TW201137517A - Radiation-sensitive composition, insulation film formation method, insulation film and solid photographic component - Google Patents

Abstract

This invention provides a radiation-sensitive composition, an insulation film formation method, an insulation film and a solid photographic component suitable for the formation of an insulation film for assembly of a photoelectric conversion portion in a solid photographic component such as a CCD, a CMOS, etc. The radiation-sensitive resin composition of this invention contains a black colorant, polymer with phenolic hydroxyl group, a radiation-sensitive acid generator, and a cross-linker carrying out cross-linking reaction by the acid.

Description

201137517 VI. Description of the Invention: [Technical Field] The present invention relates to a linear composition for radiation radiation, a method for forming an insulating film, an insulating film, and a solid-state imaging device. More specifically, it relates to a sensitive radiation linear composition, an insulating film forming method, an insulating film, and a solid-state imaging element which are suitable for forming an insulating film for assembling a photoelectric conversion portion in a solid-state imaging device such as a CCD or a CMOS. [Prior Art] In recent years, the performance of electronic cameras including digital cameras, cameras, on-board cameras, digital computers with photography functions, mobile phones, electronic booklets, etc., which have solid-state imaging devices such as CCDs and CMOSs improve. In the solid-state imaging device, in order to reduce the dark current, prevent a decrease in the dynamic range, and stabilize the operation of the peripheral circuit, and suppress the deterioration of the image quality, the photoelectric conversion unit included in the solid-state imaging device usually shields the unnecessary light. For example, it is known in patent documents 1 and 2. In these documents, a light-shielding film containing a black colorant and a resin disposed on the periphery of an effective pixel region (photographing portion) of a photoelectric conversion portion in a solid-state imaging device is disclosed. Further, Patent Document 3 discloses a linear composition for forming a light-shielding film containing a carbon black, an acrylic resin, an acrylic monomer, and a photopolymerization initiator. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2006-156801 [Patent Document 2] Japanese Patent Laid-Open No. 00 7 - 1 1 5 9 2 1 [Patent Document 3] [Summary of the Invention] [Problem to be Solved by the Invention] The insulating film which is first formed on a substrate (including a ruthenium oxide film substrate or the like) is formed by linearly forming a sensitive radiation using a light-shielding film. The aforementioned light shielding film. In other words, the step of forming an insulating film on the substrate and the step of forming a light-shielding film on the insulating film by this step are required in the production of the solid-state imaging device or the like. Therefore, in order to simplify the steps (improve the yield), the steps of the edge film and the step of forming the light shielding film are required to be an outer layer of an insulating film having both insulating properties and light blocking properties. It is also excellent in yttrium oxide film (Si 02 ) and electrode properties. An object of the present invention is to provide a method for forming a radiation sensitive linear composition film excellent in insulating property, light blocking property, and adhesion for assembling a radiation-sensitive linear composition and a photoelectric conversion portion in a solid-state imaging device, and an insulating film and Solid photographic element. [Means for Solving the Problem] The present invention is as follows. Things, in the pre-surface, shape, at least must be formed to form a formable material. These are not suitable for the film, and the material is insulated. -6-201137517 [1] A sensitive radiation linear composition characterized by (A) black agent' (B) a polymer having a phenolic hydroxyl group, (C) a sensitive radiation linear acid generator, (D) a crosslinking agent which undergoes a crosslinking reaction by the action of an acid. [2] The radiation sensitive linear composition according to the above [1], wherein the polymer having a phenolic hydroxyl group as described above is a condensate of a compound having a phenolic hydroxyl group and a compound having a methyl group. [3] The sensitive radiation linear composition according to the above item (1), wherein the polymer having a phenolic hydroxyl group (B) is a polymer having a structural unit of polymerizable unsaturated bond cleavage of hydroxystyrene. The sensitive radiation linear composition according to the above item [1], wherein the (B) polymer having a phenolic hydroxyl group is a condensate containing a compound having a phenolic hydroxyl group and a compound having a methyl group and having a hydroxystyrene [5] The linear radiation-sensitive composition of the above-mentioned (1), wherein the (D) crosslinking agent is a compound containing a methylol group. [6] The sensitive radiation linear composition of the above item [1], which further comprises (E) a crosslinked polymer particle. [7] The linear composition of the sensitive radiation according to any one of the above [1] to [6] A sensitive radiation linear composition for forming an insulating film for assembling a photoelectric conversion portion in a solid-state imaging device. [8] A method for forming an insulating film, which is a sister of a photoelectric conversion portion in a solid-state imaging device Insulating film The forming method is characterized in that: (1) a step of forming a coating film composed of the linear radiation composition of the above-mentioned (73), and at least pair formation on the substrate having the electrode portion. a step of exposing the film other than the coating film on the electrode portion, and (3) a step of developing the film after the exposure. [9] An insulating film characterized by the above [8] [10] An insulating film which is obtained by the linear composition of the radiation of any one of the above [1] to [6]. [1] 1] A solid-state imaging device comprising at least a photoelectric conversion portion, an insulating film according to the above item [9], and an electrode portion. [Effect of the Invention] According to the sensitive radiation linear composition of the present invention, insulation can be formed. An insulating film excellent in properties, light-shielding property, and adhesion. In particular, the radiation-sensitive linear composition is suitable for forming an insulating film for assembling a photoelectric conversion portion in a solid-state imaging device such as a CCD or a CMOS. When the film is formed, An insulating film having excellent insulating properties, light-shielding properties, and adhesion. Therefore, it is possible to reduce the conventional process without requiring separate insulating portions and light-shielding portions, and is suitable for a solid-state imaging device including a solid-state imaging device such as a CCD or a CMOS. In the field of the electronic device, the solid-state imaging device of the present invention is provided with an insulating film having excellent insulating properties, light-shielding properties, and adhesion to the -8 - 201137517. Therefore, it can be applied to a solid-state imaging device including a solid-state imaging device including a CCD or a CMOS. EMBODIMENT OF THE EMBODIMENT OF THE INVENTION The present invention will be described in detail below. In the present specification, "(meth)propenyl" means propylenyl and methacryloyl, "(methyl)" "Acrylate" means acrylate and methacrylate. [1] Linear radiation sensitive composition The sensitive linear composition of the present invention is characterized by (A) black agent (hereinafter also referred to as "black agent (A)" (B) a polymer having a phenolic hydroxyl group (hereinafter also referred to as "polymer (B)"), (C) a radiation-sensitive linear acid generator (hereinafter also referred to as "acid generator (C)") and (D) by acid A crosslinking agent that acts to carry out a crosslinking reaction (hereinafter also referred to as "crosslinking agent (D)"). This sensitive radiation linear composition can be suitably used for forming an insulating film for assembling a photoelectric conversion portion in a solid-state imaging device such as a CCD or a CMOS. (A) Black agent The black agent (A) refers broadly to a compound that absorbs infrared rays. Specifically, 'expresses 1 part by mass relative to polymethacrylic acid (weight average molecular weight converted by polyphenylene hydride by gel permeation chromatography; 50, 〇〇〇), 1 part by mass of black agent and A The composition of 50 parts by mass of ethyl ethyl ketone is coated by a spin coating method and then heated by a heating plate at 1 Torr.

