JP5562591B2 - Colored curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a colored curable composition suitable for forming a pattern using a dry etching method, a color filter using the same, and a method for producing the same.

  For example, a solid-state imaging device is provided with a color filter in which colored pixels of a plurality of colors such as red pixels, green pixels, and blue pixels are two-dimensionally arranged on a support such as a semiconductor substrate. In this solid-state imaging device, the number of pixels has increased remarkably in recent years, and the pixel size has been remarkably reduced when compared with a conventional solid-state imaging device having the same inch size. Also, as the pixel size decreases, the performance requirements for color separation become stricter. To maintain device characteristics such as color shading characteristics and color mixing prevention, the performance required for color filters is reduced to thinner, rectangular, and between each colored pixel. Therefore, there is a demand for performance such as eliminating an overlap region where colors overlap each other.

  As a method for manufacturing such a color filter, a photolithographic method has been widely used. In the photolithography method, a colored photosensitive composition is applied and dried on a support to form a colored layer, and then the colored layer is subjected to pattern exposure / development to form a first color (for example, green) colored pixel. In the same manner, the remaining colored pixels are formed.

  However, with the miniaturization of pixels of solid-state imaging devices, pattern formation by the so-called photolithography method makes it difficult to achieve both the spectral characteristics of the color filter and the pattern formability in response to the demand for finer and thinner color filters. It is coming. Specifically, in a color filter for a solid-state imaging device, the thickness of the colored pattern is thin, for example, the thickness is 1 μm or less, and the pixel pattern size is 2 μm or less (for example, 0.5 to 2.0 μm). It tends to be sized.

  In particular, as the film thickness decreases, the relative amount of pigments and other colorants in the film increases, while the amount of components other than colorants that contribute to photolithographic properties in the film relatively decreases. Formability is a pattern when the cross section is observed, although there is an effect of improving the shape of the pattern observed from the top surface even when correction of OPC or the like is performed for a pattern formation request less than 2.0 μm. There is a problem that the shape has a round pattern edge and poor rectangularity. This is because color filters using pigment dispersions (color filters prepared by photolithography using colored radiation-sensitive compositions in which pigments are dispersed in various compositions) are affected by light scattering during exposure with pigments. Thus, it is known that the roundness of the pattern edge becomes remarkable.

  In particular, recently, for example, the formation of a 1.4 μm pattern has been questioned due to the demand for higher definition of color filters for solid-state imaging devices, and the resolution of the conventional photolithographic method is close to the limit.

  A processing method using a dry etching method has been proposed as an effective method for realizing pattern miniaturization and thinning for a color filter manufacturing method using a photolithographic method. The dry etching method has been conventionally employed as a method for forming a pattern (each colored pixel) into a rectangle, and a pattern forming method combining a photolithographic method and a dry etching method has been proposed (for example, Patent Document 1). ~ 2).

  Moreover, the manufacturing method of the color filter which has a colored pattern formation process which forms a 1st colored layer on a support body and forms a 1st stopper layer on the formed 1st colored layer is disclosed ( For example, see Patent Document 3). In this case, when a multi-color filter is manufactured, the first color filter layer is polished by, for example, CMP (Chemical Mechanical Polishing) as a final process to obtain a flat color filter. In the case of polishing, since the first color filter layer has a stopper layer and has CMP resistance, overpolishing is prevented and the process window can be widened.

JP 2001-249218 A JP 2006-339376 A JP 2009-31723 A

  However, in order to prevent the polishing of the first color filter layer from proceeding excessively by CMP as described above, it is necessary to install a stopper layer as a lower layer of the layer to be polished. It is a concern that the installation of the stopper layer itself increases the number of processes and complicates the process, which is disadvantageous in terms of manufacturing cost.

  The present invention has been made in view of the above, and is colored and cured having resistance (hereinafter, sometimes referred to as “polishing stopper property”) that is difficult to receive an excessive planarization treatment such as overpolishing when the film is formed. In the case of forming a multicolor pattern by applying a planarization treatment (polishing by CMP or the like) to the colored layer on the colored pattern formed by the dry etching method, and the production composition, while keeping the manufacturing cost low, A color filter manufacturing method capable of producing a color filter having a desired pattern thickness without giving an excessive flattening process such as overpolishing to an existing colored pattern, and a color having a desired pattern thickness, hue and color density An object is to provide a filter and to achieve the object.

  In the present invention, for example, after providing a colored layer of the second color, the third color,... So as to cover the colored pattern of the first color processed into a desired pattern, the colored layers of the second and subsequent colors are provided. When a multicolor pattern is formed by polishing until the colored pattern of the first color is at least exposed, a predetermined amount of inorganic particles are dispersed in the colored pattern (colored layer) of the first color. Thus, the inventors have obtained knowledge that the resistance during the flattening process (polishing by CMP or the like) has been drastically improved, and has been achieved based on such knowledge.

Specific means for achieving the above object are as follows.
<1> It contains a colorant, inorganic particles, and a curable compound, and is used for pattern formation by a dry etching method. The mass ratio of the inorganic particles to the total solid content is 0.8% to 4.0%, at least one curable compound is a polyfunctional epoxy compound, which is the polyfunctional epoxy compound mass ratio is colored curable composition Ru 1% to 35% der in respect to the total solid content.
<2> The colored curable composition according to <1>, wherein the inorganic particles are transparent inorganic particles.
<3> The colored curable composition according to <1> or <2>, wherein the inorganic particles are at least one selected from silica particles, zirconia particles, and alumina particles.
<4> The colored curable Kumiso-cho composition according to any one of <1> to <3>, wherein the inorganic particles are silica particles.
<5> The colored curable composition according to any one of <1> to <4>, wherein an average particle size of the inorganic particles is 50 nm or less.
<6> The colored curable composition according to any one of <1> to <5>, wherein the inorganic particles have an average particle diameter of 10 nm to 30 nm.
<7> The colored curable composition according to any one of <1> to <6>, further including an acid anhydride.

< 8 > A first coloring layer that includes a coloring agent, inorganic particles, and a curable compound on the support, and forms a first colored layer using a colored curable composition that is used for pattern formation by a dry etching method. A layer forming step, a first pattern forming step of forming a first colored pattern by dry-etching the first colored layer, a colorant and a first colored pattern forming surface side of the support; The 2nd colored layer formation process which forms a 2nd colored layer using the 2nd colored curable composition which contains a curable compound and content with respect to the total solid of an inorganic particle is less than 0.8 mass%. When, the formed second color layer, the first color pattern is seen contains and a flattening process step of treating planarized to expose least, producing a color filter composed of colored patterns of a plurality of colors It is characterized by It is a manufacturing method of chromatography filter.
< 9 > A first coloring that includes a coloring agent, inorganic particles, and a curable compound on the support, and forms a first colored layer using a colored curable composition that is used for pattern formation by a dry etching method. A layer forming step, a first pattern forming step of forming a first colored pattern by dry-etching the first colored layer, a colorant and a first colored pattern forming surface side of the support; The n-th colored layer is formed using an n-th (n ≧ 2) colored curable composition containing a curable compound and having a content of less than 0.8% by mass of the inorganic particles based on the total solid content. And forming the n-th colored layer and the first colored pattern by dry etching to form a concavo-convex pattern for forming an (n + 1) th (n ≧ 2) colored pattern. N + 1th pattern formation step And n + 1 (n ≧ 2) colored curability containing a colorant and a curable compound on the surface of the support on which the concave / convex pattern is formed, and the content of the inorganic particles with respect to the total solid content is less than 0.8% by mass. At least one of the (n + 1) th colored layer forming steps for forming the (n + 1) th colored layer using the composition, and an n layer (n ≧ 2) formed on the first colored pattern forming surface side of the support of a colored layer, said saw including a planarizing step, a first color pattern is planarized to expose least, of the color filter, which comprises forming a color filter consisting of n + 1 color colored pattern of It is a manufacturing method.

< 10 > Including a colorant , inorganic particles , and a curable compound, the mass ratio of the inorganic particles to the total solid content is 0.8% to 4.0%, and at least one of the curable compounds is a polyfunctional epoxy. It is a color filter provided with at least 1 type of colored pattern which is a compound and is a hardened | cured material of the colored curable composition whose mass ratio of the said polyfunctional epoxy compound with respect to the total solid is 1%-35% .
< 11 > A colorant , inorganic particles , and a curable compound, the mass ratio of the inorganic particles to the total solid content is 0.8% to 4.0%, and at least one of the curable compounds is a polyfunctional epoxy. It is a color filter provided with at least 1 type of coloring pattern which is a compound and the mass ratio of the said polyfunctional epoxy compound with respect to the total solid is 1%-35% .
< 12 > A solid-state imaging device including the color filter according to < 10 > or < 11 >.

