JP2008176184A - Method for manufacturing color filter - Google Patents

Abstract

A color filter manufacturing method by a dry etching method, which can manufacture a color filter having fine and rectangular pixels, is provided.
An etching stopper layer is formed on a first colored layer provided on a support, and the first colored layer corresponding to a region where the second colored layer is to be formed is removed by a dry etching method. . A second colored layer is formed so as to fill the removed region, and then the second colored layer formed on the etching stopper layer is removed by a dry etching method. Next, the first colored layer corresponding to the region where the third colored layer is to be formed is removed by a dry etching method. Production of a color filter in which a third colored layer is formed so as to embed the removed region, and then the etching stopper layer and the third colored layer laminated on the second colored layer are removed until the etching stopper layer is exposed. Is the method.
[Selection figure] None

Description

  The present invention relates to a method for manufacturing a color filter using a dry etching method.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. Colored pixels are formed, and a color filter can be obtained by repeating this operation for each necessary color.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 4).

  In recent years, color filters for solid-state imaging devices have been desired to have higher definition, and a technique using a dye has been proposed (for example, see Patent Document 5). However, a curable composition containing a dye is generally inferior to a pigment in terms of various performances such as light resistance, heat resistance, solubility, and coating uniformity. In particular, in the case of the use for producing a color filter for a solid-state imaging device, a film thickness of 1.5 μm or less is required, so that a large amount of dye must be added to the curable composition. There are various problems, such as insufficient adhesion, insufficient curing, and loss of dye even in the exposed area, which makes pattern formation extremely difficult.

  In addition, in the liquid crystal display device and the solid-state imaging device, the pixel size is being reduced, and the color filter is also required to be reduced. In particular, miniaturization of a solid-state imaging device is remarkable, and a high-resolution technique with a size of less than 2.0 μm is required, and the resolution of the conventional photolithographic method is becoming a limit.

  In contrast to the color filter manufacturing method using the photolithographic method, a dry etching method has been known for a long time as a method for forming a fine pattern with a thinner film. The dry etching method has been conventionally employed as a method for forming a pattern on a dye-deposited thin film (see, for example, Patent Document 6). With regard to the thin film formation, the film thickness is set to the same level as the spectral characteristics compared to the photolithographic system. However, it is possible to form a thin film having a thickness of 1/2 or less. In addition, a pattern formation method combining a photolithography method and a dry etching method has been proposed (see, for example, Patent Document 7).

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375 JP-A-55-146406 JP 2001-249218 A

However, in the formation of a thin film by vapor deposition, contamination of the vapor deposition apparatus is unavoidable, and it is a heavy load for the production of a color filter. Further, since the pixel is formed only with the pigment or the dye, the adhesion with the lower planarization film or the upper layer is poor, which is one of the causes of the yield not increasing.
In the production of a color filter by dry etching, the second color material applied on the first layer and the first layer are removed when forming and etching the second color layer. There is a problem that it is difficult to simultaneously remove the coloring material of the second layer applied to the region. In the case of separately removing the second layer coloring material applied on the first layer and the second layer coloring material applied to the region from which the first layer has been removed, There were problems such as an increase in cost and cost increase.

  The present invention has been made in view of the above problems, and is a method of manufacturing a color filter using a dry etching method, which is capable of manufacturing a color filter having fine and rectangular pixels. It is an object to provide a method.

Specific means for solving the above problems are as follows.
<1> (a) A first colored layer forming step for forming a first colored layer on a support; and (b) formation of an etching stopper layer for forming an etching stopper layer on the first colored layer. And (c) a first photoresist layer forming step of forming a photoresist layer on at least the etching stopper layer; and (d) removing the partial region of the photoresist layer to thereby remove the etching stopper. A first image forming step of forming an image on the layer, and (e) an image formed by the first image forming step, the etching stopper layer and the first colored layer in the partial region, A first etching step for removing the photoresist layer by dry etching, and (f) a first photoresist for removing the photoresist layer remaining after the first etching step. And (g) forming a second colored layer different from the first colored layer on the partial region from which the first colored layer has been removed and the etching stopper layer. (H) a second photoresist layer forming step of forming a photoresist layer on the second colored layer, and (i) removing the photoresist layer other than the partial region. A second image forming step for forming an image on the second colored layer, and (j) an image formed by the second image forming step is formed on at least the etching stopper layer. A first colored layer removing step of removing the second colored layer by a dry etching method until the etching stopper layer is detected; and (k) a second photoresist layer remaining after the colored layer removing step is removed. Photore A method for producing a color filter comprising a step of removing a dyst layer.

<2> The method for producing a color filter according to <1>, further including at least one group of process groups in which the steps (c) to (g) are performed in this order.
<3> The method for producing a color filter according to <1>, further including at least one group of process groups in which the steps (c) to (k) are performed in this order.

<4> The method for producing a color filter according to any one of <1> to <3>, further comprising a flattening process step of performing a flattening process on a surface of at least the formed colored layer. It is.

  ADVANTAGE OF THE INVENTION According to this invention, it is a manufacturing method of the color filter which used the dry etching method, Comprising: The manufacturing method of the color filter which can manufacture the color filter which has a fine and rectangular pixel can be provided.

[First colored layer forming step]
The method for producing a color filter of the present invention includes (a) a first colored layer forming step of forming a first colored layer on a support.
<Support>
Examples of the support in the present invention include soda glass, borosilicate glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These supports may be formed with black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.

<Colored layer>
The colored layer in the present invention can constitute at least one of the pixels of the color filter in the present invention.
In the present invention, the first colored layer is preferably formed by applying a colored curable composition containing a colorant. By using the colored curable composition, the adhesion to the support or the undercoat layer provided on the support can be improved, and the yield during production can be improved.

  Furthermore, in this invention, it is preferable to perform provision of the said colored curable composition by application | coating. As a coating method, the colored curable composition can be applied on at least the support by a method such as spin coating, cast coating, roll coating, or slit coating. By applying the colored curable composition by coating, the colored curable composition can be more uniformly applied on the support.

In the present invention, as the colored curable composition, a non-photosensitive colored thermosetting composition or a colored photocurable composition can be preferably used.
The colored layer in the present invention is more preferably formed using a non-photosensitive colored thermosetting composition from the viewpoint of spectral characteristics.

(Colored thermosetting composition)
The non-photosensitive colored thermosetting composition in the present invention preferably contains a colorant and a thermosetting compound.

-Colorant-
The colorant that can be used in the present invention is not particularly limited, and various conventionally known dyes and pigments can be used alone or in combination.

  Examples of the pigment that can be used in the present invention include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible, and considering the handling properties, the average particle size of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

  Examples of pigments that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;
C. I. Pigment orange 36, 71;
C. I. Pigment red 122,150,171,175,177,209,224,242,254,255,264;
C. I. Pigment violet 19, 23, 32;
C. I. Pigment blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment Black 1

  In the present invention, when the colorant is a dye, it can be uniformly dissolved in the composition to obtain a non-photosensitive thermosetting colored resin composition.

  The dye that can be used as the colorant constituting the composition in the present invention is not particularly limited, and conventionally known dyes for color filters can be used.