S -9 - 201137517 The film with a film thickness of 20 μm has a light transmittance of 12% or less at a wavelength of 12 OOnm. The black agent (A) may, for example, be carbon black, titanium bismuth, iron oxide, manganese oxide, graphite or a dye. Among these, carbon black and titanium black are preferred. The carbon black is, for example, furnace black, hot black, acetylene black or the like. Further, as the carbon black, for example, a product name manufactured by Mitsubishi Chemical Corporation, #2400 ' #23 50 ' #23 00, #2200, #1000, #980, #970, #960, #95 0 >#900 can be used. '#8 5 0 > MCF88, #650, MA600, MA7, MA8, MA11, MA 1 0 0, Μ A 2 2 0, IL 3 Ο B, IL 3 1 B, IL7B, IL11B, IL52B, #4000, #4010 , #55 , #52 ' #50 , #47 ' #45, #44, #40, #33, #32, #30, #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950, DiablackA, Diab 1 ackN220M, Diab 1 ackN23 4, DiablackI, DiablackLI, Diablackll, D i ab 1 a ckN 3 3 9, D i ab 1 ac k SH, D i ab 1 ack SHA , DiablackLH, DiablackH, DiablackHA, DiablackSF, D i ab 1 a ckN 5 5 0 M, DiablackE, DiablackG, DiablackR, DiablackN760M, DiablackLP; Trade names made by Cancav, thermaxN990, N991, N907, N908, N990, N991, N908 : Asahi Carbon Company's trade name, 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 company's trade name, ColorBlack F w 2 0 0 ' ColorBlack Fw2 ' ColorBlack Fw2V ' ColorBlack Fwl , ColorBlack Fwl8 , ColorBlack S170 , ColorBlack -10- 201137517 S 1 6Ο, Specia 1B1 ack6, SpecialB1 ack5 'Specia 1B1 ack4 'SpecialBlack4A, PrintexU 'Printex V, Printex 140U, Printex 1 40V, etc. In addition, Japanese Laid-Open Patent Publication No. Hei 11-60988, Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The resin-coated carbon black disclosed in Japanese Laid-Open Patent Publication No. Hei 9- No. Hei. The carbon black is preferably an insulating carbon black. Insulating carbon black refers to carbon black which exhibits insulation properties, that is, a volume resistance 値 of 1 〇 6 Ω · cm or more, for example, on the surface of carbon black particles, and is coated with organic matter or when the volume resistance of the powder is measured by the following method. The organic substance is chemically bonded (grafted) or the like, and the surface of the carbon black particle has an organic compound. The carbon black is dispersed in a state of a mass ratio of 20:80 to a copolymer having a benzyl methacrylate having a molar ratio of 70:30 and a repeating structural unit derived from methacrylic acid (weight average molecular weight: 30,000). In propylene glycol monomethyl ether, a dispersion was obtained. Then, this dispersion was applied onto a chromium substrate having a thickness of 1.1 mm and 10 cm x 10 cm to prepare a coating film having a dry film thickness of 3 μm. Next, this coating film was heat-treated at 200 ° C for 1 hour in an oven. Then, using a high resistivity meter ("HirestaUP (MCP-HT450)" manufactured by Mitsubishi Chemical Corporation, JIS K6911, the volume resistance 値 was measured at a temperature of 23 ° C and a relative humidity of 65%. In the present invention, the volume 値 of the carbon ruthenium is preferably 1 〇 8 Ω · cm or more, more preferably 109 Q. cm or more.

S -11 - 201137517 In addition, the aforementioned titanium black is, for example, low in TiO, Ti0125, Ti203, Ti407, butyl 13〇5, etc. (1^0"1$ forks each 4, 1$乂$7, 乂/\<1.75) Sub-titanium oxide: titanium nitride; TiOxNy (〇·2 < χ < 0.8, 0.6 < y < l · 2 ) titanium oxynitride, etc. 8 low-order titanium oxide, for example, is described in Japanese Patent Publication No. 5 2 - 1 2 In the case of the titanium dioxide and the titanium metal powder, the obtained compound is heated at a temperature of 55 ° C to 1100 ° C in a vacuum or a reducing atmosphere; it is described in JP-A-64-1 1 5 72, The aqueous titanium oxide and the titanium metal powder are heated in an inert atmosphere in the presence of a baking treatment auxiliary agent containing a compound such as ruthenium, aluminum, ruthenium or tungsten. Further, for example, titanium oxynitride has In the case of the titanium dioxide or the titanium hydroxide powder, the titanium oxide or the titanium hydroxide powder is reduced in the presence of ammonia at a temperature of about 550 ° C to 950 ° C. For example, the trade name of Mitsubishi Materia, 10S, 12S, 13M, 13M-C, 13R, 13R-N: Ako-chemical The product name of the company, the TilackD ultrafine particle form, etc. The titanium black may be used as a surface treatment. The number average particle diameter of the black agent (A) is preferably 4 Q nm or less from the viewpoint of dispersion stability and sedimentation prevention. More preferably, it is 5 to 4 Å, more preferably 5 to 3 Onm. Further, the aforementioned number average particle diameter may be 値 measured by an electron microscope. The content of the black agent (A) in the linear composition of the sensitizing radiation is The polymer (B) to be described later is 1 part by mass (however, when the phenolic low score -12-201137517 sub-compound described later is blended, when the total of the polymer (B) and the inert low molecular compound is 100 parts by mass) Preferably, it is 0.1 to 200 parts by mass, more preferably 0 to 5 to 12 parts by mass, still more preferably 5 to 40 parts by mass. When the content of the black agent (A) is within the above range, an insulation having sufficient light shielding property can be obtained. The film, that is, the transmittance at a temperature of 2 3 ° C when the light having a wavelength of 1,00 Onm is applied to the insulating film having a thickness of 20 μm, preferably 20% Τ or less, more preferably 15% Τ or less, more preferably It is 10% Τ or less. When the content of the black agent (A) is more than 200 parts by mass, the insulating film When the black agent (A) is used, it is preferable to use a black agent (A) as a dispersoid and to disperse it in a black agent dispersion liquid of a dispersion medium. The solvent (G) to be described later is used for the linear composition of the radiation. In this case, the solvent (G) may be used alone or in combination of two or more. Further, when the amount of the dispersing medium is 100 parts by mass of the coloring agent (A), it is preferably 200 to 1200 parts by mass, more preferably 30 to 1 part by mass. A dispersing agent or a dispersing aid may be further added to the black agent dispersion. The dispersing agent or dispersing aid is not particularly limited as long as it can stabilize the black agent (A) in the composition and does not agglomerate. For example, it may be in any form such as a cationic system, an anion system, a nonionic system or an amphoteric system, and may further contain an inorganic element such as sand or may be a polymer. Specifically, for example, a modified acrylic acid-based copolymer, an acrylic copolymer, a polyurethane, a polyester 'decane coupling agent, an alkylammonium salt of a polymer copolymer or a phosphate ester a salt 'cationic comb type graft polymer or the like. Cationic comb type

S -13- 201137517 A branched polymer refers to a polymer having a complex basic group (cationic functional group), a polymer having a structure in which two or more molecules of a branched polymer are graft-bonded, such as dry polymerization. The material is a polyethyleneimine, and the branched polymer portion is a polymer composed of a ring-opening polymer of ε·caprolactone. Among these, 'preferably a modified acrylic copolymer, a polyurethane, a cationic comb graft polymer, and a decane coupling agent, γ-glycidoxypropyltrimethoxydecane, γ - Methyl propyl decene oxytrimethoxy decane and its hydrolysis condensate. Such dispersing agents or dispersing aids are commercially available, for example, modified acrylic copolymers, such as Disperbyk-2000, Disperbyk-2001 (above, BYK), polyurethanes such as Disperbyk-161. , Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above BYK), SOLSPERSE 76500 (manufactured by Lubrizol Co., Ltd.), SOLSPERSE 5000, SOLSPERSE 37500, cationic comb type For example, there are SOLSPERSE 24000 (manufactured by Lubrizol Co., Ltd.) and ajisuper PB821 ' aj isuper P B 822 (manufactured by ajinomoto-fine-techno Co., Ltd.). These dispersing agents or dispersing aids can be used alone or in combination 2 More than one kind. When the dispersing agent or the dispersing aid is used, the content of the dispersing agent or the dispersing aid is appropriately adjusted by a combination of the type of the black agent (A) to be used, the type of the dispersing agent, and the like. When the amount of the black agent (A) is 100 parts by mass, it is preferably 100 parts by mass or less, more preferably 0.5 to 100 parts by mass, still more preferably -14 to 201137517 10 to 50 parts by mass. When the content of the dispersant or the dispersing aid is 100 parts by mass or less, a linear radiation sensitive composition having excellent developability can be obtained. Further, the preparation method of the black agent dispersion is, for example, a black agent (A) in a dispersion medium, in the presence of an additive such as a dispersant, using a pulverizer, a rod mill, a bead mill, and a roll mill. A blackening agent dispersion can be prepared by pulverizing and mixing. (B) Polymer having a phenolic hydroxyl group The polymer (B) having a phenolic hydroxyl group is an alkali-soluble polymer when it is developed by an alkali developing solution. The "alkali-soluble" means that when the aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is 1 part by mass, 10 parts by mass or more of the polymer (B) can be dissolved in the aqueous solution. As the polymer (B), for example, a condensate of a compound having a phenolic hydroxyl group and a compound having a fluorenyl group (hereinafter also referred to as "polymer (B1)") can be used. The above-mentioned compound having a phenolic hydroxyl group, for example, phenol, m_methyl hydrazine, p-methyl hydrazine, hydrazine-methyl hydrazine, etc.; 2,5-dimethyl hydrazine, 3,5-dimethyl hydrazine, 3 , xylenols such as 4-xylenol and 2,3-xylenol; m-ethylphenol, ethylidene 〇-ethyl hydrazine, pt-butyl hydrazine, p-octyl, 2, Alkylphenols such as 3,5-trimethylhydrazine; P-methoxyphenol 'm-methoxyphenol' 3,5-dimethoxyphenol, 2-methoxy-4-methyl a phenolic phenol, an m-ethoxy phenol, a p-ethoxy phenol, a propoxy phenol, a P-propoxy phenol, an m-butoxy phenol, a p-butoxy phenol, or the like; a dialkylphenol such as methyl-4-isopropylphenol; m_chloranil, p_

