Composition for forming coating film for removing foreign matter

Abstract

Provided is a simple method for removing foreign matter formed on a substrate in a semiconductor device manufacturing process, and a foreign matter-removing coating film-forming composition used in such a method. A composition is a foreign matter-removing coating film-forming composition that includes a polymer selected from the group consisting of phenol novolak, polyhydroxystyrene derivative, and carboxylic acid-containing polymer, and a solvent, and is capable of forming a coating film that dissolves in a developer, the composition including 50% by mass or more of the polymer relative to the entire solid content of the composition.

Description

Technical Field

[0001] This invention relates to a coating composition for removing foreign matter formed on a substrate using a simple method, a method for removing foreign matter from a substrate, a substrate processing method, and a method for manufacturing a multilayer substrate. Preferably, it relates to a coating composition for removing foreign matter formed for use in the temporary bonding process of semiconductor wafers in semiconductor device manufacturing. Background Technology

[0002] In the manufacture of semiconductor devices, especially in the so-called back-end processes, a process has been studied in which a semiconductor substrate (wafer) is attached to a support substrate, and then back-side grinding (polishing), wiring fabrication, etc. are performed, and then the support substrate is peeled off to obtain the desired semiconductor substrate.

[0003] When bonding a support substrate, the wafer is bonded using an adhesive (a liquid composition containing polymers, a back-grinding tape, a dicing tape, etc.) that is resistant to subsequent processes (heating processes, chemical treatment processes), and then the semiconductor substrate is peeled off. However, sometimes the adhesive layer contained in the adhesive remains on the substrate as foreign matter (residue). This is particularly noticeable when the adhesive layer is formed directly on the surface of the semiconductor substrate where wiring, etc., has been pre-formed. This foreign matter sometimes cannot be completely removed even by washing with known organic solvents, liquid chemical reagents, etc.

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

[0005] A composition for forming a coating to remove foreign matter using polyamic acid material has been disclosed (Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2018 / 159665

[0009] Patent Document 2: International Publication No. 2017 / 056746

[0010] Patent Document 3: International Publication No. 2020 / 008965 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] The problem to be solved by the present invention is to provide a simple method for removing foreign matter formed on a substrate, such as in a temporary bonding process of a semiconductor wafer in semiconductor device manufacturing, or foreign matter already present on a semiconductor substrate, and to provide a coating composition for foreign matter removal used in such a method.

[0013] Furthermore, the foreign matter removal coating of this invention is not limited to the temporary bonding process as long as it is used to remove foreign matter from the substrate.

[0014] Methods for solving problems

[0015] The present invention includes the following solutions.

[0016] [1] A composition comprising a polymer and a solvent, and capable of forming a coating film for removing foreign matter, which is soluble in a developer.

[0017] The polymers mentioned above are selected from polymers containing phenolic hydroxyl groups and polymers containing carboxyl groups, and the composition contains more than 50% by mass of the polymers mentioned above relative to the total solid components in the composition.

[0018] [2] According to the composition described in [1], the polymer containing phenolic hydroxyl groups is a phenolic varnish or a polyhydroxystyrene derivative.

[0019] [3] According to the composition described in [1], the above-mentioned carboxyl-containing polymer is selected from (meth)acrylic resins, polyvinylbenzoic acid and carboxymethyl cellulose.

[0020] [4] The composition according to any one of [1] to [3] comprises a crosslinking agent and / or an additive.

[0021] [5] According to the composition described in [4], the crosslinking agent contains epoxy groups.

[0022] [6] A coating for removing foreign matter, characterized in that it is a sintered product of a coating film formed from any one of the compositions described in [1] to [5].

[0023] [7] A method for removing foreign matter includes the following steps: a step of coating a substrate with the composition described in any one of [1] to [5] and firing it to form a coating film; a step of forming foreign matter on the coating film; and a step of removing the coating film and the foreign matter together with a developing solution.

[0024] [8] According to the method described in [7], the above-mentioned process for forming foreign matter includes:

[0025] The process of forming an adhesive layer on the above-mentioned coating; and the process of subsequently peeling off the above-mentioned adhesive layer.

[0026] [9] According to the method described in [8], the foreign matter is the peeling residue of the adhesive layer.

[0027]

[10] A substrate processing method comprising the following steps:

[0028] The process of coating a first substrate with the composition described in any one of [1] to [5] and firing it to form a coating film;

[0029] The process of forming an adhesive layer on the above coating film;

[0030] The process of temporarily attaching the second substrate to the first substrate via the aforementioned adhesive layer;

[0031] The process of peeling the second substrate from the first substrate; and

[0032] The process of removing the coating and adhesive layer remaining on the first substrate after the second substrate has been peeled off using a developing solution.

[0033]

[11] A method for manufacturing a multilayer substrate, comprising the following steps: coating a first substrate with the composition described in any one of [1] to [5] and firing it to form a coating film;

[0034] The process of forming an adhesive layer on the above coating film; and

[0035] The process of attaching the second substrate to the first substrate.

[0036]

[12] A composition for removing foreign matter present on a substrate for semiconductor manufacturing, the composition comprising a polymer and a solvent, wherein the polymer is selected from polymers containing phenolic hydroxyl groups and polymers containing carboxyl groups, and the composition comprises more than 50% by mass of the polymer in total relative to the solid components in the composition.

[0037]

[13] The composition according to

[12] comprises a crosslinking agent and / or an additive.

[0038]

[14] A composition for removing 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 acid dianhydride compound and (b) a diamine compound having at least one carboxyl group.

[0039]

[15] A method for removing foreign matter includes the following steps: coating a substrate containing foreign matter with the composition described in any one of

[12] to

[14] and firing it to form a coating film containing foreign matter; and removing the coating film together with the foreign matter using a developing solution.

