JPH10133013A - Color filter, solid-state image pick-up device and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter and a solid-state image pick-up device which are possessed of both an excellent spectral sensitivity characteristic of a dye and an excellent weather resistance of a pigment. SOLUTION: An ontip color filter is formed by a color resist using a composition composed by the intercalation dye in clay as a coloring material. As the clay for intercalation, hydrotalcites or smectites being lamellar clay minerals are preferably used. In the ontip color filter, a pigmentation dye is used as the coloring material which is possessed of both the excellent spectral sensitivity characteristic of the dye and the excellent weather resistance of the pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a solid-state imaging device having a color filter and an on-chip color filter, and a method for manufacturing the same.

[0002]

2. Description of the Related Art On-chip color filters in solid-state imaging devices, liquid crystal display devices and the like have been manufactured by a dyeing method before. This dyeing method is to pattern a photosensitive composition on a substrate to be dyed such as casein or gelatin, pattern the substrate to be dyed using this photosensitive composition, and then fix and dye the substrate to be dyed. Is the way.

That is, in the dyeing method, after a substrate to be dyed is formed at a desired position, the substrate to be dyed is dyed with a dye or the like having a desired spectral characteristic, fixed, and then subjected to a formalin treatment or the like. To enhance the adhesion. Thus, in the staining method,
Since it is necessary to strengthen the fixation for each color, the process is very complicated, and it is difficult to control the degree of dyeing.

[0004] Therefore, recently, in order to simplify the process, a color resist method has been adopted as a method of manufacturing an on-chip color filter instead of a dyeing method. The color resist method is a method for producing an on-chip color filter by uniformly dispersing a coloring material in a photosensitive composition and coloring the same, and patterning the colored photosensitive composition by a photolithography method. . The color resist method includes a method using a dye as a coloring material and a method using a pigment.

[0005]

However, the color resist method using a pigment as a color material has a narrower range of selection of spectral characteristics and performs fine adjustment as compared with the color resist method using a dye as a color material. Therefore, it has been difficult to use it as an alternative to the dyeing method.

[0006] On the other hand, the color resist method using a dye as a coloring material not only has remarkably inferior weatherability than the color resist method using a pigment as a coloring material, but also has a dye fixing step and a fixing method which are inferior to dyeing methods. Since there was no reinforcing step and the dye was simply dispersed in the resin, the weather resistance was poor.

[0007]

The color filter according to the present invention is characterized in that a coloring material is a composition obtained by intercalating a dye with clay.

In the color filter according to the present invention, it is preferable that hydrotalcites or smectites are used as the clay.

In the color filter according to the present invention, hydrotalcites having an ion-exchangeable anion between layers or smectites having an ion-exchangeable cation between layers are used as the clay. It is preferable that the dye be exchanged with the anion or the cation by an action to be electrically coupled between the layers.

[0010] The color filter according to the present invention is characterized in that hydrotalcites having an ion-exchangeable anion between layers are used as the clay, and at least a part of the anion is substituted with an organic acid. Is preferred.

The color filter according to the invention of the present application has a pKa expressed as pKa = -LogKa where the acid dissociation constant is Ka.
It is preferable to use the organic acid having a Ka of 5.0 or less.

In the color filter according to the present invention, the organic acid preferably has an aromatic ring.

In the color filter according to the present invention, it is preferable that smectites having an ion-exchangeable cation between layers are used as the clay, and that at least a part of the cation is substituted with alkylammonium. .

In the color filter according to the present invention, the alkylammonium preferably has three or more carbon chains having 8 or more carbon atoms.

The method for producing a color filter according to the invention of the present application is a method for producing a hydrotalcite having an ion-exchangeable anion between layers, wherein at least a part of the anion is substituted with an organic acid, A step of dispersing in a first solvent containing at least one of an organic solvent, a step of dissolving a dye in a second solvent containing at least one of water and an organic solvent, and the first and second solvents Mixing the dyes and exchanging the dye with the hydrotalcites by exchanging the anion and the dye to form a coloring material by removing the water and the organic solvent. A step of dispersing the coloring material in the photosensitive composition, and a step of selectively exposing the photosensitive composition to patterning.

