll was rewound at m / sec, and this was repeated twice to reduce the gas, organic material, and moisture adhering to the sheet surface. Next, the transfer speed was adjusted so that the film was moved in the first chamber and the second chamber at a transfer speed of 65 mm / min.

The film was conveyed into the first chamber adjusted to a vacuum degree of 1.33 × 10 ^-1 Pa (10 ^-3 Torr) using argon gas as a carrier gas, and the surface temperature of the film was controlled to 165 ° C. Meanwhile, amorphous titanium dioxide was formed into a film having a thickness of 250 nm by a high frequency sputtering method. Next, the film on which amorphous titanium dioxide is formed is evacuated in advance (3.99 × 10 ^-1 Pa (3 × 10 ^-3 Torr), and then high-purity nitrogen gas containing 3% by volume of hydrogen gas is used. Atmosphere (flow rate is 1 l / mi per 1 l of the inner volume of the second chamber)
n), the film was loaded into the second chamber adjusted to
The mixture was heated to 65 ° C., and while maintaining the temperature, it was irradiated with ultraviolet rays (wavelength: 172 nm, light intensity: 50 mW / cm ² ) by an excimer lamp having a planar irradiation part (irradiation time was 1 minute. Equivalent). The film carried out from the second chamber was wound into a roll and taken out from the vacuum system.

When the X-ray diffraction intensity of the obtained photo-annealed film was examined, a diffraction peak was measured at 2θ of 25.260, which was 5 times the peak value at the same position before photo-annealing, and the crystallinity was improved. Was shown to be higher. Further, as a result of examining the contact angle of the film, it was 2.5 °,
It was confirmed to be a superhydrophilic surface. from this result,
It was confirmed that the photo-annealing process changed the amorphous or low crystalline titanium dioxide to high crystalline.

Example 2 In this example, a chamber for performing the first step (first chamber) and a chamber for performing the second step (second chamber)
And a heating means for degassing were arranged in a common vacuum system. A 0.15 mm thick highly heat resistant polycarbonate sheet wound in a roll is rewound in a common vacuum system (vacuum degree: 1.33 × 10 ⁻³ Pa (10 ⁻⁵ Torr)) and heated at 180 ° C. Linear velocity of 4 mm /
The roll was rewound four times per second to reduce the gas, organic material and moisture adhering to the sheet surface. Next, the transport speed was adjusted so that the sheet was moved in the first chamber and the second chamber at a transport speed of 30 mm / min.

The sheet was conveyed into a first chamber adjusted to a vacuum degree of 1.33 × 10 ^-1 Pa (10 ^-3 Torr) using argon gas as a carrier gas, and the surface temperature of the sheet was adjusted to 16
While controlling at 5 ℃, by high frequency sputtering method,
Amorphous titanium dioxide was formed into a film having a thickness of 250 nm. Next, the sheet on which the amorphous titanium dioxide was formed was evacuated in advance (3.99 × 10 ⁻¹ Pa (3 × 10 ⁻³ Torr), and then,
High-purity nitrogen gas atmosphere containing 3.8% by volume of hydrogen gas (flow rate of 2.5 l / m per 1 l of the inner volume of the second chamber)
In), the film was loaded into the second chamber, and the film was heated to 145 ° C. While maintaining that temperature,
Ultraviolet rays (wavelength: 330 nm, light intensity: 80 mW / cm ² ) were irradiated by an excimer lamp (irradiation time was 15
Equivalent to 0 seconds). The film carried out from the second chamber was wound into a roll and taken out from the vacuum system.

When the X-ray diffraction intensity of the obtained photo-annealed film was examined, a diffraction peak was measured at 2θ of 25.260, which was 4.2 times the peak value at the same position before the optical annealing. It was shown that the crystallinity became high.
As a result of examining the contact angle of the film, the contact angle was 2.9 °, and it was observed that the film had a strong hydrophilic surface. From this result, it was confirmed that the low-crystallinity titanium dioxide was changed to high crystallinity by the annealing treatment.

Example 3 In this example, the chamber for performing the first step (first chamber
-) And a chamber for performing the second step (second chamber),
A heating device for degassing, and the first chamber and the second chamber.
A looper, which is a means for storing the sheet base material, is
Then, an apparatus in which these are arranged in a common vacuum system was used.
205μm thick polycarbonate film with ITO
Place the rolls of the paper in a common vacuum system and rewind
Clean with a water bath and an acetone bath with sound waves, and then roll it again.
It was rolled up. After that, the vacuum degree of the common vacuum system
1.33 x 10 ^-3Pa (10^-FiveTorr), and then
While rewinding the sheet from the roll, the surface temperature of the sheet is 1
Heat the sheet from the back side to 70 ° C and put it in the looper.
Cool the seat by adjusting the loop length (looper
After a passage time of 1 minute), the film was rewound into a roll. Next, before
Rewind the sheet and carry out the first cham
Transport speed to move between the chamber and the second chamber.
I adjusted.

