JP2000266922A - Manufacture of color filter and manufacturing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a color filter having sharp edge parts of each pixel by preventing re-elution of an electrodeposition film formed once, and a manufacturing device of the color filter, to be used in the method. SOLUTION: In this manufacturing method of a color filter containing a process for forming a color filter layer comprising a colored electrodeposition film 21, by arranging a substrate 10 formed by laminating an optically transparent conductive film 12 and a photo-semiconductor thin film 13 having a photo- electromotive function, successively on an optically transparent supporter 11, so that at least the photo-semiconductor thin film 13 is in contact with a aqueous electrolyte 20 containing electrodeposition material including coloring material, and by irradiating light selectively, and by generating a photo-electromotive force to the light irradiation part of the photo-semiconductor thin film 13, and by depositing electrodeposition material electrochemically, a bias voltage is applied on the substrate 10 at least during the period when the substrate 10 is in contact with the aqueous electrolyte 20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technology for manufacturing a color filter used for various display devices such as a CCD camera and a liquid crystal display device and a color sensor.
The present invention relates to a method for producing a color filter including a method for producing a colored layer and a black matrix. In particular,
The present invention relates to a novel color filter manufacturing method capable of easily forming a colored layer and a black matrix with high resolution without using a photolithography technique.

[0002]

2. Description of the Related Art At present, as a method for producing a color filter, (1) a dyeing method, (2) a pigment dispersion method, (3) a printing method, (4) an ink jet method, and (5) an electrodeposition method are known. I have. The first dyeing method is to form a water-soluble polymer layer for dyeing on a glass substrate, pattern it into a desired shape through a photolithography process, and then immerse it in a dye solution to be colored. Get the pattern. This was repeated three times. (Red), G. (Green), B.I. (Blue) color filter layer is obtained. Due to its high transmittance and abundant hues, and the high degree of perfection of its technology, it is currently widely used for color solid-state imaging devices (CCD). However, since a dye is used, it is inferior in light resistance and the number of manufacturing steps is large. Therefore, a method for manufacturing a color filter for a liquid crystal display device (LCD) is being replaced by a pigment dispersion method.

[0003] In the second pigment dispersion method, first, a resin layer in which a pigment is dispersed is formed on a glass substrate, and this is patterned through a photolithography step. This was repeated three times. G. FIG. B. To obtain a color filter layer. This manufacturing method has a high degree of technology perfection and is the most mainstream method in recent years. However, it has a drawback in that the number of steps is large and the cost is high. In the third printing method, a pigment is dispersed in a thermosetting resin, and printing is performed for three times.
Times to repeat G. FIG. B. And then applying heat to cure the resin to obtain a color filter layer. This method is described in R. G. FIG. B. Photolithography is not required in the layer forming step, but the obtained color filter is inferior in resolution and film thickness uniformity.

In the fourth ink-jet method, first, after forming an ink-receiving layer made of a water-soluble polymer, a desired pattern is subjected to a hydrophilizing / hydrophobic treatment, and ink is applied to the hydrophilized portion by the ink-jet method. Spray R. G. FIG. B. To obtain a color filter layer. This method is also described in R.
G. FIG. B. No photolithography is required for the layers, but the resulting color filter is inferior in resolution.
In addition, it is highly probable that color mixing occurs between adjacent filter layers, and is inferior in positional accuracy. In the fifth electrodeposition method, a high voltage of about 100 V is applied to a pre-patterned transparent electrode in an electrolytic solution in which a pigment is dispersed in a water-soluble polymer to form an electrodeposition film by electrodeposition coating. And this is repeated three times. G. FIG. B. To obtain a color filter layer. In this method, a transparent electrode is previously patterned by photolithography, and this is used as an electrode for electrodeposition. Therefore, the method has a drawback that the shape of the pattern is limited and cannot be used for a TFT liquid crystal.

In general, a color filter for a liquid crystal cannot be used only with a color filter layer, and it is necessary to cover a gap between each fine filter cell with a black matrix. A photolithography method is usually used also for forming a black matrix, which is one of the major factors for cost increase. Therefore, if a color filter with high resolution and excellent pattern accuracy can be manufactured by a simple process without going through complicated processes such as photolithography, including the formation of a black matrix, the manufacturing cost will be significantly reduced. become. In addition, recent C
With the development of PU, the demand for a display capable of displaying video information and communication information at a high resolution has been increased, and accordingly, a technology for easily manufacturing a finely patterned color filter has been desired.

[0006]

SUMMARY OF THE INVENTION The present inventors have developed a method for producing a color filter using a photoelectrodeposition method in order to solve the above-mentioned problems, and have filed a patent application for this method (Japanese Patent Application No. Hei. -135410, Japanese Patent Application No. 9-2974
No. 66, etc., Japanese Patent Application No. 10-162170, Japanese Patent Application No. 10-
197564). According to this method, a color filter having a fine pattern with high resolution can be stably manufactured by simple steps including formation of a black matrix.

However, even if a fine pattern is formed, the electrodeposited film once formed may be re-eluted if left in an electrolytic solution for a long time without applying a bias voltage. There is a possibility that a part will be lost or the edge profile will be degraded.

An object of the present invention is to provide a method for easily producing a color filter containing a black matrix, and an apparatus for producing a color filter used in the method. Another object of the present invention is to provide a method of manufacturing a color filter capable of coping with a fine and complicated pixel pattern, and an apparatus for manufacturing a color filter used in the method. In particular, the present invention provides a method for manufacturing a color filter having sharp edges at each pixel by preventing re-elution of an electrodeposited film formed once, and an apparatus for manufacturing a color filter used in the method. Aim.

[0009]

In order to solve the above-mentioned problems, a method of manufacturing a color filter according to the present invention has a light-transmitting conductive film on a light-transmitting support, and an optical semiconductor having a photovoltaic function. The substrate on which the thin films are sequentially laminated is disposed so that at least the optical semiconductor thin film is in contact with an electrolytic solution containing an electrodeposition material containing a coloring material that precipitates due to a change in hydrogen ion concentration, and is selectively irradiated with light, A method for producing a color filter, comprising the steps of generating a photoelectromotive force in a light irradiation portion of the optical semiconductor thin film and electrochemically depositing the electrodeposition material to form a color filter layer composed of a colored electrodeposition film. A constant bias voltage is applied to the substrate at least while the substrate and the electrolyte are in contact with each other. According to the method of the present invention, the bias voltage is applied while the substrate is in contact with the electrolytic solution even when light is not irradiated, so that the once formed electrodeposition film does not deteriorate.

Preferably, the bias voltage is synchronized with the contact time between the substrate and the electrolyte.

Further, the present invention provides a liquid tank capable of storing an electrolytic solution, a substrate in which a light-transmitting conductive film and an optical semiconductor thin film having a photovoltaic function are sequentially laminated on a light-transmitting support. Means for fixing at least the optical semiconductor thin film so as to contact the electrolyte, light irradiation means for selectively irradiating the substrate with light, and a sensor for sensing the contact between the electrolyte in the liquid tank and the substrate, Means for applying a bias voltage to the substrate in synchronization with a signal from the sensor.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 2 shows one embodiment of a method for manufacturing a color filter usable in the present invention, and FIG. 1 shows one embodiment of an apparatus for manufacturing a color filter used in the method. A substrate 10 (FIG. 2A) in which a support 11, a conductive film 12, and an optical semiconductor thin film 13 are sequentially laminated, a counter electrode 23, and a reference electrode 25 are arranged as shown in FIG. Substrate 1
0 indicates that at least the optical semiconductor thin film 13 is
Are arranged by a jig 26 or the like so as to contact with.
An electrodeposition material containing at least a coloring material is dissolved or dispersed in the aqueous electrolyte solution 20. Next, the substrate 10 is irradiated with light 30 via the photomask 31 while applying a bias voltage to the conductive film 12 from the potentiostat 24. The light 30 is first formed into an image on the surface 31 a of the photomask by an imaging optical lens 32 disposed between a light source (not shown) and the photomask 31.

The formed incident light 30 is applied to the photomask 3
The light passes through the imaging optical lens 33 disposed between the substrate 1 and the substrate, and enters the substrate 10 from the support 11 side. The incident light 30 forms the image pattern of the photomask 31 on the surface 13 a of the optical semiconductor thin film 13 by the imaging optical lens 33. As a result, a photoelectromotive force is generated in the light irradiation portion of the optical semiconductor thin film 13, and the potential of the optical semiconductor thin film 13 is reduced by the generated photoelectromotive force and the bias voltage supplied from the potentiostat 24. When the threshold value of the electrodeposition of the electrodeposition material is exceeded, the colored electrodeposition film
Is formed (FIG. 2B). This is referred to as "R. G. FIG. B. This is performed for each of the electrodeposition liquids containing the color material to form a color filter layer having a desired pattern (FIG. 2).
(C)).

