Composition for forming coating film for removing foreign matter, and semiconductor substrate

Abstract

A composition for forming a coating film for removing foreign matters, which contains a solvent and a polymer that contains a structural unit represented by formula (1), and which is capable of forming a coating film that can be removed by a removal liquid. [In formula (1), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of an imide group deprotected by a base. ] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a composition for forming a foreign matter removing coating film, a foreign matter removing coating film, a semiconductor substrate, and a method for producing a processed semiconductor substrate, which can prevent foreign matter from remaining on a substrate by a simple method. Background Art

[0002] In the manufacture of semiconductor devices, particularly in the so-called post-process, a process is studied in which a semiconductor substrate (e.g., a wafer) is affixed to a supporting substrate, back grinding (grinding), wiring production steps, etc. are performed, and then the supporting substrate is peeled off to obtain the desired semiconductor substrate.

[0003] In such a process, foreign matter is sometimes generated and it is required to be removed. Therefore, for example, Patent Documents 1 and 2 disclose a composition for forming a substrate processing film on the surface of a semiconductor substrate, and a process for removing foreign matter from the substrate surface, wherein tiny particles on the substrate surface can be removed efficiently and the formed substrate processing film can be easily removed from the substrate surface.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2017 / 056746

[0007] Patent Document 2: International Publication No. 2020 / 008965 Summary of the invention

[0008] Problems to be solved by the invention

[0009] On the other hand, when the semiconductor substrate is pasted to the support substrate, the semiconductor substrate is pasted by a resistant adhesive layer (e.g., a liquid composition containing a polymer, a back grinding tape, a dicing tape, etc.) in a subsequent process (e.g., a heating process, a liquid treatment process, etc.). Then, a process of peeling off the semiconductor substrate is performed. At this time, the adhesive layer sometimes remains on the substrate as a foreign matter (residue). This occurs particularly significantly when an adhesive layer is directly formed on the surface of a semiconductor substrate on which wiring, etc., is pre-formed on the substrate. The foreign matter sometimes cannot be completely removed even by washing with a known organic solvent, a liquid chemical, etc.

[0010] Therefore, an object of the present invention is to provide a method for producing a processed semiconductor substrate which can prevent the peeling residue of the adhesive layer from remaining on the semiconductor substrate by a simple method.

[0011] In addition, in the process after the semiconductor substrate is attached to the support substrate, a high heating temperature (for example, 300° C.) is sometimes used. Even in the case of such a high-temperature treatment, a composition for forming a coating film for removing foreign matter is required that can prevent foreign matter from remaining on the substrate by a simple method. In other words, a composition for forming a coating film for removing foreign matter that can obtain a heat-resistant coating film for removing foreign matter is required.

[0012] Therefore, an object of the present invention is to provide a composition for forming a foreign matter removing coating film capable of obtaining a foreign matter removing coating film having heat resistance, and a method for producing a foreign matter removing coating film, a semiconductor substrate, and a processed semiconductor substrate using the composition.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, and have completed the present invention having the following gist.

[0015] That is, the present invention includes the following aspects.

[0016] [1] A composition for forming a coating film for removing foreign matter, comprising a polymer and a solvent and capable of forming a coating film that can be removed by a removing liquid;

[0017] The above-mentioned polymer is a polymer containing a structural unit represented by the following formula (1).

[0018]

[0019] [In formula (1), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of an imide group which is deprotected by a base.]

[0020] [2] The composition according to [1], wherein the removing liquid is an alkaline removing liquid.

[0021] [3] The composition according to [1] or [2], wherein the removing liquid contains 50% by mass or more of an organic solvent.

[0022] [4] The composition according to any one of [1] to [3], comprising at least one of a crosslinking agent and an additive.

[0023] [5] A coating film for removing foreign matter, the coating film being formed from the composition according to any one of [1] to [4].

[0024] [6] The foreign matter removing coating film according to [5], wherein the reduction in film thickness when heated at 250° C. for 10 minutes in a nitrogen atmosphere is 5% or less.

[0025] [7] A semiconductor substrate having the foreign matter removing coating film according to [5] or [6].

[0026] [8] A method for manufacturing a processed semiconductor substrate, comprising the following steps:

[0027] Step 1A of manufacturing a laminate by laminating the semiconductor substrate and the supporting substrate described in [7] via the foreign matter removing coating film;

[0028] Step 2A of processing the laminate;

[0029] Step 3A of peeling the supporting substrate from the laminate; and

[0030] The semiconductor substrate or the supporting substrate is cleaned with a removing liquid to remove the foreign matter removing coating film. 4A step.

[0031] [9] The method for manufacturing a processed semiconductor substrate according to [8], wherein in the step 4A, foreign matter is removed together with the foreign matter removing coating film.

[0032]

[10] According to the method for manufacturing a processed semiconductor substrate described in [8], the above-mentioned step 1A is a step of manufacturing a laminated body by bonding the above-mentioned semiconductor substrate and the above-mentioned supporting substrate via the above-mentioned foreign matter removal coating film and the adhesive layer.

[0033]

[11] The method for manufacturing a semiconductor substrate according to

[10] , wherein in the step 4A, foreign matter is removed together with the foreign matter removing coating film, and the foreign matter is a peeling residue of the adhesive layer.

[0034]

[12] The method for manufacturing a processed semiconductor substrate according to any one of [8] to

[11] , wherein the processing includes connecting the semiconductor substrate to a second semiconductor substrate.

[0035]

[13] A method for manufacturing a processed semiconductor substrate, comprising the following steps:

[0036] Step 1B of manufacturing a laminate by laminating a semiconductor substrate and a supporting substrate via a foreign matter removing coating film and an adhesive layer;

[0037] Step 2B of processing the laminate;

[0038] Step 3B of peeling the supporting substrate from the laminate; and

[0039] Step 4B of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the foreign matter removing coating film,

[0040] The processing includes connecting the semiconductor substrate to a second semiconductor substrate.

[0041] Effects of the Invention

[0042] According to one embodiment of the present invention, a method for manufacturing a processed semiconductor substrate can be provided, which can prevent the peeling residue of the adhesive layer from remaining on the semiconductor substrate by a simple method.

[0043] Furthermore, according to one embodiment of the present invention, a composition for forming a foreign matter removing coating film capable of obtaining a foreign matter removing coating film having heat resistance, a foreign matter removing coating film using the composition, a semiconductor substrate, and a method for producing a processed semiconductor substrate can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1A This is a schematic cross-sectional view (part 1) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0045] Figure 1B This is a schematic cross-sectional view (part 2) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0046] Figure 1C This is a schematic cross-sectional view (part 3) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0047] Figure 1D This is a schematic cross-sectional view (part 4) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0048] Figure 1E This is a schematic cross-sectional view (part 5) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0049] Figure 1F This is a schematic cross-sectional view (part 6) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0050] Figure 1G It is a schematic cross-sectional view (part 7) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0051] Figure 1H It is a schematic cross-sectional view (part 8) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0052] Fig. 1I It is a schematic cross-sectional view (part 9) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0053] Figure 1JIt is a schematic cross-sectional view (No. 10) for explaining an example of a method for manufacturing a processed semiconductor substrate.

[0054] Figure 1K It is a schematic cross-sectional view (No. 11) for explaining an example of a method for manufacturing a processed semiconductor substrate. DETAILED DESCRIPTION

[0055] (Coating film forming composition for removing foreign matter)

[0056] The foreign matter removing coating film-forming composition of the present invention contains a polymer and a solvent.

[0057] The foreign matter removing coating film-forming composition is preferably capable of forming a coating film that can be removed by a removing liquid.

[0058] <Polymer>

[0059] The polymer is a polymer containing a structural unit represented by the following formula (1).

[0060]

[0061] [In formula (1), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of an imide group which is deprotected by a base.]

[0062] Examples of the protecting group of the imide group in R that is deprotected by a base include a methyl group, a cyclohexyl group, a hydroxyethyl group, a benzyl group, and a phenyl group.

[0063] Examples of the base include bases contained in an alkaline removing solution.

[0064] The coating film obtained from the foreign matter removing coating film-forming composition exhibits good heat resistance due to the polymer containing the structural unit represented by formula (1).

[0065] Furthermore, the coating film obtained from the foreign matter removing coating film-forming composition is derived from the structural unit represented by formula (1) and can be removed by a removing liquid.

