Coating composition for removing foreign matter and semiconductor substrate

Abstract

A coating film forming composition for removing foreign matter, comprising a polymer and a solvent, and capable of forming a coating film removable by a removal liquid, wherein the polymer is a polymer comprising structural units represented by the following formula (1) [in formula (1), R 1 R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. 2 R represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 3 R indicates an alkyl group with 1 to 10 carbon atoms that can be substituted, or an aromatic hydrocarbon group that can be substituted. 2 and R 3 It can also be used with R 2 and R 3 The carbon and oxygen atoms between them form a ring, which may also contain heteroatoms other than the oxygen atom.

Description

Technical Field

[0001] The present invention relates to a coating composition for removing foreign matter that can easily prevent foreign matter residues on a substrate, a coating for removing foreign matter, a semiconductor substrate, and a method for manufacturing the processed semiconductor substrate. Background Technology

[0002] In the manufacturing of semiconductor devices, especially in the so-called back-end processes, a process has been studied in which a semiconductor substrate (e.g., a wafer) is attached to a support substrate, and then back-side grinding (sharpening), wiring, and other processes are performed, followed by peeling off the support substrate to obtain the desired semiconductor substrate.

[0003] Such processes sometimes generate foreign matter that needs to be removed. Therefore, for example, Patent Documents 1 and 2 disclose a substrate processing film forming composition and a substrate processing method for efficiently removing minute particles from the substrate surface and easily removing the formed substrate processing film from the substrate surface during the process of forming a substrate processing film on the surface of a semiconductor substrate and removing foreign matter from the substrate surface.

[0004] Existing technical documents

[0005] Patent documents

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

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

[0008] The problem that the invention aims to solve

[0009] On the other hand, when attaching a semiconductor substrate to a support substrate, the semiconductor substrate is attached using an adhesive layer (e.g., a liquid composition containing a polymer, back-grinding tape, dicing tape, etc.) that is resistant to subsequent processes (e.g., heating processes, chemical treatment processes, etc.). Alternatively, a support substrate with an adhesive layer can be used. Then, a process to peel off the semiconductor substrate is performed. At this time, the adhesive layer or the adhesive layer of the support substrate sometimes remains on the substrate as foreign matter (residue). This is particularly noticeable when the adhesive layer is formed directly on the surface of a semiconductor substrate on which wiring is pre-formed, or when a support substrate with an adhesive layer is directly attached. This foreign matter sometimes cannot be completely removed even by cleaning with known organic solvents, liquid chemicals, etc.

[0010] Therefore, there is a need for a simple method to prevent peeling residues from adhesive layers, etc., from remaining on the semiconductor substrate.

[0011] On the other hand, when using a film (foreign matter removal coating) for this purpose, resistance to organic solvents is sometimes required when organic solvents are used in subsequent processes. Furthermore, it is required that the film can be easily removed from the semiconductor substrate after the process of peeling off the semiconductor substrate (removability).

[0012] Therefore, the object of the present invention is to provide a "coating composition for removing foreign matter" that can produce a coating film for removing foreign matter with solvent resistance and easy removal, as well as a method for manufacturing a coating film for removing foreign matter, a semiconductor substrate, and a processed semiconductor substrate using the composition.

[0013] Methods for solving problems

[0014] As a result of in-depth research conducted by the inventors and others in order to solve the above-mentioned problems, they discovered that the above-mentioned problems could be solved, and thus completed the present invention having the following contents.

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

[0016] [1] A coating film forming composition for removing foreign matter, comprising a polymer and a solvent, and capable of forming a coating film removable by a removal liquid, wherein...

[0017] The aforementioned polymer is a polymer containing the structural unit represented by the following formula (1);

[0018]

[0019] In equation (1), R 1 R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. 2 R represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 3 R indicates an alkyl group with 1 to 10 carbon atoms that can be substituted, or an aromatic hydrocarbon group that can be substituted. 2 and R 3 It can also be used with R 2 and R 3 The carbon and oxygen atoms between them form a ring, which may also contain heteroatoms other than the aforementioned oxygen atoms.

[0020] [2] As in [1], wherein the aforementioned polymer is a polymer that further comprises structural units derived from (meth)acrylate compounds, (meth)acrylamide compounds, or styrene compounds.

[0021] [3] The composition of [1] or [2], wherein the aforementioned removal liquid is an alkaline removal liquid.

[0022] [4] The composition of any one of [1] to [3], wherein the aforementioned removal liquid is a removal liquid containing 50% by mass or more of an organic solvent.

[0023] [5] The composition of any one of [1] to [4] contains at least one of a crosslinking agent and an additive.

[0024] [6] A coating for removing foreign matter, which is formed from a composition of any one of [1] to [5].

[0025] [7] A semiconductor substrate having a coating for removing foreign matter as in [6].

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

[0027] The first step of manufacturing a laminate involves bonding a semiconductor substrate, as shown in [7], and a support substrate through a coating used for removing foreign matter, in the manner described above.

[0028] The second process of processing the laminate,

[0029] The third step of peeling the aforementioned support substrate from the laminate, and...

[0030] The fourth step involves cleaning the aforementioned semiconductor substrate or the aforementioned support substrate with a removal solution to remove the aforementioned coating used for removing foreign matter.

[0031] [9] The method for manufacturing a processed semiconductor substrate as described in [8], wherein foreign matter is removed together with the coating for removing foreign matter in the aforementioned fourth step.

[0032]

[10] A method for manufacturing a processed semiconductor substrate, such as [8] or [9], wherein the first step is a step of manufacturing a laminate by bonding the semiconductor substrate and the support substrate together through the coating and adhesive layer for removing foreign matter.

[0033]

[11] In the semiconductor substrate manufacturing method of

[10] , in the aforementioned fourth step, foreign matter that serves as the peeling residue of the aforementioned adhesive layer is removed together with the aforementioned coating for removing foreign matter.