[0040] The effects of the invention

[0041] In particular, during the temporary wafer bonding process of semiconductor wafers, the foreign matter removal coating of the present invention is formed on a substrate (processing substrate) in advance. This substrate is then bonded to a support substrate using an adhesive layer. The support substrate is then peeled off from the substrate using a wafer peeling process, followed by washing the substrate with a developing solution. This allows for the simultaneous and complete removal of foreign matter from both the foreign matter removal coating and the coating itself. Furthermore, by removing the substrate processing film containing foreign matter present on the surface of the semiconductor manufacturing substrate due to certain factors from the substrate surface, foreign matter can be easily removed from the semiconductor manufacturing substrate. This significantly reduces defects caused by foreign matter in semiconductor manufacturing equipment, contributing to an increased yield of good wafers.

[0042] The foreign matter removal coating of the present invention is particularly resistant to the processing (heat, chemical reagents) of the semiconductor substrate after temporary bonding when used in the temporary bonding process of semiconductor wafers. Detailed Implementation

[0043] <Composition for Foreign Object Removal and Film Formation>

[0044] The foreign matter removal coating film forming composition of the present invention is characterized in that it comprises a polymer and a solvent, and is capable of forming a coating film soluble in a developer solution. The polymer is selected from polymers containing phenolic hydroxyl groups and polymers containing carboxyl groups. These polymers are soluble in the developer solution.

[0045] Preferably, the polymer containing phenolic hydroxyl groups is phenolic varnish or polyhydroxystyrene derivative.

[0046] Preferably, the above-mentioned polymers containing carboxyl groups are selected from (meth)acrylic resins, polyvinylbenzoic acid, or carboxymethyl cellulose.

[0047] Furthermore, the composition is characterized by comprising at least 50% by mass of the polymer relative to the solid components in the composition. Preferably, it comprises at least 60% by mass, at least 70% by mass, at least 80% by mass, or at least 90% by mass.

[0048] <Phenolic Varnish>

[0049] Phenolic varnish (phenolic varnish resin) can use substances that have been used in positive photosensitive materials and the like without restriction. Examples include resins obtained by polymerizing phenols and aldehydes in the presence of an acid catalyst.

[0050] Examples of the aforementioned phenols include, for instance, 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; and ethylphenol, m-ethylphenol, p-ethylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, and m-butylphenol. Alkylphenols such as p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; polyphenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and phlorogallol; alkyl polyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (each alkyl group has 1 to 4 carbon atoms); α-naphthol, β-naphthol, hydroxydiphenyl compounds, bisphenol A, etc. These phenols can be used alone or in combination of two or more.

[0051] Examples of aldehydes mentioned above include formaldehyde, oligoformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes can be used alone or in combination of two or more.

[0052] Examples of acid catalysts 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, diethylsulfuric acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate.

[0053] The phenolic varnish of this application can be a naphthol-cresol varnish obtained by polymerizing α-naphthol and β-naphthol.

[0054] <Polyhydroxystyrene derivatives>

[0055] The polyhydroxystyrene derivatives of this application are obtained by polymerizing hydroxystyrene with substituents. Preferably, they have the following unit structures.

[0056]

[0057] (In formula (1), R represents a halogen atom, carboxyl group, nitro group, cyano group, methylenedioxy group, acetoxy group, methylthio group, amino group, or alkoxy group with 1 to 9 carbon atoms. n represents an integer from 1 to 4. When n is 2 or more, the n Rs can be the same or different.)

[0058] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0059] Examples of alkoxy groups with 1 to 9 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl - n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2,-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, n-heptyloxy, n-octyloxy, and n-nonyloxy.

[0060] <(Meth)Acrylic Resins>

[0061] The (meth)acrylic resin of this application can use substances that have been conventionally used in positive photosensitive materials without limitation, such as resins obtained by polymerizing polymerizable monomers having (meth)acryloyl groups in the presence of a free radical polymerization initiator.

[0062] Examples of polymerizable monomers having a (meth)acrylyl group include, for instance, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, trifluoroethyl methacrylate, and tetrafluoropropyl methacrylate, as well as acrylamides such as diacetone acrylamide; tetrahydrofurfuryl methacrylate, dialkylaminoethyl methacrylate, glycidyl methacrylate, methacrylic acid, α-bromo(methacrylic acid), α-chloro(methacrylic acid), β-furanyl(methacrylic acid), and β-styryl(methacrylic acid). These polymerizable monomers having a (meth)acrylyl group can be used alone or in combination of two or more.

[0063] Examples of free radical polymerization initiators include organic peroxides such as benzoyl peroxide, dicumyl peroxide, and dibutyl peroxide; and azobisisobutyronitrile and azobispentonitrile compounds such as azobisisobutyronitrile.

[0064] In addition to polymerizable monomers containing (meth)acryloyl groups, the aforementioned acrylic resins can also contain polymerizable styrene derivatives such as copolystyrene, vinyltoluene, and α-methylstyrene, which are substituted at the α-position or in the aromatic ring; esters of vinyl alcohols such as acrylonitrile and vinyl-n-butyl ether; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; and one or more polymerizable monomers such as fumaric acid, cinnamic acid, α-cyanocinonic acid, itaconic acid, and crotonic acid.

[0065] In addition, in this specification, "(meth)acrylic acid" refers to both "acrylic acid" and "methacrylic acid".

[0066] Polyvinylbenzoic acid

[0067] The polyvinylbenzoic acid of this application is obtained, for example, by polymerizing 4-vinylbenzoic acid as shown below using a known method.

[0068]

[0069] <Carboxymethyl cellulose>

[0070] The carboxymethyl cellulose of this application has the structure shown below.