[0066] Therefore, the foreign matter removing coating film-forming composition of the present invention is a composition that can prevent foreign matter from remaining on a substrate by a simple method and is a composition that can obtain a coating film having heat resistance.

[0067] In addition, the coating film obtained by the foreign matter removal coating film forming composition of the present invention is also excellent in resistance to laser irradiation. Therefore, in the manufacturing method of the processed semiconductor substrate described later (first embodiment), in the 3A step of peeling the support substrate from the laminate, a laser can be used.

[0068] The polymer may have a structural unit other than the structural unit represented by formula (1). Such a structural unit is not particularly limited, and may be a structural unit derived from a compound having a polymerizable unsaturated bond.

[0069] The proportion of the structural unit represented by formula (1) in the polymer is not particularly limited, but is preferably 50 mol% or more of all structural units, more preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0070] The weight average molecular weight of the polymer is not particularly limited, but is preferably 1,000 to 50,000, and more preferably 1,500 to 30,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0071] The polymer is obtained, for example, by polymerizing monomers including a compound represented by the following formula (1A).

[0072]

[0073] [In formula (1A), X has the same meaning as X in formula (1).]

[0074] Examples of the compound represented by formula (1A) include maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-hydroxyethylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and maleic anhydride.

[0075] The polymerization method is not particularly limited, and examples thereof include radical polymerization.

[0076] For example, the polymer can be obtained by homopolymerization of the compound represented by the maleimide formula (1A) or copolymerization with other monomers.

[0077] The monomer used for polymerization may also include monomers other than the compound represented by formula (1A). As such monomers, for example, compounds having polymerizable unsaturated bonds may be cited. As specific examples, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, acrylonitrile, etc. may be cited, but are not limited to these.

[0078] Specific examples of the acrylate compound include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, and glycidyl acrylate, but are not limited to these.

[0079] Specific examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate, but are not limited to these.

[0080] Specific examples of the acrylamide compound include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide, but are not limited to these.

[0081] Specific examples of the methacrylamide compound include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-benzyl methacrylamide, N-phenyl methacrylamide, N,N-dimethyl methacrylamide, and N-anthryl methacrylamide, but are not limited thereto.

[0082] Specific examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited to these.

[0083] Specific examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene, but are not limited to these.

[0084] The content of the polymer in the foreign matter removing coating film-forming composition is not particularly limited, but is preferably 0.01 to 60% by mass, more preferably 0.1 to 40% by mass, and particularly preferably 0.5 to 30% by mass, based on the solid content.

[0085] <<Removal liquid>>

[0086] The removing liquid is not particularly limited as long as it can remove the coating film formed from the coating film-forming composition for removing foreign matter.

[0087] The coating film is formed on, for example, a semiconductor substrate. Removal in this case means removal from the semiconductor substrate.

[0088] Here, as a method of removal, there can be mentioned removal by dissolution, removal by peeling, etc. As removal by peeling, there can be mentioned, for example, peeling from an adherend by swelling.

[0089] The removing liquid may contain water or an organic solvent.

[0090] The removing liquid may contain 50% by mass or more of an organic solvent.

[0091] Examples of the organic solvent 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-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, and N-methylpyrrolidone.

[0092] As the removing liquid, for example, an alkaline removing liquid can be mentioned.

[0093] The alkaline removing liquid contains a base. Examples of the base include ammonia, inorganic alkaline compounds, quaternary ammonium hydroxide, amines, and hydrazine.

[0094] The alkaline removing liquid may be a developer or a cleaning liquid used in a semiconductor manufacturing process and exhibits alkalinity. For example, as a developer, NMD-3 (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tokyo Ohka Kogyo Co., Ltd.) may be cited.

[0095] Examples of the inorganic base compound include potassium hydroxide, sodium hydroxide, lithium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and the like.

[0096] Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and choline.

[0097] Examples of the amine include ethanolamine, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, and ethylenediamine.

[0098] Examples of hydrazine include hydrazine monohydrate and the like.

[0099] Alternatively, the alkaline removing solution may be SC-1 (ammonia-hydrogen peroxide solution).

[0100] <Solvent>

[0101] As the solvent contained in the composition for forming a coating film for removing foreign matter, for example, 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-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. can be used.

[0102] These solvents can be used alone or in combination of two or more.

[0103] Furthermore, a high boiling point solvent such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate may be mixed and used.

[0104] The foreign matter removing coating film-forming composition can be easily prepared by, for example, uniformly mixing the respective components, and can be used in a solution state by being dissolved in an appropriate solvent.

[0105] The thus prepared foreign matter removing coating film-forming composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm, etc. The thus prepared foreign matter removing coating film-forming composition also has excellent long-term storage stability at room temperature.

[0106] The solid content ratio in the foreign matter removing coating film forming composition is not particularly limited as long as each component is uniformly dissolved, and is, for example, 0.5 to 50% by mass, and, for example, 1 to 30% by mass. The solid content here refers to the components obtained by removing the solvent component from all the components of the foreign matter removing coating film forming composition.

[0107] In the present invention, foreign matter refers to substances other than the target substance attached to the substrate. In semiconductor device manufacturing, it refers to substances that are not required in semiconductor device manufacturing. For example, particles attached to the wafer, metal impurities, residues after etching, and residues from peeling off the adhesive layer can be cited.

[0108] The coating film for removing foreign matter is particularly preferably used in the process of bonding chips to each other with an adhesive and then peeling off the adhesive. The coating film of the present invention is formed in advance before applying the adhesive, and then foreign matter (residue of the adhesive layer) is peeled off after the chip bonding and peeling steps.

[0109] The foreign matter removing coating film can also be used to remove foreign matter already present on the semiconductor substrate.

[0110] The so-called foreign matter removal coating is dissolved in the removal liquid, which means that if the removal liquid is used for immersion, washing, etc., the coating is dissolved in the removal liquid and no longer exists on the adherend such as the substrate. The so-called dissolution in the present invention means that the film formed on the substrate is removed from the film thickness initially formed by, for example, at least 90% (i.e., the film thickness of the residual film is less than 10% of the initial film thickness), or at least 95% (i.e., the film thickness of the residual film is less than 5% of the initial film thickness), or at least 99% (i.e., the film thickness of the residual film is less than 1% of the initial film thickness), and most preferably, 100% is removed (i.e., the film thickness of the residual film is 0% of the initial film thickness (no residual film)).

[0111] It is preferred that the composition contains at least one of a cross-linking agent and an additive.

[0112] <Cross-linking agent>

[0113] It is preferred that the above cross-linking agent contains an epoxy group.

[0114] The crosslinking agent may also contain a compound having at least two epoxy groups. As such a compound, there is no particular limitation as long as it is a compound having an epoxy group. For example, 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-tri[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 and bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, etc. can be cited.

[0115] Examples of the compound having at least two epoxy groups include the following.

[0116] Examples of the epoxy resin having an amino group include YH-434 and YH434L (trade names of Nippon Steel Chemical & Material Co., Ltd.).

[0117] Examples of the epoxy resin having an oxidized cyclohexene structure include Erylin GT-401, Erylin GT-403, and Erylin GT- 301, Stereotype GT-302, Stereotype 2021, Stereotype 3000 (trade name, manufactured by Stereo Chemical Co., Ltd.), etc.

[0118] Examples of the bisphenol A type epoxy resin include Etotron 1001, Etotron 1002, Etotron 1003, Etotron 1004, and Etotron. Etotron 1007, Etotron 1009, Etotron 1010, Etotron 828 (above, trade name manufactured by Oil Chemicals Co., Ltd.), etc.

[0119] As a bisphenol F type epoxy resin, Epicoat 807 (made by Yuka Chemical Epix Corporation, trade name) etc. are mentioned, for example.

[0120] Examples of the phenol novolac type epoxy resin include EPICO 152 and EPICO 154 (both manufactured by Yuka Chemical Industry Co., Ltd., trade names), EPPN 201 and EPPN 202 (both manufactured by Nippon Kayaku Co., Ltd., trade names), and the like.

[0121] Examples of the cresol novolac type epoxy resin include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and Epicode 180S75 (trade name, manufactured by Yuka Chemical Epoxi Co., Ltd.).