The sheet was conveyed into the first chamber adjusted to a vacuum degree of 3.99 × 10 ^-1 Pa (3 × 10 ^-3 Torr) using argon gas as a carrier gas, and the surface temperature of the sheet was adjusted to 161 ° C. While controlling, titanium dioxide in a low crystalline state having a film thickness of 150 nm was formed on the ITO film by the RF sputtering method. Next, the sheet on which the amorphous titanium dioxide was formed was evacuated in advance (3.99 × 10 ⁻¹ Pa (3 × 10 ⁻³ Torr), and then,
High-purity nitrogen gas atmosphere containing 2% by volume of hydrogen gas (flow rate of 50 ml / mi per 1 l of inner volume of the second chamber)
n), the sheet is loaded into the second chamber and adjusted to 15 sheets.
The mixture was heated to 0 ° C., and while maintaining the temperature, ultraviolet rays (wavelength: 172 nm, light intensity: 80 mW / cm ² ) were irradiated for 100 seconds by an excimer lamp. At this time, in the second chamber, the sheet base material did not move during the optical annealing process, while the sheet base material sent from the first chamber was stored by the looper. The sheet carried out from the second chamber was wound into a roll and taken out from the vacuum system.

About the titanium dioxide thin film before and after the annealing treatment, ultraviolet light (1 KWHg-Xe lamp, 365 nm,
110 mW / cm ² ) was irradiated, and the current-voltage characteristics (photoelectric conversion efficiency) at that time were examined. As a result, a photocurrent of 2.0 mA / cm ² per unit area could be observed in the ultraviolet light irradiation portion. The result is shown in Fig. 6.
Shown in. As is clear from FIG. 6, after the optical annealing,
The photocurrent density is remarkably increased, which proves that the crystallinity of the low crystalline titanium dioxide is increased by the photoannealing treatment. Furthermore, by X-ray diffraction, 2θ is 2
At 5.260, it was observed that the X-ray diffraction peak was about 3 times higher at d = 3.52Å. This indicates the anatase type (1, 0, 1) plane.

Reference Example 1 (Production of Color Filter) Using the sheet having the crystalline titanium dioxide thin film produced in Example 3 as a substrate for producing a color filter, a color filter was produced as follows.
As the electro-deposition device, a close-disposition type electro-deposition device was used. The ITO film of the substrate was used as a working electrode for electrodeposition. <Formation of Red Colored Film> A styrene-acrylic acid copolymer resin (weight average molecular weight 15,500, styrene / acrylic acid molar ratio 65:35, acid value 120) and a red ultrafine particle pigment are contained in a mass solid content. Resin / pigment = 1: 1 dispersed at a ratio of 6% by mass of solid content R (pH = 7.
8, conductivity = 7 mS / cm) was prepared.

As shown in FIG. 4, the substrate is arranged so that the photosemiconductor thin film is in contact with the electrodeposition liquid R, and the surface of the substrate on which the photosemiconductor thin film is not provided (hereinafter referred to as "rear face"). ) Was closely attached to the photomask for the red filter. The ITO film is used as a working electrode, and the bias potential difference of the working electrode is plus 1.7 V with respect to the saturated calomel electrode.
A voltage was applied to the ITO conductive film from the potentiostat so that Then, a mercury xenon lamp (made by Yamashita Denso Co., Ltd .: wavelength 36
When light was irradiated for 10 seconds at 5 nm: light intensity 50 mW / cm ² , a red pattern having a uniform thickness of 1.0 μm was formed only on the irradiated area (selected area) on the surface of the photosemiconductor thin film. .

<Formation of Green Colored Film> Electrodeposition was performed in the same manner as the red colored film except that the pigment was changed to a phthalocyanine green type ultrafine particle pigment and the resin / pigment (mass ratio) was 1: 0.7. Liquid G was prepared, a green colored film was formed in the same manner, and washed with pure water. A uniform green pattern having a film thickness of 1.0 μm was formed. <Formation of Blue Colored Film> Except that the pigment is changed to a phthalocyanine blue-based ultrafine particle pigment, an electrodeposition liquid B is prepared in the same manner as the red colored film, and a blue colored film is formed in the same manner, and pure water is added. Washed. A uniform blue pattern having a film thickness of 1.0 μm was formed.

