Coating film-forming composition for removing foreign matter

Abstract

The present invention provides: a simple method for removing foreign substances that are formed on a substrate during a semiconductor device production process; and a composition for forming a coating film for foreign substance removal, said coating film being used in the above-described method. A composition for forming a coating film for foreign substance removal, said composition containing a polymer and a solvent and being capable of forming a coating film that dissolves in a developer liquid, wherein: the polymer is selected from among phenolic novolacs, polyhydroxystyrene derivatives and carboxylic acid-containing polymers; and the polymer is contained in an amount of 50% by mass or more relative to the total solid content in the composition.

Description

[Technical Field]

[0001] The present invention relates to a coating film-forming composition for removing foreign matter, a method for removing foreign matter from a substrate, a substrate processing method, and a method for manufacturing a laminated substrate, which can easily remove foreign matter formed on a substrate. The present invention relates to a coating film-forming composition for removing foreign matter, which is preferably used in a semiconductor wafer temporary bonding step in the manufacture of a semiconductor device. [Background technology]

[0002] In the manufacture of semiconductor devices, particularly in the so-called post-processing, a process is being considered in which a semiconductor substrate (wafer) is attached to a support substrate, then back-grinding (grinding), wiring formation processes, etc. are performed, and then the support substrate is peeled off to obtain a desired semiconductor substrate.

[0003] When attaching the wafer to a support substrate, the wafer is attached using an adhesive (such as a liquid composition containing a polymer, backgrinding tape, or dicing tape) that is resistant to subsequent processes (heating and chemical treatment processes), and then the semiconductor substrate is peeled off. However, during this process, the adhesive layer contained in the adhesive may remain on the substrate as foreign matter (residue). This occurs particularly noticeably when the adhesive layer is formed directly on the surface of a semiconductor substrate on which wiring or the like has already been formed. This foreign matter may not be completely removed even by cleaning with known organic solvents, liquid chemicals, or the like.

[0004] There is also the problem of removing foreign matter already present on a substrate for semiconductor manufacturing. For example, Patent Documents 2 and 3 disclose a composition for forming a substrate processing film and a substrate processing method that can efficiently remove minute particles on the substrate surface and easily remove the formed substrate processing film from the substrate surface in a process of forming a substrate processing film on the surface of a semiconductor substrate and removing foreign matter from the substrate surface.

[0005] A coating film-forming composition for removing foreign matter, which uses a polyamic acid material, has been disclosed (Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2018 / 159665 [Patent Document 2] International Publication No. 2017 / 056746 [Patent Document 3] International Publication No. 2020 / 008965 Summary of the Invention [Problem to be solved by the invention]

[0007] The problem to be solved by the present invention is to provide a simple method for removing foreign matter formed on a substrate during, for example, a semiconductor wafer temporary bonding step in the manufacture of a semiconductor device, or foreign matter already present on a semiconductor substrate, and to provide a coating film-forming composition for removing foreign matter to be used in such a method.

[0008] The coating film for removing foreign matter of the present invention is not limited to the temporary bonding process described above, as long as it is used to remove foreign matter from a substrate. [Means for solving the problem]

[0009] The present invention encompasses the following. [1] A coating film-forming composition for removing foreign matter, which comprises a polymer and a solvent and can form a coating film that dissolves in a developer, The composition, wherein the polymer is selected from a phenolic hydroxyl group-containing polymer and a carboxy group-containing polymer, and the polymer accounts for 50 mass % or more of the total solid content of the composition. [2] The composition according to [1], wherein the phenolic hydroxyl group-containing polymer is a phenol novolak or a polyhydroxystyrene derivative. [3] The composition according to [1], wherein the carboxyl group-containing polymer is selected from a (meth)acrylic resin, polyvinyl benzoic acid, or carboxymethyl cellulose. [4] The composition according to any one of [1] to [3], wherein the composition contains a crosslinking agent and / or an additive. [5] The composition according to [4], wherein the crosslinking agent contains an epoxy group. [6] A coating film for removing foreign matter, which is a fired product of a coating film made of the composition according to any one of [1] to [5]. [7] A method for removing foreign matter, comprising the steps of applying the composition according to any one of [1] to [5] onto a substrate and baking the composition to form a coating film, forming foreign matter on the coating film, and removing the coating film together with the foreign matter using a developer. [8] The step of forming the foreign matter comprises: The method according to [7], comprising the steps of forming an adhesive layer on the coating film, and then peeling off the adhesive layer. [9] The method according to [8], wherein the foreign matter is a peeled residue of the adhesive layer.

[10] The composition according to any one of [1] to [5] is applied to a first substrate and baked. forming a coating film; forming an adhesive layer on the coating film; a step of temporarily attaching a second substrate to the first substrate via the adhesive layer; peeling the second substrate from the first substrate; and a step of removing the coating film remaining on the first substrate together with the adhesive layer using a developer after the second substrate has been peeled off.

[11] A step of applying the composition according to any one of [1] to [5] onto a first substrate and baking it to form a coating film; forming an adhesive layer on the coating film; and A method for manufacturing a laminated substrate, comprising the step of attaching a second substrate to the first substrate.

[12] A coating film-forming composition used to remove foreign matter present on a substrate for semiconductor manufacturing, the composition comprising a polymer and a solvent, the polymer being selected from a phenolic hydroxyl group-containing polymer and a carboxyl group-containing polymer, and the polymer is contained in an amount of 50 mass% or more based on the total solid content of the composition.

[13] The composition according to

[12] , wherein the composition contains a crosslinking agent and / or an additive.

[14] A coating film-forming composition used to remove foreign matter present on a substrate for semiconductor manufacturing, the composition comprising a polymer and a solvent, wherein the polymer is a polyamic acid having structural units derived from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound having at least one carboxyl group.

