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  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/10—Epoxy resins modified by unsaturated compounds
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  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6342—Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating
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  • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
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Definitions

• the present invention relates to a composition for forming a protective film having excellent resistance to a wet etching solution for semiconductors in a lithography process in semiconductor manufacturing.
• the present invention also relates to a method for manufacturing a substrate with a resist pattern to which the protective film is applied, and a method for manufacturing a semiconductor device.
• Patent Document 1 discloses a protective film-forming composition for a basic hydrogen peroxide aqueous solution containing a specific cross-linking agent.
• the resist underlayer film When the resist underlayer film is used as an etching mask and the underlying substrate is processed by wet etching, the resist underlayer film has a good masking function against the wet etching solution during the underlayer substrate processing (that is, the masked portion can protect the substrate. ) Is required. In such a case, the resist underlayer film will be used as a protective film for the substrate. Further, when the unnecessary protective film is removed by dry etching after wet etching, the protective film has a high etching rate (high etching rate) so that it can be quickly removed by dry etching so that the underlying substrate is not damaged. A protective film is required.
• An object of the present invention is to solve the above problems.
• the reaction product (P) of the diepoxy compound (B) and the bifunctional or higher-functional proton-generating compound (C) is represented by the following formula (1):
• Q 1 is represented by the following formula in the formula (2) (3):
• R 2 is a direct bond, an alkylene group having 1 to 10 carbon atoms which may be interrupted by —O—, —S— or —SS—, and 2 to 6 carbon atoms.
• the divalent organic group represents an alkenylene group, an alicyclic hydrocarbon ring having 3 to 10 carbon atoms, or a divalent organic group having at least one aromatic hydrocarbon ring having 6 to 14 carbon atoms.
• Alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, halogen atom, hydroxy group, nitro group, cyano group, methylidene group, 1 carbon atom number Z 1 and Z 1 may be substituted with at least one group selected from the group consisting of an alkoxy group of to 6 and an alkoxycarbonyl group of 2 to 6 carbon atoms and an alkylthio group of 1 to 6 carbon atoms. Represents any of -COO-, -OCO-, -O-, and -S-, respectively.)
• Q 2 is a compound represented by the following formula of the formula (2) (4):
• R 1 represents a direct bond or an alkylene group having 1 to 5 carbon atoms
• n1 and m represent an integer of 0 or 1
• Z 2 represents the following formula (5), formula (6) or Equation (7):
• X is the following formula (8), formula (9) or formula (10):
• R 11 , R 12 , R 13 , R 14 and R 15 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and carbon. Represents an alkenyl group, a benzyl group or a phenyl group having 3 to 6 atoms, and the phenyl group is an alkyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group and an alkoxy group having 1 to 6 carbon atoms.
• the protective film-forming composition according to claim 4 or 5 which is represented by (may be).
• the cross-linking agent (K) is the following formula (11) or formula (12):
• Q 2 is .R 8, R 9, R 11 and R 12 which represents single bond or m2 monovalent organic group each represent a hydrogen atom or a methyl group
• R 7 and R 10 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms, respectively.
• n9 is an integer of 1 ⁇ n9 ⁇ 3
• n10 is an integer of 2 ⁇ n10 ⁇ 5
• n11 is an integer of 0 ⁇ n11 ⁇ 3
• n12 is an integer of 0 ⁇ n12 ⁇ 3
• n12 is an integer of 3 ⁇ (n9 + n10 + n11 + n12) ⁇ 6. Shown.
• n13 is an integer of 1 ⁇ n13 ⁇ 3
• n14 is an integer of 1 ⁇ n14 ⁇ 4
• n15 is an integer of 0 ⁇ n15 ⁇ 3
• n16 is an integer of 0 ⁇ n16 ⁇ 3
• Shown. m2 represents an integer of 2 to 10.
• the protective film-forming composition according to [9] which is a compound selected from the compound represented by, melamine compound, guanamine compound, glycoluril compound and urea compound.