[0122] Examples of alicyclic epoxy resins include Denil EX-252 (trade name, manufactured by Nortronics Co., Ltd.), CY175, CY177, CY179 (above, CIBA-GEIGY Made by AG, trade name), アラルダイトCY-182, アラルダイトCY-192, アラルダイトCY-184 (above, CIBA-GEIGY Made by AG, trade name), Etocon 200, Etocon 400 (above, made by Dainippon Industrial Co., Ltd., trade name), Etocon 871, Etocon 87 2 (above, product name manufactured by Oil Chemicals Co., Ltd., trade name), ED-5661, ED-5662 (above, product name manufactured by Semantec Co., Ltd., product name), etc.

[0123] Examples of aliphatic polyglycidyl ethers include Denac EX-611 and Denac EX-612. , デナコールEX-614, デナコールEX-622, デナコールEX-411, デナコールE X-512、デナコールEX-522、デナコールEX-421、デナコールEX-313、デNautilus EX-314, Nautilus EX-321 (trade name manufactured by Nautilus Co., Ltd.), etc.

[0124] 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, preferably 15 to 45 parts by mass, relative to 100 parts by mass of the polymer. The content of the compound having at least two epoxy groups is preferably 5 parts by mass or more relative to 100 parts by mass of the polymer from the viewpoint of the degree of hardening of the coating film and prevention of mixing with the adhesive layer, and is preferably 70 parts by mass or less relative to 100 parts by mass of the polymer from the viewpoint of solubility in the removing liquid.

[0125] <Additives>

[0126] The foreign matter removing coating film-forming composition may contain a light absorbing compound, a surfactant, an adhesion aid, a rheology modifier, and silica particles as additives.

[0127] The light-absorbing compound is not particularly limited as long as it is a compound that absorbs at the exposure wavelength used. It is preferable to use a compound having an aromatic ring structure such as an anthracene ring, a naphthalene ring, a benzene ring, a quinoline ring, a triazine ring, etc. In addition, from the viewpoint of not impairing the solubility of the coating film for removing foreign matter in the removing solution, it is preferable to use a compound having a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group.

[0128] Examples of the light-absorbing compound having a large absorption for light of a wavelength of 248 nm include 1-naphthoic acid, 2-naphthoic acid, 1-naphthol, 2-naphthol, 1-aminonaphthalene, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 6-bromo-2-hydroxynaphthalene, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid ... 8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic 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-naphthalene dicarboxylic acid, 1-hydroxy-2-naphthalene dicarboxylic acid, 3-hydroxy-2-naphthalene dicarboxylic acid, 6-hydroxy-2-naphthalene dicarboxylic acid, 1-bromo- 2-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-naphthalenetetracarboxylic acid, 3,5-dihydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2,6-dichloro-1-naphthol, 2-hydroxy-3-naphthoic acid methyl ester, 6-hydroxy- 2-naphthoic acid methyl ester, 3-hydroxy-7-methoxy-2-naphthoic acid methyl ester, 3,7-dihydroxy-2-naphthoic acid methyl ester, 2,4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-naphthalenethiol, 4-methoxy-1-naphthol, 6-acetoxy-2-naphthoic acid, 1,6-dibromo-1-naphthol, 2,6-dibromo-1,5-dihydroxynaphthalene, 1-acetyl-2-naphthol, 9-anthracenecarboxylic acid, 1,4,9,10-tetrahydroxyanthracene, 1,8,9-trihydroxyanthracene, etc.

[0129] In addition, examples of light-absorbing compounds having a large absorption for light of a wavelength of 193 nm include benzoic acid, 4-methylbenzoic acid, phthalic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), 2-methoxybenzoic acid, isophthalic acid (isophthalic acid), terephthalic 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-phthalic 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, pyromellitic acid, trimesic anhydride, 2-s[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, etc.

[0130] Furthermore, in order to suppress sublimation during firing for forming a foreign matter removing coating film, these light absorbing compounds may be reacted with a polymer or a compound having one or more reactive groups.

[0131] For example, in the case of a light-absorbing compound having a carboxyl group or a phenolic hydroxyl group, tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(oxiranyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris(p-(2,3-epoxypropyloxy)phenyl)propane, 1,2-epoxy-4-(oxiranyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris(p-(2,3-epoxypropyloxy)phenyl)propane, 1, Compounds obtained by reacting a polymer containing a structure having an epoxy group 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 the like; and glycidyl methacrylate.

[0132] The above-mentioned light-absorbing compound can be used alone or in combination of two or more. When a light-absorbing compound is used, its content is, for example, 1 to 300 parts by mass, or 1 to 200 parts by mass, and further, 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 content of the light-absorbing compound is 300 parts by mass or less relative to 100 parts by mass of the polymer, the solubility of the coating film for removing foreign matter in the removing liquid is excellent, or the coating film for removing foreign matter is not easily mixed with the adhesive layer.

[0133] The composition for forming a coating film for removing foreign matter may contain an acid generator. Examples of the acid generator include thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, other organic sulfonic acid alkyl esters, bis(4-tert-butylphenyl)iodide, Photoacid generators such as trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, phenyl-bis(trichloromethyl)-s-triazine, benzoin toluenesulfonate, and N-hydroxysuccinimide trifluoromethanesulfonate are used as needed in an amount of, for example, 10% by mass or less, preferably 3% by mass or less, based on the solid content of the foreign matter removing coating film forming composition.

[0134] In the composition for forming a coating film for removing foreign matter, a polyphenol compound or a compound containing a carboxyl group may be added for the purpose of accelerating the dissolution rate in the removal solution. Such compounds are not particularly limited, and 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'-spirobiindane-5,5',6,6'-tetrol, 4,4'-(9-fluorenyl)biphenol, bisphenol-AP, bisphenol- P, 5-α,α-dimethyl-4-hydroxybenzyl salicylic acid, α,α,α'-tri(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, mellitic acid, 2,3-naphthalene dicarboxylic acid, 4-hydroxyphthalic acid dicarboxylic 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, 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, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, and polymers containing carboxylic acids or carboxylic anhydrides such as polyacrylic acid, polymethacrylic acid, polyamic acid, and polymaleic anhydride. The addition amount of the above-mentioned compound is, for example, 20% by mass or less, preferably 10% by mass or less, in the solid content of the foreign matter removing coating film forming composition, and is used as needed.

[0135] In the composition for forming a coating film for removing foreign matter, 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, and a trimethylsilyl group, may be added for the purpose of adjusting the dissolution rate in the removing solution.

[0136] 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 pivalate.

[0137] These compounds can easily generate carboxyl groups or phenolic hydroxyl groups in the presence of an acid, thereby obtaining compounds having improved solubility in an alkaline removing solution.

[0138] Therefore, these compounds are preferably added to the composition for forming a coating film for removing foreign matter together with a photoacid generator. That is, in the foreign matter removing coating film formed by the composition for forming a coating film for removing foreign matter comprising the above-mentioned compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid and a photoacid generator, for the exposed portion thereof, 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 an acid is regenerated by the acid generated by exposure from the photoacid generator, and as a result, the solubility of the foreign matter removing coating film in the exposed portion in the alkaline removing solution is improved. In contrast, for the unexposed portion, the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of an acid does not change, and the solubility of the foreign matter removing coating film in the alkaline removing solution of the portion is not improved. 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, a difference in solubility in an alkaline removing solution can be created between the exposed portion and the non-exposed portion of the foreign matter removing coating film after exposure, thereby facilitating pattern formation by development.

[0139] When 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 an acid is used, the content thereof is, for example, 50 to 1 part by mass, or 30 to 5 parts by mass, or 20 to 10 parts by mass, relative to 100 parts by mass of the polymer. When a photoacid generator is used together with 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, the content thereof is, for example, 0.1 to 30 parts by mass, or 0.5 to 20 parts by mass, or 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.

[0140] The composition for forming a coating film for removing foreign matter may 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 allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan tristearate, Eftopt EF301, EF303, EF352 (trade names of Tokem Projects), Megafac F171, F173 (trade names of DIC Corporation), Fluorade FC430, FC431 (trade names of Sumitomo SULI-EM (trade name), ASHIGADO AG710, S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC (trade name)), etc. fluorine-based surfactants, organosiloxane polymer KP341 (Shin-Etsu Chemical (trade name)), etc. The blending amount of these surfactants is usually 0.2% by mass or less, preferably 0.1% by mass or less in all the components of the composition for forming a coating film for removing foreign matter. These surfactants can be added alone or in combination of two or more.