The method of manufacturing a color filter according to the present invention is directed to a method for producing a smectite having an ion-exchangeable cation between layers, wherein at least a part of the cation is substituted with alkylammonium, a water-soluble organic solvent. Dispersing in a first solvent containing at least one of the following,
Dissolving the dye in a second solvent containing at least one of water and an organic solvent; and mixing the first and second solvents to exchange the cation and the dye for the smectite. Forming a coloring material by removing the water and the organic solvent after intercalating the dye into the dye, dispersing the coloring material in a photosensitive composition, And patterning by selectively exposing the substrate to light.

The solid-state imaging device according to the invention of the present application is characterized in that it has an on-chip color filter in which a composition obtained by intercalating a dye with clay is used as a coloring material.

The method of manufacturing a solid-state imaging device according to the invention of the present application is directed to a method for producing a hydrotalcite having an ion-exchangeable anion between layers, wherein at least a part of the anion is substituted with an organic acid. And dispersing the dye in a first solvent containing at least one of an organic solvent; and dissolving a dye in a second solvent containing at least one of water and an organic solvent. A step of intercalating the dye with the hydrotalcites by exchanging the anion and the dye by mixing solvents, and then removing the water and the organic solvent to form a coloring material. And a step of selectively exposing the photosensitive composition to a pattern of an on-chip color filter. It is set to.

The method for manufacturing a solid-state imaging device according to the present invention is directed to a method for manufacturing a smectite having an ion-exchangeable cation between layers, wherein at least a part of the cation is substituted by alkylammonium. A step of dispersing in a first solvent containing at least one of a solvent and a step of dissolving a dye in a second solvent containing at least one of water and an organic solvent; Mixing the dye and exchanging the dye for the smectites by exchanging the cation and the dye, and then removing the water and the organic solvent to form a coloring material; and Dispersing the material in the photosensitive composition, and selectively exposing the photosensitive composition to process into an on-chip color filter pattern. It is a symptom.

In the color filter according to the invention of the present application, since a composition obtained by intercalating a dye with clay is used as a coloring material, a pigmented dye is used as a coloring material.

Further, if hydrotalcites or smectites, which are layered clay minerals, are used as clay for intercalation, the dye is easily intercalated between the layers and the interlayer spacing is easily expanded,
Large amounts of dye can be intercalated.

If the dye is ion-exchanged by the intercalation and the dye is electrically connected between the layers of hydrotalcites or smectites, the dye molecules are strongly fixed between the layers. .

If at least a part of the interlayer anions of the hydrotalcites is replaced by an organic acid, the molecules of the organic acid are large, so that the interlayer spacing is widened and a large amount of dye is intercalated. Can be done.
In addition, since an organic acid is present between the layers, the direct influence of hydrotalcites on the coloring group of the intercalated dye is suppressed, and the change in the spectral sensitivity characteristics of the dye is prevented. I have.

In addition, since the polar portion of the organic acid is electrically coupled to the inside of the hydrotalcite, and the non-polar portion of the organic acid is disposed on the surface of the hydrotalcite,
An affinity for an organic solvent having a small polarity is generated, and the coloring material is easily dispersed uniformly in the organic solvent.

When at least a part of the interlayer anion of the hydrotalcite is substituted with an organic acid having a pKa of 5.0 or less, the intercalated dye is strongly bonded to the hydrotalcite. Have been.

Further, when at least a part of the interlayer anion of the hydrotalcite is substituted with an organic acid having an aromatic ring, the dye having an aromatic ring can be converted into a hydrotalcite. It is easy to blend in, and the dye is easily intercalated between the layers of hydrotalcites.

If at least a part of the interlayer cation of smectites is substituted by alkylammonium, the molecule of alkylammonium is large, so that the interlayer distance is widened and a large amount of dye is intercalated. Can be. In addition, the influence of smectites on the coloring group of the dye intercalated between the layers is suppressed, and the change in the spectral sensitivity characteristics of the dye is prevented.

Moreover, although the interlayer surface is also on the surface, the polar portion of the alkyl ammonium is electrically connected to the inside of the smectites, and the non-polar portion of the alkyl ammonium is disposed on the surface of the smectites. Affinity to an organic solvent having a small amount is generated, and the coloring material is easily dispersed uniformly in the organic solvent.