• a method for manufacturing a substrate with a resist pattern which comprises a step of then exposing and developing to form a resist pattern, and is used for manufacturing a semiconductor.
• a protective film is formed on a semiconductor substrate on which an inorganic film may be formed on the surface using the protective film forming composition according to any one of [1] to [13], and the protective film is formed on the protective film.
• a resist pattern is formed, the protective film is dry-etched using the resist pattern as a mask to expose the surface of the inorganic film or the semiconductor substrate, and a wet etching solution for semiconductor is used using the protective film after dry etching as a mask.
• a method for manufacturing a semiconductor device which comprises a step of wet etching and cleaning the inorganic film or the semiconductor substrate.
• the protective film forming composition of the present invention is required to have, for example, the following characteristics in a well-balanced manner in the lithography process in semiconductor manufacturing. (1) It has a good masking function against the wet etching solution when processing the base substrate, (2) it has a high dry etching rate, and (3) it has excellent flatness of the stepped substrate. By having the performances (1) to (3) in a well-balanced manner, microfabrication of the semiconductor substrate can be easily performed.
• alkylene group having 1 to 10 carbon atoms examples include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, and t-butylene group.
• Cyclobutylene group 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n- Butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1 -Methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group , 2-Ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pent
• alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, and t.
• cyclobutyl group 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl- n-Butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2 -Ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-
• aryl group having 6 to 40 carbon atoms examples include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorphenyl group, and a p-chlor.
• alkenyl group having 2 to 10 carbon atoms examples include an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group and a 3-butenyl group.
• 2-Methyl-1-propenyl group 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl Group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2- Ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl Group, 3-methyl-2-butenyl Group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2- Propenyl group
• alkenylene group having 2 to 6 carbon atoms is a divalent group excluding one hydrogen atom from the alkenyl groups having 2 to 6 carbon atoms in the above "alkenyl group having 2 to 10 carbon atoms”. Say what became.
• Examples of the "aliphatic hydrocarbon ring having 3 to 10 carbon atoms" include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptan, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, and bicyclo [2.1.0]. ] Pentane, bicyclo [3.2.1] octane, tricyclo [3.2.1.0 2,7 ] octane, spiro [3,4] octane and the like.
• aromatic hydrocarbon ring having 6 to 14 carbon atoms refers to one having an aromatic hydrocarbon ring having 6 to 14 carbon atoms among the above "aryl groups having 6 to 40 carbon atoms”.
• alkenyl group having 2 to 6 carbon atoms the double bond of the alkenyl group having 2 to 6 carbon atoms in the above “alkenyl group having 2 to 10 carbon atoms" is a triple bond.
• alkoxy group having 1 to 20 carbon atoms examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group.
• n-pentyloxy group 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl- n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group , 3-Methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n -Butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl- n-butoxy group, 1,1,2-tri
• alkoxycarbonyl group having 1 to 6 carbon atoms examples include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group and the like.
• alkylthio group having 1 to 6 carbon atoms examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group and a hexylthio group.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the protective film-forming composition of the present application contains a reaction product (P) of a diepoxy compound (B) and a bifunctional or higher-functional proton-generating compound (C), and the following formula (P) is added to the end of the reaction product (P). 1):
• Ar represents an aryl group having 6 to 40 carbon atoms
• n represents an integer of 2 to 10
• —Y— represents —OCO—, —O— or —S—.
• the functional group contained in the bifunctional or higher functional proton-generating compound (C) is a functional group that generates a proton, and is preferably selected from a hydroxyl group, a carboxy group, a thiol group, an amino group and an imide group.
• the bifunctional or higher functional proton generating compound (C) may be an acid dianhydride.
• the protective film-forming composition of the present application is a reaction product (P) of a diepoxy compound (B) and a bifunctional or higher proton generating compound (C), but is bifunctional or trifunctional or 4 with the diepoxy compound (B). It is preferably a reaction product (P) with the functional proton-generating compound (C), and is a reaction product (P) between the diepoxy compound (B) and the bifunctional or trifunctional proton-generating compound (C).