[0141] The foreign matter removing coating film-forming composition may contain silica particles. Examples of the silica particles include silicone powder having a predetermined average particle size, and silica sol containing silica having a predetermined average particle size.

[0142] Specific examples of the silicone powder include silicone powder KMP series manufactured by Shin-Etsu Chemical Co., Ltd., such as KMP-600, KMP-601, KMP-602, KMP-605, and X-52-7030, but are not limited to these.

[0143] Specific examples of colloidal silica (silica sol) include MA-ST-S (methanol-dispersed silica sol), MT-ST (methanol-dispersed silica sol), MA-ST-UP (methanol-dispersed silica sol), trade names MA-ST-M (methanol-dispersed silica sol), MA-ST-L (methanol-dispersed silica sol), IPA-ST-S (isopropyl alcohol-dispersed silica sol), IPA-ST (isopropyl alcohol-dispersed silica sol), IPA-ST-UP (isopropyl alcohol-dispersed silica sol), IPA-ST-L (isopropyl alcohol-dispersed silica sol), IPA-ST-ZL (isopropyl alcohol-dispersed silica sol), and NPC-ST- 30 (silica sol dispersed in n-propyl cellosolve), PGM-ST (silica sol dispersed in 1-methoxy-2-propanol), DMAC-ST (silica sol dispersed in dimethylacetamide), XBA-ST (silica sol dispersed in a xylene / n-butanol mixed solvent), trade names EAC-ST (silica sol dispersed in ethyl acetate), PMA-ST (silica sol dispersed in propylene glycol monomethyl ether acetate), MEK-ST (silica sol dispersed in methyl ethyl ketone), MEK-ST-UP (silica sol dispersed in methyl ethyl ketone), MEK-ST-L (silica sol dispersed in methyl ethyl ketone), MIBK-ST (silica sol dispersed in methyl isobutyl ketone), etc., but are not limited to these.

[0144] (Coating for removing foreign matter)

[0145] The foreign matter removing coating film of the present invention is formed from the foreign matter removing coating film-forming composition of the present invention.

[0146] The foreign matter removing coating film of the present invention preferably has a film thickness reduction of 5% or less when heated at 250° C. for 10 minutes in a nitrogen atmosphere.

[0147] The foreign matter removing coating film of the present invention can be formed, for example, as follows.

[0148] The foreign matter removing coating film forming composition of the present invention is applied to a semiconductor substrate by a suitable coating method such as a spin coater, a coater, or dipping, and then fired to form a foreign matter removing 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.

[0149] The thickness of the foreign matter removing coating film is usually 5 nm to 1 μm, preferably 10 nm to 500 nm, and most preferably 15 nm to 300 nm.

[0150] The dissolution rate of the formed foreign matter removing coating in the removing solution, as the rate of reduction of the film thickness, is, for example, 0.1 nm to 50 nm per second, preferably 0.2 nm to 40 nm per second, and more preferably 0.3 to 20 nm per second. If the dissolution rate is lower than this, the time required to remove the foreign matter removing coating becomes longer, resulting in a decrease in productivity.

[0151] The foreign matter removing coating film formed by the foreign matter removing coating film forming composition of the present invention can control the dissolution rate of the foreign matter removing coating film in the removing solution by changing the firing conditions during formation. Under the condition of a certain firing time, the higher the firing temperature, the slower the dissolution rate of the foreign matter removing coating film in the removing solution can be formed.

[0152] The coating film for removing foreign matter can be exposed after the film is formed. Exposure can be performed on the entire surface of the wafer or through a mask with a specified pattern. For exposure, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) and F2 excimer laser (wavelength 157nm) can be used. After exposure, post-exposure heating (PEB: Post Exposure Bake) can also be performed as needed.

[0153] (Semiconductor substrate)

[0154] The semiconductor substrate of the present invention has the foreign matter removing coating film of the present invention thereon.

[0155] The main material constituting the entire semiconductor substrate is not particularly limited as long as it can be used for such an application, and examples thereof include silicon, silicon carbide, and compound semiconductors.

[0156] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc-shaped semiconductor substrate. It should be noted that the disc-shaped semiconductor substrate does not need to have a completely circular surface, and for example, the periphery of the semiconductor substrate may have a straight portion called an orientation flat, or may have a cutout called a notch.

[0157] The thickness of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1,000 μm.

[0158] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 100 to 1,000 mm.

[0159] The semiconductor substrate may have a bump. A bump is a protruding terminal.

[0160] When the semiconductor substrate has the bump, the semiconductor substrate has the bump on the support substrate side.

[0161] In a semiconductor substrate, bumps are usually formed on the surface where a circuit is formed. The circuit may be a single layer or a multilayer. There is no particular limitation on the shape of the circuit.

[0162] In the semiconductor substrate, the surface (back surface) opposite to the surface having the bumps is a surface to be processed.

[0163] The material, size, shape, structure, and density of the bumps included in the semiconductor substrate are not particularly limited.

[0164] Examples of the bump include a ball bump, a printed bump, a stud bump, and a plated bump.

[0165] Generally, the height, radius, and pitch of the bumps are appropriately determined based on the following conditions: the bump height is about 1 to 200 μm, the bump radius is 1 to 200 μm, and the bump pitch is 1 to 500 μm.

[0166] As the material of the bump, for example, low melting point solder, high melting point solder, tin, indium, gold, silver, copper, etc. can be cited. The bump can be composed of only a single component or a plurality of components. More specifically, SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, etc. can be cited as alloy platings with Sn as the main component.

[0167] Furthermore, the bump may have a stacked-layer structure including a metal layer formed of at least any one of these components.

[0168] An example of the semiconductor substrate is a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm.

[0169] (Method for manufacturing processed semiconductor substrate)

[0170] <First embodiment>

[0171] A first embodiment of a method for manufacturing a processed semiconductor substrate of the present invention includes a 1A step, a 2A step, a 3A step, and a 4A step.

[0172] The step 1A is a step of manufacturing a laminate by bonding the semiconductor substrate of the present invention (the semiconductor substrate having the foreign matter removing coating film of the present invention) and a supporting substrate via the foreign matter removing coating film.

[0173] The step 2A is a step of processing the laminate.

[0174] Step 3A is a step of peeling the supporting substrate from the laminate.

[0175] The step 4A is a step of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the coating film for removing foreign matter.

[0176] In the first embodiment, the foreign matter removal coating of the present invention having heat resistance is used as the foreign matter removal coating. Therefore, even when a high temperature treatment is performed in the 2A step, the foreign matter removal coating is not prone to abnormality, and foreign matter can be prevented from remaining on the substrate by a simple method.

[0177] <<Step 1A>>

[0178] The step 1A is a step of manufacturing a laminate by bonding the semiconductor substrate of the present invention (the semiconductor substrate having the foreign matter removing coating film of the present invention) and a supporting substrate via the foreign matter removing coating film.

[0179] The support substrate is not particularly limited as long as it can support the semiconductor substrate when the laminate (for example, semiconductor substrate) is processed, and examples thereof include a glass support substrate.

[0180] The shape of the support substrate is not particularly limited, and an example thereof may be a disk shape.

[0181] The thickness of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 500 to 1,000 μm.

[0182] The diameter of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 100 to 1,000 mm.

[0183] An example of the support substrate is a glass wafer having a diameter of 300 mm and a thickness of about 700 μm.

[0184] The step 1A is preferably a step of manufacturing a laminate by bonding a semiconductor substrate and a supporting substrate together via a foreign matter removing coating film and an adhesive layer.

[0185] The adhesive layer is not particularly limited as long as the supporting substrate can be peeled from the laminate in step 3A.

[0186] The adhesive layer can be formed by a known adhesive and method. As an adhesive, for example, a coating type wafer temporary adhesive described in International Publication No. 2015 / 190438, a temporary bonding material of Thin Materials (Nissan Chemical Co., Ltd.), a temporary bonding material for semiconductor wafers made by Toray Co., Ltd., WaferBOND (registered trademark) CR-200, HT-10.10 (made by Brywell Science Co., Ltd.), a tape adhesive (for example, a back grinding tape (for example, 3MTM temporary fixing adhesive tape ATT-4025 (made by Slim Equipment Co., Ltd.)) can be used. Co., Ltd.), E series, P series, S series (trade names made by Lintech Co., Ltd.), ICLOSTEP (registered trademark) (made by Mitsui Chemicals Toselo, Ltd.)), dicing tape (for example, solvent-resistant dicing tape (trade name made by Nitto Denko Corporation), temperature-sensitive adhesive sheet Intermolecular (registered trademark) tape (made by NITTA Co., Ltd.), Intermolecular (registered trademark) tape (made by Anka Techno Co., Ltd.) etc.).