[0034]

[12] A method for manufacturing a processed semiconductor substrate as described in any of [8] to

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

[0035] [Invention Effects]

[0036] Furthermore, according to the present invention, a "coating composition for removing foreign matter" that can produce a "coating for removing foreign matter that has solvent resistance and easy removability" can be provided, as well as a method for manufacturing a coating for removing foreign matter using the composition, a semiconductor substrate, and a processed semiconductor substrate. Attached Figure Description

[0037] Figure 1A A schematic cross-sectional view (1) is provided for illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0038] Figure 1B A schematic cross-sectional view (2) is provided to illustrate an example of a method for manufacturing a processed semiconductor substrate.

[0039] Figure 1C A schematic cross-sectional view (3) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0040] Figure 1D A schematic cross-sectional view (4) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0041] Figure 1E A schematic cross-sectional view (5) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0042] Figure 1F A schematic cross-sectional view (6) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0043] Figure 1G A schematic cross-sectional view (7) is provided to illustrate an example of a method for manufacturing a processed semiconductor substrate.

[0044] Figure 2A A schematic cross-sectional view (1) is provided to illustrate another example of a method for manufacturing a processed semiconductor substrate.

[0045] Figure 2B A schematic cross-sectional view (2) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0046] Figure 2C A schematic cross-sectional view (3) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0047] Figure 2D A schematic cross-sectional view (4) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0048] Figure 2E A schematic cross-sectional view (5) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0049] Figure 2F A schematic cross-sectional view (6) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0050] Figure 2GA schematic cross-sectional view (7) is provided to illustrate another example of a method for manufacturing a processed semiconductor substrate.

[0051] Figure 2H A schematic cross-sectional view (8) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0052] Figure 2I A schematic cross-sectional view (9) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0053] Figure 2J A schematic cross-sectional view (10) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0054] Figure 2K A schematic cross-sectional view (11) illustrating another example of a method for manufacturing a processed semiconductor substrate. Detailed Implementation

[0055] (A coating-forming composition for removing foreign matter)

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

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

[0058] <Polymer>

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

[0060]

[0061] In equation (1), R 1 R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. 2 R represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 3 R indicates an alkyl group with 1 to 10 carbon atoms that can be substituted, or an aromatic hydrocarbon group that can be substituted. 2 and R 3 It can also be used with R 2 and R 3 The carbon and oxygen atoms between them form a ring, which may also contain heteroatoms other than the aforementioned oxygen atoms.

[0062] As R 1 Alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, and propyl.

[0063] As R 2Alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl.

[0064] As R 3 Substituents in alkyl groups having 1 to 10 carbon atoms that can be substituted include, for example, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, and aromatic groups. Examples of aromatic groups include aromatic hydrocarbon groups. Examples of aromatic hydrocarbon groups include phenyl and naphthyl groups.

[0065] As R 3 Substituents in the substituted aromatic hydrocarbon groups can be exemplified by, for example, halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, etc.

[0066] In this invention, halogen atoms may include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0067] R 2 and R 3 It can also be used with R 2 and R 3 The carbon and oxygen atoms between them form a ring, which may contain heteroatoms other than the aforementioned oxygen atoms.

[0068] Examples of this type of ring include 4-membered rings to 7-membered rings.

[0069] Examples of such rings include cyclic ethers, lactone rings, and cyclic carbonates.

[0070] Examples of heteroatoms that a ring can contain include oxygen, nitrogen, and sulfur atoms.

[0071] As R 1 The preferred atoms are hydrogen atoms and methyl groups.

[0072] As R 2 Methyl or ethyl compounds are preferred.

[0073] As R 3 Preferably, it is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[0074] The inventors believe that the acetal structure of formula (1) acts as a protecting group of the carboxyl group, imparts solubility of the polymer to the solvent, and improves the coatability of the coating composition for removing foreign matter.

[0075] On the other hand, during the process of forming a coating from a coating-forming composition for removing foreign matter, carboxyl groups are generated by the detachment of the acetal structure (e.g., by heat or a catalyst). The generated carboxyl groups impart solvent resistance to the coating by reacting with each other or by reacting with the crosslinking agent in the presence of the crosslinking agent. Furthermore, the generated carboxyl groups facilitate the removal of the coating by a removal liquid.

[0076] Therefore, the coating obtained from the coating film forming composition for removing foreign matter exhibits good solvent resistance. Furthermore, the coating obtained from the coating film forming composition for removing foreign matter can be removed by a removal solution.

[0077] Therefore, the coating film forming composition for removing foreign matter of the present invention is a composition that can easily prevent foreign matter residue on the substrate, and is a composition that can obtain a coating film with good solvent resistance and easy removability.

[0078] The structural unit represented by equation (1) can be exemplified by the following structural units. In the following structural units, R... 1 The alkyl group represents 1 to 3 hydrogen atoms or carbon atoms, preferably hydrogen atoms or methyl groups.

[0079]

[0080] The structural unit represented by formula (1) is, for example, derived from a compound represented by formula (1A) below.

[0081]

[0082] In formula (1A), R 1 R 2 and R 3 , respectively with R in equation (1) 1 R 2 and R 3 (Same meaning)

[0083] Polymers may also contain structural units other than those represented by formula (1).

[0084] Examples of such structural units include those derived from (meth)acrylate compounds, (meth)acrylamide compounds, or styrene compounds.

[0085] Furthermore, in this invention, (meth)acrylate compounds mean acrylate compounds or methacrylate compounds. The same applies to (meth)acrylamide compounds.

[0086] As structural units derived from (meth)acrylate compounds, examples of structural units represented by the following formula (2-1) can be cited.

[0087] As structural units derived from (meth)acrylamide compounds, examples of structural units represented by the following formula (2-2) can be cited.

[0088] As structural units derived from styrene compounds, examples of structural units represented by the following formulas (2-3) can be cited.

[0089]

[0090] In equations (2-1) to (2-3), R 11 R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. 12 R represents a monovalent base with 1 to 20 carbon atoms. 13 R represents a monovalent base with 1 to 20 hydrogen or carbon atoms. 14 Each group independently represents a halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, or a monovalent group with 1 to 10 carbon atoms. m represents an integer from 0 to 5.

[0091] R 12 and R 13 The number of carbon atoms in it can be 1 to 20 or 1 to 10.

[0092] R 12 and R 13 The monovalent groups containing 1 to 20 carbon atoms can also contain heteroatoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms.

