JP2005062499A - Method for forming electrodeposition film and electrodeposition film forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming an electrodeposition film with excellent controlling property for film thickness by which growth of a film due to deposition of the electrodeposition component in an unexpected region is suppressed and a desired pattern can be formed with high definition at low cost. <P>SOLUTION: In a film forming substrate 5 having successive layers of a conductive film 2, a hydrophilic optical semiconductor thin film 3 having both of photocatalytic and photovoltaic functions, and a water repellent film 4 containing an organic material in contact with the optical semiconductor thin film 3, the optical semiconductor thin film 3 of the substrate 5 is selectively irradiated with light. After the water repellent film 4 in the selected irradiated region is removed to form a hydrophilic part 6, the hydrophilic part 6 is brought into contact with an aqueous electrolyte liquid containing a film forming material the solubility or dispersibility of which with an aqueous liquid decreases by changes in pH, and further the substrate is irradiated with light to form an electrodeposition film in the hydrophilic part 6. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrodeposition film forming method and an electrodeposition film forming apparatus, and is not based on a photolithographic process, and in particular, a color filter, a microlens, an optical circuit, etc. used in various display elements and color sensors such as a CCD camera and a liquid crystal display The present invention relates to an electrodeposited film forming method and an electrodeposited film forming apparatus suitable for producing a light guide used in the invention.

  The electrodeposition method is widely used as a method capable of forming a thin film with a uniform film thickness. However, for example, in the production of a color filter, a patterning step by photolithography is required such as forming a pre-patterned electrode. Since the pattern shape is limited and a high voltage of about 70V to 200V is required, there is a disadvantage that it cannot be applied to a substrate having TFTs. Therefore, as an electrodeposition method used in a method for manufacturing a color filter, research on an inexpensive method capable of directly forming a colored layer on a pixel electrode of a liquid crystal monitor drive substrate is underway.

  The inventors of the present invention have focused on a compound that is already water-soluble and whose solubility or dispersibility in an aqueous liquid decreases due to a change in pH, and by exposing the substrate to contact with an electrolytic solution containing the compound. Have proposed a photo-deposition technique (hereinafter also referred to as “photo-deposition method”) that can form a desired thin film pattern (see, for example, Patent Documents 1 and 2). In this photo-deposition method, an organic or inorganic optical semiconductor is used as a substrate, and this is irradiated with light in a pattern to partially change the pH at the optical semiconductor interface in the electrolytic solution, thereby depositing a polymer film. Form. Subsequently, when the substrate is pulled up from the electrolytic solution, the electrolytic solution adhering to the substrate due to surface tension or the like is washed with a low-pressure water flow that does not cause film damage, such as immersion in pure water or flowing water (for example, Patent Literature 3).

  The film formation technique based on the photo-deposition method does not require a photolithography process and can be formed at a low voltage. For example, in the case of a color filter, it has excellent transparency and color purity, and has a high-definition and complicated pixel pattern. The black matrix can be easily formed and the cost can be reduced. As a technology to meet the demand for higher resolution and higher resolution of video information and communication information in recent years, it is preferable in that stable production of color filters with high resolution and excellent pattern accuracy is possible and complicated. The cost reduction can be satisfied at the same time by a simple method that does not include a number of processes and has a small number of processes.

  However, in the photo-deposition method, the electrodeposition component deposited from the electrolytic solution due to the photocatalytic ability of the photo-semiconductor thin film also grows on the outer periphery of the pattern formed by irradiation with active light, and is completely removed even by washing. Cannot be removed (see, for example, Patent Document 4), the edge of the desired pattern shape is blurred, or the electrodeposition component deposited on the hydrophilic non-exposed photo-semiconductor thin film adheres to the desired The shape of could not be satisfied.

  On the other hand, there has been a report on a fine patterning formation technique using photocatalytic activity (see, for example, Patent Documents 5 to 7). That is, by applying a water-repellent substance on the surface of the photocatalyst film and irradiating with a desired pattern of active light, active oxygen having a very large oxidizing power is generated on the surface of the photocatalyst film, and organic substances in contact with this are oxidatively decomposed, A hydrophilic photocatalyst film is exposed in a desired pattern, and an aqueous ink is carried on the surface of the exposed photocatalyst film to obtain an image. The photocatalyst film is known to be amphiphilic, and an oil-based ink can be used to obtain an image by using an oil-repellent substance instead of a water-repellent substance.

In the above technique, the ink is supported from the reversibility of the amphiphilic photocatalyst film part and the water-repellent film part or the oil-repellent film part, and it is sufficient that a desired pattern is formed in the printing application. This is not taken into consideration, and the film thickness control is actually difficult.
Japanese Patent No. 3152192 Japanese Patent No. 3257474 JP 2002-317297 A JP 2002-317297 A JP-A-9-131914 JP 2000-343848 A JP 2000-280437 A

  As described above, when forming an electrodeposition film using an electrolytic solution containing a compound whose solubility or dispersibility in aqueous liquid decreases due to a change in pH, adhesion of the electrodeposition component to unnecessary portions is avoided, At present, an electrodeposition film forming technique that can effectively prevent the fineness of the edge from being lost and can also control the film thickness has not been established yet.

  The present invention has been made in view of the above, and an electrodeposition film by a photo-deposition method using an aqueous electrolyte solution containing a compound (film-forming material) whose solubility or dispersibility in an aqueous liquid decreases due to a change in pH. In the case of forming an electrodeposition film, the above-mentioned problem that the fineness of the pattern shape is impaired is solved, and a desired pattern can be formed with high definition and at low cost, and the electrodeposition film forming method having excellent film thickness controllability It is another object of the present invention to provide an electrodeposition film forming apparatus and to achieve the object.

Specific means for solving the above problems are as follows.
<1> The said optical semiconductor of the film | membrane formation board | substrate which has an electroconductive film, the hydrophilic optical semiconductor thin film which has a photocatalytic capability, and a photovoltaic capability, and the water-repellent film containing the organic material which touched this optical semiconductor thin film in order An image forming step of selectively irradiating the thin film with active light and removing the water-repellent film in a selected region of the irradiated optical semiconductor thin film to form a hydrophilic portion; and solubility or dispersion in aqueous liquid by changing pH In the state where the film-forming substrate is disposed so that at least the hydrophilic part is in contact with an aqueous electrolytic solution containing a film-forming material whose properties are lowered (hereinafter also simply referred to as “electrolytic solution”), An electrodeposition step of applying an voltage between the hydrophilic portion and the counter electrode by irradiating active light, and depositing the film-forming material on the hydrophilic portion to form an electrodeposited film. It is a forming method.

<2> In the image forming step, the hydrophilic layer is formed by decomposing the water-repellent film by photocatalytic action of the optical semiconductor thin film when irradiated with active light and washing and removing the decomposition product. It is an electrodeposition film forming method as described in <1>.
<3> The image forming step is the electrodeposition film forming method according to <1> or <2>, wherein the active light is selectively irradiated using a photomask.
<4> At least the conductive film is light-transmitting, and the image forming step and / or electrodeposition step is performed on the non-water repellent film-forming side of the film forming substrate (the water repellent film as viewed from the optical semiconductor thin film). Is the electrodeposition film forming method according to any one of <1> to <3>, wherein the active light is irradiated from the side on which no is provided;
<5> The electrodeposition according to any one of <1> to <4>, wherein the active light is selectively irradiated in a state where an inorganic substance is not adhered to the film surface of the water repellent film of the film forming substrate. This is a film forming method. A photomask is placed on the non-water repellent film-forming side of the film forming substrate, or laser irradiation is performed so that the surface of the water repellent film is exposed so that the oxidative decomposition of the water repellent film can be accelerated. Can be done.

  <6> The optical semiconductor of the film forming substrate, comprising a conductive film, a hydrophilic optical semiconductor thin film having a photocatalytic ability and a photovoltaic ability, and a water repellent film containing an organic material in contact with the optical semiconductor thin film in order. First irradiation means for selectively irradiating a thin film with active light and forming a hydrophilic portion in a selected region of the irradiated optical semiconductor thin film, and a film forming material whose solubility or dispersibility in aqueous liquid is lowered due to pH change An electrodeposition tank that contains an aqueous electrolyte solution containing the film, and a film deposition mechanism that includes an arrangement mechanism that arranges the film-forming substrate so that at least a hydrophilic portion formed by the first irradiation means is in contact with the aqueous electrolyte solution Means, second irradiation means for further irradiating the hydrophilic part of the film forming substrate disposed on the film forming means so that at least the hydrophilic part is in contact with the aqueous electrolyte, and the electrodeposition In contact with the aqueous electrolyte of the tank An electrodeposition electrode provided with a counter electrode that can be energized with the hydrophilic portion, and that applies a voltage between the hydrophilic portion and the counter electrode when irradiated by the second irradiation means. A film forming apparatus.

<7> The electrodeposition film forming apparatus according to <6>, further including a cleaning unit configured to clean the irradiated selected region after irradiation by the first irradiation unit.
<8> The electrodeposition film forming apparatus according to <6> or <7>, wherein the first irradiation unit further includes a mask unit that selectively irradiates or blocks active light.
<9> The electrodeposition film forming apparatus according to <8>, wherein the first irradiation unit is configured such that the mask unit is disposed on a water repellent film non-forming surface side of the film forming substrate.
<10> At least the conductive film is light transmissive, and the first irradiation unit and / or the second irradiation unit irradiates the active light from the water repellent film non-formation side of the film forming substrate. The electrodeposition film forming apparatus according to any one of <6> to <9>.

  <11> In any one of <6> to <10>, in place of the first irradiation unit and the second irradiation unit, an exposure unit also serving as the first irradiation unit and the second irradiation unit. This is an electrodeposition film forming apparatus. As a result, when irradiating a desired pattern with active light using a photomask, the same photomask and light source are used for irradiating to oxidatively decompose the water repellent film and to form an electrodeposited film. It is possible to reduce the cost by configuring the first irradiation means and the second irradiation means described above in the apparatus configuration as a single exposure means that also serves as these. In addition, when the first irradiation means includes a decomposition treatment tank as described later, the aqueous liquid contained in the tank can be used as an electrodeposition tank instead of the electrolytic solution.

  According to the present invention, when an electrodeposition film is formed by a photo-deposition method, film growth due to adhesion of an electrodeposition component to an unplanned region is suppressed, and a desired pattern can be formed with high definition and at low cost. It is possible to provide an electrodeposition film forming method and an electrodeposition film forming apparatus that can form a film and have excellent film thickness controllability.