S -15- 201137517 Hydroxy aromatic compounds such as chlorophenol, hydrazine chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, naphthol, etc. Among these, cresols are preferred. Further, the compound having a phenolic hydroxyl group may be used alone or in combination of two or more. The aforementioned compound having a methyl group, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, hydrazine-hydroxybenzaldehyde , m-hydroxybenzaldehyde, ρ-hydroxybenzaldehyde, hydrazine-chlorobenzaldehyde, m-chlorobenzaldehyde, P-chlorobenzaldehyde, guanidine-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzene Formaldehyde, hydrazine-methylbenzaldehyde, m-methylbenzaldehyde, P-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furaldehyde, chloroacetaldehyde, and the like For example, there are chloroacetaldehyde diethyl acetal and the like. Among these, formaldehyde is preferred. Further, the compound having a methyl group may be used alone or in combination of two or more. The polymer (B1) can be obtained, for example, by a compound having a phenolic hydroxyl group as a main component and undergoing an addition condensation reaction with a compound having a methyl group in the presence of an acidic catalyst. The acidic catalyst may be, for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like. These acidic catalysts may be used alone or in combination of two or more. Further, as the polymer (B1), a commercially available phenol resin such as a phenol resin or a cresol resin can be used. As the polymer (B), a polymer having a structural unit (b 1 ) having a phenolic hydroxyl group (hereinafter simply referred to as "structural unit (b丨)"] can be used (also referred to as "polymer" under -16-201137517 (B2)") (except polymer (B1)). The structural unit (b 1 ) is, for example, a hydroxystyrene unit (i.e., a unit in which a polymerizable unsaturated bond in hydroxystyrene is cleaved), an isopropenyl unit (i.e., a polymerizable unsaturated group in isopropenylphenol) Preferably, the unit for which the bond is cracked is preferably a hydroxystyrene unit. a monomer which can form a structural unit (bl), for example, p-isopropenylphenol, m-isopropenylphenol, 0-isopropenylphenol, p-hydroxystyrene, m-hydroxystyrene, anthracene-hydroxybenzene A compound containing a phenolic hydroxyl group such as ethylene. Among these, 'p-isopropenylphenol, p-hydroxystyrene is preferred. The above structural unit (b 1 ) can be obtained, for example, from a monomer which protects a phenolic hydroxyl group with a t-butyl group, an acetal group or the like. The obtained polymer and copolymer can be converted into a structural unit having a phenolic hydroxyl group by deprotection by a known method such as an acid catalyst. The phenolic hydroxyl group-protected monomer is, for example, an acetal-protected hydroxystyrene such as ρ-1·methoxyethoxystyrene or P-1-ethoxyethoxystyrene. T-butoxystyrene, t-butoxycarbonyloxystyrene' is a nonyloxystyrene or the like. The polymer (B2) may contain only one or two or more structural units (bl). The aforementioned polymer (B2) of the present invention may contain structural units derived from other monomers in addition to the aforementioned structural unit (bl) (b2) ) [The following is only referred to as "structural unit (b2)"]. The "other monomer" of the above structural unit (b 2 ) may be formed, for example, styrene, α-methylstyrene, fluorene-methylstyrene, m-methylstyrene.

S -17- 201137517 styrenes such as p-methylstyrene, fluorene-methoxystyrene, m-methoxystyrene, p-methoxystyrene; (meth)acrylic acid, maleic acid , fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, etc., or their anhydrides; methyl esters and ethyl esters of unsaturated carboxylic acids , η-propyl ester, i-propyl ester, η-butyl ester, i-butyl ester, sec-butyl vinegar, t-butyl vinegar ' η-pentyl ester ' η-hexane vinegar 'cyclohexyl vinegar, 2-hydroxyethyl ester , 2-hydroxypropyl ester, 3-hydroxypropyl ester, 2,2-dimethyl-3-hydroxypropyl ester, benzyl ester, isodecyl ester, tricyclodecyl ester, 1-adamantyl ester, etc. (A Acrylonitrile, maleonitrile, fumaronitrile, crotononitrile, mesocarbonitrile, citracarbonitrile, itacononitrile and other unsaturated nitriles; (methyl) acrylamide, crotonamide, maleamide , unsaturated amides such as fumarine, mesaconamine, cimolamide, itaconamide, etc.; maleic imine, Ν-phenyl maleimide, Ν-cyclohexylma Unsaturated quinone imines such as quinone imines: bicyclo [2.2.1] hept-2-ene (norbornene), tetracyclic [4.4.0.1 2, 5.17'10] Dodec-3-ene, cyclobutene, cyclopentene, cyclooctene, dicyclopentadiene 'tricyclo[5.2.1.〇2'6]decene, etc. a compound of a family skeleton; Ρ-divinylbenzene, m-divinylbenzene, fluorene-divinylbenzene, diallyl phthalate, ethylene glycol di(meth)acrylate, propylene glycol II ( Methyl) acrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, polyethylene glycol di(meth) acrylate vinegar, polypropylene glycol di(meth) acrylate; a cross-linking monomer such as polyethylene glycol divinyl ether such as triethylene glycol divinyl ether 18-201137517; an unsaturated alcohol such as (methyl) allyl alcohol, N-vinylaniline, or vinyl Pyridines, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, anthracene-vinylimidazole, anthracene-vinylcarbazole, and the like. Among them, styrene and fluorene-methoxystyrene are preferred. Further, the polymer (Β2) may contain only one type or two or more types of structural units (b2). Particularly, the polymer (B2) is preferably composed of a structural unit (b 1 ), and the structural unit (bl) is a resin obtained by providing a monomer of a hydroxystyrene unit. The polymer (B) is preferably one of the following constituents. At this time, an excellent insulating film can be formed due to the insulating property, the light blocking property, and the adhesion. (1) a condensate of a compound having a phenolic hydroxyl group and a compound having a fluorenyl group, (2) a polymer having a structural unit which is cleaved by a polymerizable unsaturated bond in a basic state, (3) having A condensate of a compound having a phenolic hydroxyl group and a compound having a fluorenyl group, and a polymer having a structural unit having a polymerizable unsaturated bond in hydroxystyrene to be cracked. Further, the polymer (B) is preferably one having a glass transition temperature (τ g ) exceeding 0 〇C. The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography of the polymer (B) is preferably from the viewpoints of resolution, thermal repellency, heat resistance and residual film ratio of the insulating film. For 500~300,000, -19-201137517 more preferably 600~150,000, more preferably 1, 〇〇〇~100,000. The polymer (B) may be used alone or in combination of two or more. (C) sensitizing radiation linear acid generator The foregoing acid generator (C) is a compound which generates an acid by irradiation with radiation or the like. The acid generator (C) acts as a catalyst for generating an acid by irradiation of radiation or the like, and produces a crosslinking reaction by a crosslinking agent (D) which will be described later. The acid generator (C) is, for example, an onium salt compound, a halogen-containing compound, a diazoketone compound, an anthraquinone compound, a sulfonate compound, a sulfonimide compound, a diazomethane compound or the like. The onium salt compound may, for example, be an iodine salt, a phosphonium salt, a scale salt, a diazo salt, a pyridyl salt or the like. Specific examples of preferred gun salts are diphenyl iodide trifluoromethanesulfonate, diphenyl iodide p-toluenesulfonate, diphenyl iodide hexafluoroantimonate, diphenyl iodine hexafluorophosphate Phosphate, diphenyl iodine tetrafluoro citrate 'triphenyl sulfonium trifluoromethane sulfonate 'triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, 4-third butyl Phenyldiphenylphosphonium trifluoromethanesulfonate, 4-tert-butylphenyl. diphenylphosphonium p-toluenesulfonate, 1-(4,7-dibutoxy-buphthyl)tetrahydrogen Thiophene trifluoromethanesulfonate, 4-(phenylthio)phenyl-phenylphenanthroline (pentafluoro(ethyl)trifluoroacetate, etc. The halogen-containing compound is, for example, a halogen-containing alkyl hydrocarbon compound, A halogen-containing alkyl heterocyclic compound, etc. A preferred example of a halogen-containing compound, 1,1 〇-dibromo-η-decane, 1,1-bis(4-chlorophenyl)-2,2,2- Trichloroethane, phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethane) -s-triazine, naphthyl-bis(trichloro-20-201137517 methyl)-s-diindole, 2-[2-(furan-2-yl) Ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6- An s-triazine derivative such as bis(trichloromethyl)-S-triazine. The above diazoketone compound is, for example, a 1,3-diketone-2-diazo compound, a diazonium phthalide compound, or a diazonaphthalene compound. Examples of the quinone compound compound and the like include a 1,2-naphthoquinonediazide-4-sulfonate compound of a phenol type, etc. The above hydrazine compound is, for example, a β-ketoxime compound, a β-sulfonyl maple compound, and the like. Specific examples of the α-diazo compound and the like of the compound include 4-parabenylmethylhydrazine, tricresylbenzoquinone methyl milling, bis(phenylsulfonyl)methane, etc. The aforementioned sulfonic acid ester compound is, for example, an alkyl group. Sulfonic acid esters, haloalkyl sulfonates, aryl sulfonates, imino sulfonates, etc. More preferred examples are benzoin tosylate 'stea phenol trifluoromethane sulfonate Acid ester, hydrazine-nitrobenzyl trifluoromethane sulfonate, hydrazine-nitrobenzyl hydrazine-toluene sulfonate, etc. Specific examples of the aforementioned imine sulfonium compound are Ν-(trifluoromethylsulfonate) Alkyl imine, hydrazine-(trifluoromethylsulfonate Benzene diimide, Ν-(trifluoromethylsulfonyloxy)diphenylmaleimide, fluorenyl-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5- Alkene-2,3-dimethylimine, ν-(trifluoromethylsulfonyloxy)naphthylimine, etc. Specific examples of the above diazomethane compound are bis(trifluoromethylsulfonyl) Nitromethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, etc. The acid generator (C) is preferably a gun salt compound, more preferably a hydroxyl group-containing phosphonium salt compound. These acid generators (C) may be used alone or in combination of two or more.