After the colored electrodeposition film 21 is formed, the substrate 10
Are disposed again as shown in FIG. 1 (however, the photomask 31 is not disposed). When the substrate 10 is entirely irradiated with light in an aqueous electrolytic solution 20 in which an electrodeposition material containing a black coloring material, for example, carbon black is dissolved or dispersed, photovoltaic emission occurs only in a region where the colored electrodeposition film 21 is not formed. Electric power is generated, and the black electrodeposition film 22 containing carbon black only in the region
Is formed (FIG. 2D). Alternatively, aqueous electrolyte 2
0, a black matrix may be formed only in a region where the colored electrodeposition film 21 is not formed by applying a bias voltage. However, in this case, a material having a high insulating property is selected as the electrodeposition material so that the colored electrodeposition film 21 has an insulating property.
When a black electrodeposition film is formed only with a bias voltage, a bias voltage is applied so as to exceed the electrodeposition threshold of the electrodeposition material. Thus, a color filter containing a color filter layer and carbon black can be easily produced without using photolithography. As described above, it is preferable to form the black matrix by the electrodeposition method, but it is also possible to form the black matrix by using an ultraviolet curable resin or the like.

FIG. 2 shows that after the colored electrodeposition film 21 is formed,
Although the method of performing the step of forming the black matrix has been described, the method is not limited to this, and after forming the black matrix including the black electrodeposition film 22, the colored electrodeposition film 21 is formed.
May be formed. In this case, even in the step of forming the black matrix, light is selectively irradiated according to a desired black matrix pattern, and the photoelectromotive force and the bias voltage generated in the light-irradiated portion cause the electrodeposition containing the black coloring material. The material is electrodeposited. Even when light is selectively irradiated from the support side according to the pattern of the black matrix, the surface 13 of the optical semiconductor thin film is formed by the imaging optical lens.
a on the photomask 3 so that the incident light is imaged.
1. The imaging optical lenses 32 and 33 are arranged. Thereafter, the step of forming the colored electrodeposition film 21 is performed, for example, by R.
G. FIG. B. By repeating three times for each layer, a color filter can be prepared. R. G. FIG. B. In the layer formation process, the last layer to be formed is not selectively irradiated with light, and is irradiated with light from the entire surface of the substrate, or only by applying a bias voltage, to form a colored electrodeposition film. Can also be formed. It is preferable to form the last colored electrodeposition film in this manner, since the gap such as whitening can be filled with the last electrodeposition film, and a color filter having more defects can be produced. After the colored electrodeposition film and the black matrix are formed on the substrate 10, the color filter may be transferred to another glass substrate or the like.

By the way, the electrodeposited film is re-dissolved little by little while it is immersed in the electrodeposition solution immediately after its formation. In addition, in the washing step provided between the formation steps of the respective color filter layers, the color filter layers are gradually re-dissolved while being immersed in pure water. Also, in order to shorten the drying and curing time of the existing electrodeposited film in order to shorten the process, the drying process is shortened and the existing electrodeposited film is kept dry.
The most effective method is to perform a photo-deposition process after coloring, but in this case, the existing electrodeposition film is immersed in the electro-deposition solution while remaining dry to cause further re-dissolution. Even if the re-melting time is short, the edge of the photo-deposited film is undesirably cut off.

However, if a bias voltage which is originally required only for light irradiation is constantly applied to the substrate, such re-dissolution hardly proceeds. This is due to the effect that the electrolysis of water progresses little by little by the bias voltage and the change in the hydrogen ion concentration around the electrodeposited film is suppressed, and the pigments and conductive polymers that constitute the electrodeposited film are attracted to the substrate by electrophoresis. This is probably due to the combined effects that can be obtained.

FIG. 1 shows data obtained by confirming the above-mentioned effects through experiments.
0 is shown. FIG. 10 shows the results obtained by measuring the film deposition amount by the E-QCM (Electrochemical Quartz Crystal Microbalance method) using the electrodeposition solution used in the present invention. The vertical axis indicates the relative film deposition amount, and the horizontal axis indicates the bias voltage based on the standard caramel electrode.
The solid line indicates the hysteresis characteristics when the bias voltage of the electrodeposition liquid used in the present embodiment is changed. First, the film is not deposited while the bias voltage is low (the solid line A in FIG. 9).
When it becomes larger than the Schottky barrier between the electrolyte and the semiconductor, deposition starts at once (portion B of the solid line in FIG. 9). afterwards,
Even if the bias voltage is lowered below the Schottky barrier (the portion C in the solid line in FIG. 9), the film deposition amount hardly decreases. It can be seen that redissolution of the film starts only when the bias voltage becomes close to 0, and the deposition amount approaches 0. Since the electrodeposited film is isotropically etched by the re-dissolution, the edge is shaved. Therefore, in the present invention, the edge is not cut by continuously applying a bias voltage to the substrate after the electrodeposition, and the quality of the electrodeposited film can be improved.

In this case, it is most convenient to apply the bias voltage applied at the time of light irradiation as it is without the trouble of control.
The effect is recognized as shown in FIG. Also, needless to say, applying a high bias voltage that breaks the Schottky barrier between the electrolyte and the semiconductor will result in the formation of an electrodeposited film on the entire substrate irrespective of the light irradiation pattern, which is preferable. Absent.

The bias voltage may be applied at least while the substrate is in contact with the electrolytic solution or the cleaning solution. For example, by synchronizing the timing at which the substrate and the electrodeposition liquid or the substrate and the cleaning water come into contact with the timing at which the bias voltage is applied, it is possible to minimize the deterioration of the edge profile due to the re-dissolution of the electrodeposition film. Therefore, if the multi-color electrodeposition liquid and the washing water can be continuously switched while the bias voltage is being applied, the drying process is not required at all, and the edge profile is not deteriorated. Can be manufactured. An electric circuit for measuring the resistance between the substrate and the electrolytic solution or the cleaning liquid, a triangulation type measuring the liquid level from above as a sensor for detecting that the substrate is in contact with the electrolytic solution or the cleaning liquid And a sensor that detects the liquid level by blocking the light with the electrolytic solution as the liquid level rises. When a bias voltage is also applied to the cleaning water, it is necessary to use pure water to which Na ⁺ ions or Cl ⁻ ions that do not affect the formation of the electrodeposited film are added slightly.

In the present invention, it is not essential to use an imaging optical system, but it is preferable. An imaging optical system that can be used in the present invention is a means for forming an image-like light on the surface of an optical semiconductor thin film. For example, an imaging lens for forming light from a light source on a photomask, and And an imaging lens for forming an image of transmitted light from the mask on the surface of the optical semiconductor on the substrate. An exposure apparatus incorporating such an imaging optical system includes, for example, a projection type exposure apparatus, and can be suitably used in the present invention. In the present invention, since the light is irradiated from the support side of the substrate, it is preferable that the distance between the imaging optical lens and the imaging surface (the surface of the optical semiconductor thin film) is set to be greater than the thickness of the substrate. On the other hand, if the focal length is long, the resolving power tends to decrease, and the distance between the image forming optical system and the image forming plane cannot be extremely increased from the viewpoint of the design of the exposure apparatus. Therefore, practically, the distance between the imaging optical lens and the imaging surface is 1 mm to 5 mm.
It is preferable to arrange them so as to be within a range of 0 cm.

When an imaging optical lens is used as the imaging optical system, the depth of focus of the imaging optical system lens is ± 10 μm or more.
It is preferably ± 100 μm. When the depth of focus of the imaging optical system lens is within the above range, even if the substrate fixed to the jig has a deflection or the like, light can be imaged on the semiconductor surface by relatively easy adjustment. it can.

The substrate used in the method for manufacturing a color filter of the present invention is a substrate in which a light-transmitting conductive film and an optical semiconductor thin film having a photovoltaic function are sequentially laminated on a light-transmitting support. As the support, various light-transmitting materials can be used. For example, glass, plastic, or the like is preferably used.