If the alkylammonium has three or more carbon chains having 8 or more carbon atoms, the interlayer distance can be further increased and the dye can be intercalated between the carbon chains. In addition, the dye can be intercalated in a larger amount, and the intercalated dye is not easily removed.

In the method for producing a color filter according to the invention of the present application, a solution in which hydrotalcites or smectites are dispersed in a solvent containing at least one of water and an organic solvent and a solution in which a dye is dissolved are used. Since the coloring material is formed by mixing, a coloring material that is a pigmented dye can be formed using a water-insoluble dye.

The solid-state imaging device according to the invention of the present application has an on-chip color filter in which a composition obtained by intercalating a dye with clay is used as a coloring material. Color material.

In the method for manufacturing a solid-state imaging device according to the present invention, a method in which hydrotalcites or smectites are dispersed in a solvent containing at least one of water and an organic solvent, and a solution in which a dye is dissolved are used. Are mixed to form the coloring material of the on-chip color filter, so that a pigmented dye as a coloring material of the on-chip color filter can be formed using a water-insoluble dye.

[0033]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, first to third embodiments of the present invention applied to an on-chip color filter in a solid-state imaging device, a liquid crystal display device, and the like and a method of manufacturing the same will be described. First, a first embodiment will be described. In the first embodiment, a water-soluble dye is used as a starting material for a coloring material, and the dye is intercalated into hydrotalcites, which are layered clay minerals.

The first embodiment has steps 1 to 4. Briefly, in step 1, the interlayer anion is adjusted to facilitate the intercalation of the dye between the layers of the hydrotalcites. In step 2, the interlayer distance is increased to facilitate the intercalation of the dye between the layers of the hydrotalcite, and the hydrotalcite has an affinity for the organic solvent.

In the step 3, the dye is intercalated between the layers of the hydrotalcite to convert the dye into a pigment.
In step 4, an on-chip color filter is formed using a resist in which a pigment-forming dye formed by intercalating a dye between hydrotalcite layers is dispersed.

Next, each step will be described in detail. Basic skeleton of the composition of the hydrotalcite _{Mg 6 Al 2 (OH) 16} CO 3 · 4H
_{In the} hydrotalcites used in the first embodiment, at least a part of Mg of the hydrotalcite is substituted with a divalent metal such as Cu, Ni, Co, Zn, Fe, and Mn. At least part of Al may be Ga, Ni, Co, Fe,
It may be substituted with a trivalent metal such as Mn and Cr.

By the way, the anion exchangeable anion between the layers of such hydrotalcites is (CO ₃ ) ^2-
With only this, intercalation between the layers is not easy, the amount of the dye held between the layers is small, and a dark color cannot be obtained.

[0038] ^{Therefore, F -, Cl -, Br} -, I -, (ClO
_{^{4) -, (NO 3)}} -, (ClO 3) -, (IO 3) -, OH -,
(SO ₄ ) ^2- , (S ₂ O ₃ ) ^2- , (WO ₄ ) ^2- , (CrO ₄ ) ^2-
, [Fe (CN) ₆ ] ^3- , [Fe (CN) ₆ ] ^4- , [SiO (OH) ₃ ] ^-
It is preferable to substitute at least a part of (CO ₃ ) ^2- before use.

Therefore, in step 1, for example, Cl ^- or (N
O ₃₎ ^- and (SO ₄₎ in order to perform this replacement in ^2, etc., by bubbling nitrogen gas in pure water, to remove the carbon dioxide dissolved from the atmosphere into pure water, pure water After dispersing hydrotalcites in it, NaCl, KCl,
Anion exchange with NaNO ₃ , KNO ₃ etc.
H ₂ CO ₃ such as HCl, HNO ₃ , H ₂ SO ₄ etc. with a concentration of about 1N
Or anion exchange by desorbing carbon dioxide using a stronger acid.

Further, Mg (NO ₃ ) ₂ or MgCl _{2 is used} as a part of the Mg source as a starting material when synthesizing hydrotalcites.
₂ or use Al (NO ₃ ) ₂ or
Even if AlCl ₃ is used, hydrotalcites in which Cl ⁻ or (NO ₃ ) ⁻ are arranged between layers can be easily obtained.