[Electrodeposition film forming method]
The electrodeposition film forming method of the present invention comprises an image forming step of selectively removing a water-repellent film on a film-forming substrate to form a hydrophilic portion in an image-like manner, and the formed hydrophilic portion (that is, exposing an optical semiconductor thin film). And an electrodeposition step of forming an electrodeposition film by depositing a film forming material on the part). In addition, the decomposition product decomposed and generated in the image forming process is washed or removed, or the unnecessary electrolytic solution adhering in the electrodeposition process is washed and removed, or the drying process for drying the film forming substrate, etc. Other processes may be provided as appropriate.

-Substrate for film formation-
First, the film forming substrate will be described in detail. The film forming substrate according to the present invention is formed by sequentially laminating a conductive film, an optical semiconductor thin film, and a water-repellent film in contact with the optical semiconductor thin film (in some cases, from the substrate side on an insulating substrate). It is a thing. As the conductive film, ITO, indium oxide, nickel, aluminum, copper, and the like are suitable, and the conductive film can also be configured to have a supporting function as described later (see FIG. 1- (b)). . Further, as the optical semiconductor thin film, a titanium oxide thin film as described below is suitable, and as the water repellent film, a compound as described below is suitable which has water repellency and can be decomposed by the photocatalytic ability of the adjacent optical semiconductor thin film. It is. In addition, a glass plate, a quartz plate, a plastic film, an epoxy substrate, or the like is preferable as the substrate in the case where an insulating substrate (hereinafter also referred to as “insulating substrate”) is provided.

  When light is irradiated from the non-water repellent film-forming side of the film forming substrate, that is, when light is irradiated to the optical semiconductor thin film through the conductive film and possibly the insulating substrate, the conductive film and the insulating substrate transmit light. Conversely, when light is irradiated to the optical semiconductor thin film through the electrolytic solution, the water repellent film needs to be light transmissive, and the conductive film and the insulating substrate are not necessarily light. It need not be permeable.

  FIG. 1 shows a configuration example of a film forming substrate according to the present invention. In FIG. 1- (a), a film forming substrate 5 is configured by sequentially laminating a conductive film 2, an optical semiconductor thin film 3, and a water repellent film 4 on an insulating substrate 1 from the insulating substrate 1 side. It is a thing. Further, unlike the film forming substrate 5 ′ shown in FIG. 1- (b), the optical semiconductor thin film 3 and the water repellent film 4 are formed on the conductive film 2 that also serves as a support function without providing an insulating substrate. It can also be configured by sequentially stacking.

Next, the optical semiconductor thin film according to the present invention will be described.
As the optical semiconductor thin film, basically, any thin film semiconductor having hydrophilicity (preferably transparent) having photocatalytic action by light irradiation and generating electromotive force by light irradiation can be used. . The hydrophilicity here refers to a property that is more familiar with water and easier to get wet with the water-repellent film, and can generally be expressed as a contact angle with water. In the present invention, the contact angle particularly during light irradiation. Is a state of 20 ° or less. Specific examples include TiO ₂ (titanium oxide) and ZnO. Among these, titanium oxide has an absorption of only 400 nm or less, is transparent, and can easily form an n-type semiconductor. Therefore, it can be used as it is as a substrate for manufacturing an optical device.

  Methods for providing a titanium oxide semiconductor thin film include thermal oxidation methods, sputtering methods, electron beam evaporation methods (EB methods), ion plating methods, sol-gel methods, etc., and these methods can be used as an n-type semiconductor. Good one is obtained.

  However, when it is provided on a material having low heat resistance such as a plastic film, it is necessary to select a film forming method that does not adversely affect the plastic film. Although the sol-gel method can form titanium oxide with high optical activity as an optical semiconductor, it needs to be sintered at 500 ° C., so a titanium oxide film is formed on a plastic film substrate having only heat resistance of about 200 ° C. It is difficult. Therefore, when a plastic film substrate is used, it is possible to form a film at a temperature as low as possible, preferably at 200 ° C. or less, and a sputtering method, particularly an RF sputtering method, which is a film forming method with relatively little damage to the substrate. Preferably used. The RF sputtering method is also preferable from the viewpoint that an anatase-type titanium oxide thin film having high optical activity can be obtained (the electron beam method and the ion plating method are not preferable because the substrate is heated at around 200 ° C.).

Next, the water-repellent film according to the present invention will be described.
The water-repellent film can be used as long as it basically has water repellency and is decomposed by the photocatalytic ability (photocatalytic action) of the optical semiconductor thin film. The water repellency herein refers to a property that exhibits a water repellency that reduces the wettability of the aqueous electrolyte solution and makes it difficult for the film-forming material deposited in the electrodeposition process to adhere to it. In the present invention, the contact angle is 70 ° or more. For example, when an optical semiconductor thin film is composed of titanium oxide, the contact angle of titanium oxide when it is not irradiated is usually about 65 °, but it becomes hydrophilic when irradiated with ultraviolet light, and further, a water repellent film (contact angle of 70 ° C. or more). By laminating, it is possible to provide a large difference in hydrophilicity between the titanium oxide surface and the water repellent film surface during light irradiation.

The water-repellent film is composed mainly of an organic material. Examples of the organic material include saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid. Suitable examples include unsaturated fatty acids such as linolenic acid.
Examples of the method of providing the water repellent film include a spin coating method and a coating method using a nozzle. A uniform water repellent film can be obtained by these methods.

  Among these, caproic acid, caprylic acid, oleic acid, linoleic acid, and linolenic acid are preferable because they are liquid at room temperature and film formation by the spin coating method is easy. Furthermore, in view of the oxidative degradation due to the photocatalytic function of the optical semiconductor thin film described later, saturated fatty acids and unsaturated fatty acids having a relatively short straight chain and few double bonds are preferred, and caproic acid, caprylic acid, and oleic acid are particularly preferred. Is preferred.

  The thickness of the water repellent film is preferably in the range of 2 nm to 10 μm. When the film thickness is less than 2 nm, an electrodeposited film grown on the water-repellent film on the outer periphery of the portion where the water-repellent film has been removed by oxidative decomposition (that is, the hydrophilic portion) is oxidized and decomposed. However, if it exceeds 10 μm, it takes a long time for the oxidative decomposition of the water-repellent film, which may reduce the production efficiency. More preferably, it is 10 nm-1 micrometer. Within this range, the growth of the electrodeposited film on the water-repellent film is particularly small, and the water-repellent film can be oxidatively decomposed in a relatively short time. Can be formed.

-Image formation process-
In the image forming step, a water-repellent material containing a conductive film, a hydrophilic photo-semiconductor thin film having photocatalytic ability and photovoltaic ability, and an organic material in contact with the photo-semiconductor thin film (in some cases, from the substrate side to an insulating substrate) And selectively irradiating the photo-semiconductor thin film with active light on the film-forming substrate having a film sequentially, thereby removing the water-repellent film in the selected region of the photo-semiconductor thin film selectively irradiated. The hydrophilic part which the thin film exposed is formed.

  In the image forming process, when active light is selectively irradiated in a desired pattern onto the optical semiconductor thin film, the water repellent film is oxidized and decomposed in the selectively irradiated region (selected region) by the photocatalytic action of the optical semiconductor thin film. Therefore, the water-repellent film belonging to the selected region is removed, and an optical semiconductor thin film having higher hydrophilicity than the water-repellent film appears. The oxidative decomposition is preferably performed in a state where the optical semiconductor thin film is in contact with an aqueous liquid. In the process of oxidative decomposition of the water-repellent film, a decomposition product can be generated, but particularly when titanium oxide suitable for the present invention is used as an optical semiconductor thin film, when oxidative decomposition is performed in contact with water, Due to the superhydrophilic function of titanium oxide, water is adsorbed to the titanium oxide, causing the decomposition products to float, and the water-repellent film in the selected region irradiated with active light can be quickly removed. The aqueous liquid is water or a mixed liquid of water and a hydrophilic organic solvent.

  The oxidative decomposition means that an active light is irradiated onto a photo-semiconductor thin film having photocatalytic activity (photocatalytic action) to form a pair of electrons and holes on the thin film. It means that the water repellent film which is an organic substance existing in the vicinity is oxidized and decomposed. This oxidizing power is very strong and it is possible to oxidize almost all organic substances to the final product. Further, when the surface of the optical semiconductor thin film is brought into contact with water, the water is captured as hydroxyl radicals (OH). Since OH is so-called active oxygen and has a property of being very easily reacted with other substances, the decomposition of the water-repellent film is further promoted. On the other hand, when an inorganic material such as a photomask is brought into close contact with the side of the film forming substrate on which the water repellent film is provided, and an active light is irradiated from the water repellent film side through the photomask to the active semiconductor thin film, the inorganic photo When the mask is in close contact, the oxidative decomposition of the water-repellent film is inhibited, and active oxygen is not generated.

  Moreover, said superhydrophilic function means that the said OH has the property which is easy to become familiar with water. This property promotes the removal of the water-repellent film by forming a water film between decomposition products formed by oxidizing the water-repellent film. However, in the process of oxidative decomposition, decomposition products may adhere with a water film in between, and if photodeposition is performed as it is, there is a high possibility that it will be incorporated into the electrodeposition film. Since the fineness is lost, as described later, it is more preferable to perform cleaning so as not to damage the electrodeposition film during the formation of the water-repellent film or the electrodeposition film.

-Washing process-
A cleaning step can be provided as necessary between the image forming step and the electrodeposition step described later and after the electrodeposition step described later. As described above, when decomposition products are attached with a water film in the process of oxidative decomposition, or when unnecessary electrolytic solution is attached to the film-forming substrate after photodeposition due to surface tension, etc. It is desirable to wash the electrodeposition film so that the final electrodeposition film does not lack fineness, is damaged by the impact pressure applied, or does not dry and adhere.

  Examples of the cleaning method include immersion in pure water or other aqueous liquids, flowing water, and a method of jetting or jetting aqueous liquids or humidified air. Preferably, the aqueous liquid or humidified air is applied to a low pressure of 0.01 to 1000 KPa. It is possible to remove the decomposition products and the electrolytic solution adhering to the film forming substrate using a nozzle by supplying pressure. Details thereof are described in JP-A No. 2002-317297.