• the reaction product (P) of the diepoxy compound (B) and the bifunctional proton generating compound (C) is preferable.
• the reaction product (P) has the following formula (2):
• Q 1 and Q 2 represents a divalent organic group
• a 1 to A 6 represents a hydrogen atom, a methyl group or an ethyl group.
• Q 1 is represented by the following formula in the formula (2) (3):
• R 2 is a direct bond, an alkylene group having 1 to 10 carbon atoms which may be interrupted by —O—, —S— or —SS—, and 2 to 6 carbon atoms.
• the divalent organic group represents an alkenylene group, an alicyclic hydrocarbon ring having 3 to 10 carbon atoms, or a divalent organic group having at least one aromatic hydrocarbon ring having 6 to 14 carbon atoms.
• Alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, halogen atom, hydroxy group, nitro group, cyano group, methylidene group, 1 carbon atom number Z 1 and Z 1 may be substituted with at least one group selected from the group consisting of an alkoxy group of to 6 and an alkoxycarbonyl group of 2 to 6 carbon atoms and an alkylthio group of 1 to 6 carbon atoms. Represents any of -COO-, -OCO-, -O-, and -S-, respectively.) It is preferably represented by.
• Q 2 is a compound represented by the following formula of the formula (2) (4):
• R 1 represents a direct bond or an alkylene group having 1 to 5 carbon atoms
• n1 and m represent an integer of 0 or 1
• Z 2 represents the following formula (5), formula (6) or Equation (7):
• X is the following formula (8), formula (9) or formula (10):
• R 11 , R 12 , R 13 , R 14 and R 15 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and carbon. Represents an alkenyl group, a benzyl group or a phenyl group having 3 to 6 atoms, and the phenyl group is an alkyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a cyano group and an alkoxy group having 1 to 6 carbon atoms.
• the Ar preferably contains benzene, naphthalene and anthracene structures.
• the n is preferably an integer of 2 to 4.
• diepoxy compound (B) of the present application include the compounds (a-1) to (a-24) listed below.
• bifunctional or higher functional proton-generating compound (C) of the present application include the compounds (b-1) to (b-27) listed below.
• the protective film-forming composition of the present application is obtained by reacting the diepoxy compound (B), the bifunctional or higher-functional proton-generating compound (C), and the compounds (c-1) to (c-14) exemplified below. It may be the produced reaction product (P).
• the protective film forming composition of the present application may further contain a cross-linking agent (K).
• the cross-linking agent (K) is the following formula (11) or formula (12):
• Q 2 is .R 8, R 9, R 11 and R 12 which represents single bond or m2 monovalent organic group each represent a hydrogen atom or a methyl group
• R 7 and R 10 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms, respectively.
• n9 is an integer of 1 ⁇ n9 ⁇ 3
• n10 is an integer of 2 ⁇ n10 ⁇ 5
• n11 is an integer of 0 ⁇ n11 ⁇ 3
• n12 is an integer of 0 ⁇ n12 ⁇ 3
• n12 is an integer of 3 ⁇ (n9 + n10 + n11 + n12) ⁇ 6. Shown.
• n13 is an integer of 1 ⁇ n13 ⁇ 3
• n14 is an integer of 1 ⁇ n14 ⁇ 4
• n15 is an integer of 0 ⁇ n15 ⁇ 3
• n16 is an integer of 0 ⁇ n16 ⁇ 3
• Shown. m2 represents an integer of 2 to 10.
• It may be a compound selected from the compound described in WO2014 / 208542 represented by, melamine compound, guanamine compound, glycoluril compound and urea compound.
• the melamine compound include, but are not limited to, hexamethylol melamine, hexamethoxymethyl melamine, and hexamethoxyethyl melamine, which are compounds in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated or a mixture thereof.
• examples thereof include hexaacyloxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated, or a mixture thereof.
• epoxy compound examples include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and trimethylolethane triglycidyl ether.
• the guanamine compound include, but are not limited to, a compound in which 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethylolguanamine are methoxymethylated or a mixture thereof, tetramethoxyethylguanamine, and the like.