S -21 - 201137517 used. The content of the acid generator (c) is 100 parts by mass based on the viewpoint of the sensitivity, the solution, the shape of the pattern, and the like of the composition (but when the phenolic low molecular compound described later is used, the polymer (B) When the total amount of the phenolic compound is 100 parts by mass, it is preferably 〇1 to 1 〇, more preferably 0.3 to 5 parts by mass. When the content of the acid generator (c) is 〇.1~ parts by mass, it is preferred in terms of sensitivity and pattern shape. (D) Crosslinking agent which crosslinks by the action of an acid. The role of acid is to carry out the crosslinking reaction. In the reaction, the crosslinking agent reacts with each other or with other components (polymer (B)) to form a three-dimensional cross-linking structure, and the "cross-linking reaction" means forming an ionic bond. Or a chemical bond such as a covalent bond. The crosslinking agent (D) is, for example, a compound (d 1 ) having two or more alkyl ether amine groups in the molecule (hereinafter referred to as "amine-containing compound (d 1 ); oxirane-containing compound (d2)) : a propylene oxide-containing compound (d3); an isocyanate-containing compound (including a blocker); an aldehyde group-containing phenol compound such as 0-hydroxyformaldehyde; 2,6-bis(hydroxymethyl)-P-, etc. A phenolic compound containing a methylol group, etc. Among these, a compound selected from at least one selected from the group consisting of an amine group-containing compound (dl) and an epoxy ring-containing compound (d2) is preferred. Among them, a hydroxymethyl group is used. Preferably, the crosslinking agent (D) can be blended with the composition of each component, etc., and the image is a component of a lowering weight. For example, a new material is used.适-22- 201137517 When selected, the crosslinking agent (D) may be used alone or in combination of two or more. The above-mentioned amine-containing compound (d 1 ) is, for example, (poly)methylolated melamine, (poly) Among the nitrogen compounds such as methylolated glycoluril, (poly)methylolated benzene melamine, (poly)methylolated urea An alkyl etherified compound of all or a part (at least 2) of an active methylol group (CH2OH group), wherein the alkyl group constituting the alkyl ether, for example, a methyl group, an ethyl group or a butyl group, may be mutually The same or different. The methylol group which has not been alkylated can be self-condensed in one molecule or condensed between two molecules, and as a result, an oligomer component can be formed. Specifically, hexamethoxymethylmelamine can be used. , hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. The linear composition of the sensitive radiation has an amine group-containing compound (d 1 ), which can provide resolution and resistance to drugs. The oxirane-containing compound (d2) may be an oxirane ring, for example, a phenolic epoxy resin or a cresol epoxy resin. Bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylene type epoxy resin, naphthol-xylene type epoxy resin, phenol_naphthol type epoxy resin, phenol - Dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic ring Epoxy resin such as oxyresin; resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, neopentyl glycol condensate Glycerol ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexyl

S -23- 201137517 A polyfunctional glycidyl compound such as a diol diglycidyl ether or a sorbitol polyglycidyl ether. It is preferred to have an epoxide-containing compound (d2) which is excellent in resolution and drug resistance. The crosslinking agent (D) is preferably an amine group-containing compound (dl) or an epoxy group-containing compound (d2), and an amine group-containing compound (d 1 ) and an epoxide group-containing compound (d2) may be used in combination. When the total amount is 100% by mass, the epoxy group-containing compound (d2) is preferably 50% by mass or less, more preferably 5 to 40% by mass. When it is used in such a mass ratio, it is preferable because it does not affect high resolution and can form an insulating film excellent in chemical resistance. When the content of the crosslinking agent (D) is 100 parts by mass of the polymer (B) (when the phenolic low molecular compound described later is blended, when the total of the polymer (B) and the phenolic low molecular compound is 100 parts by mass), It is preferably 1 to 1 part by mass, more preferably 5 to 50 parts by mass. When the content of the crosslinking agent (D) is 1 to 1 part by mass, the curing reaction proceeds sufficiently, and the formed insulating film has a high resolution, and has a good pattern shape, and is excellent in heat resistance and electrical insulating properties. Therefore, it is better. (E) Crosslinked polymer particles The sensitive radiation linear composition of the present invention may further contain crosslinked polymer particles. When the crosslinked polymer particles are contained, an excellent insulating film can be formed by the insulating property and the adhesiveness. Therefore, it is preferred to use a crosslinkable monomer having two or more unsaturated polymerizable groups in the crosslinked polymer particles. (hereinafter, simply referred to as "crosslinkable monomer") and selected from -24 to 201137517, the Tg of the crosslinked polymer particles is one or more of 〇〇C or less, and the other monomer j is copolymerized. In particular, at least one of the other monomers is a functional group other than a polymerizable group such as a carboxyl group, an epoxy group, an amine group, an isocyanate group or a hydroxyl group. More preferably, the crosslinked polymer particles have a polystyrene-equivalent weight average molecular weight of usually 1,000,000 or more. Further, the haze of the solution when the crosslinked polymer particles are 20% by mass of an ethyl lactate solution The haze of the 50% by mass of the ethyl lactate solution of the polymer (B) is usually 5% or less. The crosslinkable monomer is, for example, divinylbenzene or diene. Propyl phthalic acid, ethylene glycol di(meth) propylene Ester, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(a) a compound having a plurality of polymerizable unsaturated groups, such as an acrylate, etc. Among them, divinylbenzene is preferred. The other monomers mentioned above are, for example, butadiene, isoprene, and dimethylbutadiene. a diene compound such as chloropentadiene or 1,3-pentadiene; (meth)acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α- An unsaturated nitrile compound such as ethoxy acrylonitrile 'crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile or fumaric acid dinitrile; (meth) acrylamide, hydrazine, hydrazine '-Methylene bis(methyl) acrylamide, hydrazine, Ν'-extended ethyl bis(methyl) acrylamide, hydrazine, Ν'-hexamethylene bis(methyl) propylene