[0187] The adhesive may be a wafer adhesive used in a specific wafer processing system (for example, Zero Newton (registered trademark) (manufactured by Tokyo Ohka Kogyo Co., Ltd.)).

[0188] In addition, as the adhesive layer, an adhesive layer, an adhesive tape, or a substance called a temporary fixing material can be used. As such a substance, for example, an adhesive layer described in International Publication No. 2021 / 225163, an adhesive layer described in International Publication No. 2022 / 065376, and a light-curing adhesive layer described in International Publication No. 2022 / 065388 can be cited.

[0189] For example, the back grinding tape is composed of a base film, an adhesive layer, and a release film. The base film has been a soft thermoplastic film such as ethylene-vinyl acetate copolymer (EVA) in the past, but the use of a rigid stretch film such as polyethylene terephthalate (PET) has also been tried for the purpose of improving the support of the wafer. Then, the improvement has been further developed, and a laminated design of two films with different elastic moduli, such as a laminated design of PET and an ethylene copolymer, and a laminated design of polypropylene (PP) and an ethylene copolymer, has been reported.

[0190] Adhesives are generally acrylic acid-based. Acrylic acid-based adhesives are known to be designed by reacting an acrylic acid-based copolymer with a monomer having a low glass transition temperature such as butyl acrylate as the main raw material with a hardener to make it cross-linked. The back grinding tape is used because it is attached to the circuit surface of the chip, so there is concern about contamination from the adhesive after the tape is peeled off. Therefore, it is assumed that even if the adhesive remains, it can be removed by washing with water, and designs using emulsion-based adhesives have also been reported, but it is difficult to completely remove. Therefore, by forming the coating film for removing foreign matter of the present invention on the circuit surface, an adhesive layer is formed, so that foreign matter (residues of the adhesive layer) during the subsequent peeling process can be completely removed by washing with a removing liquid, and no damage will occur to the wiring parts such as the circuit.

[0191] The thickness of the adhesive layer is not particularly limited, and is, for example, 5 μm to 500 μm, preferably 10 μm to 300 μm, more preferably 20 μm to 200 μm, and particularly preferably 30 μm to 150 μm.

[0192] Before performing the step 1A, the adhesive layer may be formed on the foreign matter removing coating film, on the supporting substrate, or on the semiconductor substrate.

[0193] The bonding is performed, for example, under heating and pressure.

[0194] The heating temperature is not particularly limited as long as it is room temperature (25° C.) or higher, but is usually 50° C. or higher. From the viewpoint of avoiding excessive heating, it is usually 220° C. or lower, and in one embodiment, 170° C. or lower.

[0195] The load is not particularly limited as long as the substrates and layers can be bonded together without damaging the substrates and layers, and is, for example, 0.5 to 50 kN.

[0196] In addition, as the pressure during lamination, for example, 0.1 to 20 N / mm 2 It should be noted that the pressure refers to the pressure per unit area (mm) of the substrate in contact with the jig to which the load is applied. 2 ) force (load).

[0197] The degree of reduced pressure is not particularly limited as long as the substrate and the layer can be bonded together without damaging the substrate or the layer, and is, for example, 10 to 10,000 Pa.

[0198] When an adhesive layer is used, the purpose is to remove foreign matter as peeling residue of the adhesive layer together with the coating for removing foreign matter in step 4A so that there is no foreign matter on the semiconductor substrate. The layer structure of the laminate manufactured in step 1A can be semiconductor substrate / coating for removing foreign matter / adhesive layer / support substrate.

[0199] Furthermore, when an adhesive layer is used, the purpose is to remove foreign matter as peeling residue of the adhesive layer together with the foreign matter removing coating film in the 4A step so that no foreign matter exists on the supporting substrate, and the layer structure of the laminate produced in the 1A step may be semiconductor substrate / adhesive layer / foreign matter removing coating film / supporting substrate. In this case, the supporting substrate can be easily reused.

[0200] In order to prevent foreign matter from being present on the semiconductor substrate and the supporting substrate, the layer structure of the laminate produced in step 1A may be semiconductor substrate / foreign matter removing coating film / adhesive layer / foreign matter removing coating film / supporting substrate.

[0201] The laminated body manufactured in step 1A may have a laser lift-off layer between the semiconductor substrate and the support substrate. When the laminated body has the laser lift-off layer, in step 3A, for example, the support substrate can be peeled off from the laminated body by irradiating the laser lift-off layer with laser light. The laser light is irradiated to the laser lift-off layer from the support substrate side having laser light transmittance, for example.

[0202] In the case where the laminate has a laser stripping layer, the purpose is to remove foreign matter that is the stripping residue of the laser stripping layer and the adhesive layer together with the foreign matter removing coating in the 4A step so that there is no foreign matter on the semiconductor substrate. The layer structure of the laminate manufactured in the 1A step can be, for example, semiconductor substrate / foreign matter removing coating / laser stripping layer / adhesive layer / support substrate.

[0203] In the case where the laminate has a laser lift-off layer, the laminate produced in the 1A step may have a layer structure of, for example, semiconductor substrate / adhesive layer / laser lift-off layer / foreign matter removal coating film / support substrate, with the purpose of removing foreign matter as the peeling residue of the laser lift-off layer and the adhesive layer together with the foreign matter removal coating film in the 4A step so that no foreign matter exists on the support substrate. In this case, the support substrate can be easily reused.

[0204] Furthermore, if the laser lift-off layer residues remain on the adhesive layer after the support substrate is peeled off from the laminate by irradiating the laser lift-off layer with laser, foreign matter from the laser lift-off layer may be reattached to the semiconductor substrate or the support substrate, or the adhesive layer cleaning time may be prolonged. In order to prevent these situations, the laminate manufactured in step 1A may have a layer structure of semiconductor substrate / adhesive layer / foreign matter removal coating film / laser lift-off layer / support substrate, or semiconductor substrate / laser lift-off layer / foreign matter removal coating film / adhesive layer / support substrate for the purpose of removing the laser lift-off layer residues on the adhesive layer.

[0205] <<Step 2A>>

[0206] The step 2A is a step of processing the laminate.

[0207] The processing in step 2A is not particularly limited, and examples thereof include polishing of a semiconductor substrate, forming a through electrode of a semiconductor substrate, connecting a semiconductor substrate to a second semiconductor substrate, etc. The processing in step 2A may include one of these processings, or may include two or more.

[0208] <<Grinding Process>>

[0209] The grinding process of the semiconductor substrate is not particularly limited as long as the surface of the semiconductor substrate opposite to the surface of the coating film for removing foreign matter is ground to make the semiconductor substrate thinner, and examples thereof include physical grinding using abrasives and grindstones.

[0210] The polishing process can be performed using a general polishing device used for polishing a semiconductor substrate (for example, a silicon wafer).

[0211] The thickness of the semiconductor substrate is reduced by the polishing process, and a semiconductor substrate thinned to a desired thickness is obtained. The thickness of the thinned semiconductor substrate is not particularly limited, and may be, for example, 30 to 300 μm, or 30 to 100 μm.

[0212] <<Through-electrode formation process>>

[0213] For example, a through electrode for achieving electrical connection between thinned semiconductor substrates when a plurality of thinned semiconductor substrates are stacked may be formed on a polished semiconductor substrate.

[0214] Therefore, after the grinding process and before the lift-off step, a through-electrode forming process of forming a through-electrode in the ground semiconductor substrate may be included.

[0215] The method of forming the through-electrode on the semiconductor substrate is not particularly limited, and examples thereof include forming a through-hole and filling the formed through-hole with a conductive material.

[0216] The through-holes are formed by, for example, photolithography.

[0217] The through-holes are filled with the conductive material by, for example, a plating technique.

[0218] It should be noted that, in the step 2A, the through-electrode forming process may be performed without performing the polishing process.

[0219] <<Connection Process>>

[0220] The connection process is, for example, a process of connecting the semiconductor substrate and the second semiconductor substrate.