The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.
Although the coloring agent content rate in the total solid of the colored thermosetting composition in this invention is not specifically limited, Preferably it is 30-60 mass%. By setting the content to 30% by mass or more, an appropriate chromaticity as a color filter can be obtained. Moreover, photocuring can fully be advanced by setting it as 60 mass% or less, and the strength reduction as a film | membrane can be suppressed.

-Thermosetting compound-
The thermosetting compound that can be used in the present invention is not particularly limited as long as the film can be cured by heating. For example, a compound having a thermosetting functional group can be used. As the thermosetting compound, for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group, and an acyloxymethyl group are preferable.

  More preferable thermosetting compounds include (a) an epoxy compound, (b) a melamine compound, a guanamine compound, and a glycoluril substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A compound or a urea compound, (c) a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Among these, a polyfunctional epoxy compound is particularly preferable as the thermosetting compound.

  Although the total content of the thermosetting compound in the colored thermosetting composition varies depending on the material, it is preferably 0.1 to 50% by mass with respect to the total solid content (mass) of the curable composition. 0.2-40 mass% is more preferable, and 1-35 mass% is especially preferable.

-Various additives-
In the colored thermosetting composition of the present invention, various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, and a high amount other than those described above are included in the range that does not impair the effects of the present invention. Molecular compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, dispersants, and the like can be blended.

~binder~
The binder is often added at the time of preparing the pigment dispersion, does not require alkali solubility, and may be soluble in an organic solvent.

  The binder is preferably a linear organic polymer that is soluble in an organic solvent. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

As the acrylic resin, a copolymer comprising monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, for example, benzyl methacrylate / methacrylic acid, Each copolymer such as benzyl methacrylate / benzylmethacrylamide, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.
By dispersing the colorant in these binders at a high concentration, it is possible to impart adhesion to the lower layer and the like, which also contributes to the coated surface shape during spin coating and slit coating.

~ Curing agent ~
In this invention, when using an epoxy resin as a thermosetting compound, it is preferable to add a hardening | curing agent. There are many types of curing agents for epoxy resins, and their properties, pot life with resin and curing agent mixture, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used. An appropriate curing agent must be selected according to the purpose of use, use conditions, working conditions, and the like. The curing agent is described in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of the curing agent are as follows.
Those that act catalytically include tertiary amines, boron trifluoride-amine complexes, those that react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc .; Examples include diethylenetriamine, polyamide resin, and medium temperature curing examples such as diethylaminopropylamine and tris (dimethylaminomethyl) phenol; examples of high temperature curing include phthalic anhydride and metaphenylenediamine. In terms of chemical structure, in the case of amines, diethylenetriamine as an aliphatic polyamine; metaphenylenediamine as an aromatic polyamine; tris (dimethylaminomethyl) phenol as a tertiary amine; phthalic anhydride as an acid anhydride; polyamide resin Polysulfide resin, boron trifluoride-monoethylamine complex; Synthetic resin initial condensate includes phenol resin, dicyandiamide and the like.

  These curing agents react with an epoxy group by heating and polymerize to increase the crosslinking density and cure. For thinning, both the binder and the curing agent are preferably as small as possible. In particular, the curing agent is 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less with respect to the thermosetting compound. It is preferable that

~ Curing catalyst ~
In order to achieve a high colorant concentration in the present invention, curing by reaction between epoxy groups is effective in addition to curing by reaction with the curing agent. For this reason, a curing catalyst can be used without using a curing agent. The addition amount of the curing catalyst is about 1/10 to 1/1000, preferably about 1/20 to 1/500, more preferably 1/30, based on the mass of the epoxy resin having an epoxy equivalent of about 150 to 200. It can be cured with a slight amount of about 1/250.
~solvent~
The colored thermosetting composition in the present invention can be used as a solution dissolved in various solvents. Each solvent used in the colored thermosetting composition in the present invention is basically not particularly limited as long as the solubility of each component and the coating property of the colored thermosetting composition are satisfied.

~ Dispersant ~
The dispersant can be added to improve the dispersibility of the pigment. As the dispersant, known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorosurfactant, and a polymer dispersant.
As these dispersants, many types of compounds are used. For example, phthalocyanine derivatives (commercially available products EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol); organosiloxane polymer KP341 (Shin-Etsu) Chemical Industry Co., Ltd.), (Meth) acrylic acid type (co) polymer polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) ) And other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate , Sorbita Nonionic surfactants such as fatty acid esters; Anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400 , EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by San Nopco) Various Solsperse dispersants (manufactured by Nippon Lubrizol) such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F 8, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co.) and Isonetto S-20 (manufactured by Sanyo Chemical Co.) and the like

  The dispersants may be used alone or in combination of two or more. The amount of the dispersant added in the colored thermosetting composition of the present invention is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

~ Other additives ~
Various additives can be further added to the non-photosensitive colored curable composition of the present invention as necessary. Specific examples of the various additives include the various additives described in the above colored photocurable composition.

The 1st colored layer in this invention can be formed by the process of apply | coating said colored thermosetting composition to a support body, and drying and forming a 1st colored layer.
Specifically, for example, a colored thermosetting composition containing a solvent is applied on a support directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, or the like. Can be formed.
The specific thickness of the first colored layer is preferably 0.005 μm to 0.9 μm, more preferably 0.01 μm to 0.8 μm, and more preferably 0.02 μm to 0.65 μm. preferable.

  It is preferable that the 1st colored layer formation process in this invention further includes a heating process (it may be a post-baking process). Specifically, the colored layer is formed by applying a colored thermosetting composition to a support to form a coating film, and then thermally curing the coating film by a heating process. The heating step may be performed at the same time as drying after coating, or a separate thermosetting step may be provided after coating and drying. In the heating step, a known heating means such as an oven or a hot plate is used, preferably 130 ° C. to 300 ° C., more preferably 150 ° C. to 280 ° C., particularly preferably 170 ° C. to 260 ° C., preferably 10 ° C. Second to 3 hours, more preferably 30 seconds to 2 hours, particularly preferably 60 seconds to 60 minutes. However, considering the production, the time required for curing is preferably as short as possible.

(Colored photocurable composition)
In the present invention, a colored photocurable composition can be used as the colored curable composition. For the colored photocurable composition, for example, the matters described in paragraph numbers 0017 to 0064 of JP-A-2005-326453 can be applied as they are.

[Etching stopper layer forming process]
The method for producing a color filter of the present invention includes (b) a step of forming an etching stopper layer on the first colored layer. By providing the etching stopper layer, fluctuations in the film thickness of the first colored layer due to the subsequent process can be suppressed, and the transmission spectral characteristics of the color filter pixels can be easily controlled.
The etching stopper layer in the present invention is not particularly limited as long as the etching rate is lower than the colored curable composition layer (colored layer), but is formed of a curable composition that is transparent to visible light. It is preferable. Thereby, a color filter can be manufactured without completely removing the etching stopper layer. Here, being transparent to visible light means that the transmittance of visible light is 95% or more. The visible light transmittance can be measured by, for example, a spectrophotometer: U-4100 manufactured by Hitachi, Ltd.