-Electrodeposition process-
In the electrodeposition step, the film-forming substrate is placed so that at least the hydrophilic part formed in the image forming step is in contact with an aqueous electrolyte solution containing a film-forming material whose solubility or dispersibility in aqueous liquid decreases due to a change in pH. In the placed state, the hydrophilic portion is further irradiated with active light to apply a voltage between the hydrophilic portion and the counter electrode, and a film forming material is deposited on the hydrophilic portion to form an electrodeposition film. Specifically, the electrodeposition film is disclosed in JP-A-10-119414, JP-A-11-189899, JP-A-11-15418, JP-A-11-174790, JP-A-11-133224, It is formed using the photo-deposition method described in Kaihei 11-335894.

  The photo-deposition method uses a photovoltaic force generated in an optical semiconductor thin film, and a film-forming substrate is applied to an aqueous electrolyte containing a film-forming material whose solubility or dispersibility in an aqueous liquid is lowered by changing pH. By irradiating light to the optical semiconductor thin film (hydrophilic portion) in a state where the optical semiconductor thin film (that is, the hydrophilic portion) is in contact with the electrolytic solution, the optical semiconductor thin film (hydrophilic portion) is irradiated between the optical semiconductor thin film and the counter electrode. In this method, a film forming material is deposited on the optical semiconductor thin film (hydrophilic portion) by applying a voltage. This photo-deposition method is characterized in that a film having a uniform film thickness can be accurately formed at a low voltage (5 V or less) as compared with the conventional electrodeposition method.

(Aqueous electrolyte)
The aqueous electrolytic solution used in the photo-deposition method according to the present invention has at least a change in pH, that is, the solubility or dispersibility in an aqueous liquid is lowered due to the change in pH, and is deposited on the optical semiconductor thin film from the electrolytic solution. Includes film-forming material to be deposited. If one or more kinds of film forming materials have such a film forming property, even when various refractive index control materials (which will be described later) having no film forming ability alone are dispersed in the electrolytic solution, Then, it is taken into the film-forming material and fixed in the electrodeposition film.

  As the aqueous electrolyte solution, a coloring material (dye or the like) having electrodeposition properties as a film-forming material itself is dissolved in an aqueous liquid (water or a mixture of a hydrophilic organic solvent and water). A dispersed material or a film-forming material in which an electrodepositable polymer material is dispersed together with a colorant that does not have electrodeposition by itself can be used. In the latter, when the polymer material aggregates and precipitates to form a film, it is taken into the film and colors the film. “Electrodeposition” as used herein means that a colorant or a polymer material precipitates due to a decrease in solubility or dispersibility in the electrolyte due to a change in pH of the electrolyte accompanying application of an electric current or electric field to the electrolyte. Means that.

Examples of the dye (film forming material) whose solubility or dispersibility is lowered by changing the pH condition include ionic dyes. Further, an ionic dye and a pigment can be used in combination.
Examples of ionic dyes include triphenylmethane phthalide, phenosadine, phenothiazine, fluorescein, indolylphthalide, spiropyran, azaphthalide, diphenylmethane, chromenopyrazole, leucooramine, azomethine, Rhodamine lactal, naphtholactam, triazene, triazole azo, thiazole azo, azo, oxazine, thiazine, benzthiazole azo, quinoneimine dyes, and hydrophilic with carboxyl, amino, or imino groups Sexual dyes and the like.

  As an acidic dye, for example, Pro Jet Farst Yellow 2 manufactured by Zeneca is easily dissolved in pure water (pH 6 to 8) and exists as an anion in an aqueous solution, but becomes insoluble and precipitates when the pH is 6 or less. Has properties. At pH 4 or higher, it takes a reduced state and dissolves in water, but in the region below pH 4, it is oxidized and becomes a neutral state. And pigment materials having carboxyl groups whose solubility varies greatly depending on the hydrogen ion concentration (pH) of the solution (specifically, water-resistant improved inkjet dyes that dissolve in water at pH 6 or higher but precipitate below it). .

  Some basic dyes have amino groups or derivatives thereof. One of the quinoneimine dyes is an oxazine-based basic dye, Cathilon Pure Blue 5GH (CIBasic Blue 3), and a thiazine-based basic dye, methylene blue. (CIBasic Blue 9), and these are in an oxidized state and develop color when the pH is 10 or less, but are reduced and insolubilized and precipitated when the pH is higher. Other basic dyes include Victoria Bull-B and Rhodamine 6G.

  In addition, as a coloring material that does not have electrodeposition itself but is dispersed in an aqueous liquid together with an electrodeposition polymer material, a known pigment such as red, green, and blue can be used without any particular limitation. However, the smaller the pigment particle size, the better the hue reproducibility. In the case of producing a color filter, from the viewpoint of transparency and dispersibility of the color filter layer, the average particle diameter of the pigment is particularly preferably 200 nm (0.2 μm) or less, and 100 nm (0.1 μm) or less. Is preferred. In addition, as the colorant for the color filter, the present inventors also use the colorants described in JP-A-11-105418 and JP-A-11-157198 as materials suitable for the photo-deposition method. Can do.

  Electrodepositable polymer materials (film-forming materials) whose solubility or dispersibility in aqueous liquids decreases due to changes in pH have a group that ionically dissociates from a unit having a hydrophobic group (hydrophobic unit) A copolymer containing a unit (ion dissociation unit) from a monomer and having a hydrophobic unit ratio of 55 to 70% with respect to the sum of the hydrophobic unit and the ion dissociation unit is preferable. Examples of the ion dissociating group include a carboxyl group, an amino group, a sulfo group, and a quaternary ammonium group.

  Preferred electrodepositable polymer materials include, for example, 1) one or more monomers (monomers having a hydrophobic group) selected from alkenes, styrene and derivatives thereof, and vinylnaphthalene and derivatives thereof, and 2) acidic groups capable of ion dissociation. A copolymer containing each constitutional unit from one or more monomers containing is preferably used. In addition to the above-mentioned monomers, other monomers, for example, a copolymer containing each structural unit from one or more of α, β-ethylenically unsaturated carboxylic acid alkyl ester (other monomers) are preferably used.

Units composed of monomers selected from alkene, styrene and derivatives thereof, and vinyl naphthalene and derivatives thereof, which are monomers of 1), are highly hydrophobic and strongly adsorb pigment fine particles to stabilize pigment dispersion. Further, the structural unit contributes to the water resistance of the formed image due to its hydrophobicity, and also gives the image portion fastness. Furthermore, the structural unit also affects the suppression of the ion dissociation function of the monomer containing an acidic group capable of ion dissociation of the copolymer.
Alkenes preferably have about 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and may have other substituents as long as the hydrophobicity is not significantly impaired.
Styrene and its derivatives include styrene, α-methyl styrene, α-ethyl styrene, and those in which the benzene ring of these styrene and its derivatives is substituted with a substituent that does not significantly impair the hydrophobicity, or further increases the hydrophobicity. Can be mentioned. Examples of vinyl naphthalene and derivatives thereof include vinyl naphthalene, vinyl naphthalene in which the naphthalene ring is substituted with a substituent that does not greatly impair the hydrophobicity or a substituent that further increases hydrophobicity.
Among them, alkenes, styrene and derivatives thereof are useful hydrophobic monomers having high controllability during the production of the copolymer.

  The constitutional unit from the monomer containing an acidic group capable of ion dissociation, which is the monomer of 2), has a function of dissolving the copolymer in an alkaline aqueous medium, and the monomer includes α, β-ethylenic monomers. Unsaturated carboxylic acid is mentioned preferably, for example, methacrylic acid, acrylic acid, maleic anhydride or its monoester, fumaric acid or its monoester, itaconic acid or its monoester, crotonic acid and the like. In particular, methacrylic acid and acrylic acid are preferable from the viewpoint of the above functions.

  The structural unit from the α, β-ethylenically unsaturated carboxylic acid alkyl ester, which is another monomer, is a component that imparts flexibility to the copolymer. The alkyl group of the α, β-ethylenically unsaturated carboxylic acid alkyl ester preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. For example, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and butyl methacrylate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, maleic acid esters such as dimethyl maleate and diethyl maleate And fumaric acid esters such as dimethyl fumarate and diethyl fumarate.

  Further, when a monomer having a crosslinkable group is further added to the monomer as described above, the strength and heat resistance of the film can be improved. Examples of the monomer having a crosslinkable group include glycidyl (meth) acrylate, (meth) acrylic acid azide, 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Showa Denko K.K. Product name: Karenz MO1-BN), 4-((meth) acryloyloxymethyl) ethylene carbonate, (meth) acryloylmelamine, and the like. Although these crosslinkable monomers differ depending on the type of monomer used, they are generally contained in an electrodepositable polymer compound in an amount of 1 to 20 mol%.

  The copolymer obtained from the monomers 1) and 2) can be obtained by changing the pH of the liquid, and then passing the supernatant through a well-dissolved state (homogeneous transparent solution) to a cloudy state (transient state from dissolution to precipitation). This results in precipitation (two-layer separation), but the copolymer has a specific structural unit in addition to an acidic group, so the pH region where the cloudy liquid is generated is narrow, and the transition from a well-dissolved state to precipitation is steep. is there. Therefore, even when the pH is lowered slightly, that is, even when a minute voltage is applied, the solubility of the copolymer is drastically reduced, and an electrodeposited film is deposited.

  The precipitation phenomenon that causes a supernatant from a dissolved state of an electrodepositable polymer material such as a copolymer or the like is such that the amount of change in pH is within 2 and preferably within 1.0. When the amount of pH change is within 2, the film can be deposited instantly even when the pH changes sharply, the cohesive force of the deposited film is high, and the re-dissolution rate in the electrolyte is reduced. Is excellent. On the other hand, when the ratio is larger than 2, the film deposition speed for obtaining a sufficient thin film structure is decreased, and the water resistance of the film is insufficient (resulting in a decrease in resolution).

The pH characteristics of the copolymer can be evaluated by an “EQCM method” which is an electrochemical phenomenon analysis method. The EQCM measuring device stores a copolymer solution whose pH characteristics are to be measured in a container, and a sensor (having a crystal resonator and a working electrode), a counter electrode and a reference electrode are placed in the solution, and voltage is applied to these. It is connected to the apparatus, and the applied voltage applied between the counter electrode and the working electrode is changed to examine the change in the amount of the copolymer deposited on the working electrode.
In addition to the phenomenon of precipitation in the copolymer solution that causes a supernatant from a well-dissolved state to occur even if the amount of pH change is small, the once precipitated copolymer maintains its precipitation state despite the increase in pH. Thus, it is preferable not to redissolve, that is, to exhibit hysteresis characteristics. What shows this characteristic is that, in the change of applied voltage-copolymer adhesion amount by the EQCM method, even when the hydrogen ion concentration is slightly increased, the copolymer film is rapidly deposited (for example, on the +1.8 V anode electrode). ) And the hydrogen ion concentration of the liquid is lowered (for example, when the voltage is decreased from +1.0 V to +0.2 V), or the pH is changed to a higher hydroxyl ion concentration range (for example, −0. Even when the voltage is increased from 5 V to -1.5 V), the copolymer film deposited on the anode electrode is maintained without being dissolved.
The copolymer suitable in the present invention has the above-described structural units, and thus exhibits hysteresis characteristics, which greatly contribute to the production of fine patterns with high accuracy. When the acidic group of the copolymer is a carboxyl group, the contribution to this hysteresis characteristic is large.