On the other hand, if the interaction between the hydrotalcites and the dye intercalated between the layers is too strong, the coloring group of the dye is affected, and the spectral sensitivity characteristics of the dye change. Therefore, in step 2, at least a part of the interlayer anion of hydrotalcites is replaced with an organic acid.

For this substitution, first, hydrotalcites are sufficiently dispersed in pure water or a solvent that is a lower alcohol such as ethanol or 2-propanol or a mixed solution of pure water and a lower alcohol. A liquid is obtained. Also, in the same solvent as described above, fully disperse the organic acid,
Liquid B is obtained.

Then, while stirring the solution A with a magnetic stirrer or the like, the solution B is gradually added to the solution A little by little, and the stirring is continued for at least 12 hours or more, preferably 24 hours or more. During this stirring, the organic acid is intercalated between the layers of the hydrotalcites, and at least a part of the interlayer anion is replaced with the organic acid.

It is important that the organic acid which can be used in this case is a substance capable of strengthening the bond between the hydrotalcites and the dye and improving the weather resistance of the color filter. For that purpose, pKa expressed as pKa = -LogKa with the acid dissociation constant as Ka needs to be 5.0 or less, and desirably 3.5 or less.

In this case, the organic acid has a certain molecular size so that the dye can be easily intercalated between the layers of hydrotalcites in Step 3 described later. It is necessary that the material be capable of increasing the interlayer spacing of hydrotalcites. Further, it is a substance having an aromatic (benzene) ring present in the dye so that the dye can be easily used in the hydrotalcite and the dye can be uniformly dispersed in the hydrotalcite. It is desirable.

Organic acids meeting the above requirements include benzoic acid, salicylic acid (ortho-hydroxybenzoic acid) and its isomers (para-hydroxybenzoic acid, meta-hydroxybenzoic acid) and derivatives thereof.

The derivatives include -R substitution (R is an optionally substituted alkyl group), -cycloalkyl substitution, -aryl substitution, -phenyl substitution, -naphthyl substitution, -RCO substitution, -RCOOH substitution, -RCOOR '
Substituted, chlorinated, chlorate substituted iodine substitutions, iodate substituted, fluorine-substituted, fluorine-acid-substituted, -OH substituted, -NO ₂
Substitution, -CO ₂ substitution, -NH ₃ substitution, -NHR substitution (R
Are benzoic acid, salicylic acid and isomers thereof which are alkyl groups.

Benzoic acid substituted with —SO ₃ M (M is a hydrogen atom, an alkali metal atom, a quaternary, ie, an alkylammonium having four carbon chains, etc.), —SO ₂ NHR-substituted benzoic acid,
It may be an isomer or derivative of salicylic acid.

For example, p-toluenesulfonic acid is an excellent organic acid for use in the present invention. Also, -SO ₃
H-substituted aromatic acids are strong acids as organic acids and have a pKa
Is small, so that it has high weather resistance and is suitable for use in the present invention.

After the above-described treatment of replacing at least a part of the interlayer anions of the hydrotalcites with an organic acid, if there is an excess of an organic acid that is not fixed between the layers, the weather resistance and the resist properties may be reduced. Performance is adversely affected. Therefore, the excess organic acid is washed and separated by dispersing the hydrotalcites subjected to the substitution treatment with the organic acid in a good solvent for the organic acid and performing centrifugation or the like. After this washing and separation, the hydrotalcites are dried to a powder.

When the hydrotalcite peels off at the interlayer, the interlayer also becomes the surface. When the substitution treatment of the hydrotalcites with the organic acid is performed as described above, the polar portion of the organic acid is electrically coupled to the inside of the hydrotalcites, and the non-polar portion of the organic acid is converted to the hydrotalcite. Since it is arranged on the surface of the sites, affinity for a less polar organic solvent is generated. Therefore, the pigmented dye formed in the subsequent step 3 can be uniformly dispersed in the resist in the subsequent step 4.