[15] A method for removing foreign matter, comprising the steps of applying the composition according to any one of

[12] to

[14] onto a substrate on which foreign matter is present and baking the composition to form a coating film containing the foreign matter, and removing the coating film together with the foreign matter using a developer. [Effects of the Invention]

[0010] In particular, during the wafer temporary bonding process for semiconductor wafers, the contaminant removal coating film of the present invention is formed on a substrate (substrate for processing) in advance, and the substrate is bonded to a support substrate using an adhesive layer. The support substrate is then peeled off from the substrate in a wafer peeling process, and the substrate is then washed with a developer. This allows the contaminant removal coating film of the present invention and any contaminants on the contaminant removal coating film to be completely removed simultaneously. Furthermore, by removing from the substrate surface a substrate treatment film that has incorporated contaminants present on the surface of a semiconductor manufacturing substrate for some reason, the contaminants can be easily removed from the semiconductor manufacturing substrate. This significantly reduces defects due to contaminants in the production of semiconductor manufacturing equipment, contributing to an increase in the yield of good wafers.

[0011] The coating film for removing foreign matter of the present invention, particularly when used in the temporary bonding step of semiconductor wafers, is resistant to the semiconductor substrate processing process (heat, chemicals) after temporary bonding. DETAILED DESCRIPTION OF THE INVENTION

[0012] <Coating film-forming composition for removing foreign matter> The coating film-forming composition for removing foreign matter of the present invention comprises a polymer and a solvent, and is capable of forming a coating film that dissolves in a developer, wherein the polymer is selected from the group consisting of a phenolic hydroxyl group-containing polymer and a carboxyl group-containing polymer. These polymers are soluble in a developer.

[0013] The phenolic hydroxyl group-containing polymer is preferably a phenol novolak or a polyhydroxystyrene derivative.

[0014] The carboxy group-containing polymer is preferably selected from a (meth)acrylic resin, polyvinyl benzoic acid, or carboxymethyl cellulose.

[0015] Furthermore, the polymer is contained in an amount of 50% by mass or more, preferably 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total solid content of the composition.

[0016] <Phenol novolac> Phenol novolak (novolak resin) can be any of those conventionally used in positive-type photosensitive materials and the like, without any restrictions, and examples thereof include resins obtained by polymerizing phenols and aldehydes in the presence of an acid catalyst.

[0017] Examples of the phenols include phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; o-ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert Examples of suitable phenols include alkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol and phloroglucinol; alkyl polyhydric phenols such as alkylresorcinol, alkylcatechol and alkylhydroquinone (all alkyl groups having 1 to 4 carbon atoms); α-naphthol, β-naphthol, hydroxydiphenyl and bisphenol A. These phenols may be used alone or in combination of two or more.

[0018] Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc. These aldehydes may be used alone or in combination of two or more.

[0019] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfate, and paratoluenesulfonic acid; and metal salts such as zinc acetate.

[0020] The phenol novolak of the present invention may be naphthol cresol novolak in which α-naphthol or β-naphthol is polymerized.

[0021] <Polyhydroxystyrene derivatives> The polyhydroxystyrene derivative of the present invention is obtained by polymerizing hydroxystyrene having a substituent, and preferably has the following unit structure: [ka] (In formula (1), R represents a halogen atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, or an alkoxy group having 1 to 9 carbon atoms. n represents an integer of 1 to 4. When n is 2 or greater, the n Rs may be the same or different.)

[0022] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0023] Examples of the alkoxy group having 1 to 9 carbon atoms 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, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4- Examples include a methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, a 1-ethyl-2-methyl-n-propoxy group, an n-heptyloxy group, an n-octyloxy group, and an n-nonyloxy group.

[0024] <(Meth)acrylic resin> The (meth)acrylic resin of the present application may be any resin that has been conventionally used in positive-type photosensitive materials and the like, without any limitations. Examples of the (meth)acrylic resin include a resin obtained by polymerizing a polymerizable monomer having a (meth)acrylic group in the presence of a radical polymerization initiator.

[0025] Examples of the polymerizable monomer having a (meth)acrylic group include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid pentyl ester, (meth)acrylic acid hexyl ester, (meth)acrylic acid heptyl ester, (meth)acrylic acid octyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid nonyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid undecyl ester, (meth)acrylic acid Examples of the polymerizable monomer having a (meth)acrylic group include alkyl (meth)acrylates such as dodecyl acrylate, trifluoroethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; acrylamides such as diacetone acrylamide; tetrahydrofurfuryl (meth)acrylate, dialkylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid. These polymerizable monomers having a (meth)acrylic group may be used alone or in combination of two or more.

[0026] Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, dicumyl peroxide, and dibutyl peroxide; and azobis compounds such as azobisisobutyronitrile and azobisvaleronitrile.

[0027] In addition to the polymerizable monomer having a (meth)acrylic group, the acrylic resin may be copolymerized with one or more polymerizable monomers such as polymerizable styrene derivatives substituted at the α-position or at the aromatic ring, such as styrene, vinyltoluene, and α-methylstyrene; esters of vinyl alcohol, such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters, such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid. In this specification, "(meth)acrylic" means both "acrylic" and "methacrylic".

[0028] <Polyvinyl benzoic acid> The polyvinylbenzoic acid of the present invention can be obtained, for example, by polymerizing 4-vinylbenzoic acid shown below by a known method. [ka]

[0029] <Carboxymethyl cellulose> The carboxymethyl cellulose of the present application has the structure shown below. [ka] (wherein n represents the number of repeating units)

[0030] Furthermore, the coating film-forming composition for removing foreign matter of the present application may include a polymer that is a polyamic acid having structural units derived from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound having at least one carboxyl group, as described in International Publication No. 2018 / 159665. The polymer may be a polyamic acid having structural units derived from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound having at least one carboxyl group, and structural units derived from (a) a tetracarboxylic dianhydride compound and (c) a diamine compound different from (b). The (c) diamine compound may be a diamine compound having no carboxyl group.