[0071]

[0072] R = H or CH2CO2H

[0073] (In the formula, n represents the number of repeating units)

[0074] Furthermore, the foreign matter removal coating film forming composition of this application may comprise a polymer of polyamic acid as described in International Publication No. 2018 / 159665, having structural units derived from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound having at least one carboxyl group. The aforementioned 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).

[0075] The diamine compound in (c) above can be a diamine compound without a carboxyl group.

[0076] Examples of polyamic acids contained in the coating film forming composition for removing foreign matter according to the present invention include, for example, the following polyamic acids (29) to (41) (where p1, p2, p3, and p4 represent the proportions of each structure in the polyamic acid). Here, (29) to (36) are polyamic acids made from a tetracarboxylic dianhydride compound and two diamine compounds, (37) and (38) are polyamic acids made from two tetracarboxylic dianhydride compounds and a diamine compound, (39) is polyamic acid made from two tetracarboxylic dianhydride compounds and two diamine compounds, and (40) and (41) are polyamic acids made from a tetracarboxylic dianhydride compound and a diamine compound.

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] Furthermore, the contents of International Publication No. 2018 / 159665 are incorporated herein by reference to the express disclosure in their entirety.

[0085] The weight-average molecular weight of the polymer used in this application, determined by gel permeation chromatography (GPC) and converted to polystyrene, is, for example, 1,000 to 100,000, or 1,000 to 50,000, preferably 2,000 to 50,000. When the weight-average molecular weight is below 1,000, the solubility of the resulting foreign matter removal coating in the solvent used for the adhesive layer becomes high, resulting in mixing with the adhesive layer (layer mixing). When the weight-average molecular weight is above 100,000, the solubility of the resulting foreign matter removal coating in the developer becomes insufficient, resulting in residue after development.

[0086] <Solvent>

[0087] The foreign matter removal and coating film forming composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components, and can be used in solution form by dissolving in a suitable solvent. As such solvents, 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, 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 ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 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, N-methylpyrrolidone, etc. 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 used in combination.

[0088] The prepared foreign matter removal coating resin composition solution is preferably filtered using a filter with a pore size of approximately 0.2 μm before use. This prepared foreign matter removal coating resin composition solution also exhibits excellent long-term storage stability at room temperature.

[0089] Regarding the proportion of solid components in the coating film-forming composition for foreign matter removal of the present invention, there is no particular limitation as long as all components are uniformly dissolved; for example, it is 0.5 to 50% by mass, or 1 to 30% by mass. Here, solid components refer to the components remaining after removing the solvent components from all components of the coating film-forming composition for foreign matter removal.

[0090] In this invention, "foreign matter" refers to any substance other than the target substance that adheres to the substrate. In the semiconductor device manufacturing process, it refers to substances that are not required during the manufacturing process. Examples include particles adhering to the wafer, metallic impurities, etching residue, adhesive stripping residue, etc.

[0091] The foreign matter removal coating of the present invention is particularly preferred in the process of bonding wafers together with an adhesive and then peeling off the adhesive. In order to pre-form the coating of the present invention before applying the adhesive, the foreign matter (adhesive residue) after the bonding and peeling process of the wafers is then removed.

[0092] The foreign matter removal coating of the present invention can also be used to remove foreign matter that already exists on a semiconductor manufacturing substrate.

[0093] The term "dissolution of the coating by the developing solution" in this invention refers to the fact that if the coating is immersed or washed using the developing solution described later, the coating dissolves in the developing solution and becomes non-existent on the substrate. In this invention, "dissolution" means that, using the method described in the examples, at least 90% (i.e., the thickness of the residual film is less than 10% of the initial film thickness), or at least 95% (i.e., the thickness of the residual film is less than 5% of the initial film thickness), or at least 99% (i.e., the thickness of the residual film is less than 1% of the initial film thickness), and most preferably 100% (i.e., the thickness of the residual film is 0% of the initial film thickness (no residual film)).

[0094] Preferably, the above composition contains a crosslinking agent and / or additives.

[0095] <Cross-linking agent>

[0096] Preferably, the crosslinking agent contains epoxy groups.

[0097] The aforementioned crosslinking agent may contain a compound having at least two epoxy groups. There is no particular limitation on the type of compound, as long as it has 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, trimethylolpropane triglycidyl ether, bisphenol A-diglycidyl ether, pentaerythritol polyglycidyl ether, etc.

[0098] In addition, the production tool has two or more chemical base compounds, and the production tool has a chemical base resin, which can be produced as YH-434, YH434L (Nippon Steel Chemical & Material Co., Ltd. system, product name), and the production tool has a chemical compound. As a result, it is possible to produce Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celoxide 2021, Celoxide 3 000 (manufactured by Daicel Chemical Co., Ltd., trade name), as a double-phenol A-type ring-oxy resin, can produce Epicote 1001, Epicote 1002, Epicote 1003, Epicote 1004, Epicote 1007, Epicote 1009, Epicote 1010, Epicote 828 (all manufactured by Yuka Shell Epoxy Co., Ltd., trade name), as a double-phenol F-type ring-oxy resin, can produce Epicote 8 07 (Yuka Shell Epoxy Co., Ltd. system, product name), etc., produced by Yuka Shell Epoxy Co., Ltd., pure lacquer type environmental resin, available Epicoat 152, Epicoat 154 (all above, Yuka Shell Epoxy Co., Ltd. system, product name) ), EPPN201, EPPN202 (all Nippon Kasei Co., Ltd., product name), etc., made with pure lacquer type glass resin, available EOCN-102, EOCN-103S, EOCN-1 04S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Chemical Co., Ltd., trade names), Epicote 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd., trade name), etc., as epicoat-type epicoat resin, can be used to produce Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd., trade name), CY175, CY177, CY179 (all manufactured by CIBA-GEIGY AG, trade name), Araldite CY-182, Araldite CY-192, Araldite CY-184 (all manufactured by CIBA-GEIGY AG (product name), Epiclon 200, Epiclon 400 (both manufactured by Dainippon Ink & Commerce Co., Ltd., product name), Epicote 871, Epicote 872 (both manufactured by Yuka Shell Epoxy Co., Ltd., product name), ED-5661, ED-5662 (both manufactured by Celanese Coating Co., Ltd., product name), etc., as aliphatic polymerized glycerolite, can be used to produce Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321 (manufactured by Nagase ChemteX Co., Ltd., product name), etc.

