WO2016125782A1 - Nouveau composé ester alicyclique, copolymère (méth)acrylique, et composition de résine fonctionnelle les contenant - Google Patents

Nouveau composé ester alicyclique, copolymère (méth)acrylique, et composition de résine fonctionnelle les contenant Download PDF

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WO2016125782A1
WO2016125782A1 PCT/JP2016/053035 JP2016053035W WO2016125782A1 WO 2016125782 A1 WO2016125782 A1 WO 2016125782A1 JP 2016053035 W JP2016053035 W JP 2016053035W WO 2016125782 A1 WO2016125782 A1 WO 2016125782A1
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group
carbon atoms
meth
formula
general formula
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宏幸 棚木
博康 田中
哲彦 水阪
古川　喜久夫
堀越　裕
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三菱瓦斯化学株式会社
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Publication of WO2016125782A1 publication Critical patent/WO2016125782A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention includes a novel lactone (meth) acrylate compound suitable for resists for KrF, ArF, and F2 excimer lasers, and chemically amplified resist materials for X-rays, electron beams, and EUV (extreme ultraviolet light), and the novel compounds.
  • the present invention relates to a (meth) acrylic copolymer and a photosensitive resin composition containing the copolymer.
  • Photolithography is widely used in the manufacture of various electronic devices. In photolithography, miniaturization has been promoted by shortening the wavelength of the light source.
  • a chemically amplified resist is generally used.
  • a composition of a chemically amplified resist used as a solution is composed of a functional resin as a main agent, and It contains a photoacid generator, as well as several additives.
  • the functional resin which is the main component, is important to have well-balanced characteristics such as etching resistance, substrate adhesion, transparency to the light source used, and development speed, which determine resist performance. .
  • the functional resin used in the photoresist for excimer laser is generally a polymer having a vinyl compound or acrylate as a repeating unit.
  • a hydroxystyrene resin is proposed (Patent Document 1)
  • an acrylic resin having adamantyl (meth) acrylate as a basic skeleton is proposed ( Patent Documents 2 to 6).
  • Non-patent Document 1 a method using a photoacid generator having a large skeleton structure
  • Patent Document 7 a method using a resin containing a monomer having a photoacid generator
  • resist a resist
  • JP 2006-243474 A Japanese Patent Laid-Open No. 4-39665 JP 10-319595 A JP 2000-26446 A JP 2003-167346 A JP 2004-323704 A JP 2012-168502 A JP 2005-331918 A JP 2008-129388 A
  • the problem of the present invention is that the KrF excimer laser, ArF excimer laser, F2 excimer laser, X-ray, electron beam, and resist material for EUV lithography impair sensitivity, resolution, substrate adhesion, and etching resistance. And developing a resist capable of improving line edge roughness (LER), and providing a functional resin composition that is technically preferable for increasing the integration density of semiconductor substrate circuits, which will continue to advance in the future. . *
  • a lactone (meth) acrylate compound having a specific structure is a KrF excimer laser, ArF excimer laser, F2 excimer laser, X-ray, electron beam or It has been found that it is a useful compound capable of forming a fine pattern in a lithography operation performed by EUV (extreme ultraviolet light) or the like. That is, the present invention is as follows.
  • a lactone (meth) acrylate compound represented by the general formula (1) (In formula (1), R 1 represents a hydrogen atom or a methyl group; R 2 represents hydrogen, an aliphatic alkyl group having 1 to 10 carbon atoms, or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms; R 3 represents hydrogen, an alkoxycarbonyl group represented by the formula (2), an aliphatic alkyl group having 1 to 10 carbon atoms, or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms; In this case, R 2 and R 3 may be bonded to each other to form an alicyclic structure having 3 to 10 carbon atoms; n 1 represents an integer of 0-2.
  • R 4 represents an aliphatic alkyl group having 1 to 13 carbon atoms or an alkyl group having an alicyclic structure having 3 to 13 carbon atoms; the broken line represents a bond in the compound of the formula (1). Represents the location.
  • a (meth) acrylic copolymer having a repeating unit represented by the general formula (6) (In the formula (6), R 1 to R 3 and n1 are the same as in the formula (1), and the point * represents a bonding site with an adjacent repeating unit.)