• examples thereof include a compound in which 1 to 4 methylol groups of tetraacyloxyguanamine and tetramethylolguanamine are acyloxymethylated, or a mixture thereof.
• glycol uril compound examples include, for example, a compound in which 1 to 4 methylol groups of tetramethylol glycol uryl, tetramethoxyglycol uryl, tetramethoxymethyl glycol uryl, and tetramethylol glycol uryl are methoxymethylated or a mixture thereof, tetra.
• examples thereof include a compound in which 1 to 4 methylol groups of methylol glycol uryl are acyloxymethylated, or a mixture thereof.
• urea compound examples include a compound in which 1 to 4 methylol groups of tetramethylol urea, tetramethoxymethyl urea, and tetramethylol urea are methoxymethylated, or a mixture thereof, and tetramethoxyethyl urea.
• the compound containing an alkenyl ether group include, but are not limited to, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, and tetramethylene.
• Glycoldivinyl ether neopentyl glycol divinyl ether, trimethylpropan trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylol Propane trivinyl ether and the like can be mentioned.
• glycol uryl compounds are preferable, and specifically, compounds in which 1 to 4 methylol groups of tetramethylol glycol uryl, tetramethoxyglycol uryl, tetramethoxymethyl glycol uryl, and tetramethylol glycol uryl are methoxymethylated, or compounds thereof.
• the mixture a compound in which 1 to 4 methylol groups of tetramethylol glycol uryl are asyloxymethylated, or a mixture thereof is preferable, and tetramethoxymethyl glycol uryl is preferable.
• examples of the cross-linking agent (K) include a compound having a partial structure of the following formula (5-1) and a polymer or oligomer having a repeating unit of the following formula (5-2).
• R 11 , R 12 , R 13 and R 14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and these alkyl groups can use the above-mentioned examples.
• M1 is 1 ⁇ m1 ⁇ 6-m2
• m2 is 1 ⁇ m2 ⁇ 5
• m3 is 1 ⁇ m3 ⁇ 4-m2
• m4 is 1 ⁇ m4 ⁇ 3.
• the above compounds can be obtained as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd.
• the compound of the formula (6-22) can be obtained under the trade name TMOM-BP of Asahi Organic Materials Industry Co., Ltd.
• the amount of the cross-linking agent added varies depending on the coating solvent used, the underlying substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 0.001 with respect to the total solid content of the protective film forming composition. It is 80% by mass, preferably 0.01 to 50% by mass, and more preferably 0.1 to 40% by mass.
• These cross-linking agents may cause a cross-linking reaction by self-condensation, but if cross-linking substituents are present in the above-mentioned polymer of the present invention, they can cause a cross-linking reaction with those cross-linking substituents.
• the protective film-forming composition of the present invention may contain a cross-linking catalyst as an optional component in order to promote the cross-linking reaction.
• a cross-linking catalyst in addition to an acidic compound and a basic compound, a compound that generates an acid or a base by heat can be used, but a cross-linking acid catalyst is preferable.
• the acidic compound a sulfonic acid compound or a carboxylic acid compound can be used, and as a compound that generates an acid by heat, a thermoacid generator can be used.
• sulfonic acid compound or carboxylic acid compound examples include p-toluene sulfonic acid, trifluoromethane sulfonic acid, pyridinium trifluoromethane sulfonate (pyridinium trifluoromethane sulfonic acid), pyridinium-p-toluene sulfonate, salicyl acid, camphor sulfonic acid, 5- Examples thereof include sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, pyridinium-4-phenolsulfonate, benzenedisulfonic acid, 1-naphthalenesulfonic acid, 4-nitrobenzenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid. ..
• thermoacid generator examples include K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, and TAG2689 (manufactured by King Industries). And SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).
• cross-linking catalysts can be used alone or in combination of two or more.
• an amine compound or an ammonium hydroxide compound can be used, and as a compound in which a base is generated by heat, urea can be used.
