JP2006301101A - Light-shielding/antireflection multilayer film, method for forming the same, solid-state imaging element having the same, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light-shielding/antireflection multilayer film which has satisfactory linearity of a film edge and is excellent in weatherability, to provide a solid-state imaging element which can reduce occurrence of spurious signals caused by stray light and is free from color defect, and to provide a simplified manufacturing method of the solid-state imaging element. <P>SOLUTION: The light-shielding/antireflection multilayer film is made by laminating: a light-shielding film comprising a metal thin film or a metal compound thin film; and an antireflection film directly formed on the light-shielding film, wherein the antireflection film contains a black coloring agent having an average primary particle size of 30 nm or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection laminated film used for a solid-state imaging device such as a CCD or CMOS, a method for forming the same, a solid-state imaging device having the same, and a method for manufacturing the same.

The metal light-shielding film on the charge transfer electrode used in conventional solid-state imaging devices reflects incident light, so halation occurs in the photolithography process of the color filter and microlens that are formed in the subsequent process, and the formed color This was a cause of deteriorating the shape of filters, microlenses and the like.
This also affects the performance as a solid-state imaging device, and the reflected light from the metal light-shielding film is further reflected at the interface in the device and should not be incident as stray light (light receiving sensor) Part), which is a factor that generates false signals.

Currently, in order to prevent the generation of reflected light from the metal light shielding film, an antireflection film is provided immediately above the metal light shielding film or between the pixels of the color filter to prevent the generation of reflected light.
As such a technique, it has been disclosed that a black filter is provided thereon in order to reduce reflection on the light shielding film (see, for example, Patent Document 1), and the black filter layer is not formed by a staining method. It is described that a pigment dispersion type resist may be used.
However, although there is a description of a dyeing method / pigment dispersion type black filter, it is difficult to realize a high optical density and low reflectance with a thin film because the dyeing method is the main, and use a dye. Therefore, it is considered difficult to achieve high performance in terms of heat resistance and light resistance.

In addition, a technique for reducing reflection from the light shielding film by providing a colored film by a staining method on the light shielding film is disclosed (for example, see Patent Document 2).
However, the antireflection film by the dyeing method has problems in terms of heat resistance and weather resistance, and the antireflection function is not sufficient.

Furthermore, a method of forming a nitride film such as Ti as an antireflection film on an aluminum light shielding film is disclosed (for example, see Patent Documents 3 and 4).
However, this method requires many steps and is very complicated, and since a nitride film is formed on the aluminum light shielding film, a local battery can be formed during etching, and the aluminum light shielding film is easily corroded. Therefore, in order to form a light shielding film with a good shape, the number of steps further increases.
JP 7-161950 A JP-A-3-276678 JP-A-6-342896 JP-A-6-61463

An object of the present invention is to provide a light-shielding / anti-reflection laminated film having excellent film edge linearity and excellent weather resistance.
A further object of the present invention is to provide a solid-state imaging device in which the generation of false signals due to stray light is reduced, and a manufacturing method that can be simplified.

In view of the above situation, the present inventors have conducted intensive research and found that a photosensitive composition for an antireflection film in which carbon used as a resist for processing a metal light-shielding film is dispersed is used to form an antireflection film. As a result, it has been found that a multilayered film of a metal light-shielding film and an antireflection film in which carbon is dispersed can significantly reduce the number of processes when manufacturing a solid-state imaging device, and the present invention has been completed.
That is, the present invention is achieved by the following means.

  <1> A light shielding / antireflection laminated film in which a light shielding film made of a metal thin film or a metal compound thin film and an antireflection film directly formed on the light shielding film are laminated, wherein the antireflection film has an average primary particle diameter And a black colorant having a thickness of 30 nm or less.

<2> The light shielding / antireflection laminated film according to claim 1, wherein the black colorant is at least one selected from carbon black and titanium black.

<3> The above <1> or <2 wherein the antireflection film is formed by a photolithography method using a composition containing the black colorant, an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator. > The light-shielding / antireflection laminated film described in>.

<4> A metal thin film is formed on a substrate, and then a coating film of a composition containing a black colorant, an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator is formed, and pattern exposure is performed on the coating film. And forming a resist film on the metal thin film by development, and then performing an etching process to remove the metal thin film in a portion not covered with the resist film to obtain a light-shielding / antireflection laminated film. Manufacturing method of light shielding / antireflection laminated film.

<5> The light-shielding / antireflection multilayer film according to any one of <1> to <3> is formed on the transfer electrode via an insulating film, and a planarization film and a plurality of pixels are formed thereon. A solid-state imaging device comprising a color filter film, a planarizing film, and a microlens sequentially formed.

<6> The solid-state imaging device according to <5>, wherein the antireflection film has a thickness of 1 μm or less.
<7> The solid-state imaging device according to <5> or <6>, wherein a maximum diameter of the pixel is 5 μm or less.

<8> A light shielding / antireflection laminated film is formed on the transfer electrode formed on the wafer by the method described in <4> above, and then a planarizing film, a color filter film composed of a plurality of pixels, A method of manufacturing a solid-state imaging device, comprising forming a chemical film and a microlens in this order.

ADVANTAGE OF THE INVENTION According to this invention, the linearity of the edge of a film | membrane can be provided and the antireflection laminated film excellent in the weather resistance can be provided.
Furthermore, according to the present invention, it is possible to provide a solid-state imaging device that reduces the generation of false signals due to stray light and does not cause image quality degradation such as flare, and can provide a simplified method for manufacturing a solid-state imaging device.

The light shielding / antireflection laminated film of the present invention is a laminated film in which a light shielding film made of a metal thin film or a metal compound thin film and an antireflection film directly formed on the light shielding film are laminated. It contains a black colorant having an average primary particle size of 30 nm or less.
The antireflection film in the laminated film in which the antireflection film is provided on the light shielding film of the metal thin film contains a black colorant having an average primary particle diameter of 30 nm or less, thereby improving the linearity of the film edge, It can be set as the laminated film excellent in the weather resistance.
Hereinafter, the present invention will be described in detail.

≪Light-shielding / anti-reflection laminated film≫
The light shielding / antireflection laminated film of the present invention has a structure in which a light shielding film and an antireflection film are directly laminated, and the antireflection film contains a black colorant. The antireflection film can further contain other components as required.

<Black coloring>
As the black colorant that can be used in the present invention, various known black pigments and black dyes can be used. In particular, from the viewpoint of realizing a high optical density with a small amount, carbon black, titanium black, titanium oxide, oxidation Iron, manganese oxide, graphite, and the like are preferable. Among them, it is preferable to include at least one of carbon black and titanium black, and carbon black is particularly preferable.
The black colorant may be used alone or in combination of two or more.