  • R 41 represents hydrogen or a methyl group
  • R 42 to R 43 may be the same or different, each represents an alkyl group having 1 to 4 carbon atoms, and R 44 represents 1 to 4 carbon atoms
  • R 44 represents 1 to 4 carbon atoms
  • R 41 represents hydrogen or a methyl group
  • R 42 to R 44 may be the same or different and each represents one group selected from the group consisting of a hydrogen element, a hydroxyl group, a methyl group, and an ethyl group.
  • the point * represents a bonding point with an adjacent repeating unit.
  • a photosensitive resin composition comprising the (meth) acrylic copolymer according to any one of the above and a photoacid generator.
  • the lactone (meth) acrylate compound of the present invention is suitable as a raw material for various resin compositions such as various functional polymers having heat resistance, surface hardness, chemical resistance, and lipophilicity.
  • the lactone (meth) acrylate compound of the present invention is a component of a chemically amplified resist copolymer especially for KrF excimer laser, ArF excimer laser, F2 excimer laser, X-ray, electron beam, and EUV (extreme ultraviolet light). When used as, the line edge roughness (LER) can be improved without impairing the etching resistance and substrate adhesion.
  • the lactone (meth) acrylate compound of the present invention is represented by the general formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an aliphatic alkyl group having 1 to 10 carbon atoms or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms, and preferably R 2 represents an aliphatic alkyl group having 1 to 5 carbon atoms or 3 carbon atoms.
  • R 2 is an aliphatic alkyl group having 1 to 3 carbon atoms or an alkyl group having an alicyclic structure having 5 to 7 carbon atoms
  • R 3 represents an alkoxycarbonyl group represented by the formula (2), an aliphatic alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), or 3 to 10 carbon atoms (preferably 5 to 8 carbon atoms).
  • R 4 represents an aliphatic alkyl group having 1 to 13 carbon atoms or an alkyl group having an alicyclic structure having 3 to 13 carbon atoms.
  • R 4 represents 2 to 8 carbon atoms.
  • an alkyl group having an alicyclic structure of 5 to 10 carbon atoms; a broken line represents a bonding site in the compound of the formula (1).
  • the lactone (meth) acrylate compound (1) of the present invention is specifically exemplified below. However, it is not limited to these.
  • R 1 is a hydrogen atom or a methyl group.
  • R 3 is exemplified below.
  • the broken line in Formula (13) represents the coupling
  • the ketolactone compound represented by the general formula (3) is subjected to a reduction reaction and represented by the general formula (4).
  • the (meth) acrylic acid compound represented by the general formula (5) can be reacted, but is not limited thereto.
  • R 2 , R 3 and n 1 are the same as those in the general formula (1).
  • R 2 , R 3 and n 1 are the same as those in the general formula (1).
  • R 1 is the same as in general formula (1).
  • R 5 is one group selected from the group consisting of a hydroxyl group, a halogen atom, and a (meth) acryloyloxy group.
  • a halogen atom such as chlorine.
  • the ketolactone compound represented by the general formula (3) of the present invention is exemplified below.
  • R 3 is the same as in general formula (1).
  • Decane-2,6-dione, 1-oxaspiro [4.4] nonane-2,6-dione, 1-oxaspiro [4.6] undecane-2,6-dione, tertiary butyl 2-acetyl -5-Oxotetrahydrofuran-2-carboxylate is preferable from the viewpoint of availability, and for example, those synthesized according to the methods described in Non-Patent Documents 3 to 5 can be used.
  • the (meth) acrylic acid compound represented by the general formula (5) of the present invention is exemplified below.
  • (meth) acrylic acid chloride is preferable from the viewpoint of reactivity, and commercially available products such as acryloyl chloride (model number A0147) and methacryloyl chloride (model number M0556) manufactured by Tokyo Chemical Industry Co., Ltd. can be obtained. .
  • the manufacturing method of the lactone (meth) acrylate compound represented by the general formula (1) will be described in detail.
  • the reduction reaction of the ketolactone compound represented by the general formula (3) will be described.
  • a known reduction reaction is used for this reaction, but the reaction by hydride reduction is preferable because the operation is easy and the yield is good.
  • the reducing agent is added in an amount of 0.5 to 5.0 molar equivalents, preferably 0.6 to 3.0 molar equivalents, more preferably 0.8 to 1.5 molar equivalents relative to the ketolactone compound. If it is in the above-mentioned range, the reaction proceeds sufficiently, and the yield of the hydroxylactone compound represented by the general formula (4), which is the target product, is high and economically preferable.
