TWI444673B - Color filter, method of producing the same, and solid-state image pickup device - Google Patents

Description

Color filter, its manufacturing method and solid-state imaging device

The present invention relates to a color filter, a method of manufacturing the same, and a solid-state imaging device, and more particularly to a color filter that can be suitably fabricated by dry etching.

In recent years, the high pixelation of solid-state imaging devices has become remarkable, and thus the size of images has been gradually reduced. In addition, as the size of the image is reduced, the size of the pixels assembled in the image pickup element will become smaller and smaller. As the number of pixels is reduced, the light sensitivity of one of the basic performances of the image sensor is reduced, and it is necessary to concentrate the light on the light receiving element.

Therefore, in order to maintain the characteristics of the color separation, color shading, color mixing, and the like, the performance required for the color filter has been required to be thinned, rectangular, and non-overlapping between the films.

Conventionally, most of the methods for producing color filters have gradually adopted lithography (lithography). The photolithography method is a method of producing a color filter by applying a radiation-sensitive resin composition such as a colored curable composition onto a substrate, drying it to form a coating film, and then performing the coating film. The pattern is exposed, developed, baked to form colored pixels, and the colors are repeated for this operation. Since the photolithography method is based on the photolithography process of photo-semiconductor fabrication, the initial investment suppression is possible, and the high-precision exposure, the overlay accuracy, etc. of the photolithography process are suitable for the production of color filters. Methods have been widely used.

However, in the case of producing a color filter by photolithography, it is necessary to use an alkali-soluble resin in addition to a photosensitive curing agent such as a photoinitiator or a monomer because a photosensitive composition is used. Therefore, the content of the coloring agent in the total solid content becomes low, and as a result, it has a drawback that the film thickness becomes thick. When a photocurable component is contained, it is difficult to achieve a film thickness of a color filter of 0.7 μm or less. As a result, the light transmittance and the color depth characteristics are deteriorated, which causes a color mixture to easily occur.

Furthermore, as the resolution of the photolithography approaches the diffraction limit of light, the shape of the color filter tends to be incapable of becoming a rectangle. For example, in the case where the second color filter is formed on the carrier on which the first color filter is formed, the second color filter is superimposed on the first color filter, which may cause a problem of poor color mixing. .

In order to overcome the above problems, a method of patterning a color filter by dry etching has been proposed (for example, refer to Patent Document 1).

Patent Document 1: Japanese Patent Laid-Open No. 2006-222291

In the manufacture of a color filter using a dry etching method, in order to etch an unnecessary portion of a predetermined color filter and a planarization layer of the lower layer thereof, as shown in FIG. 3, between the color filters 18 and 20 There is a problem that the film thickness is unevenly formed.

Further, in general, excessive etching treatment is necessary, and damage (cutage) of the carrier 12 tends to occur. 4A to 4C schematically show the steps of forming a color filter by dry etching. For example, in the case where a predetermined pattern is formed by dry etching to remove the coloring layer 18 on the carrier 12 (Fig. 4A), the portion of the carrier 12 in the field of removing the colored layer 18 is also cut, and a height difference of 32 occurs. Situation (Fig. 4B). As described above, when the height difference 32 occurs on the carrier 12, the thickness of the colored layer 18 is different (Fig. 4C), and the flatness is deteriorated to easily cause a decrease in the color separation performance. In this manner, when the dry etching method is employed, there is a problem that the base is reduced by etching, the unevenness of the film thickness, and the coloring property are deteriorated.

Further, after the end of the etching is detected, in order to remove the residue from the carrier, there is a case where excessive etching treatment is performed. At this time, in the case where the organic film is present on the carrier, it is difficult to avoid the occurrence of damage of the carrier in the case of performing an over-etching treatment.

In particular, even when a fluorine-based gas which is dry-etched by an isotropic direction is used for the rectangular shape of the color filter, and a SiO ₂ -based transparent film such as SOG is introduced into the lower layer of the color filter, etching tolerance is obtained. There is a problem that the portion of the carrier (substrate) is reduced, and the film thickness between the respective colored layers is easily unevenly formed.

The present invention has been made in view of the above problems, and an object thereof is to provide a color filter, a method of manufacturing the same, and a solid-state imaging device including the color light-emitting sheet, which is manufactured by applying a dry etching method. In this case, the reduction of the substrate is also suppressed, and the thickness uniformity of the colored layer is high.

Technical means of solving problems

In order to achieve the above object, in the present invention, a color filter, a method of manufacturing the same, and a solid-state imaging device are provided:

<1> A color filter characterized in that an oxide layer containing at least one metal selected from Ti, Ta, Zn, and Zr is provided on a carrier, and coloring is formed through a layer containing the metal oxide. Floor.

<2> The color filter according to <1>, wherein the layer containing the metal oxide has a thickness of 0.2 μm or less.

<3> A color filter according to <1> or <2>, wherein the layer containing the metal oxide is an amorphous TiO ₂ layer.

<4> A method for producing a color filter, the method comprising:

Forming a step of forming an oxide layer containing at least one metal selected from Ti, Ta, Zn, and Zr on the support;

a step of forming a colored layer on a layer containing the metal oxide; and

The step of forming a pattern of color filters by dry etching to remove portions of the colored layer.

<5> The method for producing a color filter according to <4>, wherein a composition of a precursor polymer and a solvent obtained by using a metal alkoxide containing at least one metal selected from Ti, Ta, Zn and Zr, A sol-gel method is used to form a layer containing the metal oxide.

<6> A solid-state imaging device characterized by comprising a color filter as disclosed in <1> to <3>.

Effect of invention

According to the present invention, even in the case of manufacturing by dry etching, it is possible to provide a color filter, a method of manufacturing the same, and a solid-state imaging device having the color filter thereof, and the reduction of the substrate is suppressed, and the thickness of the colored layer is suppressed. The uniformity is high.

Embodiment of the invention

Hereinafter, the present invention will be specifically described with reference to the accompanying drawings.

The present inventors have intensively studied the technique of manufacturing a color filter by dry etching, and found that a coloring layer is formed by forming a specific metal oxide layer on a carrier and interposing a layer containing the metal oxide. The peeling of the carrier by dry etching can be effectively suppressed, and the present invention can be further repeated.

Fig. 1 is a view showing an embodiment of a solid-state imaging device having a color filter according to the present invention. The solid-state imaging device 10 is formed by arranging the light-emitting diodes 14 on one surface of a semiconductor substrate (carrier) 12, and is formed on the opposite side of the substrate 12 to contain metal oxide selected from Ti, Ta, Zn, and Zr. Object layer 16. On the metal oxide layer 16, a color layer (color filter) 18 and 20 of two colors are alternately formed on the surface of the substrate 12 in accordance with each of the light-emitting diodes 14. Further, a flattening layer 22 which is flattened to cover the color layers 18 and 20 of the respective colors is provided, and the microlens 24 is provided on the planarizing layer 22 so as to correspond to the formation regions of the colored layers 18 and 20.