[0221] The second semiconductor substrate is not particularly limited, and examples thereof include those mentioned in the description of the semiconductor substrate.

[0222] The connection process is performed, for example, under heating. In addition, the connection process is performed, for example, under pressure.

[0223] The heating temperature is not particularly limited, and examples thereof include 100°C to 350°C.

[0224] In the connection process, for example, the wiring of the semiconductor substrate and the wiring of the second semiconductor substrate are electrically connected. Such connection is performed by connecting the ends of the wirings to each other, for example.

[0225] There are no particular restrictions on the material, shape, and structure of the wiring in the semiconductor substrate.

[0226] There are no particular restrictions on the material, shape, and structure of the wiring in the second semiconductor substrate.

[0227] <Step 3A>

[0228] The step 3A is a step of peeling the support substrate from the laminate. The step 3A can be said to be a step of separating the semiconductor substrate and the support substrate.

[0229] Examples of the stripping method include, but are not limited to, solvent stripping, stripping using light irradiation (laser, non-laser), mechanical stripping using a mechanical material with a sharp portion (so-called a die bonder), and manual stripping between a semiconductor substrate and a supporting substrate.

[0230] In particular, when the laminate includes an adhesive layer formed using an organic resin that absorbs light and undergoes the necessary modification required to improve the peeling ability, the adhesive layer can be peeled off by irradiating laser light from the supporting substrate side, for example.

[0231] The laser irradiation is performed using ultraviolet light having a wavelength of 190 nm to 400 nm or 190 nm to 600 nm (eg, 308 nm, 355 nm, 532 nm), for example.

[0232] The peeling can be done by making the processing energy density of the pulsed laser 50 to 500 mJ / cm 2 So proceed left and right.

[0233] When the laminate includes an adhesive layer, peeling usually occurs inside the adhesive layer or at the interface between the adhesive layer and an adjacent substrate or layer (eg, a foreign matter removing coating film). Peeling inside the adhesive layer means that the adhesive layer is cracked.

[0234] <Step 4A>

[0235] The step 4A is a step of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the coating film for removing foreign matter.

[0236] On the semiconductor substrate peeled from the supporting substrate, for example, a foreign matter removing coating film remains, and therefore, the foreign matter removing coating film is removed with a removing liquid.

[0237] In the step 4A, for example, foreign matter is removed together with the foreign matter removing coating film.

[0238] In the step 4A, for example, foreign matter which is a peeling residue of the adhesive layer is removed together with the foreign matter removing coating film.

[0239] Examples of the removing liquid include the removing liquids mentioned in the description of the foreign matter removing coating film-forming composition of the present invention.

[0240] The cleaning method is not particularly limited, and examples thereof include a method of immersing the semiconductor substrate on which the foreign matter removing coating film remains in a removing liquid, and a method of spraying the removing liquid onto the semiconductor substrate on which the foreign matter removing coating film remains.

[0241] The washing conditions are not particularly limited, and for example, the temperature of the washing liquid is 5° C. to 50° C. The washing time is appropriately selected from 2 to 500 seconds or 3 to 400 seconds.

[0242] For example, the foreign matter removing coating film can be easily peeled off at room temperature (eg, 25° C.) preferably using a commonly used 2.38 mass % tetramethylammonium hydroxide aqueous solution.

[0243] <Second embodiment>

[0244] The second embodiment of the method for manufacturing a processed semiconductor substrate of the present invention includes step 1B, step 2B, step 3B, and step 4B.

[0245] The step 1B is a step of manufacturing a laminate by bonding a semiconductor substrate and a supporting substrate together via a foreign matter removing coating film and an adhesive layer.

[0246] The step 2B is a step of processing the laminate.

[0247] Step 3B is a step of peeling the supporting substrate from the laminate.

[0248] The step 4B is a step of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the coating film for foreign matter removal.

[0249] The processing includes connecting the semiconductor substrate to a second semiconductor substrate.

[0250] In the second embodiment, by using the foreign matter removing coating film, even when the semiconductor substrate is supported by the supporting substrate and the semiconductor substrate is connected to the second semiconductor substrate, it is possible to prevent the peeling residue of the adhesive layer from remaining on the semiconductor substrate.

[0251] <<Step 1B>>

[0252] The step 1B is a step of manufacturing a laminate by bonding a semiconductor substrate and a supporting substrate together via a foreign matter removing coating film and an adhesive layer.

[0253] Examples of the semiconductor substrate include those exemplified in the description of the semiconductor substrate of the present invention.

[0254] As the supporting substrate, for example, the supporting substrate exemplified in the description of step 1A can be mentioned.

[0255] The foreign matter removing coating film used in the second embodiment is not limited to the foreign matter removing coating film of the present invention, and various coating films can be used as long as it is a film that can remove the peeling residue of the adhesive layer.

[0256] Examples of such coating films include coating films described in International Publication No. 2018-159665 and coating films described in International Publication No. 2022-019287.

[0257] The thickness of the foreign matter removing coating film is usually 5 nm to 1 μm, preferably 10 nm to 500 nm, and most preferably 15 nm to 300 nm.

[0258] The foreign matter removing coating film is preferably formed on a semiconductor substrate.

[0259] The method for forming a foreign matter removing coating film on a semiconductor substrate is not particularly limited, and examples thereof include a method in which a composition for forming a foreign matter removing coating film is applied to the semiconductor substrate by an appropriate coating method such as a spin coater, a coater, or dipping, and then the composition is fired.

[0260] The adhesive layer is not particularly limited as long as the supporting substrate can be peeled from the laminate in step 3B.

[0261] As an adhesive layer, the adhesive layer illustrated in the 1A step is mentioned, for example.

[0262] Before performing step 1B, the adhesive layer may be formed on the foreign matter removing coating film, on the supporting substrate, or on the semiconductor substrate.

[0263] When an adhesive layer is used, the purpose is to remove foreign matter as peeling residue of the adhesive layer together with the coating for removing foreign matter in step 4B so that there is no foreign matter on the semiconductor substrate. The layer structure of the laminate manufactured in step 1B can be semiconductor substrate / coating for removing foreign matter / adhesive layer / support substrate.

[0264] Furthermore, when an adhesive layer is used, the purpose is to remove foreign matter as peeling residue of the adhesive layer together with the foreign matter removing coating film in the 4B step so that no foreign matter exists on the supporting substrate, and the layer structure of the laminate produced in the 1B step may be semiconductor substrate / adhesive layer / foreign matter removing coating film / supporting substrate. In this case, the supporting substrate can be easily reused.

[0265] In order to prevent foreign matter from being present on the semiconductor substrate and the supporting substrate, the layer structure of the laminate produced in step 1B may be semiconductor substrate / foreign matter removing coating film / adhesive layer / foreign matter removing coating film / supporting substrate.

[0266] The laminated body manufactured in step 1B may have a laser lift-off layer between the semiconductor substrate and the support substrate. When the laminated body has the laser lift-off layer, in step 3B, for example, the support substrate can be peeled off from the laminated body by irradiating the laser lift-off layer with laser light. The laser light is irradiated to the laser lift-off layer from the support substrate side having laser light transmittance, for example.

[0267] In the case where the laminate has a laser stripping layer, the purpose is to remove foreign matter that is the stripping residue of the laser stripping layer and the adhesive layer together with the foreign matter removing coating in the 4B step so that there is no foreign matter on the semiconductor substrate. The layer structure of the laminate manufactured in the 1B step can be, for example, semiconductor substrate / foreign matter removing coating / laser stripping layer / adhesive layer / support substrate.

[0268] In the case where the laminate has a laser lift-off layer, the laminate produced in step 1B may have a layer structure of, for example, semiconductor substrate / adhesive layer / laser lift-off layer / foreign matter removal coating film / support substrate, with the purpose of removing foreign matter as the peeling residue of the laser lift-off layer and the adhesive layer together with the foreign matter removal coating film in step 4B so that no foreign matter exists on the support substrate. In this case, the support substrate can be easily reused.

[0269] Furthermore, if the laser lift-off layer residues remain on the adhesive layer after the support substrate is peeled off from the laminate by irradiating the laser lift-off layer with laser, foreign matter from the laser lift-off layer may be reattached to the semiconductor substrate or the support substrate, or the adhesive layer cleaning time may be prolonged. In order to prevent these situations, the laminate manufactured in step 1B may have a layer structure of semiconductor substrate / adhesive layer / foreign matter removal coating film / laser lift-off layer / support substrate, or semiconductor substrate / laser lift-off layer / foreign matter removal coating film / adhesive layer / support substrate for the purpose of removing the laser lift-off layer residues on the adhesive layer.