[0031] Examples of polyamic acids contained in the coating film-forming composition for removing foreign matter of the present invention include the following polyamic acids (29) to (41) (where p1, p2, p3, and p4 represent the proportions of each structure in the polyamic acid): (29) to (36) are polyamic acids produced from one tetracarboxylic dianhydride compound and two diamine compounds, (37) and (38) are polyamic acids produced from two tetracarboxylic dianhydride compounds and one diamine compound, (39) is polyamic acid produced from two tetracarboxylic dianhydride compounds and two diamine compounds, and (40) and (41) are polyamic acids produced from one tetracarboxylic dianhydride compound and one diamine compound.

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka] The contents of International Publication No. 2018 / 159665 are incorporated herein by reference to the same extent as if expressly set forth in their entirety.

[0039] The weight-average molecular weight of the polymer of the present application, measured by gel permeation chromatography (GPC) in terms of polystyrene, is, for example, 1,000 to 100,000, or 1,000 to 50,000, and preferably 2,000 to 50,000. If the weight-average molecular weight is 1,000 or less, the solubility of the resulting coating film for removing foreign matter in the solvent used in the adhesive layer increases, which can result in intermixing with the adhesive layer. If the weight-average molecular weight is 100,000 or more, the solubility of the resulting coating film for removing foreign matter in the developer can be insufficient, resulting in the presence of residues after development.

[0040] <Solvent> The coating film-forming composition for removing foreign matter of the present invention can be easily prepared by uniformly mixing the above-mentioned components, and is used in the form of a solution by dissolving it in a suitable solvent. Examples of such solvents that can be used 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, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents can be used alone or in combination of two or more. Furthermore, high boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate can be mixed and used.

[0041] The coating film resin composition solution for removing foreign matter prepared in this manner is preferably used after being filtered using a filter with a pore size of about 0.2 μm. The coating film resin composition solution for removing foreign matter prepared in this manner also has excellent long-term storage stability at room temperature.

[0042] The solid content of the coating film-forming composition for removing foreign matter of the present invention is not particularly limited as long as each component is uniformly dissolved, but is, for example, 0.5 to 50 mass %, or, for example, 1 to 30 mass %. Here, the solid content is the total component of the coating film-forming composition for removing foreign matter excluding the solvent component.

[0043] In the present invention, foreign matter refers to substances other than the intended object that adhere to a substrate. In the semiconductor device manufacturing process, foreign matter refers to substances that are unnecessary in the semiconductor device manufacturing process. Examples of foreign matter include particles, metal impurities, post-etching residues, adhesive peeling residues, etc. that adhere to a wafer.

[0044] The coating film for removing foreign matter of the present invention is particularly preferably used in a process in which wafers are bonded together with an adhesive and then the adhesive is peeled off, by forming the coating film of the present invention before applying the adhesive, and then removing foreign matter (adhesive residue) after the wafer bonding and peeling processes. The coating film for removing foreign matter of the present invention can also be used to remove foreign matter already present on a substrate for semiconductor manufacturing.

[0045] The phrase "the coating film for removing foreign matter of the present invention dissolves in a developer" means that the coating film dissolves in the developer and disappears from the substrate when the substrate is immersed in the developer, washed, or the like, as described below. Dissolution in this invention means that the film formed on the substrate by the method described in the Examples is removed by at least 90% or more of its initial thickness (i.e., the remaining film thickness is 10% or less of the initial thickness), or by at least 95% or more (i.e., the remaining film thickness is 5% or less of the initial thickness), or by at least 99% or more (i.e., the remaining film thickness is 1% or less of the initial thickness), and most preferably 100% (i.e., the remaining film thickness is 0% of the initial thickness (no remaining film)). Preferably, the composition comprises a crosslinking agent and / or an additive.

[0046] <Crosslinking agent> The crosslinking agent preferably contains an epoxy group. The crosslinking agent may contain a compound having at least two epoxy groups. Such compounds are not particularly limited as long as they contain epoxy groups. Examples include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A diglycidyl ether, and pentaerythritol polyglycidyl ether.

[0047] Examples of compounds having at least two epoxy groups include epoxy resins having an amino group, such as YH-434 and YH434L (trade names, manufactured by Nippon Steel Chemical & Material Co., Ltd.); epoxy resins having a cyclohexene oxide structure, such as Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (trade names, manufactured by Daicel Chemical Industries, Ltd.); bisphenol A type epoxy resins, such as Epikote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (all trade names, manufactured by Yuka Shell Epoxy Co., Ltd.); and bisphenol F type epoxy resins, such as Epikote 807 (trade names, manufactured by Yuka Shell Epoxy Co., Ltd.). Examples of phenol novolac epoxy resins include Epicoat 152 and 154 (both manufactured by Yuka Shell Epoxy Co., Ltd., trade names), EPPN201 and 202 (both manufactured by Nippon Kayaku Co., Ltd., trade names), etc. Examples of cresol novolac epoxy resins include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd., trade names), and Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd., trade name), etc. Examples of alicyclic epoxy resins include Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd., trade names), CY175, CY177 and CY179 (all manufactured by CIBA-GEIGY Co., Ltd., trade names), etc. Examples of the aliphatic polyglycidyl ether include Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, and EX-321 (trade names, manufactured by Nagase ChemteX Corporation).