ADVANTAGE OF THE INVENTION According to this invention, the colored curable composition which has the tolerance (polishing stopper property) which cannot receive excessive planarization processes, such as overpolishing, when forming into a film can be provided. Also,
According to the present invention, when a multicolor pattern is formed by performing a planarization process (polishing by CMP or the like) on a colored layer on a colored pattern formed by a dry etching method, the manufacturing cost is kept low, It is possible to provide a method of manufacturing a color filter that can produce a color filter having a desired pattern thickness without giving an excessive coloration process such as overpolishing to an existing colored pattern. further,
According to the present invention, a color filter having a desired hue and color density can be provided.

  As described above, in the present invention, when manufacturing a color filter having a desired hue, color density, and resolution (pattern shape) and a solid-state imaging device equipped with the same while reducing the manufacturing cost to a low level, It is possible to build a color filter structure and manufacturing technology with an expanded process window.

It is a schematic sectional drawing which shows the structural example of a color filter and a solid-state image sensor. It is process drawing which shows an example of the flow which produces a color filter with the manufacturing method of the color filter of this invention. It is process drawing which shows the other example of the flow which produces a color filter with the manufacturing method of the color filter of this invention.

  Hereinafter, the colored curable composition of the present invention, the color filter of the present invention using the same, and the production method thereof will be described in detail.

<Colored curable composition>
The colored curable composition of the present invention includes at least a colorant, inorganic particles, and a curable compound, and is used for pattern formation by a dry etching method. In particular, an existing pattern ( For example, it has a composition suitable for the planarization treatment of a colored layer (for example, the second color) on the first color coloring pattern).

In the present invention, by including inorganic particles in addition to the colorant and the curable compound, a colored layer to be planarized (polishing by CMP or the like; hereinafter, sometimes simply referred to as “polishing”). An existing pattern (for example, a colored pattern of the first color) located in a lower layer (a layer closer to the support) (hereinafter also referred to as a “layer to be polished”) has a polishing stopper property, so that a stopper is provided in a separate process. Without providing a layer, a desired amount of polishing can be performed while suppressing overpolishing, and a color filter having a desired hue and color density can be produced.
As a result, it is possible to increase the process window when manufacturing the color filter while reducing the manufacturing cost.

As the colored curable composition of the present invention, either a photosensitive colored photocurable composition or a non-photosensitive colored thermosetting composition can be used.
[Colored photocurable composition]
The colored photocurable composition contains at least a colorant and a photocurable component. Among these, the “photocurable component” is a photocurable composition generally used in the photolithography method, and includes a binder resin (alkali-soluble resin, etc.), a polymerization component (polymerizable monomer, etc.), a photopolymerization initiator, and the like. A composition containing at least can be used. 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.

[Colored thermosetting composition]
The colored thermosetting composition contains a colorant and a thermosetting compound, and the colorant concentration in the total solid content is preferably 50% by mass or more and less than 100% by mass. By increasing the colorant concentration, a thinner color filter can be obtained. In addition, when each colored pixel of the color filter is formed using a dry etching method, that is, using only a colored thermosetting composition, the photocurable component is removed from each colored pixel (each colored layer), and the cured component of each layer is changed. By using only the thermosetting component, the ratio of the coloring component can be increased. As a result, each colored pixel can be made thinner and good spectral characteristics can be obtained.

Hereinafter, each component which comprises a colored curable composition is demonstrated.
-Colorant-
The colored curable composition of the present invention contains at least one colorant. The colorant is not particularly limited, and various conventionally known dyes and pigments can be used alone or in combination.

  Examples of the pigment 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 such pigments include the following. However, the present invention is not limited to these. From the viewpoint of blue separability, it is desirable to further contain a violet dye in the blue dye. Thereby, even when the blue pattern / pixel is formed of a thin film, the spectral characteristics can be further improved.

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 a dye is used as the colorant, the dye can be uniformly dissolved in the composition to obtain a non-photosensitive colored thermosetting composition.
There is no restriction | limiting in particular as dye, A well-known dye can be used for conventional color filters.

  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 there is no limitation in particular as content in the total solid of the coloring curable composition of a coloring agent, Preferably it is 30-80 mass%, More preferably, it is 50-80 mass%. When the content of the colorant is 30% by mass or more, moderate chromaticity is obtained as a color filter, and it is more effective to obtain a pattern having a desired hue, color density, and pattern shape (pattern cross section is rectangular). . Moreover, hardening can fully be advanced because the content rate of a coloring agent is 70 mass% or less, and the strength reduction as a film | membrane can be suppressed.

-Inorganic particles-
The colored curable composition of the present invention contains at least one kind of inorganic particles. The material of the inorganic particles is preferably transparent so that visible light can be transmitted within an addition amount range of 20% by mass or less with respect to the total solid content of the composition, and is not particularly limited among known inorganic particles. You can choose.

  Here, the transparent inorganic particle means that the composition is formed as a 1.0 μm coating film with the above content, and the transmission of light that is transmitted when the transmittance of visible light (400 to 700 nm) is measured. Particles with a rate of 90% or higher.

  Examples of the inorganic particles include compound particles such as oxides, nitrides, carbides, borides, and sulfides, metal particles, and the like. Specific examples of the inorganic particles include, for example, particles such as silica, alumina, and zirconia as oxides, and silica particles are preferable. Silica particles include, for example, anhydrous silica such as colloidal silica and vapor phase silica, and hydrous silica.

The average particle diameter of the inorganic particles is preferably 50 nm or less in terms of the volume average particle diameter of the secondary particles, and more preferably in the range of 10 to 30 nm. When the average particle diameter is 50 nm or less, transparency is obtained. For example, when a color pattern such as a color filter is produced, the hue and color unevenness of the colorant are not impaired, and a desired color tone and color density can be easily obtained. Become.
The volume average particle diameter of the inorganic particles is a value measured using Microtrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.).

  Moreover, you may use a commercial item as an inorganic particle. Examples of inorganic particles on the market include colloidal silica, for example, organosilica sol manufactured by Nissan Chemical Co., Ltd., such as MEK-ST, PMA-ST, PGM-ST, etc., and OSCAL manufactured by Catalytic Chemical Industry Co., Ltd. (Oscal) 1132, 1232, 1332, 1432, 1532, 1632, 1622, 1722, 1724 (above, organic solvent dispersion) and the like. Examples of alumina are manufactured by Kawaken Fine Chemical Co., Ltd. Examples of zirconia include nano-use ZR (r) [zirconia sol] manufactured by Nissei Sangyo Co., Ltd., and the like.

The content ratio (mass ratio) with respect to the total solid content of the colored curable composition of inorganic particles is preferably in the range of 0.8 to 20%. When the content ratio of the inorganic particles with respect to the total mass of the composition is 0.8% by mass or more, over-polishing of the existing pattern is effectively prevented when the surface is flattened by polishing such as CMP, and the desired thickness and hue And a color filter having a color density can be manufactured. In addition, when the content of the inorganic particles is 20% by mass or less, there is little change in the color tone (color value) with respect to the film thickness, so that there is little influence on the film thickness of the colored curable composition, and easy etching during dry etching processing. This is advantageous in terms of the characteristics (a high rate can be maintained).
Especially, the range of 2.0-10 mass% is more preferable for the content ratio with respect to the total solid of the colored curable composition of inorganic particles.

-Curable compound-
The colored curable composition of the present invention contains at least one curable compound.
As the curable compound, a polymerization component (polymerizable monomer, etc.) and a photopolymerization initiator are used when it is configured to be photosensitive, and when it is configured to be non-photosensitive (thermosetting), the film is cured by heating. Is used. The polymerization component, photopolymerization initiator, and the like for the photosensitivity are as described above.

  The curable compound used when constituting non-photosensitive (thermosetting) is not particularly limited as long as the film can be cured by heating. For example, a compound having a thermosetting functional group may be used. it can. As such a 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. Examples thereof include 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, an epoxy compound is preferable, and a polyfunctional epoxy compound is particularly preferable.

  As the epoxy compound, a resin having an epoxy group and crosslinkability can be appropriately selected and used. Examples of the epoxy resin include bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline. Divalent glycidyl group-containing low molecular weight compounds such as trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl ether, trivalent glycidyl group-containing low molecular weight compounds represented by TrisP-PA triglycidyl ether, etc. Similarly, tetravalent glycidyl group-containing molecular weight reduction represented by pentaerythritol tetraglycidyl ether, tetramethylol bisphenol A tetraglycidyl ether, etc. Of polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl (meth) acrylate, 2,2-bis (hydroxymethyl) -1-butanol Examples thereof include glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct and the like.

  Examples of these thermosetting compounds include thermosetting compounds described in paragraph numbers [0034] to [0048] of JP-A-2008-292548.

  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 colored thermosetting composition. 0.2-40 mass% is more preferable, and 1-35 mass% is especially preferable.

-Acid anhydride-
The colored curable composition of the present invention preferably contains an acid anhydride. By containing an acid anhydride, it is possible to improve the crosslinkability of the curable compound, particularly the epoxy compound, by thermal curing.