[0270] <<Step 2B>>

[0271] The step 2B is a step of processing the laminate.

[0272] In the step 2B, the processing of the laminate includes a connection process between the semiconductor substrate and the second semiconductor substrate. That is, the processing includes connecting the semiconductor substrate and the second semiconductor substrate.

[0273] The second semiconductor substrate is not particularly limited, and examples thereof include those mentioned in the description of the semiconductor substrate.

[0274] The 2B step may include a polishing process, a through-electrode forming process, and the like as other processes.

[0275] As the connection process, for example, the connection process described in the step 2A can be cited.

[0276] As the polishing treatment, for example, the polishing treatment described in step 2A can be cited.

[0277] As the through-electrode forming process, for example, the through-electrode forming process described in the 2A step can be cited.

[0278] In the connection process, for example, the wiring of the semiconductor substrate and the wiring of the second semiconductor substrate are electrically connected. Such connection is performed by, for example, connecting the ends of the wirings to each other.

[0279] There are no particular restrictions on the material, shape, and structure of the wiring in the semiconductor substrate.

[0280] There are no particular restrictions on the material, shape, and structure of the wiring in the second semiconductor substrate.

[0281] <<Step 3B>>

[0282] The step 3B is a step of peeling the support substrate from the laminate. The step 3B can be said to be a step of separating the semiconductor substrate and the support substrate.

[0283] As a specific example of the step 3B, for example, the specific examples exemplified in the step 3A can be cited.

[0284] <<Step 4B>>

[0285] The step 4B is a step of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the coating film for foreign matter removal.

[0286] As a specific example of the step 4B, for example, the specific examples exemplified in the step 4A can be cited.

[0287] For example, a foreign matter removing coating film remains on the semiconductor substrate peeled from the supporting substrate, and therefore, the foreign matter removing coating film is removed with a removing liquid.

[0288] In the step 4B, for example, foreign matter which is a peeling residue of the adhesive layer is removed together with the foreign matter removing coating film.

[0289] Examples of the removing liquid include the removing liquids mentioned in the description of the foreign matter removing coating film-forming composition of the present invention.

[0290] The cleaning method is not particularly limited, and examples thereof include a method of immersing the semiconductor substrate on which the foreign matter removing coating film remains in a removing liquid, and a method of spraying the removing liquid onto the semiconductor substrate on which the foreign matter removing coating film remains.

[0291] The washing conditions are not particularly limited, and for example, the temperature of the washing liquid is 5° C. to 50° C. The washing time is appropriately selected from 2 to 500 seconds or 3 to 400 seconds.

[0292] For example, the foreign matter removing coating film can be easily peeled off at room temperature (eg, 25° C.) preferably using a commonly used 2.38 mass % tetramethylammonium hydroxide aqueous solution.

[0293] Hereinafter, an example of the second embodiment will be described using drawings.

[0294] First, a semiconductor substrate 1 having wiring 1A is prepared. Figure 1A ).

[0295] Next, a foreign matter removing coating film 2 ( Figure 1B ).

[0296] On the other hand, a glass substrate 4 ( Figure 1C ).

[0297] Furthermore, Figure 1B The semiconductor substrate 1 having the foreign matter removing coating film 2 shown in FIG. Figure 1CThe glass substrate 4 having the adhesive layer 3 is arranged so that the foreign matter removing coating film 2 and the adhesive layer 3 face each other and are bonded ( Figure 1D ,and Figure 1E ).

[0298] Next, the surface of the semiconductor substrate 1 opposite to the surface on the foreign matter removing coating film 2 side is polished to make the semiconductor substrate 1 thinner ( Figure 1F ). Furthermore, the wiring 1A is exposed.

[0299] Next, Figure 1F The laminated body shown in the figure and the second semiconductor substrate 5 having the wiring 5A are arranged in such a manner that the surface of the semiconductor substrate 1 opposite to the surface on the foreign matter removing coating film 2 side faces the surface on which the wiring 5A of the second semiconductor substrate 5 is exposed, and are bonded ( Figure 1G ,and Figure 1H ).

[0300] Next, the adhesive layer 3 and the glass substrate 4 are separated from the semiconductor substrate 1 ( Fig. 1I ). The separation can be easily performed by, for example, irradiating the adhesive layer 3 with laser light to reduce the adhesive force of the adhesive layer 3 .

[0301] On the foreign matter removal coating film 2 after separation, the peeling residue 3A of the adhesive layer 3 remains ( Fig. 1I and Figure 1J ). Therefore, the foreign matter removing coating film 2 is removed by the removing liquid ( Figure 1K ). Thus, it is possible to prevent the peeling residue 3A as foreign matter from remaining on the semiconductor substrate 1.

[0302] The method for manufacturing a processed semiconductor substrate of the present invention can be suitably used for hybrid bonding for connecting semiconductor substrates to each other.

[0303] <Other embodiments>

[0304] One embodiment of the present invention can be a method for removing foreign matter already present on a semiconductor manufacturing substrate. For example, as described in International Publication No. 2017 / 056746 and International Publication No. 2020 / 008965, a substrate treatment film is formed on the surface of a semiconductor substrate, and in the process of removing foreign matter from the substrate surface, the tiny particles on the substrate surface can be efficiently removed, and the formed substrate treatment film can be easily removed from the substrate surface. The substrate treatment film forming composition and the substrate treatment method. The foreign matter removal coating composition of the present invention can also be used in the same method / purpose as described above.

[0305] The above example is specifically described below. In this application example, as a composition for forming a coating film on a semiconductor substrate, a composition for forming a coating film for removing foreign matter of the present invention is used. First, a coating film forming process is performed. That is, the composition for forming a coating film for removing foreign matter is applied to the semiconductor substrate to form a coating film. The semiconductor substrate can be an unprocessed state, a so-called full-plate substrate (planar) in a state where various films are formed, or a material whose shape of wiring, etc. is processed in order to manufacture a semiconductor device. As a coating method, for example, spin coating (spin coating), cast coating, roller coating, etc. can be cited. Next, by heating (baking) and / or decompressing the coating film, a part or all of the solvent contained in the coating film is efficiently removed, so that the solidification and / or hardening of the solid components contained in the coating film can be promoted. Here, the so-called "solidification" refers to solidification, and the so-called "hardening" refers to the increase in molecular weight by linking molecules to each other (for example, cross-linking, polymerization, etc.). A coating film is formed by such operation. At this time, for example, particles attached to the circuit of the semiconductor substrate are introduced into the coating film and are efficiently pulled away from the circuit, etc. Next, the coating film removal step is performed. That is, a removal liquid that dissolves the coating film is supplied to the coating film, thereby removing all the coating film from the semiconductor substrate. As a result, the particles are removed from the semiconductor substrate together with the coating film.

[0306] Example

[0307] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples at all.

[0308] <Determination of molecular weight>

[0309] The weight average molecular weight of the polymers shown in the following synthesis examples of this specification is the measurement result obtained by gel permeation chromatography (hereinafter, abbreviated as GPC). The measurement was performed using a GPC apparatus manufactured by Tosoh Corporation, and the measurement conditions and the like were as follows.

[0310] ·GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801〔Registered trademark〕(Showa Denko K.K.)

[0311] Column temperature: 40°C

[0312] Solvent: dimethylformamide (DMF)

[0313] Flow rate: 1.0ml / min

[0314] · Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0315] <a. Synthesis of polymer>

[0316] <Synthesis example 1>

[0317] After dissolving 15 g of maleimide and 0.15 g of azobisisobutyronitrile in 61.2 g of propylene glycol monomethyl ether, the temperature was raised to 55° C. under nitrogen. The reaction was then performed for 72 hours to obtain a solution of a polymer compound. The solution was then reprecipitated with water and dried in a vacuum oven. GPC analysis of the obtained polymer compound was performed, and the weight average molecular weight was 7400 in terms of standard polystyrene.

[0318]

[0319] <b. Preparation of composition>

[0320] <Example 1>

[0321] To 0.1 g of the polymer compound obtained in Synthesis Example 1 was added 4.9 g of propylene glycol monomethyl ether, and the mixture was filtered using a polyethylene microfilter having a pore size of 0.10 μm to prepare a resin composition solution.