  • the solvent commercially available products that are generally available can be used, and various solvents such as alcohols, ethers, hydrocarbons, and halogen-based solvents can be appropriately used as long as they do not inhibit the reaction.
  • a reducing agent such as sodium borohydride with a relatively low reducing power
  • an alcohol solvent is suitable.
  • a dehydrating solvent should be used. preferable.
  • the amount of the solvent is 1 to 100 parts by mass, preferably 5 to 10 parts by mass with respect to 1 part by mass of the ketolactone compound represented by the general formula (3).
  • reaction temperature and reaction time depend on the substrate concentration and the catalyst used, the reaction temperature is generally ⁇ 20 ° C. to 100 ° C., the reaction time is 1 hour to 10 hours, and the pressure is normal pressure, reduced pressure or increased pressure. it can.
  • the reaction can be performed by appropriately selecting a known method such as a batch system, a semi-batch system, or a continuous system.
  • the (meth) acrylic compound represented by the general formula (5) is isolated without isolating the hydroxylactone compound represented by the general formula (4).
  • the lactone (meth) acrylate compound of the general formula (1) can also be obtained by reacting with an acid compound.
  • the (meth) acrylic acid compound represented by the general formula (5) is 0.5 to 100 molar equivalents, preferably 1 to 20 molar equivalents relative to the hydroxylactone compound represented by the general formula (4). Preferably 1.2 to 5 molar equivalents are used. If it is this range, reaction will fully advance and the yield of the lactone (meth) acrylate compound represented by General formula (1) which is a target object is also high and economically preferable.
  • the solvent used for obtaining the product commercially available products can be used.
  • various solvents such as alcohols, ethers, hydrocarbons, and halogen solvents can be appropriately used as long as they do not inhibit the reaction. Since water inhibits the reaction, it is preferable to use a dehydrated solvent.
  • reaction temperature and reaction time depend on the substrate concentration and the catalyst used, the reaction temperature is generally ⁇ 20 ° C. to 100 ° C., the reaction time is 1 hour to 10 hours, and the pressure is normal pressure, reduced pressure or increased pressure. it can.
  • the reaction can be performed by appropriately selecting a known method such as a batch system, a semi-batch system, or a continuous system.
  • a polymerization inhibitor may be added to the series of reactions, and commercially available products can be used.
  • a polymerization inhibitor may be added to the series of reactions, and commercially available products can be used.
  • 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N- (1-naphthyl)
  • Nitroso compounds such as hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, N, N'-dimethyl-p-nitrosoaniline, phenothiazine, methylene blue, 2-mercapto Sulfur-containing compounds such as benzimidazole, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-is
  • Quinones such as hydroxynes, hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, 2 , 2-methylenebis- (6-t-butyl-4-methylphenol) and other phenols, N-hydroxyphthalimide and other imides, cyclohexane oxime, p-quinone dioxime and other oximes, and dialkylthiodipropinates Can be mentioned.
  • the addition amount is 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (meth) acrylic acid compound represented by the general formula (5).
  • the lactone (meth) acrylate compound represented by the general formula (1) obtained by the reaction is separated by known purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon and the like. It can be isolated and purified as a desired high purity monomer by a purification method or a combination thereof.
  • a (meth) acrylic copolymer can be obtained by copolymerizing the lactone (meth) acrylate compound represented by the general formula (1) of the present invention.
  • the (meth) acrylic copolymer can be used for a functional resin used in a photoresist.
  • the (meth) acrylic copolymer of the present invention has a repeating unit represented by the general formula (6) derived from the general formula (1). Furthermore, a copolymer containing at least one kind selected from the repeating units represented by the general formulas (7) to (8) and the repeating unit represented by the general formula (9) is preferable in order to improve resist performance. is there.
  • the (meth) acrylic copolymer may contain a structure represented by the general formula (9) or the general formulas (10) to (11) as a repeating unit.
  • R 21 represents hydrogen or a methyl group
  • R 22 represents an alkyl group having 1 to 4 carbon atoms
  • R 23 represents a cycloalkyl group or alicyclic alkyl group having 5 to 20 carbon atoms.
  • the point * represents a bonding point with an adjacent repeating unit.
  • R 22 represents an alkyl group having 1 to 3 carbon atoms
  • R 23 is a cycloalkyl group having 5 to 10 carbon atoms or an alicyclic alkyl group.