Examples of the acid anhydride include phthalic anhydride, nadic anhydride, maleic anhydride, succinic anhydride, and the like. Of these, phthalic anhydride is preferable because it has little influence on pigment dispersion.
An amine compound is generally used as an epoxy curing agent, but has advantages such as a relatively long pot life.

  As content in the colored curable composition of an acid anhydride, the range of 10-40 mass% is preferable with respect to content of a curable compound (especially epoxy compound), and the range of 15-30 mass% is more. preferable. When the content of the acid anhydride is 10% by mass or more, the crosslinking density of the curable compound, particularly epoxy, can be improved, and the mechanical strength can be increased. The components are suppressed, which is advantageous for increasing the concentration of the coloring material.

-Various additives-
In the colored curable composition, various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, a polymer compound other than those described above, and an interface are added as necessary, as long as the effects of the present invention are not impaired. An activator, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a dispersant, 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.

  Examples of acrylic resins include copolymers consisting of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, such as benzyl methacrylate / methacrylic acid, benzyl Each copolymer such as 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 above-mentioned colorant in these binders at a high concentration, it is possible to impart adhesion to the lower layer, etc., and these contribute to the coating surface state during spin coating and slit coating (colored layer formation). ing.

[Curing agent]
When using an epoxy resin as the curable compound, it is preferable to add a 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 explained in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of curing agents are shown below.

  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, for 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 realize a composition having a high colorant concentration, curing by reaction between epoxy groups is effective in addition to curing by reaction with a 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 is used as a solution dissolved in various solvents. The solvent is not particularly limited as long as the solubility of each component and the coating property of the colored thermosetting composition are satisfied.

[Dispersant]
By containing the dispersant, the dispersibility of the pigment can be improved. 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 the dispersant, many types of compounds can be used. For example, phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol); organosiloxane polymer KP341 (Shin-Etsu) (Made by Chemical Industry Co., Ltd.), (meth) acrylic acid type (co) polymer polyflow No.75, No.90, No.95 (made by Kyoeisha Yushi Chemical Co., Ltd.), W001 (made 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) Agents: Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Nippon Lubrizol); Adeka Pluronic L31, F38, L42, L44, L61, L64, 68, 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 said dispersing agent may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of the dispersant added to the colored thermosetting composition is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

~~ Preparation method of colored thermosetting composition ~~
A preferred method for preparing the colored thermosetting composition will be described. However, the present invention is not limited to this.
For the colored thermosetting composition, a method using a pigment having finely divided pigment particles and a sharp particle size distribution is suitable. Specifically, a method using a pigment constituted by including 75% by mass or more of pigment particles having an average particle size of about 0.01 μm and a particle size in the range of 0.01 ± 0.005 μm is preferable. In order to adjust the particle size distribution of the pigment within the above range, the pigment dispersion method is particularly important. As such a dispersion method, for example, dry dispersion (kneading dispersion treatment) in which a high-viscosity state is dispersed using a roll mill such as a kneader or two-roll, and a relatively low-viscosity state using a three-roll or bead mill is used. A dispersion method combining wet dispersion (fine dispersion treatment) for dispersion may be mentioned. In the dispersion method, it is also preferable to co-disperse two or more pigments, or not to use a solvent or to reduce the amount of use as much as possible during the kneading dispersion treatment, or to use various dispersants. Further, in order to relieve the solvent shock, it is preferable to add the resin component separately at the time of the kneading dispersion treatment and at the time of the fine dispersion treatment (use in two divisions). In order to prevent reaggregation of the pigment particles, it is preferable to use a resin component having excellent solubility. Furthermore, it is also effective to use high hardness ceramics or beads with a small particle diameter for the beads of the bead mill used during the fine dispersion treatment. In addition, as said resin component, the above-mentioned alkali-soluble resin can be used, for example.

In the present invention, in particular, two or more pigments are used, and two or more pigments are further dispersed in a high viscosity state of 50000 mPa · s or more, and then further dispersed in a low viscosity state of 1000 mPa · s or less. It is preferable to use a different colorant.
Generally, these pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization for drying, a large amount of heat energy is given to dry it to form a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.

  In the method for preparing the colored thermosetting composition, when the colorant is a pigment, first, the viscosity after kneading and dispersing the above-mentioned binder into the colorant (pigment) is 50,000 mPa · s or more (preferably 50,000 to 100). , 000 mPa · s) is preferably kneaded and dispersed so as to have a relatively high viscosity. Here, the kneading dispersion treatment may be high viscosity dispersion or dry dispersion. Then, if necessary, the above-mentioned binder is additionally added to the dispersion after the kneading dispersion treatment so that the viscosity after the fine dispersion treatment is 1000 mPa · s or less (preferably 100 mPa · s or less). It is preferable to perform fine dispersion treatment. The fine dispersion treatment may be low viscosity dispersion or wet dispersion.

  In the kneading and dispersing treatment, the solvent ratio is preferably 0 to 20% by mass with respect to the dispersion. Thus, when the dispersion is performed without using much solvent, wetting of the surface of the pigment particles with the constituent component mainly composed of the resin component of the vehicle can be promoted, and the interface formed by the pigment particle surface is The solid / gas interface between the pigment particles and air can be converted to a solid / solution interface between the pigment particles and the vehicle solution. When the interface formed by the surfaces of the pigment particles is converted from air to a solution and mixed and stirred, the pigment can be dispersed to a fine state close to the primary particles.

  Thus, in order to highly disperse the pigment, it is effective to convert the interface formed by the pigment particle surface from air to a solution. Such conversion requires a strong shearing force or compressive force. For this reason, in the said kneading | mixing dispersion | distribution process, it is preferable to use a high viscosity thing as a to-be-kneaded material using the kneader which can exhibit strong shearing force and compressive force.

  In the fine dispersion treatment, it is preferable to mix and stir together with fine dispersion media such as glass or ceramic. Furthermore, it is preferable that the ratio of the solvent at the time of a fine dispersion process is 20-90 mass% of to-be-dispersed material. At the time of the fine dispersion treatment, since it is necessary to distribute the pigment particles uniformly and stably to a fine state, a disperser capable of imparting impact force and shear force to the agglomerated pigment particles; It is preferable to use a low-viscosity material.

  When the colorant is a dye, it is not necessary to perform the dispersion step as described above, and it is only necessary to dissolve it together with the binder in an appropriate solvent.

  When a thermosetting compound such as an epoxy resin, inorganic particles, a curing catalyst or a curing agent is added to the pigment dispersion or dye solution thus obtained, or when the binder is already a thermosetting compound Can add a thermosetting function by adding inorganic particles, a curing catalyst and a curing agent, and a colored thermosetting composition in the present invention can be prepared by adding a solvent as necessary.

<Color filter and manufacturing method thereof>
The color filter of the present invention is a colored pattern in which at least one of the patterns constituting the color filter includes a colorant and inorganic particles. The color filter of the present invention is not particularly limited as long as at least one pattern is formed so as to contain a colorant and inorganic particles, but the pattern is subjected to a dry etching method and a planarization treatment. From the viewpoint of securing a desired pattern thickness, hue, and color density when formed, the color filter of the present invention is preferably produced by the following method for producing a color filter of the present invention.

  The method for producing a color filter of the present invention comprises a first colored layer forming step of forming a first colored layer using the colored curable composition of the present invention described above, and the formed first colored layer. And a first pattern forming step for forming a first colored pattern by dry etching.

In the method for producing a color filter of the present invention, by using a colored curable composition containing inorganic particles, external force resistance such as improved scratch resistance on the surface of the colored pattern is given, and for example, inorganic particles are included. When the second coloring pattern (for example, the second color pixel) is formed on the first coloring pattern (for example, the first color pixel) by performing a flattening process (such as polishing such as CMP), the first coloring pattern is used. Thus, a colored pattern having a desired pattern thickness, hue and color density can be obtained.
In particular, it is effective for producing a color filter for a solid-state imaging device in which a micro size such as a thickness of 1 μm or less and / or a pixel pattern size of 2 μm or less (for example, 0.5 to 2.0 μm) is required. .

Here, the solid-state imaging device will be briefly described with reference to FIG. 1 as an example.
As shown in FIG. 1, the solid-state imaging device 10 includes a light receiving element (photodiode) 32 provided on a silicon substrate, a color filter 13, a planarizing film 14, a microlens 15, and the like. In the present invention, the planarizing film 14 is not necessarily provided. In FIG. 1, in order to clarify each part, the ratios of the thicknesses and widths are disregarded and some of them are exaggerated.

  The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. Further, an intermediate layer or the like may be provided between the support and the color filter 13 as long as the present invention is not impaired.