The solid-state imaging device 10 having the color filter of the present invention is particularly suitable for the case of being manufactured by dry etching. Hereinafter, a method of manufacturing the color filter according to the present invention and the solid-state imaging device 10 including the same will be specifically described.

2A to 2C are parts showing steps of a method of manufacturing the color filter of the present invention.

[Metal oxide layer forming step]

First, on the carrier 12, an oxide layer 16 containing at least one metal selected from Ti, Ta, Zn and Zr is provided. Further, the carrier 12 is preferably selected depending on the application. For example, in the case of manufacturing a solid-state imaging device, a semiconductor substrate can be used, and in the case of manufacturing a liquid crystal display device, a glass substrate can be used.

The method of forming the metal oxide layer 16 on the carrier 12 is not particularly limited, and for example, it can be formed by a sol-gel method using a vapor deposition method, a sputtering method, a CVD method, or a coating method. The metal oxide layer 16 formed on the carrier 12 is preferably an amorphous metal oxide layer from the viewpoint of inactivation of the photocatalyst, and particularly preferably an amorphous TiO ₂ layer. For example, a composition of a precursor polymer and a solvent obtained by using a metal alkoxide of a metal selected from Ti, Ta, Zn, and Zr is used to form the metal oxide layer 16 by a sol-gel method. Thereby, a layer made of an amorphous metal oxide can be formed on the carrier 12. Further, a layer containing two or more kinds of metal oxides among the above metal oxides may be formed.

The sol-gel method coats the precursor polymer (metal alkoxide derivative) on the substrate 12. The hydrolysis in the drying step is accelerated, and further dehydration condensation in the heating step to form a metal oxide.

The precursor polymer used in the sol-gel method is represented by the formula M(OR ¹ ) _a or R ² _b M(OR ³ ) _c , and more than one selected from the partial hydrolyzate and the condensate. The metal alkoxide derivative is used as a main component, and this precursor polymer is dissolved in an organic solvent to be produced. M is a metal atom selected from Ti, Ta, Zn and Zr. It is preferably Ti. Examples of the alkyl group having 1 to 8 carbon atoms independently of R ¹ , R ² and R ³ include a methyl group, an ethyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group and an octyl group. a is the valence of M, b and c are each an integer of 1 or more, and b+c is the valence of M. Such a precursor polymer is commercially available, for example, the trade name of Rasa Industries Co., Ltd.: TI-44, VR7; the trade name of the High Purity Chemical Research Institute Co., Ltd.: SYM-T105, SYM-ZR04, SYM-ZN20, etc.

The organic solvent dissolves the above-mentioned precursor polymer and selects an organic solvent which does not affect the substrate 12. Specific examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; esters such as ethyl acetate and butyl acetate; and other ethers; Class or ketone. The organic solvent may be used alone or in combination of two or more.

The organic solvent is usually set to be 70% by mass or more, preferably 80 to 99.9% by mass. Further, the concentration of the solid component of the precursor polymer or the like is 30% by mass or less, preferably 0.01 to 20% by mass.

The metal oxide layer 16 can directly apply the composition containing the precursor polymer and the solvent described above to the carrier 12, or can be applied to the carrier 12 via another layer, and then dried to form a coating film. It is formed by performing heat treatment.

A method of applying a composition containing a precursor polymer and a solvent onto the carrier 12 can be carried out by a coating method such as spin coating, slit coating, cast coating, or roll coating.

The specific thickness of the metal oxide layer 16 is preferably from 0.01 μm to 0.20 μm, more preferably from 0.05 μm to 0.10 μm, to form a coating film. When the thickness of the metal oxide layer 16 is 0.01 μm or more, damage to the carrier 12 due to dry etching described later can be more reliably suppressed. On the other hand, when it is 0.20 μm or less, the decrease in the light transmittance due to the metal oxide layer 16 can be effectively suppressed.

Further, the metal oxide layer 16 is transparent with respect to light in the visible light region, and the refractive index is preferably from 1.7 to 2.0, more preferably from 1.7 to 1.9. It is desirable that the metal oxide layer 16 be formed such that the effects of reflection and interference are about a minimum film thickness and refractive index.

The heat treatment of the coating film may be carried out simultaneously with the drying after application, or a heat hardening step of another route may be provided after the coating is dried. This heat treatment uses a conventional heating means such as an oven or a hot plate, and specifically, it can be at 130 to 400 ° C, preferably 150 to 280 ° C, for 10 seconds to 3 hours, more preferably. It is carried out in the range of 60 seconds to 60 minutes. However, when considering productivity, the time required for hardening is as short as possible.

The degree of crystallization of the metal oxide layer 16 can be controlled according to the temperature and time of the heat treatment. Specifically, the metal oxide layer 16 has a degree of crystallization of 10% or less, preferably 3% or less.

If the degree of crystallization of the metal oxide layer 16 is 10% or less, the photocatalytic action becomes inactive, for example, in the case where an organic layer is formed between the carrier 12 and the metal oxide layer 16, the tightly bonded organic layer is suppressed. Deterioration will be possible.

[Coloring layer forming step]

After the metal oxide layer 16 is formed on the carrier 12, a coloring layer 18 is formed on the metal oxide layer 16.

The colored layer 18 constitutes a pixel of a color calender. The colored layer 18 is preferably formed via a curable composition containing a colorant. Examples of the curable composition include a colored photocurable composition and a non-photosensitive colored thermosetting composition. From the viewpoint of spectral characteristics, it is preferred to use a non-photosensitive colored thermosetting composition to form a colored layer. 18.

(A) colored photocurable composition

The colored photocurable composition which can be used in the present invention contains at least a coloring agent and a photocurable component. In addition, the "photocurable component" is a photocurable composition which is usually used in a photolithography method, and at least a binder resin (such as an alkali-soluble resin) and a photosensitive polymer component (photopolymerization into a monomer) can be used. A composition of a photopolymerization initiator or the like.

For the colored photocurable composition, for example, the matters disclosed in paragraph numbers 0017 to 0064 of JP-A-2005-326453 can be suitably used.

The color layer forming step in the present invention includes the step of previously applying the above-described color-light-curable composition to the metal oxide layer 16 provided on the carrier 12, followed by drying to form a coating film (coating film formation) Step); and performing a heat treatment step (post-baking step).