  • R 31 represents hydrogen or a methyl group
  • R 32 to R 33 may be the same or different, each represents an alkyl group having 1 to 4 carbon atoms
  • R 34 represents 1 to 4 carbon atoms.
  • a group selected from the group consisting of a cycloalkyl group having 5 to 20 carbon atoms and an alicyclic alkyl group, and any two of R 32 to R 34 are bonded to each other to form a carbon number 2 to 20 alicyclic structures may be formed, and the point * represents a bonding site with an adjacent repeating unit.
  • R 22 represents an alkyl group having 1 to 3 carbon atoms
  • R 23 is a cycloalkyl group having 5 to 10 carbon atoms or an alicyclic alkyl group.
  • the alicyclic structure may include a plurality of rings such as an adamantyl group.
  • R 41 represents hydrogen or a methyl group
  • R 42 to R 44 may be the same or different, and one group selected from the group consisting of a hydrogen element, a hydroxyl group, a methyl group, and an ethyl group
  • the point * represents a bonding point with an adjacent repeating unit.
  • R 51 represents hydrogen or a methyl group
  • R 52 represents a methyl group or an ethyl group
  • n 51 represents 0 to 2
  • n 52 represents 1 to 3
  • a point * is adjacent.
  • R 61 represents hydrogen or a methyl group
  • R 62 represents methylene (—CH 2 —) or oxa (—O—)
  • R 63 is the same or different, and represents a hydroxyl group, a halogen group
  • n 61 represents 0 to 2
  • a point * represents a bonding site with an adjacent repeating unit.
  • the monomer raw material of the repeating unit represented by the general formula (8) 2-cyclohexyl-2- (meth) acryloyloxypropane, 2- (4-methylcyclohexyl) -2- (meth) acryloyloxypropane, Examples thereof include 2-adamantyl-2- (meth) acryloyloxypropane and 2- (3- (1-hydroxy-1-methylethyl) adamantyl) -2- (meth) acryloyloxypropane.
  • Commercial products can be used as these monomers, and Daicel products can be easily obtained.
  • ⁇ - (meth) acryloyloxy- ⁇ -butyrolactone As the monomer raw material of the repeating unit represented by the general formula (10), ⁇ - (meth) acryloyloxy- ⁇ -butyrolactone, ⁇ - (meth) acryloyloxy- ⁇ -butyrolactone, (meth) acryloyloxypant Examples include lactones. Commercial products can be used as these monomers, and products of Osaka Organic Chemical Industry Co., Ltd. can be easily obtained.
  • the repeating units represented by the general formulas (7) and (8) have a function of dissociating with an acid. That is, when the repeating unit represented by the general formulas (7) and (8) reacts with an acid generated from a photoacid generator at the time of exposure, a carboxylic acid group is generated, so that the copolymer is converted to alkali-soluble. be able to.
  • a repeating unit having such a structure and performance is defined as an acid dissociable group.
  • the repeating unit represented by the general formula (9) can further improve solvent solubility, substrate adhesion, and affinity for an alkaline developer.
  • a repeating unit having a hydroxyl group is preferable because it has a high effect of improving resolution.
  • a repeating unit having such a structure and performance is defined as a polar group.
  • the repeating unit represented by the general formulas (10) and (11) has a lactone group, and improves solvent solubility, substrate adhesion, and affinity for an alkaline developer.
  • a repeating unit having such a structure and performance is defined as a lactone group.
  • the repeating unit represented by the general formula (6) also has a lactone and therefore belongs to the lactone group.
  • the repeating unit represented by the general formula (6) contains 20 to 80 mol%, preferably 30 to 60 mol%.
  • the polymer contains the repeating units represented by the general formulas (7) to (11)
  • at least one repeating unit represented by the general formulas (7) to (8) is 20 to 80 in total. Mol%, preferably 40 to 60 mol%.
  • the repeating unit represented by the general formula (9) contains 10 to 50 mol%, preferably 15 to 40 mol%.
  • the polymer contains the repeating units represented by the general formulas (10) to (11), it contains 5 to 40 mol% in all components.
  • the polymerization reaction is performed while dissolving a monomer as a repeating unit in a solvent, adding a catalyst, and heating or cooling.