S -25- 201137517 decylamine, N-hydroxymethyl (meth) acrylamide, n-(2-hydroxyethyl) (meth) acrylamide, hydrazine, hydrazine-bis(2-hydroxyethyl) (Methyl) acrylamide, ethyl crotonate, decyl cinnamate, etc.; ethyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meth) acrylate such as butyl methacrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate or polypropylene glycol (meth) acrylate a compound; an aromatic vinyl compound such as styrene, α-methylstyrene, anthracene methoxystyrene, ρ·hydroxystyrene' ρ_isopropenylphenol; bisphenolphthalein diglycidyl ether, ethylene Epoxy (meth) acrylates, hydroxyalkyl (meth) acrylates and polycondensates obtained by reacting dimethyl diglycidyl ether with (meth)acrylic acid, hydroxyalkyl (meth) acrylate or the like Urethane (meth) acrylates, glycidyl groups obtained by the reaction of isocyanates An epoxy group-containing unsaturated compound such as acrylate or (meth)allyl glycidyl ether; (meth)acrylic acid, itaconic acid, and succinic acid-β-(meth)acryloxyethyl ester , β-(meth)acryloxyethyl maleate, β-(meth)acryloxyethyl sulfate, hexahydrophthalic acid-β_(meth)acryloxyethyl ester, etc. An unsaturated acid compound; an amino group-containing unsaturated compound such as dimethylamino (meth) acrylate or diethylamino (meth) acrylate; (meth) acrylamide, dimethyl An unsaturated amino group-containing compound such as (meth)acrylamide: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc. A hydroxyl group unsaturated compound or the like. Among these other monomers, preferred are butadiene, isoprene, diene compounds such as dimethyl-26-201137517-butadiene, chloropentadiene, and pentadiene, and isoprene- Alkene, (meth)acrylonitrile, (meth)acrylic acid esters, phenylethylene, 'P-pyridylstyrene, P-isopropenylphenol, glycidyl (meth)propionate, (Meth)acrylic acid, hydroxyalkyl (meth) acrylate, and the like. When the crosslinked monomer is used in the production of the crosslinked polymer particles, when the total amount of the monomers for copolymerization is 100% by mass, it is preferably 20% by mass, more preferably 2 to 1% by mass. . Further, when the crosslinked polymer particles are produced, when the above diene compound (particularly butadiene) is used as the other monomer, the amount of the diene compound used is 1 〇〇 mass of the monomers for copolymerization. When % is used, it is preferably 20 to 80% by mass 'more preferably 3 to 7 % by mass. When the amount of the diene compound to be used is from 20 to 80% by mass, the crosslinked polymer particles become rubbery soft fine particles, which prevent cracking of the cured product such as the insulating film formed, and can form an insulating film having excellent durability. . Further, the average particle diameter of the crosslinked polymer particles is usually from 30 to 500 nm, preferably from 40 to 2 nm, more preferably from 50 to 12 nm. The method for controlling the particle size of the crosslinked polymer particles, for example, when the crosslinked polymer particles are synthesized by emulsion polymerization, 'the number of micelles in the emulsion polymerization is controlled by the amount of the emulsifier used, and the particles can be adjusted. path. In addition, the average particle diameter of the crosslinked polymer particles is measured by a light scattering flow distribution measuring apparatus (manufactured by Otsuka Electronics Co., Ltd., model "LPA-3000"), and the dispersion of the crosslinked polymer particles is diluted according to a usual method, and then measured. The crosslinked polymer particles of these may be used alone or in combination of two or more.

S -27- 201137517 used. The content of the crosslinked polymer particles in the linear composition for sensitive radiation of the present invention is 1 part by mass of the polymer (B) (but when the phenolic low molecular compound described later is blended, the polymer (B) and the phenolic property are low. When the total of the molecular compound is 100 parts by mass, it is preferably from 0.5 to 50 parts by mass, more preferably from 1 to 30 parts by mass. When the content of the crosslinked polymer particles is from 0.5 to 50 parts by mass, an excellent insulating film can be formed by insulation and adhesion. Further, it is excellent in compatibility or dispersibility with other components, and can improve heat resistance and the like of the formed insulating film or the like. (F) Other additives The sensitive radiation linear composition of the present invention may contain other additives as necessary within the range which does not impair the effects of the present invention. The other additives include, for example, a phenolic low molecular compound, a adhesion aid, a sensitizer, an inhibitor, a flat agent, a surfactant, an oxidation inhibitor, an ultraviolet absorber, and a coagulation inhibitor. By using the aforementioned phenolic low molecular compound, the sensitivity and resolution of the linear composition of the radiation sensitive radiation can be improved. The aforementioned phenolic low molecular compound is, for example, 4,4'-{1-[4-[2-(4-phenylphenyl)-2-propyl]phenyl]ethylene (611^1丨(161^) )}bisphenol, 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol, 4,4'-di Hydroxydiphenylmethyl, 4,4,-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, anthracene, fluorene-bis(4-hydrylphenyl)-1-phenyl Tris(4-phenyl)phenyl, ι, 3_bis[ι_(4-amino)-1-methylethyl]benzene, I,4·bis[1-(4-diphenyl) 1,-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-i-methylethyl-28 - 201137517 ]-l,3-dihydroxybenzene, ι, Ϊ́-bis(4-hydroxyphenyl)-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane, 1,1,2,2-tetrakis (cardiohydroxyphenyl)ethane, etc. The phenolic low molecular weight compound may be used alone or in combination of two or more. The phenolic low molecular weight compound is preferably used in an amount of 40 parts by mass or less, preferably 40 parts by mass or less, based on 100 parts by mass of the polymer (B). More preferably, the above-mentioned adhesion aid is used for the mass separation to improve the adhesion between the insulating film and the substrate. The adhesion promoter may, for example, be a functional decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. Specifically, for example, trimethoxymethyl decyl benzoic acid, γ-Methoxypropoxypropyltrimethoxydecane, vinyl ethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethyl Oxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 1,3,5-fluorene-tris(trimethoxymethylidenepropyl)trimeric isocyanate, etc. The adhesion promoter may be used alone or in combination of two or more. The content of the adhesion promoter is 100 parts by mass of the polymer (however, when the phenolic low molecular compound described later is blended, the polymer (Β) When the total amount of the phenolic low molecular compound is 100 parts by mass, it is preferably 10 parts by mass or less, more preferably 0.2 to 10 parts by mass, still more preferably 0.5 to 8 parts by mass. It is not necessary to contain particles or metal compound particles other than the above black agent (Α). In the case of metal particles or metal compound particles, sufficient insulating properties may not be obtained. -29- 201137517 (G) Solvent The sensitive radiation linear composition of the present invention is usually composed of the above components dissolved or dispersed in a solvent. The solvent is, for example, an alkanediol monoalkyl ether, an alkylene glycol monoalkyl ether acetate, other ether compounds, a ketone compound, an alkyl lactate, other ester compounds, an aromatic hydrocarbon, a guanamine compound, a lactone. Compounds, etc. These may be used alone or in combination of two or more. The alkanediol monoalkyl ethers are, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-η-propionic acid, ethylene glycol mono-n-butanthene diethylene glycol monocarboxylic acid, diethyl Glycol monoethyl hydrazine, diethylene glycol mono-η-propyl ether, diethylene glycol mono-b-butyl hydrazine, diethylene glycol monomethyl ketone, diethylene glycol monoacetic acid, propylene glycol monomethyl ether, propanol mono Acetic acid, propanol mono-η-propionic acid, propylene glycol mono-n-butyric acid, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-η-propyl ether, dipropanol mono-η-butyl ether, Dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and the like. The alcoholic vinegar of a single alcohol in the hospital is, for example, ethylene glycol monomethyl ether acetate vinegar, ethylene glycol monoethyl ether acetate, diethylene glycol monocarboxylic acid acetic acid vinegar, diethylene glycol monoethyl ketone acetate, Propyl alcohol monomethyl ether acetate 'propylene glycol monoethyl ether acetate, etc. Other ether compounds are, for example, diethylene glycol dicarboxylic acid, diethylene glycol monoethyl ether, monoethyl alcohol methyl ether, diethylene glycol Diethyl ether, tetrahydrofuran, etc., such as methyl ethyl ketone 'methyl _ η pentanone, cyclohexanone, 2-heptanone, 3-heptanone, and the like. The lactic acid vinegar may, for example, be methyl lactate, ethyl lactate, lactic acid propylene -30-201137517, or isobutyl lactate.