[0093] R 12 and R 13 A monovalent group containing 1 to 20 carbon atoms can also have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings.

[0094] R 12 and R 13 The monovalent group containing 1 to 20 carbon atoms can have halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, etc.

[0095] R 12 and R 13 Monovalent groups with 1 to 20 carbon atoms can be exemplified by, for example, substituted alkyl groups or substituted aromatic groups.

[0096] Examples of substituents in substituted alkyl groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, and substituted aromatic groups.

[0097] Examples of substituents in substituted aromatic groups include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, alkyl groups with 1 to 6 carbon atoms that can be substituted by halogen atoms, and alkoxy groups with 1 to 6 carbon atoms that can be substituted by halogen atoms.

[0098] Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, and butyl.

[0099] Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0100] R 14 The carbon atoms in a carbon atom group numbering 1 to 10 are monovalent groups, and may also contain heteroatoms. Examples of heteroatoms include oxygen atoms and nitrogen atoms.

[0101] As R 14 The monovalent group containing 1 to 10 carbon atoms can have halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, epoxy groups, etc.

[0102] As R 14 The monovalent group with 1 to 10 carbon atoms in it can be exemplified by alkyl groups with 1 to 6 carbon atoms that can be replaced by halogen atoms, alkoxy groups with 1 to 6 carbon atoms that can be replaced by halogen atoms, etc.

[0103] Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, and butyl.

[0104] Examples of alkoxy groups with 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, and butoxy.

[0105] Specific examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, 4-hydroxyphenyl acrylate, anthracene methyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 2-methoxyethyl acrylate, tetrahydrofuran methyl acrylate, 2-methyl-2-adamantane acrylate, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0106] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 4-hydroxyphenyl acrylate, anthracene methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofuran methyl methacrylate, 2-methyl-2-adamantane methacrylate, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0107] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N-(4-hydroxyphenyl)acrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0108] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N-(4-hydroxyphenyl)methacrylamide, N,N-dimethylmethacrylamide, and N-anthraylmethacrylamide.

[0109] Specific examples of styrene compounds include styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc., but are not limited to these.

[0110] The polymer may further have other structural units. Examples of monomers from which such structural units are derived include, but are not limited to, acrylic acid, methacrylic acid, vinyl compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0111] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc.

[0112] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited to these.

[0113] The viewpoint is that the lower limit of the molar ratio of the structural unit represented by formula (1) to all structural units of the polymer is not particularly limited, and the effect of the present invention can be well obtained. The molar ratio of the structural unit represented by formula (1) is preferably 20 mol% or more, more preferably 45 mol% or more, and particularly preferably 65 mol% or more.

[0114] The viewpoint is that the upper limit of the molar ratio of the structural unit represented by formula (1) to all structural units of the polymer is not particularly limited, and the effect of the present invention can be well obtained. The molar ratio of the structural unit represented by formula (1) is preferably 100 mol% or less, more preferably 95 mol% or less, and particularly preferably 90 mol% or less.

[0115] The lower limit of the molar ratio of the total structural units from (meth)acrylate compounds, structural units from (meth)acrylamide compounds, and structural units from styrene compounds (hereinafter sometimes referred to as "total structural units (2)") relative to all structural units of the polymer is not particularly limited, and the effect of the present invention can be well obtained. The molar ratio of total structural units (2) is preferably more than 0 mol%, more preferably 10 mol% or more.

[0116] From the viewpoint that the upper limit of the molar ratio of the total structural unit (2) to all structural units of the polymer is not particularly limited, the molar ratio of the total structural unit (2) is preferably 60 mol% or less, more preferably 45 mol% or less.

[0117] The view that the molar ratio of the structural unit represented by Equation (1) and the total structural unit (2) relative to the total structural units of the polymer is not particularly limited, and the effect of the present invention can be well obtained, is preferably 80 mol% to 100 mol%, more preferably 90 mol% to 100 mol%.

[0118] Polymers can be homopolymers or copolymers. When a polymer is a copolymer, it can be a random copolymer or a block copolymer.

[0119] There are no particular restrictions on the manufacturing method of the polymer.

[0120] Polymers can be manufactured by polymerizing monomers using conventional methods such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferred, in which a polymerization initiator can be used, for example, to polymerize the monomers.

[0121] Polymerization initiators can be organic peroxides or diazo compounds.

[0122] Organic peroxides include, for example, acyl peroxides, peroxydicarbonates, peroxyesters, and peroxysulfonates.

[0123] Diacyl peroxides include, for example, diacetyl peroxide, diisobutyl peroxide, didecyl peroxide, benzoyl peroxide, succinic acid peroxide, etc.

[0124] Examples of peroxydicarbonates include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diallyl peroxydicarbonate, etc.

[0125] Peroxy esters include, for example, tert-butyl peroxyisobutyrate, tert-butyl neodecanoate, and cumene peroxyneodecanate.

[0126] Peroxide sulfonates, for example, acetylcyclohexylsulfonyl peroxide, etc.

[0127] Examples of diazo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(isobutyric acid) dimethyl ester, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(4-methoxy-2,4-dimethoxypentanone), and 2,2'-azobis(2-cyclopropylpropionitrile).

[0128] When polymerization needs to be completed in a short time, it is preferable to use a polymerization initiator with a decomposition half-life of less than 10 hours at 80°C. Such polymerization initiators are preferably benzyl peroxide or 2,2'-azobisisobutyronitrile; more preferably 2,2'-azobisisobutyronitrile.

[0129] The amount of polymerization initiator used is, for example, 0.0001 to 0.2 equivalents, preferably 0.0005 to 0.1 equivalents, relative to the total amount of monomers used.

[0130] The solvent used for polymerization is not particularly limited as long as it is unrelated to the polymerization reaction and is compatible with the resulting polymer. Examples include aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, esters, amides, sulfoxides, alcohols, and polyol derivatives.

[0131] Examples of aromatic hydrocarbons include benzene, toluene, and xylene.

[0132] Examples of alicyclic hydrocarbons include cyclohexane.

[0133] Examples of aliphatic hydrocarbons include n-hexane and n-octane.

[0134] Examples of ketones include acetone, methyl ethyl ketone, and cyclohexanone.