• Examples of the amine compound include triethanolamine, tributanolamine, trimethylamine, triethylamine, trinormalpropylamine, triisopropylamine, trinormalbutylamine, tri-tert-butylamine, trinormaloctylamine, triisopropanolamine, phenyldiethanolamine and stearyl.
• Examples thereof include diethanolamine, tertiary amines such as diazabicyclooctane, and aromatic amines such as pyridine and 4-dimethylaminopyridine.
• primary amines such as benzylamine and normal butylamine, and secondary amines such as diethylamine and dinormal butylamine are also mentioned as amine compounds. These amine compounds can be used alone or in combination of two or more.
• ammonium hydroxide compound examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and cetyltrimethylammonium hydroxide. Examples thereof include phenyltrimethylammonium hydroxide and phenyltriethylammonium hydroxide.
• the compound for which a base is generated by heat for example, a compound having a thermal instability group such as an amide group, a urethane group or an aziridine group and producing an amine by heating can be used.
• a compound having a thermal instability group such as an amide group, a urethane group or an aziridine group and producing an amine by heating
• urea benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyldimethylphenylammonium chloride, benzyldodecyldimethylammonium chloride, benzyltributylammonium chloride, and choline chloride are also examples of compounds that generate a base by heat.
• the content thereof is 0.0001 to 20% by mass, preferably 0.01 to 15% by mass, based on the total solid content of the protective film-forming composition. It is preferably 0.1 to 10% by mass.
• the protective film-forming composition of the present invention may contain, as an optional component, a surfactant in order to improve the coatability on the semiconductor substrate.
• a surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene.
• Polyoxyethylene alkylaryl ethers such as nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitantri Polysorbate such as sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
• Nonionic surfactants such as oxyethylene sorbitan fatty acid esters, Ftop [registered trademarks] EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafuck [registered trademarks] F171, F173, R -30, R-40, R-40-LM (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard [registered trademark] AG710, Surflon [registered trademark] S-382 , SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
• surfactants can be used alone or in combination of two or more.
• the content thereof is 0.0001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the protective film-forming composition. is there.
• the protective film-forming composition of the present invention can be prepared by dissolving each of the above components in an organic solvent (S), and is used in a uniform solution state.
• the organic solvent (S) of the protective film-forming composition according to the present invention is particularly limited as long as it is a compound containing at least one set of two hydroxyl groups adjacent to each other in the molecule or a solvent capable of dissolving the polymer thereof. Can be used without.
• the protective film forming composition according to the present invention is used in a uniform solution state, it is recommended to use an organic solvent generally used in the lithography process in combination in consideration of its coating performance. ..
• organic solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone and the like are preferable.
• propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.
• a light absorbing agent, a rheology adjusting agent, an adhesion auxiliary agent and the like can be added to the protective film forming composition of the present invention.
• Rheology modifiers are effective in improving the fluidity of the protective film-forming composition.
• Adhesive aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.
• Examples of the light absorber include commercially available light absorbers described in "Technology and Market of Industrial Dyes” (CMC Publishing) and “Dye Handbook” (edited by Synthetic Organic Chemistry Association), for example, C.I. I. Disperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,60,64,66,68,79,82,88,90,93,102,114 and 124; C.I. I. D isperse Orange 1,5,13,25,29,30,31,44,57,72 and 73; C.I. I. Disperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199 and 210; C.I.
• the above-mentioned absorbent is usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the protective film forming composition.
• the rheology adjuster mainly improves the fluidity of the protective film-forming composition, and particularly for the purpose of improving the film thickness uniformity of the protective film and the filling property of the protective film-forming composition inside the hole in the baking process.
• phthalate derivatives such as dimethylphthalate, diethylphthalate, diisobutylphthalate, dihexylphthalate, and butylisodecylphthalate
• adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate, and di.
• Maleic acid derivatives such as normal butylmalate, diethylmalate, and dinonylmalate, oleic acid derivatives such as methyl olate, butyl oleate, and tetrahydrofurfuryl oleate, or stearic acid derivatives such as normal butyl stearate and glyceryl stearate can be mentioned. it can.