The conductive film can be widely used as long as it has conductivity and is light-transmissive. For example, Al,
Examples include metals such as Zn, Cu, Fe, Ni, and Cr, and metal oxides such as ITO (indium-tin oxide) and tin dioxide. Alternatively, a conductive carbon material, a conductive ceramic material, or the like can be used. The conductive film can be formed on the support by a conventionally known method such as an evaporation method, a sputtering method, and a CVD method.

As the optical semiconductor thin film, any one can be used as long as it generates a photoelectromotive force by light irradiation. Optical semiconductors include an n-type optical semiconductor and a p-type optical semiconductor, and any optical semiconductor can be used in the present invention. further,
pn in which an n-type optical semiconductor thin film and a p-type optical semiconductor thin film are laminated
When using an optical semiconductor thin film having a junction structure, such as an optical semiconductor thin film having a pin junction obtained by laminating an optical semiconductor thin film having an junction, or an n-type optical semiconductor thin film, an i-type optical semiconductor thin film, and an n-type optical semiconductor thin film, High output photocurrent can be obtained reliably,
This is preferable because the contrast of the image becomes higher.

The optical semiconductor thin film used in the present invention may be made of an inorganic optical semiconductor or an organic optical semiconductor. As the inorganic optical semiconductor, Ga-N, diamond, C-BN, SiC, Zn
Se, TiO ₂ , ZnO and the like can be mentioned. Examples of the organic optical semiconductor include polyvinyl carbazole, polyacetylene, and the like. Among them, oxide optical semiconductors such as TiO ₂ and ZnO are preferable because they are not oxidized and are stable even in an aqueous electrolyte solution. In particular, TiO ₂ has high light sensitivity,
It is preferable because it has high permeability. The optical semiconductor thin film can be formed using a conventionally known thermal oxide film method, sputtering method, electron beam evaporation method, or the like.

[0027] When forming a film of the n-type optical semiconductor thin film with TiO _2, preliminarily subjected to reduction treatment in TiO _2, it is preferable to use TiO ₂ crystals of high anatase optically active. If a crystal having high optical activity is used, an optical semiconductor thin film having high photosensitivity can be manufactured. Anatase TiO ₂
When oxygen is reduced, oxygen atoms are eliminated to form TiO _{2 -X} , and the optical activity is further increased. As a method of the reduction treatment, a method of performing a heat treatment in an atmosphere of hydrogen gas may be mentioned. The heating condition is heating at about 500 ° C. for 1 hour (J. Electrochem. Soc., Vol. 1).
41, No. 3, p. 660, 1994, Y.C. Hamas
(described in aki et al.) and the like. However, as a result of the study by the present inventors, it has been found that the heat treatment can be performed at a relatively low temperature and in a short time by performing a heat treatment while flowing a hydrogen-mixed nitrogen gas at a predetermined flow rate. For example, by subjecting TiO ₂ powder to heat treatment at about 360 ° C. for 10 minutes while flowing 3% hydrogen mixed nitrogen gas at a flow rate of 1 liter / min,
It can be reduced to TiO _2-X by heat treatment at a relatively low temperature for a short time.

Next, the colored electrodeposition material contained in the aqueous liquid in which the substrate is immersed will be described. The colored electrodeposition material includes at least a ionic molecule whose solubility changes due to a change in the pH of the solution and a coloring material such as a dye, a pigment, or a pigment, which is a coloring molecule for forming a colored electrodeposition film. . The coloring material itself may be an ionic molecule, and in this case, the colored electrodeposition material may be composed only of the coloring material. The ionic molecule may be an anionic molecule or a cationic molecule, and is selected according to the polarity of the optical semiconductor thin film used.

Which of the ionic molecules is selected as the electrodeposition material can be determined based on the change characteristic of the solubility corresponding to the change of the pH of the ionic molecule. The electrodeposition material used in the present invention depends on the pH change of the solution,
Those having the property of rapidly changing solubility are preferred.
For example, it is preferable that the solution changes its state (dissolved state → precipitated or precipitated → dissolved state) in response to a pH change of ± 1.0 of the solution, more preferably, in response to a pH change of ± 0.5. If an ionic molecule having such a solubility property is used as an electrodeposition material, an electrodeposition film can be produced more quickly,
Further, an electrodeposition film having excellent water resistance can be produced. Further, the ionic molecules used as the electrodeposition material undergo a state change (dissolved state → precipitation change and precipitation →
Change in dissolved state), ie, p
The change to the precipitated state corresponding to the decrease or increase of H must be steep, and the change to the dissolved state corresponding to the increase or decrease of pH needs to be slow.

Examples of the ionic coloring materials include triphenylmethanephthalide, phenosadine, phenothiazine, and the like.
Fluorescein type, indolylphthalide type, spiropyran type, azaphthalide type, diphenylmethane type, chromenopyrazole type, leuco auramine type, azomethine type, rhodamine lactal type, naphtholactam type, triazene type, triazole azo type, thiazole azo type, azo system,
Oxazine, thiazine, benzothiazole azo,
Examples include quinone imine dyes and hydrophilic dyes having a carboxyl group, an amino group, or an imino group.

For example, rose bengal and eosin, which are fluorescein dyes, are reduced and dissolved in an aqueous solution having a pH of 4 or more, but are oxidized and precipitate in an aqueous solution having a pH of less than 4. Further, an oxazine-based basic dye Cathilon Pure Blue 5GH
(CI Basic Blue 3) and thiazine-based basic dye methylene blue (CI Basic BL 1).
ue 9) is in an oxidized state and dissolved in water having a pH of 10 or less, but is in a reduced state in water having a pH of 10 or more and is insolubilized and precipitated. Although there is no such structural change,
Generally, the solubility of a hydrophilic dye having a carboxyl group, an amino group, or an imino group greatly changes due to a change in pH of an aqueous solution. For example, a water-resistance-improved inkjet dye having a carboxyl group is soluble in water having a pH of 6 or more, but is insoluble in water having a pH of less than 6 and precipitates.

When the colored electrodeposition material comprises a pigment and an ionic molecule, the ionic molecule is preferably a polymer capable of forming a transparent film. For example, a polymer having an anionic carboxyl group, a polymer having a cationic amino group or an imino group, and the like can be given. A water-soluble acrylic resin, which is a kind of polymer having a carboxyl group, is soluble in water having a pH of 6 or more, but is insoluble in water having a pH of less than 6, and precipitates. By dispersing the pigment in this polymer,
When the polymer is electrodeposited on the substrate, the pigment is taken in to form a film, so that a colored electrodeposition film is formed on the substrate.

The polymer used for the electrodeposition material of the present invention is:
It is necessary to have an appropriate hydrophilicity for dissolving or dispersing in an aqueous liquid and an appropriate hydrophobicity for preventing the electrodeposited film from being dissolved again in an aqueous liquid once formed. Therefore, the polymer has both a hydrophobic group and a hydrophilic group in the structure. As a guide for a polymer satisfying such a function, the number of the hydrophobic groups of the monomer constituting the polymer is in the range of 40 to 80% of the total of the hydrophilic group and the hydrophobic group of the monomer. In addition, 50% or more of the hydrophilic group portion changes from a hydrophilic group to a hydrophobic group due to a change in pH, and has an acid value of 30-6.
A value of 00 is preferred from the viewpoints of deposition properties and stability of the electrodeposited film.
Even if the polymer is composed of one kind of monomer,
A copolymer composed of two or more monomers may be used.

As the colored electrodeposition material, a mixture of two or more ionic molecules having the above properties (including a mixture of the same polarity molecules and a mixture of the different polarity molecules) can also be used. A mixture of an on dye and a pigment having the above properties,
Mixtures composed of various combinations, such as a mixture of an ionic polymer having the above characteristics and a colorant, can be used. Even if the material itself does not have the ability to form an electrodeposition film, by combining it with an ionic molecule having the above properties,
It can be taken in during the formation of the electrodeposited film and become a component for forming the colored electrodeposited film. When the colored electrodeposition material is composed of an ionic polymer and a coloring material, if the solid content by weight of the coloring material is from 30% by weight to 95% by weight, the stability of the colored electrodeposition film and the color tone of the coloring layer are improved. It is preferable in that it becomes higher.

