Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B3/00—Simple or compound lenses
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
  • H10F39/80—Constructional details of image sensors
  • H10F39/806—Optical elements or arrangements associated with the image sensors
  • H10F39/8063—Microlenses

Definitions

• the present invention relates to a photosensitive resin composition for forming a microlens, which contains a specific alkali-soluble polymer, a photoacid generator, and a solvent.
• a photosensitive resin composition for microlenses produced by a reflow method.
• a CCD/CMOS image sensor is known as a solid-state image sensor.
• a T0F (T i me o f F l i g h t) type range image sensor used for three-dimensional (3D) cameras has been developed.
• the TO F method is a method that measures the distance to the measurement target by detecting the flight time until the light emitted from the light source is reflected by the measurement target and received by the sensor.
• the image sensor that uses this T ⁇ F method can acquire highly accurate three-dimensional range images by detecting range information for each pixel.
• a CCD/CMOS image sensor is provided with a microlens in order to improve light collection efficiency.
• a reflow method is known as one of the methods for producing the microlens (see, for example, Patent Document 1). That is, a photosensitive resin composition is applied on a substrate, and a pattern having a rectangular cross-section is formed by photolithography, and then the rectangular pattern is melted and flowed by heat treatment to obtain surface tension. Is a method for producing a lens shape.
• a photosensitive resin composition containing a polymer, a photoacid generator, a solvent, and titanium black is known (see Patent Document 2).
• the polymer in the photosensitive resin composition described in Patent Document 2 is a polymer having a first constitutional unit having a group in which an acid group is protected by an acid-decomposable group and a second constitutional unit having a crosslinkable group. And at least one of the polymer having the first constitutional unit and the polymer having the second constitutional unit is satisfied.
• the above-mentioned photosensitive resin composition is for forming microlenses, particularly for forming microlenses produced by the reflow method. ⁇ 2020/175036 2 ⁇ (: 170? 2020/004145
• Patent Document 1 Japanese Patent Laid-Open No. 20 0 6—3 3 7 9 5 6
• Patent Document 2 International Publication No. 2 0 15/1 2 5 8 7 0 Summary of Invention
• the photosensitive resin composition for forming a microlens is required to be capable of forming a pattern having a desired shape by a photolithography method. Then, in order to form a pattern having a desired shape, it is required to suppress the generation of a residue after developing with an alkaline developer. Further, in order to manufacture a microlens by the reflow method, the pattern needs to be reflowable. Further, when a coating film such as a flattening film is formed on the manufactured microlens by a coating method, the film-forming composition used usually contains a solvent, and thus the manufactured microlens has a solvent resistance. It is required to have it.
• the present invention solves all the above problems. That is, the present invention contains the following (8) component, the following (Mitsu) component and the following ( ⁇ 3) component, and at least 0.5 mass% of the (Mami) component relative to 100 mass% of the () component. It is a photosensitive resin composition for microlenses containing.
• X 1 and X 2 each independently represent an alkylene group having 2 to 4 carbon atoms, Represents an acid dissociable group, and 2 represents a blocked isocyanate group.
• the acid dissociable group is, for example, a group represented by the following formula (3).
• the blocked isocyanate group is, for example, a group represented by the following formula ( ⁇ ) or the following formula ( ⁇ ).
• X represents a bond with the alkylene group represented by X 2 , Represents a methyl group or an ethyl group, represents a methyl group, and 3 represents an integer of 0 to 3.
• the copolymer may further include at least one of a structural unit represented by the following formula (4 3 ) and a structural unit represented by the following formula (4 13).
• the photo-acid generator is, for example, diphenyl [4-(phenylthio)phenyl] sulfonium salt compound, or 1 ⁇ 1-(trifluoromethanesulfonyloxy).
• the photosensitive resin composition for microlenses is coated on a substrate. ⁇ 2020/175036 5 ⁇ (: 170? 2020 /004145
• a method for manufacturing a microlens which comprises the step of:
• the photosensitive resin composition for microlenses of the present invention can form a pattern having a rectangular cross section by a photolithography method, and does not cause a residue in an exposed portion where the pattern is not formed after development. , It is possible to prevent the residue from being generated even at the bottom of the formed pattern. Furthermore, the pattern is reflowable, and using the photosensitive resin composition for microlenses of the present invention, a thick film (maximum height of 10 to 20) microlenses having solvent resistance is prepared. can do.