[0099] 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. When the content of the compound having at least two epoxy groups is less than 5 parts by mass, the curing degree of the coating for removing foreign matter is sometimes insufficient, for example, it dissolves in the adhesive layer and mixes with each other. When it exceeds 70 parts by mass, sufficient solubility in the developer is not obtained.

[0100] <Additives>

[0101] The foreign matter removal and coating formation composition of the present invention may contain light-absorbing compounds, surfactants, adhesive aids, and rheology modifiers as additives.

[0102] (Light-absorbing compounds)

[0103] As a light-absorbing compound, there are no particular limitations as long as it absorbs the exposure wavelength used. Compounds with aromatic ring structures such as anthracene, naphthalene, benzene, quinoline, or triazine are preferred. Furthermore, from the viewpoint of not impairing the solubility of the coating in the developer, compounds with phenolic hydroxyl, carboxyl, or sulfonic acid groups are preferred.

[0104] Examples of light-absorbing compounds that exhibit strong absorption of light at a wavelength of 248 nm include, for example, 1-naphthoic acid, 2-naphthoic acid, 1-naphthol, 2-naphthol, 1-aminonaphthol, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 6-bromo-2-hydroxynaphthoic acid, 1,2-naphthoic acid, 1,3-naphthoic acid, 1,4-naphthoic acid, 1,5-naphthoic acid, 1,6-naphthoic acid, 1,7-naphthoic acid, 1,8-naphthoic acid, etc. -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, 6-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 1-bromo-2-naphthoic acid 1-Hydroxy-3-naphthoic acid, 1-bromo-4-hydroxy-3-naphthoic acid, 1,6-dibromo-2-hydroxy-3-naphthoic acid, 3-hydroxy-7-methoxy-2-naphthoic acid, 1-amino-2-naphthol, 1,5-dimercaptonaphthalene, 1,4,5,8-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2,6-dichloro-1-naphthoic acid, methyl 2-hydroxy-3-naphthoic acid, 6-hydroxy-2-naphthoic acid Methyl naphthanoate, methyl 3-hydroxy-7-methoxy-2-naphthanoate, methyl 3,7-dihydroxy-2-naphthanoate, 2,4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-naphthiophenol, 4-methoxy-1-naphthol, 6-acetoxy-2-naphtholic acid, 1,6-dibromo-1-naphthol, 2,6-dibromo-1,5-dihydroxynaphthol, 1-acetyl-2-naphthol, 9-anthracarboxylic acid, 1,4,9,10-tetrahydroxyanthracene, 1,8,9-trihydroxyanthracene, etc.

[0105] Furthermore, examples of light-absorbing compounds that exhibit strong absorption of light at a wavelength of 193 nm include, for example, benzoic acid, 4-methylbenzoic acid, phthalic acid, isophthalic acid, terephthalic 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, trimellitic acid, 1,4-phthalic acid, 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, and 3,4-dihydroxybenzoic acid. Formic acid, 3,5-dihydroxybenzoic acid, 4-acetylbenzoic acid, pyromellitic acid, pyromellitic tricarboxylic acid anhydride, 2-[bis-(4-hydroxyphenyl)-methyl]benzoic acid, 3,4,5-trihydroxybenzoic acid, 2-benzophenone carboxylic 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, etc.

[0106] In addition, these absorbent compounds can be used to suppress sublimation during firing of coatings used to remove foreign matter, by reacting them with polymers or compounds having one or more reactive groups.

[0107] For example, in the case of light-absorbing compounds having carboxyl groups or phenolic hydroxyl groups, compounds 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 Compounds obtained by reacting polyfunctional epoxy compounds such as diglycidyl 2-cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether, and polymers containing epoxy groups such as glycidyl methacrylate. Examples include polymers having the unit structures shown in (42), (43), and (44) below, and compounds shown in (45). In formula (45), Ar represents a benzene ring, naphthalene ring, or anthracene ring that can be substituted by an alkyl group, an alkoxy group, 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, a carboxyl group, a phenoxy group, an acetyl group, an alkoxycarbonyl group, or a vinyl group.

[0108]

[0109] The aforementioned absorbent compounds can be used alone or in combination of two or more. When using a light-absorbing compound, its content, relative to 100 parts by mass of the polymer, is, for example, 1 to 300 parts by mass, or 1 to 200 parts by mass, or even, for example, 1 to 100 parts by mass, or 5 to 100 parts by mass. When the absorbent compound content exceeds 300 parts by mass, sometimes the solubility of the foreign matter removal coating in the developer decreases, or the foreign matter removal coating mixes with the adhesive layer.

[0110] The foreign matter removal and film-forming composition of the present invention may contain an acid-generating agent. Examples of acid-generating agents include 2,4,4,6-tetrabromocyclohexadienone, benzoin toluene sulfonate, 2-nitrobenzyl toluene sulfonate, other alkyl sulfonates of organic sulfonates, and bis(4-tert-butylphenyl)iodide. Photoacid generators include trifluoromethane sulfonate, triphenylsulfonium trifluoromethane sulfonate, phenyl-bis(trichloromethyl)triazine, benzoin toluene sulfonate, and N-hydroxysuccinimide trifluoromethane sulfonate. The amount of acid generator added is, as needed, 10% by mass or less, preferably 3% by mass or less, of the solid components of the coating film-forming composition for foreign matter removal.