  Further, the pH of the electrolytic solution containing the copolymer having such hysteresis characteristics is preferably from 0.5 to 4 from the pH point (white turbidity starting pH point) at which the supernatant is generated from the dissolved state and precipitation occurs. It is preferable to be in the pH range higher than 0.0, more preferably in the pH range higher than 1.0 to 3.0.

  As the degree of polymerization of the polymer material used as the film forming material, a range of 6,000 to 25,000 is preferable from the viewpoint of obtaining good film forming performance. Moreover, More preferably, it is 9,000-20,000. If the degree of polymerization is lower than 6,000, it may be easily re-dissolved, and if it is higher than 25,000, solubility in an aqueous liquid may be insufficient, and the liquid may become cloudy or precipitate may be formed. .

  In addition, the acid value of the polymer material used as the film forming material is preferably in the range of 60 to 300 from the viewpoint of obtaining good film forming characteristics. The range of 90-195 is more preferable. If the acid value is less than 60, the solubility in an aqueous liquid becomes insufficient, the solid content concentration of the electrolytic solution cannot be increased to an appropriate value, the liquid becomes cloudy or precipitates are formed, and the liquid viscosity is low. If it exceeds 300, the formed film may be easily dissolved again.

  A polymer material having hysteresis characteristics can be obtained by appropriately adjusting the type of hydrophilic group and hydrophobic group, the balance between hydrophilic group and hydrophobic group, acid value, molecular weight, and the like. The polymer material contained in the electrolytic solution according to the present invention can be composed of any combination of the above materials as long as the thin film formability is not impaired, and can be the same as a mixture of two or more types of anionic molecules. Mention may be made of mixtures of polar molecules or mixtures of heteropolar molecules such as mixtures of anionic and cationic molecules.

(Refractive index)
Next, the refractive index control at the time of depositing the electrodeposition film will be described.
The electrodeposition film may be composed only of a film-forming material such as the above-mentioned electrodepositable polymer material. In this case, since the refractive index is about 1.4 to 1.6, the microscopic refractive index is higher. In order to obtain a lens array, in addition to the polymer material, inorganic electrolyte fine particles (refractive index control material) having a high light refractive index are dispersed in the electrolyte, and the film itself is deposited together with the polymer material. It is also possible to control the refractive index.

As the inorganic oxide fine particles, those having a refractive index of about 1.8 to 2.8 are preferably used. For example, TiO ₂ , ZnO, ZrO ₂ , ITO and the like can be used. Rutile-type titanium oxide fine particles are preferred because they have a large refractive index control range and high stability. Moreover, when obtaining a low refractive index, a fluorine compound typified by magnesium fluoride can be preferably used. The number average particle diameter of the inorganic oxide fine particles is preferably from 0.2 to 150 nm, more preferably from 2 to 20 nm, from the viewpoint of dispersibility in the electrolytic solution and transparency of the electrodeposition film. When the number average particle diameter is less than 0.2 nm, the production costs of the fine particles and the electrolyte solution may increase, and it may be difficult to stabilize the quality. Since it exceeds 1/10 of 1.5 μm which is a band, the loss of transmitted light and internal diffuse reflection may be caused and the transmitted light loss may increase. The amount of addition is appropriately determined in consideration of the refractive index required for an optical component such as a microlens array and the mechanical strength of the optical component. It is also possible to change the refractive index of the polymer by attaching a substituent to the film-forming polymer material.

(conductivity)
The conductivity of the electrolyte is related to the deposition speed, in other words, the amount of deposition, and the higher the conductivity, the thicker the film deposited in a given time and saturates at about 20 mS / cm. . Therefore, when the electrical conductivity is insufficient with the polymer material alone, the deposition speed can be controlled by adding ions that do not affect the deposition, such as NH ₄ ⁺ ions or Cl ⁻ ions. Usually, the electrolytic solution increases the conductivity by adding a supporting salt. Supporting salts generally used in the field of electrochemistry include alkali metal salts such as NaCl and KCl, and tetraalkylammonium salts such as ammonium chloride, ammonium nitrate, and tetraethylammonium perchlorate (Et ₄ NClO ₄ ). These supporting salts can also be used in the present invention.

(PH)
Naturally, the pH of the electrolyte also affects the formation of the thin film. For example, if the film is deposited under the condition that the solubility of the film-forming molecule is saturated before the film is deposited, it is difficult to redissolve after the thin film is formed. However, when the film is formed at the pH of the unsaturated solution, even if a thin film is formed, the film starts to redissolve as soon as light irradiation is stopped. Therefore, since it is desirable to form the thin film at a pH of the solution that saturates the solubility, it is possible to adjust the electrolyte using acid or alkali at the desired pH.

In particular, in the photo-deposition method, as described above, a film can be formed at a low voltage by considering the relationship between the pH of the electrolytic solution and the deposition start point, or by using an electrolytic solution having hysteresis characteristics.
In ordinary electrodeposition coating, an applied voltage of 70 V or more is applied, and the pH of the electrolyte is set to be considerably higher than the deposition start point of the electrodeposition material, thereby causing an irreversible reaction based on the Kolbe reaction on the electrodeposition substrate. Film formation is performed. However, in the formation of such a high voltage film, bubbles are generated, resulting in non-uniform electric field distribution on the electrode surface, non-uniform film quality, and irregularities on the film surface due to bubble defoaming. Or a fine pattern with good resolution and smoothness cannot be formed with good reproducibility. On the other hand, in this case, even if the voltage is simply lowered, the film re-dissolves immediately when the voltage application is stopped, and a fine pattern with good resolution cannot be formed. On the other hand, by using the electrolytic solution having the above characteristics, there is an advantage that it easily deposits even when a low voltage is applied and does not immediately re-dissolve even when the voltage application is stopped. The voltage application referred to here means the sum of the photovoltaic voltage generated in the optical semiconductor thin film by light irradiation or the bias voltage supplementarily added thereto. The applied voltage is preferably 9 V or less, more preferably 5 V or less. In the case where a film can be formed only by photovoltaic power, it is not necessary to apply a bias voltage. Depending on the semiconductor to be used, when a bias voltage higher than the voltage depending on the semiconductor band gap is applied, there is a problem that the Schottky barrier between the semiconductor and the solution necessary for the formation of photovoltaic power is broken, There is a limit to the bias voltage that can be applied.

  Although the electrodeposition film forming method of the present invention is based on the photo-deposition method, the film thickness obtained by the photo-deposition method corresponds to the amount of light irradiated to the optical semiconductor thin film. The selected region (hydrophilic portion) of the optical semiconductor thin film is irradiated with a predetermined adjusted amount of active light so that a film thickness corresponding to the cross-sectional shape can be obtained.

The selective irradiation of light to the optical semiconductor thin film can be performed by light irradiation through a photomask or laser light irradiation.
For example, in the case of forming a microlens, when light is irradiated through a photomask in which each portion through which light is transmitted (hereinafter referred to as an opening) is circular, the light irradiated on the optical semiconductor thin film. The intensity of the portion corresponding to the circumferential edge and the portion corresponding to the central portion of each opening of the photomask is less light intensity than the portion corresponding to the central portion. A difference in exposure intensity occurs in each pattern. Therefore, even in the photovoltaic power generated in the optical semiconductor thin film, a difference occurs in the photovoltaic power between the portion corresponding to the circumferential edge portion and the portion corresponding to the central portion, and the corresponding film thickness is generated. . That is, the obtained film pattern has a circular planar shape, and a lens-like film is formed in which the film thickness in the cross-sectional shape decreases toward the periphery of the circle.

  In the photomask, the shape or curvature of each lens cross section can be freely controlled by providing gradation so that the intensity of light transmitted through the opening decreases from the center of the opening to the periphery of the circle. For example, a minute dot that does not transmit light is formed in the opening of the photomask, and at this time, the light intensity passing through each opening is directed from the center to the periphery by decreasing the density of the dots from the periphery to the center of the opening. This can be done by a method of decreasing. At that time, the distribution of the dot density can be adjusted so that a film thickness corresponding to the curvature of the lens is formed. Further, when selective light irradiation to the optical semiconductor thin film is performed with laser light, the film thickness corresponding to the lens shape or curvature is formed when the laser light irradiation intensity is desired, particularly when forming a microlens array. By irradiating in such a manner, it is possible to control so as to obtain a microlens array having a set lens shape or curvature. In this case, the laser light has an intensity distribution that changes according to a predetermined lens shape pattern, for example, a Gaussian beam of laser light, that is, a laser light beam whose light intensity decreases from the center to the periphery of the beam as it is. A target lens-shaped pattern can be obtained.

  When a photomask is used for light irradiation when forming an electrodeposition film having a uniform thickness, light irradiation for removing the water-repellent film by oxidative decomposition and light for forming the electrodeposition film Irradiation can be performed using the same photomask and light source, which is economical because it is not necessary to prepare a photomask or light source individually.

In the electrodeposition process, water evaporates from the liquid surface of the electrolytic solution, and solids such as polymer compounds are deposited on the liquid surface and adhere to the substrate to form residues, or the solids are taken into the formed film. In rare cases, it may cause inconveniences such as preventing the formation of a uniform film. Therefore, it is preferable to maintain the relative humidity in the vicinity of the electrolyte surface at 50% or more. Furthermore, during the deposition of the electrodeposited film, the electrolyte may dry and adhere near the contact portion on the side in contact with the electrolyte, and a thin, narrow strip-like dry residue may remain. In this case, it is possible to cut the side part, but since the cost increases as the cutting process is added, it is possible to increase the relative humidity in the vicinity of the part in contact with the electrolytic solution of the film forming substrate. preferable. In this case, it is preferable to keep the relative humidity at 70% or higher in consideration of preventing the generation of dry residue.
That is, for example, when further cleaning is performed after the electrodeposition film is formed, the relative humidity in the vicinity of the film-forming substrate is consistent from at least immediately before the electrode-coated film-formed substrate is pulled up from the electrolyte until the cleaning is completed. Therefore, it is preferable to keep it at 50% or more. Furthermore, by maintaining the ratio at 70% or more, it is possible to effectively prevent the formation of a narrow strip-like residue on the side of the substrate.