• the present invention provides Component, (8) component and ( ⁇ 3) component, and the () component
• the photosensitive resin composition for microlenses which contains at least 0.5 mass% of the (min) component with respect to 100 mass%.
• the photosensitive resin composition for a microlens of the present invention is a positive photosensitive resin composition.
• the solid content obtained by removing the solvent from the photosensitive resin composition for a microlens of the present invention is usually 1% by mass to 50% by mass.
• the components of the photosensitive resin composition for a microlens of the present invention, excluding the solvent, are defined as the solid content.
• the component () in the photosensitive resin composition for a microlens of the present invention includes a structural unit represented by the formula (1), a structural unit represented by the formula (2) and the formula (2). ⁇ 2020/175036 6 ⁇ (: 170? 2020/004145
• the copolymer is a copolymer having a structural unit represented by 3) and having a weight average molecular weight of 500 to 250.
• the copolymer is not limited to an evening polymer (ternary copolymer) obtained from three types of monomers, but a copolymer obtained from four types of monomers or a copolymer obtained from five types of monomers. May be
• the weight average molecular weight of the copolymer is a value obtained by gel permeation chromatography ( ⁇ ) using polystyrene as a standard sample.
• the structural unit represented by the above formula (1) is represented by the following formula (13), for example.
• the structural unit represented by the formula (1) is not limited to the structural unit represented by the following formula (13) as long as it is a structural unit having an acid dissociable group.
• the acid dissociable group is a group that is dissociated by an acid to become an alkali-soluble group.
• the acid is an acid generated from the photoacid generator of component (N) upon exposure
• the alkali-soluble group is a carboxy group.
• the monomer forming the structural unit represented by the formula (1) include 1-methoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, 1-propoxyethyl (meth)acrylate. , 1 — Isopropoxyethyl (meth) acrylate, 1 _ 1 ⁇ ! — Butoxyethyl (meth) acrylate ⁇ 2020/175036 7 ⁇ (: 170? 2020 /004145
• the structural unit represented by the above formula (2) is a structural unit having a hydroxy group as a crosslinkable group.
• Specific examples of the monomer forming the structural unit represented by the formula (2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. .. These monomers may be used alone or in combination of two or more.
• the structural unit represented by the formula (3) is represented by, for example, the following formula (3) or the following formula (30).
• the structural unit represented by the formula (3) is not limited to the structural unit represented by the following formula (3 units) or the following formula (30) as long as it is a structural unit having a block isocyanate group.
• the blocked isocyanate group is a group in which an isocyanate group (1 1 ⁇ 1(30)) is blocked by a protective group capable of thermal elimination, that is, a group obtained by reacting an isocyanate group with a blocking agent.
• Specific examples of the monomer forming the structural unit represented by the formula (3) include 2-isocyanatoethyl methacrylate, 2-isocyanateethyl acrylate, and other isocyanate-containing (meth)acrylates, and methylethylketone oxime, Examples thereof include compounds to which a blocking agent such as caprolactam, 3,5-dimethylpyrazole and diethyl malonate is added. These monomers may be used alone or in combination of two or more.
• the () component of the copolymer may further include at least one of the formula (4 3) and a structural unit Formula represented (4 spoon) structural unit represented by.
• monomers that forms the structural unit represented by the formula (4 3 methylation (meth) acrylate, ethyl (meth) acrylate, _ propyl (meth) acrylate, isopropyl (meth) acrylate, 1 ⁇ _ Butyl (meth)acrylate, isobutyl (meth)acrylate, ⁇ "-butyl (meth)acrylate, Pentyl (meth)acrylate, cyclopentyl (meth)acrylate, _ Hexyl (meth) acrylate and cyclohexyl (meth) acrylate.