• These rheology adjusters are usually added in a proportion of less than 30% by mass based on the total solid content of the protective film-forming composition.
• Adhesive aids are mainly added for the purpose of improving the adhesion between the substrate or resist and the protective film forming composition, and particularly preventing the resist from peeling off during development.
• Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, and phenyltriethoxy.
• Alkoxysilanes such as silane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazans such as trimethylsilylimidazole, methyloltrichlorosilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -aminopropyl Silanes such as triethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazol, thiouracil, Examples thereof include heterocyclic compounds such as mercaptoimidazole and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea
• the solid content of the protective film forming composition according to the present invention is usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass.
• the solid content is the content ratio of all the components excluding the solvent from the protective film forming composition.
• the proportion of the polymer in the solid content is preferably 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass in this order.
• the substrate with a resist pattern according to the present invention can be produced by applying the above-mentioned protective film forming composition on a semiconductor substrate and firing it.
• Examples of the semiconductor substrate to which the protective film forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphate, gallium nitride, indium nitride, and aluminum nitride. ..
• the inorganic film is, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum deposition. It is formed by the method, spin coating method (spin-on-glass: SOG).
• the inorganic film examples include a polysilicon film, a silicon oxide film, a silicon nitride film, a silicon nitride film, a BPSG (Boro-Phospho Silicone Glass) film, a titanium nitride film, a titanium oxynitride film, a tungsten nitride film, and a gallium nitride film. , And a gallium nitride film.
• the protective film forming composition of the present invention is applied onto such a semiconductor substrate by an appropriate coating method such as a spinner or a coater. Then, a protective film is formed by baking using a heating means such as a hot plate.
• the baking conditions are appropriately selected from a baking temperature of 100 ° C. to 400 ° C. and a baking time of 0.3 minutes to 60 minutes.
• the bake temperature is preferably 120 ° C. to 350 ° C. and the bake time is 0.5 minutes to 30 minutes, and more preferably the bake temperature is 150 ° C. to 300 ° C. and the bake time is 0.8 minutes to 10 minutes.
• the film thickness of the protective film formed is, for example, 0.001 ⁇ m to 10 ⁇ m, preferably 0.002 ⁇ m to 1 ⁇ m, and more preferably 0.005 ⁇ m to 0.5 ⁇ m. If the temperature at the time of baking is lower than the above range, cross-linking may be insufficient, and it may be difficult to obtain resistance of the formed protective film to a resist solvent or a basic aqueous hydrogen peroxide solution. On the other hand, if the baking temperature is higher than the above range, the protective film may be decomposed by heat.
• the exposure is performed through a mask (reticle) for forming a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used.
• An alkaline developer is used for development, and the development temperature is appropriately selected from 5 ° C. to 50 ° C. and the development time is 10 seconds to 300 seconds.
• Examples of the alkaline developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and the like.
• Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and the like.
• An aqueous solution of an alkali such as a quaternary ammonium salt, cyclic amines such as pyrrole and piperidine can be used.
• an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the aqueous solution of the alkalis for use.
• the preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline.
• a surfactant or the like can be added to these developers.
• a method of developing with an organic solvent such as butyl acetate to develop a portion of the photoresist in which the alkali dissolution rate has not been improved can also be used.
• the protective film is dry-etched using the formed resist pattern as a mask. At that time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the semiconductor substrate is exposed. Expose the surface.
• a desired pattern can be obtained by wet etching with a semiconductor wet etching solution using the protective film after dry etching (if the resist pattern remains on the protective film, the resist pattern is also used) as a mask. It is formed.
• etching solution for semiconductors a general chemical solution for etching a wafer for semiconductors can be used, and for example, a substance showing acidity and a substance showing basicity can be used.
• the acidic substance examples include hydrogen peroxide, hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrogenfluoride, buffered hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, or a mixture thereof. ..
• an organic amine such as ammonia, sodium hydroxide, potassium hydroxide, sodium cyanide, potassium cyanide, or triethanolamine is mixed with a hydrogen peroxide solution to make the pH basic.