[Electrodeposition film forming device]
The electrodeposition film forming apparatus according to the present invention provides active light on the optical semiconductor thin film of the film forming substrate, which has the conductive film, the hydrophilic optical semiconductor thin film, and the water-repellent film in contact with the optical semiconductor thin film. A first irradiation means for image-forming a hydrophilic portion from which the water-repellent film is removed in a selected region of the irradiated optical semiconductor thin film, an electrodeposition bath containing an aqueous electrolyte, and at least A film forming means having an arrangement mechanism for disposing a film forming substrate so that the hydrophilic portion formed by the first irradiation means is in contact with the aqueous electrolyte, and at least the hydrophilic portion is in contact with the aqueous electrolyte. A second irradiating means for further irradiating the hydrophilic portion of the film forming substrate disposed on the film forming means with active light; and the hydrophilic portion disposed at a position in contact with the aqueous electrolyte in the electrodeposition tank; It has a counter electrode that can be energized and is irradiated by the second irradiation means. Voltage in which the current supply means for applying, in the structure of between hydrophilic part and the counter electrode when.

  The electrodeposition film is formed by a photo-deposition method, that is, a hydrophilic part is formed by the first irradiation means by the film-forming means in an aqueous electrolyte solution containing a film-forming material whose solubility or dispersibility in aqueous liquid is reduced by pH change. When the hydrophilic portion (photosemiconductor thin film) is placed in contact with the hydrophilic portion (photosemiconductor thin film) and the hydrophilic portion (photosemiconductor thin film) is irradiated with light by the second irradiating means, the hydrophilic portion (light A voltage is applied between the semiconductor thin film) and the counter electrode to deposit a film forming material on the hydrophilic portion.

  The first irradiation means can be suitably configured as shown in FIG. 2, for example. FIG. 2 is a schematic cross-sectional view for explaining that the hydrophilic portion 6 is formed by irradiating the selected region of the optical semiconductor thin film with light. That is, as shown in FIG. 2, a light source (not shown) for irradiating ultraviolet rays and a second image-forming optical lens 11 and a first light source that are sequentially provided from the light source toward the irradiation direction and image the received light. The image forming optical system including the image forming optical lens 13 and the photomask 12 provided between the first image forming optical lens 13 and the second image forming optical lens 11 can be configured. .

  The film-forming substrate 5 on which the hydrophilic portion 6 is to be formed is arranged so that the surface of the insulating substrate 1 and the first imaging optical lens 13 face each other, and the water-repellent film of the insulating substrate 1 The active light can be irradiated by forming an image on the water repellent film side of the optical semiconductor thin film 3 through the insulating substrate 1 from the side where 4 is not provided (the water repellent film non-formed surface side). When the hydrophilic portion is formed by oxidative decomposition of the water-repellent film by photocatalytic action of the optical semiconductor thin film when irradiated with light, as shown in FIG. 2- (b), the decomposition treatment tank 14 containing the aqueous liquid 20a and the conductivity A configuration in which an electrode plate 15 that is connected to the membrane 2 and enables energization with the aqueous liquid 20a is further provided is more preferable. In this embodiment, the oxidative decomposition can be performed in contact with water, and the water-repellent film in the selected region irradiated with light is floated more rapidly by the superhydrophilic function of titanium oxide as described above. be able to.

  Further, instead of the imaging optical system described above, a mirror reflection optical system may be used. The same applies to the second irradiation means described later.

  When the hydrophilic portion is formed by the configuration shown in FIG. 2- (b) using the film forming substrate 5 of FIG. 1- (a), the film forming substrate 5 for forming the hydrophilic portion is first used as the water repellent film 4. In addition, the optical semiconductor thin film 3 is disposed in the decomposition treatment tank 14 so as to be in contact with the aqueous liquid 20a, and is further connected to the electrode plate 15 disposed in the aqueous liquid 20a on the conductive film 2 in a state where the film forming substrate is connected. When the pattern light that has passed through the imaging / mirror reflection optical system is selectively imaged on the optical semiconductor thin film 3, the water repellent film undergoes oxidative decomposition in the selected region of the optical semiconductor thin film on which the pattern light is imaged. It is lifted and removed, and a hydrophilic portion 6 is formed in which the optical semiconductor thin film is exposed as a concave shape.

  For example, as shown in FIG. 4, the film forming means includes an electrodeposition tank 14 ′ containing an aqueous electrolyte solution 20 b containing a film forming material whose solubility or dispersibility in an aqueous liquid is lowered due to a change in pH, and a film forming means. An arrangement mechanism (not shown) for holding the substrate 5 by holding or sucking the edge thereof and moving the substrate 5 so that at least the hydrophilic portion 6 formed by the first irradiation means is in contact with the electrolytic solution 20b. And can be configured.

  Although the arrangement mechanism is not shown in the drawing, the arrangement mechanism is configured so that the optical semiconductor thin film exposed at least by the hydrophilic portion 6 can be arranged in a predetermined direction so as to come into contact with the electrolytic solution by gripping and sucking the film forming substrate. For example, the edge of the film forming substrate is gripped, or the water repellent film non-formed surface (for example, the exposed surface of the insulating substrate 1 in FIG. 1- (a)) in which the hydrophilic portion is not formed is sucked. For example, a mechanism that can be held and moved by sucking using a mechanism such as the like can be provided.

  The electrodeposition tank constituting the film forming means is further provided with an energizing means. The energizing means includes a counter electrode capable of energizing the hydrophilic portion of the film forming substrate disposed at a position in contact with the aqueous electrolyte in the electrodeposition tank, and the hydrophilic portion when irradiated by the second irradiating means. Voltage application between the electrode and the counter electrode. For example, as shown in FIG. 4, a potentiostat 18 for applying a bias voltage, a counter electrode 17 disposed in an electrodeposition tank so as to be in contact with an electrolytic solution 20b accommodated, and a saturated calomel electrode 16 as a reference electrode. It can be configured in a tripolar manner. As a result, a bias voltage can be applied as required, and an electromotive force is generated between the hydrophilic portion and the counter electrode when irradiated with active light with or without the bias voltage applied. An electrodeposition film can be formed on the portion.

  The second irradiating means further irradiates the hydrophilic part with active light in a state where the film forming substrate on which the hydrophilic part has been formed by the first irradiating means is disposed so that the hydrophilic part is in contact with the electrolytic solution. The second irradiating means may be further provided separately from the first irradiating means, or the first irradiating means and the second irradiating means may be constituted by a single exposure means, and the functions of both means may be combined. It can also be. In the case of a single configuration, the device configuration can be simplified and further cost reduction can be achieved.

  The second irradiation means can be suitably configured in the same manner as the first irradiation means described above (see FIG. 2). That is, as shown in FIG. 2, for example, a light source (not shown) for irradiating ultraviolet rays and a second imaging optical lens 11 and a second imaging optical lens 11 that are sequentially provided from the light source toward the irradiation direction and image the received light. An image forming optical system including one image forming optical lens 13 and a photomask 12 provided between the first image forming optical lens 13 and the second image forming optical lens 11. it can.

In the first and second irradiation means, the second imaging optical lens 11 constituting the imaging optical system and the non-water-repellent film-forming surface of the film-forming substrate 5 (for example, in the case of FIG. 1- (a), insulating) From the viewpoint of handling, the distance from the conductive substrate (light transmissive) 1) is preferably in the range of 1 mm to 50 cm, and the focal depth of the second imaging optical lens is ± from the point of accuracy and handling It is preferably in the range of 10 ± 100 μm.
In addition, when the photomask and the optical semiconductor thin film can be brought close to each other due to the device configuration, it is not necessary to use a device equipped with an imaging optical system or a mirror reflection optical system as described above, and parallel light or close contact Light irradiation can be performed by a mold exposure apparatus.

Examples of the light source used for the irradiation of active light in the first and second irradiation means include a mercury lamp, a mercury xenon lamp, and a high-pressure mercury lamp.
Further, when a Hg-Xe uniform irradiation light source is used as the light source, for example, instead of the imaging / mirror reflection optical system shown in FIG. 2, an Hg-Xe uniform irradiation light source is arranged on the upper part of the film forming substrate 5; In addition, the photomask is brought into close contact with the insulating substrate 1 of the film forming substrate 5, or the insulating substrate thickness is set to 0.2 mm or less, so that light diffraction is prevented and an electrodeposited film (eg, integrated) is obtained. High-precision microlens array) can be formed.

  When exposure over a long period of time is possible, light irradiation is possible even with an inexpensive scanning laser writing apparatus. In this case, instead of the imaging / mirror reflection optical system and the photomask shown in FIG. 2, a scanning laser writing device for laser beam irradiation such as a He—Cd laser can be used. Examples of the laser beam include a Gaussian beam, that is, a beam having a light intensity that is stronger toward the center of the beam and becomes weaker as it spreads from the center to the periphery. For example, when a laser beam is irradiated on a predetermined position by turning on / off the laser beam. Microlenses whose curvature and the like are determined according to the beam diameter are formed in an array. In addition, a proximity type exposure apparatus can be used as long as the pattern resolution allows.

  Although the case where light irradiation is performed from the water repellent film non-formation surface side where the water repellent film is not formed on the film forming substrate 5 has been described above, exposure may be performed from the water repellent film formation surface side. In the case of exposure from the water-repellent film side, the film-forming substrate is immersed in an aqueous solution or an electrolytic solution, but does not absorb ultraviolet rays that are irradiated not only by the aqueous solution but also by the electrolytic solution according to the present invention. The optical semiconductor thin film can be irradiated with light through an aqueous solution or an electrolytic solution. However, light absorption cannot be ignored if the hydrophilic part of the desired shape cannot be formed or the film grows and becomes thicker. Therefore, it is possible to irradiate light from the surface where the water repellent film is not formed. desirable.