• Specific examples of the monomer forming the structural unit represented by the above formula (4) are 1 ⁇ 1-cyclohexylmaleamide and 1 ⁇ 1-phenylmaleimide. These monomers may be used alone or in combination
• the content rate of the structural unit represented by the formula (3) is, for example,
• the content rate of the structural unit represented by the above formula (43) is, for example, 0 ⁇ ! ⁇ I% to 600 ⁇ ! ⁇ I %, of the structural unit represented by the above formula (4)
• Content rate is for example
• the content of the structural unit represented by the formula (2) and the structural unit represented by the formula (3) is higher than the upper limit value, when a pattern is formed by the photolithographic method, exposure to a developing solution is performed. There is a risk that the pattern of the desired shape cannot be obtained because the solubility of the part is insufficient. Since the copolymer of the component () has the structural unit represented by the formula (2) and the structural unit represented by the formula (3), the crosslinking reaction proceeds by baking. Therefore, the content ratio of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (3) is preferably equimolar. Since the structural unit represented by the above formula (43) and the structural unit represented by the above formula (4) can adjust the glass transition point (Cho 9) of the copolymer by the content ratio, The reflow property of the pattern can be easily controlled.
• the method for obtaining the copolymer of the above (8) component is not particularly limited.
• the monomer forming the structural unit represented by the above formula (1), the monomer forming the structural unit represented by the above formula (2) and the structural unit represented by the above formula (3) are At least one of the monomer to be formed, and optionally the monomer to form the structural unit represented by the formula (4 3) and the monomer to form the structural unit represented by the formula (4 10) is used as a polymerization initiator.
• a solvent in the presence usually 50 ° ⁇ to 1 ⁇ 2020/175036 10 boxes (: 170? 2020 /004145
• the copolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the photosensitive resin composition for microlenses of the present invention without isolation in this state.
• the (min) component in the photosensitive resin composition for microlenses of the present invention is a photoacid generator.
• the photo-acid generator is not particularly limited as long as it is a compound capable of generating an acid upon exposure. Specific examples of the compound include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.
• onium salt compound examples include diphenyl iodonium hexafluorophosphate, diphenyl iodonium trifluoromethanesulfonate, and diphenyl iodonium nonafluoro.
• Examples include phonium salt compounds.
• onium salt compounds sulfonium salt compounds, and more preferably diphenyl [4- (phenylthio) phenyl] sulfonium salt compound as a compound which the acid is generated by exposure using a ⁇ (365 n m).
• the sulfonimide compound examples include 1 ⁇ 1_ (trifluoromethanesulfonyloxy) succinimide, 1 ⁇ 1_ (nonafluoro-_ butanesulfonyloxy) succinimide, 1 ⁇ 1_ (camphorsulfonyloxy) succinimide, 1 ⁇ 1_ (trifluoromethanesulfonyloxy) _ 1,8—naphthalimide, 1 ⁇ 1_ (trifluoromethanesulfonyloxy) _2—alkyl-1,8—naphthalimide, 1 ⁇ 1_ (trifluoromethanesulfonyloxy) _3 —alkyl 1, Examples include 8-naphthalimide and 1 ⁇ 1-(trifluoromethanesulfonyloxy)-4-alkyl-1,8-naphthalimide.
• 1 ⁇ 1-(trifluoromethanesulfonyloxy) examples include 8-naphthalimide and 1
• disulfonyldiazomethane compound examples include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(_toluenesulfonyl)diazomethane, bis(2,2, 4-dimethylbenzenesulfonyl) diazomethane, and methylsulfonyl-toluenesulfonyldiazomethan.
• ADEKA ARCRUZ registered trademark
• the photo-acid generator as the component (M) is contained in an amount of at least 0.5 mass% based on 100 mass% of the component ().
• the content of the photo-acid generator is less than 0.5% by mass, the acid-dissociable group of the component () does not dissociate and the alkali-soluble group does not develop. Therefore, when the pattern is formed by the photolithography method, the solubility of the exposed portion in the developer may be insufficient, and a pattern having a desired shape may not be obtained.
• the upper limit of the content of the photo-acid generator varies depending on the strength of the acid generated by exposure. For example, the stronger the acid generated from the photo-acid generator upon exposure is, the smaller the upper limit of the content of the photo-acid generator can be.
• the photo-acid generator As the photo-acid generator, ADEKA ARCRUZ (registered trademark) 3 When 606 is used, the upper limit of its content is, for example, 5 mass% with respect to 100 mass% of the component (8). When the content of the photo-acid generator is too large, when the pattern is formed by the photolithography method, the photo-acid generator is likely to remain as a residue in the exposed area after development.