  In the present invention, as the curable composition used for forming the etching stopper layer, a composition containing a polymer compound curable by heat can be preferably used. As said high molecular compound, a polysiloxane type polymer and a polystyrene type polymer can be mentioned as a preferable thing, for example. Among them, a material known as a spin-on-glass (SOG) material, or a thermosetting composition mainly composed of a polystyrene derivative or a polyhydroxystyrene derivative can be mentioned as a more preferable one. In the present invention, it is particularly preferable to use a thermosetting composition containing a polyhydroxystyrene derivative from the viewpoint of ease of process.

  Specific examples of the polystyrene derivative and polyhydroxystyrene derivative include, for example, Maruka Linker (manufactured by Maruzen Chemical Co., Ltd.) (Marca Linker CMM, CHM, CST, etc.), VP Series (VP 2500, VP 8000) manufactured by Nippon Soda Co., Ltd. VP15000 etc.). Specific examples of the SOG material include OCD Type-7 manufactured by Tokyo Ohka Co., Ltd., ACCUGLASS P-5S manufactured by Honeywell, HSG series manufactured by Hitachi Chemical Co., Ltd., and the like.

  The thermosetting composition containing the polyhydroxystyrene derivative in the present invention can be prepared as a solution by diluting an acid generator, a crosslinking agent and other additives with an organic solvent in addition to the polyhydroxystyrene derivative. This solution can be formed as an etching stopper layer by spin-coating and drying the solution on a substrate and then performing post-baking.

By making the etching rate of the etching stopper layer lower than that of the colored curable composition layer, it is possible to satisfactorily remove the laminated colored layer. That is, it is important that the etching resistance of the etching stopper layer is better than the etching resistance of the colored curable composition layer. Thus, the etching stopper layer can be used to detect the end point of the etching process.
As an index indicating the etching resistance of the curable composition for forming the etching stopper layer, for example, Onishi parameters (reference documents: JP-A Nos. 2004-294638 and 2005-146182) can be used. In the present invention, when the parameter value of the colored curable composition is 3.5 to 4.5, the parameter value of the curable composition forming the etching stopper layer is 2.5 or less. Therefore, it can be determined that selectivity can be secured for the colored curable composition layer. The Onishi parameter can be calculated by the following formula (I).

(C + O + H) / (C−O) Formula (I)
In formula (I), C, O, and H represent the number of moles of carbon atoms, oxygen atoms, and hydrogen atoms, respectively, in the structural repeating unit of the polymer. An example of calculating Onishi parameters is shown below. It should be noted that the calculation was performed by rounding off the three decimal places.

Example 1. Fluorene acrylate compound (when n = 1)
(C + O + H) / (C-O) = (33 + 6 + 25) / (33-6) = 2.37
Example 2. Epoxy compound (C + O + H) / (C−O) = (8 + 2 + 12) / (8-2) = 3.66
Example 3 Polyhydroxystyrene derivative (C + O + H) / (C−O) = (8 + 1 + 8) / (8-1) = 2.42

  From the above calculation results, it can be seen that, for example, a composition containing a fluorene acrylate compound or a polyhydroxystyrene derivative can be used as the curable composition for forming the etching stopper layer.

In the present invention, the etching stopper layer can be formed as a cured film obtained by applying the curable composition onto the first colored layer, drying it, and curing it with heat or the like.
Specifically, for example, the curable composition can be formed by coating on the first colored layer by a coating method such as spin coating, slit coating, cast coating, or roll coating.
The thickness of the etching stopper layer is preferably in the range of 5 to 2000 nm, preferably in the range of 100 to 500 nm, from the viewpoint of reducing the thickness of the color filter layer as much as possible and over-etching resistance. It is more preferable.

[First photoresist layer forming step]
The method for producing a color filter of the present invention includes (c) a first photoresist layer forming step of forming a photoresist layer on at least the etching stopper layer.
(Photoresist layer)
As described above, after the etching stopper layer is formed and cured on the first colored layer, a photoresist layer (photosensitive resin layer) is formed on the etching stopper layer. Specifically, a positive or negative photosensitive resin composition is applied on the etching stopper layer and dried to form a photoresist layer. In the formation of the photoresist layer of the present invention, it is preferable to perform a pre-bake treatment.

As the positive or negative photosensitive resin composition, for example, the matters described in paragraph Nos. 0112 to 0117 of Japanese Patent Application No. 2006-155227 can be preferably applied to the present invention.
As the coating method of the photosensitive resin, the above-described coating method can be suitably used.
The specific thickness of the photosensitive resin layer is preferably 0.01 μm to 3 μm, preferably 0.1 μm to 2.5 μm, and more preferably 0.15 μm to 2 μm.

[First image forming step]
The method for producing a color filter of the present invention includes (d) a first image forming step of forming an image on the etching stopper layer by removing a partial region of the photoresist layer.
In the present invention, it is preferable that a partial region of the photoresist layer is a region on a support where a second colored layer different from the first colored layer (an already formed colored layer) is formed. . Thereby, the pixel formed by the second colored layer can be a fine and rectangular pixel.
In the first image forming step, the photoresist layer is exposed in an image-like manner corresponding to a region where the second colored layer is formed on the support, and developed with a developer to form an etching mask (pattern image). ) Can be formed.

  In the present invention, an image in which the photoresist layer in the region where the second colored layer is formed on the support is removed is formed on the etching stopper layer. As a result, the etching stopper layer is exposed like the image. On the other hand, in the etching stopper layer, the region other than the region where the second colored layer is formed on the support is covered with the photoresist layer.

  In the color filter manufactured by the manufacturing method of the present invention, by forming the second colored layer on the support, in addition to the pixels constituted by the first colored layer, another type of pixel is further added. Can be formed. Since the photoresist layer serving as a mask material can be miniaturized and has rectangularity, each pixel of the color filter manufactured by the manufacturing method of the present invention can be formed in a fine and rectangular shape.

  The photoresist layer is exposed to a positive or negative photosensitive resin composition through a predetermined (image-like) mask pattern, such as g-line, h-line, i-line, preferably i-line. It can be done by applying.

  As the developer, any developer can be used as long as it does not affect the colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[First etching step]
The method for producing a color filter of the present invention includes: (e) the first colored layer and the etching stopper layer in a region where the second colored layer is formed in an image-like manner formed by the first image forming step. Including a first etching step of removing by a dry etching method.
As described above, in the first image forming step, only the region corresponding to the region on the support on which the second colored layer is formed is exposed in the etching stopper layer. In this state, for example, by performing anisotropic etching by plasma etching treatment using an etching gas, the etching stopper layer and the first coloring of the lower layer are formed like the image formed in the first image forming step. The layer can be removed.

In the present invention, it is preferable to manage the overetch rate with an endpoint detector. Thus, even if the support surface is Si ₃ N ₄ which is a passivation film, or the support is a curable resin transparent to visible light, the amount of scraping of the support due to the etching process can be reduced. Can be suppressed.

As the gas used for the dry etching process in the present invention, a known gas can be used. Among them, O ₂ , CF _{4 and the} like are preferable. Representative examples of the dry etching method include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102. Such a method as described in such publications is known.

[First photoresist layer removal step]
The method for producing a color filter of the present invention includes (f) a first photoresist layer removing step of removing a photoresist layer remaining after the first etching step.
After completion of the etching process, the mask resist (photosensitive resin layer after curing) is removed with a special stripping solution or solvent.

