JPH01134306A - Production of color filter - Google Patents

Abstract

PURPOSE:To eliminate cracks or surface roughness of a substrate for dyeing caused by the effect of a developing soln. or a rinsing soln. and to eliminate also discoloration due to elution of a dye by forming a protecting layer of a specified copolymer and removing unnecessary parts of the protecting layer by dry etching. CONSTITUTION:For example color layers and resist-printing protecting layer are laminated alternately and repeatedly on a photoreceiving part of a solid image pickup element, and a surface protecting layer 10 is formed of a copolymer consisting of a copolymer expressed by formula I or II. In formulas I and II, each R<1> and R<3> is H, 1-5C alkyl; R<2> is H, 1-5C alkyl, etc. Then, a resist 11 is formed on the layer 10, and the resist 11 on a scribe line 12 and bonding pad 13 are removed, and a color filter is produced by executing dry etching. By this method, problems accompanying a development are eliminated, and a layer 10 having high transparency in a visible region is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to CCD (charge coupled device), BBD (packet coupled device)
, CID (charge injection φ device)
The present invention relates to a method of manufacturing color filters for solid-state imaging devices, liquid crystal display devices, etc.

[Prior Art] Conventionally, the following two methods are mainly known as methods for manufacturing color filters for liquid crystal display elements and solid-state image sensors.

First, a dyeable coating film-forming material is applied onto a transparent substrate such as glass or a solid-state imaging device (light-receiving surface), and is cured to form a dyed substrate layer. After forming a first color pattern using a resist on the dyed substrate layer, the exposed dyed substrate portion is dyed with a first color dye having the required spectral characteristics, and then the resist is peeled off. By this, a hue pattern of the first color is formed. Next, hue patterns of a second color, a third color, etc. are formed by repeating the same procedure, and finally a surface protective layer is formed. This manufacturing method is a method in which a single dyed substrate layer is dyed into a plurality of hue patterns.

Another manufacturing method is to uniformly apply a dyeable coating film-forming material imparted with photosensitivity onto a substrate and dry it to form a photosensitive dyed substrate layer. Next, portions of the substrate layer that will become the first color pattern portions are selectively exposed to light to photocure, and then developed, and portions of the substrate layer other than the predetermined pattern are removed.

Next, the obtained first color pattern is dyed with a dye having predetermined spectral characteristics. Next, a transparent protective layer having dye resistance, that is, not dyed by dye, is formed over the entire surface of the substrate and the dyed first color hue pattern. Next, in order to form a hue pattern of a second color, a third color, etc., the photosensitive coating film-forming material is applied onto the thus formed protective layer to form a photosensitive dyeing substrate layer, and selectively dyed. The steps of exposure, development, dyeing and protective layer formation are repeated as many times as necessary, and finally a surface protective layer is formed. In color filters manufactured using this manufacturing method, each hue pattern is separated by a protective layer to prevent mutual dyeing and is independent, and the overall hue pattern layer and protective layer are laminated alternately. It has a similar shape.

In any of the above methods, the protective layer provided for resisting dyeing or for surface protection is required to have high transparency, particularly high light transmittance in the entire visible region.

By the way, for example, the portion of the protective layer corresponding to the bonding pad portion of the solid-state image sensor may be removed as the main portion, and a portion of the protective layer may be removed as an unnecessary portion due to reasons such as the need to provide an opening. be. Therefore, conventional methods have been adopted in which a photosensitive material is used as a material for forming such a protective layer, and after patterning, important parts are photocured, and then unnecessary parts are removed by a development process.

[Problems to be Solved by the Invention] However, the developing solution and rinsing solution used to remove unnecessary parts of the protective layer are generally highly flammable organic solvents, and when used in large quantities, there are environmental concerns. There were various problems. In addition, the conditions for this development process are strictly limited, and problems such as cracks and surface roughness in the dyed substrate layer, as well as fading due to the elution of the dye in the dyed substrate, can occur, making it possible to produce excellent color filters at high prices. There was a problem in that it could not be manufactured using an effective skewer.

[Means for Solving the Problems] The present invention solves the above-mentioned problems, and includes a step of forming a protective layer for resisting dyeing or surface protection of the dyed layer;
In the method for manufacturing a color filter on a substrate, the protective layer is formed of a monomer represented by the following general formula (I) (hereinafter referred to as monomer ) and a monomer represented by the following general formula (II) (hereinafter referred to as monomer (2)), and the unnecessary portions of the protective layer are removed by dry etching. The present invention provides a method for manufacturing a color filter.