[0048] The content of the compound having at least two epoxy groups is, for example, 5 to 70 parts by mass, or 10 to 60 parts by mass, and preferably 15 to 45 parts by mass, relative to 100 parts by mass of the polymer. If the content of the compound having at least two epoxy groups is less than 5 parts by mass, the degree of curing of the coating film for removing foreign matter may be insufficient, and the coating film may dissolve in the adhesive layer, causing intermixing. If the content exceeds 70 parts by mass, sufficient solubility in the developer may not be obtained.

[0049] <Additives> The coating film-forming composition for removing foreign matter of the present invention may contain, as additives, a light-absorbing compound, a surfactant, an adhesion aid, and a rheology adjuster.

[0050] (light-absorbing compound) The light-absorbing compound is not particularly limited as long as it has absorption at the exposure wavelength to be used. Compounds having an aromatic ring structure such as an anthracene ring, a naphthalene ring, a benzene ring, a quinoline ring, or a triazine ring are preferably used. Furthermore, from the viewpoint of not inhibiting the solubility of the coating film for removing foreign matter in a developer, compounds having a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group are preferably used.

[0051] Examples of light-absorbing compounds that have a large absorption for light with a wavelength of 248 nm include 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-naphthol, 2-naphthol, 1-aminonaphthalene, 1-hydroxy-2-naphthalenecarboxylic acid, 3-hydroxy-2-naphthalenecarboxylic acid, 3,7-dihydroxy-2-naphthalenecarboxylic acid, 6-bromo-2-hydroxynaphthalene, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. carboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene Hydroxynaphthalene, 6-hydroxy-1-naphthalenecarboxylic acid, 1-hydroxy-2-naphthalenecarboxylic acid, 3-hydroxy-2-naphthalenecarboxylic acid, 6-hydroxy-2-naphthalenecarboxylic acid, 1-bromo-2-hydroxy-3-naphthalenecarboxylic acid, 1-bromo-4-hydroxy-3-naphthalenecarboxylic acid, 1,6-dibromo-2-hydroxy-3-naphthalenecarboxylic acid, 3-hydroxy-7-methoxy-2-naphthalenecarboxylic acid, 1-amino-2-naphthol, 1,5-dimercaptonaphthalene olefin, 1,4,5,8-naphthalenetetracarboxylic acid, 3,5-dihydroxy-2-naphthalenecarboxylic acid, 1,4-dihydroxy-2-naphthalenecarboxylic acid, 2-ethoxy-1-naphthalenecarboxylic acid, 2,6-dichloro-1-naphthol, 2-hydroxy-3-naphthalenecarboxylic acid methyl ester, 6-hydroxy-2-naphthalenecarboxylic acid methyl ester, 3-hydroxy-7-methoxy-2-naphthalenecarboxylic acid methyl ester, 3,7-dihydroxy-2-naphthalenecarboxylic acid methyl ester, 2,Examples of such an anthracene include 4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-naphthalenethiol, 4-methoxy-1-naphthol, 6-acetoxy-2-naphthalenecarboxylic acid, 1,6-dibromo-1-naphthol, 2,6-dibromo-1,5-dihydroxynaphthalene, 1-acetyl-2-naphthol, 9-anthracenecarboxylic acid, 1,4,9,10-tetrahydroxyanthracene, and 1,8,9-trihydroxyanthracene.

[0052] Examples of light-absorbing compounds that have a large absorption for light with a wavelength of 193 nm include benzoic acid, 4-methylbenzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, 2-methoxybenzoic acid, isophthalic acid, terephthalic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-acetoxybenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, trimesic acid, 1,4-benzenedicarboxylic acid, 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-acetylbenzoic acid, pyrrole, and the like. Examples of the hydroxybenzoic acid include ric acid, trimesic anhydride, 2-[bis-(4-hydroxyphenyl)-methyl]benzoic acid, 3,4,5-trihydroxybenzoic acid, 2-benzophenonecarboxylic acid, m-phenylbenzoic acid, 3-(4'-hydroxyphenoxy)benzoic acid, 3-phenoxybenzoic acid, phenol, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 2-methylphenol, 3-methylphenol, 4-methylphenol, 1,3,5-trihydroxybenzene, 2,2-bis-4-hydroxyphenylpropane, 2-hydroxybiphenyl, 2-aminophenol, 3-aminophenol, 4-aminophenol, and 4-benzyloxyphenol.

[0053] Furthermore, these absorptive compounds can be used by reacting them with a polymer or a compound having one or more reactive groups in order to suppress sublimation during baking to form a coating film for removing foreign matter.

[0054] For example, in the case of a light-absorbing compound having a carboxyl group or a phenolic hydroxyl group, compounds obtained by reacting with a polyfunctional epoxy compound such as tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris(p-(2,3-epoxypropoxy)phenyl)propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether, or a polymer containing a structure having an epoxy group such as glycidyl methacrylate, can be used. Examples include polymers having unit structures represented by the following formulas (42), (43), and (44), and compounds represented by formula (45): In formula (45), Ar represents a benzene ring, naphthalene ring, or anthracene ring optionally substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a hydroxyl group, a thiol group, a thioalkyl group having 1 to 5 carbon atoms, a carboxyl group, a phenoxy group, an acetyl group, an alkoxycarbonyl group having 1 to 5 carbon atoms, or a vinyl group. [ka]

[0055] The above-mentioned absorbing compounds can be used alone or in combination of two or more. When a light-absorbing compound is used, the content thereof is, for example, 1 to 300 parts by mass, or 1 to 200 parts by mass, or, for example, 1 to 100 parts by mass, or 5 to 100 parts by mass, relative to 100 parts by mass of the polymer. If the absorbing compound exceeds 300 parts by mass, the solubility of the foreign matter removal coating film in the developer may decrease, or intermixing of the foreign matter removal coating film with the adhesive layer may occur.