[0135] Examples of ethers include tetrahydrofuran and dioxane.

[0136] Examples of esters include ethyl acetate and butyl acetate.

[0137] Examples of amides include N,N-dimethylformamide and N,N-dimethylacetamide.

[0138] Examples of sulfoxides include dimethyl sulfoxide.

[0139] Examples of alcohols include methanol and ethanol.

[0140] Examples of polyol derivatives include ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate.

[0141] These can be used individually or in combination of two or more.

[0142] The polymerization temperature is not particularly limited as long as it does not cause side reactions such as migration or cessation reactions, and the polymerization is completed by consuming the monomer. It is preferred to carry out the polymerization in a temperature range above -100°C and below the boiling point of the solvent.

[0143] Furthermore, the concentration of the monomer relative to the solvent is not particularly limited, and is typically 1 to 40% by mass, preferably 10 to 30% by mass.

[0144] The polymerization reaction time can be selected appropriately, usually ranging from 2 hours to 50 hours.

[0145] The weight-average molecular weight of the polymer is not particularly limited, but is preferably 5,000 to 75,000, more preferably 10,000 to 50,000. Furthermore, the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0146] The content of polymer in the coating-forming composition for removing foreign matter 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, relative to the solid content.

[0147] <<Removal Solution>>

[0148] As a removal liquid, there are no particular limitations as long as it can remove the coating formed from the coating forming composition for removing foreign matter.

[0149] The coating is formed, for example, on a semiconductor substrate. Removal here refers to removal from the semiconductor substrate.

[0150] Here, as a form of removal, examples include dissolution removal and peeling removal. Peeling removal, for example, involves peeling off the adhered material through swelling.

[0151] The removal solution may contain water or organic solvents.

[0152] The removal solution may contain more than 50% by mass of organic solvent.

[0153] Examples of organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0154] Removal solutions include, for example, alkaline removal solutions and acidic removal solutions.

[0155] Alkaline removal solutions contain alkalis. Examples of alkalis include ammonia, inorganic alkaline compounds, quaternary ammonium hydroxide, amines, and hydrazine.

[0156] Alkaline removal solutions are developing or cleaning solutions used in semiconductor manufacturing processes, and may also be alkaline. For example, a developing solution such as NMD-3 (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is an example.

[0157] Examples of inorganic alkaline compounds 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, etc.

[0158] Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and choline.

[0159] Examples of amines include ethanolamine, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyl diethylamine, dimethylethanolamine, triethanolamine, ethylenediamine, etc.

[0160] Examples of hydrazine include hydrazine monohydrate.

[0161] In addition, the alkaline removal solution can also be SC-1 (ammonia-hydrogen peroxide solution).

[0162] Acid removal solutions contain acids. Examples of acids include inorganic acids and organic acids. Examples of inorganic acids include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and hydrofluoric acid.

[0163] Acid removal solutions can be, for example, aqueous solutions containing dilute hydrofluoric acid.

[0164] Furthermore, the acid removal solution may be, for example, an aqueous solution containing sulfuric acid and hydrogen peroxide, or an aqueous solution containing acetic acid or a chelating agent. Examples of chelating agents include organic acids, salts of organic acids, amino acids, and derivatives of amino acids.

[0165] <Solvent>

[0166] Solvents contained in the coating-forming composition for removing foreign matter may include, 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 ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0167] These solvents can be used alone or in combination of two or more.

[0168] Furthermore, it can be used in combination with high-boiling-point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate.

[0169] A film-forming composition for removing foreign matter, for example, can be easily prepared by uniformly mixing the components and can be dissolved in a suitable solvent for use in a solution state.

[0170] The coating composition for removing foreign matter prepared in this manner is preferably filtered through a filter with a pore size of approximately 0.2 μm before use. The coating composition for removing foreign matter prepared in this manner also exhibits excellent long-term storage stability at room temperature.

[0171] The proportion of solid components in the film-forming composition for removing foreign matter is not particularly limited as long as all components dissolve uniformly, for example, 0.5 to 50% by mass, or, for example, 1 to 30% by mass. Here, solid components refer to the components remaining after removing solvent components from all components of the film-forming composition for removing foreign matter.

[0172] In this invention, foreign matter refers to any substance other than the target object adhering to the substrate. In semiconductor device manufacturing, foreign matter is an unwanted substance. Examples of foreign matter include particles adhering to the wafer, metallic impurities, etching residue, and adhesive layer peeling residue.

[0173] The coating for removing foreign matter is particularly preferred for use in the process of bonding wafers together with an adhesive and then peeling off the adhesive. The coating of the present invention is formed in advance before the adhesive is applied, and then the foreign matter (residue of the adhesive layer) after the wafer bonding and peeling process is removed.

[0174] The coating used for removing foreign matter can also be used to remove foreign matter that is already present on a semiconductor substrate.

[0175] The coating used for removing foreign matter dissolves in the removal solution, meaning that when the coating is immersed or cleaned with the removal solution, it dissolves in the removal solution and becomes no longer present on the substrate or other adherent material. In this invention, "dissolution" means that the film formed on the substrate is removed from its original thickness, for example, by at least 90% (i.e., the remaining film thickness is less than 10% of the original film thickness), or by at least 95% (i.e., the remaining film thickness is less than 5% of the original film thickness), or by at least 99% (i.e., the remaining film thickness is less than 1% of the original film thickness), and most preferably by 100% (i.e., the remaining film thickness is 0% of the original film thickness (no remaining film)).

[0176] The aforementioned composition preferably contains at least one of a crosslinking agent and an additive.

[0177] <Cross-linking agent>

[0178] There are no particular restrictions on crosslinking agents.

[0179] Crosslinking agents have a structure different from that of polymers.

[0180] The preferred crosslinking agent is an amino resin crosslinking agent or a phenolic resin crosslinking agent.

[0181] Amino resin crosslinking agents are addition condensations of amino compounds such as melamine or guanidine with formaldehyde.

[0182] Phenolic resin crosslinking agents refer to the addition condensation products of compounds with phenolic hydroxyl groups and formaldehyde.

[0183] Examples of crosslinking agents include compounds having two or more of the following structures.