General Formula (I) (In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R2 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.) General Formula (II) (wherein, R3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 5).
) Examples of the monomer I include 4'-acryloxychalcone, 4'-methacryloxychalcone,
4'-(α-ethyl)-acryloxychalcone, 4'
-(α-propyl)-acryloxychalcone, 4'-(
α-Butyl)acryloxychalcone, 4'-acryloxy-4-methoxychalcone, 4'-acryloxy-4-
Ethoxychalcone, 4'-methacryloxy-4-methoxychalcone, 4'-methacryloxy-4-ethoxychalcone, 4'-(α-ethyl)acryloxy-4-
Methoxychalcone, 4'-(α-butyl)acryloxy-4-methoxychalcone, 4'-(α-butyl)acryloxy-4-ethoxychalcone, 4'-acryloxy-4-butoxychalcone, 4'-methacryloxy-4
-butoxychalcone, 4'-acryloxy-4-methylchalcone, 4'-acryloxy-4-ethylchalcone, 4'-methacryloxy-4-butylchalcone, etc. Among these compounds, 4'-methacryloxy-4-methylchalcone, etc. Chloroxychalcone is preferred.

Examples of the monomer (2) represented by the general formula (II) include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propylacrylate, α-n-butyl acrylate, and α-n-butyl acrylate. glycidyl acid, 3,4-epoxybutyl acrylate,
3゜4-epoxybutyl methacrylate, 4,5-epoxypentyl methacrylate, 6,7-epoxypentyl acrylate, 6,7-epoxypentyl methacrylate, 6,7-ethyl acrylate Among these compounds, epoxypentyl, etc. can be mentioned.
In the general formula (II), it is preferable that R3 is a hydrogen atom, a methyl group or an ethyl group, and n is 1 or 2.

The copolymerization ratio of monomer (1) and monomer (2) is preferably 1 to 100 moles of monomer (1) to 11 moles of monomer. If the proportion of monomer H in this copolymerization ratio is less than 1 mole, the resulting copolymer will be colored because monomer I has the property of slightly absorbing visible light. Not only does the transparency of the formed coating film decrease, but also the adhesion between the coating film and the substrate tends to deteriorate.

If the proportion of monomer (1) exceeds 100 moles in the copolymerization ratio, the resulting copolymer will have insufficient sensitivity to radiation, making it impossible to obtain a good cured coating film.

Furthermore, monomer (1) and monomer (2) may be copolymerized with other monomers, such as methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylate, etc. Ethyl acid, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, acrylic 2-hydroxypropyl acid, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, other acrylic acid or methacrylic acid compounds, styrene, α-methylstyrene, p- Examples include vinyl aromatic compounds such as methylstyrene, vinylnaphthalene, butadiene, isoprene, piperylene, dimethylbutadiene, and other diene compounds.

The copolymerization ratio of the other monomers is usually 0.00 to 1 mole of the total amount of monomer (1) and monomer (2). It is about 2 moles or less.

The copolymer used in the present invention preferably has a polystyrene equivalent number average molecular weight of 10.000 to 500,000. If the molecular weight is less than 10,000, the sensitivity is low, and therefore the coating film In case of curing large radiation doses are required. On the other hand, the molecular weight is 5
If it exceeds 00,000, the copolymer solution tends to gel and its storage stability becomes insufficient.

Next, a method for producing the above-mentioned copolymer will be described.

The solvent used in the production of the copolymer used in the present invention is particularly limited as long as it dissolves the monomer and polymerization initiator, dissolves the produced copolymer, and does not react itself. For example, ketone solvents such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, ethyl ether, isopropyl ether, diisoamyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol , dioxane, ether solvents such as tetrahydrofuran, ester solvents such as ethyl formate, propyl formate, n-butyl formate, ethyl acetate, isopropyl acetate, 〇-butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. Examples include solvents.

Furthermore, the polymerization initiator used in the production of the copolymer used in the present invention is not particularly limited, and an intra-membrane radical polymerization initiator can be used, such as azobisisobutyronitrile, etc. Examples include azo compounds; peroxy compounds such as benzoyl peroxide and dicumyl peroxide. The amount of the polymerization initiator used is usually 1/1.000 to 1/200 mole based on 1 mole of the total amount of monomers used for polymerization. If the amount of the polymerization initiator used is too small, the polymerization yield will decrease, and if the amount used is too large, it will be difficult to obtain a copolymer with the desired molecular weight. In addition, the polymerization temperature is usually in the range of 20 to 120°C.