<Formation of Black Matrix> Carbon black powder (average particle diameter 80 nm) was dispersed in the polymer material / carbon black = 1/1 in volume ratio in place of the pigment used for forming the red colored film, and solid Using an electrodeposition liquid K (pH = 7.8, conductivity = 8 mS / cm) with a partial concentration of 7% by mass,
Electrodeposition was performed in the same manner as in the case of forming the red film except that the entire surface was exposed for 10 seconds by the same exposure device without using a photomask, and a black matrix was formed in the region where the colored film was not formed. A high-resolution flexible color filter having a fine pixel pattern and excellent surface smoothness was obtained.

Reference Example 2 The electrodeposited substrate of Reference Example 1 was prepared by forming a 100-nm-thick ITO film on a 0.25-mm-thick polyether sulfone sheet, and crystallizing titanium dioxide on the ITO film in the same manner as in Example 3. Styrene, which is a polymer material having a crosslinkable group introduced, is used instead of the polymer material of each electrodeposition liquid (for red, green, blue and black matrix) of Reference Example 1 Acrylic acid / methacrylic acid 2-
(O- [1 ′ Methylpropylideneamino] carboxyaminoethyl) copolymer [molecular weight 13,000, styrene content 65 mol%, acid value 125, methacrylic acid 2- (O
-[1'-Methylpropylideneamino] carboxyamino) ethyl content 3.3 mol%] was used, except that the electrodeposition solution R, the electrodeposition solution G, the electrodeposition solution B and the electrodeposition solution K were used. In the same manner as in Example 4, red with a uniform thickness of 1.0 μm,
Green and blue colored films and a black matrix were formed on the substrate. <Baking> The substrate on which the colored film and the black matrix were formed was thermally crosslinked at 170 ° C. for 30 minutes. A flexible color filter consisting of fine pixel patterns, having high resolution, excellent surface smoothness and excellent solvent resistance was obtained. Polymer material of each electrodeposition liquid (for red, green, blue and black matrix) of Example 3 changed to a polyether sulfone having a substrate thickness of 0.25 mm provided with ITO having a thickness of 100 nm Was replaced with a styrene / acrylic acid / methacrylic acid ester copolymer [molecular weight 13,000 hydrophilic group / (hydrophilic group + hydrophobic group) molar ratio 65% #value 125,] which is a polymer material with a crosslinkable group introduced. Coloring of red, green and blue with a uniform thickness of 1.0 μm was performed in the same manner as in Example 3 except that the electrodeposition liquid R, the electrodeposition liquid G, the electrodeposition liquid B and the electrodeposition liquid K were used. The film and the black matrix were formed on the substrate. <Baking> The substrate on which the colored film and the black matrix were formed was thermally crosslinked at 170 ° C. for 30 minutes. A flexible color filter consisting of fine pixel patterns, having high resolution, excellent surface smoothness and excellent solvent resistance was obtained.

Reference Example 3 In this example, an example in which a color filter is manufactured using an electrodeposition apparatus (manufactured by Ushio Denki Co., Ltd.) equipped with a projection type exposure apparatus as shown in FIG. 5 is shown. . The electrodeposition substrate is the same as that used in Reference Example 1, and the electrodeposition liquid has the same composition as in Reference Example 2, and the electrodeposition liquid R, the electrodeposition liquid G, the electrodeposition liquid B and the electrodeposition liquid. K was used. In the projection type exposure apparatus of the electrodeposition apparatus (manufactured by USHIO INC.), The focal length between the imaging optical lens and the imaging surface (exposed surface of the photovoltaic compound thin film) is 15 mm, and the focal depth is ± 70 μm. did. The electrodeposition substrate was placed so that the titanium dioxide thin film was in contact with the electrodeposition liquid, and the exposure device was adjusted so that light was imaged on the imaging surface by the imaging optical lens.
Light intensity of irradiation ultraviolet ray (wavelength 365nm) is 90mW / c
In the same manner as in Reference Example 2, except that the irradiation time was changed to 5 seconds for m ² , the electrodeposition solution R, the electrodeposition solution G, the electrodeposition solution B, and the electrodeposition solution K were sequentially changed. As a result, a uniform R, G and B film having a film thickness of 1.0 μm and a black matrix were produced. However, when producing a black matrix, the entire surface was exposed from the back surface. Finally, baking was performed in the same manner to obtain a color filter.