Next, a step 3 is carried out in which the dye is intercalated between the layers of the hydrotalcites which have been subjected to the substitution treatment with the organic acid in the step 2 to convert the dye into a pigment. For this pigmentation, first, in a solvent that is pure water or a lower alcohol such as ethanol or 2-propanol or a mixed solution of pure water and a lower alcohol, hydrotalcites that have been subjected to a substitution treatment with an organic acid are added. Fully dispersed, C
Obtain a liquid. Further, the dye is dissolved in the same solvent as described above to obtain a solution D.

Then, while stirring the solution C with a magnetic stirrer or the like, the solution D is gradually added to the solution C little by little, and the stirring is continued for at least 24 hours or more, preferably for 48 hours or more. During this stirring, the dye is intercalated between the layers of the hydrotalcites that have been subjected to the substitution treatment with the organic acid.

At this time, the stirring time, ie, the reaction time is longer than that in the case of the substitution treatment with the organic acid, because the molecules of the dye are large and the diffusion of hydrotalcites between the layers is sterically hindered. This is because curation requires time. Since the liquid mixture of the liquid C and the liquid D contains water or lower alcohol which lowers the performance of the resist, the solid content from which these are removed is obtained as a pigment dye.

After the above intercalation, both the dye and the organic acid are present between the layers of the hydrotalcites. Then, the polar portion of the dye and the organic acid is electrically coupled to the inside of the hydrotalcites, and the non-polar portion of the dye and the organic acid is disposed on the surface of the hydrotalcites. Affinity is even higher. Therefore, the pigmented dye formed in the step 3 can be more uniformly dispersed in the resist in the subsequent step 4.

In the first embodiment, since hydrotalcites whose exchangeable ions between layers are anions are used and the dye is water-soluble, strong ions such as SO ₃ Na group and SO ₃ H group are used. Any structure dye can be used as long as it is an anionic dye having a polar functional group and is water-soluble.

For example, azo dyes, xanthene dyes, phthalocyanine dyes, triphenylmethane dyes, anthraquinone dyes, metal complex salt azo dyes and the like can be used. In addition, an acidic dye or a reactive dye having a reactive group which is an acidic dye and has a reactive group can be appropriately selected from a dye handbook or the like and used.

Next, Step 4 of forming an on-chip color filter using the color resist in which the pigment dye formed in Step 3 is dispersed is performed. In this step 4, 400 nm
A pigmented dye finely divided into the following diameters is uniformly dispersed in the photosensitive composition to form a high-resolution color resist, and this color is formed on a semiconductor substrate forming a solid-state imaging device or a liquid crystal display device. A resist is applied, and the color resist is patterned by a lithography method to form an on-chip color filter.

As the above-mentioned steps, conventionally known steps can be adopted. In a color resist method using a pigment as a coloring material, generally, a photosensitive resin monomer such as novolak or acrylic, a polymerization initiator, a polymerization accelerator, a surface treatment agent for improving adhesion, and a pigment for stably dispersing the pigment. A pigment is dispersed in an organic solvent together with a dispersing agent, an anti-aggregation agent, and the like, which are resins, to form a color resist. In the first embodiment, the pigmented dye formed in step 3 is used.

Next, a second embodiment will be described. This second
The embodiment differs from the first embodiment only in that a water-insoluble dye is used as a starting material of a coloring material. Therefore, the dye is interposed between the layers of the hydrotalcites that have been treated with an organic acid. Only the solvent used in the step 3 of intercalating the dye into a pigment is different from the first embodiment.

The solvent used in step 3 of the second embodiment includes methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, N-
Methyl pyrrolidone, cyclopentanone, cyclohexanone, ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dioxane, dimethylformamide, etc., alone or in combination of two or more Use a mixture of components.

The solution E is obtained by sufficiently dispersing hydrotalcites which have been subjected to a substitution treatment with an organic acid in this solvent. Also, in the same solvent as described above, dissolve the dye,
Obtain liquid F. Then, while stirring the solution E with a magnetic stirrer or the like, the solution F is gradually added to the solution E little by little, and the stirring is continued for at least 24 hours or more, preferably 48 hours or more. During this stirring, the dye is intercalated between the layers of the hydrotalcites that have been subjected to the substitution treatment with the organic acid.

