JPS592009A - Manufacture of color filter - Google Patents

Abstract

PURPOSE:To eliminate dyeing stages after pattern formation and to obtain a color filter with superior spectral characteristics without causing trouble such as color mixing by forming a pattern with a photoresist colored with a dye, forming a transparent protective layer on the surface of the colored layer, and repeating said stages. CONSTITUTION:A solid-state image pickup element is coated with polybutadiene resin, and the resin is dried to smoothen the surface of the element. The smoothened surface is coated with a photoresist prepared by adding an aqueous soln. of a yellow dye and methyl-gamma-styrylpyridinium-methyl sulfate in an aqueous soln. of polyvinyl alcohol, and the photoresist is dried, exposed to ultraviolet rays through a mask having a desired pattern, and developed to form a pattern of a yellow colored layer. A transparent protective layer of polybutadiene is formed on the pattern, and a blue colored layer having a prescribed pattern is formed using a photoresist contg. a blue dye. A transparent protective layer convering the blue colored layer is then formed. Thus, a color filter with superior spectral characteristics is obtd. in simplified stages in a short time.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a method for manufacturing a color filter, and more specifically, to a method for manufacturing a color filter, and more specifically, a method for easily obtaining a color filter having good spectral characteristics without causing color mixture or the like. The present invention relates to a possible method of manufacturing color filters.

[Technical background of the invention and its problems]

2. Description of the Related Art Color filters for solid-state imaging devices used in color television cameras and the like have conventionally been manufactured, for example, by a method shown in FIG.

That is, first, a photoresist material such as polyvinyl alcohol (PVA)-ammonium dichromate (AD(:)) is applied onto a substrate such as a glass substrate or a solid-state image sensor. A transparent pattern is formed by exposing the film to ultraviolet rays, followed by development, rinsing, and heat drying.

This transparent batten is immersed in a dyeing solution containing a coloring substance such as a dye, subjected to dyeing and embedding treatment, then washed with water and dried to be fixed, forming a single layer of color filter. Ru. By repeating the above operations, the desired color filter is manufactured.

However, the above-mentioned manufacturing method has the problem that the manufacturing process is extremely double-tracked and requires a furnace top. That is, in the above treatment, if the heating and drying treatment is not carried out sufficiently during the formation of the transparent batten, the transparent batten may swell during the dyeing process and may peel off from the substrate in some cases. Therefore, it takes at least several hours to about one day to form one layer of color filters, and there is a problem that a completed color filter product cannot be obtained in a short time.

Furthermore, during drying after dyeing, the transparent batten may devitrify depending on the drying conditions, so there is a problem in that care must be taken in controlling the conditions.

Furthermore, when forming another color filter layer on top of the formed nine-color filter layer, if the transparent tabs are misaligned, the colors of the colored tabs will mix with each other, resulting in a decrease in spectral characteristics. are doing.

[Purpose of the invention]

The purpose of the present invention is to solve the above-mentioned nine problems and provide a color filter that does not cause color mixture and has good spectral characteristics.
The object of the present invention is to provide a method for manufacturing a color filter that can be easily obtained.

[Summary of the Invention] As a result of extensive studies, the inventors of the present invention have found that it is possible to achieve the above object by using a photoresist material colored with a dye and providing a transparent protective layer between each color filter layer. The inventors have discovered that the following can be achieved, and have completed the present invention.

That is, the method for manufacturing a color filter of the present invention is a color filter formed by laminating a colored layer on a solid-state image pickup device, and includes forming the colored layer using a photoresist material colored with a dye. It is characterized by forming a transparent protective layer on the surface of each colored layer.

In the following, the invention will be explained in more detail.

In the present invention, first, for the purpose of smoothing the surface of the solid-state image sensor, it is preferable to provide a transparent layer on the surface of the solid-state image sensor by applying and drying a polymer material.

The thickness of this transparent layer should be sufficient for smoothing, and is preferably 0.1 to 5 pm.

It is then possible to manufacture a color filter according to the standard 70-sheet diagram shown in FIG. That is, a colored resist consisting of a dye and a photoresist material is applied onto the solid resist, dried (prebaked), and then exposed to ultraviolet light through a shadow mask having a desired pattern. Next, this element is developed, rinsed and heat treated (
The colored layer of the color filter is formed by post-baking.

In addition, in the above-mentioned treatment, it is preferable that the baking treatment is performed at, for example, 40 to 80° C. for about 10 to 30 minutes. In addition, the post-baking treatment is performed, for example, at a temperature of 80 to
IF) It is preferable to perform the treatment at 0°C for about 10 to 60 minutes.