The average particle diameter (average primary particle diameter) of the black colorant is the average primary particle diameter from the viewpoint of generating protrusions in the antireflection film pattern and affecting the yield in the production of a solid-state imaging device. Is preferably small. In order to improve the effect of the present invention, particularly the linearity of the edge of the pattern of the antireflection film, the average primary particle diameter of the black colorant needs to be 30 nm or less. Especially, in order not to generate protrusions at the edge portion, the average primary particle size (particle size) is preferably 5 to 25 nm, more preferably 5 to 20 nm, and particularly preferably 5 to 15 nm.
The content of the black colorant in the antireflection film of the present invention is not particularly limited, but is preferably as high as possible to obtain a high optical density with a thin film, preferably 1 to 90% by mass, 3-70 mass% is still more preferable, and 5-50 mass% is especially preferable.
If the amount of black colorant is too small, it is necessary to increase the film thickness in order to obtain a high optical density. If the amount of black colorant is too large, photocuring will not proceed sufficiently and the strength of the film will be reduced, or during alkali development. However, the development latitude tends to be narrow.

  As a mass ratio when a plurality of black colorants are used in combination and carbon black is used as a main component, the mass ratio with the black colorant used in combination with carbon black is preferably in the range of 95: 5 to 60:40, 95 : 5-70: 30 are more preferable, and 90: 10-80: 20 are still more preferable. The mass of the black colorant used in combination is the total mass thereof. By setting the mass ratio of the black colorant used in combination with the carbon black to be in the range of 95: 5 to 60:40, there is a tendency that the dispersion liquid is not aggregated and a stable coating film without unevenness can be produced.

  Examples of the carbon black in the present invention include carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850 manufactured by Mitsubishi Chemical Corporation. , MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Da Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP. Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2, ColorBlack Fw1, ColorBlack 170, BlackBlack, BlackBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140 And the like can be given.

  The carbon black in the present invention preferably has insulating properties. The carbon black having an insulating property is a carbon black exhibiting an insulating property when the volume resistance as a powder is measured by the following method. For example, an organic substance is adsorbed, coated, or coated on the surface of the carbon black particles. It means having an organic compound on the surface of carbon black particles, such as chemically bonded (grafted).

A coating solution is prepared by dispersing carbon black in propylene glycol monomethyl ether so that benzyl methacrylate and methacrylic acid have a molar ratio of 70:30 copolymer (mass average molecular weight 30,000) and 20:80 mass ratio. Then, it was applied on a chromium substrate having a thickness of 1.1 mm, 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm, and the coating film was further heat-treated in a hot plate at 220 ° C. for about 5 minutes. A volume resistivity value is measured in an environment of 23 ° C. and a relative humidity of 65% by applying with a high resistivity meter manufactured by Mitsubishi Chemical Corporation, conforming to JISK6911, and Hirestar UP (MCP-HT450). Carbon black having a volume resistance value of 10 ⁵ Ω · cm or more, more preferably 10 ⁶ Ω · cm or more, and particularly preferably 10 ⁷ Ω · cm or more is preferable.

  Examples of carbon black include, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, JP-A-11-80584, and JP-A-9. The resin-coated carbon black disclosed in JP-A-124969 and JP-A-9-95625 can be used.

The antireflection film in the present invention is a photo using the composition containing the black colorant, the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator (hereinafter also referred to as “composition in the present invention”). It is preferable to form by lithography. The composition generally uses a solvent, and the other components can be added as necessary.
Hereinafter, the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, the solvent, and other components will be described.

<Alkali-soluble resin>
Although the composition in this invention is not specifically limited, It is preferable to contain alkali-soluble resin.

  As the alkali-soluble resin used, conventionally known alkali-soluble resins can be used. (I) Maleic anhydride (MAA), methacrylic acid (MA), isobutyl methacrylate (IBMA), acrylic acid (AA), and At least one acid component monomer selected from fumaric acid (FA), and (ii) (meth) acrylic ester monomers such as alkyl polyoxyethylene (meth) acrylate, benzyl (meth) acrylate, and alkyl (meth) acrylate, And (iii) It is preferable from an appropriate viewpoint with respect to alkali image development to contain an acrylic copolymer with at least 1 or more types of monomers among polymerizable monomers, such as styrene.

  The molar content of the acid component monomer in the alkali-soluble resin is 5 to 50 mol%, preferably 10 to 40 mol%.

  Moreover, 1-60 mass% is preferable, as for content of the alkali-soluble resin in the composition in this invention, 3-50 mass% is more preferable, and 5-40 mass% is especially preferable. If the content of the alkali-soluble resin is less than 1% by mass, the progress of development is delayed, which may increase the production cost. On the other hand, if it exceeds 60% by mass, a good pattern profile may not be obtained.

In the composition in this invention, other alkali-soluble resin can also be used together as the alkali-soluble resin in addition to the acrylic copolymer. The alkali-soluble resin is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution.
Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer as described in JP-A Nos. 59-53836 and 59-71048, There are maleic acid copolymers, partially esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition to this, a polymer having a hydroxyl group and an acid anhydride added thereto is also useful.

  Of these, multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are particularly preferred. In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer. Moreover, in order to raise the intensity | strength of a cured film, alcohol soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) propane, and epichlorohydrin can also be contained.

  Examples of the acrylic copolymer include a multi-component copolymer of benzyl (meth) acrylate / (meth) acrylic acid / and other monomers, and 2-hydroxypropyl (meth) described in JP-A-7-140654. Acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene Macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like. The development characteristics of the composition in the present invention can be further improved by using two or more of these acrylic copolymers together.

<Photopolymerizable compound>
The composition for forming an antireflective film in the present invention contains a photopolymerizable compound in that the pattern of the antireflective film can be subjected to pattern exposure and the patterned antireflective film formed by exposure can be cured by light. Is preferred.
Next, the photopolymerizable compound used in the composition in the present invention will be described.
A general polymerizable monomer can be used as the photopolymerizable compound.
The polymerizable monomer has at least one addition-polymerizable ethylene group. A compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable, and a tetrafunctional or higher acrylate compound is more preferable.

  Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meta ) Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, Poly (meth) of pentaerythritol or dipentaerythritol after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as ri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in JP-B-49-43191 and JP-B-52-30490 To mention That. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  Further, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can also be used as photopolymerizable compounds.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and a structure in which these acryloyl groups are interposed via ethylene glycol or propylene glycol residues are preferable. These oligomer types are also used. These photopolymerizable compounds can be used alone or in combination of two or more.
The content of the photopolymerizable compound in the composition according to the present invention is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass, and particularly preferably 5 to 100% of the total solid content of the composition. -50 mass%. If the amount of the photopolymerizable compound used is too small or more than the above range, it is not preferable because curing is insufficient.

<Photopolymerization initiator>
The photopolymerization initiator in the present invention is not particularly limited as long as it can polymerize the photopolymerizable compound and the alkali-soluble resin. Conventionally known photopolymerization initiators can be used.

  Examples of the photopolymerization initiator include active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, 3-aryl-substituted coumarin compounds, and at least one lophine dimer.

  Among the active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, the halomethyloxadiazole compound is 2-halomethyl-5 represented by the following general formula IV described in JP-B-57-6096. -Vinyl-1,3,4-oxadiazole compounds are mentioned.

In general formula IV, W represents a substituted or unsubstituted aryl group, and X represents a hydrogen atom, an alkyl group, or an aryl group. Y represents a fluorine atom, a chlorine atom or a bromine atom. n represents an integer of 1 to 3.
Specific compounds of the general formula IV include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4- Examples include oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole.

  Examples of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds represented by the following general formula V described in JP-B-59-1281, and the following general formulas described in JP-A-53-133428. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by VI and 4- (p-aminophenyl) -2,6-di-halomethyl represented by the following general formula VII -S-triazine compound is mentioned.

In general formula V, Q represents Br or Cl. P is, -CQ ₃ (Q is as defined _{above), - NH 2, -NHR,} -N (R) 2, or -OR (wherein, R represents a phenyl or alkyl group). n represents an integer of 0 to 3. W represents an aromatic group which may be substituted, a heterocyclic group which may be substituted, or a monovalent group represented by the following general formula VA.

  In the general formula VA, Z is —O— or —S—, and R is as defined above.

In the general formula VI, X represents Br or Cl. m and n are integers of 0-3.
R ′ represents a group represented by the following general formula VIA.

In the general formula VIA, R ₁ represents a hydrogen atom or ORc (Rc is an alkyl, cycloalkyl, alkenyl, aryl group), and R ₂ represents a Cl, Br, alkyl, alkenyl, aryl, or alkoxy group.

In general formula VII, R ₁ and R ₂ are the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a group represented by general formula VIIA or VIIB below. R ₃ and R ₄ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y are the same or different and each represents Cl or Br. m and n are the same or different and represent 0, 1 or 2.

In the general formulas VIIA and VIIB, R ₅ , R ₆ and R _{7 each} represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group. Examples of substituents in substituted alkyl groups and substituted aryl groups include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, etc. Is mentioned.

In the general formula VII, R ₁ and R ₂ may form a heterocycle consisting of a nonmetallic atom together with the nitrogen atom bonded thereto, and in this case, examples of the heterocycle include those shown below. It is done.

  Specific examples of general formula V include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethyl). And aminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

  Specific examples of general formula VI include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [ 4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4, 6-bis-trichloromethyl-s-to Azine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy- Naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, etc. Can be mentioned.

  Specific examples of the general formula VII include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p -N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p- N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl)- -Triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro) Methyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo -PN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) Aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m- Chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro- p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s Triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o- Chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxycarbonylmethyl) amino] phenyl] -1,3,5-tri Examples include azine.

  The following sensitizers can be used in combination with these initiators. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) ) Benzophenone (or Mihira) Ketone), p- (diethylamino) benzophenone, benzoanthrone, 7- {L-4-chloro-6- (diethylamino) -S-triazinyl (2), 1-amino} -3-phenylcoumarin, etc. Examples thereof include benzothiazole compounds described in Japanese Patent No. 48516.

  Moreover, the said 3-aryl substituted coumarin compound is a compound shown, for example by the following general formula VIII.

R ₈ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group), and R ₉ represents a hydrogen atom or a carbon atom. An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula VIIIA (preferably a methyl group, an ethyl group, a propyl group, a butyl group, a group represented by the general formula VIIIA, particularly preferably Represents a group represented by the general formula VIIIA).
R ₁₀ and R ₁₁ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group), or a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group, Fluoromethyl group, trifluoromethyl group, etc.), C1-C8 alkoxy group (for example, methoxy group, ethoxy group, butoxy group), C6-C10 aryl group (for example, phenyl group) which may be substituted, amino A group, —N (R ₁₆ ) (R ₁₇ ), a halogen atom (for example, Cl, Br, F); Preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, -N (R ₁₆ ) (R ₁₇ ), and Cl.
R ₁₂ represents an optionally substituted aryl group having 6 to 16 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, cumyl group). Examples of the substituent include an amino group, —N (R ₁₆ ) (R ₁₇ ), an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), and 1 to 8 carbon atoms. Haloalkyl group (for example, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.), C1-C8 alkoxy group (for example, methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group, halogen atom (for example, Cl, Br, F).
R ₁₃ , R ₁₄ , R ₁₆ and R ₁₇ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group). R ₁₃ and R ₁₄ and R ₁₆ and R ₁₇ are bonded to each other to form a heterocyclic ring (for example, a piperidine ring, piperazine ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.) with a nitrogen atom. Also good.
R ₁₅ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group). Group), an optionally substituted aryl group having 6 to 10 carbon atoms (eg, phenyl group), amino group, N (R ₁₆ ) (R ₁₇ ), and halogen atom (eg, Cl, Br, F). Zb represents = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably, = O, = S, = C (CN) ₂ , and particularly preferably = O. R ₁₈ and R ₁₉ are the same or different and each represents a cyano group, —COOR ₂₀ , or —COR ₂₁ . R ₂₀ and R ₂₁ are each an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, A trifluoromethyl group and the like, and an optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group).

  Particularly preferred 3-aryl-substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula IX.

  Lophine dimer means 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.

  Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxy). Phenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.

In the present invention, other known compounds can be used in addition to the above initiators.
For example, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatics substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallyl disclosed in US Pat. No. 3,549,367 Combination of imidazole dimer / p-aminophenyl ketone, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Thial-s-triazine compounds are exemplified.
Further, Adeka optomer SP-150, 151, 170, 171, N-1717, N1414, etc. manufactured by Asahi Denka Co., Ltd. can be used as the polymerization initiator.