Examples of colored electrodeposition materials containing two or more coloring materials are shown below. A mixture of molecules of the same polarity, for example, an anionic molecule capable of forming an electrodeposition film, an aqueous solution of a mixture of rose bengal (red) and an anionic molecule brilliant blue (blue) having no ability to form an electrodeposition film, is mixed with an n-type light in an aqueous solution. When the substrate on which the semiconductor thin film is laminated is immersed, and a current or the like is applied so that the substrate has a positive potential and light irradiation is performed, a purple electrodeposited film same as the solution is formed on the light irradiation portion. This is because Brilliant Blue is incorporated into Rose Bengal, which has the ability to form an electrodeposited film, and the film is formed. As described above, when two or more kinds of molecules having the same polarity are used as a mixture, it is sufficient that at least one kind of ions has an electrodeposition film forming ability.

A mixture of molecules having different polarities, for example, ProFast Jet, which is anionic and capable of forming an electrodeposited film.
Catilon Pure Blue 5GH, which is cationic and has the ability to form an electrodeposition film with Yellow2 (yellow)
The substrate on which the n-type optical semiconductor thin film is laminated is immersed in an aqueous solution mixed with (blue), and a current or the like is applied so that the substrate has a positive potential and light irradiation is performed. A deposited film is formed. On the other hand, when light irradiation is performed while supplying a current or the like so that the substrate has a negative potential, a blue electrodeposition film (Cathilon Pure Blue) is formed on the light irradiation portion.
An electrodeposition film of 5 GH is formed. As described above, when a mixture of molecules of different polarities is used, if the polarity of the optical semiconductor thin film and the polarity of the applied voltage are changed, an electrodeposited film of a different color may be formed using the same colored electrodeposition material. it can.

When a water-insoluble pigment is used as the coloring material of the colored electrodeposition material, the pigment is dissolved in an aqueous solution of an ionic polymer material having an electrodeposition film forming ability, for example, a water-soluble acrylic resin or a water-soluble styrene resin. What is necessary is just to disperse and use. The pigment is taken in when the water-soluble polymer forms the electrodeposited film, and a colored electrodeposited film is produced. As the pigment, any conventionally known pigment can be used.

These colored electrodeposition materials are used after being dissolved or dispersed in an aqueous liquid. Here, the aqueous liquid refers to a liquid containing water as a main component and to which various additives are added within a range that does not impair the effects of the present invention.

For the purpose of increasing the electrodeposition speed, an electrolyte may be added to the aqueous liquid in addition to the colored electrodeposition material. The addition of a salt, which is an electrolyte, increases the conductivity of the solution. As a result of the study by the present inventors, the conductivity in the aqueous liquid is correlated with the electrodeposition rate (in other words, the amount of electrodeposition) (FIG. 3). The thickness of the film is increased, and the conductivity is about 100 mS / cm.
Saturates at ² Therefore, by adding ions that do not affect the formation of the electrodeposited film, for example, Na ⁺ ions or Cl ⁻ ions, the electrodeposition speed can be increased. It is preferable to add a salt to the electrolyte so that the volume resistivity in the electrolyte is 10 Ω · cm or more and 10 ⁶ Ω · cm or less.

The film thickness formed within a certain time becomes significantly larger as the temperature is higher. Therefore, it is preferable to control the temperature so that the temperature of the electrolytic solution is kept constant, since the thickness of the electrodeposited film can be made uniform and a colored electrodeposited film having higher smoothness can be formed.

The pH of the aqueous liquid before light irradiation is preferably set within a range of ± 2 from the pH at which the state of the electrodeposition material used changes. If the pH of the aqueous liquid is set in such a range, the dissolution of the colored electrodeposition material in the aqueous liquid becomes saturated before the electrodeposition film is formed. As a result, once the electrodeposited film is formed, it is difficult to redissolve in the liquid after the film is formed, so that the electrodeposited film can be manufactured stably. The pH of the aqueous liquid is adjusted to the above range by adding an acidic or alkaline substance which does not affect the electrodeposition characteristics.

When the substrate is immersed in the aqueous liquid, it is sufficient that at least the optical semiconductor thin film is in contact with the aqueous liquid, and the entire substrate can be completely immersed in the liquid, or only the optical semiconductor thin film can be immersed in the liquid. It may be in contact.

Next, a description will be given of the pH change of the aqueous liquid in the vicinity of the substrate and the mechanism of the formation of the colored electrodeposition film accompanying the pH change. Generally, when donating soaked current or voltage platinum electrode in an aqueous solution, OH in the aqueous solution of the vicinity of the anode ^-
The ions are consumed to become O ₂ , and the hydrogen ions increase to p
H decreases. This is because the following reaction in which the hole (p) and the OH ^- ion are linked occurs near the anode. 2OH ⁻ + 2p ⁺ → 1/2 (O ₂ ) + H ₂ O However, for this reaction to occur, a certain voltage (threshold voltage) is required.
Is required, the reaction proceeds and the pH in the aqueous solution changes only after exceeding the threshold voltage.
Decreases and the pH increases near the cathode). If the photovoltaic power alone does not exceed the electrodeposition threshold for the electrodeposition material,
Applying a current or voltage to the conductive film of the substrate in advance and applying a bias voltage, irradiating light to cause a photoelectromotive force in the optical semiconductor, and setting only the light irradiated portion to a potential exceeding the threshold value,
The above reaction proceeds only in the aqueous solution near the light irradiation part of the substrate. As a result of the progress of the reaction, the pH of the aqueous solution near the light-irradiated portion changes, and the solubility of the colored electrodeposition material changes accordingly, and a colored electrodeposition film is formed only in the light-irradiated portion.

Accordingly, in the present invention, the magnitude of the current or voltage previously supplied to the substrate (light-transmitting conductive film in the substrate) compensates for the potential generated in the substrate by the photovoltaic force generated by the optical semiconductor thin film, and Need to be set so that the potential of the reference voltage reaches the threshold voltage. On the other hand, the current or voltage previously supplied to the substrate (the light-transmitting conductive film in the substrate) is
It is necessary to set the size not to exceed the Schottky barrier. If the current or voltage supplied to the substrate in advance is too large, the Schottky barrier is broken, current flows also in the area not irradiated with light, and an electrodeposition film is formed on the entire area of the optical semiconductor substrate, and the color electrodeposition film is formed. This is because the arrangement cannot be controlled. For example, the photovoltaic power of TiO ₂ is about 0.6 V
Therefore, if the coloring material is electrodeposited at 2.0 V,
When light irradiation is performed while applying a bias voltage of 1.4 V, the potential of the light irradiation portion of the substrate (optical semiconductor film) becomes 0.6 V + 1.4.
V = 2.0V, exceeding the threshold voltage required for electrodeposition,
A colored electrodeposition film is formed only on the light irradiation part.

In a conventional method for producing a color filter using an electrodeposition technique, for example, the methods described in JP-A-5-119209 and JP-A-5-157905, the electrodeposition voltage is from 20 V to 80 V. Highly, a polymer is used as an electrodeposition material, and an electrodeposition film is formed using a redox reaction of the polymer. In the present invention, since the electrodeposition film is formed by the above mechanism, the substrate (optical semiconductor thin film) at the time of electrodeposition is formed.
Can be lower than the Schottky barrier, and as a result, it is possible to provide a manufacturing method which has high controllability and can cope with fine pixel arrangement. The voltage of the substrate (optical semiconductor thin film) at the time of electrodeposition is preferably 5 V or less.

Next, the combination of an optical semiconductor and a colored electrodeposition material will be described. In the present invention, in the formation of photovoltaic,
A Schottky barrier generated at an interface in contact with an optical semiconductor and a barrier of a pn junction or a pin junction are used. FIG. 5A schematically shows a Schottky barrier generated at the interface between the n-type optical semiconductor and the aqueous liquid, and FIG. 5B schematically shows a pin junction barrier. For example, when an n-type optical semiconductor is used (FIG. 5A), when the n-type optical semiconductor side is made negative,
Since the current flows in the forward direction, the current flows, but conversely,
When the n-type optical semiconductor side is positive, that is, a Schottky junction between the n-type optical semiconductor and the aqueous liquid forms a barrier, and no current flows. However, even in a state where the current does not flow with the n-type optical semiconductor side being positive, when light is irradiated, electron-hole pairs are generated from the n-type optical semiconductor thin film, the holes move to the solution side, and the current flows. In this case, the material to be electrodeposited must be an anionic molecule because the n-type optical semiconductor is set at a positive potential. Accordingly, a combination of an n-type optical semiconductor and an anionic molecule is formed, and conversely, a cation is electrodeposited in a p-type optical semiconductor. In particular, it is preferable to use a colored electrodeposition material containing a compound having a carboxyl group when an n-type optical semiconductor is used and a compound having an amino group or an imino group when a p-type semiconductor is used. pn
When a junction or pin junction semiconductor thin film is used, current or voltage is applied so that the semiconductor film portion is in the forward direction and the interface with the liquid is in the opposite direction.