(B) coloring thermosetting composition

In the present invention, as described above, the non-photosensitive colored thermosetting composition can be used to form the colored layer 18. In the non-photosensitive color thermosetting composition of the present invention, the coloring agent and the thermosetting compound are contained, and the concentration of the coloring agent in the total solid content is preferably 50% by mass or more and less than 100% by mass.

-Colorant-

The coloring agent which can be used in the present invention is not particularly limited, and one of various conventional dyes or pigments or a mixture of two or more kinds can be used.

Examples of the pigment which can be used in the present invention include various conventional inorganic pigments or organic pigments. Further, in the case of an inorganic pigment or an organic pigment, it is preferred to use a pigment having an average particle diameter as small as possible in consideration of high light transmittance; if the handleability is considered, the average particle diameter of the pigment is higher. It is preferably from 0.01 μm to 0.1 μm, more preferably from 0.01 μm to 0.05 μm.

In the present invention, preferred pigments can be exemplified by the following pigments, but are not limited by such pigments:

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/Purple 19, 23, 32;

C. I. Pigment/Blue 15:1, 15:3, 15:6, 16, 22, 60, 66;

C. I. Pigment/Brown 1.

In the case where the coloring agent is a dye, the coloring agent can be uniformly dissolved in the thermosetting resin composition to obtain a non-photosensitive thermosetting coloring resin composition.

In the present invention, the dye which can be used as the coloring agent is not particularly limited, and a conventional dye can be used as the color calendering sheet.

As the chemical structure, a pyrazole azo system, an anilino azo system, a triphenylmethane system, an anthracene system, an anthrapyridone system, a benzene group, an oxophthalocyanine (Oxonol) system, or a pyrazole triazole azo system can be used. , pyridone azo, phthalocyanine, phenothiazine A dye such as a pyrrolopyrazine-imine, a xanthene, a phthalocyanine, a benzopyran or an indigo.

The coloring agent content in the total solid content of the colored thermosetting composition of the present invention is not particularly limited, but is preferably 50% by mass or more and 100% by mass or less, more preferably 55% by mass or more and 90% by mass. %the following. By setting the content to 50% by mass or more, the color calender sheet can obtain an appropriate chromaticity. In addition, since the photocuring can be sufficiently accelerated by setting it to less than 100% by mass, it is possible to suppress a decrease in strength of the film.

Thermosetting compound

The thermosetting compound which can be used in the present invention is not particularly limited as long as it can be cured by heating. For example, a compound having a thermosetting functional group can be used. The thermosetting compound is, for example, preferably a compound having one selected from the group consisting of an epoxy group, a methylol group, an alkoxymethyl group and a decyloxymethyl group.

Further preferred thermosetting compounds include (a) an epoxide, (b) a melamine compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and a fluorenyloxymethyl group, and three a polycyanodiamine compound, a glycoluril compound or a urea compound, (c) a phenol compound, a naphthol compound or a oxindole substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and a fluorenyloxymethyl group Compound. Among them, a polyfunctional epoxide which is particularly useful as the thermosetting compound is particularly preferable.

The total content of the thermosetting compound in the colored thermosetting composition varies depending on the substrate, and is preferably from 0.1 to 50% by mass based on the total solid content (mass) of the curable composition. It is preferably from 0.2 to 40% by mass, particularly preferably from 1 to 35% by mass.

- Various additives -

In the colored thermosetting composition of the present invention, various additives such as a binder, a hardener, a curing catalyst, a solvent, a filler, a polymer compound other than the above, a surfactant, and the like may be blended as necessary. Adhesion promoter, antioxidant, ultraviolet absorber, anti-coagulant, dispersant, and the like.

-Adhesives -

When the adhesive is added to the pigment dispersion, the amount of the pigment dispersion is large, so that alkali solubility is not necessary, and it is preferably soluble in an organic solvent.

The binder is preferably a linear organic high molecular polymer and is soluble in an organic solvent. Such a linear organic polymer is a polymer having a carboxylic acid in a side chain, and is disclosed, for example, in Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, and No. Sho. a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer disclosed in each of the publications of Japanese Patent Publication No. Sho 54-25957, JP-A-59-53836, and JP-A-59-71048. A maleic acid copolymer, a partially esterified maleic acid copolymer or the like, and an acid cellulose derivative having a carboxylic acid in a side chain are also useful.

From the viewpoint of heat resistance, among these various adhesives, polyhydroxystyrene resin, polyoxyalkylene resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

The acrylic resin is a copolymer of a selected monomer such as benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate or (meth)acrylamide, for example, Preferred are copolymers such as benzyl methacrylate/methacrylic acid, benzyl methacrylate/benzylmethacrylamide, KS Resistor-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (Daisel Chemical Industry Co., Ltd.) and so on.

By dispersing the coloring agent at a high concentration in the adhesive or the like, adhesion to the lower layer or the like can be imparted, and these adhesives also contribute to the coating surface shape at the time of spin coating or slit coating.

~ hardener ~

In the case where an epoxy resin is used as the thermosetting compound, a hardener is preferably added. Since the type of hardener of epoxy resin is extremely large, the properties, the time of use of the mixture of the resin and the hardener, the viscosity, the hardening temperature, the hardening time, the heat dissipation, etc. vary greatly depending on the type of hardener used, and have to be An appropriate curing agent is selected for the purpose of use of the cured film, the conditions of use, the working conditions, and the like. The hardener is explained in detail in Chapter 5 of "Epoxy Resin (Japan Shengshengtang)" edited by Yukihiro. When the example of the hardening touch is listed, it becomes as follows:

Examples of the catalytic action include a third amine and a boron trifluoride-amine complex; and a stoichiometric reaction with a functional group of the epoxy resin: a polyamine, an acid anhydride, etc.; Examples of the room temperature hardening include diethylenetriamine and polyamidamine resins; examples of the intermediate temperature hardening include diethylaminopropylamine and tris(dimethylaminomethyl)phenol; examples of high temperature hardening are exemplified. : phthalic anhydride, m-phenylenediamine, and the like. Further, when viewed according to the chemical structure type, examples of the aliphatic polyamine in the amines include diethylenetriamine; the aromatic polyamines may be m-phenylenediamine; and the third amines may be exemplified by tris(dimethylamine). Examples of the acid anhydride include phthalic anhydride, polyamine resin, polysulfide resin, and boron trifluoride-monoethylamine complex; and synthetic resin initial condensates include phenol resin and other two Cyanamide and the like.

These hardeners are those which are reacted with an epoxy group by heating to be polymerized, and the crosslinking density is increased to be hardened. In order to reduce the thickness of the adhesive, the curing agent and the curing agent are preferably in a very small amount. In particular, the hardening agent is preferably 35 mass% or less, more preferably 30 mass% or less, and still more preferably 25 or less. Below mass%.