  In this invention, the usage-amount of a photoinitiator is 0.1-10.0 mass% of the total solid of the composition in this invention, Preferably it is 0.5-5.0 mass%. When the amount of the initiator used is less than 0.1% by mass, the polymerization is difficult to proceed, and when it exceeds 10.0% by mass, the film strength is weakened.

<Solvent>
In the composition in the present invention, the solvent used as necessary is appropriately selected according to the solubility, coating property, and safety of the composition.
Solvents used in preparing the composition in the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. Butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropion 3-oxypropionic acid alkyl esters such as methyl acid and ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2- Oki Methyl propionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion Ethyl acetate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones For example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xyres.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like are preferably used.

  These solvents may be used alone or in combination of two or more.

<Other ingredients>
In the composition of the present invention, for the purpose of improving the dispersibility of the colorant, or if necessary, various conventionally known additives such as fillers, polymer compounds other than the alkali-soluble resins, and surface actives other than those described above. An agent, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.

  Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group A polymer having an acid anhydride added thereto, an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; a nonionic, a kachin-based, an anionic surfactant, etc. Specifically, a phthalocyanine derivative (commercially available product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxy Ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (manufactured by BASF, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 Nonionic surfactants such as W004, W005, W017 (manufactured by Yusho) and the like; EFKA-46, EFKA-47, EFKA-47EA, EF Polymer dispersion such as A polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco) Agents: Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei);

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone;
And an aggregation inhibitor such as sodium polyacrylate.

  Further, when promoting the alkali solubility of the unirradiated part and further improving the developability of the composition in the present invention, the composition in the present invention is an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the composition of the present invention. For example, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol , T-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. Is useful.

-Method for producing composition for forming antireflection film-
The composition for forming an antireflection film in the present invention uses the black colorant (hereinafter, also simply referred to as “colorant”), the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator, and further, if necessary. The other components to be prepared can be prepared by mixing with the solvent and mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

In the kneading and dispersing step, the surface of the colorant particles of the raw material is promoted to wet with the constituent components mainly composed of the resin component of the vehicle, and the solid colorant particles and vehicle solution are solidified from the solid / gas interface between the colorant particles and air. / Convert to solution interface.
In the fine dispersion step, the colorant particles are dispersed to a fine state close to the primary particles by mixing and stirring together with a dispersion medium for fine particles of glass or ceramic.
Therefore, in the kneading and dispersing step, it is necessary to convert the interface formed by the colorant particle surface from air to a solution. Therefore, a strong shearing force and compressive force are required. desirable.
On the other hand, in the fine dispersion step, it is necessary to uniformly and evenly distribute the particles to a fine state, and a disperser that gives impact force and shear force to the agglomerated colorant particles, A relatively low viscosity is desirable.
Specifically, the uniform and stable dispersion means that projections are not generated in the antireflection multilayer film pattern for the solid-state imaging device formed on the substrate and that the antireflection effect is uniform. For this purpose, the average primary particle size (particle size) of the black colorant in the antireflection multilayer film composition is preferably in the above-mentioned range.
The average primary particle size can be measured using electron microscopy.

In the kneading and dispersing step in the production of the composition for forming an antireflection film in the present invention, for example, first, a black colorant, a dispersant or a surface treatment agent, an alkali-soluble resin, and a solvent are kneaded. The machines used for kneading are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single-screw and twin-screw extruders, etc., which disperse while giving a strong shearing force.
Next, a solvent and an alkali-soluble resin (the remainder used in the kneading step) are added, and a particle size of 0.1 to 1 mm is mainly used using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. It is finely dispersed with beads made of glass, zirconia or the like.
It is possible to omit this kneading step. In that case, beads are dispersed with a pigment and a dispersant or a surface treatment agent, an alkali-soluble resin and a solvent. In this case, the remaining alkali-soluble resin in the kneading step is preferably added during the dispersion.
For details on kneading and dispersing, see T.W. C. Also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964).

<Method for producing light-shielding / anti-reflection laminated film>
The method for producing a light shielding / antireflection laminated film of the present invention comprises forming a metal thin film on a substrate, and then coating the composition containing the black colorant, alkali-soluble resin, photopolymerizable compound and photopolymerization initiator. After forming a resist film only on the metal thin film by pattern exposure and development on the coating film, etching is performed to remove the metal thin film in a portion not covered with the resist film. Thus, a light shielding / antireflection laminated film is obtained.

Hereinafter, the light shielding / antireflection laminated film and the method for producing the same according to the present invention will be described in detail with reference to FIG. 1, but the present invention is not limited thereto.
1 (A)-(B)-(D) are cross-sectional views showing an example of a light shielding / antireflection laminated film of the present invention and a manufacturing process thereof. 1 (A)-(B)-(C)-(D) are cross-sectional views showing an example of a conventional manufacturing process.

Hereinafter, the manufacturing method of the light shielding / antireflection multilayer film 12 of the present invention will be described.
First, the transfer electrode 5 is formed on the insulating film 13 formed on the substrate (wafer) 1 (step A), and the insulating film 13 is formed again thereon, and the light shielding film is formed on the insulating film 13. A metal or metal compound thin film 6 is formed.
Next, a coating film 8 of the composition according to the present invention is formed on the metal thin film 6 as a photoresist, and pattern exposure is performed by irradiating the pattern 18 of the transfer electrode with radiation 18 such as i-line through the MAX 17 (step B above). ).
Subsequently, a development process is performed to form a resist 8, the metal thin film 6 not protected by the resist 8 is removed by etching, and the metal thin film (light-shielding film) 6 is reflected on the transfer electrode 5 via the insulating film 13. A light shielding / antireflection laminated film 12 comprising the prevention film 8 is formed (D process).

On the other hand, the conventional antireflection film is manufactured with the drawings (A)-(B)-(C)-(D).
That is, following the step B, development processing is performed to form a resist 8, the metal thin film 6 not protected by the resist 8 is removed by etching, and the insulating film 13 and the metal thin film (light-shielding film) are formed on the transfer electrode 5. ) 6 is formed, and finally the resist film 8 remaining on the insulating film is removed to form the light shielding film 6 on the wafer. Further, an antireflection film 8 is formed on the light shielding film (D process).