  A P well 31 is provided on the silicon substrate, and a photodiode 32 is provided on a part of the surface of the P well. The photodiode 32 is formed by performing heat treatment after ion-implanting N-type impurities such as P and As into a part of the surface of the P-well. Further, an impurity diffusion layer 33 having an N-type impurity concentration higher than that of the photodiode 32 is provided in a region different from the part of the surface of the P well 31 of the silicon substrate. The impurity diffusion layer 33 is formed by ion-implanting an N-type impurity such as P or As and then performing a heat treatment. The impurity diffusion layer 33 serves as a floating diffusion layer that transfers charges generated when the photodiode 32 receives incident light. Fulfill. In addition to the well 31 being a P-type impurity layer and the photodiode 32 and the impurity diffusion layer 33 being an N-type impurity layer, the well 31 is an N-type impurity layer, and the photodiode 32 and the impurity diffusion layer 33 being a P-type impurity layer. You can also

An insulating film 37 such as SiO ₂ or SiO ₂ / SiN / SiO ₂ is provided on the P well 31, the photodiode 32, and the impurity diffusion layer 33, and poly Si, tungsten, An electrode 34 made of tungsten silicide, Al, Cu or the like is provided. The electrode 34 serves as the gate of the gate MOS transistor, and can serve as a transfer gate for transferring charges generated in the photodiode 32 to the impurity diffusion layer 33. Further, a wiring layer 35 is formed above the electrode 34. Above the wiring layer 35, a BPSG film 36 and a P-SiN film 38 are provided. The interface between the BPSG film 36 and the P-SiN film 38 is formed so as to curve downward above the photodiode 32, and serves as an in-layer lens for efficiently guiding incident light to the photodiode 32. Fulfill. On the BPSG film 36, a planarizing film layer 39 is formed for the purpose of planarizing the surface of the P-SiN film 38 or the uneven portions other than the pixel region.

  A color filter 13 is formed on the planarizing film layer 39. In the following description, a colored film (so-called solid film) formed on a silicon substrate without dividing the region is referred to as a “colored (red, green, blue) layer”, and is formed by dividing the region into a pattern. A colored film (for example, a film patterned in a stripe shape) is referred to as a “colored (red, green, blue) pattern”. In addition, among the colored patterns, a colored pattern (for example, a colored pattern patterned into a square) that is an element constituting the color filter 13 is referred to as a “colored (red, green, blue) pixel”.

Here, as a form in which regions are divided into patterns (forms to be patterned), a resist pattern is formed on a colored layer in addition to a form in which a photosensitive colored film is patterned by exposure and development. A pattern in which a colored layer is patterned by etching using this resist pattern as an etching mask, a colored layer is formed so as to be embedded in a patterned concave portion provided on a silicon substrate, and a concave portion is formed among the formed colored layers. The form etc. which patternize by removing the part which protruded are included.

  The color filter 13 includes a plurality of two-dimensionally arranged red pixels (second color pixels) 20R, green pixels (third color pixels) 20G, and blue pixels (first color pixels) 20B. The colored pixels 20R, 20G, and 20B are formed above the light receiving element 32, respectively. The green pixels 20G are formed in a checkered pattern, and the blue pixels 20B and the red pixels 20R are formed between the green pixels 20G. In FIG. 1, in order to explain that the color filter 13 is composed of pixels of three colors, the colored pixels 20R, 20G, and 20B are displayed in a line.

  The planarization film 14 is formed so as to cover the upper surface of the color filter 13 and planarizes the color filter surface. This planarization layer is not necessarily required when performing planarization as in the color filter manufacturing method of the present invention described later.

  The microlens 15 is a condensing lens disposed with the convex surface facing upward, and is provided above the planarizing film 14 (or a color filter when no planarizing film is provided) and above the light receiving element 32. Each microlens 15 efficiently guides light from the subject to each light receiving element 32.

-First colored layer forming step-
The 1st colored layer formation process in the manufacturing method of the color filter of this invention forms a 1st colored layer using the colored curable composition of the above-mentioned this invention.

  The colored layer can be formed by applying the colored curable composition onto a support by a coating method such as spin coating, slit coating, or spray coating, and drying to form a colored layer.

  The thickness of the colored layer here is preferably in the range of 0.3 to 1 μm, more preferably in the range of 0.35 to 0.8, and more preferably in the range of 0.35 to 0.7 μm.

-1st pattern formation process-
In the color pattern manufacturing method of the present invention, in the first pattern forming step, the first colored layer formed in the colored layer forming step is dry-etched to form a first colored pattern.

  The first coloring pattern may be a coloring pattern provided as the first color on the support, or may be provided as a pattern for the second color or the third color on the support having an existing pattern depending on the case. It may be a colored pattern.

  The dry etching process can be performed using the etching gas with the patterned photoresist layer as a mask for the first colored layer formed in the colored layer forming step. Specifically, a resist formation step of forming a photoresist layer on the colored layer on the support, and processing the photoresist layer into a predetermined pattern by exposure and development, a resist pattern (patterned photoresist layer) ) And a dry etching process for dry etching the colored layer using the formed resist pattern as an etching mask. In addition, after the dry etching is completed, a photoresist removal process for removing the photoresist can be further provided.

[Resist formation process]
In the resist forming step, a photoresist layer is further formed on the colored layer on the support. Specifically, a photoresist layer can be formed by applying a positive or negative photosensitive resin composition on the colored layer and drying it. In forming the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive photosensitive resin composition is used. The positive photosensitive resin composition includes positive photosensitivity to ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including excimer lasers, electron beams, ion beams, and X rays. A positive resist composition suitable for resist can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, as the positive photosensitive resin composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive-type photosensitive resin composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by light irradiation with a wavelength of 500 nm or less to generate a carboxyl group, and as a result, the alkali-insoluble state becomes alkali-soluble. It is what you use. Since this positive photoresist has remarkably excellent resolution, it is used for manufacturing integrated circuits such as ICs and LSIs. Examples of the quinonediazide compound include a naphthoquinonediazide compound.

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, preferably 0.2 to 2.5 μm, and more preferably 0.3 to 2 μm. Note that the photoresist layer can be suitably applied by using the above-described application method.

[Processing process]
In the processing step, the photoresist layer is processed into a predetermined pattern by exposure and development to form a resist pattern. The formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By removing the photoresist layer in a desired pattern by exposure and development, a resist pattern is formed by removing the photoresist layer in the region where the colored pattern is to be formed, and an etching mask used in the next etching step Can be provided on the colored layer.

  The exposure of the photoresist layer is performed by exposing the positive or negative photosensitive resin composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

  Any developer can be used as long as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the colored layer containing the colorant. Combinations of solvents and alkaline aqueous solutions can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

[Dry etching process]
In the dry etching step, the colored layer is dry etched using the resist pattern formed in the processing step as an etching mask. Representative examples of dry etching 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, and the like. There is a method described in this publication.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), a first stage etching is performed to a region (depth) where the support is not exposed, and a nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively.
(2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
(3) The first-stage etching is performed according to the etching time calculated in (2).
(4) The second stage etching is performed according to the etching time calculated in (2). Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
(5) Overetching time is calculated with respect to the total time of (3) and (4), and overetching is performed.

The mixed gas used in the first-stage etching process preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed.
Further, the second etching step and the over-etching step may be performed by performing etching to a region where the support is not exposed by a mixed gas of fluorine-based gas and oxygen gas in the first etching process, and then damage the support. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

  It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount refers to the remaining film thickness of the film to be etched.

  Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

[Photoresist removal process]
In the photoresist removal step, the photoresist layer (that is, the etching mask) remaining after the etching is removed. The removal of the photoresist layer includes a step of applying a stripping solution or a solvent on the photoresist layer so that the photoresist layer can be removed, and a step of removing the photoresist layer using cleaning water. Is preferred.

  As a process of applying a stripping solution or solvent on the photoresist layer to make the photoresist layer removable, for example, the stripping solution or solvent is applied on at least the photoresist layer, and the paddle is stagnated for a predetermined time. A step of developing 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.

  Examples of the step of removing the photoresist layer using cleaning water include a step of removing the photoresist layer by spraying cleaning water onto the photoresist layer from a spray type or shower type spray nozzle. it can. 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 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. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine, etc. Preferred are monoethanolamine, diethanolamine and triethanolamine, and more preferred is 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- Preferred examples include 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 N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

  The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably contains at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

  When removing with a stripping solution, it is only necessary that the photoresist layer formed on the colored pattern is removed, and even if the deposit is an etching product on the side wall of the colored pattern, It may not be completely removed. A deposit means an etching product deposited and deposited on the side wall of a colored layer.

  As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

  In the method for producing a color filter of the present invention, after the first colored layer forming step and the first pattern forming step, the first colored pattern further includes a colorant and a curable compound, and includes inorganic particles. The second coloring is performed using the second colored curable composition having a content of less than 0.8% by mass with respect to the total solid content (preferably containing no inorganic particles (content of 0 (zero) mass%)). A second colored layer forming step for forming a layer, and a flattening step for flattening the formed second colored layer until at least the first colored pattern is exposed. The form is preferred.