~ Hardening catalyst ~

In the present invention, in order to achieve a high concentration of the coloring agent, in addition to hardening due to the reaction with the curing agent, hardening by the reaction of the main epoxy groups with each other is effective. Therefore, it is also possible to use a hardening catalyst without using a hardener. The amount of the hardening catalyst added is about 1/10 to 1/1000, preferably about 1/20 to 1/500, based on the mass of the epoxy resin having an epoxy equivalent of about 150 to 200. Further, it is more preferably about 1/30 to 1/250 of a small amount to harden.

~ Solvent ~

The colored thermosetting composition of the present invention can be used as a solution which is dissolved in various solvents. The respective solvents of the colored thermosetting composition which can be used in the present invention are not particularly limited as long as they satisfy the solubility of each component or the coatability of the coloring curable composition. For example, the above-mentioned organic solvent used at the time of forming a metal oxide layer is mentioned.

~Dispersant~

The dispersant can be added to increase the dispersibility of the pigment. The dispersant can be used by appropriately selecting a conventional dispersant, and examples thereof include a cationic surfactant, a fluorine-based surfactant, and a polymer dispersant.

For the dispersing agent, a plurality of compounds can be used, and examples thereof include a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Efka)), SOLSPERS 5000 (manufactured by Lubrizol Co., Ltd.), and an organic siloxane polymer KP341 (Japan). Shin-Etsu Chemical Co., Ltd., (meth)acrylic (co)polymer POLYFLOW No. 75, No. 90, No. 95 (Japan Kyoritsu Chemical Co., Ltd.), W001 (Japan Yushang ( Cationic surfactants, etc.; polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, polyethylene oxide octyl phenyl a nonionic surfactant such as ether, polyethylene oxide nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, Anionic surfactants such as W005 and W017 (made by Yusei Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer-100, EFKA polymer-400, EFKA polymer-401, Polymer dispersant such as EFKA Polymer-450 (above Japan Morishita Industrial Co., Ltd.), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 (Sannopco) ; SOLSPERS 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various SOLSPERS dispersants (made by Lubrizol, Japan); ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by Nippon Seiko Co., Ltd.) and ISONET S-20 (made by Japan Sanyo Chemical Co., Ltd.).

These dispersing agents may be used singly or in combination of two or more. In general, the amount of the coloring thermosetting composition in the present invention of the dispersing agent is preferably from 0.1 to 50 parts by mass based on 100 parts by mass of the pigment.

~Other additives~

In the non-photosensitive color thermosetting composition of the present invention, various additives can be further added as necessary. Specific examples of the various additives include, for example, various additives disclosed in the above-mentioned JP-A-2005-326453.

In the coloring layer 18 of the present invention, for example, the colored thermosetting composition described above can be applied onto the metal oxide layer 16 of the carrier 12 and dried. Specifically, for example, a coloring thermosetting composition of the present invention containing a solvent is applied onto the metal oxide layer 16 of the carrier 12 by a coating method such as spin coating, slit coating, cast coating, or roll coating. The color layer 18 is formed.

The thickness of the colored layer 18 is preferably from 0.005 μm to 0.9 μm, more preferably from 0.05 μm to 0.8 μm, still more preferably from 0.1 μm to 0.7 μm, from the viewpoint of functioning as a color light-emitting sheet and thinning.

Preferably, the color layer forming step in the present invention further comprises a heating step (which may also be a post-baking step). Specifically, the colored thermosetting composition can be applied onto the metal oxide layer 16 provided on the carrier 12 to form a coating film, and then the coating film can be thermally cured to form the coloring layer 18 via a heating step. This heating step may be carried out simultaneously with the drying after coating, or may be provided with a thermal hardening step of another route after coating drying. The heating step is a conventional heating means such as an oven or a hot plate, preferably 130 ° C to 300 ° C, more preferably 150 ° C to 280 ° C, and particularly preferably 170 ° C to 260 ° C. It is more preferably from 30 seconds to 3 hours, more preferably from 30 seconds to 2 hours, and particularly preferably in the range of about 60 seconds to 60 minutes. However, when considering productivity, the time required for hardening is as short as possible.

[dry etching step]

Next, a portion of the colored layer 18 is removed by dry etching to form a colored calender. Specifically, dry etching is performed by using the photoresist layer as a mask, and the exposed portion of the colored layer 18 is removed, and the colored layer 18 can be processed into a desired shape (for example, a rectangular shape).

Forming a photoresist layer

As described above, after the metal oxide layer 16 and the coloring layer 18 are sequentially laminated on the carrier 12, a photoresist layer (photosensitive resin layer) 26 is formed on the colored layer 18. Specifically, a positive or negative photosensitive resin composition is applied onto the colored layer 18 and dried to form a photoresist layer 26. In the formation of the photoresist layer 26, it is more preferable to perform a prebaking treatment.

For the positive or negative photosensitive resin composition, for example, in the present invention, the items disclosed in paragraphs 0112 to 0117 of JP-A-2007-11324 are suitably employed.

The positive photosensitive resin composition can be used in a positive type suitable for radiation sensing of ultraviolet rays, electron beams, ion beams, X-rays, and the like containing ultraviolet rays (g-line, i-line), excimer/laser, and the like. A positive resist composition for photoresists. Among the radiations, as the radiation for exposing the photosensitive resin composition layer, a g-line or an i-line is preferable, and among them, i-line exposure is more preferable.

The coating method of the photosensitive resin composition can be suitably carried out by the above-described coating method, that is, spin coating, slit coating, cast coating, roll coating, or the like. Further, the thickness of the photoresist layer 26 is preferably from 0.01 μm to 3 μm, more preferably from 0.1 μm to 2.5 μm, further preferably from the viewpoint of functioning as a mask for dry etching and easy removal after dry etching. It is 0.15 μm to 2 μm.

- Image formation (patterning) -

The photoresist layer 26 is removed by a pattern to form an image on the colored layer 18. Here, the colored layer 18 may be a layer composed of a single colored layer, or may be a layer composed of two or more colored layers.

For example, in the case where the second colored layer 20 different from the colored layer (first colored layer) 18 formed on the metal oxide layer 16 is formed, the first colored layer is formed in the region where the second colored layer 20 is formed. 18 is removed to remove portions of the photoresist layer 26 (Fig. 2A). In this case, it is possible to correspond to a desired pattern, for example, to expose the photoresist layer 26 in a pattern corresponding to the region where the second colored layer 20 is formed on the metal oxide layer 16, and develop it by developing with a developing liquid. A mask for etching (pattern image).