[0322] <Comparative Example 1>

[0323] After adding 4.9 g of propylene glycol monomethyl ether to 0.1 g of polyhydroxystyrene VP-15000 (manufactured by Tosoh Corporation), the mixture was filtered using a polyethylene microfilter having a pore size of 0.10 μm to prepare a resin composition solution.

[0324] <Preparation Example 1>

[0325] In a 600 mL stirring container for a stirrer, 80 g of an MQ resin containing polysiloxane and a vinyl group (manufactured by Wacker Chemi Co., Ltd.) as the polyorganosiloxane (a1), 2.52 g of a linear polydimethylsiloxane containing SiH groups (manufactured by Wacker Chemi Co., Ltd.) having a viscosity of 100 mPa·s as the polyorganosiloxane (a2), 5.89 g of a linear polydimethylsiloxane containing SiH groups (manufactured by Wacker Chemi Co., Ltd.) having a viscosity of 70 mPa·s as the polyorganosiloxane (a2), and 0.22 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemi Co., Ltd.) as a polymerization inhibitor (A3) were added, and the mixture was stirred for 5 minutes using a stirrer (autorotation-revolution mixer ARE-500 manufactured by Shinky Co., Ltd.) to obtain a mixture (I).

[0326] 0.147 g of a platinum catalyst (manufactured by Wacker Chemi Co., Ltd.) as a platinum group metal catalyst (A2) and 5.81 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi Co., Ltd.) having a viscosity of 1000 mPa·s as a polyorganosiloxane (a1) were stirred for 5 minutes in a stirrer to obtain a mixture (II).

[0327] 3.96 g of the mixture (II) was added to the mixture (I), and the mixture was stirred for 5 minutes with a stirrer to obtain a mixture (III).

[0328] Finally, the obtained mixture (III) was filtered through a 300-mesh nylon filter to obtain an adhesive composition 1. The viscosity of the adhesive measured with a viscometer (rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.) was 10,000 mPa·s.

[0329] <c. Film thickness reduction and alkali dissolution test under high temperature conditions>

[0330] The resin composition solutions prepared in Example 1 and Comparative Example 1 were applied to a silicon wafer by a spin coater. A heat-cured film (film thickness 40 nm) was formed by firing at 220°C on a hot plate for 3 minutes. The cured film was further subjected to high-temperature treatment at 300°C on a hot plate for 2 hours. As a result, for the film obtained from the resin composition solution prepared in Example 1, the film thickness reduction was suppressed to within 5%, but for the film obtained from the resin composition solution prepared in Comparative Example 1, a 35% film thickness reduction was observed. The film was further immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute. For the film obtained from the resin composition solution prepared in Example 1, it was confirmed that it was easily dissolved in NMD-3, but for the film obtained from the resin composition solution prepared in Comparative Example 1, it was not dissolved in NMD-3.

[0331] <d. Checking the gap when placing the bonded substrates under high temperature conditions>

[0332] The resin composition solution prepared in Example 1 was applied on a 300 mm glass wafer (manufactured by Corning Co., Ltd. (CTE7.8), thickness 700 μm) serving as a wafer (support) on the carrier side using a rotary coater, and heated on a hot plate at 220° C. for 3 minutes to form a thermally cured film (film thickness 40 nm).

[0333] Next, the adhesive composition 1 prepared in Modulation Example 1 was coated on a 300-mm silicon wafer (thickness: 770 μm) on the device side with a spin coater to form an adhesive composition layer to a thickness of 65 μm. Next, a pre-fabricated glass wafer with a thermosetting film (wafer on the carrier side) and the silicon wafer with the adhesive composition layer were bonded together in a vacuum bonding apparatus (manufactured by ZEUS Microtech Co., Ltd., full-automatic temporary bonding apparatus XBS300) with the thermosetting film and the adhesive composition layer sandwiched therebetween to produce a laminate. Then, the device-side wafer was placed on the bottom and heat-treated on a hot plate at 170°C for 7 minutes, and then at 190°C for 7 minutes to cure the adhesive composition, obtaining a laminate (1).

[0334] The obtained laminate (1) was heated in a vacuum heating apparatus in a nitrogen atmosphere at 300°C for 2 hours. After heating, the appearance was visually confirmed to check for changes such as voids and peeling. As a result, no changes were confirmed in the appearance confirmation before and after heating, indicating that it has resistance even under the conditions of 300°C for 2 hours.

[0335] <e. Defect inspection and evaluation after development treatment>

[0336] The resin composition solution prepared in Example 1 was coated on a silicon wafer with a spin coater. A sample (Sample A) with a thermosetting film (film thickness: 40 nm) formed thereon was produced by baking on a hot plate at 205°C for 1 minute. In addition, a sample (Sample B) was further produced by subjecting this cured film to a high-temperature treatment on a hot plate at 300°C for 30 minutes. Further, the films of these samples were immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds. The silicon wafers on which the coating films were completely dissolved in NMD-3 were evaluated for the removability of the coating films after development by using a defect inspection apparatus (manufactured by KLA-Tencor Corporation, Surfscan SP2XP) to evaluate the entire surface of the silicon wafer. The number of defects with a defect size of 100 nm or more was compared. As a result, no change in the number of defects was observed in Samples A and B. It was confirmed that the developability remained unchanged after the high-temperature treatment at 300°C and had resistance.

[0337] Explanation of symbols

[0338] 1 Semiconductor substrate

[0339] 1A Wiring

[0340] 2 Coating film for foreign matter removal

[0341] 3 Adhesive layer

[0342] 4 Glass substrate

[0343] 5Second semiconductor substrate

[0344] 5A wiring.

Claims

1. A composition for forming a coating film for removing foreign matter, comprising a polymer and a solvent and capable of forming a coating film that can be removed by a removing liquid, The polymer is a polymer comprising a structural unit represented by the following formula (1): In the formula (1), X represents an oxygen atom or NR, and R represents a hydrogen atom or a protecting group of an imide group which can be deprotected by a base. The composition according to claim 1 , wherein the removing solution is an alkaline removing solution. 3 . The composition according to claim 1 , wherein the removing solution contains 50% by mass or more of an organic solvent. The composition according to claim 1 , comprising at least one of a cross-linking agent and an additive. 5 . A foreign matter removing coating film formed from the composition according to claim 1 . 6 . The foreign matter removing coating film according to claim 5 , wherein a reduction in film thickness when heated at 250° C. for 10 minutes in a nitrogen atmosphere is 5% or less. 7 . A semiconductor substrate comprising the foreign matter removing coating film according to claim 5 .

8. A method for manufacturing a processed semiconductor substrate, comprising the following steps: Step 1A of manufacturing a laminate by laminating the semiconductor substrate according to claim 7 and a supporting substrate via the foreign matter removing coating film; Step 2A of processing the laminate; Step 3A of peeling the supporting substrate from the laminate; and The semiconductor substrate or the supporting substrate is cleaned with a removing liquid to remove the foreign matter removing coating film. 4A step. 9 . The method for manufacturing a processed semiconductor substrate according to claim 8 , wherein in the step 4A, foreign matter is removed together with the foreign matter removing coating film.

10. The method for manufacturing a processed semiconductor substrate according to claim 8, wherein the step 1A is a step of manufacturing a laminate by bonding the semiconductor substrate and the supporting substrate via the foreign matter removing coating film and the adhesive layer. 11 . The method for manufacturing a semiconductor substrate according to claim 10 , wherein in the step 4A, foreign matter is removed together with the foreign matter removing coating film, and the foreign matter is a peeling residue of the adhesive layer. 12 . The method for manufacturing a processed semiconductor substrate according to claim 8 , wherein the processing includes connecting the semiconductor substrate to a second semiconductor substrate.

13. A method for manufacturing a processed semiconductor substrate, comprising the following steps: Step 1B of manufacturing a laminate by laminating a semiconductor substrate and a supporting substrate via a foreign matter removing coating film and an adhesive layer; Step 2B of processing the laminate; Step 3B of peeling the supporting substrate from the laminate; and Step 4B of washing the semiconductor substrate or the supporting substrate with a removing liquid to remove the foreign matter removing coating film, in, The processing includes connecting the semiconductor substrate to a second semiconductor substrate.

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