When exposing to ultraviolet rays, it is possible to carry out appropriate exposure using, for example, a mask aligner for semiconductor manufacturing.

Development and rinsing may be carried out by methods normally employed in the production of color filters.
A method is adopted in which the material is immersed for about 0 seconds, rinsed, and then rinsed with methanol or the like.

To manufacture a color filter, a polymer material is then applied on the color filter layer and dried to form a transparent protective layer, and then a colored resist is applied in the same manner as above and the same operation is repeated. All you have to do is return it.

In the manufacturing method of the present invention, it is of course possible to manufacture a color filter consisting of three colored layers of red, actual and green, but from the point of view of simplifying the process etc., it is possible to manufacture a color filter consisting of colored layers of two colors of blue and yellow. It is preferable to produce a complementary color filter consisting of colored layers.

The thickness of each colored layer formed in the present invention is
It is preferable that it is 0.5-2 micrometers. Film thickness is 0.5μ
This is because if it is less than m, it is difficult to obtain a color density suitable for a color filter, and if it exceeds zpm, there are drawbacks such as the film not being cured by ultraviolet irradiation.

Further, in the present invention, the thickness of the transparent protective layer formed between each colored layer is preferably 0.1 to 2 μm.

The stone photoresist material constituting the colored resist used in the present invention can be any of those normally used in the production of colored Filno capes. Such photoresist materials include, for example, T
PRSFPR (manufactured by Tokyo Ohka Kogyo ■), KPR, KTF
Commercially available resist materials such as R (manufactured by Kodak ■), AZ (manufactured by Shipley ■), etc. Examples include known resist materials such as chemically modified PVA.

Further, as the dye which is another component of the colored resist of the present invention, any dye can be used as long as it satisfies the color filter spectral characteristic curve. Such surface dyes include blue dyes and yellow dyes used in the production of complementary color filters, red dyes, green dyes, and the blue dyes used in the production of ordinary color filters. Specifically, the following dyes are used.

As a blue dye, for example, Sumifix Turkis Blue G1 Sumifix Turkis Blue E? ,
Sumifix Turkis Blue HGF Sunol i
-Ring Brilliant Sky Blue R1 Suminol Leveling Sky Blue R1 Suminol Leveling Blue AGG, Sumilite Spra Blue G (and above,
(manufactured by Susumu Kagaku ■), Solar Cyanine 6G, Solar Pear Blue AFX, Acid Brilliant Blue (manufactured by Mitsui Toatsu ■), etc. The blending amount of these blue dyes is preferably 0.01-10% by weight, more preferably 0.5-5% by weight based on the photoresist material.
Weight%.

Examples of yellow dyes include Suminol i-Ring Yellow MR, Suminol Leveling Yellow 0-NR, and Suminol Fast Yellow 20F.

Suminol Milling Yellow 3G, Suminol Milling Yellow 4G, Suminol Fast Yellow G
1 Sumilite Yellow GR, Sumikaron Yellow 4
GL (manufactured by Susumu Kagaku ■), Kayanol Milling Yellow O1 Kayanol Ixa-N5G, Kayajion Yellow P! SG, Kayashiru Yellow GG (all above,
(manufactured by Nippon Kayaku ■), Selmazol Yellow R, Selmazol Ye 1l-GR.

Examples include Chrysophenine KG, Direct First Yellow, Aminyl Yellow 5GL, and Solar Pure Yellow. The blending amount of these yellow dyes is preferably 0.01-10% by weight, more preferably 0.5-5% by weight based on the photoresist material.
It is.

Examples of the red dyes include Suminol Fast Red B (manufactured by Sumitomo Kagaku ■), Eisen Brilliant Scarlet's) 3RH (manufactured by Osugaya Kagaku ■), and Kayaku Ashida-Damin FB (manufactured by Nippon Kayaku ■). The blending amount of these red dyes is 0.
．． The amount is preferably 01-10% by weight, more preferably 0.5-5% by weight.

As a green dye, for example, Sumilan Green BL (
Examples of these products include Eisenbooslan Olive Green GLH (manufactured by Udougaya Chemical), Diamond Acidocyanine Green GWA (manufactured by Mitsubishi Chemical Industries, Ltd.), and Brilliant Milling Green B (Mitsui Toatsu@#). The blending amount of these green dyes is preferably 0.01-10% by weight, more preferably 0.1-5% by weight, based on the photoresist material.

The dye used in the present invention is one or more dyes selected from the above-mentioned group.

When using these dyes, commercially available dyes may not dissolve in the photoresist material because they contain sodium chloride, sodium sulfate, and the like. In order to avoid such problems, it is preferable to perform appropriate treatment such as purification as necessary before use.