Hereinafter, an example of the electrodeposition film forming apparatus of the present invention will be further described with reference to FIGS.
The electrodeposition film forming apparatus shown in FIGS. 3 and 4 performs an image forming unit 100 for performing an image forming process for oxidizing and removing the water-repellent film as shown in FIG. 3, a cleaning unit 110 for performing a cleaning process, and a drying process. The drying unit 120, the electrodeposition booth 200 for performing the electrodeposition process and the cleaning process by the photo-deposition method and the drying unit 210 for performing the drying process as shown in FIG. It is constructed so that each process can be continuously performed on the substrate. The electrodeposition booth 200 is partitioned from the outside, and is provided with a loading / unloading port for loading / unloading the film forming substrate and a door (both not shown) for closing the loading / unloading port.

  The image forming unit 100 includes a decomposition treatment tank 14 containing water and an electrode plate 15 that is connected to the conductive film 2 and enables energization with the water 20 a, and has a hydrophilic portion in a selected region of the film forming substrate 5. The exposure apparatus 10 (first irradiation means) is formed. The exposure apparatus 10 is further provided with a light source (not shown) for irradiating ultraviolet light to the decomposition treatment tank 14 and the electrode plate 15, and a second light source for imaging the received light. An imaging optical system including the imaging optical lens 11 and the first imaging optical lens 13, and a photomask provided between the first imaging optical lens 13 and the second imaging optical lens 11. 12 is provided.

  The decomposition treatment tank 14 accommodates the aqueous liquid 20a, and can arrange the film forming substrate 5 together with the water repellent film 4 so that the optical semiconductor thin film 3 is in contact with the aqueous liquid 20a in the upper opening. ing.

  The imaging optical system exemplified here is a projection type exposure apparatus, and light from the light source is imaged on the photomask 12 through the second imaging optical lens 11, and the light patterned through the photomask 12 is Further, an image is formed on the surface of the optical semiconductor thin film 3 of the film forming substrate 5 via the first imaging optical lens 13.

A cleaning unit 110 is provided downstream of the image forming unit 100 in the substrate transport direction. The cleaning unit 110 is provided with a cleaning device 21 below the cleaning unit 110, and the surface of the film-forming substrate 5 on the side where the hydrophilic part 6 is formed by selectively removing the water-repellent film 4 (hydrophilic part formation). It can be cleaned by jetting almost perpendicularly to the surface. The cleaning device 21 can eject the aqueous liquid from the ejection nozzle, and can eject humidified air or the like. Further, as shown in FIG. 3, the film forming substrate 5 is configured to be independently movable in the arrow direction B or B ′, and the cleaning device 21 is configured to be independently movable in the arrow direction A or A ′. Cleaning can be performed by fixing one of the substrate and the cleaning apparatus and moving the other, or by moving both in different directions or at different speeds in the same direction.
Further, when the aqueous liquid is ejected from the ejection nozzle, a door or a partition (not shown) can be provided between the film forming process and the cleaning process, and thus the aqueous liquid for cleaning is added to the electrolytic solution 20a. It is desirable to prevent contamination.

  A drying unit 120 is provided further downstream of the cleaning unit 110 in the substrate transport direction. The drying unit 120 is provided with a drying device 22 capable of blowing gas (nitrogen gas, air, etc.) from a nozzle at the lower part thereof, and blows air to the hydrophilic portion forming surface of the cleaned film forming substrate. It can be dried. Similarly to the cleaning device 21, the drying device 22 can be configured to be movable.

  The film forming substrate 5 dried in the drying unit 120 is continuously transported to the electrodeposition booth 200 configured as shown in FIG. 4 provided downstream of the substrate transport path. The electrodeposition booth 200 removes an electrodeposition apparatus 9 for forming an electrodeposition film on the hydrophilic portion 6 of the film forming substrate 5 on which the hydrophilic portion 6 is formed, and an unnecessary electrolytic solution adhering to the film forming substrate 5. And a humidity sensor 19 and a humidifier 20 for keeping the relative humidity in the vicinity of the film forming substrate 5 at 50% or more. The humidity sensor 19 and the humidifier 20 are connected to the control device 21, and at least a predetermined relative humidity (from the time immediately before the film forming substrate 5 on which the electrodeposition film is formed to the time when the film is pulled up from the electrolytic solution to the time when the cleaning is completed. 50% or more).

  The electrodeposition apparatus 9 is an exposure apparatus 10 ′ (second exposure device) that further irradiates the hydrophilic portion with active light in a state where the film-forming substrate 5 is disposed in the electrodeposition tank 14 ′ so that the hydrophilic portion 6 is in contact with the electrolytic solution. A film deposition apparatus 20 for forming an electrodeposition film having a suction cup (arrangement mechanism) (not shown) for placing the electrodeposition tank 14 'and the film forming substrate in contact with the electrolytic solution; A potentiostat 18 for applying a voltage, a counter electrode 17 and a saturated calomel electrode (reference electrode) 16 disposed in an electrolyte 20b accommodated therein, and a hydrophilic portion and a counter electrode when irradiated by the exposure apparatus 10 ′ And a three-pole energization system (energization means) for applying a voltage between the two. The exposure apparatus 10 ′ is configured in the same manner as the exposure apparatus 10 (first irradiation means) described above, and is brought into contact with the electrolytic solution 20b at the upper opening of the electrodeposition tank 14 ′ in the electrodeposition booth 200. It is configured such that light can be irradiated to the disposed film forming substrate 5 through a light transmitting window 201 (at least a synthetic quartz glass plate or the like that transmits irradiated light).

  The electrodeposition tank 14 ′ accommodates an electrolytic solution 20 b containing a film forming material whose solubility or dispersibility in aqueous liquid is reduced due to a change in pH (hydrogen ion concentration), and a film forming substrate is formed in the upper opening thereof. The optical semiconductor thin film in the hydrophilic portion can be arranged so as to be in contact with the electrolytic solution 20b. Further, a counter electrode 15 and a saturated calomel electrode 16 are provided at the bottom of the electrodeposition tank so as to be immersed in the electrolytic solution 20b. The conductive film of the counter electrode 15 and the saturated calomel electrode 16 and the film forming substrate is as follows. Each of them is electrically connected to the potentiostat 18 so that a bias voltage can be appropriately applied under the control of the control device 21 as necessary.

  The imaging optical system here is also a projection type exposure apparatus as described above, and the light from the light source is imaged on the photomask 12 through the second imaging optical lens 11 and patterned through the photomask 12. The light is further imaged on the exposed surface of the optical semiconductor thin film exposed at the hydrophilic portion 6 through the light transmissive window 201 via the first imaging optical lens 13.

  The electrodeposition booth 200 is isolated from the outside, and the relative humidity is maintained at 50% or more (preferably 70% or more) by the humidity sensor 19 and the humidifier 20 provided in the room. Further, as shown in FIG. 4, the imaging optical system is disposed outside the electrodeposition booth 200, and even when the internal humidity of the electrodeposition booth 200 is increased, condensation or fogging occurs on the lens and the optical performance deteriorates. In addition, the precision parts used in the exposure device or the like are not rusted to cause troubles such as equipment life, performance degradation, equipment failure and the like. In particular, since manufacturing equipment is expensive, the defects directly increase costs.

  The humidity sensor 19 and the humidifier 20 are connected to a control device 21 so that the electrodeposition booth 200 can be controlled in an appropriate relative humidity range based on the humidity measured by the humidity sensor 19. As the humidifier 20, for example, a known ultrasonic humidifier, a heating humidifier, a vaporizing humidifier, or the like can be appropriately selected and used. Also, instead of using a humidifier, using a cleaning fluid such as an aqueous liquid or humidified air used in the cleaning process, for example, before the film forming substrate is carried into the booth, the cleaning fluid is supplied from the cleaning nozzle into the booth. You may make it eject. This is advantageous in that the device configuration is simpler.

In addition, a cleaning device 23 is further provided inside the electrodeposition booth 200 so that it can be cleaned by being ejected substantially perpendicularly to the surface of the film forming substrate 5 on the side where the electrodeposition film is formed. . The cleaning device 23 is configured in the same manner as the cleaning device 21 described above, and either one of the film forming substrate and the cleaning device is fixed and the other is moved, or both are moved in different directions or in the same direction. Cleaning can be accomplished by moving at different speeds.
When cleaning is performed by the cleaning device 23, a door or a partition (not shown) can be provided between the electrodeposition process and the cleaning process, and thus the aqueous solution for cleaning is not mixed into the electrolytic solution 20b. It is desirable to make it.

  A drying unit 210 is installed downstream of the electrodeposition booth 200 adjacent to the substrate conveyance path. The drying unit 210 is configured in the same manner as the drying unit 120 described above, and can be dried by blowing gas (nitrogen gas, air, etc.) onto the cleaned electrodeposition surface of the film forming substrate 5.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
(Example 1)
-Production of substrate for film formation-
First, a conductive thin film made of ITO is formed to a thickness of 75 nm by RF sputtering on a non-alkali glass substrate (7059 glass) having a thickness of 0.4 mm, and an anatase-type titanium oxide thin film having a thickness of 110 nm is further formed on the film. (Photo semiconductor thin film) was formed. Next, a 3% by mass solution of oleic acid in which 3% by mass of oleic acid is added to methanol is prepared. This solution is further applied onto the titanium oxide thin film using a spin coater, and then heated at 70 ° C. for 5 minutes. Then, by evaporating methanol, a water-repellent oleic acid film having a thickness of 50 nm was formed. As described above, a film-forming substrate 5 having the structure shown in FIG. 1A was obtained, in which the ITO film 2, the titanium oxide thin film 3, and the oleic acid film 4 were sequentially laminated on the glass substrate 1.

-Preparation of electrolyte solution-
Next, pigment-containing electrolytes K, R, G, and B were prepared as follows.
Disperse styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group (hydrophilic group + hydrophobic group) molar ratio 65%, acid value 150) and carbon black powder (particle size 50 nm) at a volume ratio of 1: 1. Further, 5% by mass of ethylene glycol was added, and then tetramethylammonium hydroxide and ammonium chloride were further added to adjust the pH to 7.8 and the conductivity of 6 mS / cm to obtain an electrolytic solution K. Next, in the preparation of the electrolytic solution K, instead of carbon black powder, an azo red ultrafine pigment (particle size 80 nm), a phthalocyanine green ultrafine pigment (particle size 80 nm), or a phthalocyanine blue ultrafine pigment ( Electrolytic solutions R, G, and B (all having a pH of 7.8 and an electrical conductivity of 6 mS / cm) were obtained in the same manner as the electrolytic solution K, except that each particle size was 80 nm.