-Second colored layer forming step-
The second colored layer forming step includes a colorant and a curable compound on the first colored pattern, and the second colored curable property is less than 0.8% by mass with respect to the total solid content of the inorganic particles. A 2nd colored layer is formed using a composition. As a 2nd colored curable composition, content with respect to the total solid of the inorganic particle in the above-mentioned photosensitive colored photocurable composition or non-photosensitive colored thermosetting composition is 0.8. A composition of less than mass% (preferably not containing inorganic particles) can be used.
Further, the second colored layer can be formed in the same manner as the method for forming the first colored layer described above.

-Flattening process-
In the flattening process in the color filter manufacturing method of the present invention, the second colored layer formed in the second colored layer forming process is flattened until at least the existing first colored pattern is exposed. As a result, a plurality of colored patterns are formed. The second colored layer is not limited to one color and may be two or more colors. Thereby, the color filter comprised by the coloring pattern of 2 colors or 3 colors or more can be formed.

  The planarization process is performed on the second colored layer (for example, a green layer or a red layer) until at least the first colored pattern (for example, a blue pattern including inorganic particles) is exposed. For example, when a green layer is formed on a blue pattern containing inorganic particles, a green pattern is formed between the blue patterns by flattening the green layer until at least the blue pattern is exposed. A color filter of a color can be produced.

  As the planarization process, from the viewpoint of simplifying the manufacturing process and manufacturing cost, an etch back process that dry-etches the entire exposed surface of the support, or a chemical that mechanically and mechanically polishes the entire exposed surface of the support. Examples thereof include a polishing process such as a mechanical mechanical polishing (CMP) process.

As a slurry used for polishing (CMP) treatment, it is preferable to use an aqueous solution having a pH of 9 to 11 containing 0.5 to 20% by mass of SiO ₂ abrasive grains having a particle size of 10 to 100 nm. As the polishing pad, a soft type such as continuous foaming urethane can be preferably used. Using the above slurry and polishing pad, polishing can be performed under the conditions of slurry flow rate: 50 to 250 ml / min, wafer pressure: 0.2 to 5.0 psi, retainer ring pressure: 1.0 to 2.5 psi. . In addition, after the polishing process is completed, a cleaning process for precisely cleaning the surface to be polished and a dehydration process for performing a dehydration bake (preferably at 100 to 200 ° C. for 1 to 5 minutes) (dehydration process) are performed.

In the method for producing a color filter of the present invention, when producing a color filter composed of three or more colored patterns, after the first colored layer forming step and the first pattern forming step,
(A) The colorant and the curable compound are included on the first colored pattern forming surface side of the support, and the content of the inorganic particles with respect to the total solid content is less than 0.8% by mass (preferably without inorganic particles ( An nth colored layer forming step of forming an nth colored layer using an nth (n ≧ 2) colored curable composition having a content of 0 (zero) mass%));
(B) The (n + 1) th pattern forming step of forming a concavo-convex pattern for forming the (n + 1) th (n ≧ 2) colored pattern by dry-etching the formed nth colored layer and the first colored pattern In addition, a colorant and a curable compound are included on the uneven pattern forming surface side of the support, and the content of the inorganic particles with respect to the total solid content is less than 0.8% by mass (preferably does not include inorganic particles (content is 0). (Zero) mass%)) each of the n + 1th colored layer forming step of forming the (n + 1) th colored layer using the (n + 1) th (n ≧ 2) colored curable composition, or two or more steps, respectively. ,
(C) a planarization treatment step of planarizing the colored layer of the n layer (n ≧ 2) formed on the first colored pattern forming surface side of the support until at least the first colored pattern is exposed;
A configuration in which a color filter composed of an n + 1 color pattern is formed by providing is preferable.

  As a specific example, after forming a blue pattern as the first pattern, when forming a color filter of three colors of RGB by forming two colored patterns of green and red, the first colored layer formation described above is formed After the step and the first pattern forming step, further containing a red colorant and a curable compound on the first colored pattern (blue pattern) forming surface side of the support, and containing the inorganic particles with respect to the total solid content A second colored layer forming step of forming a second colored layer (red layer) using the second colored curable composition whose amount is less than 0.8% by mass; and the formed red layer (second 3rd pattern formation process which forms the uneven | corrugated pattern for carrying out the dry etching process of the colored layer) and blue pattern (1st colored pattern), and forms a 3rd colored pattern (green pattern), and a support body Uneven pattern of The third coloration is performed using a third colored curable composition containing a green colorant and a curable compound on the surface where the inorganic particles are formed and having a content of less than 0.8% by mass of the inorganic particles based on the total solid content. A third colored layer forming step for forming a layer (green layer) and two colored layers (red layer and green layer) formed on the first colored pattern forming surface side of the support are first colored. There is provided a flattening process step of performing a flattening process until the pattern (blue pattern) is exposed or until a desired amount of over-etching is completed after the exposure. In this way, a color filter composed of a coloring pattern of RGB three colors is obtained.

  Furthermore, it demonstrates concretely with reference to FIG. In FIG. 2, after forming a blue pattern first, a red layer is formed so as to cover the pattern, and a concave green pattern forming region formed by dry etching the blue pattern and the red layer simultaneously is covered. A green layer is formed on the green layer, and a flattening process is performed on the green layer to form a color filter.

  According to the order of steps shown in FIG. 2, first, in the step of forming a blue pattern, a blue colored curable composition is applied on a support, dried and prebaked to form a blue layer, and then a photoresist layer is formed. Form. After patterning this photoresist layer to obtain a resist pattern, a dry etching process is performed to form a blue pattern. After removing the remaining resist pattern, a red colored curable composition is further applied onto the support so as to cover the blue pattern, dried and prebaked to form a red layer. Thereafter, in order to form an etching mask used for dry etching, a photoresist layer is formed on the red layer, and the photoresist layer is patterned to form a resist pattern on the red layer. Using the formed resist pattern as a mask, both the blue pattern and the red layer are dry-etched to expose the support. At this time, the support is exposed in the region where the green pattern is to be formed. After removing the remaining resist pattern, a green colored curable composition is applied over the entire surface of the support so as to cover the exposed portion of the support, dried and prebaked to form a green layer. Thereafter, a flattening process is performed until at least the blue pattern is exposed from above the green layer, thereby removing both the red layer and the green layer, thereby obtaining a color filter composed of three colors of RGB.

  The flattening process includes, for example, an etch back process and a polishing process, such as first performing an etch back process on the red layer and the green layer, and then removing the remaining red layer remaining on the blue pattern by the polishing process. You may carry out in combination.

Further, as another aspect of the method for producing a color filter of the present invention, a color filter can be produced by a method as shown in FIG.
In FIG. 3, after a blue pattern is first formed, a red layer is formed so as to cover the pattern, and a flattening process is performed on the red layer to form a red pattern. Thereafter, the blue pattern and the red pattern are dry-etched to form a concave green pattern formation region, and then a green layer is formed, and the green layer is flattened to form a color filter. It is.

  According to the process order shown in FIG. 3, first, after forming a blue pattern in the same manner as the process of forming the blue pattern shown in FIG. 2, a red colored curable composition is applied to the blue pattern forming surface of the support. Dry and pre-bake to form a red layer. A red pattern is formed by performing a flattening process on the red layer until the blue pattern is at least exposed. At this time, it is a two-color pattern of blue and red. Then, a photoresist layer is formed on the blue pattern and the red pattern, and after the photoresist layer is patterned to obtain a resist pattern, a region where a green pattern is to be formed by dry etching (green pixel formation region) ) Is processed into a concave shape. Thus, in addition to the two-color pattern of blue and red, the green pixel formation region is arranged. After removing the remaining resist pattern, a green colored curable composition is further applied onto the support so as to cover the blue pattern, the red pattern and the concave region, dried and prebaked to form a green layer. Thereafter, the green layer is removed by performing a flattening process again until at least the blue pattern (or red pattern) is exposed from above the green layer, and finally, a color filter composed of three colors of RGB can be obtained.

  The width of the colored pattern (the length of one side when the pattern is square) is preferably 0.5 to 1.7 μm, more preferably 0.6 to 1.5 μm from the viewpoint of image resolution.

  Further, the thickness as the coloring pattern is preferably 0.005 μm to 0.9 μm, more preferably 0.05 μm to 0.8 μm, from the viewpoint of making the thickness of the color filter, and thus, for example, the entire thickness of the solid-state imaging device thinner. 0.1 μm to 0.7 μm is more preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. In each step, 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
-Preparation of colored curable composition-
In order to confirm the CMP rate of the colored pattern containing inorganic particles, 100 g of blue thermosetting composition BLUE (1) as follows (solid content = 18% by mass, silica / composition total solids ratio = 0.8% by mass) was prepared.