  • the reaction conditions can be arbitrarily set depending on the type of initiator, the starting method such as heat and light, temperature, pressure, concentration, solvent, additive, etc.
  • the polymerization of the (meth) acrylic copolymer of the present invention can be carried out by a known method such as radical polymerization using a radical generator such as azoisobutyronitrile or peroxide, or ionic polymerization using a catalyst such as alkyllithium or Grignard reagent.
  • solvent used in the polymerization reaction commercially available products can be used.
  • various solvents such as alcohols, ethers, hydrocarbons, and halogen solvents can be appropriately used as long as they do not inhibit the reaction.
  • the (meth) acrylic copolymer obtained by the polymerization reaction can be purified by a known method. Specifically, ultrafiltration, crystallization, microfiltration, acid washing, water washing with an electric conductivity of 10 mS / m or less, and extraction can be performed in combination.
  • the polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of the (meth) acrylic copolymer of the present invention measured by gel permeation chromatography (GPC) is 1,000 to 500,000, preferably 3, 000 to 100,000.
  • the ratio (Mw / Mn) between the Mw of the (meth) acrylic copolymer and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by GPC is 1 to 10, preferably 1 to 5. is there. A large value of this ratio is not preferable because photoresist performance such as sensitivity, resolution, and roughness deteriorates.
  • a (meth) acryl copolymer can be used individually or in mixture of 2 or more types.
  • Photoacid generators can be used as acid generators for chemically amplified resist compositions depending on the wavelength of the exposure light, while considering the thickness range of the resist coating film and its own light absorption coefficient. Can be appropriately selected.
  • examples of photoacid generators that can be used in the far ultraviolet region include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, and diazomethane compounds. Can be used.
  • onium salt compounds such as sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, and pyridinium salts are suitable for KrF excimer laser, EUV, and electron beams.
  • triphenylsulfonium triflate triphenylsulfonium nonafluorobutyrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, diphenyliodonium triflate, diphenyl Examples thereof include iodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, and the like, and the photoacid generators can be used alone or in combination of two or more.
  • the amount of the photoacid generator used is 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, per 100 parts by weight of the photosensitive resin composition.
  • the photosensitive resin composition may be used after being dissolved in a solvent.
  • a commercially available product can be used as the solvent used.
  • linear ketones such as 2-pentanone and 2-hexanone
  • cyclic ketones such as cyclopentanone and cyclohexanone
  • propylene glycol monoalkyl acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate
  • ethylene Ethylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate
  • propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether
  • Ethylene glycol monoalkyl ethers such as diethylene glycol Call dimethyl ether, diethylene glycol
  • the photosensitive resin composition may further contain an acid diffusion controller.
  • the acid diffusion control agent controls the diffusion phenomenon in the resist film of the acid generated from the acid generator by exposure, and has an action of suppressing an undesirable chemical reaction in the non-exposed region.
  • As the acid diffusion controller a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment in the resist pattern forming step is preferable. As such nitrogen-containing organic compounds, commercially available products can be used.
  • monoalkylamines such as n-hexylamine, n-heptylamine and n-octylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; triethanolamine, tripropanolamine Substituted trialcoholamines such as tributanolamine, tripentanolamine and trihexanolamine, trialkoxyalkylamines such as trimethoxyethylamine, trimethoxypropylamine, trimethoxybutylamine and triethoxybutylamine; aniline, N, Aromatic amines such as N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline and diphenylamine; amine compounds such as ethylenediamine, formaldehyde Amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrroli
  • the photosensitive resin composition of the present invention may contain various additives such as a surfactant, a quencher, a sensitizer, an antihalation agent, a storage stabilizer, and an antifoaming agent as necessary. it can.
  • a method for forming a resist pattern using the photosensitive resin composition of the present invention will be described.
  • a resist film is formed by applying the photosensitive resin composition onto a substrate such as a silicon wafer, metal, plastic, glass, or ceramic by an application means such as a spin coater, a dip coater, or a roller coater. After the coating is formed, heat treatment is appropriately performed at about 50 ° C. to 200 ° C., and exposure is performed through a predetermined mask pattern.
  • the thickness of the coating film is 0.01 to 5 ⁇ m, preferably 0.02 to 1 ⁇ m, more preferably 0.02 to 0.1 ⁇ m.
  • Light beams of various wavelengths can be used for the exposure.
  • far ultraviolet rays such as F 2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), EUV ( Wavelength 13 nm), X-rays, electron beams and the like.