[0056] The coating film-forming composition for removing foreign matter of the present invention can contain an acid generator. Examples of acid generators include thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, and photoacid generators such as bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, benzoin tosylate, and N-hydroxysuccinimide trifluoromethanesulfonate. The acid generator is added in an amount of 10% by mass or less, preferably 3% by mass or less, based on the solids content of the coating film-forming composition for removing foreign matter, as needed.

[0057] To the coating film-forming composition for removing foreign matter of the present invention, a polyhydric phenol compound or a carboxyl group-containing compound can be added in order to accelerate the dissolution rate in a developer. Such compounds are not particularly limited, but examples thereof include tris-hydroxyphenylethane, bisphenol-A, bisphenol-S, 4,4'-isopropylidene-di-o-cresol, 5-tert-butylpyrogallol, hexafluorobisphenol-A, 3,3,3',3'-tetramethyl-1,1'-spirobisindan-5,5',6,6'-tetrol, 4,4'-(9-fluorenylidene)diphenol, bisphenol Polyphenols such as bisphenol-AP, bisphenol-P, 5-α,α-dimethyl-4-hydroxybenzyl salicylate, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 5,5'-di-tert-butyl-2,2',4,4'-tetrahydroxybenzophenone, pyromellitic acid, phthalic acid, trimellitic acid, 4-sulfophthalic acid, benzenehexacarboxylic acid, 2,3-naphthalenedicarboxylic acid, 4-hydroxybenzophenone, Examples of suitable carboxylic acids include polycarboxylic acids such as hydroxyphthalic acid, 3,4-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 3,3'-,4,4'-biphenyltetracarboxylic acid, 3,3'-,4,4'-benzophenonetetracarboxylic acid, 3,3'-,4,4'-diphenylethertetracarboxylic acid, 3,3'-,4,4'-diphenylsulfonetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclohexanetetracarboxylic acid, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid; and carboxylic acid or carboxylic acid anhydride-containing polymers such as polyacrylic acid, polymethacrylic acid, polyamic acid, and polymaleic anhydride. The amount of the compound added is 20% by mass or less, preferably 10% by mass or less, based on the solid content of the coating film-forming composition for removing foreign matter, as needed.

[0058] To the coating film-forming composition for removing foreign matter of the present invention, a compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid, such as a tert-butyl group, a tetrahydropyranyl group, a 1-ethoxyethyl group, or a trimethylsilyl group, can be added for the purpose of adjusting the dissolution rate in a developer.

[0059] Examples of such compounds include di-tert-butyl malonate, tert-butyl acetate, tert-butyl propionate, tert-butyl acetoacetate, tert-amyl acetate, benzoic acid-tert-butyl ester, and tert-butyl pivalate. Further examples include compounds of formulas (46) to (54). [ka] [ka]

[0060] These compounds can easily generate a carboxyl group or a phenolic hydroxyl group in the presence of an acid, thereby providing a compound with increased solubility in an alkaline developer. Therefore, these compounds are preferably added to the coating film-forming composition for removing foreign matter together with a photoacid generator. That is, in a foreign matter removal coating film formed from the coating film-forming composition for removing foreign matter, which contains the above-mentioned compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of acid and a photoacid generator, the acid generated from the photoacid generator upon exposure regenerates the carboxyl group or phenolic hydroxyl group of the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of acid in the exposed portions, resulting in an increase in the solubility of the foreign matter removal coating film in alkaline solutions in the exposed portions. In contrast, in the unexposed portions, there is no change in the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of acid, and this does not increase the solubility of the foreign matter removal coating film in alkaline solutions in those portions. Therefore, by using a compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid together with a photoacid generator, it becomes possible to make a difference in solubility in an alkaline developer between the exposed and unexposed areas of the coating film for removing foreign matter after exposure, making it easier to form a pattern by development.

[0061] When the compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid is used, the content thereof is, for example, 50 to 1 part by mass, or 30 to 5 parts by mass, or for example, 20 to 10 parts by mass, relative to 100 parts by mass of the polymer. When a photoacid generator is used together with a compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid, the content thereof is, for example, 0.1 to 30 parts by mass, or 0.5 to 20 parts by mass, or for example, 1 to 10 parts by mass, relative to 100 parts by mass of the compound having a carboxyl group or a phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid.

[0062] (surfactant) The coating film-forming composition for removing foreign matter of the present invention can contain a surfactant. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Examples of suitable surfactants include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171 and F173 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 0.2% by mass or less, and preferably 0.1% by mass or less, of all the components of the coating film-forming composition for removing foreign matter of the present invention. These surfactants may be added alone or in combination of two or more.

[0063] <Coating film for removing foreign matter, and method for manufacturing the coating film for removing foreign matter> The coating film-forming composition for removing foreign matter of the present invention is applied to a semiconductor substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, etc.) by a suitable application method such as a spinner, a coater, or immersion, and then baked to form a coating film for removing foreign matter. The baking conditions are appropriately selected from a baking temperature of 80°C to 300°C and a baking time of 0.3 to 60 minutes.

[0064] The coating film for removing foreign matter of the present invention has a thickness of usually 1 μm to 5 nm, preferably 500 to 10 nm, and most preferably 300 to 15 nm.

[0065] The dissolution rate of the formed coating film for removing foreign matter in a photoresist developer is 0.1 to 50 nm per second, preferably 0.2 to 40 nm per second, and more preferably 0.3 to 20 nm per second. If the dissolution rate is lower than this range, the time required to remove the coating film for removing foreign matter will be longer, resulting in a decrease in productivity.