<Composition of thermosetting composition BLUE (1)>
-Pigment dispersion (manufactured by Sanyo Color Co., Ltd., BLUE dispersion) ... 78.48 g
BLUE pigment (PB15: 6 / PV23 = 100: 25) / dispersant / dispersion resin Solid content: 19.3 mass%, pigment mass: 13.83 mass%
・ Colloidal silica sol ... 0.15g
(Propylene glycol monomethyl ether-dispersed silica sol, solid content: 30% by mass, SiO ₂ : 30% by mass, particle size: 10 to 20 nm)
・ Thermosetting resin ... 2.25g
(Daicel Chemical Industries, Ltd., lactone-modified epoxy resin)
・ Methylphthalic anhydride ・ ・ ・ 0.45g
・ Surfactant (fluorine surfactant) ... 0.02g
・ Propylene glycol monomethyl ether acetate ・ ・ ・ 18.3g
(PGMEA, additive solvent)

  The thermosetting composition BLUE (1) obtained above was applied onto a Si substrate, dried, and post-baked at 220 ° C. for 5 minutes.

-Evaluation of polishing resistance-
Polishing was performed on the film surface after the post-bake treatment under the following conditions, and the film thickness before and after polishing was measured. A film thickness difference Δ value before and after polishing was obtained from the obtained value to obtain a polishing rate and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Condition>
Polishing method: Polishing with Semispase 25 (Cab slurry manufactured by Cabot): Polishing with DIW (Deionized water) (water polish) = 1: 19
・ Polishing time: 1 minute ・ WAFER rotation speed: 50 rpm
・ Platen rotation speed: 30rpm
Pressure: 1.2 psi
・ Film thickness measurement: Contact type step gauge deck tack
<Evaluation criteria>
A: Δ value ≦ 15 nm / min
○: 15 nm / min <Δ value ≦ 50 nm / min
Δ: 50 nm / min <Δ value ≦ 100 nm / min
×: Δ value> 100 nm / min

  When the polishing rate was calculated from the film thickness before and after polishing, the polishing rate was 17.2 nm / min. This value was found to be sufficiently small as a polishing rate and can function as a polishing stopper.

-Evaluation of etching properties-
Furthermore, etching was performed under the following etching conditions, and evaluation was performed according to the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Etching conditions>
・ Etching device: Μ-621 (manufactured by Hitachi High-Technologies Corporation)
Gas flow rate: Ar / N ₂ / CF ₄ / O ₂ = 500/500/25/50 ml
Etching time: 60 seconds Bias: RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W
-Electrode height: 68 mm
・ Pressure: 2.5Pa
<Evaluation criteria>
A: Etching rate> 200 nm / min
○: 150 nm / min <etching rate ≦ 200 nm / min
Δ: 100 nm / min ≦ etching rate ≦ 150 nm / min
X: Etching rate <100 nm / min

  As a result of confirming the etching property, the etching rate was 280.0 nm / min, and it was confirmed that the etching property was sufficient.

(Examples 2-9)
In Example 1, the thermosetting composition was prepared by changing the amount of inorganic particles, colorant and the like, and the polishing rate and the etching rate were evaluated in the same manner. The evaluation results are shown in Table 1 below.
As a result, as shown in Table 1 below, it was confirmed that suppression of the polishing rate equivalent to or higher than that of Example 1 could be achieved. In addition to the blue thermosetting composition, red and green thermosetting compositions RED and GREEN were also prepared, and both had a sufficient polishing rate suppressing effect as in the case of blue.

(Example 10)
In Example 1, the colloidal silica sol used as the inorganic particles was changed to a zirconia dispersion, and 100 g of blue thermosetting composition BLUE (6) shown below (solid content = 18% by mass, total solid of zirconia / composition) Minutes ratio = 3.4% by mass). Further, the polishing rate and the etching rate were evaluated in the same manner as in Example 1.
As a result, as shown in Table 1 below, it was confirmed that the polishing rate could be suppressed to be equal to or higher than that of Example 1.

<Composition of thermosetting composition BLUE (6)>
・ Pigment dispersion (manufactured by Sanyo Color Co., Ltd., BLUE dispersion) ... 75.49g
BLUE pigment (PB15: 6 / PV23 = 100: 25) / dispersant / dispersion resin Solid content: 19.3 mass%, pigment mass: 13.83 mass%
・ Zirconia dispersion: 6.07 g
(Propylene glycol monomethyl ether dispersion ZrO ₂ , solid content: 12% by mass, ZrO ₂ : 10% by mass, particle size: 10 to 20 nm)
・ Thermosetting resin ... 2.25g
(Daicel Chemical Industries, Ltd., lactone-modified epoxy resin)
・ Methylphthalic anhydride ・ ・ ・ 0.45g
・ Surfactant (Fluorosurfactant) ... 0.015g
・ Propylene glycol monomethyl ether acetate: 15.72g
(PGMEA, additive solvent)

(Example 11)
In Example 10, the zirconia dispersion was titanium dispersion in the composition of the thermosetting composition BLUE (6) was changed to (TTO-51C, manufactured by Ishihara Sangyo Kaisha Ltd.), a blue heat-curable composition BLUE (7) 100 g (solid content = 18 mass%, titania / total solid content ratio of composition = 3.4 mass%) was prepared. Further, the polishing rate and the etching rate were evaluated in the same manner as in Example 1.

(Comparative Examples 1-3)
Preparation of the blue thermosetting composition BLUE (1) of Example 1, the green thermosetting composition GREEN (1) of Example 8, and the red thermosetting composition RED (1) of Example 9 In the same manner as in each example except that the colloidal silica sol which is an inorganic particle was not used, the blue thermosetting composition BLUE (8), the green thermosetting composition GREEN (2), and A red thermosetting composition RED (2) was prepared and further subjected to coating and post-baking treatment, polishing, and evaluation (calculation of polishing rate and etching rate). The evaluation results are shown in Table 1 below.

  As a result, any of the thermosetting compositions has a polishing rate exceeding 100 nm, and only a film that is easily polished can be obtained as compared with the thermosetting compositions of Examples including inorganic particles. It was an insufficient level from the viewpoint of imparting the properties to the existing colored pattern.

(Example 12)
Using the blue thermosetting composition BLUE (1) prepared above, the green thermosetting composition GREEN (3) and the red thermosetting composition RED (3) having the following composition, the following is shown. In this manner, a color filter array composed of three colors of RGB was produced.
A first colored pattern was formed using the blue thermosetting composition BLUE (1) as a coating solution for forming a first colored layer, and the polishing stopper property (process suitability) was evaluated.

<Preparation of thermosetting composition GREEN (3)>
Various components having the following composition were mixed to prepare 100 g of thermosetting composition GREEN (3) (solid content = 12% by mass, pigment content ratio in the solid content: 57.40% by mass).
<Composition of thermosetting composition GREEN (3)>
・ Pigment dispersion (GREEN dispersion, manufactured by Oriental Kasei Co., Ltd.) ... 45.968 g
GREEN pigment (PY139: PG36: PG7 = 35: 80: 20) / dispersant / dispersion resin solid content: 24.8% by mass
・ Thermosetting resin ... 0.50g
(Daicel Chemical Industries, Ltd., lactone-modified epoxy resin)
・ Monomer (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMP-6BO) ... 0.10g
・ Surfactant (fluorinated surfactant) ... 0.006g
・ Propylene glycol monomethyl ether acetate 53.42g
(PGMEA, additive solvent)

<Preparation of thermosetting composition RED (3)>
Components of the following composition were mixed to prepare a thermosetting composition RED (3) 100 g (solid content = 12% by mass, pigment content ratio in the solid content: 61.6% by mass).
<Composition of thermosetting composition RED (3)>
・ Pigment dispersion (made by Toyo Ink, RED dispersion) ... 56.998 g
RED pigment (PR254: PY139 = 100: 45) / dispersant / dispersion resin Solid content: 20% by mass
・ Thermosetting resin ... 0.50g
(Daicel Chemical Industries, Ltd., lactone-modified epoxy resin)
・ Monomer (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMP-6BO) ... 0.10g
・ Surfactant (fluorinated surfactant) ... 0.006g
・ Propylene glycol monomethyl ether acetate: 42.366 g
(PGMEA, additive solvent)

<Production of color filter>
(Formation of the first layer)
-First step-
A CMOS sensor substrate is prepared as a support, and a blue thermosetting composition BLUE (1) is applied thereon so that the thickness after drying and post-baking is 0.50 μm and dried. Post baking was performed at 5 ° C. for 5 minutes to form a blue film (first colored layer).

-Second step-
Subsequently, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) is applied onto the blue film after post-baking with a spin coater, and a pre-bake treatment is performed at 90 ° C. for 1 minute. A photoresist layer was formed to a thickness of 0.8 μm.

Next, the formed photoresist layer was subjected to pattern exposure at an exposure amount of 140 mJ / cm ² using an i-line stepper (FPA 3000i5, manufactured by Canon Inc.), and the photoresist layer temperature or ambient temperature was 110 ° C. for 1 minute. Then, heat treatment (PEB treatment) was performed. Thereafter, paddle development was performed with developer FHD-5 (tetramethylammonium hydroxide (TMAH): 2.38 mass%, manufactured by Fuji Film Electronics Materials) for 1 minute, and then rinsed with pure water. Further, post-baking is performed at 110 ° C. for 1 minute to remove the photoresist layer in the region where the second color (RED (red)) color pattern is to be formed, and to form BLUE and GREEN color patterns. A photoresist layer was formed on the blue film region to be formed. The resist pattern was a line / space type stripe pattern in which line-shaped convex patterns were arranged at predetermined intervals. At this time, a stripe pattern was formed so that the pattern size was 1.0 μmL / S (line / space; the same applies hereinafter). The mask bias was −0.05 μm.