When forming the colored layer in the present invention, the above-mentioned photoresist material and dye are mixed in water, or a predetermined amount of these is mixed in condensate, and then a smoothed solid-state photographic material is used. It is preferable to apply the coating onto the element using a method such as a spin code method or a silk screen method.

In the present invention, the polymer material used for the transparent protective layer formed on the transparent layer or colored layer for the purpose of smoothing the surface of the solid-state image sensor is capable of forming a transparent film. There are no particular restrictions as long as it is. Examples of such polymeric materials include polyvinyl alcohol, gelatin, casein, polystyrene, polyacrylic ester, polymethacrylic ester, acrylic resin,
Examples include polycarbonate resins and polyiodide resins, and one or more resins selected from the group consisting of these resins are used.

To form the above-mentioned transparent layer or transparent protective layer, the above-mentioned polymeric material adjusted to an appropriate viscosity is coated using a method such as a spin code method or a silk screen method, and then This can be achieved by drying for about 10 to 30 minutes at a temperature range of -150°C.

〔Effect of the invention〕

The method of the present invention can be used to form conventional resist patterns.
Compared to the method of dyeing, this method directly forms a colored resist pattern layer, so the process is simplified. Therefore, it has the advantage that a large amount of color filters can be manufactured in a short period of time.

Further, in the color filter obtained by the method of the present invention, since each colored layer is covered with a transparent protective layer, problems such as color mixing do not occur.

Therefore, it is possible to obtain a solid-state imaging device with excellent spectral characteristics.

[Embodiments of the invention]

In the following, the present invention will be explained in more detail with reference to Examples.

Polybutadiene resin was applied onto a charge-coupled device (CCU) solid-state imaging device and dried at 200 C for 60 minutes to smooth the surface.

Next, 4 parts by weight of a 10% aqueous solution of polyvinyl alcohol (degree of polymerization 1500) 1066 containing 1.7 mol% of methyl-r-styrylpyridinium methyl sulfate and Suminol Milling Yellow MR (manufactured by Sumitomo Chemical ■) as a yellow dye were added. Add the solution mixed with aqueous solution 3 a@ to the above C
It was coated onto a CD solid-state imaging device using a spinner to a film thickness of i and am. After drying in air at 80° C. for 30 minutes, it was exposed to 365 mm ultraviolet rays at 600 mJ/cd through a shadow mask having a desired pattern. Next, the film was developed with water for 20 seconds, rinsed with methanol, and dried at 100° C. for 30 minutes to form a yellow colored layer.

When the spectral characteristics of the CCD solid-state imaging device obtained by the above-mentioned treatment were measured, it was confirmed that the spectral characteristics were comparable to those formed by conventional dyeing methods.

A transparent protective layer was formed on this solid-state imaging device by applying polybutadiene to a dry film thickness of 1 μm and post-baking at 1150° C. for 30 minutes.

Next, a polyvinyl alcohol aqueous solution containing the above methyl-r-styrylpyridinium methyl sulfate 10.e
A solution containing a 4% by weight aqueous solution 3.e of Kayanol Turkey Blue (manufactured by Nippon Kayaku ■) as a blue dye was applied using a spinner to a film thickness of 1/1 ffl. After drying in air at 80°C for 30 minutes, apply 25311ffl through a shadow mask with a desired pattern.
and 365 nm ultraviolet light at 2000 mJ/-. Next, the film was developed with water for 10 seconds, rinsed with methanol, and then dried at Zoo° C. for 30 minutes to form a blue colored layer.

Furthermore, using FSR (manufactured by Fuji Yakuhin Kogyo ■), it was applied so that the dry film thickness was 1.5 μm, and after exposure,
By performing a boss baking treatment at 60° C. for 30 minutes, a transparent protective layer was formed, and a complementary color filter was formed.

When the color filter thus obtained was observed using a microspectrophotometer, it was confirmed that the blue and yellow colored layers were completely mixed colors. Furthermore, when the spectral characteristics of this color filter were measured, it was confirmed that it was comparable to the color filter obtained by the dyeing method.

[Brief explanation of the drawing]

Figure 1 is a flow sheet diagram for manufacturing a color filter using the conventional method, and Figure 2 is a flow sheet diagram for manufacturing a color filter using method 1 of the present invention.
- Sheet diagram. Figure 1 Figure 2

Claims (1)

[Claims] A method for manufacturing a color filter in which a colored layer is formed by laminating a colored layer on a solid-state image sensor, comprising: forming the colored layer by forming a pattern using a photoresist material colored with a dye; A method for producing a color filter, further comprising forming a transparent protective layer on the surface of each colored layer.