As described above, unlike the conventional manufacturing method, the manufacturing method of the light-shielding / antireflection laminated film of the present invention can reduce the number of manufacturing steps.
More specifically, in the process of manufacturing a conventional laminated film of a light shielding film and an antireflection film made of TiN, the following 24 steps are required.
1) Aluminum film formation, 2) TiN film formation, 3) Positive resist application, 4) Pre-bake, 5) TiN etching pattern exposure, 6) Development, 7) Rinse, 8) Post-bake, 9) Etching of TiN film, 10) Cleaning of substrate, 11) Drying, 12) Stripping positive resist with amine stripping solution, 13) Drying, 14) Applying positive resist, 15) Prebaking, 16) AL etching Pattern exposure, 17) Development, 18) Rinse, 19) Post bake, 20) Etching of aluminum film, 21) Cleaning of substrate, 22) Drying, 23) Stripping positive resist with amine stripper, 24) Drying On the other hand, the process for producing the light shielding / antireflection laminated film obtained in the present invention is greatly shortened as follows, and the process for producing a solid-state imaging device can be greatly simplified. The
1) Film formation of aluminum, 2) Application of antireflection film, 3) Pre-bake, 4) Exposure, 5) Development, 6) Rinse, 7) Post-bake, 8) Etching of aluminum film, 9) Cleaning of substrate 10) Dry

  Examples of the substrate that can be used in the present invention include a photoelectric conversion element substrate used for a solid-state imaging device, for example, a silicon substrate, an organic semiconductor substrate, and the like. A color filter that forms each pixel, such as a peripheral circuit such as a register, a signal detection unit, and a drive circuit, may be formed.

Further, the insulating film is not particularly limited, and for example, a SiN thin film can be used. A well-known thing can be used as a transfer electrode.
The light shielding film is made of a metal thin film or a metal compound thin film, and an aluminum thin film having an anodic oxide film on the surface. In particular, although not particularly limited, an aluminum-based alloy containing a refractory metal such as aluminum, Ta, Ti, Cu, Si, or Cr as a trace component can be used. Among these, an aluminum alloy thin film containing Ta and Ti as trace components and an aluminum thin film light-shielding film having an anodized film are preferable. The method for forming the light shielding film is not particularly limited, but sputtering is preferable.

  A coating method for coating and forming the antireflection film can be used without any particular limitation, and examples thereof include coating methods such as spin coating, slit coating, cast coating, and roll coating.

Although it does not specifically limit as a radiation used for this light irradiation, Although it can use, it can select a wavelength suitably based on the photoinitiator to be used.
As the radiation, it is possible to use radiation having an emission line spectrum for g-line (436 nm), h-line (405 nm), i-line (365 nm), j-line (310 nm), and the like.

The development is preferably an alkali development treatment, and the non-light-irradiated portion is eluted into the alkaline aqueous solution by the exposure, and only the photocured portion remains. As a developing solution, the photocurable film layer of the light non-irradiated part is dissolved. Any developer can be used as long as it does not dissolve the light irradiation part.
After the excess developer is removed by washing and drying, heat treatment (post-bake) can be performed at a temperature of 50 to 240 ° C. Thus, a photocuring film can be manufactured. Thereby, an antireflection film is obtained.
Since the composition for antireflective film contains a black colored material that exhibits a filler effect, the antireflective laminated film of the present invention is excellent in processability without being deformed by heat treatment after film formation, and carbon black is used. Especially when used.

  Drying (prebaking) of the composition layer according to the present invention applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds with a hot plate, oven, etc., and at a temperature of 70 to 130 ° C. 60 to 180 seconds, preferably 90 to 120 ° C. and more preferably 90 to 120 seconds.

  The coating thickness (antireflection film after drying) of the composition in the present invention is generally 2.0 μm or less, but the photoelectric conversion element formed on a substrate such as a silicon wafer accompanying the miniaturization of pixels. From the viewpoint of thinning the effective optical functional layer from the upper surface (substrate surface) to the lower surface of the on-chip microlens, it is preferably 1.0 μm or less, more preferably 0.7 μm or less, and most preferably 0.5 μm or less. By setting the thickness to 1.0 μm or less, it is easy to reduce the thickness of the optical functional layer and the size of the pixels in the solid-state imaging device.

  The reflectance of the antireflection film of the present invention is preferably 35% or less, more preferably 25 when the irradiation light is irradiated at an irradiation angle of 5 ° with a thickness of 0.5 μm and a wavelength region of 350 to 800 nm. % Or less, most preferably 20% or less.

Any developer can be used as long as it dissolves the antireflection film for a solid-state imaging device of the present invention and does not dissolve the radiation irradiated portion. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used, and among them, an alkaline developer is preferably used.
Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention. The development temperature is usually 20 ° C. to 50 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium. Concentration of an alkaline compound such as hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution dissolved so as to be% is preferably used. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with water after image development.

The post-baking is a post-development heating for complete curing, and can usually be performed at a temperature of about 200 ° C. to 220 ° C. (hard baking).
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.
In addition to the post-bake treatment, the coating film may be cured by irradiating ultraviolet rays with a high-pressure mercury lamp or the like while heating (post-cure treatment).

  An overcoat layer (flattening layer) can be provided on the color filter layer in the solid-state imaging device described later of the present invention. Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it has excellent transparency in the visible light region, and when the resin component of the photocurable composition for color filter and the resin component of the composition for antireflection film are mainly composed of acrylic resin, adhesion An acrylic resin composition is desirable from the viewpoint of superiority. In particular, a photo-curable (meth) acrylic resin for a photoresist used in a color filter is preferable because matching with the manufacturing process of the color filter is improved.

≪Solid-state imaging device≫
In the solid-state imaging device of the present invention, the antireflection laminated film is formed on the transfer electrode via an insulating film, and a planarizing film, a color filter film composed of a plurality of pixels, a planarizing film, and a microlens are formed thereon. It is characterized by being formed sequentially.
The other configuration is not particularly limited, and a conventionally known configuration can be adopted.
Although the solid-state image sensor of this invention is demonstrated using FIG. 1 below, it is not limited to this.

  FIG. 1 is a block diagram showing an example of a solid-state imaging device according to the present invention, in which a light shielding / antireflection laminated film comprising a light shielding film 6 and an antireflection film formed so as to cover the side surface of the light shielding film 6 is used. .