The exposure of the photoresist layer 26 can be positive or negative by using a gutter pattern of a predetermined (pattern pattern) by using a g-line, an h-line, an i-line, or the like, preferably an i-line. The resin composition is exposed to light.

The developing solution does not affect the coloring layer 18 containing the coloring agent, and any type of display can be used as long as it dissolves the exposure portion of the positive photoresist and the uncured portion of the negative photoresist. Like liquid. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used.

Through such an image forming step, as shown in FIG. 2A, a portion of the surface of the first colored layer 18 (the surface opposite to the side to which the metal oxide layer 16 is joined) is exposed on the pattern. In the first colored layer 18, a portion other than the region where the second colored layer 20 is formed on the metal oxide layer 16 is in a state of being covered by the photoresist layer 26.

By using the photoresist layer 26 as a photomask, the second colored layer 20 is formed on the metal oxide layer 16, and another pixel can be formed in addition to the pixel formed by the first colored layer 18. The photoresist layer 26 to be a photomask may be made finer, and since it has a rectangular shape, each pixel of the color filter manufactured by the method of the present invention can be formed finely and rectangularly.

- dry etching -

Next, the exposed portion of the first colored layer 18 is removed by dry etching using a fluorine-based gas, and the metal oxide layer 16 is exposed to a pattern corresponding to the region where the second colored layer 20 is formed (Fig. 2B) ). That is, among the coloring layer 18 formed on the metal oxide layer 16, the region not covered by the photoresist layer 26 is removed by dry etching, and corresponds only to the position of the region where the second colored layer 20 is formed. The metal oxide layer 16 is exposed. At this time, the metal oxide layer 16 interposed between the carrier 12 and the coloring layer 18 is responsible for automatically stopping the etching, and the reduction of the carrier 12 is effectively suppressed.

In order to form a rectangular shape of a color filter, an anisotropic etching is sought, and in particular, a fluorine-based gas can be used. Although the fluorine-based gas can be a conventional fluorine-based gas, a gas of a fluorine-based compound represented by the following formula (I) is preferred:

C _n H _m F _l (I)

[In the formula, n represents 1 to 6, m represents 0 to 13, and 1 represents 1 to 14. ]

Examples of the fluorine-based gas represented by the formula (I) include CF ₄ , C ₂ F ₆ , C ₃ F ₃ , C ₂ F ₄ , C ₄ F ₈ , C ₄ F ₆ , and C ₅ F _{8 .} At least one of the group of CHF ₃ is formed. The fluorine-based gas in the present invention can be used by selecting one type of gas from the group, or can be used by combining two or more kinds of gases.

The fluorine-based gas in the present invention is preferably at least one selected from the group consisting of CF ₄ , C ₂ F ₆ , C ₄ F ₈ and CHF ₃ , more preferably CF, from the viewpoint of maintaining the squareness of the portion to be etched. ₄ and / or C ₂ F ₆ , especially CF _{4 is} particularly desirable.

The etching rate of the fluorine-based gas of the metal oxide layer 16 is usually from 1 to 10 nm/min.

The dry etching conditions using a fluorine-based gas can employ, for example, the following conditions:

Gas: CF ₄ flow rate 100~300sccm

O ₂ flow 10~100sccm

Output: 300 ~ 600W

Pressure: 1 ~ 4Pa

The dry etching apparatus (manufactured by Hitachi High Technologies Co., Ltd.) can accelerate the radical reaction and increase the etching rate by mixing the fluorine-based gas and oxygen. The ratio of the fluorine-based gas to the oxygen (fluorine-based gas/oxygen) is preferably 2/1 to 8/1 in terms of the flow ratio. By setting it as this range, it is possible to prevent the adhesion of the etching product to the side wall of the photoresist layer during the etching process, and the peeling of the photoresist layer 26 in the photoresist layer removing step to be described later becomes easily. Among them, the ratio of the fluorine-based gas to the oxygen gas is preferably from 2/1 to 6/1, in view of maintaining the squareness of the portion to be etched and also preventing re-adhesion toward the side surface of the photoresist of the etching product. 3/1 to 5/1 is especially ideal.

From the viewpoint of maintaining the partial pressure of the etching plasma to control the stability and the perpendicularity of the shape to be etched, in addition to the fluorine-based gas and oxygen, the mixed gas of the fluorine-based gas and the oxygen preferably further contains other gases, at least a halogen-based gas of a rare gas such as helium (He), neon (Ne), argon (Ar), krypton (Kr) or xenon (Xe), a chlorine atom, a fluorine atom or a halogen atom of a bromine atom (for example, CCl ₄ At least one selected from the group consisting of CClF ₃ , AlF ₃ , AlCl _{3 ,} etc., N ₂ , CO, and CO ₂ , more preferably selected from the group consisting of Ar, He, Kr, N ₂ and Xe At least one, further preferably, contains at least one selected from the group consisting of He, Ar, and Xe.

However, it is possible to maintain the partial pressure control stability of the etching plasma and the perpendicularity of the shape to be etched, and a mixed gas containing only a fluorine-based gas and oxygen may be used.

In addition to the fluorine-based gas and the oxygen gas, the content of the gas which can be contained is preferably 25 or less, more preferably 10 or more and 20 or less, and particularly preferably 14 or more and 18 or less. .

In the etching step in the present invention, it is preferred to use the following method to determine the etching processing time in advance:

1) Calculate the etching rate (nm/min.) in the etching step.

2) The etching time is used to calculate the processing time required for etching the desired thickness by the etching rate calculated as described above.

This etching rate can be calculated by taking the relationship between the etching time and the residual film. In addition, the dry etching processing time can also be controlled via the end point detection.

The etching treatment time in the present invention is preferably performed by etching within 10 minutes, more preferably within 7 minutes. Further, since the metal oxide layer 16 functions to stop the etching, in order to remove the exposed portion of the colored layer 18, dry etching can be performed slightly more than the etching treatment time calculated as described above, and damage of the carrier 12 can be prevented.

The internal pressure of the etching step chamber in the present invention is preferably from 2.0 to 6.0 Pa, more preferably from 4.0 to 5.0 Pa. When the internal pressure of the cavity is within this range, the rectangularity of the pattern can be improved, and by-products generated by etching can be prevented from adhering to the photoresist layer 26.

For example, the internal pressure of the chamber can be adjusted by appropriately controlling the flow rate of the etching gas and the degree of pressure reduction of the chamber.

In the etching step in the present invention, the temperature of the carrier 12 is preferably 30 ° C or more and 100 ° C or less. Thereby, it is possible to further control the adhesion of the etching by-products toward the side wall of the photoresist layer during the etching process, and it is possible to facilitate the peeling of the photoresist layer 26 in the photoresist layer removing step to be described later. Among them, the carrier temperature is preferably from 30 ° C to 80 ° C, especially from 40 ° C to 60 ° C, especially from the viewpoint of maintaining the squareness of the portion to be etched and suppressing the reattachment of the etching by-product toward the sidewall of the photoresist layer. .