In order to apply a current or a voltage to the light-transmitting conductive film, it is necessary to provide a current path for supplying the current or the voltage to a side edge or the like of the conductive film. A potentiostat or the like is used for supplying current or voltage.

[0048]

EXAMPLE 1 As shown in FIG. 4, a transparent conductive film of ITO was formed to a thickness of 100 nm on a non-alkali glass substrate (7059 glass) having a thickness of 0.5 mm by sputtering, and a TiO ₂ film of 250 nm was formed. . Next, a reduction treatment was performed to improve the photocurrent characteristics of TiO ₂ . In the reduction treatment, the TiO ₂ film was annealed at 300 ° C. for 10 minutes in pure nitrogen gas mixed with 3% hydrogen gas.

As shown in FIG. 1, this substrate was placed in a tripolar arrangement generally used in electrochemical applications, and a styrene-acrylic acid copolymer (molecular weight: 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio) was used. 65%, an aqueous solution containing a pigment dispersed oxide 150) and an azo-based red ultrafine pigment in a one-to-one in solid content of an electrolyte solution, to the saturated calomel electrode using the TiO ₂ electrode as the working electrode, acting The bias voltage applied to the electrodes was 1.8 V, and ultraviolet rays were selectively irradiated from the back side of the substrate. For UV irradiation, a projection type exposure apparatus manufactured by Ushio was used (light intensity at a wavelength of 365 nm, 50 mW / cm ² ). The projection type exposure apparatus was adjusted so that an image was formed once on the photomask and further formed on the surface of titanium oxide, which is the back surface of the substrate, via an optical lens. Exposure for 2 seconds with this apparatus resulted in the formation of a red mask filter pattern only in the area where the light was irradiated on the TiO ₂ surface.

FIG. 6 shows the details of the process of forming a red mask filter pattern using the apparatus shown in FIG. First, the substrate was set in a liquid tank filled with an electrolytic solution. A bias voltage was applied in synchronization with a signal from a sensor that sensed the contact of the electrolyte with the substrate. After the completion of the ultraviolet irradiation, the bias voltage applied to the working electrode was released, and at the same time, the substrate was removed from the liquid tank. Next, shower cleaning, which is generally used for substrate cleaning, was performed so that the water flow hits the substrate at right angles to the edge profile of the electrodeposited film as much as possible. After the completion of the shower cleaning, water droplets were wiped off by blowing clean air onto the substrate. Thereafter, the resulting mask pattern was dried by being left for about 5 minutes.

Next, in the step shown in FIG. 6, a styrene-acrylic acid copolymer (molecular weight 13,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 65%, oxidation 150) and phthalocyanine green-based ultrafine pigment were An aqueous solution containing a pigment dispersed at a solid content ratio of 1: 1 is used as an electrolyte, a TiO ₂ electrode is used as a working electrode with respect to a saturated calomel electrode, and a bias voltage applied to the working electrode is set to 1.8 V to adjust the substrate. When selectively exposed for 2 seconds from the back side using the same exposure apparatus, a green mask filter pattern was formed only on the illuminated area on the TiO ₂ surface.

Similarly, in the step shown in FIG. 6, a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group)
(Mol ratio of 65%, oxidation 150) and a phthalocyanine blue-based ultrafine pigment dispersed at a solid content ratio of 1: 1 as an aqueous solution containing a pigment as an electrolyte, and a TiO ₂ electrode as a working electrode with a saturated calomel electrode Then, when the bias voltage applied to the working electrode was set to 1.8 V and the substrate was selectively exposed for 2 seconds from the back side of the substrate using the same exposure apparatus, a blue mask filter pattern was formed only in the region where light was irradiated on the TiO ₂ surface. As a result, a color filter layer was formed. The edge profile of the color filter layer thus formed was sharper than that of the color filter layer to which a bias voltage was applied only during light irradiation.

Finally, after sufficiently drying the color filter layer, a styrene-acrylic acid copolymer (molecular weight: 13,00
0, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65%, oxidation 150) and carbon black powder (average particle diameter 80nm) in a solid content ratio of 1 to 1
Using a TiO ₂ electrode as a working electrode for a saturated calomel electrode in an aqueous solution containing a pigment dispersed in
When a voltage was applied to 0 V for 2 seconds, a region without the color filter layer was covered with the carbon thin film, and a black matrix was formed. The sensor for sensing the contact between the substrate and the electrolyte may have an electric circuit independent of the potentiostat as shown in FIG.
A triangulation type optical sensor that measures the liquid level from above may be used, or a sensor that detects the liquid level by blocking the light with the electrolyte as the liquid level rises. Good.

Example 2 As shown in FIG. 4, a transparent conductive film of ITO was formed to a thickness of 100 nm on a non-alkali glass substrate (7059 glass) having a thickness of 0.5 mm by sputtering, and a TiO ₂ film of 250 nm was formed. Next, a reduction treatment was performed to improve the photocurrent characteristics of TiO ₂ . In the reduction treatment, the TiO ₂ film was annealed at 300 ° C. for 10 minutes in pure nitrogen gas mixed with 3% hydrogen gas.

The substrate was placed in a tripolar arrangement commonly used in electrochemical applications, as shown in FIG. 1, in a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) mole). (A 65% ratio, oxidation 150) and an azo red ultrafine particle pigment dispersed in a 1: 1 solid content ratio are used as an electrolyte in an aqueous solution containing a pigment, and a TiO ₂ electrode is used as a working electrode against a saturated calomel electrode. The bias voltage applied to the working electrode was set to 1.8 V, and ultraviolet rays were selectively irradiated from the back side of the substrate. For UV irradiation, a projection type exposure apparatus manufactured by Ushio was used (light intensity at a wavelength of 365 nm, 50 mW / cm ² ). The projection type exposure apparatus was adjusted so that an image was formed once on the photomask and further formed on the surface of titanium oxide, which is the back surface of the substrate, via an optical lens. Exposure for 2 seconds with this apparatus resulted in the formation of a red mask filter pattern only in the area where the light was irradiated on the TiO ₂ surface.

FIG. 7 shows the details of the process of forming a red mask filter pattern using the apparatus shown in FIG. First, the substrate was set in a liquid tank, and an electrolytic solution was injected into the liquid tank. A bias voltage of 1.0 V was applied in synchronization with a signal from a sensor that sensed the contact of the electrolyte with the substrate. After the ultraviolet irradiation was completed, the bias voltage applied to the working electrode was released, and at the same time, the electrolytic solution was extracted from the liquid tank. Next, washing water obtained by adding a small amount of salt to pure water was injected into the liquid tank, and a bias voltage was applied in synchronization with a signal from a sensor that sensed the contact of the washing water with the substrate. The washing water should have a constant flow rate,
Unnecessary electrodeposition liquid attached was washed away. At the same time when the bias voltage was released again, the washing water was removed from the liquid tank, and water droplets were wiped off by blowing clean air on the substrate. Thereafter, the resulting mask pattern was dried by being left for about 5 minutes.

Next, in the step shown in FIG. 7, a styrene-acrylic acid copolymer (molecular weight 13,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 65%, oxidation 150) and phthalocyanine green-based ultrafine pigment were An aqueous solution containing a pigment dispersed in a solid content ratio of 1 to 1 was used as an electrolytic solution, a TiO ₂ electrode was used as a working electrode with respect to a saturated calomel electrode, and a bias voltage applied to the working electrode was set to 1.8 V. When selectively exposed for 2 seconds from the back side using the same exposure apparatus, a green mask filter pattern was formed only on the illuminated area on the TiO ₂ surface. Similarly, in the step shown in FIG. 7, the styrene-acrylic acid copolymer (molecular weight 13,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 65%, oxidized 150) and phthalocyanine blue-based ultrafine particle pigment were mixed in a solid content ratio. The aqueous solution containing the pigment dispersed one-to-one as described above is used as the electrolyte, the TiO ₂ electrode is used as the working electrode with respect to the saturated calomel electrode, and the bias voltage applied to the working electrode is 1.8.
When the substrate was selectively exposed to V for 2 seconds from the back side of the substrate using the same exposure apparatus, a blue mask filter pattern was formed only in the region where light was irradiated on the TiO ₂ surface, and a color filter layer was formed. The edge profile of the color filter layer thus formed was sharper than that of the color filter layer to which a bias voltage was applied only during light irradiation.