The base solvent used in the production of the copolymer used in the present invention is usually 0.5 to 4 times the amount of all monomers (
heavy enclosure).

In addition, the copolymer used in the present invention includes monomer H
As a catalyst for ring-opening the epoxy group, amines, carboxylic acids, carboxylic acid anhydrides, etc. can also be added.

The copolymer used in the present invention is usually prepared as a solution for forming a coating film by dissolving it in a suitable solvent, such as the solvent used in the production of the copolymer. This solution is applied onto a substrate having a dyed substrate layer, and examples of the application method include a spray coating method, a roll coating method, and a spin coating method.

For the copolymer coating formed on the dyed substrate layer,
Usually, heat treatment is performed at 50 to 100° C. for about 10 minutes to 1 hour to remove the solvent from the coating film, and then the coating is cured by irradiation with radiation such as ultraviolet rays or electron beams. here,
For example, in the case of ultraviolet rays, the irradiation amount is usually 50 to 1,000 mJ/c- for ultraviolet rays with a wavelength of 365 nm. In the conventional method of manufacturing color filters, in which the radiation irradiation is carried out by alternately layering layers to be dyed and anti-dyeing films,
- It is also possible to stack several layers and then do it, instead of doing it one layer at a time. In that case, the amount of radiation irradiated will be higher than in the case of one layer.

In the method of the present invention, unnecessary portions of the protective layer that are removed by dry etching include, for example, portions corresponding to bonding pads of a solid-state imaging device, portions corresponding to scribe lines, and the like.

In the dry etching method used in the method of the present invention, unnecessary parts of the protective layer obtained by curing the composition are etched with a suitable material such as a negative resist made of a polyisoprene cyclized product or a novola resin. A physical dry etching method such as the sub-bottom etching method in which the entire surface is masked with a positive resist and ions with high kinetic energy are irradiated; Machining unnecessary parts of the protective layer using high-temperature plasma
Examples include chemical dry etching methods such as plasma etching methods that involve sowing.

Alternatively, the parts other than unnecessary parts of the protective layer may be masked using the composition used as the protective layer, and then dry etched.

In this case, the mask and the protective layer have the same dry etching rate, so the mask needs to be thicker than the protective layer.

The above dry etching method usually uses a high frequency power of 50 to 250 W and a vacuum of 0.1 to 10 Torr.
It is carried out by flowing oxygen at ~500 ml/min.

Further, dry etching methods other than those described above include an ion beam etching method in which unnecessary portions of the protective layer are selectively scanned with an ion beam without providing a mask in advance.

In the dry etching method described above, if a negative resist, positive resist, etc. is used as a mask, the dry etching method may also be used to remove the mask, but the mask may be removed using a resist stripping solution. You may.

The method of the present invention includes a conventional method for manufacturing a color filter,
In other words, it can be broadly classified into the following two manufacturing methods.

The first manufacturing method includes (I) a step of forming a photosensitive dyed substrate layer on a substrate;
i) selectively exposing and developing the first color patterned portion of the substrate layer; (I11) after the above phenomenon, dyeing the first color patterned portion with a dye having predetermined spectral characteristics; and (Iv) a step of forming a protective layer on the entire surface of the substrate after the dyeing, to form a pattern of the first color, and then using the protective layer formed in step (Iv) as a substrate, using the steps (i) to (Iv
) is repeated for the required number of colors to form a required number of hue patterns in a laminated state. According to the present invention, after lamination, unnecessary portions of the protective layer are removed by dry etching, and the substrate used in step (i) is, for example, a transparent substrate such as glass or plastic, or a solid-state imaging device. The formation of the photosensitive dyed substrate layer is
This can be carried out by uniformly applying a photosensitive polymer compound solution onto a substrate using a roller coat, dipping, spinner, etc., and drying it. Specific examples of polymer compounds that will become the photosensitive dyeing substrate layer include water-soluble natural polymer compounds such as gelatin, casein, fish glue, and egg white, and water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylonitrile. The compound may be a photosensitizer, such as dichromates such as ammonium dichromate, sodium dichromate, potassium dichromate, p-diazophenylamine, 1-diazo-4-dimethylaminobenzene hydrofluoroborate, 1-diazo-4-dimethylaminobenzene hydrofluoroborate, etc. Diazonium salts such as sulfates in diazo-3-methyl-4-dimethylaniline, 1-diazo-3-monoethylnaphthylamine, etc., and their paraformaldehyde condensates, 4,4'-diazidostilbene-2,2-disulfone Acids and their salts, 2
．． Azidosulfonic acid compounds such as 6-bis(4-azidobenzal-2-sulfonic acid) cyclohexanone and its salts are soluble in solvents such as water, and are soluble in polymers by active light such as ultraviolet rays. -COOH, -N
Examples include compositions in which a compound capable of forming a coordinate bond with a group having a non-coexisting electron pair such as H2, -OH, -CONH2, and >CO is mixed. The amount of the photosensitizer added is usually 1 to 50%, preferably 10 to 30%, based on the weight of the polymer compound. The thickness of the photosensitive dyed substrate layer thus formed is preferably in the range of 0.3 to 2 μm.