As shown in FIG. 1, the solid-state imaging device of the present invention has a plurality of light receiving sensor portions 2 that perform photoelectric conversion on a surface layer portion of a substrate made of a silicon substrate 1.
In addition, a vertical transfer register 3 having a CCD structure for transferring charges formed by the light receiving sensor unit 2 is provided adjacent to the light receiving sensor unit 2, and a horizontal transfer is provided at one end of the vertical transfer register 3. A register (not shown) is provided.
A signal detection unit and an output amplifier are formed at the final stage of the horizontal transfer register (not shown), and a peripheral circuit unit such as a drive circuit is formed in the peripheral unit. On the vertical transfer register 3 and the horizontal transfer register of the CCD structure, a light shielding / antireflection laminated film 12 is provided in this order so as to cover the transfer electrode 5 via an insulating film (interlayer film) 13. The light shielding film 6 is formed by a sputtering apparatus.
Further, a flattening film 7 is provided on the entire silicon substrate on which the light shielding / antireflection laminated film 12 is formed, if necessary. Usually, an insulating film 13 is formed between the planarizing film 7 and the silicon substrate 1.
The light shielding / antireflection laminated film 12 is provided with an antireflection film 8 on the light shielding film 6.

Further, a color filter 9 (illustrating three hues of R, G, and B) including a plurality of pixels is provided on the silicon substrate on which the light shielding / antireflection laminated film 12 and the planarizing film 7 are formed.
The RGB pixels are positioned so that the center of each pixel is directly above the center of the light receiving sensor unit 2, and a part of each of the two sides of each color filter pattern on the light shielding / antireflection laminated film 12 is light shielding / antireflection. It overlaps on the laminated film 12.
The maximum diameter of the rectangular unit pixel for each color of the color filter 9 is generally 1.5 to 20 μm or less, but among them, the effective use of a substrate such as a silicon wafer, the miniaturization of a device using a solid-state imaging device, among others. Is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less from the viewpoint of high speed operation of the solid-state imaging device.

  A planarizing film 10 is provided on the color filter 9. Furthermore, an on-chip microlens 11 for condensing is formed.

  The solid-state imaging device of the present invention is characterized by having the light shielding / antireflection laminated film, and the form thereof is not particularly limited, and many forms are possible.

Next, although the manufacturing method of the solid-state image sensor of this invention is demonstrated using FIG. 2, it does not specifically limit, Any well-known manufacturing method can be used. As apparent from FIG. 1, the flat film 7 is essential in the solid-state imaging device of the present invention. Other forms other than the form shown in FIG. 2 can be manufactured by the same method.
As the planarizing film, in addition to a coating film such as a resin film, various metal films such as metal films, nitride films, and oxide films, and metal compound films formed by a vacuum film forming method are used.

(Circuit part formation)
The light receiving sensor unit 2, the charge transfer unit 3, the transfer electrode 5, and peripheral circuit units (not shown) such as a signal detection unit / output amplifier / drive circuit are formed on the surface layer of the silicon substrate 1. The substrate can be produced by a conventionally known method.

(Creation of light shielding / antireflection laminated film)
The light shielding film (metal thin film) 6 (thickness is, for example, 0.01 to 1.0 μm, preferably 0.02 to 0.5 μm, directly on the entire surface of the substrate or through an interlayer film (insulating film) 13. .).

After applying the composition for forming an antireflective film obtained above by spin coating, the film thickness after heating with a hot plate at a surface temperature of 90 ° C. for 120 seconds is 0.5 μm. Adjust and apply uniformly onto the substrate on which the aluminum light-shielding film 6 is formed.
Next, the substrate coated with the composition for forming an antireflection film is heat-treated at 90 ° C. for 120 seconds with a hot plate to form a dry coating film (antireflection film).
Next, exposure is performed with an i-line stepper, FPA-3000i5 + manufactured by Canon Inc., through a mask for forming a stripe pattern having a line width of 1 μm on the aluminum light-shielding film 6, and tetramethylammonium hydroxide (TMAH). Paddle development is performed for 60 seconds at 23 ° C. using a 0.3% aqueous solution, and then rinsed with pure water for 20 seconds in a spin shower, followed by washing with pure water. Thereafter, the attached water droplets are removed by blowing air, the substrate is naturally dried, and an image pattern of the antireflection film 8 exposing the aluminum light shielding film 6 to be etched is obtained.

[Etching process]
In the present invention, the aluminum film is etched as follows by wet etching having excellent mass productivity.
First, the substrate on which the antireflection film 8 from which the aluminum film to be etched is exposed is immersed in the following etching solution for 110 seconds. After the exposed aluminum is dissolved, the etching solution is removed by washing with water and air is supplied. The water droplets are removed by spraying, and the light shielding / preventing laminated film 12 is formed in the portion covered with the antireflection film 6.

<Etching liquid composition>
80% by volume of phosphoric acid
Nitric acid 5% by volume
Acetic acid 10% by volume
Ion exchange water 5% by volume

[Formation of planarization film]
A flattening film agent (for example, COLOR MOSAIC CT-3100L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on the silicon substrate 1 on which the light shielding / antireflection laminated film 12 is formed, and then the substrate is heated using a hot plate. Heating at 220 ° C. for 4 minutes forms a planarizing film 7 having a thickness of 1 μm.

[Formation of color filter (CF)]
Using a blue color resist (for example, COLOR MOSAIC-EXIS SB-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.) on the substrate on which the planarizing film 7 has been formed, the coating rotation speed during spin coating is applied. Thereafter, the film is adjusted so that the film thickness after heat treatment with a hot plate at a surface temperature of 100 ° C. for 120 seconds becomes 1.1 μm and uniformly applied.
Exposed with an i-line stepper, FPA-3000i5 + manufactured by Canon Inc., through a mask having a pattern in which square pixels each having a side of 2 μm are arranged, and using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) Then, paddle development is performed at 23 ° C. for 60 seconds, and then rinsed with pure water for 20 seconds in a spin shower, followed by washing with pure water. Thereafter, the attached water droplets are removed by blowing air, and the substrate is naturally dried to obtain a blue color filter pattern 9B.
Repeat the same process for Green (using COLOR MOSAIC-EXIS SG-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.) and Red (using COLOR MOSAIC-EXIS SR-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.). The color filters 9G and 9R are obtained on the light receiving sensor portion 2 on the substrate.

(Formation of flattening film on color filter and creation of solid-state image sensor)
A flattening film agent (COLOR MOSAIC CT-3100L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on the silicon substrate on which the color filter 9 is formed, and then the substrate is heated on a hot plate at 220 ° C. for 4 minutes. Then, the planarizing film 10 is formed. Further, the microlens 11 is formed thereon.
The obtained silicon substrate is subjected to dicing packaging to obtain a solid-state imaging device.

  Hereinafter, the present invention will be specifically described with reference to examples, but the contents of the present invention are not limited thereto. In Examples, parts and% mean parts by mass and% by mass unless otherwise specified.