-Third step-
The dry etching process was implemented on condition of the following, the blue film formed with the blue thermosetting composition BLUE (1) was processed, and the pattern was formed in uneven | corrugated shape.
<Etching conditions>
Etching device: U-621 (manufactured by Hitachi High-Technologies Corporation)
Gas flow rate: Ar / N ₂ / O ₂ = 500/500/100 sccm
-Bias: RF power: 800W, antenna bias: 400W, wafer bias: 200W
-Electrode height: 68 mm
・ Pressure: 2.5Pa
・ Etching time: 65 sec (Over etching rate 20%)

-Fourth step-
The photoresist layer used as an etching mask was stripped under the following conditions.
<Peeling conditions>
-Substrate temperature: 50 ° C
-Stripper: MS230C (manufactured by FUJIFILM Electronics Materials)
・ Peeling time: 120 sec (paddle processing)
・ Rinse: Spray with pure water for 60 seconds (0.2 Pa)
Spin drying: 2000 rpm for 30 seconds

  Next, dehydration was performed at 120 ° C. for 2 minutes using a hot plate, and the formation of the first pattern was completed. As a result, a 1.0 μmL / S stripe pattern (first colored pattern) of the blue thermosetting composition BLUE (1) was formed.

(Formation of the second layer)
-First step-
As described above, the thermosetting composition RED (3) as the second colored curable composition is applied to the uneven surface of the CMOS substrate on which the uneven pattern is formed, and the thickness after drying and post-baking is set. It applied so that it might be set to 0.40 micrometer, and was dried. Thereafter, post-baking was performed at 220 ° C. for 5 minutes, and a red film serving as the second layer was formed as the second colored layer.

(Formation of third layer)
-First step-
Subsequently, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) is applied onto the red film after post-baking with a spin coater, and a pre-bake treatment is performed at 90 ° C. for 1 minute. A photoresist layer was formed to a thickness of 1.0 μm.

Next, the formed photoresist layer was subjected to pattern exposure at an exposure amount of 140 mJ / cm ² using an i-line stepper (FPA 3000i5, manufactured by Canon Inc.), and the photoresist layer temperature or ambient temperature was 110 ° C. for 1 minute. Then, heat treatment (PEB treatment) was performed. Thereafter, paddle development was performed with developer FHD-5 (tetramethylammonium hydroxide (TMAH): 2.38 mass%, manufactured by Fuji Film Electronics Materials) for 1 minute, and then rinsed with pure water. Further, post-baking is performed at 110 ° C. for 1 minute to remove the photoresist layer in the region where the third color (GREEN (green)) coloring pattern is to be formed, and to form BLUE and RED coloring patterns. A photoresist layer was formed in the region of the red film to be formed. The resist pattern was formed to be a Bayer array pattern having a pattern size of 1.0 μm. The mask bias was −0.05 μm.

-Second step-
A dry etching process was performed under the following conditions, the first colored layer (blue film) and the second colored layer (red film) were processed, and a pattern was formed in an uneven shape.
<Etching conditions>
Etching device: U-621 (manufactured by Hitachi High-Technologies Corporation)
Gas flow rate: Ar / N ₂ / O ₂ = 500/500/100 sccm
-Bias: RF power: 800W, antenna bias: 400W, wafer bias: 200W
-Electrode height: 68 mm
・ Pressure: 2.5Pa
・ Etching time: 80 sec (Over etching rate 20%)

-Third step-
The photoresist layer used as an etching mask was stripped under the following conditions.
<Peeling conditions>
-Substrate temperature: 50 ° C
-Stripper: MS230C (manufactured by FUJIFILM Electronics Materials)
・ Peeling time: 120 sec (paddle processing)
・ Rinse: Spray with pure water for 60 seconds (0.2 Pa)
Spin drying: 2000 rpm for 30 seconds

  Next, dehydration was performed at 120 ° C. for 2 minutes using a hot plate, and the processing of the region for forming the third layer (third pattern) was completed.

-Fourth step-
After drying and post-baking the thermosetting composition GREEN (3) as the third colored curable composition on the uneven surface of the CMOS substrate on which the same pattern as the third pattern is formed as described above The coating was applied so as to have a thickness of 0.40 μm and dried. Thereafter, post-baking was performed at 220 ° C. for 5 minutes, and a green film serving as a third layer was formed as a third colored layer.

-Fifth step-
Next, CMP polishing treatment was performed on the colored layer forming surface of the CMOS substrate until the first pattern (blue film) appeared under the following conditions.
<Condition>
Polishing method: Semispace 25
[Polishing with Cabot CMP slurry: Polishing with DIW (deionized water) (water polish) = 1: 19]
Polishing time: 2 minutes (after the first pattern exposure, the overpolishing time was 30 seconds)
・ WAFER rotation speed: 50 rpm
・ Platen rotation speed: 30rpm
-Pressure: 1.2 psi

-Sixth step-
After the polishing, the polished surface was washed with pure water for 30 seconds, and a cleaning process after polishing was performed. After spin drying, dehydration treatment was performed at 120 ° C. for 2 minutes using a hot plate.

  As described above, a color filter in which a 1.0 μm square rectangular RGB three-color coloring pattern was formed was produced.

<Evaluation of residual film, shape, and flatness>
About the obtained color filter, in order to confirm a film thickness and a pattern shape, the cross section was observed with scanning electron microscope S4800 (made by Hitachi High-Technologies Corporation, SEM). Moreover, in order to confirm flatness, Tilt observation was performed.
As a result, the thickness of the first pattern (blue film) is 0.485 μm, which is a film thickness reduction of 0.015 μm with respect to the set film thickness of 0.50 μm, depending on the first layer (BLUE (1)). The effect of the polishing stopper could be confirmed. Further, the blue film, the red film, and the green film were all uniform in thickness, and the flatness was good.

(Example 13)
The green thermosetting composition GREEN (1) prepared in Example 8 and the blue thermosetting composition BLUE (8) containing no inorganic particles prepared in Comparative Example 1 were prepared in Example 12. Using a red thermosetting composition RED (3) that does not contain inorganic particles, a color filter array composed of three colors of RGB was prepared according to the procedure shown below.
A first colored pattern was formed using the green thermosetting composition GREEN (1) as a coating solution for forming a first colored layer, and the polishing stopper property (process suitability) was evaluated.

<Production of color filter>
(Formation of the first layer)
-First step-
A CMOS sensor substrate is prepared as a support, and a green thermosetting composition GREEN (1) is applied thereon so that the thickness after drying and post-baking is 0.50 μm, and dried. Post-baking was carried out at 5 ° C. for 5 minutes to form a green film (first colored layer).

-Second step-
Subsequently, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto the green film after post-baking with a spin coater, and a pre-bake treatment is performed at 90 ° C. for 1 minute. A photoresist layer was formed to a thickness of 0.8 μm.

Next, the formed photoresist layer was subjected to pattern exposure at an exposure amount of 200 mJ / cm ² using an i-line stepper (FPA 3000i5, manufactured by Canon Inc.), and the photoresist layer temperature or atmospheric temperature was 110 ° C. for 1 minute. Then, heat treatment (PEB treatment) was performed. Thereafter, paddle development was performed with developer FHD-5 (tetramethylammonium hydroxide (TMAH): 2.38 mass%, manufactured by Fuji Film Electronics Materials) for 1 minute, and then rinsed with pure water. Further, post-baking is performed at 110 ° C. for 1 minute to remove the photoresist layer in the region where the second color (RED (red)) color pattern is to be formed, and to form BLUE and GREEN color patterns. A photoresist layer was formed on the blue film region to be formed. The resist pattern was an island pattern, and the size of the island pattern was such that the size of the region where the green colored pattern was to be formed was 1.0 μm. The mask bias was −0.05 μm.

-Third step-
The dry etching process was implemented on condition of the following, the green film formed with the green thermosetting composition GREEN (1) was processed, and the pattern was formed in uneven | corrugated shape.
<Etching conditions>
Etching device: U-621 (manufactured by Hitachi High-Technologies Corporation)
Gas flow rate: Ar / N ₂ / O ₂ = 500/500/100 sccm
-Bias: RF power: 800W, antenna bias: 400W, wafer bias: 200W
-Electrode height: 68 mm
・ Pressure: 2.5Pa
・ Etching time: 60 sec (Over etching rate 20%)

-Fourth step-
The photoresist layer used as an etching mask was stripped under the following conditions.
<Peeling conditions>
-Substrate temperature: 50 ° C
-Stripper: MS230C (manufactured by FUJIFILM Electronics Materials)
・ Peeling time: 120 sec (paddle processing)
・ Rinse: Spray with pure water for 60 seconds (0.2 Pa)
Spin drying: 2000 rpm for 30 seconds

  Next, dehydration was performed at 120 ° C. for 2 minutes using a hot plate, and the formation of the first pattern was completed. As a result, a 1.0 μm island pattern (first colored pattern) was formed from the green thermosetting composition GREEN (1).