The photoresist layer removing step in the present invention includes (1) a step of applying a stripping solution or a solvent on the photoresist layer to make the photoresist layer removable, and (2) the photoresist layer, And removing with washing water.
As a process of applying a stripping solution or solvent on the photoresist layer to make it removable, for example, a paddle development process in which the stripping solution or solvent is applied on at least the photoresist layer and stagnated for a predetermined time. Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

The step of removing the photoresist layer using cleaning water includes, for example, a step of removing the photoresist layer by spraying cleaning water onto the photoresist layer from a spray type or shower type spray nozzle. Can do.
As the washing water, pure water can be preferably used.
Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the photoresist layer is more effectively removed by moving the support from the center of the support to the end of the support more than twice during the step of removing the photoresist layer and spraying the cleaning water. Can be removed.

The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. Examples of organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester compounds. 7) polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenol compounds, 10) nitrogen compounds, 11) sulfur compounds, and 12) fluorine compounds.
The stripping solution in the present invention preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine and the like. Monoethanolamine, diethanolamine, triethanolamine, and more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH).

  Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2-pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like are preferable, N-methyl-2-pyrrolidone and N-ethylmorpholine are preferable, and N-methyl-2-pyrrolidone (NMP) is more preferable.

The stripping solution in the present invention preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and among them, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine and triethanolamine More preferably, the cyclic nitrogen-containing compound includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and further includes monoethanolamine and N-methyl-2-pyrrolidone. preferable.
The content of the acyclic nitrogen-containing compound is 9 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the stripping solution, and the content of the cyclic nitrogen-containing compound is 65 parts by mass or more and 70 parts by mass or less. It is desirable.
Moreover, it is preferable that the stripping solution in the present invention is obtained by diluting a mixture of a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

[Second colored layer forming step]
In the method for producing a color filter of the present invention, (g) the partial region from which the first colored layer is removed (the region on the support on which the second colored layer is formed) and the etching stopper layer are A second colored layer forming step of forming a second colored layer different from the first colored layer;
Here, it is preferable that the second colored layer contains at least a colorant different from the colorant contained in the first colored layer.

In the second colored layer forming step in the present invention, the colored curable composition is applied onto the support from which the first colored layer has been removed and the etching stopper layer to form the second colored layer. It is preferable to do. As the colored curable composition used in this step, the above-described colored curable composition can be suitably used. The application of the colored curable composition is preferably carried out by coating, and for the application of the colored curable composition, the matters described in the “first colored layer forming step” can be applied as they are.
Furthermore, in the present invention, it is preferable to use a colored photocurable composition or a colored thermosetting composition as the colored curable composition, and it is more preferable to use a colored thermosetting composition. For the colored photocurable composition and the colored thermosetting composition, the matters described in the “first colored layer forming step” can be applied as they are.

In the present invention, the colored curable composition is applied not only to the region where the first colored layer is removed, but also to the region where the first colored layer having the etching stopper layer as the uppermost layer remains. To do. Thereby, a colored curable composition can be more reliably provided to the area | region from which the 1st colored layer was removed.
As described above, the color filter manufacturing method of the present invention is formed by embedding a curable composition containing a colorant for each color into a concave portion formed in an existing colored layer, at least a second color layer or more. It is characterized by doing.

  The colored curable composition applied on the region from which the first colored layer has been removed and the etching stopper layer is cured by the post-baking step described above, whereby a second different from the first colored layer. A colored layer can be formed.

[Second photoresist layer forming step]
The method for producing a color filter of the present invention includes (h) a second photoresist layer forming step of forming a photoresist layer on the second colored layer.
In the second photoresist layer forming step, a positive or negative photosensitive resin composition is applied on the second colored layer formed on the support and the etching stopper layer, and then dried. A photoresist layer is formed. In forming the photoresist layer, it is preferable to further perform a pre-bake treatment. Regarding the photosensitive resin composition, the coating method, and the film thickness of the photoresist layer, the matters described in the first photoresist layer forming step can be applied as they are.

[Second image forming step]
The method for producing a color filter of the present invention includes (i) a second image forming step of forming an image on the second colored layer by removing the photoresist layer other than the partial region.
In the second image forming step, the photoresist layer formed in the second photoresist layer forming step is exposed in an image-like manner corresponding to a partial region where the second colored layer is formed on the support. Then, development with a developer can form an etching mask (pattern image).

  In the present invention, an image from which the photoresist layer corresponding to the region other than the region on the support for forming the second colored layer is removed is formed on the second colored layer. As a result, at least the second colored layer formed on the etching stopper layer is exposed like the image. On the other hand, the region where the second colored layer is formed on the support is in a state covered with a photoresist layer.

[First colored layer removal step]
The method for producing a color filter of the present invention includes: (j) a second image formed on at least the etching stopper layer until the etching stopper layer is detected in an image-like manner formed by the second image forming step. A first colored layer removing step of removing the colored layer by a dry etching method;

  At least the second colored layer formed on the etching stopper layer is removed by using the dry etching method described above until the etching stopper layer is detected, so that the etching stopper layer is interposed on the first colored layer. Thus, the second colored layer formed can be removed. Thereby, the color purity of the pixel which consists of a 1st colored layer can be made high.

In the colored layer removing step in the present invention, the end point of the colored layer removing step is determined by detecting the etching stopper layer formed on the first colored layer. This makes it possible to easily determine the end point of the colored layer removal step, so that a color filter in which each pixel has a uniform film thickness can be manufactured.
Examples of the method for detecting the etching stopper layer in the colored layer removing step include an endpoint detector and etching time management. In the present invention, it is preferable to detect with an endpoint detector from the viewpoint of controlling the etching amount of the etching stopper layer.

[Second photoresist layer removing step]
The method for producing a color filter of the present invention includes (k) a second photoresist layer removing step of removing a photoresist layer remaining after the second etching step.
The photoresist layer remaining after the first colored layer removing step is removed by the second photoresist layer removing step. Thereby, a color filter having a pixel made of the first colored layer having an etching stopper layer formed on the uppermost layer and a pixel made of the second colored layer can be manufactured. For the second photoresist layer removal step, the matters described in the first photoresist layer removal step can be applied as they are.

In this invention, it is preferable to further include at least one group of the process group which performs said (c)-(g) in this order. By carrying out the process group once, it is possible to form another colored layer (for example, other colors other than the two colors) different from the two colored layers (for example, two colors) already formed. A color filter composed of three (for example, three colors) colored layers can be manufactured.
In the present invention, a color filter having higher rectangularity and no color mixing can be manufactured by further including at least one group of process groups in which the steps (c) to (g) are sequentially performed.

In this invention, it is preferable that at least 1 group of the process group which performs said (c)-(k) in this order is further included. By carrying out the process group once, it is possible to form another colored layer (for example, other colors other than the two colors) different from the already formed two colored layers (for example, two colors). A color filter composed of three (for example, three colors) colored layers can be manufactured.
In the present invention, by further including at least one group of process groups in which the steps (c) to (k) are sequentially performed, each of the pixel formed of the first colored layer and the pixel formed of the second colored layer is more A pixel with high color purity can be obtained.