Finally, after sufficiently drying the color filter layer, a styrene-acrylic acid copolymer (molecular weight: 13,00
0, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65%, oxidation 150) and carbon black powder (average particle diameter 80nm) in a solid content ratio of 1 to 1
The TiO ₂ electrode is used as a working electrode for a saturated calomel electrode in an aqueous solution containing a pigment dispersed in
6V from the back side of the substrate, 2
After exposure for 2 seconds, the carbon thin film was covered only in the region without the color filter layer to form a black matrix. The sensor for detecting the contact between the substrate and the electrolytic solution and the contact between the substrate and the washing water may have an electric circuit independent of the potentiostat as shown in FIG. A triangulation-type optical sensor for measurement may be used.

Example 3 As shown in FIG. 4, a non-alkali glass substrate having a thickness of 0.5 mm
(7059 glass) sputtered with ITO transparent conductive film
100nm film by sol-gel method on ITO thin film
 TiO_TwoWas formed. In film formation, spin coating on ITO substrate
With TiO_TwoAlkoxide (Nippon Soda, Atron NTi-092)
After forming a film at a rotation speed of 1500 rpm for 20 seconds, about 1 hour at about 500 ° C
Heat the substrate between_TwoWas formed. In the reduction process,
Pure nitrogen gas mixed with 3% hydrogen gas as in Example 1.
In, TiO at 300 ℃ for 10 minutes _TwoWas annealed.

The substrate was placed in a trielectrode arrangement, which is common in electrochemistry as shown in FIG. 1, in a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) mole). An aqueous solution containing a pigment obtained by dispersing the azo-based red ultrafine particle pigment at a solid content ratio of 1: 1 with a 65% ratio, oxidation 150) and an azo red
The TiO ₂ electrode was used as a working electrode with respect to the saturated calomel electrode, and the bias voltage applied to the working electrode was 1.8 V, and ultraviolet rays were selectively irradiated from the back side of the substrate. For UV irradiation, a projection type exposure apparatus manufactured by Ushio was used (light intensity at a wavelength of 365 nm, 50 mW / cm ² ). The projection type exposure apparatus was adjusted so that an image was formed once on the photomask and further formed on the surface of titanium oxide, which is the back surface of the substrate, via an optical lens. Exposure for 2 seconds with this apparatus resulted in the formation of a red mask filter pattern only in the area where the light was irradiated on the TiO ₂ surface.

FIG. 8 shows details of the step of forming a red mask filter pattern by the apparatus shown in FIG. First, the substrate was set in a liquid tank filled with an electrolytic solution. A bias voltage was applied in synchronization with a signal from a sensor that sensed the contact of the electrolyte with the substrate. After the completion of the ultraviolet irradiation, the bias voltage applied to the working electrode was released, and at the same time, the substrate was removed from the liquid tank. Next, the substrate was set in a separately prepared liquid tank filled with cleaning water, and a bias voltage of 1.0 V was again applied to the working electrode in synchronization with a signal from a sensor that sensed contact between the substrate and the cleaning water. The washing water had a constant flow rate so that the unneeded electrodeposition liquid attached was washed away. At the same time when the bias voltage was released again, the substrate was removed from the liquid tank, and water droplets were wiped off by blowing clean air onto the substrate. Thereafter, the resulting mask pattern was dried by being left for about 5 minutes.

Next, in the step shown in FIG. 8, a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group)
Of phthalocyanine green-based ultra-fine particle pigment in a molar ratio of 65: 1 and a phthalocyanine green-based ultrafine particle pigment dispersed at a solid content ratio of 1: 1 as an electrolyte, and a TiO ₂ electrode as a working electrode with a saturated calomel electrode. Then, when the bias voltage applied to the working electrode was set to 1.8 V and the substrate was selectively exposed for 2 seconds from the back side of the substrate using the same exposure apparatus, a green mask filter pattern was formed only in the area where light was irradiated on the TiO ₂ surface. Been formed. Similarly, in the step shown in FIG. 8, a styrene-acrylic acid copolymer (molecular weight 13,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 65%, oxidation 150) and phthalocyanine blue-based ultrafine particle pigment were solidified. An aqueous solution containing a pigment dispersed in a ratio of 1 to 1 is used as an electrolyte, a TiO ₂ electrode is used as a working electrode with respect to a saturated calomel electrode, and a bias voltage applied to the working electrode is set to 1.8 V from the back side of the substrate. When selectively exposed for 2 seconds using the same exposure apparatus, a blue mask filter pattern was formed only in the region where light was irradiated on the TiO ₂ surface, and a color filter layer was formed. The edge profile of the color filter layer thus formed was sharper than that of the color filter layer to which a bias voltage was applied only during light irradiation.

Finally, after sufficiently drying the color filter layer, a styrene-acrylic acid copolymer (molecular weight: 13,00
0, saturated in an aqueous solution containing a pigment in which a hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65%, oxidized 150) and carbon black powder (average particle diameter 80 nm) are dispersed at a solid content ratio of 1: 1. When the TiO ₂ electrode was used as the working electrode for the calomel electrode, and the working electrode was set to 1.6 V and exposed from the back side of the substrate for 2 seconds using an exposure apparatus without a mask, a carbon thin film was formed only in the area without the color filter layer. A covering black matrix could be formed. The sensor for detecting the contact between the substrate and the electrolytic solution and the contact between the substrate and the washing water may have an electric circuit independent of the potentiostat as shown in FIG. A triangulation-type optical sensor for measurement may be used.

Example 4 As shown in FIG. 4, a transparent conductive film of ITO was formed to a thickness of 100 nm on a non-alkali glass substrate (7059 glass) having a thickness of 0.5 mm by sputtering, and a 200 nm film was formed on the ITO thin film by a sol-gel method.
TiO ₂ was formed. Film formation by spin coating on ITO substrate
An alkoxide of TiO ₂ (Atron NTi-092, manufactured by Nippon Soda) was formed into a film at a rotation speed of 1500 rpm for 20 seconds, and then heated at about 500 ° C. for 1 hour to form a TiO ₂ film. In the reduction process, Example 1
30% in pure nitrogen gas mixed with 3% hydrogen gas
The TiO ₂ film was annealed at 0 ° C. for 10 minutes.

This substrate was placed in a trielectrode arrangement, which is common in electrochemistry, as shown in FIG. 1, in a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic / (hydrophilic group + hydrophobic group) mole). 65%, oxidation 150) and carbon black powder (average particle size 8
(0 nm) in an aqueous solution containing a pigment in which the solid content ratio is dispersed in a ratio of 1 to 1, using a TiO ₂ electrode as a working electrode with respect to a saturated calomel electrode, setting the working electrode to 1.6 V, and selecting ultraviolet light from the back side of the substrate. Irradiation. For UV irradiation, a projection-type exposure apparatus manufactured by Ushio was used (wavelength 36
5 nm light intensity 50 mW / cm ² ). The projection type exposure apparatus was adjusted so that an image was formed once on the photomask and further formed on the surface of titanium oxide, which is the back surface of the substrate, via an optical lens. After exposure for 2 seconds with this apparatus, a thin line pattern of a black matrix was drawn only in a region where light was irradiated on the TiO ₂ surface.

FIG. 8 shows the details of the process of forming a black matrix fine line pattern using the apparatus shown in FIG.
First, the substrate was set in a liquid tank filled with an electrolytic solution.
A bias voltage was applied in synchronization with a signal from a sensor that sensed the contact of the electrolyte with the substrate. After the completion of the ultraviolet irradiation, the bias voltage applied to the working electrode was released, and at the same time, the substrate was removed from the liquid tank. Next, the substrate was set in a separately prepared liquid tank filled with cleaning water, and a bias voltage of 1.0 V was again applied to the working electrode in synchronization with a signal from a sensor that sensed contact between the substrate and the cleaning water. The washing water had a constant flow rate so that the unneeded electrodeposition liquid attached was washed away. At the same time when the bias voltage was released again, the substrate was removed from the liquid tank, and water droplets were wiped off by blowing clean air onto the substrate. Thereafter, the resulting mask pattern was dried by being left for about 5 minutes.