As the solvent used in Step 3 of the second embodiment, the same solvent as that of the photosensitive composition can be used, and this solvent does not contain water or lower alcohol which lowers the performance of the resist. Therefore, the step of removing these as in the above-described first embodiment is not required. Therefore,
A color resist can be obtained by simply mixing a mixture of the solution E and the solution F with a solvent containing the photosensitive composition.

The water-insoluble dye in the second embodiment needs to have high solubility in an organic solvent,
-SO ₃ M group (M represents a hydrogen atom, an alkali metal atom, quaternary i.e. alkyl ammonium and the like of the carbon chain are four) of water-soluble dyes described in the embodiment section of -SO ₂ N
HR group (R is an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group,
Those substituted with an aryl group, a phenyl group, a naphthyl group, an RCOOR 'group and the like are used.

Next, a third embodiment will be described. This third
In the embodiment, smectites such as montmorillonite are used as the layered clay mineral for intercalating the dye. Smectites have ion-exchangeable cations between the layers, and the interlayer cations are interlayer anions of hydrotalcites (CO ₃ ) ^2-
Ion exchange is easier than

For this reason, it is not necessary to adjust the interlayer cation in step 1 as in the first and second embodiments. Therefore, in the third embodiment, the interaction between the smectites and the dye intercalated between the layers suppresses the influence of the coloring groups of the dyes, and the dye is intercalated between the smectites. In order to facilitate the process, the interlayer distance is increased, and further, Step 2 for immediately giving the smectites an affinity for the organic solvent is immediately performed.

Since the exchangeable ions between the layers of smectites are cations, the interlayer cations are exchanged with the cations in step 2 of the third embodiment. But,
For cations with a small ionic radius, such as metal cations,
Since the interlayer spacing cannot be increased, there is no effect of facilitating the intercalation of the dye between the smectite layers. Therefore, in step 2 of the third embodiment, an alkyl ammonium ion is used.

However, the interlaminar spacing that can be extended by ion exchange with alkylammonium depends on the length of the carbon chain, that is, the number of carbon atoms. With an alkylammonium having about 4 or less carbon atoms, the interlaminar spacing can be sufficiently increased. It is not suitable for intercalating large molecular dyes. For this reason, it is important to use an alkyl ammonium having 8 or more carbon atoms in the carbon chain.

Furthermore, primary or secondary alkylammonium having one or two carbon chains is arranged planarly with respect to the interlayer of smectites and is not arranged three-dimensionally, so that the interlayer spacing is increased. Less is. Further, even when the dye is intercalated, the dye does not have a structure in which the dye enters between the carbon chains of the alkyl ammonium, and the dye is easily detached. For these reasons, three or four carbon chains
The book tertiary or quaternary alkyl ammonium is suitable.

Next, a step 3 is carried out in which the dye is intercalated between the layers of the smectites subjected to the alkylammonium substitution treatment in the step 2 to convert the dye into a pigment. For this pigmentation, first, the smectites which have been subjected to the alkylammonium substitution treatment are dispersed in an aqueous, aqueous-organic mixed or organic solvent. Which solvent is used is selected according to the hydrophilicity / hydrophobicity of the surface of smectites.

The surface of smectites becomes more hydrophobic as the number of carbon atoms in the carbon chain of the alkylammonium substituted for the interlayer cation increases and as the rate of substitution of the interlayer cation by the alkylammonium increases. Therefore, as it becomes more hydrophobic, a water-organic mixed solvent is used rather than an aqueous solvent, and an organic solvent is used more than a water-organic mixed solvent.

In the following, tetra-n-decylammonium is used as the alkylammonium.
Step 3 in the case where the substitution rate of the interlayer cation of smectites by decyl ammonium is 80% is shown.

First, while stirring a solvent which is pure water or a lower alcohol such as ethanol or 2-propanol or a mixed solution of pure water and a lower alcohol, the solvent is replaced with tetra-n-decylammonium. The smectites are gradually added little by little and dispersed sufficiently to obtain a liquid G. Further, the dye is dissolved in the same solvent as described above to obtain the H solution.