[Planarization process]
In the present invention, it is preferable to further include a flattening process step of performing flattening process on at least the surface of the formed colored layer. Thereby, a color filter having high color purity and excellent flatness can be produced.
In the planarization treatment step, the steps (a) to (k) are performed in this order, and the steps (c) to (g) are further performed in this order to form an etching stopper formed on the first colored layer. It can be performed after the third colored layer is formed on the layer, on the second colored layer, and on the support. In addition, the steps (a) to (k) are performed in this order, and the steps (c) to (k) are further performed in this order, and the first colored layer having an etching stopper layer formed on the uppermost layer; The second colored layer from which the third colored layer formed thereon has been removed and the third colored layer can also be formed on the support.

In the planarization process, the stepped portion of the colored layer protruding from the surface of the etching stopper layer is selectively etched or polished. Further, the end point of the planarization process can be detected when the etching stopper layer is exposed.
Examples of the planarization process include an etch back process and a CMP process. In the etch back process, either a mode in which the photoresist layer is formed on the colored layer or a mode in which it is not formed may be used. Further, a planarization film may be formed after further forming a planarization film on the colored layer so that there is no surface unevenness.

  In the present invention, an exposure process for exposing the dicing line, the scribe line, and the PAD portion can be further provided. In the exposing step, the color filter layer and the region to be protected can be covered with a photoresist layer and exposed by ashing or etching. Thereafter, the photoresist layer can be dissolved and removed with an organic solvent or the like. Either the aspect implemented after forming each said layer, and the aspect implemented after apply | coating and heat-processing the colored layer of the last layer, and planarizing by an etch-back or polishing process may be sufficient as the said exposure process. .

Hereinafter, one aspect of a method for producing a color filter of the present invention will be described with reference to the drawings.
(A) 1st colored layer formation process As shown in FIG. 1, the coloring thermosetting composition matched with a predetermined | prescribed color component is apply | coated to the surface of the support body 1 by a desired film thickness, and a post-baking process is performed. 1st colored layer 2 is formed.

(B) Etching stopper layer formation process As shown in FIG. 2, the thermosetting composition which has SOG material, a polystyrene derivative, or a polyhydroxystyrene derivative as a main component is apply | coated on the 1st colored layer 2, and heat processing is carried out. Then, the etching stopper layer 3 having a thickness of 100 to 500 nm is formed.

(C) First Photoresist Layer Formation Step As shown in FIG. 3, a positive or negative photoresist composition is applied on the etching stopper layer 3 and a pre-bake treatment is performed, so that a photoresist layer 4 having a desired film thickness is formed. Form.

(D) First Image Forming Step As shown in FIG. 4, an exposure process is performed through a photomask having an opening pattern corresponding to a region where the second colored layer is to be formed in the photoresist layer 4, and the latent image is formed. An image region 5 is formed.
FIG. 5 shows a state after the photoresist layer portion of the latent image region 5 to be removed is removed by development processing. The photoresist layer is removed on the support to form an etching stopper layer exposed portion 6, and this etching stopper layer exposed portion 6 corresponds to a region where the first colored layer is to be removed. An etching stopper layer laminated on the first colored layer in which the photoresist layer is removed only in the region where the second colored layer is formed on the support, and the first colored layer and the third and subsequent colored layers are formed. The upper photoresist layer 4 is left.

(E) First Etching Step Next, as shown in FIG. 6, dry etching is performed using the photoresist layer 4 as a mask, the etching stopper layer 3 and the first colored layer 2 are removed, and the second colored layer is removed. A region for forming (support exposed portion 7) is formed.

(F) First photoresist layer removing step After performing the etching process, the photoresist layer 4 is dissolved and removed with a stripping solution or the like. After the completion of the first photoresist layer removing step, as shown in FIG. 7, only the support exposed portion 7 that forms the second colored layer has a shape in which the first colored layer 2 and the etching stopper layer 3 are removed. . FIG. 8 is a plan view of FIG. 7 viewed from the colored layer forming surface side of the support.

(G) Second colored layer forming step Coloring associated with the color components of the second colored layer on the support 1 on which the first colored layer 2 and the etching stopper layer 3 are formed as shown in FIG. The thermosetting composition is applied in a film thickness in which the region 8 as the second colored layer forming portion is embedded, and post-baking is performed to form the second colored layer 9.

(H) Second photoresist layer forming step As shown in FIG. 10, a positive or negative photoresist is applied onto the colored thermosetting composition 9 corresponding to the color component of the second colored layer, and prebaking treatment is performed. To form a photoresist layer 10 having a desired film thickness.

(I) Second Image Forming Step As shown in FIG. 11, the photoresist layer 10 is exposed through a photomask having an opening pattern corresponding to a region other than a region where the second colored layer is to be formed. The latent image area 11 is formed. Then, the photoresist layer portion of the latent image area 11 to be removed is removed by development processing.
As shown in FIG. 12, only the region where the second colored layer is formed on the support is covered with the photoresist layer 10, and the region on which the first colored layer 2 is formed. The photoresist layer is removed, and the second colored layer 9 formed on the etching stopper layer 3 is exposed.

(J) First colored layer removal step The second colored layer 9 is removed by dry etching using the photoresist layer 10 after development as a mask until the etching stopper layer 3 is exposed. FIG. 13 shows a state after removing the second colored layer formed on the etching stopper layer 3.

(K) Second Photoresist Layer Removal Step After performing the etching process, the photoresist layer 10 is dissolved and removed with a stripping solution or the like. After completion of the photoresist layer removing step, the second colored layer formed on the etching stopper layer 3 other than the region 8 which is the second colored layer forming portion is removed as shown in FIG. Further, only the etching stopper layer 3 is laminated on the first colored layer 2. FIG. 15 is a plan view of FIG. 14 viewed from the colored layer non-formation surface side of the support.

(C ′) Third Photoresist Layer Forming Step As shown in FIG. 16, a positive or negative photoresist composition is applied on the etching stopper layer 3 and the region 8 which is the second colored layer forming portion, and prebaked. To form a photoresist layer 12 having a desired film thickness.

(D ′) Third Image Forming Step As shown in FIG. 17, an exposure process is performed through a photomask having an opening pattern corresponding to a region where a third colored layer is to be formed in the photoresist layer 12, A latent image region 13 is formed.
FIG. 18 shows a state after the photoresist layer portion of the latent image region 13 to be removed is removed by development processing. The photoresist layer corresponding to the latent image region is removed to form an etching stopper layer exposed portion 14, and this etching stopper layer exposed portion 14 is formed in a region where the first colored layer and the etching stopper layer are to be removed. It corresponds. The photoresist layer is removed only in the region where the third colored layer is formed on the support, leaving the photoresist layer 12 on the second colored layer and on the etching stopper layer laminated on the first colored layer. It is.

(E ′) Second Etching Step As shown in FIG. 19, the dry etching process is performed only on the region where the third colored layer is formed using the photoresist layer 12 after the development process as a mask. At this time, the dry etching process removes not only the first colored layer 2 but also the etching stopper layer 3 at the same time, and the support surface in the region (support exposed portion 15) for forming the third colored layer is exposed. To do.

(F ′) Third Photoresist Layer Removal Step After performing the etching process, the photoresist layer is dissolved and removed with a stripping solution or the like. After the removal step is completed, the etching stopper layer 3 and the first colored layer 2 are removed from the support exposed portion 15 for forming the third colored layer as shown in FIG. FIG. 21 is a plan view of FIG. 20 viewed from the colored layer non-formation surface side of the support.