In the etching step, for example, by controlling the temperature of the wafer stage to 30° C. or higher and 100° C. or lower, the temperature of the carrier 12 can be 30° C. or higher and 100° C. or lower.

The dry etching conditions in the etching step differ depending on the material of the colored layer, the layer thickness, and the like. Hereinafter, preferred conditions other than the above conditions will be described:

1) The gas flow rate is preferably 1500 mL/min (0 ° C, 1013 hPa) or less, more preferably 500 to 1000 mL/min (0 ° C, 1013 hPa).

2) The high frequency system can be selected from 400 kHz, 60 MHz, 13.56 MHz, 2.45 GHz, etc., and can be processed with an RF power of 50 to 2000 W, preferably 100 to 1000 W.

3) The relationship between source power (RF) and bias voltage, RF power / antenna bias / substrate bias (wafer bias) are preferably 600 ~ 1000W / 300 ~ 500W / 150 ~ 250W, more preferably 700 ~900W/350~450W/200W.

The etching step in the present invention preferably includes an overetching treatment step. By performing the over-etching treatment step, the etching residue can be effectively removed in a state where the pattern rectangularity is directly maintained, and the occurrence of damage of the carrier 12 can be more effectively suppressed according to the presence of the metal oxide layer 16.

This overetching treatment is the same as the etching step, and a mixed gas of a fluorine-based gas and oxygen can be used.

The overetching process preferably sets the overetching time. Although the over-etching time can be arbitrarily set, it is preferable to remove 30% or less of the total processing time of the dry etching treatment of the colored layer 18 from the viewpoint of maintaining the etching resistance of the photoresist and the rectangularity of the etched pattern, and more preferably 5 ~ 25%, especially 15 to 20% is particularly desirable.

- removal of the photoresist layer -

After dry etching, the remaining photoresist layer 26 is removed via a dedicated stripper or solvent.

The removal of the photoresist layer 26 preferably includes a step of imparting a stripping liquid or a solvent on the photoresist layer 26 to make it possible to remove the photoresist layer 26; and using a washing water to remove the photoresist. The step of layer 26.

The step of removing the liquid or solvent from the photoresist layer 26 is possible, and for example, a blistering method in which at least a stripping solution or a solvent is applied to the photoresist layer 26 and stagnated for a predetermined period of time is exemplified. Like steps. The time for stopping the stripping solution or the solvent is not particularly limited, and is preferably from several tens of seconds to several minutes.

Further, the step of using the washing water to remove the photoresist layer 26 may, for example, be a step of spraying the washing water onto the photoresist layer 26 from the spray type or spray nozzle to remove the photoresist layer 26. .

The washing water is preferably capable of using pure water.

Further, the injection nozzle may be exemplified by an injection nozzle including the entire carrier within its injection range, or a movable injection nozzle whose movable range includes the injection nozzle of the entire carrier. In the case where the ejection nozzle is movable, the photoresist layer 26 can be more efficiently removed by moving the cleaning water twice or more from the center portion of the carrier to the end portion of the carrier in the step of removing the photoresist layer 26. .

The stripping liquid generally contains an organic solvent, and may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether or an acetal-based compound, 5) a ketone or an aldehyde-based compound, and 6) an ester-based compound. 7) a polyol compound, 8) a carboxylic acid or an anhydride thereof, 9) a phenol compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound.

The stripping liquid in the present invention preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine can be mentioned. And diethanolamine, triethanolamine, etc., preferably monoethanolamine, diethanolamine, triethanolamine, more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH).

Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α-methylpyridine. , β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperidine , piperidine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-dimethylpyridine, 2,6-lutidine, etc.; preferably N-A Further, 2-pyrrolidone, N-ethylmorpholine; more preferably N-methyl-2-pyrrolidone (NMP).

The stripping liquid in the present invention preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and more preferably, the acyclic nitrogen-containing compound is selected from at least one of ethanolamine, diethanolamine and triethanolamine. A cyclic nitrogen-containing compound is at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethylmorpholine; further preferably, it contains monoethanolamine and N-methyl-2-pyrrolidone.

The content of the acyclic nitrogen-containing compound is preferably 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the peeling liquid, and the content of the cyclic nitrogen-containing compound is 65 parts by mass or more and 70 parts by mass or less.

Further, the stripping liquid in the present invention is preferably a stripping solution in which pure water is used to dilute a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound.

In the photoresist removing step in the present invention, it is preferable to remove the photoresist layer 26 formed on the colored layer 18 even in the case where deposits of etching products are adhered to the sidewalls of the colored layer 18, Deposits may also not be completely removed. Here, the deposit means that the etching product adheres to and deposits on the side wall of the colored layer 18.

- formation of other colored layers -

In the method of manufacturing the color filter of the present invention, after the photoresist layer 26 is removed, a portion in which the colored layer 18 and the metal oxide layer 16 are exposed on the pattern is formed on the carrier 12 as described above. . Next, as shown in FIG. 2C, the exposed portion of the metal oxide layer 16 is formed by forming a coloring layer 20 different from the coloring layer 18 formed on the metal oxide layer 16, for example, capable of producing two colors. The color filters 28 of the colored layers 18, 20. For example, by using the colored curable composition for forming the colored layer 20, the entire surface is cured by the same method as the formation of the colored layer 18, and then dry etching, polishing, or the like is performed to expose the colored layer 18 again. Thereby, the two coloring layers 18 and 20 are alternately formed in the plane of the substrate 12.

Furthermore, the different pattern patterns are used, from the photoresist layer forming step to the photoresist layer removing step, in this order, and then, a new color is formed by the exposed portion of the metal oxide layer 16. Layers, for example, can also produce 3-color color filters.

- formation of planarization layer and microlens -

In the case of manufacturing the solid-state imaging device 10 as shown in FIG. 1, after the color light-emitting sheet is patterned, the planarization layer 22 is formed on the coloring layers 18, 20 of the color light-emitting sheet by a conventional method. Further, a microlens 24 is formed thereon. Further, the planarizing layer 22 can be formed by spin coating using a transparent resin such as an acrylic, epoxy or polyimide. Further, the microlens 24 can be formed by spin coating and reflow treatment using an acrylic resin, a phenol resin or the like. Thereby, the solid-state imaging device 10 having the structure shown in Fig. 1 can be produced.

According to the method as described above, it is possible to provide a color calender sheet 28 and a solid-state imaging device 10 having the same. The reduction of the base of the color calender sheet is suppressed, and the film thickness uniformity is high, and the color reproducibility is good.