Example 1
[Preparation of composition for antireflection film]
(Preparation of carbon black dispersion)
The following carbon black dispersion composition 1 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 70000 mPa · s. In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.
The following carbon black dispersion composition 2 was added to the dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3000 rpm. The obtained mixed solution was subjected to a fine dispersion treatment for 4 hours with a disperser (trade name: Dispermat GETZMANN) using 0.3 mm zirconia beads to prepare a carbon black dispersion. At this time, the viscosity of the mixed solution was 37 mPa · s.

(Composition 1 of carbon black dispersion)
Average primary particle size 15 nm carbon black (Pigment Black 7) 23 parts benzyl methacrylate / methacrylic acid copolymer 45% propylene glycol monomethyl ether acetate solution (BzMA / MAA = 70/30 Mw: 30000 solids) 22 parts Solsperse 5000 ( 1.2 parts made by Zeneca)

(Composition 2 of carbon black dispersion)
Benzyl methacrylate / methacrylic acid copolymer propylene glycol monomethyl ether acetate 45% solution (BzMA / MAA = 70/30 Mw: 30000) 22 parts Propylene glycol monomethyl ether acetate 200 parts

(Preparation of photosensitive composition for forming antireflection film)
The following components were mixed with a stirrer to prepare a photosensitive composition for forming an antireflection film.
(Composition of composition for antireflection film)
Methacrylate / acrylic acid copolymer (alkali-soluble resin: MA / AA, weight average molecular weight: 14000, nonvolatile content 50 mass%) 1.6 parts dipentaerythritol hexaacrylate 2.3 parts ethoxylated pentaerythritol tetraacrylate 0.8 Part of the above average primary particle size 15 nm carbon black dispersion 12.5 parts propylene glycol monomethyl ether acetate 17 parts ethyl-3-ethoxypropionate 11 parts triazine-based initiator ((VI) below) 1.1 parts

(Example 2 and Comparative Example 1)
In the “preparation of carbon black dispersion” in Example 1, the same procedure as in Example 1 was performed except that carbon black primary particle sizes of 25 nm and 35 nm were used instead of the carbon black average primary particle size of 15 nm. An antireflection film composition was prepared.

(Example 3)
[Creation of antireflection film]
After coating the photosensitive composition for forming an antireflective film obtained above by spin coating, the film thickness after heat treatment on a hot plate at a surface temperature of 90 ° C. for 120 seconds becomes 0.5 μm. Then, it was applied uniformly on the substrate on which the aluminum film was formed.
Next, the substrate coated with the anti-reflection film-forming photosensitive composition was heat-treated at 90 ° C. for 120 seconds with a hot plate to form a dry coating film (anti-reflection film).
Next, exposure is performed with an i-line stepper, FPA-3000i5 + manufactured by Canon Inc., through a mask for forming a stripe pattern having a line width of 1 μm on the aluminum light-shielding film 6, and tetramethylammonium hydroxide (TMAH). Paddle development was performed for 60 seconds at 23 ° C. using a 0.3% aqueous solution, then rinsed with pure water for 20 seconds in a spin shower, and further washed with pure water. Thereafter, the attached water droplets were removed by blowing air, the substrate was naturally dried, and an image pattern of the antireflection film 8 exposing the aluminum film to be etched was obtained.

(Comparative Example 2)
<Creation of antireflection film (nitride film)>
On a glass substrate, a sputtering apparatus isputter (manufactured by ULVAC, Inc.) was used to form titanium nitride (TiN) by sputtering to form a 0.1 μm antireflection film (nitride film).

Example 4
<Creation of a solid-state imaging device (when an antireflection film is formed on a flat film: FIG. 2)>
[Circuit part formation]
As shown in FIG. 2, a plurality of light receiving sensor portions 2 that perform photoelectric conversion are formed on a surface layer portion of a substrate made of a silicon substrate 1, and the light receiving sensor portion 2 is formed adjacent to the light receiving sensor portion 2. A vertical transfer register 3 having a CCD structure for transferring charges is provided, a horizontal transfer register (not shown) for transferring in the horizontal direction is provided at one end of the vertical transfer register row, and a signal detector (not shown) is provided at the end of the horizontal transfer register. And an output amplifier (not shown), and a peripheral circuit portion A (not shown) such as a drive circuit is formed in the peripheral portion.
An aluminum light-shielding film 6 was formed with a thickness of 0.3 μm on the entire surface of the substrate on which the peripheral circuit portion A and the like were formed, with an interlayer film (insulating layer 13) interposed therebetween.

[Etching process]
In the present invention, the aluminum film was etched as follows by wet etching excellent in mass productivity.
First, the substrate on which the antireflection film 8 from which the aluminum film to be etched is exposed is immersed in the following etching solution for 110 seconds. After the exposed aluminum is dissolved, the etching solution is removed by washing with water and air is supplied. The water droplets were removed by spraying, and the light shielding / antireflection multilayer film 12 was formed in the portion covered with the antireflection film.

<Etching liquid composition>
80% by volume of phosphoric acid
Nitric acid 5% by volume
Acetic acid 10% by volume
Ion exchange water 5% by volume

[Formation of planarization film]
A flattening film agent (COLOR MOSAIC CT-3100L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on a silicon substrate on which a laminated film of a light shielding film and an antireflection film is formed, and then the substrate is heated on a hot plate. The flattened film 7 having a thickness of 1 μm was formed by heating at 4 ° C. for 4 minutes.

[Formation of color filter (CF)]
Using a blue color resist (COLOR MOSAIC-EXIS SB-4000L, manufactured by FUJIFILM Electronics Materials Co., Ltd.) on the substrate on which the flattening film 7 is formed, the coating rotation speed during spin coating is The film was adjusted so that the film thickness after heat treatment on a hot plate at a temperature of 100 ° C. for 120 seconds was 1.1 μm and applied uniformly.
Exposed with an i-line stepper, FPA-3000i5 + manufactured by Canon Inc., through a mask having a pattern in which square pixels each having a side of 2 μm are arranged, and using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) Then, paddle development was performed at 23 ° C. for 60 seconds, followed by rinsing with pure water for 20 seconds in a spin shower, and further washing with pure water. Thereafter, the adhered water droplets were removed by blowing air, and the substrate was naturally dried to obtain a blue color filter pattern 9B.
Repeat the same process for Green (using COLOR MOSAIC-EXIS SG-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.) and Red (using COLOR MOSAIC-EXIS SR-4000L manufactured by FUJIFILM Electronics Materials Co., Ltd.). Color filters 9G and 9R were obtained on the light receiving sensor portion 2 on the substrate.