(G ′) Third Colored Layer Formation Step As shown in FIG. 22, corresponding to the color components of the third colored layer on the support 1 on which the first colored layer 2 and the second colored layer 8 are formed. The colored thermosetting composition to be applied is applied with a film thickness in which the region 16 which is the third colored layer forming portion is buried, and post-baking is performed to form the third colored layer 17.

(H ′) Fourth Photoresist Layer Forming Step As shown in FIG. 23, a positive or negative photoresist composition is applied on the third colored layer 17 and prebaked so as to have a desired film thickness. A resist layer 18 is formed.

(I ′) Fourth Image Forming Step As shown in FIG. 24, an exposure process is performed through a photomask having an opening pattern corresponding to a region other than the region where the third colored layer is to be formed in the photoresist layer 18. The latent image area 19 is formed. Then, the photoresist layer portion of the latent image region 19 to be removed is removed by development processing.
As shown in FIG. 25, only the region 16 for forming the third colored layer is covered with the photoresist layer 18, and the region on which the first colored layer and the second colored layer are formed. The photoresist layer is removed, and the third colored layer formed on the etching stopper layer 3 and the second colored layer 8 is exposed.

(J ′) Second Colored Layer Removal Step The third colored layer 17 is removed by a dry etching process using the developed photoresist layer 18 as a mask until the etching stopper layer 3 is exposed. FIG. 26 shows a state after removing the third colored layer formed on the etching stopper layer 3 and the second colored layer 8.

(K ′) Fourth Photoresist Layer Removal Step After performing the etching process, the photoresist layer 18 is dissolved and removed with a stripping solution or the like. After the completion of the photoresist layer removal step, as shown in FIG. 27, the third colored layer formed on the etching stopper layer 3 and the second colored layer 8 other than the region 16 which is the third colored layer forming portion. The shape is removed. Further, only the etching stopper layer 3 is formed on the first colored layer 2 and no other layers are formed on the second colored layer 8 and the third colored layer 16. . FIG. 28 is a plan view of FIG. 27 viewed from the colored layer non-forming surface side of the support.

  In the present invention, it is preferable to perform a planarization treatment step on at least the surface of the formed colored layer after the third colored layer is formed. In the planarization process, the end point can be the time when the etching stopper layer is exposed. By performing the flattening process, as shown in FIG. 29, the unevenness formed of the first colored layer, the second colored layer, and the third colored layer on which the etching stopper layer is formed is formed. No flat color filter can be produced.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

In each of the following steps, when processing using a commercially available processing solution was performed, each processing was performed according to the method specified by the manufacturer unless otherwise specified.
(Example 1)
[First step]
A green thermosetting composition “SG-5000L” (manufactured by Fuji Film Electronics Materials) was applied on a silicon substrate with a spin coater so as to form a coating film having a thickness of 0.8 μm, and then a hot plate was applied. The coating film was cured by heating at 220 ° C. for 5 minutes. The thickness of the colored layer formed of “SG-5000L” after the heat treatment was 0.65 μm.
Next, on the colored layer formed of “SG-5000L”, 100 parts by mass of ethyl 3-ethoxypropionate, 2 parts by mass of camphorsulfonic acid triphenylsulfonic acid (onium salt), tripropylamine (tertiary fatty acid amine) ) A film composed of 0.1 parts by mass, 20 parts by mass of urea formaldehyde (aminoblasts), and 50 parts by mass of a polyhydroxystyrene derivative (Maruka Linker CMM manufactured by Maruzen Chemical Co., Ltd.) has a film thickness of 500 nm. Then, post-baking treatment (200 ° C., 5 minutes) was performed to form an etching stopper layer.
Next, on the etching stopper layer, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied with a Mark 8 manufactured by Tokyo Electron, and pre-baked, so that the film thickness becomes 0.8 μm. A layer was formed.

Next, the region corresponding to the filter array of RED was exposed to 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.), and post-exposure heat treatment at 110 ° C. for 1 minute (PEB treatment). After developing for 1 minute with the developer “FHD-5” (manufactured by FUJIFILM Electronics Materials), post-baking at 120 ° C. for 2 minutes to form a RED filter array The photoresist in the power region was removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the base substrate is exposed only in the region where the RED filter array is to be formed in the state where the colored layer and etching stopper layer formed of “SG-5000L” are formed except for the region where the RED filter array is to be formed. It is in a state of being.

[Second step]
The film thickness of the region where the red thermosetting composition “SR-5000L” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) should form the RED filter array is formed on the substrate after the first step with a spin coater. After coating to a 0.8 μm coating film, the coating film was cured by heating at 220 ° C. for 5 minutes using a hot plate. The thickness of the colored layer formed of “SR-5000L” by heat treatment was 0.65 μm.

  Next, a positive photoresist “FHi622BC” (manufactured by Fujifilm Electronics Materials) was applied with a Mark 8 manufactured by Tokyo Electron and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, the region other than the region corresponding to the RED filter array was exposed to 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.), and post-exposure heat treatment (PEB treatment at 110 ° C. for 1 minute). ), After developing for 1 minute with the developer “FHD-5” (manufactured by FUJIFILM Electronics Materials), followed by post-baking for 2 minutes at 120 ° C., except for the RED filter array. The photoresist in the area was removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Etching was performed. The etching end point at this time was set to the time when the etching stopper layer was exposed. The end point was detected with an optical detection monitor.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, in a state where the colored layer formed of “SG-5000L” and the etching stopper layer are formed except the region where the RED filter array is to be formed, only the region where the RED filter array is to be formed is the RED colored layer. Is formed.

  Next, a positive photoresist “FHi622BC” (manufactured by Fujifilm Electronics Materials) was applied with a Mark 8 manufactured by Tokyo Electron and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, the area corresponding to the BLUE filter array was exposed to 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.), and post-exposure heat treatment (PEB treatment) at 110 ° C. for 1 minute. After developing for 1 minute with the developer “FHD-5” (manufactured by FUJIFILM Electronics Materials), post-baking for 2 minutes at 120 ° C. to form a BLUE filter array The photoresist in the power region was removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the region where the GREEN filter array is to be formed is the state where the colored layer and the etching stopper layer formed of “SG-5000L” are formed, and the region where the RED filter array is to be formed is “SR-5000L”. In the state in which the colored layer formed in (1) is formed, the region where the BLUE filter array is to be formed is in a state where the base substrate is exposed.

[Third step]
On the substrate after the second step, a blue thermosetting composition “SB-5000L” (Fuji Film Electronics Materials Co., Ltd.) is formed in a region where a BLUE filter array is to be formed using a spin coater. After coating so as to form an 8 μm coating film, the coating film was cured by heating at 220 ° C. for 5 minutes using a hot plate. The thickness of the colored layer formed of “SB-5000L” by heat treatment was 0.65 μm.