[0184]

[0185] (In the structure, R) 101 Indicates an alkyl group with 1 to 4 carbon atoms, or an alkoxyalkyl group with 2 to 6 carbon atoms. * indicates a bonding site.

[0186] Bonding sites, such as bonds to nitrogen atoms or carbon atoms that form aromatic hydrocarbon rings.

[0187] R 101 Preferably, it is a hydrogen atom, methyl, ethyl or a group represented by the following structures.

[0188]

[0189] (In the structure, R) 102 * indicates a hydrogen atom, methyl group, or ethyl group. * indicates a bonding site.

[0190] The crosslinking agent is preferably a melamine compound, guanidine compound, glycourea compound, urea compound, or a compound with phenolic hydroxyl groups. These can be used alone or in combination of two or more.

[0191] Examples of melamine compounds include hexamethylol melamine, hexamethoxymethyl melamine, compounds of hexamethylol melamine in which 1 to 6 hydroxymethyl groups are methoxymethylated, or mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds of hexamethylol melamine in which 1 to 6 hydroxymethyl groups are acyloxymethylated, or mixtures thereof.

[0192] Examples of guanidine compounds include tetrahydroxymethylguanidine, tetramethoxymethylguanidine, compounds of tetrahydroxymethylguanidine in which one to four hydroxymethyl groups are methoxymethylated, or mixtures thereof, tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds of tetrahydroxymethylguanidine in which one to four hydroxymethyl groups are acyloxymethylated, or mixtures thereof.

[0193] Examples of glycourea compounds include tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds of tetrahydroxymethylglycourea in which one to four hydroxymethyl groups are methoxymethylated, or mixtures thereof, compounds of tetrahydroxymethylglycourea in which one to four hydroxymethyl groups are acylmethylated, or mixtures thereof.

[0194] In addition, the glycourea compound may also be a glycourea derivative represented, for example, by the following formula (1E).

[0195]

[0196] (In formula (1E), the four R1s each independently represent methyl or ethyl, and R2 and R3 each independently represent hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, or phenyl groups).

[0197] Examples of glycourea derivatives represented by the aforementioned formula (1E) include compounds represented by formulas (1E-1) to (1E-6) below.

[0198]

[0199] The glycourea derivative represented by formula (1E) can be obtained, for example, by reacting the glycourea derivative represented by formula (2E) with at least one compound represented by formula (3d).

[0200]

[0201] (In formula (2E), R2 and R3 independently represent hydrogen atoms, alkyl groups with 1 to 4 carbon atoms, or phenyl groups, respectively, and R4 independently represents alkyl groups with 1 to 4 carbon atoms).

[0202]

[0203] (In formula (3d), R1 represents methyl or ethyl).

[0204] Examples of the glycourea derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Further, examples of the compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0205]

[0206] Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds of tetrahydroxymethylurea in which one to four hydroxymethyl groups are methoxymethylated, or mixtures thereof, and tetramethoxyethylurea.

[0207] Compounds having phenolic hydroxyl groups can be listed as, for example, compounds represented by the following formula (G-1) or formula (G-2).

[0208]

[0209] In equations (G-1) and (G-2), Q 1 It represents a single bond or an m1-valent organic group.

[0210] R 1 and R 4 They represent alkyl groups having 2 to 10 carbon atoms, or alkyl groups having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms.

[0211] R 2 and R 5 These represent hydrogen atoms or methyl groups, respectively.

[0212] R 3 and R 6 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0213] n1 is an integer of 1 ≤ n1 ≤ 3, n2 is an integer of 2 ≤ n2 ≤ 5, n3 is an integer of 0 ≤ n3 ≤ 3, and n4 is an integer of 0 ≤ n4 ≤ 3, and represents an integer of 3 ≤ (n1 + n2 + n3 + n4) ≤ 6.

[0214] n5 is an integer of 1 ≤ n5 ≤ 3, n6 is an integer of 1 ≤ n6 ≤ 4, n7 is an integer of 0 ≤ n7 ≤ 3, and n8 is an integer of 0 ≤ n8 ≤ 3, and represents an integer of 2 ≤ (n5 + n6 + n7 + n8) ≤ 5.

[0215] m1 represents an integer from 2 to 10.

[0216] In addition, compounds having phenolic hydroxyl groups can be listed as, for example, compounds represented by the following formula (G-3) or formula (G-4).

[0217] The compound represented by formula (G-1) or formula (G-2) can be obtained by reacting a compound represented by formula (G-3) or formula (G-4) below with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0218]

[0219] In equations (G-3) and (G-4), Q 2 It represents a single bond or an m2 valence organic group.

[0220] R 8 R 9 R 11 and R 12 These represent hydrogen atoms or methyl groups, respectively.

[0221] R 7 and R 10 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0222] n9 is an integer where 1 ≤ n9 ≤ 3, n 10 For 2≤n 10 Integers ≤ 5, n 11 For 0≤n 11 Integers ≤3, n 12 For 0≤n 12 Integers ≤ 3, where 3 ≤ (n ≤ 9 + n) 10 +n 11 +n 12 Integers ≤ 6.

[0223] n 13 For 1≤n 13 Integers ≤3, n 14 For 1≤n 14 Integers ≤ 4, n 15For 0≤n 15 Integers ≤3, n 16 For 0≤n 16 Integers ≤ 3, and represent 2 ≤ (n 13 +n 14 +n 15 +n 16 Integers ≤ 5.

[0224] m2 represents an integer from 2 to 10.

[0225] Q 2 The m2 valence organic groups in the text can be exemplified by, for example, m2 valence organic groups with 1 to 4 carbon atoms.

[0226] Compounds represented by formula (G-1) or formula (G-2) can be exemplified by the following compounds.

[0227]

[0228] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0229]

[0230] The above-mentioned compounds are available as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. Examples of such products include, for instance, the trade name TMOM-BP from Asahi Organic Materials Co., Ltd.

[0231] Among these, glycourea compounds are particularly preferred, specifically tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, a compound of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or a mixture thereof, a compound of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are acylmethylated, or a mixture thereof; more preferably tetramethoxymethylglycourea.