Then, while stirring the solution G with a magnetic stirrer or the like, the solution H is gradually added to the solution G little by little, and the stirring is continued for at least 24 hours or more, preferably 48 hours or more. During this stirring, the dye is intercalated between the layers of the hydrotalcites that have been substituted with tetra-n-decyl ammonium.

At this time, the stirring time, that is, the reaction time is longer than in the case of the substitution treatment with tetra-n-decylammonium, because the molecules of the dye are large and steric hindrance occurs in the diffusion of smectites between layers. This is because the intercalation requires time. When the mixed solution of the solution G and the solution H contains water or lower alcohol which lowers the performance of the resist, the solid content from which these are removed is obtained as a pigment dye. After the above intercalation, both dye and tetra-n-decylammonium exist between the layers of smectites.

Then, the polar part of the dye and the alkyl ammonium is electrically connected to the inside of the smectites,
Since the non-polar portion of the dye and the alkyl ammonium are disposed on the surface of the smectite, the affinity for the less polar organic solvent is further increased. Therefore, the pigmented dye formed in the step 3 can be more uniformly dispersed in the resist in the subsequent step 4. Also,
If a resin is used as a dispersion aid, dispersibility in the resist can be further improved.

In the third embodiment, smectites whose cations are exchangeable between the layers are cations, so that they are basic (cationic) dyes having a nitrogen base (amine or ammonium) and the like. Dyes of any structure can be used as long as they are water-soluble. For example, triphenylmethane dye, oxazine dye, azine dye, thiazine dye and the like can be used. In addition, a cationic dye can be appropriately selected and used from a dye handbook or the like.

Next, a step 4 of forming a color filter using the color resist in which the pigmented dye formed in the step 3 is dispersed is performed. This step 4 is also performed in the same manner as in the first and second embodiments. Do. However, when the same solvent as that of the photosensitive composition is used as the solvent used in step 3, the color resist can be obtained by simply mixing the mixed solution of the solution G and the solution H and the solvent containing the photosensitive composition. can get.

[0079]

According to the color filter of the present invention,
Since the pigmented dye is used as a coloring material, both the excellent spectral sensitivity characteristics of the dye and the excellent weather resistance of the pigment are provided.

Further, if hydrotalcites or smectites, which are layered clay minerals, are used as clay for intercalation, a large amount of dye can be intercalated, so that a deep color can be obtained. Can be.

If the dye is ion-exchanged by the intercalation and the dye is electrically connected between the layers of hydrotalcites or smectites, the dye molecules are strongly fixed between the layers. So
Excellent weather resistance.

If at least a part of the interlayer anion of the hydrotalcite is substituted with an organic acid, a large amount of the dye can be intercalated, so that a deep color can be obtained. Further, since the change in the spectral sensitivity characteristics of the dye is prevented, the excellent spectral sensitivity characteristics of the dye can be provided as it is. In addition, since the coloring material is easily dispersed uniformly in the organic solvent, a color having a uniform concentration distribution can be obtained.

When at least a part of the interlayer anions of hydrotalcites is substituted with an organic acid having a pKa of 5.0 or less, the intercalated dye is strongly bonded to the hydrotalcites. Has been
Excellent weather resistance.

If at least a part of the interlayer anion of hydrotalcites is substituted with an organic acid having an aromatic ring, the dye is easily intercalated between the layers of hydrotalcites. And a color having a uniform density distribution can be obtained.

Further, if at least a part of the interlayer cation of smectites is substituted by alkylammonium, a large amount of dye can be intercalated, so that a deep color can be obtained. Further, since the change in the spectral sensitivity characteristics of the dye is prevented, the excellent spectral sensitivity characteristics of the dye can be provided as it is. In addition, since the coloring material is easily dispersed uniformly in the organic solvent, a color having a uniform concentration distribution can be obtained.

In addition, if the alkylammonium has three or more carbon chains having 8 or more carbon atoms, the dye can be intercalated in a larger amount and the intercalated dye is not easily desorbed. So
Further, it is possible to obtain a color that is darker and hardly decolorized.

In the method of manufacturing a color filter according to the present invention, since a coloring material that is a pigmented dye can be formed using a water-insoluble dye, excellent spectral sensitivity characteristics of a dye selected from a wide range can be obtained. And a pigment having both excellent weather resistance of the pigment.