[0066] The coating film for removing foreign matter formed from the coating film-forming composition for removing foreign matter of the present invention can have its dissolution rate in a developer controlled by changing the baking conditions during formation. For a given baking time, the higher the baking temperature, the lower the dissolution rate of the coating film for removing foreign matter in a developer that can be formed.

[0067] The coating film for removing foreign matter of the present application may be exposed to light after the film is formed. The exposure may be performed by exposing the entire wafer or through a mask having a predetermined pattern. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), or the like may be used. After the exposure, a post-exposure bake (PEB) may be performed as necessary.

[0068] The foreign matter removal coating film is then removed using a developer. Examples of developers include aqueous alkaline solutions such as aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. The conditions for removing the foreign matter removal coating film are appropriately selected from a temperature of 5°C to 50°C and a time of 2 to 500 seconds or 3 to 400 seconds.

[0069] The coating film for removing foreign matter formed from the coating film-forming composition for removing foreign matter of the present invention can be easily peeled off at room temperature (e.g., 25°C) using a commonly used 2.38 mass% aqueous solution of tetramethylammonium hydroxide.

[0070] <Foreign object removal method> The method for removing foreign matter of the present application is a method for removing foreign matter, including the steps of applying the composition to a substrate and baking the composition to form a coating film, forming foreign matter on the film, and removing the film by applying a developer to the film.

[0071] The method may further include forming an adhesive layer after the step of forming the coating film, and then peeling off the adhesive layer. The foreign matter may be a peeled residue left after the adhesive layer is formed.

[0072] The foreign matter removal method of the present application may also be a method for removing foreign matter already present on a substrate for semiconductor manufacturing. For example, International Publication No. 2017 / 056746 and International Publication No. 2020 / 008965 disclose compositions for forming substrate processing films and substrate processing methods that can efficiently remove minute particles from the substrate surface and easily remove the formed substrate processing film from the substrate surface in a process of forming a substrate processing film on the surface of a semiconductor substrate and removing foreign matter from the substrate surface. The coating film-forming composition of the present application can also be used in the same methods and applications as those described above. The above example will be specifically described below. In this application example, the above-described coating film-forming composition for removing foreign matter is used as a composition for forming the coating film on a semiconductor manufacturing wafer. First, a coating film-forming step is performed. That is, the coating film-forming composition for removing foreign matter is applied to a semiconductor manufacturing wafer to form a coating film. The semiconductor manufacturing wafer may be in an unprocessed state or in a state where various films are formed, i.e., a solid substrate (flat), or may be processed to have a shape such as wiring for semiconductor device manufacturing. Examples of coating methods include spin coating, casting coating, and roll coating. Next, the coating film is heated (baked) and / or reduced pressure to efficiently remove part or all of the solvent contained in the coating film, thereby promoting solidification and / or hardening of the solid content contained in the coating film. Here, "solidification" means solidification, and "hardening" means that molecules bond to each other to increase the molecular weight (e.g., crosslinking, polymerization, etc.). In this manner, a coating film is formed. At this time, particles adhering to the pattern or the like are captured in the coating film and efficiently detached from the pattern or the like. Next, a coating film removal step is performed. That is, a removal liquid that dissolves the coating film is supplied onto the coating film, thereby removing all of the coating film from the semiconductor manufacturing wafer. As a result, the particles are removed from the semiconductor manufacturing wafer together with the coating film. As the removal liquid, water, an organic solvent, an alkaline aqueous solution, or the like can be used, with water and an alkaline aqueous solution being preferred, and an alkaline aqueous solution being more preferred.

[0073] Examples of the substrate include glass, metal-containing compounds, and metalloid-containing compounds. Examples of the metal-containing compounds and metalloid-containing compounds include ceramics, which are sintered bodies whose basic component is a metal oxide and are sintered by high-temperature heat treatment, inorganic solid materials such as molded bodies of inorganic compounds such as semiconductors like silicon, metal oxides or metalloid oxides (silicon oxide, alumina, etc.), metal carbides or metalloid carbides, metal nitrides or metalloid nitrides (silicon nitride, etc.), and metal borides or metalloid borides, aluminum, nickel titanium, and stainless steel (SUS304, SUS316, SUS316L, etc.), but preferably silicon substrates (e.g., semiconductor silicon wafers used in the manufacture of semiconductor devices).

[0074] <Substrate processing method> The substrate processing method includes the steps of applying the composition onto a substrate and baking it to form a coating film, forming an adhesive layer on the film, temporarily attaching another substrate to the substrate, peeling off the other substrate, and peeling off the film with a developer. The substrate processing method of the present application is applied to, for example, a so-called wafer temporary bonding process.

[0075] <Adhesive layer> The adhesive layer is formed using a known adhesive and method. Examples of the adhesive include a coating-type wafer temporary adhesive described in International Publication No. 2015 / 190438, a temporary bonding material from ThinMaterials (Nissan Chemical Industries, Ltd.), a semiconductor wafer temporary bonding material from Toray Industries, Inc., WaferBOND (registered trademark) CR-200, HT-10.10 (manufactured by Brewer Science), and tape-type adhesives (for example, backgrinding tape (for example, 3M TMTemporary fixing adhesive tape ATT-4025 (manufactured by 3M Japan Limited), E series, P series, S series (trade names manufactured by Lintec Corporation), ICROS Tape (registered trademark) (manufactured by Mitsui Chemicals Tocello Co., Ltd.)), dicing tape (for example, solvent-resistant dicing tape (trade name manufactured by Nitto Denko Corporation), temperature-sensitive adhesive sheet Intelimer (registered trademark) Tape (manufactured by Nitta Corporation), Intelimer (registered trademark) Tape (manufactured by Anchor Techno Co., Ltd.), etc.) may also be used. It may also be a wafer adhesive applied in a specific wafer handling system (for example, Zero Newton® (Tokyo Ohka Kogyo Co., Ltd.)).