[0232] The molecular weight of the crosslinking agent is not particularly limited, but is preferably below 500.

[0233] The content of the aforementioned crosslinking agent, relative to 100 parts by weight of the aforementioned polymer, is, for example, 5 to 70 parts by weight, or 5 to 60 parts by weight, preferably 5 to 45 parts by weight. From the viewpoint of the curing degree of the coating film and prevention of miscibility with the adhesive layer, the content of the crosslinking agent is preferably 5 parts by weight or more relative to 100 parts by weight of the polymer; from the viewpoint of solubility in the removal liquid, it is preferably 70 parts by weight or less relative to 100 parts by weight of the polymer.

[0234] <Additives>

[0235] The coating-forming composition for removing foreign matter may contain a curing catalyst, a light-absorbing compound, a surfactant, an adhesive aid, a rheology modifier, and silica particles as additives.

[0236] Curing catalysts, including thermal acid-generating agents and photo-acid-generating agents, can all be used, with thermal acid-generating agents being preferred.

[0237] Examples of heat-generating acid agents include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridonium-p-toluenesulfonate (pyridonium-p-toluenesulfonic acid), pyridonium hydroxybenzenesulfonic acid, pyridonium-p-hydroxybenzenesulfonic acid (pyridonium salt of p-hydroxybenzenesulfonic acid), pyridonium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0238] Examples of photoacid-generating agents include onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0239] Examples of ononium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0240] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0241] Examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0242] The solidification catalyst can be used alone, or in combination of two or more.

[0243] When using a curing catalyst, the proportion of the curing catalyst relative to the crosslinking agent is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0244] As for the light-absorbing compound, there are no particular limitations as long as it absorbs the exposure wavelength used. Compounds with aromatic ring structures such as anthracene rings, naphthalene rings, benzene rings, quinoline rings, and triazine rings are preferred. Furthermore, from the viewpoint of not hindering the solubility of the coating film for removing foreign matter in the removal solution, compounds with phenolic hydroxyl groups, carboxyl groups, or sulfonic acid groups are preferred.

[0245] Examples of light-absorbing compounds that exhibit significant absorption of light at 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-hydroxynaphthoic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, and 1,8-naphthalene. Dicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 1-bromo-2-hydroxy 1,6-Dibromo-2-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-naphthoic acid, methyl 2-hydroxy-3-naphthoic acid, 6-hydroxy-2- Methyl naphthate, methyl 3-hydroxy-7-methoxy-2-naphthate, methyl 3,7-dihydroxy-2-naphthate, 2,4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-naphthiol, 4-methoxy-1-naphthol, 6-acetoxy-2-naphtholic acid, 1,6-dibromo-1-naphthol, 2,6-dibromo-1,5-dihydroxynaphthol, 1-acetyl-2-naphthol, 9-anthracarboxylic acid, 1,4,9,10-tetrahydroxyanthracene, 1,8,9-trihydroxyanthracene, etc.

[0246] In addition, examples of light-absorbing compounds that exhibit significant absorption of light at a wavelength of 193 nm include benzoic acid, 4-methylbenzoic acid, o-phthalic acid, m-phthalic acid, terephthalic acid, 2-methoxybenzoic acid, isophthalic acid, terephthalic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-acetoxybenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, trimellitic acid, 1,4-phthalic acid, 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, and 3,4-dihydroxybenzoic acid. Benzoic acid, 3,5-dihydroxybenzoic acid, 4-acetylbenzoic acid, benzoyltetracarboxylic acid, pyromellitic anhydride, 2-S[bis-(4-hydroxyphenyl)-methyl]benzoic acid, 3,4,5-trihydroxybenzoic acid, 2-benzophenone carboxylic acid, m-phenylbenzoic acid, 3-(4'-hydroxyphenoxy)benzoic acid, 3-phenoxybenzoic acid, phenol, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 2-methylphenol, 3-methylphenol, 4-methylphenol, 1,3,5-trihydroxybenzene, 2,2-bis-4-hydroxyphenylpropane, 2-hydroxybiphenyl, 2-aminophenol, 3-aminophenol, 4-aminophenol, and 4-benzyloxyphenol, etc.

[0247] In addition, to suppress sublimation during firing of coatings used to remove foreign matter, these light-absorbing compounds can be used in combination with polymers or compounds having one or more reactive groups.

[0248] For example, in the case of light-absorbing compounds having carboxyl or phenolic hydroxyl groups, compounds such as tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, and 1,1,3-tris(p-(2,3-epoxypropoxy)phenyl)propane can be used. Compounds obtained by reacting polyfunctional epoxy compounds such as diglycidyl 1,2-cyclohexanedicarboxylate, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether, or polymers containing epoxy groups such as glycidyl methacrylate.

[0249] The aforementioned light-absorbing compounds can be used alone or in combination of two or more. When using a light-absorbing compound, its content, relative to 100 parts by weight of the polymer, is, for example, 1 to 300 parts by weight, or 1 to 200 parts by weight, or, for example, 1 to 100 parts by weight, or 5 to 100 parts by weight. When the content of the light-absorbing compound is 300 parts by weight or less relative to 100 parts by weight of the polymer, the coating for removing foreign matter has excellent solubility in the removal liquid, or the coating for removing foreign matter does not easily cause miscibility with the adhesive layer.

[0250] In coating-forming compositions for removing foreign matter, polyphenolic compounds or compounds containing carboxyl groups may be added to promote the dissolution rate of the removal solution. Such compounds are not particularly limited, and examples include tri-hydroxyphenylethane, bisphenol-A, bisphenol-S, 4,4'-isopropylidene-di-o-cresol, 5-tert-butylgallotrol, hexafluorobisphenol-A, 3,3,3',3'-tetramethyl-1,1'-spirobendindane-5,5',6,6'-tetraol, 4,4'-(9-fluoreneyl)diol, bisphenol-AP, bisphenol-P, etc. Polyphenols such as 5-α,α-dimethyl-4-hydroxybenzyl salicylic acid, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and 5,5'-di-tert-butyl-2,2',4,4'-tetrahydroxybenzophenone; benzopyrene, phthalic acid, trimellitic acid, 4-sulfophthalic acid, hexabenzoic acid, 2,3-naphthalenedicarboxylic acid, and 4-hydroxyphthalic acid. Acids, 3,4-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 3,3'-,4,4'-biphenyltetracarboxylic acid, 3,3'-,4,4'-benzophenone tetracarboxylic acid, 3,3'-,4,4'-diphenyl ether tetracarboxylic acid, 3,3'-,4,4'-diphenyl sulfone tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4- Polycarboxylic acids such as cyclobutanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclohexanetetracarboxylic acid, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic acid; polymers containing carboxylic acids or carboxylic anhydrides such as polyacrylic acid, polymethacrylic acid, polyamic acid, and polymaleic anhydride. The amount of the above compounds added, in the solid components of the coating-forming composition for removing foreign matter, is, for example, 20% by mass or less, preferably 10% by mass or less, as needed.