Next, in the step shown in FIG. 8, a styrene-acrylic acid copolymer (molecular weight 13,000, molar ratio of hydrophobic group / (hydrophilic group + hydrophobic group) 65%, oxidation 150) and phthalocyanine green-based ultrafine pigment were An aqueous solution containing a pigment dispersed at a solid content ratio of 1 to 1 was used as an electrolytic solution, a TiO ₂ electrode was used as a working electrode with respect to a saturated calomel electrode, and a bias voltage applied to the working electrode was set to 1.8 V. When selectively exposed for 2 seconds from the back side using the same exposure apparatus, a green mask filter pattern was formed only on the illuminated area on the TiO ₂ surface. Similarly, in the step shown in FIG. 8, the styrene-acrylic acid copolymer (molecular weight: 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio: 65%, oxidation: 150) and phthalocyanine blue-based ultrafine pigment were mixed in a solid content ratio. The aqueous solution containing the pigment dispersed one-to-one as described above was used as the electrolyte, the TiO ₂ electrode was used as the working electrode with respect to the saturated calomel electrode, and the bias voltage applied to the working electrode was 1.
8V and select 2V from the back side of the substrate with the same exposure apparatus.
After exposure for ₂ seconds, a blue mask filter pattern was formed only in the light-irradiated region on the TiO ₂ surface, and a color filter layer was formed. Similarly, in the step shown in FIG. 8, a styrene-acrylic acid copolymer (molecular weight: 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio: 65%, oxidation: 150) and azo red ultrafine particle pigment were solid content ratio. The aqueous solution containing the pigment dispersed one-to-one as the electrolyte is used as the electrolyte, the TiO ₂ electrode is used as the working electrode with respect to the saturated calomel electrode, the bias voltage applied to the working electrode is 1.8 V, and the same is applied from the back side of the substrate. Was selectively exposed for 2 seconds by using the exposure device of No. ₁ , a red mask filter pattern was formed only in the region where light was irradiated on the TiO ₂ surface, and a color filter layer was formed.

The black matrix and the color filter layer thus formed had a sharper edge profile than those obtained by applying a bias voltage only during light irradiation. The substrate and the electrolyte,
As a sensor for detecting the contact between the substrate and the cleaning water, a sensor having an electric circuit independent of the potentiostat as shown in FIG. 1 may be used, or a triangulation type measuring the liquid level from above may be used. An optical sensor or the like may be used.

Example 5 As shown in FIG. 4, a transparent conductive film of ITO was formed to a thickness of 100 nm on a non-alkali glass substrate (7059 glass) having a thickness of 0.5 mm by sputtering, and a 200 nm film was formed on the ITO thin film by a sol-gel method.
TiO ₂ was formed. In film formation, an alkoxide of TiO ₂ (manufactured by Nippon Soda, Atron NTi-092) was formed on an ITO substrate by spin coating at a rotation speed of 1500 rpm for 20 seconds, and then heated at about 500 ° C. for 1 hour to form TiO ₂ Was formed. In the reduction process, the embodiment
Same as 1 in 300% pure nitrogen gas mixed with 3% hydrogen gas
The film of TiO ₂ was annealed at 10 ° C. for 10 minutes.

This substrate was placed in a tripolar arrangement commonly used in electrochemical applications, as shown in FIG. 1, in a styrene-acrylic acid copolymer (molecular weight 13,000, hydrophobic / (hydrophilic group + hydrophobic group) mole). An aqueous solution containing a pigment obtained by dispersing the azo-based red ultrafine particle pigment at a solid content ratio of 1: 1 with a 65% ratio, oxidation 150) and an azo red
The TiO ₂ electrode was used as a working electrode with respect to the saturated calomel electrode, and the bias voltage applied to the working electrode was 1.8 V, and ultraviolet rays were selectively irradiated from the back side of the substrate. For UV irradiation, a projection-type exposure apparatus manufactured by Ushio was used (light intensity at a wavelength of 365 nm, 50 mW / cm ² ). The projection type exposure apparatus was adjusted so that an image was formed once on the photomask and further formed on the surface of titanium oxide, which is the back surface of the substrate, via an optical lens. Exposure for 2 seconds with this apparatus resulted in the formation of a red mask filter pattern only in the area where the light was irradiated on the TiO ₂ surface.

Next, a styrene-acrylic acid copolymer (part
13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 65%, oxidation 1
50) and phthalocyanine green ultrafine pigment
An aqueous solution containing a pigment dispersed in a ratio of 1 to 1 is used as an electrolyte.
TiO2 for saturated calomel electrode_TwoElectrode as working electrode
To 1.8V bias voltage applied to the working electrode
And selectively exposed for 2 seconds from the back side of the substrate with the same exposure apparatus.
When lit, TiO _TwoOnly the area where light is irradiated on the surface
A filter pattern was formed. Similarly,
Len-acrylic acid copolymer (molecular weight 13,000, hydrophobic group / (hydrophilic
Group + hydrophobic group) 65%, oxidation 150) and phthalocyanine
Pigments in which 1-based ultrafine pigments are dispersed at a solid content ratio of 1: 1
An aqueous solution containing
O_TwoUsing the electrode as a working electrode,
Similar exposure from the back side of the substrate with the bias voltage set to 1.8V
When selectively exposed for 2 seconds with the device, TiO_TwoLight on the surface
Blue mask filter pattern only in the irradiated area
Was formed to form a color filter layer.

FIG. 9 shows the details of the process of forming the three color filter patterns by the apparatus shown in FIG. First, the substrate was set in a liquid tank filled with a red electrolytic solution.
A bias voltage was applied in synchronization with a signal from a sensor that sensed the contact of the electrolyte with the substrate. After the completion of the ultraviolet irradiation, the red electrolytic solution was discharged while pouring washing water obtained by adding a small amount of salt to pure water into the liquid tank. This was performed until the liquid filling the liquid tank became almost completely the washing water. Then, while pouring a green electrodeposition solution into the liquid tank, the washing water was discharged. This was carried out until the concentration of the green electrodeposition solution filling the inside of the solution tank reached the original value. After the UV irradiation ends,
The green electrolyte was discharged while washing water was injected into the liquid tank. This was performed until the liquid filling the liquid tank became almost completely the washing water. Then, while pouring the blue electrodeposition solution into the liquid tank, the washing water was discharged. After the completion of the ultraviolet irradiation, the blue electrolyte was discharged while pouring the washing water into the liquid tank. This was performed until the liquid filling the liquid tank became almost completely the washing water. Finally, the substrate was removed from the liquid tank at the same time when the bias voltage was released. The edge profile of the color filter layer thus formed was sharper than that of the color filter layer to which a bias voltage was applied only during light irradiation.

Finally, after the color filter layer is sufficiently dried, it is brought into contact with an ultraviolet curable resin solution in which carbon black powder (average particle diameter 80 nm) is dispersed, and U
Upon irradiation with V light, a carbon resin thin film was formed which was cured only in the region without the color filter layer, and a black matrix could be formed. As a sensor for detecting the contact between the substrate and the electrolyte, and the contact between the substrate and the washing water, FIG.
May be one having an electric circuit independent of the potentiostat, or a triangulation type optical sensor for measuring the liquid level from above may be used.

Example 6 As shown in FIG. 4, a transparent conductive film of ITO was formed to a thickness of 100 nm on a non-alkali glass substrate (7059 glass) having a thickness of 0.5 mm by sputtering, and a 200 nm film was formed on the ITO thin film by a sol-gel method.
TiO ₂ was formed. In film formation, an alkoxide of TiO ₂ (manufactured by Nippon Soda, Atron NTi-092) was formed on an ITO substrate by spin coating at a rotation speed of 1500 rpm for 20 seconds, and then heated at about 500 ° C. for 1 hour to form TiO ₂ Was formed. In the reduction process, the embodiment
In pure nitrogen gas mixed with 3% hydrogen gas as in 1,
The TiO ₂ film was annealed at 00 ° C. for 10 minutes.