(Formation of the second layer)
-First step-
As described above, the thermosetting composition RED (3) as the second colored curable composition is applied to the uneven surface of the CMOS substrate on which the uneven island pattern is formed, and the thickness after drying and post-baking is 0. It was applied to 40 μm and dried. Thereafter, post-baking was performed at 220 ° C. for 5 minutes, and a red film serving as the second layer was formed as the second colored layer.

(Formation of third layer)
-First step-
Subsequently, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) is applied onto the red film after post-baking with a spin coater, and a pre-bake treatment is performed at 90 ° C. for 1 minute. A photoresist layer was formed to a thickness of 1.0 μm.

Next, the formed photoresist layer was subjected to pattern exposure at an exposure amount of 140 mJ / cm ² using an i-line stepper (FPA 3000i5, manufactured by Canon Inc.), and the photoresist layer temperature or ambient temperature was 110 ° C. for 1 minute. Then, heat treatment (PEB treatment) was performed. Thereafter, paddle development was performed with developer FHD-5 (tetramethylammonium hydroxide (TMAH): 2.38 mass%, manufactured by Fuji Film Electronics Materials) for 1 minute, and then rinsed with pure water. Further, post-baking is performed at 110 ° C. for 1 minute to remove the photoresist layer in the region where the third color (BLUE (blue)) coloring pattern is to be formed, and to form the GREEN and RED coloring patterns. A photoresist layer was formed in the region of the red film to be formed. The resist pattern was formed to be an island pattern having a pattern size of 1.0 μm. The mask bias was −0.05 μm.

-Second step-
A dry etching process was performed under the following conditions, the first colored layer (green film) and the second colored layer (red film) were processed, and a pattern was formed in an uneven shape.
<Etching conditions>
Etching device: U-621 (manufactured by Hitachi High-Technologies Corporation)
Gas flow rate: Ar / N ₂ / O ₂ = 500/500/100 sccm
-Bias: RF power: 800W, antenna bias: 400W, wafer bias: 200W
-Electrode height: 68 mm
・ Pressure: 2.5Pa
・ Etching time: 75 sec (Over etching rate 20%)

-Third step-
The photoresist layer used as an etching mask was stripped under the following conditions.
<Peeling conditions>
-Substrate temperature: 50 ° C
-Stripper: MS230C (manufactured by FUJIFILM Electronics Materials)
・ Peeling time: 120 sec (paddle processing)
・ Rinse: Spray with pure water for 60 seconds (0.2 Pa)
Spin drying: 2000 rpm for 30 seconds

  Next, dehydration was performed at 120 ° C. for 2 minutes using a hot plate, and the processing of the region for forming the third layer (third pattern) was completed.

-Fourth step-
The thickness after drying and post-baking the thermosetting composition BLUE (8) as the third colored curable composition on the unevenness forming surface of the CMOS substrate on which the same pattern as the third pattern is formed as described above. Was applied to a thickness of 0.40 μm and dried. Thereafter, post-baking was performed at 220 ° C. for 5 minutes, and a green film serving as a third layer was formed as a third colored layer.

-Fifth step-
Next, CMP polishing treatment was performed on the colored layer forming surface of the CMOS substrate until the first pattern (blue film) appeared under the following conditions.
<Condition>
Polishing method: Semispace 25
[Polishing with Cabot CMP slurry: Polishing with DIW (deionized water) (water polish) = 1: 19]
Polishing time: 2 minutes and 15 seconds (after the first pattern exposure, the over polishing time was 30 seconds)
・ WAFER rotation speed: 50 rpm
・ Platen rotation speed: 30rpm
-Pressure: 1.2 psi

-Sixth step-
After the polishing, the polished surface was washed with pure water for 30 seconds, and a cleaning process after polishing was performed. After spin drying, dehydration treatment was performed at 120 ° C. for 2 minutes using a hot plate.

As described above, a color filter in which a 1.0 μm square rectangular RGB three-color coloring pattern was formed was produced.
<Evaluation of residual film, shape, and flatness>
About the obtained color filter, in order to confirm a film thickness and a pattern shape, the cross section was observed with scanning electron microscope S4800 (made by Hitachi High-Technologies Corporation, SEM). Moreover, in order to confirm flatness, Tilt observation was performed.
As a result, the thickness of the first pattern (blue film) is 0.484 μm, which is a decrease in film thickness of 0.016 μm with respect to the set film thickness of 0.50 μm, depending on the first layer (GREEN (1)). The effect of the polishing stopper could be confirmed. Further, the blue film, the red film, and the green film were all uniform in thickness, and the flatness was good.

  The color filter and the manufacturing method thereof according to the present invention can be applied to a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. . The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

DESCRIPTION OF SYMBOLS 10 ... Solid-state image sensor 11 ... Support body 13 ... Color filter 20B ... Blue pixel 20R ... Red pixel 20G ... Green pixel 22, 46 ... Color filter manufacturing process

Claims (12)

It contains a colorant, inorganic particles, and a curable compound, and is used for pattern formation by a dry etching method .
The mass ratio of the inorganic particles to the total solid content is 0.8% to 4.0%,
At least one is a polyfunctional epoxy compound, the multi-mass ratio of functional epoxy compound is colored curable composition Ru 1% to 35% der respect to the total solid content of the curable compound.   The colored curable composition according to claim 1, wherein the inorganic particles are transparent inorganic particles.   The colored curable composition according to claim 1 or 2, wherein the inorganic particles are at least one selected from silica particles, zirconia particles, and alumina particles. The colored curable composition according to any one of claims 1 to 3, wherein the inorganic particles are silica particles.   The colored curable composition according to any one of claims 1 to 4, wherein an average particle diameter of the inorganic particles is 50 nm or less.   The colored curable composition according to any one of claims 1 to 5, wherein the inorganic particles have an average particle diameter of 10 nm to 30 nm.   The colored curable composition according to claim 1, further comprising an acid anhydride. A first colored layer forming step of forming a first colored layer using a colored curable composition containing a colorant, inorganic particles, and a curable compound on a support and used for pattern formation by a dry etching method. When,
A first pattern forming step of forming a first colored pattern by dry-etching the first colored layer;
A second colored curable composition containing a colorant and a curable compound on the first colored pattern forming surface side of the support and having a content of less than 0.8% by mass based on the total solid content of the inorganic particles. A second colored layer forming step of forming a second colored layer using,
A planarization treatment step of planarizing the formed second colored layer until at least the first colored pattern is exposed;
Only including, a manufacturing method of a color filter, which comprises producing a color filter comprising a colored pattern of a plurality of colors. A first colored layer forming step of forming a first colored layer using a colored curable composition containing a colorant, inorganic particles, and a curable compound on a support and used for pattern formation by a dry etching method. When,
A first pattern forming step of forming a first colored pattern by dry-etching the first colored layer;
The nth (n ≧ 2) coloration containing a colorant and a curable compound on the first colored pattern forming surface side of the support, and the content of the inorganic particles with respect to the total solid content is less than 0.8% by mass. An nth colored layer forming step of forming an nth colored layer using the curable composition;
An n + 1th pattern forming step of forming a concavo-convex pattern for forming an n + 1th (n ≧ 2) colored pattern by dry-etching the formed nth colored layer and the first colored pattern; And n + 1 (n ≧ 2) colored curability containing a colorant and a curable compound on the surface of the support on which the concave / convex pattern is formed, and the content of the inorganic particles with respect to the total solid content is less than 0.8% by mass. Each of at least one of the (n + 1) th colored layer forming steps of forming the (n + 1) th colored layer using the composition;
A planarization treatment step of planarizing an n-layer (n ≧ 2) colored layer formed on the first colored pattern forming surface side of the support until at least the first colored pattern is exposed;
Only including, a manufacturing method of a color filter, which comprises forming a color filter consisting of n + 1 color colored pattern. A colorant , inorganic particles , and a curable compound are included, the mass ratio of the inorganic particles to the total solid content is 0.8% to 4.0%, and at least one of the curable compounds is a polyfunctional epoxy compound. A color filter comprising at least one coloring pattern which is a cured product of a colored curable composition having a mass ratio of the polyfunctional epoxy compound to the total solid content of 1% to 35%. A colorant , inorganic particles , and a curable compound are included, the mass ratio of the inorganic particles to the total solid content is 0.8% to 4.0%, and at least one of the curable compounds is a polyfunctional epoxy compound. A color filter having at least one coloring pattern in which the mass ratio of the polyfunctional epoxy compound to the total solid content is 1% to 35% .   The solid-state image sensor provided with the color filter of Claim 10 or Claim 11.

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