[0251] In addition, in order to adjust the dissolution rate of the removal liquid, a compound having a carboxyl group or phenolic hydroxyl group protected by a group such as tert-butyl, tetrahydropyran, 1-ethoxyethyl and trimethylsilyl that is easily decomposed in the presence of acid may be added to the coating film forming composition for removing foreign matter.

[0252] 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 trimethylacetate.

[0253] These compounds readily generate carboxyl or phenolic hydroxyl groups in the presence of acid, thus enhancing their solubility in alkaline removal solutions.

[0254] Therefore, these compounds are preferably added together with a photoacid generator in a coating-forming composition for removing foreign matter. That is, in a coating for removing foreign matter formed from a coating-forming composition for removing foreign matter containing a compound having carboxyl or phenolic hydroxyl groups protected by the aforementioned groups that are easily decomposed in the presence of acid and a photoacid generator, in the exposed portions, the carboxyl or phenolic hydroxyl groups of the compound having carboxyl or phenolic hydroxyl groups protected by the acid generated from the photoacid generator through exposure are regenerated by the acid. As a result, the solubility of the exposed portions of the coating for removing foreign matter in alkaline removal solutions is improved.

[0255] When using the above-mentioned compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of acid, its content, relative to 100 parts by mass of the polymer, is, for example, 50 to 1 part by mass, or 30 to 5 parts by mass, or, for example, 20 to 10 parts by mass. When using the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of acid together with a photoacid-generating agent, its content, relative to 100 parts by mass of the compound having a carboxyl group or phenolic hydroxyl group protected by a group that is easily decomposed in the presence of acid, is, for example, 0.1 to 30 parts by mass, or 0.5 to 20 parts by mass, or, for example, 1 to 10 parts by mass.

[0256] The coating-forming composition for removing foreign matter may contain surfactants. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; and sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, and sorbitol monooleate. Sorbitol fatty acid esters such as sorbitol trioleate, sorbitol tristearate, etc.; nonionic surfactants such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate, etc.; Eftop Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megaface F171, F173 (manufactured by DIC Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd., trade name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name). The amount of these surfactants incorporated into the total composition for film formation used to remove foreign matter is typically 0.2% by mass or less, preferably 0.1% by mass or less. These surfactants can be added individually or in combination of two or more.

[0257] The coating-forming composition for removing foreign matter may contain silica particles. Examples of silica particles include, for instance, organosilicon powder having a specific average particle size value, or silica sol containing silica having a specific average particle size value.

[0258] Specific examples of silicone powders include, but are not limited to, the KMP series of silicone powders manufactured by Shin-Etsu Chemical Industries, Ltd., such as KMP-600, KMP-601, KMP-602, KMP-605, and X-52-7030.

[0259] 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), MA-ST-M (methanol-dispersed silica sol), MA-ST-L (methanol-dispersed silica sol), IPA-ST-S (isopropanol-dispersed silica sol), IPA-ST (isopropanol-dispersed silica sol), IPA-ST-UP (isopropanol-dispersed silica sol), IPA-ST-L (isopropanol-dispersed silica sol), IPA-ST-ZL (isopropanol-dispersed silica sol), and NPC-ST. -30 (n-propyl cellulose solvent dispersed silica sol), PGM-ST (1-methoxy-2-propanol dispersed silica sol), DMAC-ST (dimethylacetamide dispersed silica sol), XBA-ST (xylene / n-butanol mixed solvent dispersed silica sol), trade names EAC-ST (ethyl acetate dispersed silica sol), PMA-ST (propylene glycol monomethyl ether acetate dispersed silica sol), MEK-ST (methyl ethyl ketone dispersed silica sol), MEK-ST-UP (methyl ethyl ketone dispersed silica sol), MEK-ST-L (methyl ethyl ketone dispersed silica sol), MIBK-ST (methyl isobutyl ketone dispersed silica sol), etc., but not limited to these.

[0260] (Coating for removing foreign matter)

[0261] The coating for removing foreign matter of the present invention is formed by the coating forming composition for removing foreign matter of the present invention.

[0262] The coating for removing foreign matter according to the present invention can be formed, for example, as follows.

[0263] The foreign matter removal coating composition of the present invention is applied to a semiconductor substrate using a suitable coating method such as a spinner, coater, or immersion, and then fired to form a foreign matter removal coating. 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.

[0264] The thickness of the coating used for removing foreign matter is typically 5 nm to 1 μm, preferably 10 nm to 500 nm, and most preferably 15 nm to 300 nm.

[0265] Regarding the rate at which the coating film used for removing foreign matter dissolves in the removal liquid, the rate at which the film thickness decreases 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 nm to 20 nm per second. If the dissolution rate is lower than this, the time required for the coating film to remove foreign matter becomes longer, resulting in reduced productivity.

[0266] The coating for removing foreign matter formed by the coating film forming composition of the present invention allows for control of the dissolution rate of the coating film to the removal liquid by changing the firing conditions during formation. Under a given firing time, a higher firing temperature results in a coating film with a lower dissolution rate to the removal liquid.

[0267] For coatings used to remove foreign matter, exposure can be performed after the coating is formed. Exposure can be performed on the entire wafer or through a mask with a specific pattern. Exposure can be performed using KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), and F2 excimer lasers (wavelength 157nm), etc. Post-exposure baking (PEB) can also be performed as needed after exposure.