[0111] In the foreign matter removal coating film forming composition of the present invention, polyphenolic compounds and carboxyl-containing compounds may be added to promote the dissolution rate in the developer. Such compounds are not particularly limited, and examples include, for instance, tri-hydroxyphenylethane, bisphenol-A, bisphenol-S, 4,4'-isopropylidene-di-o-cresol, 5-tert-butylpyrogallol, hexafluorobisphenol-A, 3,3,3',3'-tetramethyl-1,1'-spirobinodinium-5,5',6,6'-tetraol, 4,4'-(9-fluoreneyl)biphenol, bisphenol-AP, bisphenol- P, 5-α,α-dimethyl-4-hydroxybenzyl salicylic acid, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 5,5'-di-tert-butyl-2,2',4,4'-tetrahydroxybenzophenone and other polyphenols, pyromellitic acid, phthalic acid, trimellitic acid, 4-sulfophthalic acid, hexabenzoic acid, 2,3-naphthalenedicarboxylic acid, 4-hydroxyphthalic acid Dicarboxylic acid, 3,4-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 3,3'-,4,4'-biphenyltetracarboxylic acid, 3,3'-,4,4'-benzophenone tetracarboxylic acid, 3,3'-,4,4'-diphenyl ether tetracarboxylic acid, 3,3'-,4,4'-diphenyl sulfone tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3 Polycarboxylic acids such as 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-naphthous succinic acid; polymers containing carboxylic acids or carboxylic anhydrides such as polyacrylic acid, polymethacrylic acid, polyamic acid, and polymaleic anhydride. As the amount of the above compounds added, they are used as needed in the solid components of the coating film-forming composition for foreign matter removal at an amount of 20% by mass or less, preferably 10% by mass or less.

[0112] In the foreign matter removal and film-forming composition of the present invention, in order to adjust the dissolution rate in the developer, a compound having a carboxyl group or phenolic hydroxyl group protected by a group such as tert-butyl, tetrahydropyranyl, 1-ethoxyethyl and trimethylsilyl that is easily decomposed in the presence of acid may be added.

[0113] Examples of such compounds include di-tert-butyl malonate, tert-butyl acetate, tert-butyl propionate, tert-butyl acetoacetate, tert-amyl acetate, tert-butyl benzoate, and tert-butyl neopentanoate. Furthermore, compounds of formulas (46) to (54) can be cited.

[0114]

[0115]

[0116] These compounds can readily generate carboxyl or phenolic hydroxyl groups in the presence of acid, resulting in compounds with improved solubility in alkaline developing solutions.

[0117] Therefore, these compounds are preferably added together with a photoacid generator to the coating composition for foreign matter removal. That is, in the foreign matter removal coating formed from a composition comprising a compound having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of the aforementioned acid and a photoacid generator, the exposed portions are regenerated by the acid generated by the photoacid generator during exposure, thereby regenerating the carboxyl or phenolic hydroxyl groups of the compound having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid. As a result, the solubility of the foreign matter removal coating in the exposed portions in alkaline solutions is improved. In contrast, the unexposed portions do not change in the presence of carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid, and the solubility of the foreign matter removal coating in those portions in alkaline solutions is not improved. Therefore, by using a compound having a carboxyl or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of acid with a photoacid generator, the solubility of the exposed and unexposed parts of the coating used for foreign matter removal after exposure in an alkaline developer can be differentiated, making it easier to form patterns using development.

[0118] When using the above-mentioned compound having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid, its content, relative to 100 parts by mass of the polymer, is, for example, 50 to 1 part by mass, or 30 to 5 parts by mass, or even, for example, 20 to 10 parts by mass. When using a photoacid-generating agent with the compound having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid, its content, relative to 100 parts by mass of the compound having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid, is, for example, 0.1 to 30 parts by mass, or 0.5 to 20 parts by mass, or even, for example, 1 to 10 parts by mass.

[0119] (surfactant)

[0120] The foreign matter removal and film-forming composition of the present invention may contain a surfactant. Examples of surfactants include, for instance, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol monolaurate. Polyoxyethylene sorbitan fatty acid esters and other non-ionic surfactants such as lititol tristearate and other polyoxyethylene sorbitan fatty acid esters, Etotron EF301, EF303, EF352 (Technology Co., Ltd. Manufactured by ムプロダクツ, trade name), メガファック F171, F173 (manufactured by Dainippon Chemical Industry Co., Ltd., trade name), フロラード FC430, FC431 Fluoropolymer surfactants such as Asahi Glass Co., Ltd. (manufactured by Sumitomo Silem Co., Ltd., trade name), Asahi Guard AG710, Servolon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) are used. The amount of these surfactants mixed in the total composition of the coating film-forming composition for foreign matter removal of the present invention is generally 0.2% by mass or less, preferably 0.1% by mass or less. These surfactants can be added individually or in combination of two or more.

[0121] <Coating for Foreign Object Removal, Method for Manufacturing Coating for Foreign Object Removal>

[0122] The foreign matter removal coating film forming composition of the present invention is applied to a semiconductor substrate (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, glass substrate, ITO substrate, etc.) by a suitable coating method such as spin coater, coating machine, or immersion, and then fired to form a foreign matter removal coating film. The firing conditions are appropriately selected from a firing temperature of 80°C to 300°C and a firing time of 0.3 to 60 minutes.

[0123] The thickness of the coating for removing foreign matter in this invention is typically 1 μm to 5 nm, preferably 500 to 10 nm, and most preferably 300 to 15 nm.