  • the exposure conditions such as the exposure amount are appropriately selected according to the composition of the photosensitive resin composition, the type of each additive, and the like.
  • a predetermined resist pattern is formed by developing with an alkali developer at 10 to 50 ° C. for 10 to 200 seconds, preferably at 20 to 25 ° C. for 15 to 1200 seconds.
  • alkaline developer commercially available products can be used.
  • alkaline compounds such as undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene, and 0.0001 to 10% by mass, preferably 0.01 to 5% by mass, and more preferably 0.8.
  • the developer composed of the alkaline aqueous solution may contain a water-soluble organic solvent or a surfactant.
  • a resist having excellent adhesion to a substrate and having alkali solubility can be produced, and a fine pattern can be formed with high accuracy.
  • the reaction solution was allowed to cool to 30 ° C., 100 g of heptane and 60 g of ion-exchanged water were added, transferred to a separatory funnel and shaken well, and the aqueous layer was recovered. After adding 18.5 g of 85 mass% phosphoric acid and 150 g of toluene to the aqueous layer and shaking well, the organic layer and the aqueous layer were separated. To the aqueous layer, 150 g of toluene was added again, and after shaking well, the organic layer was recovered. The collected organic layers were mixed and washed with 50 g of ion exchange water.
  • the solution temperature was kept at 50 to 60 ° C., and 22.0 g (194 mmol) of 30% aqueous hydrogen peroxide was added dropwise with a liquid feed pump over 2 hours (0.18 g / min). After completion of the dropwise addition, the mixture was stirred for 30 minutes and allowed to cool to a solution temperature of 20 to 30 ° C.
  • the reaction solution was transferred to a separatory funnel and washed with 250 g of a 20% by mass aqueous sodium sulfite solution. Then, 200 g of ethyl acetate was added to the separated aqueous layer to extract the organic layer. The collected organic layers were combined, washed with 200 g of ion exchange water, and this was performed twice.
  • the organic layer was concentrated with an evaporator to make the solution weight 65 g.
  • the mixture was cooled at 0 ° C. for 24 hours, and the precipitated crystals were collected by filtration.
  • the collected crystals were dried under reduced pressure at 40 ° C. to obtain 19.1 g of 1-oxaspiro [4,5] decane-2,6-dione (yield 64.5%).
  • the dropping funnel was charged with 3.76 g (36.0 mmol) of methacrylic acid chloride and added dropwise to the reaction solution.
  • the solution temperature was raised to 70 ° C. and stirred for 8 hours.
  • the solution temperature was brought to room temperature, 50 g of 1,2-dichloroethane was added, and then 30 g of ion-exchanged water was added for quenching.
  • the reaction solution was transferred to a 2 L separatory funnel, and the organic layer was collected. The organic layer was further washed with 30 g of 5% aqueous sodium hydrogen carbonate solution and 30 g of ion-exchanged water.
  • Stereoisomer 1 1 H-NMR spectrum (CDCl 3 ): ⁇ 1.43 to 2.69 ppm (12H, m, cyclohexane ring, methylene group of butyrolactone ring), 2.05 ppm (3H, s, methyl group of methacryloyl group) ), 4.80 ppm (1H, m, methine group of cyclohexane ring), 5.56 ppm (1H, s, methacryloyl group double bond), 6.00 ppm (1H, s, methacryloyl group double bond).
  • the solution temperature was kept at 50 to 60 ° C., and 37.1 g (389 mmol) of 35% aqueous hydrogen peroxide was added dropwise with a liquid feed pump over 3 hours (0.21 g / min). After completion of the dropwise addition, the mixture was stirred for 30 minutes and allowed to cool to a solution temperature of 20 to 30 ° C.
  • the reaction solution was transferred to a separatory funnel and washed by adding 325 g of a 20% by mass aqueous sodium sulfite solution. Then, 300 mL of ethyl acetate was added to the separated aqueous layer to extract the organic layer.
  • Stereoisomer 1 1 H-NMR spectrum (CDCl 3 ): ⁇ 1.27 (3H, d, C H 3 —CH (—O—) C—), 1.42 ppm (9H, s, t-butyl group) 1.90 (3H, s, methyl group of methacryloyl group), 2.24 to 2.60 ppm (4H, m, methylene group of butyrolactone ring), 5.38 ppm (1H, m, CH 3 —C H (— O-) C-), 5.58 ppm (1H, d, methacryloyl group double bond), 6.10 ppm (1H, d, methacryloyl group double bond).