[Examples]

Hereinafter, the examples and comparative examples of the present invention will be described, but the present invention is not limited by the examples.

<Example 1>

- Metal oxide layer formation step -

A titanium oxide precursor polymer (manufactured by Rasa Industries Co., Ltd., trade name: TI-44) was dissolved in butyl acetate using a spin coater (manufactured by Tokyo Dentsu Co., Ltd., Mark 8) to prepare a solution of 5% solid solution. The film was dropped onto a silicon wafer, coated at a number of revolutions of 2000 rpm, and baked at 200 ° C for 10 minutes to form a metal oxide layer having a film thickness of 0.1 μm.

- Colored layer forming step -

The SG-5000L (manufactured by Fujifilm Electronic Materials Co., Ltd.) was used to prepare a thermosetting composition (coloring thermosetting composition) containing a pigment, and a film thickness was obtained by a spin coater (manufactured by Tokyo Electronics Co., Ltd., Mark 8). It was applied to the metal oxide layer as a coating film of 0.8 μm. Next, heating was performed at 220 ° C for 5 minutes using a hot plate to cure the coating film to form a colored layer. The thickness of the coloring layer formed through the pigment-containing thermosetting composition was 0.6 μm.

- photoresist layer forming step -

Then, a positive photoresist (FHi622BC) (manufactured by Fujifilm Electronic Materials Co., Ltd.) was applied to a coloring layer formed by using the SG-5000L by a spin coater (manufactured by Tokyo Electronics Co., Ltd., Mark 8). The photoresist layer was formed by heat treatment at ° C for 2 minutes to a thickness of 0.8 μm.

- Image formation (patterning) steps -

Using an i-line stepper (manufactured by Canon Inc., FPA3000i5+), pattern exposure of 250 mJ/cm ² corresponding to the area of the RED filter array was performed, and after heat treatment at 110 ° C for 1 minute, the developing liquid "FHD- 5" (made by Fujifilm Electronic Materials Co., Ltd.) to perform development processing for 1 minute. Thereafter, a baking treatment was performed at 120 ° C for 2 minutes to remove the photoresist layer of the region where the RED filter array should be formed, and a sea-island pattern of a size of 1.5 μm × 1.5 μm was formed.

- dry etching step -

Next, using a dry etching apparatus (U621, manufactured by Hitachi High Technologies, Japan), RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the cavity: 4.0 Pa, substrate temperature: 50 ° C, The gas source and flow rate of the mixed gas were set to CF ₄ : 200 mL/min, Oo ₂ : 50 mL/min, and Ar: 800 mL/min to carry out an etching treatment for 117 seconds. Further over-etching treatment is performed by etching treatment using this etching condition for a total etching time of 20% for 23 seconds.

- photoresist layer removal step -

Next, a photoresist stripping liquid "MS-230C" (manufactured by Fujifilm Electronic Materials Co., Ltd.) was used to carry out a peeling treatment for 120 seconds to remove the photoresist.

In the above manner, a color filter pattern is formed to produce a monochrome color filter.

<Example 2>

In the metal oxide layer forming step of the first embodiment, a titanium oxide precursor polymer (trade name: SYM-Ti05) manufactured by High Purity Chemical Research Co., Ltd. was used using a spin coater (manufactured by Tokyo Electronics Co., Ltd., Mark 8). Dissolved in butyl acetate, and then dropped 2 ml of a solution having a solid content of 4% onto a silicon wafer, coated at a number of revolutions of 1,700 rpm, and baked at 200 ° C for 10 minutes to form a metal oxide layer having a film thickness of 0.1 μm. .

The conditions of the other steps were carried out in the same manner as in Example 1 to form a monochromatic color filter.

Metal oxide layer: contains titanium oxide.

Etching conditions

Dry etching device (manufactured by Hitachi High Technologies, U621, Japan).

RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the cavity: 4.0 Pa, substrate temperature: 50 °C.

Gas source and flow rate of mixed gas:

CF ₄ : 200 mL/min, O ₂ : 50 mL/min, Ar: 800 mL/min.

<Example 3>

In the metal oxide layer forming step of the first embodiment, a titanium oxide precursor polymer (trade name: SYM-ZrO ₂ ) manufactured by High Purity Chemical Research Co., Ltd. was used using a spin coater (manufactured by Tokyo Electronics Co., Ltd., Mark 8). The solid solution formed a 1.6% solution. 2 ml was dropped onto a ruthenium wafer, coated at a number of revolutions of 3,500 rpm, and baked at 200 ° C for 10 minutes to form a metal oxide layer having a film thickness of 0.1 μm.

The conditions of the other steps were carried out in the same manner as in Example 1 to form a monochromatic color filter.

Metal oxide layer: contains zinc oxide.

Etching conditions

Dry etching device (manufactured by Hitachi High Technologies, U621, Japan).

RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the cavity: 4.0 Pa, substrate temperature: 50 °C.

Gas source and flow rate of mixed gas:

CF ₄ : 200 mL/min, O ₂ : 50 mL/min, Ar: 800 mL/min.

<Example 4>

In the metal oxide layer forming step of the first embodiment, a zirconia precursor polymer (trade name: SYM-ZN20) manufactured by High Purity Chemical Research Co., Ltd. was used using a spin coater (manufactured by Tokyo Electronics Co., Ltd., Mark 8). 2 ml of a solution having a solid content of 2.2% was dropped onto a ruthenium wafer, coated at a number of revolutions of 3000 rpm, and baked at 200 ° C for 10 minutes to form a metal oxide layer having a film thickness of 0.1 μm.

The conditions of the other steps were carried out in the same manner as in Example 1 to form a monochromatic color filter.

Metal oxide layer: contains zirconia.

Etching conditions

Dry etching device (manufactured by Hitachi High Technologies, U621, Japan).

RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the cavity: 4.0 Pa, substrate temperature: 50 °C.

Gas source and flow rate of mixed gas:

CF ₄ : 200 mL/min, O ₂ : 50 mL/min, Ar: 800 mL/min.

<Example 5>

In the metal oxide layer forming step of the first embodiment, butyl acetate was added to a cerium oxide precursor polymer manufactured by High Purity Chemical Research Co., Ltd. using a spin coater (manufactured by Tokyo Electronics Co., Ltd., Mark 8). Name: SYM-TA05) The solid content of 10.6% of the solution was adjusted to 5% of the solid content, 2 ml was dropped onto the wafer, coated at 2000 rpm, and baked at 200 ° C for 10 minutes to form a film thickness of 0.1 μm. a metal oxide layer.