Ester, ethyl ethoxypropionate, ethyl ethoxyacetate, isopropyl lactate, η-butyl lactate, 3-methyl; ethyl hydroxyacetate

Η-amyl formate, B, η-propyl butyrate, ethyl isobutyrate butyrate, η·acetic acid isopropyl acetate, η-butyl acetate, isoamyl acetate isobutyl acetate, propionic acid η -butyl ester, ethyl butyrate, butyrate, butyl butyl butyrate, methyl acetonate, propyl propyl acetate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate The aromatic hydrocarbon is, for example, toluene, xylene or the like. The aforementioned guanamine compound is, for example, ruthenium, dimethyl dimethylamine, hydrazine, hydrazine-dimethylacetamide or the like. The lactone compound is, for example, γ-butyrolactone or the like. Among these solvents, from the viewpoints of solubility, dispersibility, coating properties, etc., preferred are propanol monomethyl ether, ethylene glycol monocarboxylic acid acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether. Acid ester, diethylene glycol dimethyl ether, diethylene glycol methyl ether 'methyl-η·pentanone' cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl acetate, η-butyl acetate, isobutyl acetate Η-amyl formate, isoamyl acetate, η-butyl propionate, ethyl butyrate, isopropyl butyrate η-butyl butyrate, ethyl pyruvate, and the like. The solvent may contain benzyl ether, di-n-hexyl ether, acetone acetone, 201137517 isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, sterol, acetate, benzoate B A high boiling point solvent such as ester, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate or the like. These high-boiling solvents may be used alone or in combination of two or more. The content of the solvent is usually from 5 to 50% by mass, preferably from 1 to 40% by mass, based on the coating property and stability of the composition. %. [2] Method for producing linear composition of sensitive radiation The method for producing the linear composition for sensitive radiation of the present invention, for example, the black agent (A), the polymer (B), and the acid in a predetermined amount in the solvent (G) A method in which the generating agent (C), the crosslinking agent (D), and other additives are added in a sub- or batchwise manner, and the like. Further, the black agent (A) may be added in the form of the black agent dispersion described above. The mixing device is, for example, a two-roller, a three-roller, a ball mill, a pulverizer, a disperser, a kneader, a two-way kneader (Ko-Kneader) 'homogenizer, a mixer, a single-axis extruder, a 2-axis extruder, and the like. After mixing, filter with a filter if necessary. [3] Insulating film and solid-state imaging device including the same. The insulating film of the present invention is obtained by the above-mentioned radiation-sensitive linear composition or by a method of forming an insulating film which will be described later. The solid-state imaging device of the present invention includes the above-described insulating film, and specifically includes at least a photoelectric conversion portion, the insulating film, and an electrode portion. In the solid-state imaging device, for example, a solid-state imaging element having a through-electrode or a solid-state imaging element having a structure such as "NeoPAC" (manufactured by OptoPAC Inc.), and a solid-state imaging element having the above-described insulating film. In the following, an insulating film for assembling a photoelectric conversion portion for a solid-state imaging device of the present invention and a solid-state imaging device of the present invention including the insulating film will be described. Representative examples of the insulating film of the present invention and the solid-state imaging device of the present invention (see Figs. 1 and 2) are exemplified. 1 is a cross-sectional view of a principal part of a solid-state imaging device 1 including an insulating film 16, and includes a support substrate 11 made of a germanium wafer or the like; a surface side of the support substrate II (hereinafter referred to as "upper side") and An inner wall surface of the through hole on the surface side (hereinafter referred to as "lower side") and an insulating layer 12 formed on the lower surface of the support substrate 11; and a wiring portion formed on the surface of the insulating layer 12 including the inner surface of the through hole 1 3; a partially formed electrode portion 15 on the surface of the wiring portion 13; a peripheral edge of the electrode portion 15, a surface of the insulating layer 12 supporting the lower surface of the substrate 11, and a wiring portion formed on the electrode portion not formed The insulating film 16 of the surface of 1-3. Further, in Fig. 1, the photoelectric conversion portion and the like disposed on the upper surface side of the support substrate 1 1 are omitted. Further, Fig. 2 is a solid-state imaging element 1' in which the exposed portion of the electrode portion 15 of the solid-state imaging device 1 of Fig. 1 is provided with a solder ball 17. [4] Method of forming an insulating film The method for forming an insulating film of the present invention is a method for forming an insulating film for assembling a photoelectric conversion portion in a solid-state imaging device, and has a feature of:

S-33-201137517 (1) a step of forming a coating film composed of a linear composition of a sensitive radiation on a substrate having an electrode portion, and (2) exposing at least a coating film other than the coating film formed on the electrode portion The step of (3) the step of developing the exposed film. Specifically, the insulating film 16 (see FIGS. 1 and 2) is applied to the insulating film forming substrate (not shown) having the electrode portion 15 on the lower surface, for example, after applying the above-described sensitive radiation linear composition of the present invention. , pre-baking to form a coating film (film). Next, the film is exposed to the pattern which is designed to expose at least the electrode portion 15 after development. Then, the unexposed portion of the film is developed and dissolved. Then, if necessary, an insulating film 16 can be obtained by performing post-baking. When the above-mentioned sensitive radiation linear composition of the present invention is applied, a known coating method such as spin coating, cast coating, or roll coating can be used. Then, the temperature at which the coating film is pre-baked can be appropriately selected depending on the constituent components of the coating film, etc., and is usually in the range of 70 to 13 (TC range, preferably 80 to 1 20 ° C). In the above range, the heat treatment is carried out in a state where the temperature is fixed, or the heat treatment is performed by combining the temperature rise and the temperature decrease. Next, for the film after the prebaking, light such as light, ultraviolet light, far ultraviolet light, electron beam, or X-ray is irradiated (radiation) The exposure is carried out. Then, the film after exposure is developed. The developing solution for imaging is usually an alkali developing solution, and the β-base developing solution is preferably, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or carbonic acid. Sodium hydrogen hydride, sodium citrate, sodium metasilicate, ammonia water 'ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, hydrogen peroxide-34-201137517 tetraethylammonium 'choline, pyrrole, An aqueous solution of piperidine, hydrazine, 8-diazabicyclo[5·4·0]-7-undecene, 1,5-diazabicyclo[4.3.0]·5-decane, etc. The aqueous solution may be an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant. Method, spray imaging, immersion imaging, liquid imaging, etc. The development time is usually 5 to 300 seconds at normal temperature (22 t~2 8 t). After development, it is usually washed with water and dried. The method is, for example, a hot plate, a heat drying using an oven, or the like; air drying using an air gun or the like. After development, the obtained patterned film (patterned film) is post-baked to become an insulating film if necessary. The temperature at which the patterned film is post-baked is appropriately selected depending on the constituent components of the patterned film, and is usually in the range of 150 to 2 50 ° C, preferably 180 to 230 ° C. The insulating film may have a single layer or a plurality of layers. The thickness of the insulating film is preferably 30 μm or less, more preferably 1 to 25 μm, and still more preferably 2 to 20 μm from the viewpoints of insulating properties, light blocking properties, and adhesion. When the thickness of the insulating film is 30 μm or less, the external light containing infrared rays can be sufficiently shielded, and an insulating film free from cracks or the like can be formed. The insulating film may have a protective film on its surface. In this case, the protective film forming material Acrylic tree can be used Composition, the epoxy resin composition, polyimide resin composition, etc. [Embodiment