  Next, a positive photoresist “FHi622BC” (manufactured by Fujifilm Electronics Materials) was applied with a Mark 8 manufactured by Tokyo Electron and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, except for the region corresponding to the BLUE filter array, 350 mJ / cm ² exposure with an i-line stepper (manufactured by Canon Inc.), post-exposure heat treatment at 110 ° C. for 1 minute (PEB treatment) ), After developing for 1 minute with the developer “FHD-5” (manufactured by FUJIFILM Electronics Materials), followed by post-baking for 2 minutes at 120 ° C., except for the BLUE filter array The photoresist in the area was removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Etching was performed. The etching end point at this time was the time when the etching stopper was exposed. The end point was detected by an optical end point detection monitor.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the region where the GREEN filter array is to be formed is the state where the colored layer and the etching stopper layer formed of “SG-5000L” are formed, and the region where the RED filter array is to be formed is “SR-5000L”. In the state in which only the colored layer formed in (1) was formed, the color filter was formed in the state in which only the colored layer formed with “SB-5000L” was formed in the region where the BLUE filter array was to be formed.

After the above steps, the RED and BLUE colored layer portions protruding as compared with the etching stopper layer surface were selectively polished by CMP (chemical mechanical polishing). At this time, the end point was detected using an etching stopper layer. The end point was detected by an optical end point detection monitor.
As a result, a color filter array having a pattern size of 1.5 μm could be formed in a rectangular shape with a flattened surface.

(Example 2)
[First step]
A green thermosetting composition “SG-5000L” (manufactured by Fuji Film Electronics Materials) was applied on a silicon substrate with a spin coater so as to form a coating film having a thickness of 0.8 μm, and then a hot plate was applied. The coating film was cured by heating at 220 ° C. for 5 minutes. The thickness of the colored layer formed of “SG-5000L” was 0.65 μm.

  Next, on the colored layer formed of “SG-5000L”, 100 parts by weight of ethyl 3-ethoxypropionate, 2 parts by weight of camphorsulfonic acid triphenylsulfonic acid (onium salt), trimethylamine (tertiary fatty acid amine) 0 .1 part by weight and a polyhydrostyrene derivative (Maruka Linker CMM manufactured by Maruzen Kagaku Co., Ltd.) 50 parts by weight were applied so that the film thickness was 500 nm, and post-baking treatment (200 ° C., 5 minutes) was performed. And an etching stopper layer was formed.

  Next, on the etching stopper layer, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied with Mark 8 manufactured by Tokyo Electron, and pre-baked, so that the film thickness becomes 0.8 μm. A layer was formed.

Next, the region corresponding to the filter array of RED was exposed to 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.), and post-exposure heat treatment at 110 ° C. for 1 minute (PEB treatment). After developing for 1 minute with the developer “FHD-5” (manufactured by FUJIFILM Electronics Materials), post-baking at 120 ° C. for 2 minutes to form a RED filter array The photoresist in the power region was removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the base substrate is exposed only in the region where the RED filter array is to be formed in the state where the colored layer and etching stopper layer formed of “SG-5000L” are formed except for the region where the RED filter array is to be formed. It is in a state of being.

[Second step]
The film thickness of the region where the red thermosetting composition “SR-5000L” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) should form the RED filter array is formed on the substrate after the first step with a spin coater. After coating to a 0.8 μm coating film, the coating film was cured by heating at 220 ° C. for 5 minutes using a hot plate. The thickness of the colored layer formed of “SR-5000L” by heat treatment was 0.65 μm.

  Next, a positive photoresist “FHi622BC” (manufactured by Fujifilm Electronics Materials) was applied with a Mark 8 manufactured by Tokyo Electron and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, an area other than the area corresponding to the RED filter array was exposed to 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.), and post-exposure heat treatment (PEB) at 110 ° C. for 1 minute. ) Processing, followed by development processing for 1 minute with the developer “FHD-5” (manufactured by FUJIFILM Electronics Materials), followed by post-baking processing at 120 ° C. for 2 minutes, and a RED filter array The photoresist in the other area was removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Etching was performed. The etching end point at this time was the time when the etching stopper was exposed. The end point was detected by an optical end point detection monitor.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the RED is formed only in the region where the RED filter array is to be formed in the state where the colored layer and the etching stopper layer formed of “SG-5000L” are formed except the region where the RED filter array is to be formed. It is in the state.

  Next, a positive photoresist “FHi622BC” (manufactured by Fujifilm Electronics Materials) was applied with a Mark 8 manufactured by Tokyo Electron and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, the area corresponding to the BLUE filter array was exposed to 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.), and post-exposure heat treatment (PEB treatment) at 110 ° C. for 1 minute. After developing for 1 minute with the developer “FHD-5” (manufactured by FUJIFILM Electronics Materials), post-baking at 120 ° C. for 2 minutes to form a RED filter array The photoresist in the power region was removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the region where the GREEN filter array is to be formed is the state where the colored layer and the etching stopper layer formed of “SG-5000L” are formed, and the region where the RED filter array is to be formed is “SR-5000L”. In the state where only the colored layer formed in (1) is formed, the region where the BLUE filter array is to be formed is in a state where the base substrate is exposed.

[Third step]
On the substrate after the second step, a blue thermosetting composition “SB-5000L” (Fuji Film Electronics Materials Co., Ltd.) is formed in a region where a BLUE filter array is to be formed using a spin coater. After coating so as to form an 8 μm coating film, the coating film was cured by heating at 220 ° C. for 5 minutes using a hot plate. The thickness of the colored layer formed of “SB-5000L” by heat treatment was 0.65 μm.

After the above steps, the BLUE colored layer formed on the etching stopper layer and the RED colored layer was selectively polished by CMP (chemical mechanical polishing). At this time, the portion of the RED colored layer formed as the second layer that protrudes from the surface of the etching stopper layer was also removed. At this time, the end point was the time when the etching stopper layer was exposed. The end point was detected by an optical end point detection monitor.
As a result, a color filter array having a pattern size of 1.5 μm could be formed in a rectangular shape with a flattened surface.

(Comparative Example 1)
In the same manner as in Example 1, a colored layer formed of the green thermosetting composition “SG-5000L” was formed.
Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied to the colored layer formed of “SG-5000L” by using Mark 8 manufactured by Tokyo Electron, and the film thickness is 0. A photoresist layer was formed to have a thickness of 8 μm. The thickness of the colored layer formed of “SG-5000L” by heat treatment was 0.65 μm.

Next, an area other than the area corresponding to the GREEN filter array was subjected to an exposure of 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.) and a post-exposure heat treatment at 110 ° C. for 1 minute. FHD-5 "(manufactured by FUJIFILM Electronics Materials Co., Ltd.) for 1 minute and then post-baked at 120 ° C. for 2 minutes to form a photoresist in the region where the RED and BLUE filter arrays should be formed. Removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the region where the GREEN filter array is to be formed has a colored layer formed of “SG-5000L”, and the base substrate is exposed in the region where the RED and BLUE filter arrays are to be formed. It is in a state.

  The film thickness of the region where the red thermosetting composition “SR-5000L” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) should form the RED filter array is formed on the substrate after the first step with a spin coater. After coating to a 0.8 μm coating film, the coating film was cured by heating at 220 ° C. for 5 minutes using a hot plate. The thickness of the colored layer formed of “SR-5000L” by heat treatment was 0.65 μm.

  Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied on the substrate and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, an area corresponding to the BLUE filter array was subjected to an exposure of 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.) and a post-exposure heat treatment at 110 ° C. for 1 minute. -5 "(manufactured by FUJIFILM Electronics Materials Co., Ltd.) for 1 minute, followed by post-baking at 120 ° C. for 2 minutes to remove the photoresist in the region where the BLUE filter array is to be formed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials), a stripping process for 60 seconds was performed to remove the photoresist. As a result, the region where the GREEN filter array is to be formed forms the RED filter array in a state where the colored layer formed of “SG-5000L” and the colored layer formed of “SR-5000L” are laminated. The region to be formed is in a state where a colored layer formed of “SR-5000L” is formed, and the region in which the BLUE filter array is to be formed is in a state in which the base substrate is exposed.

  Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied on the substrate and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, the areas other than those corresponding to the BLUE and RED filter arrays were exposed to 350 mJ / cm ² with an i-line stepper (manufactured by Canon Inc.), post-exposure heat treatment at 110 ° C. for 1 minute, and then developed. After developing for 1 minute with the liquid “FHD-5” (manufactured by FUJIFILM Electronics Materials), post-baking at 120 ° C. for 2 minutes to form a photoresist in the region where the GREEN filter array is to be formed Removed. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (Hitachi High-Technologies U-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%. At this time, the end point was the time when the GREEN colored layer was exposed. As a result, a GREEN and RED filter array was formed.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, the region where the GREEN filter array was to be formed was formed with the colored layer formed of “SG-5000L”, and the region where the RED filter array was to be formed was formed with “SR-5000L”. In the state where the colored layer is formed, the region where the BLUE filter array is to be formed is in a state where the base substrate is exposed.

[Third step]
The film thickness of the region where the BLUE filter array is to be formed with the blue thermosetting composition “SB-5000L” (manufactured by Fuji Film Electronics Materials) on the substrate after the second step is determined by a spin coater. After coating to a 0.8 μm coating film, the coating film was cured by heating at 220 ° C. for 5 minutes using a hot plate. The thickness of the colored layer formed of “SB-5000L” by heat treatment was 0.65 μm.

  Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied on the substrate and pre-baked to form a photoresist layer having a thickness of 0.8 μm.

Next, an area other than the region corresponding to the BLUE filter array was subjected to 350 mJ / cm ² exposure using an i-line stepper (manufactured by Canon Inc.) and post-exposure heat treatment at 110 ° C. for 1 minute. FHD-5 "(manufactured by FUJIFILM Electronics Materials Co., Ltd.) for 1 minute and then post-baked at 120 ° C for 2 minutes to remove the photoresist other than the region where the BLUE filter array is to be formed. did. At this time, the pattern size was 1.5 μm.

Next, in a dry etching apparatus (manufactured by Hitachi High-Technologies Corporation, M-621), RF power: 800 W, chamber pressure: 4 Pa, substrate temperature: 50 ° C., gas type and flow rate are set to Ar: 800 mL / min. , CF ₄ : 200 mL / min. , O ₂ : 50 mL / min. Then, the etching process was performed with an overetching rate of 10%. At this time, the end point was the time when the GREEN colored layer was exposed.

  Next, using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials Co., Ltd.), a stripping treatment was performed for 120 seconds to remove the photoresist. As a result, a color filter array having a pattern size of 1.5 μm could be formed. However, in this comparative example in which the removal of the colored layer was completed based on the GREEN colored layer, the thickness of each colored layer could not be formed uniformly.

It is sectional drawing which shows the state in which the 1st colored layer was formed on the support body. It is sectional drawing which shows the state in which the etching stopper layer was formed on the 1st colored layer. It is sectional drawing which shows the state in which the photoresist layer was formed on the etching stopper layer. It is sectional drawing which shows the state of the photoresist layer after exposure. It is sectional drawing which shows the state of the photoresist layer after image development processing. It is sectional drawing which shows the layer structure after a dry etching process. It is sectional drawing which shows the layer structure after a photoresist layer removal. It is the top view which showed FIG. 7 from the colored layer formation surface side of a support body. It is sectional drawing which shows the state in which the 2nd colored layer was formed. It is sectional drawing which shows the state in which the photoresist layer was formed on the 2nd colored layer. It is sectional drawing which shows the state of the photoresist layer after exposure. It is sectional drawing which shows the state of the photoresist layer after image development processing. It is sectional drawing which shows the layer structure after an etching process. It is sectional drawing which shows the layer structure after a photoresist layer removal. It is the top view which showed FIG. 14 from the colored layer non-formation surface side of a support body. It is sectional drawing which shows the state in which the photoresist layer was formed on the etching stopper layer and the 2nd colored layer. It is sectional drawing which shows the state of the photoresist layer after exposure. It is sectional drawing which shows the state of the photoresist layer after image development processing. It is sectional drawing which shows the layer structure after an etching process. It is sectional drawing which shows the layer structure after a photoresist layer removal. It is the top view which showed FIG. 20 from the colored layer non-formation surface side of a support body. It is sectional drawing which shows the state in which the 3rd colored layer was formed. It is sectional drawing which shows the state in which the photoresist layer was formed on the 3rd colored layer. It is sectional drawing which shows the state of the photoresist layer after exposure. It is sectional drawing which shows the state of the photoresist layer after image development processing. It is sectional drawing which shows the layer structure after an etching process. It is sectional drawing which shows the layer structure after a photoresist layer removal. It is the top view which showed FIG. 27 from the colored layer non-formation surface side of a support body. It is sectional drawing which shows the layer structure of a color filter after a planarization process process.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2 1st coloring layer 3 Etching stopper layer 4, 10, 12, 18 Photoresist layer 5, 11, 13, 19 Uncured latent image area 6, 14 Etching stopper layer exposure part 7, 15 Support body exposure Part 8 Second colored layer forming part 9 Second colored layer 16 Third colored layer forming part 17 Third colored layer

Claims (4)

(A) a first colored layer forming step of forming a first colored layer on the support;
(B) an etching stopper layer forming step of forming an etching stopper layer on the first colored layer;
(C) a first photoresist layer forming step of forming a photoresist layer on at least the etching stopper layer;
(D) a first image forming step of forming an image on the etching stopper layer by removing a partial region of the photoresist layer;
(E) a first etching step of removing the etching stopper layer and the first colored layer in the partial region by a dry etching method like the image formed by the first image forming step;
(F) a first photoresist layer removing step of removing the photoresist layer remaining after the first etching step;
(G) a second colored layer forming step of forming a second colored layer different from the first colored layer on the partial region from which the first colored layer has been removed and the etching stopper layer; ,
(H) a second photoresist layer forming step of forming a photoresist layer on the second colored layer;
(I) a second image forming step of forming an image on the second colored layer by removing the photoresist layer other than the partial region;
(J) First, at least a second colored layer formed on the etching stopper layer is removed by a dry etching method until the etching stopper layer is detected, like the image formed by the second image forming step. 1 colored layer removing step;
(K) a second photoresist layer removing step of removing the photoresist layer remaining after the colored layer removing step;
A method for producing a color filter comprising:   The method for producing a color filter according to claim 1, further comprising at least one group of process groups in which the steps (c) to (g) are performed in this order.   The method for producing a color filter according to claim 1, further comprising at least one group of process groups in which (c) to (k) are performed in this order. The method for producing a color filter according to any one of claims 1 to 3, further comprising a flattening process step of flattening a surface of at least the formed colored layer.

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