In the solid-state image pickup device according to the present invention, since the pigmented dye is used as the coloring material of the on-chip color filter, both the excellent spectral sensitivity characteristics of the dye and the excellent weather resistance of the pigment are provided. I have.

In the method of manufacturing a solid-state imaging device according to the present invention, a pigmented dye as a coloring material of an on-chip color filter can be formed using a water-insoluble dye. A solid-state imaging device having an on-chip color filter having both excellent spectral sensitivity characteristics and excellent weather resistance of a pigment can be manufactured.

Claims (13)

[Claims] 1. A color filter, wherein a composition comprising a dye intercalated in a clay is used as a coloring material. 2. The color filter according to claim 1, wherein hydrotalcites or smectites are used as the clay. 3. Hydrotalcites having an ion-exchangeable anion between layers or smectites having an ion-exchangeable cation between layers are used as the clay, and the dye is converted into the dye by the intercalation. The color filter according to claim 1, wherein the color filter is electrically coupled between the layers by exchanging with an anion or the cation. 4. A hydrotalcite having an ion-exchangeable anion between layers is used as the clay, and at least a part of the anion is substituted with an organic acid. The color filter according to 1. 5. pKa = −Lo where the acid dissociation constant is Ka.
The color filter according to claim 4, wherein the organic acid having a pKa expressed as gKa of 5.0 or less is used. 6. The color filter according to claim 4, wherein said organic acid has an aromatic ring. 7. The smectite having an ion-exchangeable cation between the layers is used as the clay, and at least a part of the cation is substituted with alkylammonium. Color filters. 8. The alkylammonium has 8 carbon atoms.
The color filter according to claim 7, wherein the color filter has three or more carbon chains. 9. A hydrotalcite having an ion-exchangeable anion between layers, wherein at least a part of the anion is substituted with an organic acid, a hydrotalcite containing at least one of water and an organic solvent. A step of dispersing the dye in a second solvent containing at least one of water and an organic solvent; a step of mixing the first and second solvents with each other to form a mixture with the anion. After intercalating the dye with the hydrotalcites by exchanging with the dye,
Removing the water and the organic solvent to form a coloring material; dispersing the coloring material in a photosensitive composition; and selectively exposing the photosensitive composition to patterning. A method for manufacturing a color filter, comprising: 10. A smectite having an ion-exchangeable cation between layers, wherein at least a part of the cation is substituted with alkylammonium, a first smectite containing at least one of water and an organic solvent. Dispersing in a solvent; dissolving the dye in a second solvent containing at least one of water and an organic solvent; mixing the first and second solvents to form the cation and the dye Exchanging the dye with the smectites by exchanging the dye, and then forming a coloring material by removing the water and the organic solvent; and dispersing the coloring material in the photosensitive composition. A method for producing a color filter, comprising: a step of selectively exposing the photosensitive composition to patterning. 11. A solid-state image pickup device comprising an on-chip color filter in which a composition obtained by intercalating a dye with clay is used as a coloring material. 12. A hydrotalcite having an ion-exchangeable anion between layers, wherein at least a part of the anion is substituted with an organic acid, a hydrotalcite containing at least one of water and an organic solvent. A step of dispersing the dye in a second solvent containing at least one of water and an organic solvent; a step of mixing the first and second solvents with each other to form a mixture with the anion. After intercalating the dye with the hydrotalcites by exchanging with the dye,
Removing the water and the organic solvent to form a coloring material; dispersing the coloring material in a photosensitive composition; and selectively exposing the photosensitive composition to an on-chip color filter. And a step of processing into a pattern. 13. A smectite having an ion-exchangeable cation between layers, wherein at least a part of the cation is substituted with alkylammonium, a first smectite containing at least one of water and an organic solvent. Dispersing in a solvent; dissolving the dye in a second solvent containing at least one of water and an organic solvent; mixing the first and second solvents to form the cation and the dye Exchanging the dye with the smectites by exchanging the water and the organic solvent to form a coloring material, and dispersing the coloring material in the photosensitive composition. And a step of selectively exposing the photosensitive composition to a pattern of an on-chip color filter.