• the component is a solvent.
• the solvent include ethylene glycol ⁇ 2020/175036 13 ⁇ (: 170? 2020 /004145
• Examples include 2-heptanone and arbutyrolactone. These solvents may be used alone or in combination of two or more.
• the photosensitive resin composition for microlenses of the present invention may contain a surfactant for the purpose of improving the coating property on a substrate.
• a surfactant for the purpose of improving the coating property on a substrate.
• Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octyl phenyl ether.
• Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene ⁇ polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate — polyoxyethylene sorbitan monopalmitate, polyoxyethylene ⁇ 2020/175036 14 ⁇ (: 170? 2020 /004145
• Polyoxyethylene sorbitan tristearate Polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan tristearate, and other nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, F-top (registered trademark) Mitsumi 301, Domomi 303 , Dozumi 352 (above, manufactured by Mitsubishi Material Electronic Kasei Co., Ltd.), Megafac (registered trademark)-171, same-173, same [3 ⁇ 4-30, (Above, manufactured by 0 I 0 Co., Ltd.)
• Fluorard ⁇ 430, ⁇ 431 (above, manufactured by 3M Japan Co., Ltd.), Asahi Guard (registered trademark) 807 7 10, Surflon (registered trademark) 3 _ 382, 3 010 1 and 3 ⁇ 10 02, 3 01 03, 3 10 4 and 3 (31 05, 3 10 6 (manufactured by Hachio Co., Ltd.)), 2020, F TX 2 1 20, 20 2 1 8, D2 1 2200, D2 2300, F TX -2400, D2 1 2 1, D2 220, D2 228, D2 24 etc. Futgent series (Co., Ltd.) Fluorine-based surfactants such as Neos) and organosiloxane polymers ⁇ 341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• the surfactants may be used alone or in combination of two or more.
• the content thereof is 3% by mass or less based on the content in the solid content of the composition, preferably It is 1 mass% or less, and more preferably 0.5 mass% or less.
• the photosensitive resin composition for a microlens of the present invention is a curing aid, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, an adhesion aid, if necessary, as long as the effects of the present invention are not impaired.
• a dissolution promoter such as polyhydric phenol or polyhydric carboxylic acid may be contained as other additive.
• the photosensitive resin composition for microlenses of the present invention does not require a crosslinking agent because the copolymer of the component () is self-crosslinking.
• the method for preparing the photosensitive resin composition for microlenses of the present invention is not particularly limited.
• the solution of the copolymer of the component (A) and the photoacid generator of the component (B) are There is a method in which the solvent of the component (C) is mixed at a predetermined ratio to form a uniform solution.
• a method in which the surfactant and the other additives are optionally further added and mixed can be mentioned.
• Substrate a semiconductor substrate made of silicon or the like which may be covered with a silicon oxide film, a silicon nitride film or a silicon oxynitride film, a semiconductor such as silicon which may be covered with an organic film such as a color filter or a flattening film.
• the photosensitive resin composition for microlenses of the present invention is applied by an appropriate application method such as a spinner or a coater, and then A resin film is formed by pre-baking using a heating means such as a hot plate.
• the pre-bake conditions are appropriately selected from a baking temperature of 80 ° C to 150 ° C and a baking time of 0.3 minutes to 60 minutes, preferably a baking temperature of 80 °C to 120 °C and a baking time. 0.5 to 5 minutes.
• the film thickness of the resin film formed from the photosensitive resin composition for microlenses of the present invention is 0.005 m to 30 m, and preferably 0.005 m.
• the obtained resin film is exposed through a mask (reticle) for forming a pattern having a desired shape.
• a mask for forming a pattern having a desired shape.
• near-ultraviolet rays or visible rays such as g-ray, i-ray and KrF excimer laser can be used.
• the exposed resin film is baked (post exposure bake).
• the baking conditions after exposure, baking temperature 80 ° C to 1 20 ° C, is appropriately selected from base click time 0.3 minutes to 60 minutes. ⁇ 2020/175036 16 ⁇ (: 170? 2020/004145
• the resin film is developed using an alkaline developer.
• the alkaline developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium hydroxide solutions such as choline, and ethanol.