  • a dropping funnel was charged with 20.7 g (200 mmol) of methacrylic acid chloride and dropped into the reaction solution.
  • the solution temperature was raised to 50 ° C. and stirred for 8 hours.
  • the solution temperature was brought to room temperature, and quenched by adding 100 g of ion exchange water.
  • the solution was transferred to a 500 mL separatory funnel and the organic layer was recovered, and then washed with 100 g of ion-exchanged water to recover the organic layer.
  • the solvent was concentrated in vacuo, purified by silica gel column chromatography, and the solvent was distilled off to obtain 16.2 g (yield 82.4%) of 1-ethyl-1-methacryloyloxycyclohexane.
  • the reaction solution was dropped into 500 mL of n-hexane to coagulate and purify the resin, and the resulting white powder was filtered through a membrane filter and washed with 1000 mL of n-hexane. The white powder was collected and dried overnight at 40 ° C. under reduced pressure to obtain 6.77 g of methacrylic copolymer P2.
  • the reaction solution was dropped into 500 mL of n-hexane to coagulate and purify the resin, and the resulting white powder was filtered through a membrane filter and washed with 1000 mL of n-hexane.
  • the white powder was collected and dried overnight at 40 ° C. under reduced pressure to obtain 4.94 g of methacrylic copolymer P3.
  • the reaction solution was dropped into 500 mL of n-hexane to coagulate and purify the resin, and the resulting white powder was filtered through a membrane filter and washed with 1000 mL of n-hexane.
  • the white powder was collected and dried overnight at 40 ° C. under reduced pressure to obtain 5.45 g of methacrylic copolymer P4.
  • Photopolymer compositions R1, R2, R3, and R4 were prepared by dissolving in a propylene glycol monomethyl ether acetate solvent so that the polymer concentration was 6.3% by mass.
  • this photoresist resin composition was applied on the antireflection film by spin coating.
  • a photosensitive layer having a thickness of 100 nm was formed.
  • the photosensitive layer is irradiated with a 100 nm half pitch line and space pattern (8 lines) using an electron beam drawing apparatus (ELS-7700, manufactured by Elionix). did.
  • ELS-7700 electron beam drawing apparatus
  • PEB post-baking
  • GBLMA ⁇ -methacryloyloxy- ⁇ -butyrolactone
  • Resist performance evaluation 2 The same operation as in Resist Performance Evaluation 1 was performed to prepare a photosensitive resin composition R5 using P5 obtained in Comparative Example 1 instead of methacrylic copolymers P1, P2, P3, and P4, and further comparison A photosensitive resin composition R6 was prepared using P6 obtained in Example 2. And about these photosensitive resin compositions R5 and R6, the resist performance was evaluated similarly to the resist performance evaluation 1.
  • the obtained line and space pattern was observed with FE-SEM, and the resolution and line edge roughness (LER) were measured.
  • the results are shown in Table 4.
  • the photosensitive resin compositions R1 and R3 had the same structure and composition other than the lactone as R1 and R3, respectively. It turned out that the value of LER is smaller than the thing R5 and R6.
  • the repeating units A1 and A2 contained in the photosensitive resin compositions R1 and R3 have a structure that is sterically bulkier than the repeating units A3 and A4 contained in R5 and R6. Therefore, it is considered that the diffusion of the acid dissociated during electron beam drawing was suppressed, and as a result, the roughness could be reduced.
  • Table 5 shows the results of the photosensitive resin compositions R2 and R4.
  • the copolymer composition of the photosensitive resin compositions R2 and R4 is different from the above-described R1 and R3, but these photosensitive resin compositions R2 and R4 also have the same degree as the photosensitive resin compositions R1 and R3. Good results were shown. That is, it was confirmed that the photosensitive resin compositions R2 and R4 can realize excellent resolution and a small value of LER. These results are also due to the same reason that the LER values of the photosensitive resin compositions R1 and R3 are smaller than the LER values of R5 and R6, that is, mainly due to the difference in the three-dimensional bulkiness of the repeating units. I can think of it.