S - 35 - 201137517 [Examples] The present invention will be described in more detail below, but is not intended to limit the scope of the present invention. The “parts” and “%” are the quality benchmarks unless otherwise stated. Preparation of π]sensitive radiation linear composition (1-1) Modification of black agent dispersion The black agent (A), dispersant (Η), and solvent were mixed by a bead mill at a ratio shown in Table 1 below. I), modulating the black agent dispersion (Αχ-1)~(Ax-3). Table 1 Black agent dispersion black agent (A) Dispersant (H) Solvent (1) Type (parts by mass) Species (parts by mass) Type (mass) Ax-1 A-1 (20) H-1 (5) 1- 1 (75) Ax-2 A-2 (20) H-2 (5) Bu 1 (75) Αχ—3 A-2 (20) H-3(5) 1-1 (75) Table 1 black agent (A) The details of the dispersing agent (Η) and the solvent (I) are as follows. <Black agent (A ) > A-1: carbon 黒 (particle diameter by light scattering method: 10 to 200 μηι) Α-2: titanium black (particle diameter by light scattering method: 10 to 200 μπ 〇 < Dispersant (Η ) > -36- 201137517 Η-1 : Modified acrylic block copolymer (BYK·Japan company, trade name r DISPERBYK-2001) Η-2: Surface treatment agent (BYK' Made by Japan Corporation, trade name "DISPERBYK- 1 65 j ) H-3: 3-methacryloxypropyltrimethoxydecane <Solvent (I) > 1-1 : 3-methoxybutyl B Preparation of the linear composition of the acid ester (1-2)-sensitive radiation (Examples 1 to 3) As shown in the following Table 2, the components of each of the components were prepared by mixing the respective components to prepare the radioactive composition of Examples 1 to 3. Details of each component As described below.

S -37- 201137517 Solvent (G) Type (parts by mass) Φ Ο in οο ^^ Γ"Η CO 1 1 ο ο Φ Ο *—< C^3 1 1 · ο ο Gl (56) G-2 ( 80) Additive (F) Type (parts by mass) Ν r-Ν LTD ι—· c<id —CSJ F-1 (2.5) F-2(0.1) F-1 (2.5) F-2 (0.1) Crosslinking Polymer cerium particles (E) Type (parts by mass) Ε-1 (5) Ε-1(5) El (5) Crosslinking agent (D) Type (parts by mass) D-1 (15) D-2 (5) D- 1 (15) D-2 (5) D-1 (15) D-2(5) Acid generator (C) Type (mass) C-1 (3) C-1 (3) C-1 (3) Low molecular weight Compound (6) Type (parts by mass) b-1 (10) b-1 (10) b-1 (10) .1 Polymer (B) 1_ Type (parts by mass) Ο ο Ν Ν V—^ ^ CS3 1 1 CQ CQ B-1 (70) Β-2 (20) 0 o Bu CS3 'V-^ ^^ 1 1 m cq Black agent tie solution (Αχ) r 'Type (mass) Αχ-1 (20) Ax- 2 (20) Ax-3 (20) Example 1 Example 2 Example 3 -38- 201137517 <Black agent dispersion (Αχ) >

Ax-1: the aforementioned black agent dispersion (Αχ-1)

Ax-2: the aforementioned black agent dispersion (Ax-2) < polymer (B) > Bl: m - formazan / ρ - formazan = 60 / 40 (mole ratio) composed of furfural Resin (weight average molecular weight in terms of polystyrene by gel permeation chromatography = 6500) B-2: p-hydroxy polystyrene (weight average molecular weight converted by polystyrene in gel permeation chromatography = 3000) <Low Molecular Compound (b) > !5-1: 4,4'-[1-[4-[1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylene Bisphenol <acid generator (C) > Cl: 1-(4,7-dibutoxy-1-naphthalenyl)tetrahydrothiophene trifluoromethanesulfonate <crosslinking agent (D) > D-1: hexamethoxymethyl melamine (manufactured by Mitsui Cytec Co., Ltd., trade name "Cymel 300") D-2: Trimethoprim polyglycidyl ether (manufactured by Nagasechemtex Co., Ltd., trade name "DENACOLEX321L" ”)): <crosslinked polymer particles (E ) > E-1: butadiene/acrylonitrile/hydroxybutyl methacrylate/methacrylic acid/divinylbenzene=64/20/8/6/ 2 (Morby, weight average particle diameter by light scattering method = 7〇nm) • 39- 201137517 < Additive (F) > F -1 : 3 - glycidylpropyltrimethoxydecane F-2 : diglycerin EO adduct pentafluoroindole (manufactured by the company Neos, trade name "FTX-218") <Solvent (G) > G-1: Modification of methyl-η-pentanone G-2: ethyl lactate (1 -3 )-sensitive radiation linear composition (Comparative Example 1) (1-3-1) The polymer (R-1) was prepared in a flask, 25 parts of methacrylic acid, 30 parts of fluorenyl-phenylmaleimide, 18 parts of styrene, 15 parts of benzyl methacrylate, and 2-propene oxime. 12 parts of oxyoxyethyl succinic acid was dissolved in 200 parts of cyclohexanone. Next, 2 parts of 2, 2'-azobisisobutyronitrile and 2.5 parts of α-methylstyrene dimer were added, and the mixture was heated at 80 ° C for 5 hours to obtain a polymer (R-1). The polymer (R-1) had a weight average molecular weight of 22,000 by polystyrene conversion by gel permeation column chromatography. The measurement conditions of the polystyrene-equivalent weight average molecular weight by gel permeation column chromatography of this example are as follows. <Measurement of Weight Average Molecular Weight (Mw)> A GPC column (trade name "G2000HXL", two products, "TSKgel, GMPW"), GPC (trade name "HLC-8220GPC") manufactured by Tosoh Corporation, was used. Product name "G3 000PW" 1), with flow rate: l.OmL / min, solvent: tetrahydrofuran, column temperature: 40 ° C, the range of -40-201137517, by monodisperse polystyrene as standard Gel permeation chromatography (GPC) was used for the measurement. (1 -3-2 ) Modulation of the sensitive radiation linear composition (Comparative Example 1) 20 parts of the polymer (R-1) prepared as described above, 50 parts of the above black agent dispersion (Αχ-1), and polyfunctionality Monomer (dipentaerythritol hexaacrylate (trade name "ΜΑΧ3510", manufactured by Toagosei Co., Ltd.)) 8 parts, photopolymerization initiator (2-benzyl-2-dimethylamino-4'-morpholinyl) Phenylbutanone) 2.2 parts, photopolymerization initiator (2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2,-biimidazole) 1.7 , photopolymerization initiator (4,4,-bis(diethylamino)benzophenone) 0.6 parts, hydrogen donor (2-hydrothiobenzothiazepine tl sitting) 0.8 parts, surfactant (3-glycidylpropyltrimethoxydecane) 5 parts, a surfactant (manufactured by DIC Corporation, trade name "Megafac F475") 0.6 parts, a solvent (propane monomethyl ether acetate) 丨 2_8 parts, Solvent (cyclohexanone) 10 parts were mixed, and the linear composition of the sensitive radiation of Comparative Example 1 was prepared. [2] The linear composition of the radiation sensitive composition was evaluated. The above-obtained sensitive radiation linear compositions of Examples 1 to 3 and Comparative Example 1 were obtained. Based on the following items Price. The results are shown in Table 3. (2- 1 ) Pattern shape (residue, minimum pattern size) After applying the linear composition of the sensitive radiation to the tantalum wafer substrate using a spin coater, 'prebaking on a hot plate at 110 ° C 3 Minutes (but Comparative Example 1)