[0124] The dissolution rate of the resulting foreign matter removal coating in the photoresist developer is 0.1 nm to 50 nm per second, preferably 0.2 nm to 40 nm per second, and more preferably 0.3 nm to 20 nm per second. When the dissolution rate is lower than this, the time required to remove the foreign matter removal coating increases, leading to a decrease in productivity.

[0125] The foreign matter removal coating formed by the foreign matter removal coating film forming composition of the present invention allows for control of the dissolution rate of the coating in the developing solution by changing the firing conditions during formation. Under a given firing time, a higher firing temperature results in a foreign matter removal coating with a lower dissolution rate in the developing solution.

[0126] The foreign matter removal coating of this application can be exposed after the coating is formed. Exposure can be performed on the entire wafer or through a mask with a specified pattern. Exposure can be performed using KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), and F2 excimer lasers (wavelength 157nm), etc. Post-exposure baking (PEB) can also be performed after exposure as needed.

[0127] Next, the coating for removing foreign matter is removed using a developing solution. Examples of developing solutions include 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 alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants may be added to these developing solutions. The conditions for removing the coating for removing foreign matter 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.

[0128] The foreign matter removal coating formed by the foreign matter removal coating film forming composition of the present invention can be easily peeled off at room temperature (e.g., 25°C) using a commonly used 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0129] <Methods for removing foreign objects>

[0130] The foreign matter removal method of this application is as follows, which includes the following steps: coating the above composition onto a substrate and firing it to form a coating film; forming foreign matter on the film; and removing the film by applying a developing solution to the film.

[0131] Following the above-described coating formation process, a further step may be included: forming an adhesive layer, followed by peeling off the adhesive layer. The foreign matter described above may be peeling residue from the adhesive layer formation process.

[0132] Furthermore, the foreign matter removal method of this application can be a method for removing foreign matter already present on a semiconductor manufacturing substrate. For example, as described in International Publication Nos. 2017 / 056746 and 2020 / 008965, a substrate processing film forming composition and substrate processing method are disclosed in which a substrate processing film forming composition and substrate processing method can be used to efficiently remove small particles from the substrate surface and easily remove the formed substrate processing film from the substrate surface in a process for removing foreign matter from the substrate surface. The coating film forming composition of this application can also be used in the same methods / uses as described above.

[0133] Regarding the above example, the following is a detailed explanation. In this application example, the above-mentioned foreign matter removal coating film forming composition is used as the composition for forming the above-mentioned coating film on a semiconductor manufacturing wafer. First, a coating film forming process is performed. That is, the foreign matter removal coating film forming composition is applied to the semiconductor manufacturing wafer to form a coating film. The semiconductor manufacturing wafer can be a so-called solid substrate (planar) in an unprocessed state with various films formed on it, or it can be processed into shapes such as wiring for manufacturing semiconductor devices. As coating methods, examples include spin coating, casting coating, roll coating, etc. Next, by heating (baking) and / or reducing pressure on the coating film, part or all of the solvent contained in the coating film is efficiently removed, thereby promoting the curing and / or hardening of the solid components contained in the coating film. Here, "curing" refers to solidification, and "hardening" refers to the molecular linkage and molecular weight increase (e.g., crosslinking, polymerization, etc.). The coating film is formed by this operation. At this time, particles attached to patterns, etc., are introduced into the coating film and are efficiently separated from the patterns, etc. Next, a coating removal process is performed. That is, by supplying a removal solution that dissolves the coating onto the coating, the coating is completely removed from the semiconductor manufacturing wafer. As a result, particles are removed from the semiconductor manufacturing wafer along with the coating. The removal solution can be water, organic solvents, alkaline aqueous solutions, etc., preferably water and alkaline aqueous solutions, and more preferably alkaline aqueous solutions.

[0134] Examples of substrates include glass, metal-containing compounds, and metalloid compounds. Examples of metal-containing compounds or metalloid compounds include, for example, ceramics that are sintered bodies whose basic component is a metal oxide and which are sintered by heat treatment at high temperature; semiconductors such as silicon; inorganic solid materials such as molded bodies of inorganic compounds such as metal oxides or metalloid oxides (silicon oxide, alumina, etc.), metal carbides or metalloid carbides, metal nitrides or metalloid nitrides (silicon nitrides, etc.), and metal borides or metalloid borides; aluminum; nickel-titanium; stainless steel (SUS304, SUS316, SUS316L, etc.); and preferably silicon substrates (e.g., semiconductor silicon wafers used in semiconductor device manufacturing).

[0135] <Substrate Processing Method>

[0136] A substrate processing method includes the following steps: coating the above composition onto a substrate and firing 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 developing solution.

[0137] The substrate processing method of this application is applied, for example, to a so-called temporary wafer bonding process.

[0138] <Adhesive layer>

[0139] The adhesive layer is formed using known adhesives and methods. As the adhesive, for example, coating-type temporary wafer adhesives as described in International Patent Publication No. 2015 / 190438, temporary bonding materials from ThinMaterials (Nissan Chemical Industries, Ltd.), temporary wafer bonding materials for semiconductors manufactured by Higashi Re Co., Ltd., WaferBOND (registered trademark) CR-200, HT-10.10 (Brewercy Industries Co., Ltd.), or strip adhesives (e.g., back-side polishing strips, e.g., 3M) can be used. TM Temporary fixing adhesive tape ATT-4025 (manufactured by Sleeem Japan Co., Ltd.), E series, P series, S series (manufactured by Lintec Co., Ltd., trade name), Icrost Tap (registered trademark) (manufactured by Mitsui Chemicals Azusero Co., Ltd.)), cutting tape (e.g., solvent-resistant cutting tape (manufactured by Nitto Denko Co., Ltd., trade name), temperature-sensitive adhesive tape Intelima (registered trademark) (manufactured by Nitta Co., Ltd.), Intelima (registered trademark) (manufactured by Ankertec Co., Ltd., etc.).