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Abstract

La présente invention concerne, en tant que photorésine amplifiée chimiquement, une photorésine et un composé ayant un bon équilibre grâce auquel la rugosité de bord de ligne (LER) est améliorée sans altérer les propriétés physiques de base intrinsèques dans une photorésine, comme les propriétés d'adhérence à une base et de résistance à la gravure à sec. L'invention concerne un composé ester de lactone représenté par la formule générale (1), un procédé de production de ce dernier, un copolymère (méth)acrylique comprenant la formule générale (1), et une composition de résine photosensible contenant ce dernier. (Dans la formule (1) : R1 désigne un atome d'hydrogène ou un groupe méthyle ; R2 désigne un atome d'hydrogène, un groupe alkyle aliphatique ayant 1 à 10 atomes de carbone ou un groupe alkyle ayant une structure alicyclique ayant 3 à 10 atomes de carbone ; R3 désigne un atome d'hydrogène, un groupe alcoxycarbonyle représenté par la formule (2), un groupe alkyle aliphatique ayant 1 à 10 atomes de carbone ou un groupe alkyle ayant une structure alicyclique ayant 3 à 10 atomes de carbone ; R2 et R3 peuvent se lier l'un à l'autre pour former une structure alicyclique ayant 3 à 10 atomes de carbone ; et n1 est un nombre entier compris entre 0 et 2.) (Dans la formule (2) : R4 désigne un groupe alkyle aliphatique ayant 1 à 13 atomes de carbone ou un groupe alkyle ayant une structure alicyclique ayant 3 à 13 atomes de carbone ; et la ligne en pointillés indique l'emplacement de liaison dans le composé représenté par la formule (1).)
PCT/JP2016/053035 2015-02-05 2016-02-02 Nouveau composé ester alicyclique, copolymère (méth)acrylique, et composition de résine fonctionnelle les contenant WO2016125782A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014139650A (ja) * 2012-12-21 2014-07-31 Jsr Corp フォトレジスト組成物、レジストパターン形成方法、重合体及び化合物
JP2016173513A (ja) * 2015-03-17 2016-09-29 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
CN115960054A (zh) * 2022-12-15 2023-04-14 南通常佑药业科技有限公司 一种依泽替米贝中间体的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007156450A (ja) * 2005-11-08 2007-06-21 Fujifilm Corp ポジ型レジスト組成物及び該ポジ型レジスト組成物を用いたパターン形成方法
JP2007241108A (ja) * 2006-03-10 2007-09-20 Fujifilm Corp ポジ型レジスト組成物及び該ポジ型レジスト組成物を用いたパターン形成方法
JP2014013413A (ja) * 2007-09-21 2014-01-23 Fujifilm Corp 感光性組成物、該感光性組成物を用いたパターン形成方法及び該感光性組成物に用いられる化合物
JP2015007781A (ja) * 2008-09-26 2015-01-15 富士フイルム株式会社 液浸露光用ポジ型レジスト組成物及びパターン形成方法
WO2015016027A1 (fr) * 2013-07-31 2015-02-05 Jsr株式会社 Composition de résine sensible au rayonnement, procédé de formation de motif de réserve, polymère, et composé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007156450A (ja) * 2005-11-08 2007-06-21 Fujifilm Corp ポジ型レジスト組成物及び該ポジ型レジスト組成物を用いたパターン形成方法
JP2007241108A (ja) * 2006-03-10 2007-09-20 Fujifilm Corp ポジ型レジスト組成物及び該ポジ型レジスト組成物を用いたパターン形成方法
JP2014013413A (ja) * 2007-09-21 2014-01-23 Fujifilm Corp 感光性組成物、該感光性組成物を用いたパターン形成方法及び該感光性組成物に用いられる化合物
JP2015007781A (ja) * 2008-09-26 2015-01-15 富士フイルム株式会社 液浸露光用ポジ型レジスト組成物及びパターン形成方法
WO2015016027A1 (fr) * 2013-07-31 2015-02-05 Jsr株式会社 Composition de résine sensible au rayonnement, procédé de formation de motif de réserve, polymère, et composé

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014139650A (ja) * 2012-12-21 2014-07-31 Jsr Corp フォトレジスト組成物、レジストパターン形成方法、重合体及び化合物
JP2016173513A (ja) * 2015-03-17 2016-09-29 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
CN115960054A (zh) * 2022-12-15 2023-04-14 南通常佑药业科技有限公司 一种依泽替米贝中间体的制备方法

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