• Ammonia solution can be mentioned. Specific examples include SC-1 (ammonia-hydrogen peroxide solution).
• SC-1 ammonia-hydrogen peroxide solution
• those that can make the pH basic for example, those that mix urea and hydrogen peroxide solution and cause thermal decomposition of urea by heating to generate ammonia, and finally make the pH basic.
• an acidic hydrogen peroxide solution or a basic hydrogen peroxide solution is preferable.
• These chemicals may contain additives such as surfactants.
• the operating temperature of the wet etching solution for semiconductors is preferably 25 ° C to 90 ° C, and more preferably 40 ° C to 80 ° C.
• the wet etching time is preferably 0.5 minutes to 30 minutes, and more preferably 1 minute to 20 minutes.
• the weight average molecular weights of the polymers shown in the following Synthesis Examples 1 to 4 of the present specification are measurement results by gel permeation chromatography (hereinafter, abbreviated as GPC).
• GPC gel permeation chromatography
• a GPC device manufactured by Tosoh Corporation is used for the measurement, and the measurement conditions and the like are as follows.
• Example 1 To 27.62 g of the solution containing the polymer obtained in Synthesis Example 1, 0.552 g of pyridinium trifluoromethanesulfonic acid, 18.84 g of propylene glycol monomethyl ether acetate and 152.99 g of propylene glycol monomethyl ether were added to prepare a solution. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
• Example 2 To 27.62 g of the solution containing the polymer obtained in Synthesis Example 2, 0.552 g of pyridinium trifluoromethanesulfonic acid, 18.84 g of propylene glycol monomethyl ether acetate and 152.99 g of propylene glycol monomethyl ether were added to prepare a solution. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
• Example 3 To 27.62 g of the polymer-containing solution obtained in Synthesis Example 3, 0.552 g of pyridinium trifluoromethanesulfonic acid, 18.84 g of propylene glycol monomethyl ether acetate and 152.99 g of propylene glycol monomethyl ether were added to prepare a solution. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
• Example 4 In 27.62 g of the solution containing the polymer obtained in Synthesis Example 1, 0.552 g of pyridinium trifluoromethanesulfonic acid, 1.105 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), 18.84 g of propylene glycol monomethyl ether acetate. And 152.99 g of propylene glycol monomethyl ether were added to prepare a solution. The solution was filtered using a polyethylene microfilter having a pore size of 0.02 ⁇ m to prepare a protective film-forming composition.
• the protective film forming composition prepared in Examples 1 to 3 and the film forming composition prepared in Comparative Example 1 were applied by spin coating on a silicon substrate having a titanium nitride film formed on the surface thereof, and the temperature was 220 ° C.
• a coating film having a film thickness of 100 nm was prepared by baking for 60 seconds.
• the following table shows a coating film prepared on a silicon substrate on which a titanium nitride film is formed on the surface using the protective film forming composition prepared in Examples 1 to 3 and the film forming composition prepared in Comparative Example 1.
• the results are shown in Table 2 below. “ ⁇ ” in Table 2 indicates a state in which peeling is not observed in the coating film even after 1 minute treatment, and “ ⁇ ” indicates a state in which peeling is observed in a part or all of the coating film after 1 minute treatment.
• the coating film prepared using the protective film forming composition prepared in Examples 1 to 3 has sufficient resistance to the basic aqueous hydrogen peroxide solution. .. That is, it was found that these coating films can serve as protective films against the basic aqueous hydrogen peroxide solution.
• the coating films prepared using the film-forming composition prepared in Comparative Example 1 were shown to have no resistance to the basic hydrogen peroxide aqueous solution, and these coating films were shown to have no resistance to the basic hydrogen peroxide aqueous solution. It became clear that it could not be a protective film against hydrogen peroxide.
• the protective film forming composition according to the present invention has excellent resistance when a wet etching solution is applied to substrate processing and has a high dry etching rate, so that substrate processing is easy and flattening property when applied to a stepped substrate. It provides an excellent protective film.

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