[0076] For example, backgrinding tape consists of a base film, an adhesive layer, and a release film. While soft thermoplastic films such as ethylene-vinyl acetate copolymer (EVA) have traditionally been used as base films, attempts have been made to use rigid oriented films such as polyethylene terephthalate (PET) to improve wafer support. Further improvements have since been made, with reports of laminate designs using two types of films with different elastic moduli, such as PET and ethylene-based copolymers, and polypropylene (PP) and ethylene-based copolymers.

[0077] Acrylic adhesives are commonly used. Acrylic adhesives are known to be designed by crosslinking an acrylic copolymer, primarily made from a monomer with a low glass transition temperature, such as butyl acrylate, with a curing agent. Backgrinding tape is applied to the circuit surface of a wafer, raising concerns about contamination from the adhesive after tape removal. For this reason, designs using emulsion-based adhesives have been reported, with the expectation that any remaining adhesive can be removed by washing with water, but complete removal is difficult. Therefore, by forming an adhesive layer after forming the coating film for foreign matter removal of the present application on the circuit surface, foreign matter (adhesive residue) can be completely removed by washing with a developer during the subsequent peeling process, without causing damage to the wiring of the circuit or other components.

[0078] <Laminated substrate manufacturing method> A laminated substrate having a substrate-film-adhesive layer-substrate structure can be produced through a process including applying the composition to a substrate and baking it to form a coating film, forming an adhesive layer on the film, and attaching another substrate to the coating film. Preferably, one of the layers is a semiconductor substrate and the other is a support substrate for maintaining the shape of the semiconductor substrate, and the adhesive layer is preferably one that allows the semiconductor substrate and the support substrate to be peeled off again. The adhesive layer is as described above. [Example]

[0079] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0080] Example 1 (Preparation of coating film-forming composition for removing foreign matter) To 8.1 g of naphthol cresol novolak (MN8280G, weight average molecular weight 5,000) (manufactured by Asahi Organic Chemicals Co., Ltd.), 0.27 g of 4,4'-methylenebis(diglycidylaniline) (manufactured by Nippon Steel Chemical & Material Co., Ltd.), 43.5 g of propylene glycol monomethyl ether, and 13.1 g of propylene glycol monomethyl ether acetate were added, and the mixture was stirred at room temperature for 30 minutes to prepare a solution [1] of a coating film-forming composition for removing foreign matter, which contains a polymer represented by the following formula: [ka]

[0081] (Evaluation of Coating Film-Forming Composition for Removing Foreign Matter) This solution of the coating film-forming composition for removing foreign matter [1] was applied to a silicon wafer substrate using a spinner, and then baked on a hot plate at 200°C for 60 seconds to form a coating film for removing foreign matter with a thickness of 40 nm.

[0082] The dissolution rate of the foreign matter removal coating film in a developer (Tokyo Ohka Kogyo Co., Ltd., product name NMD-3) was measured using a resist development analyzer (Litho Tech Japan Co., Ltd.). The temperature around the analyzer was 25°C. The dissolution rate of the foreign matter removal coating film formed at a baking temperature of 150°C for a baking time of 60 seconds was 3.3 nm per second. The dissolution rate of the foreign matter removal coating film formed at a baking temperature of 155°C for a baking time of 60 seconds was 2.8 nm per second, the dissolution rate of the foreign matter removal coating film formed at a baking temperature of 160°C for a baking time of 60 seconds was 1.8 nm per second, and the dissolution rate of the foreign matter removal coating film formed at a baking temperature of 165°C for a baking time of 60 seconds was 0.9 nm per second. In other words, a foreign matter removal coating film formed at a baking temperature of 150°C for a baking time of 60 seconds can be completely removed in 12 seconds, a foreign matter removal coating film formed at a baking temperature of 155°C for a baking time of 60 seconds can be completely removed in 14 seconds, a foreign matter removal coating film formed at a baking temperature of 160°C for a baking time of 60 seconds can be completely removed in approximately 22 seconds, and a foreign matter removal coating film formed at a baking temperature of 165°C for a baking time of 60 seconds can be completely removed in approximately 44 seconds, which means that foreign matter present on this foreign matter removal coating film can also be removed.

[0083] Example 2 (Synthesis of polyamic acid) A solution [C] containing polyamic acid was obtained by reacting 17.8 g of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 3.12 g of 3,5-diaminobenzoic acid, and 4.92 g of bis(4-aminophenylsulfone) in 145.6 g of propylene glycol monomethyl ether at 80°C for 20 hours. GPC analysis of the obtained polyamic acid revealed that the weight average molecular weight Mw was 8,600 (standard polystyrene equivalent) and the number average molecular weight Mn was 5,200.

[0084] (Synthesis of light-absorbing compounds) 19.0 g of 3,7-dihydroxy-2-naphthoic acid, 10 g of tris(2,3-epoxypropyl)isocyanurate, and 0.552 g of benzyltriethylammonium chloride were reacted in 118 g of cyclohexanone at 130°C for 24 hours to obtain a solution [a] containing a light-absorbing compound.

[0085] (Preparation of coating film-forming composition for removing foreign matter) To 25.0 g of the solution [C] containing polyamic acid was added 4.15 g of the light-absorbing compound solution [a], 1.13 g of 4,4'-methylenebis(N,N-diglycidylaniline), 0.825 g of 3,7-dihydroxynaphthoic acid, 0.124 g of triphenylsulfonium trifluoromethanesulfonate, 82.8 g of propylene glycol monomethyl ether, 127 g of propylene glycol monomethyl ether acetate, and 10.0 g of cyclohexanone, and the mixture was stirred at room temperature for 30 minutes to prepare a solution [5] of a coating film-forming composition for removing foreign matter.