• alkaline aqueous solutions such as amine aqueous solutions such as amine, propylamine, and ethylenediamine.
• a surfactant can be added to these developers.
• the development conditions are as follows: development temperature of 5° to 5° and development time of 10 seconds to 3
• the resin film can be easily developed at room temperature using an aqueous solution of tetramethylammonium hydroxide. After the development, appropriate rinsing is performed using, for example, ultrapure water as a rinsing solution.
• the formed pattern is reflowed by the first post bake.
• the baking temperature 1 2 0 ° ⁇ to 2 0 0 ° ⁇ is suitably selected from baking time ⁇ . 3 minutes to 6 0 min.
• 9 lines, sen line, Near-ultraviolet rays or visible rays such as excimer laser may be used to expose the entire surface of the pattern after the opening.
• the above-mentioned pattern may be subjected to post-exposure bake again.
• the post-exposure bake conditions for example, at a baking temperature of 1 2 0 ° ⁇ to 2 0 0 ° ⁇ is appropriately selected from baking time 0.
• the post-baking conditions for the second time are appropriately selected from a baking temperature of 150 ° to 250 ° and a baking time of 0.3 to 60 minutes.
• Synthesis Example Copolymer 1 is obtained () component 1 6.6 9, (snake) Single 3 as component der Ru photoacid generator 606 (KK eighty snake eight) ⁇ . 83 9 , And X-O 18 (manufactured by Neos Co., Ltd.) as a surfactant were dissolved in propylene glycol monomethyl ether 29.1 9 and propylene glycol monomethyl ether acetate 3.29, which are the components ( ⁇ ). It was used as a solution. Then, the solution was filtered using a polyethylene microfilter having a pore size of 1 to prepare a photosensitive resin composition for microlenses.
• the photo-acid generator used in this example and Examples 2 to 4, 8 and 9 described later corresponds to a derivative of 1 ⁇ 1_(acrylifluoromethanesulfonyloxy) 1,8-naphthalimide.
• Synthesis Example Copolymer 1 is obtained () component 1 8.6 9, (snake) Single 3 as component der Ru photoacid generator 606 (KK eighty snake eight) ⁇ . 37 9 , And as a surfactant, R-X-18 (manufactured by Neos Co., Ltd.) 0.00579 is dissolved in propylene glycol monomethyl ether 27.99 and propylene glycol monomethyl ether acetate 3.1, which are components ( ⁇ ), to prepare a solution. And Then, the solution was filtered using a polyethylene microfilter having a pore size of 1 to prepare a photosensitive resin composition for microlenses. ⁇ 2020/175036 22 ⁇ (: 170? 2020 /004145
• the copolymer () which is the component (18) obtained in Synthesis Example 1 and the photo-acid generator which is the component (M) ⁇ 1-1 1 0 0 (manufactured by San-Apro Co., Ltd.) 0.9 1.9, and R-X—18 (manufactured by Neos Co., Ltd.) as a surfactant, 0.005579, and propylene glycol monomethyl ether, which is the ( ⁇ ) component, 27.9.9 and propylene glycol monomethyl ether acetate. 3. was dissolved dissolved solution 1 9. Then, the solution was filtered using a polyethylene microfilter having a pore size of 1 to prepare a photosensitive resin composition for microlenses.
• the photo-acid generator used in this example corresponds to a diphenyl[ 4 -(phenylthio)phenyl]sulfonium salt compound.
• the copolymer () which is the component () obtained in Synthetic Example 1 is 18.1 9, and the component () is ⁇ 2020/175036 23 ⁇ (: 170? 2020/004145
• ⁇ 1-1 1 0 (manufactured by San-Apro Co., Ltd.) 0.9 1 9, and as a surfactant, X- 1 8 (manufactured by Neos Co., Ltd.) ⁇ 0.005 79 and a ( ⁇ ) propylene glycol monomethyl ether 2 7 is a component. 9 9 and propylene glycol monomethyl ether acetate 3. dissolved in 1 9 solvent solution. Then, the solution was filtered using a polyethylene microfilter having a pore size of 1 to prepare a photosensitive resin composition for microlenses.
• the photo-acid generator used in this example corresponds to a diphenyl[ 4 -(phenylthio)phenyl]sulfonium salt compound.