-Preparation of electrodeposition film forming device-
The electrodeposition film forming apparatus has the same configuration as that shown in FIGS. 3 and 4 described above as an example (configured by the image forming unit 100, the cleaning unit 110, the drying unit 120, the electrodeposition booth 200, and the drying unit 210). Prepared equipment. This apparatus includes a projection type exposure apparatus (focal length between the imaging optical lens 13 and the imaging surface (film surface on the water-repellent film-forming side of the titanium oxide thin film 3)) = 100 mm, and the focal depth, respectively. Has a light intensity of 100 mW / cm ^{2 with} a wavelength of 365 nm and a wavelength of 365 nm; manufactured by Ushio Electric Co., Ltd., and when the hydrophilic portion is formed, the water-repellent film 4 and the titanium oxide thin film 3 are in contact with the water 20a as shown in FIG. A hydrophilic portion is formed in a selected region of the film-forming substrate 5 arranged in the substrate, and the titanium oxide thin film 3 in the hydrophilic portion formed at the time of electrodeposition is brought into contact with the electrolytic solution 20b as shown in FIG. The electrodeposition film can be formed on the three liquid contact surfaces. In any of the projection type exposure apparatuses, a first imaging optical lens 13, a photomask 12, a second imaging optical lens 11, and a light source (not shown) are arranged in order from the film forming substrate 5.

  In the electrodeposition booth 200 of this apparatus, the film forming substrate 5 is connected to the potentiostat 18 via the ITO film 2, and the potentiostat 18 is also connected to the saturated calomel electrode (reference electrode) 16 and the counter electrode 17. The film forming substrate 5 (titanium oxide thin film 3) is used as a working electrode for the counter electrode (platinum electrode) 17. The electrodeposition tank 14 'can accommodate the prepared electrolyte 20b.

-Pattern formation by electrodeposition film-
(Image forming process)
First, the film forming substrate 5 is disposed so that the titanium oxide thin film 3 comes into contact with the water 20a together with the oleic acid film while sucking and holding the insulating substrate surface by a holding mechanism having a suction cup (not shown). As it is, the ultraviolet rays are imaged for 15 minutes from the insulating substrate 1 side of the film forming substrate 5 (the side having no oleic acid film of the film forming substrate) to the film surface of the titanium oxide thin film 3 on the oleic acid film side. After irradiation, it was separated from the water 20a. At this time, a photomask 12K for forming a black pattern in the following electrodeposition process is disposed on the photomask. In the region irradiated with ultraviolet rays (selected region), the oleic acid film was decomposed and removed by the photocatalytic action of the titanium oxide thin film, and a hydrophilic portion 6 was formed in which the titanium oxide thin film 3 was exposed in a concave shape.

(Washing process and drying process)
And since the decomposition product produced by oxidative decomposition of the oleic acid film remains on the film-forming substrate together with water, the film-forming substrate 5 is formed at the outlet of the jet nozzle of the cleaning device 21 and the film formation. The substrate 5 was transported and arranged so as to face the surface on which the hydrophilic portion was formed (hydrophilic portion forming surface). The film forming substrate 5 can be moved in the direction of the arrow B or B ′ by the holding mechanism connected to a moving mechanism (not shown), and the cleaning device 21 can be moved in the direction of the arrow A or A ′. The nozzle shape of the nozzle is configured in a slit shape. The ejection port of the ejection nozzle faces the hydrophilic portion forming surface and faces upward, so that the ejection direction of pure water is substantially parallel to the normal direction of the hydrophilic portion forming surface of the film forming substrate 5 arranged substantially horizontally. The film forming substrate 5 was passed through the curtain film water at a constant speed of 100 m / second. At this time, the striking pressure of pure water on the surface of the oleic acid film was adjusted to 2 KPa so that the oleic acid profile was not destroyed as much as possible. As a result, the decomposition products remaining with the water on the film forming substrate were uniformly removed.

  After cleaning, the film forming substrate 5 is transported to the drying unit 120 with the hydrophilic portion forming surface facing the gravity direction side, and the ejection nozzle of the drying device 22 provided below the drying unit and the hydrophilic portion forming surface face each other. Thus, the film forming substrate 5 was arranged. Then, nitrogen was blown onto the electrodeposition surface from the ejection nozzle, and drying was performed so as to blow off water droplets. In addition, it was possible to perform the drying here using clean air.

(Electrodeposition process)
Next, the electrodeposition process was performed in the electrodeposition booth 200 as follows.
The electrolytic solution K was accommodated in the electrodeposition tank 14 ′, and the film forming substrate 5 was arranged so that at least the titanium oxide thin film 3 in the hydrophilic portion 6 was in contact with the accommodated electrolytic solution K. As the photomask, the same photomask 12K as that used in the image forming process was used. Then, the titanium oxide thin film 3 is used as the working electrode with respect to the saturated calomel electrode 16, and a voltage is applied from the potentiostat 18 so that the bias voltage applied to the working electrode is 1.8 V, so that the insulating film 5 is insulated. UV light was applied for 4 seconds so that the pattern light was imaged on the liquid contact surface of the titanium oxide thin film 3 exposed at the hydrophilic portion from the conductive substrate 1 side (the hydrophilic portion non-forming surface side of the film forming substrate). At this time, a black pattern was formed on the surface of the titanium oxide thin film 3.

  Subsequently, when the film-forming substrate 5 was separated from the electrolytic solution K, unnecessary electrolytic solution K was attached to the surfaces of the electrodeposition film 7K and the oleic acid film 4, and thus the surface on which the electrodeposition film 7K was formed. The film-forming substrate 5 was transported to a cleaning process in which the cleaning device 23 in the same room was installed in a substantially horizontal state where the (electrodeposition surface) was in the direction of gravity (bottom surface).

  In this example, the image forming process and the electrodeposition process were performed using an apparatus in which [1] an image forming unit, a cleaning unit, and a drying unit, and [2] an electrodeposition booth and a drying unit were separately provided. However, instead of providing [1] and [2] separately, each process of image formation (including cleaning and drying) and electrodeposition (including cleaning and drying) can be performed in a single booth. The above [1] and [2] can be performed in a single booth, and after completion of image formation (and washing / drying), the decomposition treatment tank is replaced with the electrodeposition tank and electrodeposition (and washing / drying) is performed. ) Can also be performed. In this case, the imaging optical system, the photomask, and the cleaning apparatus can be used in common, and the apparatus configuration can be simplified and the cost can be reduced.

(Washing process and drying process)
Then, the film forming substrate 5 was disposed so that the ejection port of the ejection nozzle of the cleaning device 23 disposed on the lower right side of the electrodeposition booth 200 and the electrodeposition surface of the film forming substrate 5 face each other. The film forming substrate 5 and the cleaning device 23 can be moved in the same manner as the cleaning unit 110, and the nozzle shape of the ejection nozzle is formed in a slit shape. Curtain so that the ejection port of the ejection nozzle faces the electrodeposition surface and faces upward, and the ejection direction of pure water is substantially parallel to the normal direction of the electrodeposition surface of the film-forming substrate 5 arranged substantially horizontally While being ejected in a film shape, the film-forming substrate 5 and the ejection nozzle were moved in 10 directions reciprocally by moving them in opposite directions at a constant speed of 100 m / sec. At this time, the striking pressure of pure water on the film surface was adjusted to 2 KPa so that the profile of the electrodeposition film was not broken as much as possible. As a result, the electrolytic solution K adhering to the electrodeposition surface of the film forming substrate 5 is uniformly removed, and a film thickness of 1.% is applied to a selected region (region from which the oleic acid film is removed) of the film forming substrate. It was confirmed that a 2 μm black pattern was formed. Moreover, there was no residue in which the electrolyte solution adhered to the non-pattern part and the outer edge part, and a film could be formed with high definition.

  After cleaning, the electrodeposition booth 200 is taken out, the film forming substrate 5 is transported to the drying unit 210 while the electrodeposition surface is directed in the direction of gravity, and from the ejection nozzle to the electrodeposition surface in the same manner as the cleaning unit 110 described above. Nitrogen was blown and dried by blowing off water droplets. In addition, it was possible to carry out with clean air as well.

  Subsequently, the photomask 12K disposed in the image forming section and the electrodeposition booth is replaced with the photomask 12R for forming the red film, and the oleic acid film is oxidized by irradiating ultraviolet rays in the same manner as in the case of forming the black pattern. In addition to the decomposition and removal (image forming step), the remaining decomposition products were removed by washing, and further dried to fly off water droplets, thereby newly forming a hydrophilic portion 6 for forming a red pattern. Thereafter, in the electrodeposition booth 200, the electrolyte solution R was accommodated in the electrodeposition tank 14 'instead of the electrolyte solution K, and the film-forming substrate 5 was placed and irradiated with ultraviolet rays for 4 seconds as in the case of the black pattern formation. Thereafter, the film-forming substrate 5 was separated from the electrolytic solution R (electrodeposition process). Further, after cleaning was performed under the same conditions as in the case of forming the black pattern, it was further dried for 5 minutes so as to blow off water droplets. As a result, a red pattern having a uniform thickness of 1.2 μm was formed on the newly formed hydrophilic portion.

  Subsequently, the photomask 12R disposed in the image forming section and the electrodeposition booth is replaced with the green film forming photomask 12G, and the oleic acid film is oxidized by irradiating ultraviolet rays in the same manner as in the case of forming the black pattern. In addition to the decomposition and removal (image forming step), the remaining decomposition products were removed by washing, and further dried to fly off water droplets, thereby newly forming a hydrophilic portion 6 for forming a green pattern. Thereafter, in the electrodeposition booth 200, the electrolyte solution G was accommodated in the electrodeposition tank 14 'instead of the electrolyte solution R, and the film forming substrate 5 was placed and irradiated with ultraviolet rays for 4 seconds as in the case of the black pattern formation. Thereafter, the film-forming substrate 5 was separated from the electrolytic solution G (electrodeposition process). Further, after cleaning was performed under the same conditions as in the case of forming the black pattern, it was further dried for 5 minutes so as to blow off water droplets. As a result, a green pattern having a uniform thickness of 1.2 μm was formed on the newly formed hydrophilic portion.

  Subsequently, the photomask 12G disposed in the image forming section and the electrodeposition booth is replaced with the photomask 12B for forming the blue film, and the oleic acid film is oxidized by irradiating ultraviolet rays in the same manner as in the case of forming the black pattern. The remaining decomposed product was removed by washing while being decomposed and removed (image forming step), and further dried to fly off water droplets, thereby newly forming a hydrophilic portion 6 for forming a blue pattern. Thereafter, in the electrodeposition booth 200, the electrolyte solution B was accommodated in the electrodeposition tank 14 'instead of the electrolyte solution G, and the film-forming substrate 5 was placed and irradiated with ultraviolet rays for 4 seconds as in the case of the black pattern formation. Thereafter, the film-forming substrate 5 was separated from the electrolytic solution B (electrodeposition process). Further, after cleaning was performed under the same conditions as in the case of forming the black pattern, it was further dried for 5 minutes so as to blow off water droplets. As a result, a blue pattern having a uniform thickness of 1.2 μm was formed on the newly formed hydrophilic portion.