S-41 - 201137517 The linear composition of the sensitive radiation was prebaked on a hot plate at 90 ° C for 2.5 minutes to form a film. Next, the substrate was cooled to room temperature, and an exposure apparatus (trade name "mask aligner MA200ej, manufactured by Suss Corporation") was placed between the masks to expose ultraviolet rays of respective wavelengths of 365 nm' 405 nm and 436 nm, and the film was exposed. The exposure amount was 2 〇〇〇 mJ/cm 2 (but the exposure radiation linear composition of Comparative Example 1 was 500 mJ/cm 2 ). Then, a polyoxyethylene surfactant containing 23 ° C was used. Mass % tetramethylammonium hydroxide aqueous solution, the substrate was spray-developed for 1 minute, then washed with ultrapure water, air-dried, and then baked on a hot plate at 180 ° C for 60 minutes, on the substrate. A patterned film (film thickness: 2 μm) was formed, and the obtained patterned film was observed with an electron microscope, and the residue of the pixel pattern was determined based on the following criteria. At this time, the entire pattern was not peeled off and remained. The smallest pattern size (μιη). 〇: no residue. X: There are many residues. (2-2) Adhesion The linear composition of the sensitive radiation is applied to a glass substrate using a spin coater (the surface has a SiO 2 layer) Substrate) and surface After the foil is wafer substrate, it is pre-baked on a 1 1 〇t hot plate for 3 minutes (but the sensitive radiation linear composition of Comparative Example 1 is prebaked on a hot plate at 9 ° C for 2.5 minutes). Films Next, ultraviolet rays of respective wavelengths of 365 nm, 405 nm, and 436 nm were used to expose the film to the entire surface using an exposure apparatus (trade name "mask aligner MA200e"' manufactured by SUSS Corporation). The exposure amount at this time -42 - 201137517 is 2 00 0 mJ/cm 2 (but the sensitive radiation linear composition of Comparative Example 1 is 500 mJ/cm 2 ). Then, post-baking was performed for 60 minutes on a hot plate at 180 ° C to form an insulating film having a film thickness of 20 μm. Adhesiveness For the blank film and the insulating film for the following condition (a), 100 pieces of 1 mm square checkerboard were produced using the cutting and cutting guide according to JIS K5400, and the tape was confirmed by the tape. Sex (checkerboard test). Count the remaining checkerboard after the tape is peeled off. (a) The insulating film was placed on the substrate containing the insulating film using a highly accelerated life tester (type "TPC-212", manufactured by ESPEC) at a temperature of ll 〇 ° C and a humidity of 100% for 168 hours. (2-3) Electrical Insulation (Volume Resistivity) The linear composition of the radiation radiation was applied to a silicon wafer having a copper foil on a surface using a spin coater, and then prebaked on a hot plate at 110 ° C. Minutes (but the sensitive radiation linear composition of Comparative Example 1 was prebaked on a hot plate at 90 ° C for 2.5 minutes) to form a film. Next, ultraviolet rays of respective wavelengths of 365 nm, 405 nm, and 436 nm were exposed using an exposure apparatus (trade name "mask aligner MA200e", manufactured by SUSS Corporation) to expose the film to the entire surface. The exposure amount at this time was 2000 mJ/cm 2 (but the exposure amount of the sensitive radiation linear composition of Comparative Example 1 was 50,000 m J / c m 2 ). Then, post-baking was performed for 60 minutes on a hot plate at 180 ° C to form an insulating film having a film thickness of 20 μm. The volume resistivity was measured for the blank film and the insulating film for the following condition (b).

S -43- 201137517 (b) Using a highly accelerated life tester (type "TPC-212", manufactured by ESPEC), the substrate containing the insulating film is placed at a temperature of 1 l ° ° C and a humidity of 100%. Insulation film after hours. (2-4) Transmittance The linear composition of the radiation radiation was applied to the glass substrate using a spin coater, and then prebaked on a hot plate at 1 〇 ° C for 3 minutes (but the linear composition of the sensitive radiation of Comparative Example 1) The system was prebaked on a hot plate at 90 ° C for 2.5 minutes to form a film. Then, the substrate having the film was cooled to room temperature, and ultraviolet rays of respective wavelengths of 3, 65 nm, 405 nm, and 436 nm were exposed to an entire surface of the film by using an exposure apparatus (trade name "mask aligner MA200e" or manufactured by Suss Corporation). The exposure amount at this time was 2 000 m J/cm 2 (but the exposure radiation linear composition of Comparative Example 1 was exposed to 50,000 m J/cm 2 ). Then, post-baking was performed for 60 minutes on a hot plate at 180 ° C to form an insulating film having a film thickness of 20 μm. The transmittance is measured by using a spectrophotometer (type "V73 00", manufactured by JASCO Corporation) for the blank film and the insulating film for the various conditions (c) to (e) described below. The temperature is 23 C and the wavelength fe is 400~. l, 200 nm measurement, evaluate the transmittance at 1, 〇〇〇 nm. (c) The insulating film was placed on the substrate containing the insulating film using a constant temperature and humidity test apparatus (type "PSL-2KPH", manufactured by ESPEC) under the conditions of a temperature of 851 and a humidity of 85% for 168 hours. (d) Using a highly accelerated life tester (type "TPC-212", manufactured by ESPEC), the substrate containing the insulating film was placed at 168 hours after the temperature of 110»c and wet-44-201137517 degrees 100%. Insulating film. (e) An insulating film in which an insulating film-containing substrate was placed on a hot plate at 260 ° C for 1 hour in the air. Table 3 Example 1 Example 2 Example 3 Comparative Example 1 Pattern shape residue 〇〇〇〇 minimum pattern size (ju m) < 50 < 50 < 50 < 50 adhesion (including copper foil substrate ) Blank 100 100 100 100 Condition (a) 100 100 100 50 Adhesion (including Si〇2 substrate) Blank 100 100 100 100 Condition (a) 100 100 100 100 Electrical insulation (Ω - cm) Blank 1.3X1015 1.5X1015 1.7X1015 1.5 X109 Condition (6) 1.2X1015 1.5X1015 1.9X1015 9X108 Transmittance (%τ) Blank 0.2 <0.1 <0.1 0.2 Condition (C) 0.2 <0.1 <0.1 0.2 Condition (d) 0.2 <0.1 < 0.1 0.2 Condition (e) 0.2 < 0.1 < 0.1 0.2 [Industrial Applicability] The sensitive radiation linear composition of the present invention is suitable for forming an individual equipped with a digital camera, a camera, a car camera, and a photographing function An insulating film for assembling a photoelectric conversion unit of a solid-state imaging device of an electronic device such as a computer or a mobile phone. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A plan view showing an essential part of an example of a solid-state imaging element including an insulating film is shown in Fig. 45-201137517. Fig. 2 is a cross-sectional view of an essential part showing another example of a solid-state imaging element including an insulating film. [Description of main component symbols] 1, 1 ': Solid-state imaging element 11 : Support substrate 1 2 : Insulation layer 1 3 : Wiring part 1 5 : Electrode part 1 6 : Insulating film 1 7 : Tin ball -46-

Claims (1)

201137517 VII. Patent application scope: 1. A sensitive radiation linear composition characterized by (A) black agent, (B) polymer having phenolic hydroxyl group, (C) sensitive radiation linear acid generator, (D) A crosslinking agent which undergoes a crosslinking reaction by the action of an acid. 2. The sensitive radiation linear composition of claim 1, wherein the (B) polymer having a phenolic hydroxyl group is a condensate of a compound having a phenolic hydroxyl group and a compound having a methyl group. 3. The sensitive radiation linear composition of claim 1, wherein the (B) polymer having a phenolic hydroxyl group is a structural unit having a structural unit of polymerizable unsaturated bond cleavage of hydroxystyrene. 4. The linear composition of the radiation of claim 1, wherein the polymer having a phenolic hydroxyl group is a condensate containing a compound having a phenolic hydroxyl group and a compound having a methyl group and having a hydroxybenzene group. A polymer of structural units of ethylene polymerized unsaturated bond cracking. 5. The sensitive radiation linear composition of claim 1, wherein the (D) crosslinking agent is a compound containing a methylol group. 6. The sensitive radiation linear composition of claim 1 which further comprises (E) crosslinked polymer particles. 7. The radiation-sensitive linear composition of any one of the first to sixth aspects of the invention, which is a linear composition for forming a radiation film for forming an insulating film for assembling a photoelectric conversion portion in a solid-state imaging device. 8. A method of forming an insulating film, which is a method for forming an insulating film for assembling an electric conversion unit in a solid-state imaging device, characterized in that: (1) a substrate having an electrode portion a step of forming a coating film composed of a linear composition of a radiation sensitive agent according to claim 7 of the patent application, (2) a step of exposing at least a coating film other than the coating film formed on the electrode portion, (3) The step of developing the exposed coating film. An insulating film characterized by being formed by a method of forming an insulating film according to claim 8 of the patent application. An insulating film which is obtained by the linear composition of the sensitive radiation according to any one of claims 1 to 6 of the patent application. A solid-state imaging device 7 characterized in that it has at least a photoelectric conversion portion, an insulating film according to claim 9 of the patent application, and an electrode portion. -48-