[Formation of flattening film on color filter and creation of solid-state imaging device]
A flattening film agent (COLOR MOSAIC CT-3100L manufactured by FUJIFILM Electronics Materials Co., Ltd.) is uniformly applied on the silicon substrate on which the color filter 9 is formed, and then the substrate is heated on a hot plate at 220 ° C. for 4 minutes. Then, the planarizing film 10 was formed. Further, a microlens 11 was formed thereon.
The obtained silicon substrate was subjected to dicing, wire bonding, and packaging to obtain a solid-state imaging device.

(Comparative Example 3) <Creation of Solid-State Imaging Device (When TiN Film is Used as Antireflection Film)>
In Example 4, a nitride film having a thickness of 0.1 μm was formed under the same sputtering film forming conditions as in Comparative Example 2 so as to cover the side surface of the aluminum light-shielding film 6 as shown in FIG. Then, a solid-state image sensor was obtained.

[Evaluation]
The linearity of the Line & Space pattern obtained using the composition for antireflection film obtained from the above Examples and Comparative Examples, the reflectance of 5 ° in the antireflection film, and the shape of the CF pattern in the solid-state image sensor are as follows. The method was evaluated.

[Linearity evaluation]
Using the composition for antireflection film obtained in Examples 1 and 2 and Comparative Example 1 above, a Line & Space pattern was formed on the aluminum vapor-deposited film under the same conditions as in Example 3, and etching was performed. The light shielding / antireflection laminated film was observed and evaluated using SEM (scanning electron microscope) S-4800. The result is shown in FIG.
The aluminum film was etched as follows.
First, a mixed acid obtained by mixing 80% by volume of phosphoric acid, 5% by volume of nitric acid, 10% by volume of acetic acid, and 5% by volume of ion-exchanged water was used at a liquid temperature of 40 ° C. and immersed in an etching solution for 110 seconds.

As is apparent from FIG. 3, in the case of wet etching, the obtained Line & Space pattern is dissolved in an isotropic manner. Therefore, the aluminum film is side-etched at the boundary portion of the antireflection film pattern, and the antireflection film is completely etched. It is under the membrane.
The smaller the average primary particle diameter of carbon black, the better the linearity of the pattern edge, and the better the linearity of the underlying aluminum film etched therewith. Moreover, it turned out that there is no inferiority with the pattern formed using the positive resist.

[Evaluation of reflectivity at 5 °]
The antireflection film obtained from Example 3 and Comparative Example 2 was measured for a reflectance of 5 ° using a spectrophotometer MPC2200 (manufactured by Shimadzu Corporation).
A low reflectivity indicates that the performance of preventing the generation of false signals is prevented by preventing halation when forming color filters and microlenses. The results are shown in FIGS.

  As is clear from FIGS. 4 and 5, the antireflection film of Example 3 (FIG. 5) formed using the composition for antireflection film of the present invention shows a low reflectance at any measurement wavelength. I understood. On the other hand, the reflectance of the TiN film of Comparative Example 2 (FIG. 4) showed high reflectance at any measurement wavelength, and it was found that the value was particularly high from around 400 nm.

[Evaluation of CF pattern shape in solid-state image sensor]
The shape of the CF pattern in the solid-state imaging device obtained in Example 4 and Comparative Example 3 was observed and compared using an SEM (Scanning Electron Microscope) S-4800.

  When the reflectances of the TiN film in Comparative Example 3 and the antireflection film of Example 4 are compared, as is clear from FIG. 4, the reflectance of Example 4 is low, so that the antireflection film in the present invention is low. The shape of the color filter formed later, particularly the shape of the magenta or red color filter having a high i-line transmittance, can be made rectangular without drawing a hem. I understood. Thereby, it turned out that the antireflection film in the present invention effectively prevents halation during the formation of the color filter pattern.

1 is a configuration cross-sectional view illustrating an example of a solid-state imaging device of the present invention. It is sectional drawing which shows the manufacturing process about the light shielding / antireflection laminated film of this invention, and the conventional antireflection film. It is a figure which shows the linearity of the Line & Space pattern formed using the composition for anti-reflective films obtained in Examples 1, 2 and Comparative Example 1. It is a figure which shows the reflectance of 5 degrees of the nitride film formed by sputtering film-forming on the glass substrate of the comparative example 2. FIG. It is a figure which shows the reflectance of 5 degrees of the anti-reflective film apply | coated and formed on the glass substrate of Example 3. FIG.

Explanation of symbols

1 Substrate (wafer)
2 Photosensitive sensor 3 Vertical transfer register 4, 13 Insulating film 5 Transfer electrode 6 Light shielding film 7 Flattening film (on silicon substrate)
8 resist film (anti-reflective coating composition coating)
9 Color filters (R, G, B)
10 Flattening film (color filter shape)
11 Microlens 12 Light shielding / antireflection laminated film 17 Mask 18 Radiation

Claims (8)

A light shielding / antireflection laminated film in which a light shielding film made of a metal thin film or a metal compound thin film and an antireflection film directly formed on the light shielding film are laminated, wherein the antireflection film has an average primary particle diameter of 30 nm or less A light-shielding / anti-reflection laminated film comprising a black colorant. The light shielding / antireflection multilayer film according to claim 1, wherein the black colorant is at least one selected from carbon black and titanium black. The light-shielding / light-shielding film according to claim 1 or 2, wherein the antireflection film is formed by photolithography using a composition containing the black colorant, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator. Antireflection laminated film. A metal thin film is formed on a substrate, and then a coating film of a composition containing a black colorant, an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator is formed, and pattern exposure and development are performed on the coating film. Then, after forming a resist film on the metal thin film, etching treatment is performed to remove the metal thin film in a portion not covered with the resist film to obtain a light shielding / antireflection laminated film. Manufacturing method of antireflection laminated film. The light shielding / antireflection multilayer film according to any one of claims 1 to 3 is formed on the transfer electrode via an insulating film, and a planarizing film, a color filter film composed of a plurality of pixels, and a flat film thereon A solid-state image pickup device, wherein a chemical film and a microlens are sequentially formed. The solid-state imaging device according to claim 5, wherein a thickness of the antireflection film is 1 μm or less. The solid-state imaging device according to claim 5, wherein the maximum diameter of the pixel is 5 μm or less. A light shielding / antireflection multilayer film is formed on the transfer electrode formed on the wafer by the method according to claim 4, and then a planarizing film, a color filter film composed of a plurality of pixels, a planarizing film, and a micro A method of manufacturing a solid-state imaging device, wherein the lenses are formed in this order.

Images