  Finally, the photomask 12B arranged in the image forming unit 100 is replaced with a mask that can irradiate the non-formation regions of each color pattern of the film forming substrate 5, and ultraviolet rays are irradiated in the same manner as in the case of the black pattern formation. Then, the oleic acid film was removed by oxidative decomposition, and the remaining decomposition product was removed by washing, followed by drying so as to blow off water droplets.

  As described above, a color filter film composed of R, G, B, and K patterns could be formed on the film forming substrate 5. The formed color filter film has a sharp edge profile and a uniform thickness. There is no residue on the outer edge of the color filter film, it is high-definition, the yield due to poor appearance is avoided, and the device configuration is simplified. In addition, we were able to reduce costs.

(Example 2)
In Example 1, the oleic acid used in “-Production of substrate for film formation” was replaced with caproic acid, and a caproic acid film was formed on the titanium oxide thin film in the same manner as in Example 1. A filter membrane was formed.
The color filter film formed in this example also has a sharp edge profile and a uniform thickness. Similarly, the color filter film has no residue, is highly fine, avoids yield due to poor appearance, and is water-repellent (caproic acid film). The irradiation at the time of removing the film) was completed in 12 minutes, so that the productivity was further improved and the cost could be further reduced.

(Example 3)
In Example 1, a color filter film was formed in the same manner as in Example 1 except that the oleic acid film was removed in the image forming step while the oleic acid film was not in contact with the water 20a. As a result, it was possible to remove the oleic acid film, but it took 2 hours to remove it. Thus, although a production tact time is required as compared with Examples 1 and 2, a color filter film having a sharp edge profile and a uniform thickness is formed, and an outer edge portion of the formed color filter film is formed. There was no residue and high definition.

Example 4
In Example 2, the electrolytic solution (K, R, G, B) and photomask (12K, 12R, 12G, 12B) used in the electrodeposition process were replaced with the following electrolytic solution W and photomasks 12W _a , 12W _b , The same operation as in Example 2 was performed except that the microlens array was formed as follows. Specifically, it is as follows. The electrodeposition film forming apparatus is configured in the same manner as shown in the first embodiment.

-Preparation of electrolyte W-
Rutile-type titanium oxide fine particles (particle size 10 nm, refractive index 2.7) and styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group (hydrophilic group + hydrophobic group) molar ratio 65%, acid value 150) And 5% by mass of ethylene glycol, and further using tetramethylammonium hydroxide and ammonium chloride so that the pH is 7.8 and the conductivity is 6 mS / cm. The electrolyte solution W which was adjusted and was an aqueous dispersion (solid content rate 10 mass%) containing transparent fine particles was prepared.

-Preparation of photomask-
For the image forming process, a photomask 12W _a having a circular light transmitting portion so that exposure to a predetermined microlens shape can be performed, and for the electrodeposition process, a circular shape so as to have a predetermined microlens shape. of black fine dots on the light transmission portion from the central portion is formed such that the density is higher towards the peripheral edge of the photomask 12W _b having a density gradation (optical transparency gradations) were prepared, respectively.

-Formation of microlens array by electrodeposition film-
(Image forming process)
After replacing the photomask 12K used in Example 2 in the photomask 12W _a in the image forming unit 100, the image forming process in the same manner as in Example 2 (irradiation for removal of caproic acid film is 12 minutes) performs This was further subjected to a washing step and a drying step to form a hydrophilic portion 6 where the titanium oxide thin film 3 was exposed. Subsequently, it was carried into the electrodeposition booth 200 and an electrodeposition process was performed as follows.

(Electrodeposition process)
In the electrodeposition booth 200, the electrolytic solution W is accommodated in the electrodeposition tank 14 ', and the film-forming substrate 5 is disposed so that at least the titanium oxide thin film in the hydrophilic portion is in contact with the accommodated electrolytic solution W. the formation process different photomasks W _b is arranged. Then, the titanium oxide thin film 3 is used as the working electrode with respect to the saturated calomel electrode 16, and a voltage is applied from the potentiostat 18 so that the bias voltage applied to the working electrode is 1.8 V, so that the insulating film 5 is insulated. UV light was irradiated for 30 seconds so that the pattern light was imaged on the liquid contact surface of the titanium oxide thin film 3 exposed to the hydrophilic portion 6 from the conductive substrate 1 side (the hydrophilic portion non-forming surface side of the film forming substrate). At this time, a microlens array was formed on the surface of the titanium oxide thin film 3. Subsequently, when the film-forming substrate 5 was separated from the electrolytic solution W, unnecessary electrolytic solution W was adhered to the surfaces of the microlens array and the caproic acid film 4, and thus was washed in the same manner as in Example 2. Further, nitrogen was blown to dry the water droplets.

  The electrolytic solution W adhering to the film forming substrate 5 is uniformly removed, and a microlens array having a radius of curvature of 20 μm (refractive index: 1.65, focal length: 31 μm) is formed in the hydrophilic portion, which is a selected region. It was confirmed. There was no residue in which the electrolytic solution could adhere to the non-formation region and the outer edge of the microlens array, and the formed microlens array was controlled to a desired film thickness and formed with high definition.

(A) is sectional drawing which shows an example of the film | membrane formation board | substrate comprised by providing an insulating substrate, (b) is sectional drawing which shows an example of the film | membrane formation board | substrate comprised without providing an insulating board | substrate. It is. (A) is the schematic for demonstrating the place which light-irradiates the selection area | region of an optical semiconductor thin film, and forms the hydrophilic part, (b) makes it contact with aqueous liquid and is hydrophilic like (a). It is the schematic for demonstrating the place which forms the part. It is the schematic for demonstrating the place which forms the hydrophilic part using the exposure apparatus 10 which comprises the electrodeposition film forming apparatus of this invention. It is the schematic for demonstrating the place which forms the electrodeposition film | membrane in the hydrophilic part using the electrodeposition apparatus 9 provided with exposure apparatus 10 'which comprises the electrodeposition film forming apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Insulating substrate 2 ... Conductive film 3 ... Optical semiconductor thin film 4 ... Water-repellent film 5, 5 '... Film-forming substrate 6 ... Hydrophilic part 10 ... Exposure apparatus (1st irradiation means)
10 '... exposure apparatus (second irradiation means)
DESCRIPTION OF SYMBOLS 12 ... Photomask 16 ... Reference electrode 17 ... Counter electrode 18 ... Potentiostat 20 ... Film-forming means 21, 23 ... Cleaning apparatus

Claims (11)

A film-forming substrate comprising a conductive film, a hydrophilic photo-semiconductor thin film having photocatalytic ability and photovoltaic ability, and a water-repellent film containing an organic material in contact with the photo-semiconductor thin film in order. An image forming step of selectively irradiating light and removing the water-repellent film in a selected region of the irradiated optical semiconductor thin film to form a hydrophilic portion;
In the state where the film-forming substrate is disposed so that at least the hydrophilic part is in contact with an aqueous electrolyte solution containing a film-forming material whose solubility or dispersibility in aqueous liquid decreases due to a change in pH, the hydrophilic part is further activated. An electrodeposition step in which a voltage is applied between the hydrophilic portion and the counter electrode by irradiating light, and the film forming material is deposited on the hydrophilic portion to form an electrodeposition film;
An electrodeposition film forming method comprising:   2. The image forming step according to claim 1, wherein the water-repellent film is decomposed by the photocatalytic action of the optical semiconductor thin film when irradiated with active light, and the decomposition product is washed away to form a hydrophilic portion. The electrodeposition film forming method as described.   The electrodeposition film forming method according to claim 1, wherein in the image forming step, the active light is selectively irradiated using a photomask.   At least the conductive film is light transmissive, and the image forming step and / or electrodeposition step irradiates the active light from the water repellent film non-forming surface side of the film forming substrate. The electrodeposition film forming method according to any one of 1 to 3.   5. The electrodeposition film forming method according to claim 1, wherein the active light is selectively irradiated in a state where an inorganic substance is not adhered to the film surface of the water repellent film of the film forming substrate. A film-forming substrate comprising a conductive film, a hydrophilic photo-semiconductor thin film having photocatalytic ability and photovoltaic ability, and a water-repellent film containing an organic material in contact with the photo-semiconductor thin film in order. First irradiation means for selectively irradiating light and forming a hydrophilic portion in a selected region of the irradiated optical semiconductor thin film;
An electrodeposition tank containing an aqueous electrolyte containing a film-forming material whose solubility or dispersibility in an aqueous liquid decreases due to a change in pH, and at least a hydrophilic portion formed by the first irradiation means is in contact with the aqueous electrolyte A film forming means provided with an arrangement mechanism for arranging the film forming substrate,
Second irradiation means for further irradiating the hydrophilic part of the film-forming substrate disposed on the film-forming means so that at least the hydrophilic part is in contact with the aqueous electrolyte;
The electrodeposition tank includes a counter electrode that is disposed at a position in contact with the aqueous electrolyte solution and can be energized with the hydrophilic portion, and a voltage is applied between the hydrophilic portion and the counter electrode when irradiated by the second irradiation means. Energizing means to apply;
An electrodeposition film forming apparatus comprising:   The electrodeposition film forming apparatus according to claim 6, further comprising a cleaning unit that cleans the irradiated selected region after the irradiation by the first irradiation unit.   The electrodeposition film forming apparatus according to claim 6, wherein the first irradiation unit further includes a mask unit that selectively irradiates or blocks active light.   The electrodeposition film forming apparatus according to claim 8, wherein the first irradiating unit is configured to dispose the mask unit on a non-water repellent film forming surface side of the film forming substrate.   At least the conductive film is light transmissive, and the first irradiation means and / or the second irradiation means irradiates the active light from the water repellent film non-forming surface side of the film forming substrate. The electrodeposition film forming apparatus according to any one of claims 6 to 9.   The electrodeposition film according to any one of claims 6 to 10, further comprising an exposure unit serving as the first irradiation unit and the second irradiation unit in place of the first irradiation unit and the second irradiation unit. Forming equipment.

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