[0072]

According to the present invention, since the step of forming an amorphous thin film and the step of converting an amorphous thin film into a crystalline thin film are carried out successively, various functional thin films suitable for the use of the crystalline thin film can be obtained. It can be easily manufactured.
In particular, in the process of converting an amorphous thin film into a crystalline thin film, the heating temperature can be set to a very low temperature, and it is not necessary to scan with laser light, and only the light irradiation device irradiates the entire surface with light. Therefore, compared to the conventional method, it is possible to manufacture a highly crystalline thin film in a short time without using an expensive and precise device, and the production cost can be reduced. Further, conventionally, a special process or apparatus was required to form a crystalline thin film on a plastic substrate, but according to the present invention, a simple and non-strict process and apparatus are used to form a plastic substrate on a plastic substrate. It became possible to fabricate highly crystalline thin films. In addition, conventionally, anti-fogging treatment, anti-fouling treatment, and
In order to perform a hydrophilic treatment, after forming an amorphous thin film, it is necessary to perform a baking treatment at 400 ° C. or higher in order to highly crystallize the amorphous thin film, which requires a heat resistance of the substrate and is an advanced and complicated method. Was there. By the method of the present invention, a substrate provided with a highly crystalline optical semiconductor thin film on a plastic substrate can be easily obtained, and therefore, by attaching this substrate to the surface requiring antifogging, antifouling and hydrophilic treatment. It has become possible to obtain a desired surface texture very easily. further,
You can make a TFT drive circuit on a plastic substrate,
Alternatively, it has become possible to form a color filter film by electrodeposition by further providing an electrodeposition substrate on which a compound thin film for photovoltaic generation is further provided. In particular, in the case of a color filter, the substrate is required to have a light-transmitting property, but since the heat-resistant temperature of a light-transmitting plastic substrate is only about 200 ° C., heat treatment at about 200 ° C. It is significant that a crystalline compound thin film having a sufficiently high photoelectric conversion efficiency (photoelectromotive force) can be formed. Therefore, it is expected to be applied to flexible display panels, which are required to be more and more lightweight.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing an example of an apparatus for carrying out the method of the present invention.

FIG. 2 is a diagram showing an example of a sheet base material on which a crystalline thin film is formed by the method of the present invention.

FIG. 3 is a diagram showing an example of a sheet substrate accumulating means used in the method of the present invention, in which (A) uses a multistage roll mechanism and (B) uses a dancer roll mechanism.

FIG. 4 is a conceptual diagram showing an example of an electrodeposition device used for a photoelectric deposition method.

FIG. 5 is a conceptual diagram showing another example of the electrodeposition apparatus used for the photoelectric deposition method.

FIG. 6 is a graph showing IV characteristics of titanium oxide before and after the optical annealing treatment.

[Explanation of symbols]

A sheet base material 10, 20 Thin film forming chamber 12, 22 Amorphous thin film forming means 30 Optical annealing chamber 14, 24, 34 Sheet base material temperature control means 32 light irradiation means 40 common vacuum system 50, 52 rolls 60 Discharge treatment means

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Keiji Shimizu             430 Sakai, Nakai-cho, Ashigarakami-gun, Kanagawa Prefecture             Kunakai Fuji Xerox Co., Ltd. (72) Inventor Kazutoshi Yata             430 Sakai, Nakai-cho, Ashigarakami-gun, Kanagawa Prefecture             Kunakai Fuji Xerox Co., Ltd. F-term (reference) 4G069 AA03 BA04A BA04B BA22B                       BA48A CA11 DA06 EA08                       EC22X EC22Y FB02                 4K029 AA11 AA25 BA48 BB08 BB10                       CA05 DC35 EA08 FA05 GA00                       JA10 KA03

Claims (21)