[0140] It can be an adhesive for chips that are applied in a specific chip operating system (e.g., Zero Newton (registered trademark) (Tokyo Ohka Kogyo Co., Ltd.)).

[0141] For example, the back-side grinding belt consists of a substrate film, an adhesive layer, and a release film. Previously, soft thermoplastic films such as ethylene-vinyl acetate copolymer (EVA) were used as the substrate film, but to improve wafer support, rigid stretch films such as polyethylene terephthalate (PET) were explored. Further improvements were then made, reporting laminated designs of two films with different elastic moduli, such as laminated designs of PET and ethylene-based copolymers, and laminated designs of polypropylene (PP) and ethylene-based copolymers.

[0142] Adhesives are generally acrylic-based. Acrylic adhesives are known to be cross-linked by reacting acrylic copolymers with monomers such as butyl acrylate, which have low glass transition temperatures, with a curing agent. Back-side polishing tapes are used to adhere to the circuit surface of a chip, so there is concern about contamination from the adhesive after tape peeling. Therefore, designs using emulsion-based adhesives have been reported, assuming that any adhesive residue can be removed by washing with water, but complete removal is difficult. Therefore, by forming a foreign matter removal coating on the circuit surface using the method described in this application, an adhesive layer is formed, thereby completely removing foreign matter (adhesive residue) during subsequent peeling processes by washing with a developing solution, without damaging the wiring areas such as circuits.

[0143] <Manufacturing Method of Multilayer Substrate>

[0144] A laminated substrate having a substrate-film-adhesive-substrate configuration can be manufactured by a process including a step of coating the above-described composition onto a substrate and firing it to form a coating film, a step of forming an adhesive layer on the film, and a step of attaching another substrate to the substrate. Preferably, one substrate is a semiconductor substrate, and the other is a support substrate for maintaining the shape of the semiconductor substrate. The adhesive layer is preferably a material, for example, that allows the semiconductor substrate and the support substrate to be peeled off again. The adhesive layer is as described above.

[0145] Example

[0146] The present invention will be further described in detail below through examples, but the present invention is not limited thereto.

[0147] (Example 1)

[0148] (Preparation of a composition for coating film formation to remove foreign matter)

[0149] A solution of a coating composition for removing foreign matter containing polymers as shown below was prepared by adding 0.27 g of 4,4'-methylenebis(diglycidylaniline) (manufactured by Nippon Iron Kemikal & Materiae Co., Ltd.), 43.5 g of propylene glycol monomethyl ether, and 13.1 g of propylene glycol monomethyl ether acetate to 8.1 g of naphthol cresol phenolic varnish (MN8280G, weight average molecular weight 5,000) (manufactured by Asahi Organics Co., Ltd.) and stirring at room temperature for 30 minutes [1].

[0150]

[0151] (Evaluation of the composition for film formation in the removal of foreign matter)

[0152] A solution of the foreign matter removal coating composition[1] was applied to a silicon wafer substrate using a spin coater and then fired at 200°C for 60 seconds on a hot plate to form a foreign matter removal coating with a thickness of 40 nm.

[0153] The dissolution rate of the foreign matter removal coating in the developer solution (Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) was determined using a resist developer analyzer (manufactured by Resist Japan Co., Ltd.). The temperature around the analyzer was 25°C. The dissolution rate of the foreign matter removal coating formed at a firing temperature of 150°C and a firing time of 60 seconds was 3.3 nm per second. Furthermore, the dissolution rate of the foreign matter removal coating formed at a firing temperature of 155°C and a firing time of 60 seconds was 2.8 nm per second, at a firing temperature of 160°C and a firing time of 60 seconds was 1.8 nm per second, and at a firing temperature of 165°C and a firing time of 60 seconds was 0.9 nm per second. That is, the foreign matter removal coating formed at a firing temperature of 150°C and a firing time of 60 seconds can completely remove foreign matter in 12 seconds, the foreign matter removal coating formed at a firing temperature of 155°C and a firing time of 60 seconds can completely remove foreign matter in 14 seconds, the foreign matter removal coating formed at a firing temperature of 160°C and a firing time of 60 seconds can completely remove foreign matter in about 22 seconds, and the foreign matter removal coating formed at a firing temperature of 165°C and a firing time of 60 seconds can completely remove foreign matter in about 44 seconds. Therefore, foreign matter present on this foreign matter removal coating can also be removed.

[0154] (Example 2)

[0155] (Synthesis of polyamic acid)

[0156] A solution containing polyamic acid was obtained by reacting 17.8 g of 4,4'-(hexafluoroisopropylidene)phthalic dianhydride, 3.12 g of 3,5-diaminobenzoic acid, and 4.92 g of bis(4-aminophenyl sulfone) in 145.6 g of propylene glycol monomethyl ether at 80 °C for 20 h [C]. GPC analysis of the obtained polyamic acid was performed, yielding a weight-average molecular weight Mw = 8,600 (converted from standard polystyrene) and a number-average molecular weight Mn = 5,200.

[0157] (Synthesis of light-absorbing compounds)

[0158] A solution containing a light-absorbing compound was obtained by reacting 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 in 118 g of cyclohexanone at 130 °C for 24 hours [a].