• (18) Copolymer which is the component () obtained in Synthesis Example 1, and (photo) as the photo-acid generator, which is the component ( ⁇ )-2 1 0 3 (manufactured by San-Apro Co., Ltd.) 0.9 1.9, and R-X—18 (manufactured by Neos Co., Ltd.) as a surfactant, 0.005579, and propylene glycol monomethyl ether, which is the ( ⁇ ) component, 27.9.9 and propylene glycol monomethyl ether acetate. 3. was dissolved dissolved solution 1 9. Then, the solution was filtered using a polyethylene microfilter having a pore size of 1 to prepare a photosensitive resin composition for microlenses.
• the photo-acid generator used in this example corresponds to a diphenyl[ 4 -(phenylthio)phenyl]sulfonium salt compound.
• Synthesis Example solution of the copolymer obtained in 6 (solid concentration 35 wt%) 43.5 9 (snake) Single 3 as a photo-acid generator is a component 606 (Ltd. eighty snake eight Ltd.) 0 . 76 9, and (b) X- 1 8 (manufactured by Neos Co.) as a surfactant to 0.00 489 ( ⁇ ) propylene glycol monomethyl E over Tel 2 is a component.
• Copolymer 1 is obtained in Synthesis Example 1 () component 9.0 9, (snake) Single 3 as component der Ru photoacid generator 606 (Ltd. eighty Snake ⁇ made eight) ⁇ . 01 99 and 0.00579 as a surfactant (Neos Co., Ltd.) 0.00579 and ( ⁇ ) component propylene glycol monomethyl ether 27. 99 and propylene glycol monomethyl ether acetate. 3. a solution dissolved in 1 9. Then, the solution was filtered using a polyethylene filter having a pore size of 1 to prepare a photosensitive resin composition for microlenses. The content of the component (M) in the photosensitive resin composition for microlenses of this comparative example is less than 0.5% by mass relative to 100% by mass of the component ().
• the resin film was developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 50 seconds, rinsed with ultrapure water for 20 seconds, and dried. As a result, a pattern was formed on the silicon wafer.
• the cross-sectional shape of the obtained pattern was observed with a scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). "X" if the cross-sectional shape of the pattern is not rectangular
• the residue after development was evaluated by observing the exposed portion around the pattern formed on the silicon wafer. When a large amount of residue is observed in the exposed area where the pattern is not formed, "X" is given. When no residue is observed in the exposed area where the pattern is not formed, but when a residue is observed at the hem of the pattern. The residue after development was evaluated as “ ⁇ ”, and when no residue was observed at the exposed portion where the pattern was not formed and at the skirt of the pattern, the residue after development was evaluated. The evaluation results are shown in Table 1.
• a silicon wafer on which a rectangular pattern was formed from the photosensitive resin composition for microlenses prepared in Examples 1 to 9 and Comparative Examples 1 and 3 was placed on a hot plate and placed at 140 ° C. A minute bake was done. After the post-baking, the cross-sectional shape of the obtained pattern was observed with a scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation). The reflow property of the pattern was evaluated as “X” when the cross-sectional shape of the pattern did not change at all and “ ⁇ ” when the cross-sectional shape of the pattern changed and became a semicircle. Table 1 shows the evaluation results.
• a resin film having a film thickness of 10 was formed by prebaking at 100 ° for 90 seconds on a hot plate. Then, bake at 100 ° ⁇ for 90 seconds on the hot plate, then continue baking at 140 ° ⁇ for 5 minutes, then 220 ° ⁇ for 5 minutes. Thus, a cured film was formed on the silicon wafer. Both the pre-baking and the post-baking were performed in the atmosphere.
• the resin films formed from the photosensitive resin compositions for microlenses prepared in Examples 1 to 9 had pattern rectangularity, degree of residue after development, and pattern reflow property. In this respect, excellent results were obtained, and the cured film formed from the resin film exhibited excellent solvent resistance.
• the resin films formed from the photosensitive resin compositions for microlenses prepared in Comparative Examples 2 to 4 had good results in any of the pattern rectangularity, the degree of residue after development, and the pattern reflow property. However, it was confirmed that the cured film formed from the photosensitive resin composition for microlenses of Comparative Example 1 had low solvent resistance, indicating the superiority of the present invention.

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