[0086] (Evaluation of Coating Film-Forming Composition for Removing Foreign Matter) This solution of the coating film-forming composition for removing foreign matter [5] was applied to a silicon wafer substrate using a spinner, and then baked on a hot plate at 175°C for 60 seconds to form a coating film for removing foreign matter with a thickness of 40 nm.

[0087] The dissolution rate of the foreign matter removal coating film in a developer (trade name NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was measured using a resist development analyzer (manufactured by Litho Tech Japan Co., Ltd.). The temperature around the analyzer was 25°C. The dissolution rate of the foreign matter removal coating film formed at a baking temperature of 170°C for a baking time of 60 seconds was 2.35 nm per second, and the dissolution rate of the foreign matter removal coating film formed at a baking temperature of 175°C for a baking time of 60 seconds was 2.00 nm per second. The dissolution rate of the foreign matter removal coating film formed at a baking temperature of 180°C for a baking time of 60 seconds was 1.82 nm per second.

[0088] In other words, a foreign matter removal coating film formed at a baking temperature of 170°C for a baking time of 60 seconds can be completely removed in 17 seconds, a foreign matter removal coating film formed at a baking temperature of 175°C for a baking time of 60 seconds can be completely removed in 20 seconds, and a foreign matter removal coating film formed at a baking temperature of 180°C for a baking time of 60 seconds can be completely removed in 22 seconds, which means that foreign matter present on this foreign matter removal coating film can also be removed.

[0089] (Storage stability evaluation) The solutions of the coating film-forming compositions for removing foreign matter of Examples 1 and 2 were stored at -20°C to +35°C for one month, and then returned to room temperature. The solutions were then applied to a silicon wafer substrate using a spinner and baked on a hot plate at 120°C for 60 seconds to check for any change in film thickness. As a result, in Example 2, a decrease in film thickness from the initial film thickness was observed after one month of storage at 35°C, but in Example 1, no change in film thickness was observed.

[0090] Furthermore, solutions of the coating film-forming compositions for removing foreign matter in Examples 1 and 2 were stored at -20°C to +35°C for one month, and then returned to room temperature. The solutions were then applied to a silicon wafer substrate using a spinner, baked on a hot plate at 120°C for 60 seconds, and the development rate was measured after a development time of 10 seconds. Both solutions showed sufficiently high development rates, demonstrating sufficient foreign matter removal capabilities. Therefore, Example 1 demonstrated good storage stability in addition to foreign matter removal capabilities. [Industrial Applicability]

[0091] The present invention relates to a coating film-forming composition for removing foreign matter, a method for removing foreign matter from a substrate, a substrate processing method, and a method for manufacturing a laminated substrate, which can easily remove foreign matter formed on a substrate. The present invention can provide a coating film-forming composition for removing foreign matter, which is preferably used in a semiconductor wafer temporary bonding step in the manufacture of a semiconductor device.

Claims

1. A coating film-forming composition for removing foreign matter, which comprises a polymer and a solvent and is capable of forming a coating film that dissolves in a developer, The composition contains the polymer selected from a phenolic hydroxyl group-containing polymer and a carboxyl group-containing polymer, the phenolic hydroxyl group-containing polymer is a phenol novolak or a polyhydroxystyrene derivative, and the carboxyl group-containing polymer is a (meth)acrylic resin, polyvinyl benzoic acid, or carboxymethyl cellulose, and the polymer accounts for 50 mass% or more of the total solid content of the composition.

2. The composition described in claim 1, wherein the composition contains a crosslinking agent and / or an additive.

3. The composition described in claim 2, wherein the crosslinking agent comprises an epoxy group.

4. A coating film for removing foreign matter, characterized in that it is a fired product of a coating film made of the composition described in any one of claims 1 to 3.

5. A method for removing foreign matter, comprising the steps of applying the composition described in any one of claims 1 to 3 onto a substrate and baking it to form a coating film, forming foreign matter on the coating film, and removing the coating film together with the foreign matter using a developer.

6. The process of forming the foreign matter comprises: The method of claim 5 , further comprising the steps of forming an adhesive layer on the coating film and then peeling off the adhesive layer.

7. The method described in claim 6, wherein the foreign matter is a peeling residue of the adhesive layer.

8. A composition according to any one of claims 1 to 3, which is applied to a first substrate and baked. forming a coating film; forming an adhesive layer on the coating film; a step of temporarily attaching a second substrate to the first substrate via the adhesive layer; peeling the second substrate from the first substrate; and a step of removing the coating film remaining on the first substrate together with the adhesive layer using a developer after the second substrate has been peeled off.

9. A process of applying the composition according to any one of claims 1 to 3 onto a first substrate and baking the composition to form a coating film; forming an adhesive layer on the coating film; and A method for manufacturing a laminated substrate, comprising the step of attaching a second substrate to the first substrate.

10. A composition used to remove foreign matter present on a substrate for semiconductor manufacturing, the composition comprising a polymer and a solvent, the polymer being selected from a phenolic hydroxyl group-containing polymer and a carboxyl group-containing polymer, the phenolic hydroxyl group-containing polymer being a phenol novolac or a polyhydroxystyrene derivative, the carboxyl group-containing polymer being a (meth)acrylic resin, polyvinyl benzoic acid or carboxymethyl cellulose, and the polymer comprising 50 mass% or more of the total solid content in the composition.

11. The composition of claim 10, wherein the composition comprises a crosslinking agent and / or an additive.

12. A method for removing foreign matter, comprising the steps of applying the composition described in any one of claims 10 to 11 onto a substrate on which foreign matter is present and baking the composition to form a coating film incorporating the foreign matter, and removing the coating film together with the foreign matter using a developer.

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