The conditions of the other steps were carried out in the same manner as in Example 1 to form a monochromatic color filter.

Metal oxide layer (base layer): contains cerium oxide.

Etching conditions

Dry etching device (manufactured by Hitachi High Technologies, U621, Japan).

RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the cavity: 4.0 Pa, substrate temperature: 50 °C.

Gas source and flow rate of mixed gas:

CF ₄ : 200 mL/min, O ₂ : 50 mL/min, Ar: 800 mL/min.

<Comparative Example 1>

In the metal oxide layer forming step of the first embodiment, a methyl oxa oxide-based SOG (trade name: T-11) manufactured by Rasa Industries Co., Ltd. was used by using a spin coater (manufactured by Tokyo Electronics Co., Ltd., Mark 8). The ruthenium wafer was coated at a number of revolutions of 2000 rpm, and baked at 200 ° C for 10 minutes to form an SiO ₂ layer having a film thickness of 0.1 μm.

The conditions of the other steps were carried out in the same manner as in Example 1 to form a monochromatic color filter.

Metal oxide layer: SiO ₂ layer.

Etching conditions

Dry etching device (manufactured by Hitachi High Technologies, U621, Japan).

RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the cavity: 4.0 Pa, substrate temperature: 50 °C.

Gas source and flow rate of mixed gas:

CF ₄ : 200 mL/min, O ₂ : 50 mL/min, Ar: 800 mL/min.

- Evaluation -

With respect to the color filters produced in Examples 1 to 5 and Comparative Example 1, the reduction of the base (metal oxide layer), the adhesion of the colored layer, and the acceptability of the peeling liquid (solvent resistance) were evaluated.

<base reduction>

With respect to the color calender sheets produced in Examples 1 to 5 and Comparative Example 1, the surface of the coloring layer and the etching region obtained by a scanning electron microscope (SEM) were observed by the surface of the coloring layer obtained by a microscope (magnification: 100 times). Surface observation (magnification 30,000 times) was evaluated. The evaluation results are shown in Table 1.

~ Evaluation criteria ~

○: Base reduction was not observed.

△: Although slight reduction was observed, it was practically acceptable.

×: The reduction of the base was observed, which exceeded the practical range.

<adhesion>

The color calender sheets produced in Examples 1 to 5 and Comparative Example 1 were evaluated by surface observation (magnification: 100 times) of a coloring layer obtained by a microscope, and a checkerboard tape peeling test. The evaluation is based on the following benchmarks. The evaluation results are shown in Table 1.

~ Evaluation criteria ~

○: The adhesion was good.

△: Although some slight peeling was observed, it was practically acceptable.

×: Peeling was observed, which exceeded the practical range.

<Resistance (resistance of solvent) of the stripper removed by the photoresist layer>

The color filters produced in Examples 1 to 5 and Comparative Example 1 were evaluated by the surface loss of the coloring layer obtained by the microscope (magnification: 100 times) and the film loss by a stylus film thickness meter. The stripping solution was a photoresist stripping solution "MS-230C". The evaluation is based on the following benchmarks. The evaluation results are shown in Table 1.

~ Evaluation criteria ~

○: Insoluble in a solvent.

△: Although some slight dissolution was observed, it was practically acceptable.

X: dissolved in a solvent, the film was reduced, and exceeded the practical range.

As a result of the results shown in Table 1, the adhesion and solvent resistance of the colored layers of Examples 1 to 5 and Comparative Example 1 were within the practically acceptable range. In Comparative Example 1, the reduction of the substrate was observed, and for the excess amount, In the examples, in Examples 1 to 5, the reduction of the substrate was not observed.

10. . . Solid state camera

12. . . Carrier

14. . . Light-emitting diode

16. . . Metal oxide layer

18. . . Colored layer

20. . . Colored layer

twenty two. . . Flattening layer

twenty four. . . Microlens

26. . . Photoresist layer

28. . . Color filter

30. . . Conventional solid-state imaging device

32. . . Height difference

Fig. 1 is a schematic view showing an example of the structure of a solid-state imaging device including a color light-receiving sheet according to the present invention.

Fig. 2A is a view showing a step of manufacturing a color calender sheet of the present invention (a state after patterning).

Fig. 2B is a view showing a step of manufacturing a color filter of the present invention (a state after dry etching).

Fig. 2C is a view showing a step of manufacturing a color calender sheet of the present invention (a state in which a second coloring layer is formed).

Fig. 3 is a schematic view showing an example of a conventional solid-state imaging device manufactured by dry etching.

Fig. 4A is a view showing a conventional step (state after patterning) of a color filter by dry etching.

Fig. 4B is a view showing a conventional step (state after dry etching) for producing a color filter by dry etching.

Fig. 4C is a view showing a conventional step of producing a color filter by dry etching (a state in which a second colored layer is formed).

10. . . Solid state camera

12. . . Carrier

14. . . Light-emitting diode

16. . . Metal oxide layer

18. . . Colored layer

20. . . Colored layer

twenty two. . . Flattening layer

twenty four. . . Microlens

Claims (12)

A color filter characterized in that a layer of a metal oxide containing an oxide of at least one metal selected from Ti, Ta, Zn and Zr and having an amorphous state is provided on a carrier, and the amorphous layer is contained A layer of a metal oxide is formed to form a colored layer. A color filter according to claim 1, wherein the layer containing the amorphous metal oxide has a thickness of 0.2 μm or less. A color filter according to claim 1, wherein the layer containing the amorphous metal oxide is a layer containing amorphous TiO ₂ . A color filter according to claim 2, wherein the layer containing the amorphous metal oxide is a layer containing amorphous TiO ₂ . A color filter according to claim 1, wherein the colored layer contains an organic pigment. A method of producing a color filter, comprising: forming a layer of a metal oxide containing an oxide of at least one metal selected from Ti, Ta, Zn, and Zr and being amorphous; a step of forming a colored layer on a layer containing the amorphous metal oxide; and a step of forming a pattern of a color filter by dry etching to remove a portion of the colored layer. A method of producing a color filter according to item 6 of the patent application, wherein a metal containing at least one metal selected from Ti, Ta, Zn and Zr is used. The composition of the precursor polymer and the solvent obtained from the alkoxide is formed by a sol-gel method to form a layer containing the amorphous metal oxide. A method of producing a color filter according to claim 6, wherein the layer containing the amorphous metal oxide is a layer containing amorphous TiO ₂ . A solid-state imaging device characterized by having a color filter as in the first aspect of the patent application. A solid-state imaging device characterized by having a color filter as in the second aspect of the patent application. A solid-state imaging device characterized by having a color filter as in item 3 of the patent application. A solid-state imaging device characterized by having a color filter as in item 4 of the patent application.