The selective exposure in step (I1) can be performed according to a known method, and can be performed by irradiating through a mask with a desired pattern using a mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, etc. as a light source. After the required pattern portions are cured by exposure, unnecessary portions are removed by developing with a developer such as warm water.

The dye used in step (iii) is usually a water-soluble dye, and any of acidic, direct and basic water-soluble dyes can be used. Specific examples of dyes that can be used include the following.

(I) Red dyes include Suminol Milling Scarlet G (Sumitomo Chemical), Cibacron Scarlet G-P (Ciba Geigy), Cibacron Pronto Scarlet (Ciba Geigy), and Suminol.
Fast Red G (Sumitomo Chemical), Sumilite Splat Red 4BL (Sumitomo Chemical), Aminyl Red
E-2BL (Sumitomo Chemical), Aminyl Red? E-3
8L (Sumitomo Chemical), Azide Scarlet 901 (Sumitomo Chemical), Suminol Milling Φ Scarlet FG
(Sumitomo Chemical), Suminol Milling Orange FG
(Sumitomo Chemical), Suminol Fast Orange PO
(Sumitomo Chemical), Maxilon Red GRL (Ciba)
Geigy Co.), Erioshin Ken Scarle Soto RE (Ciba Geigy Co.), Mikawan Φ Brilliant Red 0
8BS (Mitsubishi Chemical), and light scarlet Φ
Examples include GL130% (Mitsubishi Chemical) and Kayanol Milling Red R8125 (Nippon Kayaku).

(2) Green dyes include Suminol Milling Brilliant Green 5G (Sumitomo Chemical), Acid Brilliant φ Milling Green G (Sumitomo Chemical), and Brilliant Milling Green B (Sumitomo Chemical), Mikation Olive Green 3GS (Ciba Geigy), Kayanol φ Milling Green 5
GW (Nippon Kayaku), Sooriidazole Green P-
GG (Hoechst), Paper Fast Green 5
Examples include G (Bayer).

(3) Blue dyes include Sumilite Supra Turquoise Blue G (Sumitomo Chemical), Cibacron Blue.
3G-A (Ciba Geigy), Cibachlorane Blue 8G (Ciba Geigy), Prodione Turquoise H-A (CI'C), Kayathion Turquoise
P-A (Nippon Kayaku), Kayathion Turquoise P-N
GF (Kuchihonkayaku), Sumikaron Medium Blue ΦE-FBL
(Sumitomo Chemical), Sumikalon Brilliant Blue
3-BL (Sumitomo Chemical), Suminol Leveling Sky Blue R Extra Conc (Sumitomo Chemical), Orazole φ Blue GN (Ciba Geigy), Makidion Blue 3GS (Mitsubishi Chemical), Makidion Blue・2GS (Mitsubishi Chemical), Kayanol Milling Blue GW (Nippon Kayaku), Kayasil Sky Blue R
(Nippon Kayaku), etc.

The formation of the protective layer in step (Iv) is carried out by applying and curing the composition solution according to the present invention.

The coating method of the photosensitive dyed substrate layer is not particularly limited, but spin coating, spray coating, roll coating, dipping, printing, etc. are preferred, and the thickness of the protective layer formed is 0.1 μm to 10 μm. Range is preferred. In the color filter manufactured by this method, the protective layer provided between the patterns of each hue mainly functions as a resist-dyeing protective layer for the purpose of mutually resisting dyeing, and the finally formed protective layer is the color filter's protective layer. It acts as a surface protective layer to prevent the surface from being damaged by scratches, etc.

The manufacturing method of the second color filter includes: (I) forming a dyed substrate layer on the substrate; (I1) forming a pattern of the first color on the dyed substrate layer using a resist; The process of dyeing the first color pattern part with the first color dye and then peeling off the resist, (fil) dyeing the hue pattern of the second color, third color, etc. (
This is a method consisting of (if) a step of forming by repeating the steps, and (iv) a step of finally forming a surface protective layer. According to the present invention, in step (Iv), a surface protective layer is formed by applying and curing the composition solution according to the present invention, and then unnecessary portions of the surface protective layer are removed by the dry etching described above. The various materials used in the second manufacturing method are the same as those explained in the first manufacturing method above.

[Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 5 g of a copolymer of 4'-methacryloxychalcone and glycidyl methacrylate (molar ratio of glycidyl units and chalcone units is 78:22) was dissolved in 45 g of ethyl cellosolve acetate, and this solution was dissolved in a pore size of 0.2 μm.
After filtering through a filter, the following composition for resist dyeing and surface protective layer was prepared.

First, as shown in FIG. 1(a), a solution of the above composition is spin-coated at 3,000 revolutions on a solid-state imaging device 2 which is a solid-state imaging device and has a light-receiving section 1, and then heated at 80° C. for 10 minutes. It was dried and irradiated with ultraviolet light having a wavelength of 365 nm and an intensity of 7.3 mW/cd to form a transparent base film 3.

Next, as shown in Figure 1(b), an aqueous gelatin solution containing ammonium dichromate was spin-coated onto the substrate at 3°000 rotations, dried at 80°C for 10 minutes, and then irradiated with ultraviolet rays through a mask. did. Next, development is performed with warm water to wash out and remove gelatin in the unirradiated area and ammonium dichromate in the gelatin, and heat treatment is performed at 150°C for 30 minutes to form the dyed substrate layer 4 patterned for the first color. was formed.

Next, as shown in Figure 1(C), add this to the following dyeing bath for 6 hours.
The patterned dyed substrate layer 4 was dyed by dipping at 0° C. for 5 minutes, further washed with water, and dried at 150° C. for 30 minutes to form a first color layer 5 dyed red.

Dyeing Bath Next, as shown in FIG. 1(d), a solution of the above-mentioned protective layer composition was applied over the entire surface at 3,000 revolutions, and then dyed at 80°C for 1 hour.
Dry for 0 minutes, wavelength 365 nm and intensity 7,3
Ultraviolet rays of mW/cJ were irradiated to form the first dye-resistant protective layer 6. The thickness of this protective layer was 0.6 μm.

Next, as shown in FIG. 1(e), for the second color (green) and the third color (blue), the operations from forming the dyed substrate layer to forming the protective layer are repeated in the same way, and the second color Color layer 7.2
th anti-dye protection layer 8, third color layer 9 and surface protection layer 10
was formed.

Next, as shown in FIG. 1(f), a positive resist 11 is spin-coated on the surface protection layer 10, which is the uppermost layer, and after pre-baking (80° C./10 minutes), the solid-state image sensor is coated. Scribe line 12 and pounding pad 13
The area above was exposed to light through a mask, and the exposed area was developed with an alkaline solution and dissolved and removed. After further post-baking (I30°C/30 minutes), using a 100W plasma etching device, an oxygen gas flow of ff1100m was applied.
Dry etching was carried out under the conditions of 1/min and 0.25 Torr to remove the portions of the protective layer corresponding to the scribe line 12 and the bonding pad 13, thereby obtaining the color filter shown in FIG. The obtained color filter showed excellent light transmittance throughout the visible region.

[Effects of the Invention] According to the method of the present invention, since the copolymer used has no absorption in the visible and near-ultraviolet regions, a protective layer for resisting staining and surface protection having high transparency in the entire visible region is provided. Furthermore, since the process of removing the bonding pad portions of each layer of the protective layer can be omitted, color filters that are excellent in terms of work environment and performance can be manufactured with high production efficiency.

[Brief explanation of the drawing]

FIG. 1 is a process explanatory diagram illustrating the method of the present invention, and FIG. 2 is a sectional view of a color filter obtained by the method of the present invention. 2...Solid-state image sensor 6, 8.10...Protective layer 11...
...Regist 12...Scribe line 13...
...Bonding pad Cq group

Claims (1)

[Claims] 1) A method for manufacturing a color filter on a substrate, comprising the steps of forming a protective layer for resisting dyeing or protecting the surface of the dyed layer, and removing unnecessary parts of the protective layer. In the above, the protective layer is formed of a copolymer consisting of a monomer represented by the following general formula (I) and a monomer represented by the following general formula (II), and unnecessary parts of the protective layer are A method for manufacturing a color filter, characterized in that removal is performed by dry etching. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R^2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. or an alkoxy group having 1 to 5 carbon atoms.) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R^3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is It is an integer from 1 to 5.)