[0159] (Preparation of a composition for coating film formation to remove foreign matter)

[0160] A solution of a coating composition for removing foreign matter was prepared by adding 4.15 g of a 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 trifluoromethane sulfonate, 82.8 g of propylene glycol monomethyl ether, 127 g of propylene glycol monomethyl ether acetate, and 10.0 g of cyclohexanone to a solution containing polyamic acid [C] and stirring at room temperature for 30 minutes.[5]

[0161] (Evaluation of the composition for film formation in the removal of foreign matter)

[0162] The solution of the foreign matter removal coating composition[5] was applied to a silicon wafer substrate using a spin coater and then heated on a hot plate at 175°C for 60 seconds to form a foreign matter removal coating with a thickness of 40 nm.

[0163] The dissolution rate of the foreign matter removal coating in the developer solution (Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) was determined using a resist developer analyzer (manufactured by Resist Japan Co., Ltd.). The temperature around the analyzer was 25°C. The dissolution rate of the foreign matter removal coating formed at a firing temperature of 170°C and a firing time of 60 seconds was 2.35 nm / s; the dissolution rate of the foreign matter removal coating formed at a firing temperature of 175°C and a firing time of 60 seconds was 2.00 nm / s; and the dissolution rate of the foreign matter removal coating formed at a firing temperature of 180°C and a firing time of 60 seconds was 1.82 nm / s.

[0164] That is, the foreign matter removal coating formed at a firing temperature of 170°C and a firing time of 60 seconds can completely remove foreign matter in 17 seconds, the foreign matter removal coating formed at a firing temperature of 175°C and a firing time of 60 seconds can completely remove foreign matter in 20 seconds, and the foreign matter removal coating formed at a firing temperature of 180°C and a firing time of 60 seconds can completely remove foreign matter in 22 seconds. Therefore, foreign matter present on the foreign matter removal coating can also be removed.

[0165] (Evaluation of preservation stability)

[0166] The solutions of the foreign matter removal and coating formation compositions used in Examples 1 and 2 were stored at -20°C to +35°C for one month. After the solutions were brought back to room temperature, they were coated onto a silicon wafer substrate using a spin coater and fired at 120°C for 60 seconds on a hot plate to investigate whether there was any change in film thickness. The results showed that in Example 2, a reduction in film thickness was observed compared to the initial film thickness after storage at 35°C for one month, but no change in film thickness was observed in Example 1.

[0167] Furthermore, solutions of the foreign matter removal coating film forming compositions of Examples 1 and 2 were stored at -20°C to +35°C for one month. After the solutions were restored to room temperature, they were coated onto a silicon wafer substrate using a spin coater and fired on a hot plate at 120°C for 60 seconds. The development speed was investigated with a development time of 10 seconds. The results showed that both had sufficiently high development speeds, indicating sufficient foreign matter removal capabilities. Therefore, Example 1 demonstrated good storage stability in addition to its foreign matter removal capabilities.

[0168] Industry availability

[0169] This relates to a coating composition for removing foreign matter formed on a substrate using a simple method, a method for removing foreign matter from a substrate, a substrate processing method, and a method for manufacturing a multilayer substrate. A coating composition for removing foreign matter can be provided, preferably used in the temporary bonding process of semiconductor wafers in semiconductor device manufacturing.

Claims

1. A composition comprising a polymer and a solvent, and capable of forming a coating film soluble in a developer for removing foreign matter. The polymer is selected from polymers containing phenolic hydroxyl groups and polymers containing carboxyl groups, and the composition comprises more than 50% by mass of the polymer relative to the total solid content of the composition. The polymer containing phenolic hydroxyl groups is phenolic varnish or polyhydroxystyrene derivative. The carboxyl-containing polymer is selected from (meth)acrylic resins, polyvinylbenzoic acid, and carboxymethyl cellulose.

2. The composition according to claim 1, wherein the composition comprises a crosslinking agent and / or an additive.

3. The composition according to claim 2, wherein the crosslinking agent comprises an epoxy group.

4. A coating for removing foreign matter, characterized in that, It is a sintered product of a coated film formed from the composition of any one of claims 1 to 3.

5. A method for removing foreign matter, comprising the steps of: coating a substrate with the composition of any one of claims 1 to 3 and firing it to form a coating film; forming foreign matter on the coating film; and removing the coating film and foreign matter together with a developing solution.

6. The method according to claim 5, wherein the step of forming the foreign object comprises: The process of forming an adhesive layer on the coating film; and The next step is to peel off the adhesive layer.

7. The method according to claim 6, wherein the foreign matter is peeling residue of the adhesive layer.

8. A substrate processing method, comprising the following steps: The process of coating a first substrate with the composition of any one of claims 1 to 3 and firing it to form a coating film; The process of forming an adhesive layer on the coating film; The process of temporarily attaching the second substrate to the first substrate via the adhesive layer; The process of peeling the second substrate from the first substrate; as well as The process of removing the coating and adhesive layer remaining on the first substrate after the second substrate has been peeled off using a developing solution.

9. A method for manufacturing a multilayer substrate, comprising the following steps: The process of coating a first substrate with the composition of any one of claims 1 to 3 and firing it to form a coating film; The process of forming an adhesive layer on the coating film; and The process of attaching the second substrate to the first substrate.

10. A composition for removing foreign matter present on a semiconductor manufacturing substrate, the composition comprising a polymer and a solvent, said polymer being selected from polymers containing phenolic hydroxyl groups and polymers containing carboxyl groups, said composition comprising at least 50% by mass of said polymer relative to the total solid content of the composition. The polymer containing phenolic hydroxyl groups is phenolic varnish or polyhydroxystyrene derivative. The carboxyl-containing polymer is selected from (meth)acrylic resins, polyvinylbenzoic acid, and carboxymethyl cellulose.

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

12. A method for removing foreign matter, comprising the steps of: coating the composition of claim 10 or 11 onto a substrate in which the foreign matter is present and firing it to form a coating film incorporating the foreign matter; and removing the coating film together with the foreign matter using a developing solution.

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