This substrate was subjected to electrochemical treatment as shown in FIG.
Azo with electrodeposition capability
An aqueous solution containing a red dye is used as the electrolyte, and the saturated calomel
TiO for pole_TwoUsing the electrode as a working electrode
Apply a bias voltage of 2.0 V to the back side of the substrate.
Ultraviolet light was selectively irradiated. Ushio for UV irradiation
An electric projection type exposure system was used (wavelength
365m light intensity 50mW / cm ^Two). Projection type exposure equipment
Once forms an image on the photomask and then through an optical lens
To form an image on the titanium oxide surface, which is the back side of the substrate.
Saved. Exposure for 2 seconds with this equipment gave TiO_TwoOn the surface
Red mask filter pattern only in the area where light was irradiated
Formed. Next, styrene-acrylic acid copolymerization
Body (molecular weight 13,000, hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio 65%,
Oxidation 150) and Catilon Pure Blue 5GH at a solids ratio of 1: 1
The aqueous solution containing the dye dispersed in
TiO_TwoUsing the electrode as a working electrode
The bias voltage applied to the pole is set to 2.0 V and the back side of the substrate
And then selectively exposed for 2 seconds with the same exposure equipment,
TiO_TwoBlue filter only in the area where light was irradiated on the surface
A pattern was formed. Similarly, 0.01M Pro Jet Fast
Mix Yellow2 and 0.01M Catilon Pure Blue 5GH
Using TiO for saturated calomel electrode using aqueous solution as electrolyte_TwoElectrodes
Used as a working electrode, the bias voltage applied to the working electrode
Pressure to 2.0 V and select from the back side of the substrate with the same exposure equipment.
Alternatively, when exposed for 2 seconds, TiO_TwoThe surface is illuminated with light
The green filter pattern is formed only in the area
Thus, a color filter layer was formed.

FIG. 9 shows the details of the process of forming the three color filter patterns using the apparatus shown in FIG. First, the substrate was set in a liquid tank filled with a red electrolytic solution.
A bias voltage was applied in synchronization with a signal from a sensor that sensed the contact of the electrolyte with the substrate. After the completion of the ultraviolet irradiation, the red electrolytic solution was discharged while pouring washing water obtained by adding a small amount of salt to pure water into the liquid tank. This was performed until the liquid filling the liquid tank became almost completely the washing water. Then, while pouring a green electrodeposition solution into the liquid tank, the washing water was discharged. This was carried out until the concentration of the green electrodeposition solution filling the inside of the solution tank reached the original value. After the UV irradiation ends,
The green electrolyte was discharged while washing water was injected into the liquid tank. This was performed until the liquid filling the liquid tank became almost completely the washing water. Then, while pouring the blue electrodeposition solution into the liquid tank, the washing water was discharged. After the completion of the ultraviolet irradiation, the blue electrolyte was discharged while pouring the washing water into the liquid tank. This was performed until the liquid filling the liquid tank became almost completely the washing water. Finally, the substrate was removed from the liquid tank at the same time when the bias voltage was released. The edge profile of the color filter layer thus formed was sharper than that of the color filter layer to which a bias voltage was applied only during light irradiation.

Finally, after sufficiently drying the color filter layer, a styrene-acrylic acid copolymer (molecular weight 13,000,
Saturated calomel electrode in an aqueous solution containing a pigment in which a hydrophobic group / (hydrophilic group + hydrophobic group) molar ratio of 65%, oxidized 150) and carbon black powder (average particle diameter 80 nm) are dispersed at a solid content ratio of 1: 1. The TiO ₂ electrode was used as a working electrode and the working electrode was 1.6
When the substrate was exposed to V for 2 seconds from the back side of the substrate using the same exposure apparatus, a black matrix was formed by covering the carbon thin film only in the region without the color filter layer. The sensor for detecting the contact between the substrate and the electrolytic solution and the contact between the substrate and the washing water may have an electric circuit independent of the potentiostat as shown in FIG. A triangulation-type optical sensor for measurement may be used.

[0078]

According to the method and the apparatus for manufacturing a color filter of the present invention, not only the color filter layer but also the black matrix can be obtained with a high resolution and smoothness by a simple method not including a photolithography step. A high-performance color filter can be formed at low cost. The range of use was limited by the conventional electrodeposition method,
A color filter having a complicated and fine pattern can be easily manufactured. In particular, by applying a voltage at least while the substrate is in contact with the electrolytic solution or the cleaning solution, a color filter with sharp edges at each pixel can be manufactured.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing one embodiment of a color filter manufacturing apparatus of the present invention.

FIG. 2 is a view schematically showing one embodiment of a manufacturing process of the color filter of the present invention.

FIG. 3 is a graph showing the relationship between the conductivity of an aqueous electrolyte and the amount of electrodeposition.

FIG. 4 is a diagram showing a method for manufacturing a titanium oxide film used in an example of the present invention.

5A is a schematic diagram showing an energy band of a semiconductor in the case of a Schottky junction, and FIG. 5B is a schematic diagram showing an energy band of a semiconductor in a case of a pin junction.

FIG. 6 is a flowchart of a process used in an example.

FIG. 7 is another flowchart of the process used in the example.

FIG. 8 is still another flowchart of the process used in the example.

FIG. 9 is another flowchart of the steps used in the example.

FIG. 10 is a graph showing a relationship between an applied voltage and an attached amount.

[Explanation of symbols]

Reference Signs List 10 substrate 11 light-transmitting support 12
Light-transmitting conductive film 13 Optical semiconductor thin film 20 Aqueous electrolyte 21 Colored electrodeposition film 22
Black electrodeposition film

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Eiichi Akutsu 430 Sakai-Nakai-cho, Ashigara-gun, Kanagawa Green Tech Nakai F-term in Fuji Xerox Co., Ltd. 2H042 AA06 AA09 AA15 AA26 2H048 BA02 BA11 BA62 BB01 BB02 BB13 BB14 BB15 BB24 BB42 BB46 5G435 AA00 AA17 GG12 KK07 KK10

Claims (14)

[Claims] 1. A light-transmitting conductive film on a light-transmitting support,
A substrate in which optical semiconductor thin films having a photovoltaic function are sequentially laminated is disposed such that at least the optical semiconductor thin film is in contact with an electrolytic solution containing an electrodeposition material containing a coloring material precipitated by a change in hydrogen ion concentration. Selectively irradiating light, generating a photoelectromotive force in a light irradiation portion of the optical semiconductor thin film, and electrochemically depositing the electrodeposition material to form a color filter layer composed of a colored electrodeposition film. And applying a constant bias voltage to the substrate at least while the substrate and the electrolytic solution are in contact with each other. 2. The method according to claim 1, wherein a constant bias voltage is applied to the transparent substrate in synchronization with a contact time between the substrate and the electrolyte. 3. The method according to claim 1, further comprising the step of cleaning the substrate by contacting the substrate with running water after forming the electrodeposited film, wherein a constant bias voltage is applied to the substrate in synchronization with the contact time of the substrate and the flowing water. The method according to claim 2, wherein the color filter is applied. 4. The apparatus according to claim 1, wherein the bias voltage is lower than a limit voltage at which a Schottky barrier between the optical semiconductor thin film and the electrolyte is maintained. Color filter manufacturing method. 5. The method according to claim 5, wherein the substrate is brought into contact with the electrolytic solution from a state in contact with the flowing water, and from a state in contact with the flowing water to a state in contact with the electrolytic solution. The method for producing a color filter according to claim 3, wherein the color filter is changed continuously. 6. The light-emitting device according to claim 1, wherein light is irradiated from the support side, and the irradiated light is imaged on a surface of the optical semiconductor thin film by an imaging optical system. Method for manufacturing color filters. 7. The method according to claim 1, wherein titanium oxide is used as the optical semiconductor thin film. 8. The method for producing a color filter according to claim 7, wherein titanium oxide that has been heated and reduced in a hydrogen atmosphere is used as the optical semiconductor thin film. 9. The method for producing a color filter according to claim 1, wherein the electrodeposition material is deposited within a potential difference range of 5 V or less. 10. The method according to claim 1, wherein a salt is added to the electrolyte so that the specific volume resistivity in the electrolyte is in the range of 10 Ω · cm to 10 ⁶ Ω · cm. A method for producing a color filter according to any one of the preceding claims. 11. The method according to claim 1, wherein the temperature of the electrolyte is kept constant and the electrodeposition speed is kept constant.
The method for producing a color filter according to any one of the above. 12. A liquid tank capable of storing an electrolytic solution, a substrate in which a light-transmitting conductive film and a photo-semiconductor thin film having a photovoltaic function are sequentially laminated on a light-transmitting support, comprising: Means for fixing so as to contact the electrolyte, light irradiation means for selectively irradiating the substrate with light, a sensor for sensing the contact between the electrolyte in the liquid tank and the substrate, Means for applying a bias voltage to the substrate in synchronization with a signal. 13. The color filter manufacturing apparatus according to claim 12, wherein the sensor is a sensor that measures an electric resistance between the electrolytic solution and the conductive film. 14. The sensor according to claim 1, wherein the sensor is a sensor for measuring a level of the electrolyte.
3. The color filter manufacturing apparatus according to 2.