[Claims] 1. A first step of forming an amorphous or low crystalline thin film on a continuously conveyed sheet base material under vacuum or under low gas pressure atmosphere, forming a thin film under vacuum or under gas atmosphere The sheet base material
While maintaining the temperature above 50 ℃ and below 300 ℃,
A method for forming a crystalline thin film on a sheet base material, comprising a second step of irradiating the thin film formed in the first step with light having a wavelength absorbed by the thin film. 2. The gas used in the gas atmosphere of the second step is
Hydrogen gas, oxygen gas, carbon monoxide gas, nitrogen gas, methane gas, ethylene gas, ammonia gas, silane gas,
The method for forming a crystalline thin film on a sheet base material according to claim 1, comprising one or more kinds of phosphine gas and argon gas. 3. The crystalline thin film is formed on the sheet base material according to claim 1 or 2, wherein the wavelength of light in the second step is 3 times or less the film thickness of the thin film. Method. 4. The light source in the second step is light from an ultraviolet lamp, and the amorphous or low crystalline thin film is Si,
Ge, Ga, Zr, Ti, Zn, Bi, Ta, In, Sn, As, Al, P, S
The oxides, nitrides, carbides, and composite ceramics of b, Cd, Y, Nb, V, B, Ru, Re, and Mo are contained as a main component in one or a plurality of types. 4. A method for forming a crystalline thin film on the sheet base material according to any one of 3 above. 5. The sheet base material is a polymer base material, and the maintaining temperature is in a temperature range from 50 ° C. to a heat resistant temperature of the polymer base material. A method for forming a crystalline thin film on the sheet substrate according to any one of 1. 6. The glass transition point of the polymeric material contained in the sheet base material is in the range of 10 ° C. to 250 ° C., and the maintaining temperature is from 50 ° C. to the melting point or flow starting point of the polymeric material. It is in the temperature range.
A method for forming a crystalline thin film on the sheet base material according to claim 5. 7. The material of the sheet base material is polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone, polyether sulfone, polysulfone, polyether imide, polyether ketone,
7. One or more selected from the group consisting of polyphenylene sulfide, polyarylate, polyimide, polycarbonate, epoxy resin, polyolefin, and polyaramid.
A method for forming a crystalline thin film on the sheet substrate according to any one of 1. 8. The heat insulating and heat resistant thin film is provided between the sheet base material and the amorphous or low crystalline thin film, according to any one of claims 1 to 7. A method of forming a crystalline thin film on the sheet substrate according to the item. 9. The crystalline thin film on the sheet base material according to claim 1, wherein the amorphous or low crystalline thin film is a thin film containing an oxide as a main component. How to form. 10. The amorphous or low crystalline thin film is a thin film containing titanium oxide as a main component, which is formed by a sputtering method, according to any one of claims 1 to 9. A method for forming a crystalline thin film on a sheet substrate. 11. The crystalline thin film obtained after the second step is
A thin film containing microcrystalline titanium oxide as a main component or a thin film containing one or a mixture of two or more of anatase titanium oxide, rutile titanium oxide and amorphous titanium oxide as a main component. A method for forming a crystalline thin film on the sheet substrate according to any one of claims 1 to 10. 12. The method for forming a crystalline thin film on a sheet base material according to claim 1, wherein the light amount is controlled according to the temperature of the sheet base material. 13. The method for forming a crystalline thin film on a sheet base material according to claim 1, wherein the light irradiation is performed in a pulsed manner. 14. The sheet base material according to claim 1, wherein the sheet base material has a light-transmitting thin film, a semi-conductive thin film, a conductive thin film or a patterned film. Method for forming a conductive thin film. 15. The method for forming a crystalline thin film on a sheet base material according to claim 1, wherein the sheet base material is a continuous sheet base material. 16. The sheet base material according to claim 1, wherein the sheet base material is a discontinuous sheet that is placed and conveyed on a conveying member. Method for forming crystalline thin film on. 17. The sheet according to claim 1, further comprising a step of cleaning and / or degassing the sheet base material before the first step. A method for forming a crystalline thin film on a substrate. 18. The sheet substrate according to claim 1, wherein the cleaning and / or deaeration is performed by heat treatment and / or discharge treatment of the sheet base material. Method for forming crystalline thin film on material. 19. A first chamber for forming an amorphous or low crystalline thin film and a sheet base material of 50 to 300.
A second chamber for irradiating with light having a wavelength absorbed by the thin film while maintaining the temperature at 0 ° C .; and means for transporting the sheet base material in the first chamber and the second chamber in this order, The chamber of (1) comprises means for forming an amorphous or low crystalline thin film, means for maintaining the inside of the chamber in a vacuum or low gas pressure atmosphere, and a carry-in and carry-out section for the sheet base material. A means for maintaining the sheet base material at 50 to 300 ° C., a light irradiation means for irradiating light having a wavelength absorbed by the thin film, a means for holding the chamber in a vacuum or a gas atmosphere, and a carrying-in portion for the sheet base material. An apparatus used in the method for forming a crystalline thin film on the sheet base material according to claim 1, further comprising a carry-out section. 20. The apparatus according to claim 19, wherein the first chamber, the second chamber, and the means for conveying the sheet substrate are in the same vacuum system. 21. The same vacuum system is further provided with means for cleaning and / or degassing the sheet base material before carrying it into the first chamber.
Or the device according to claim 20.