[0268] (Semiconductor substrate)

[0269] The semiconductor substrate of the present invention has a coating thereon for removing foreign matter.

[0270] As the main material constituting the entire semiconductor substrate, there are no particular limitations as long as it is used for this purpose; examples include silicon, silicon carbide, and compound semiconductors.

[0271] The shape of the semiconductor substrate is not particularly limited; for example, it can be disc-shaped. Furthermore, the surface of a disc-shaped semiconductor substrate does not necessarily have to be perfectly circular. For example, the outer periphery of the semiconductor substrate may have a straight section called an orientation plane or a notch.

[0272] The thickness of the disc-shaped semiconductor substrate can be appropriately specified according to the intended use of the semiconductor substrate, and there is no particular limitation, for example, it is 500~1,000μm.

[0273] The diameter of the disc-shaped semiconductor substrate can be appropriately specified according to the intended use of the semiconductor substrate, without special limitation, for example, 100~1,000 mm.

[0274] Semiconductor substrates can also have bumps. Bumps refer to protruding terminals.

[0275] When a semiconductor substrate has bumps, the semiconductor substrate has bumps on the side supporting the substrate.

[0276] In semiconductor substrates, bumps are typically formed on the surfaces where circuitry is formed. The circuitry can be single-layered or multi-layered. The shape of the circuitry is not particularly limited.

[0277] In a semiconductor substrate, the side opposite to the side with bumps (the back side) is the side to be processed.

[0278] There are no particular limitations on the material, size, shape, structure, or density of bumps on a semiconductor substrate.

[0279] Examples of bumps include spherical bumps, printed bumps, stud bumps, and plated bumps.

[0280] The height, radius, and spacing of bumps are usually determined by the conditions of bump height of about 1~200μm, bump radius of 1~200μm, and bump spacing of 1~500μm.

[0281] Materials used for bumps include, for example, low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. Bumps can be composed of a single component or multiple components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other Sn-based alloy plating.

[0282] In addition, the bump may also have a stacked structure comprising a metal layer consisting of at least any of these components.

[0283] One example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

[0284] (Manufacturing method of the processed semiconductor substrate)

[0285] The method for manufacturing the processed semiconductor substrate of the present invention includes a first step, a second step, a third step, and a fourth step.

[0286] The first step is to manufacture a laminate by bonding the semiconductor substrate of the present invention (a semiconductor substrate having the coating for removing foreign matter of the present invention) and the support substrate through the coating for removing foreign matter.

[0287] The second process is the process of processing the laminated body.

[0288] The third step is the process of peeling the support substrate from the laminate.

[0289] The fourth step is to clean the semiconductor substrate or support material with a cleaning solution and remove the coating used to remove foreign matter.

[0290] In the first embodiment, the heat-resistant coating of the present invention for removing foreign matter is used as the coating for removing foreign matter.

[0291] <Step 1>

[0292] The first step is to manufacture a laminate by bonding the semiconductor substrate of the present invention (a semiconductor substrate having the coating for removing foreign matter of the present invention) and the support substrate through the coating for removing foreign matter.

[0293] As a support substrate, any component that can support a semiconductor substrate when processing a laminate (such as a semiconductor substrate) is not particularly limited, and examples include flexible support substrates and glass support substrates.

[0294] The shape of the supporting substrate is not particularly limited; for example, a disc shape can be cited.

[0295] The thickness of the disc-shaped support substrate can be appropriately specified according to the size of the semiconductor substrate, without special limitation, for example, 500~1,000μm.

[0296] The diameter of the disc-shaped support substrate can be appropriately specified according to the size of the semiconductor substrate, without special limitation, for example, 100~1,000 mm.

[0297] One example of a supporting substrate is a glass wafer with a diameter of 300 mm and a thickness of about 700 μm.

[0298] The first step is preferably a step of manufacturing a laminate by bonding a semiconductor substrate and a support substrate together through a coating and an adhesive layer for removing foreign matter.

[0299] As an adhesive layer, there are no particular limitations as long as the supporting substrate can be peeled off from the laminate in the third process.

[0300] The adhesive layer can be formed using known adhesives and methods. Examples of adhesives include coating-type temporary wafer adhesives as described in International Publication No. 2015 / 190438, temporary bonding materials from Thin Materials (Nissan Chemical Co., Ltd.), temporary wafer bonding materials for semiconductors manufactured by Toray Industries, Ltd., WaferBOND (registered trademark) CR-200, and HT-10.10 (manufactured by Brewer Science). Tape-type adhesives can also be used (e.g., back-side grinding tapes, such as 3M™ temporary fixing adhesive tape ATT-4025 (3M...). (Made by Japan Co., Ltd.), E series, P series, S series (Made by Lintec Co., Ltd., trade name), Icros tape (registered trademark) (Made by Mitsui Chemicals TOHCELLO Co., Ltd.)), cutting tape (e.g., solvent-resistant cutting tape (Made by Nitto Denko Co., Ltd., trade name), temperature-sensitive adhesive sheet Intelimer (registered trademark) tape (Made by Nitta Co., Ltd.), Intelimer (registered trademark) tape (Made by AnchorTechno Co., Ltd.) etc.).

[0301] It can also be used as a wafer adhesive in specific wafer operating systems (such as Zero Newton (registered trademark) (manufactured by Tokyo Ohka Kogyo Co., Ltd.)).

[0302] Furthermore, as an adhesive layer, layers referred to as adhesive layers, adhesive tapes, or temporary fixing materials can be used. Examples of such layers include the adhesive layer described in International Publication No. 2021 / 225163, the adhesive layer described in International Publication No. 2022 / 065376, and the photocurable adhesive layer described in International Publication No. 2022 / 065388.

[0303] For example, back-grinding tape consists of a substrate film, an adhesive layer, and a release film. Regarding the substrate film, soft thermoplastic films such as ethylene-vinyl acetate copolymer (EVA) have been used previously, but rigid stretch films such as polyethylene terephthalate (PET) have also been explored to improve wafer support. Further improvements have been made, with reports of laminated designs using two films with different elastic moduli, such as a laminate of PET and an ethylene copolymer, or a laminate of polypropylene (PP) and an ethylene copolymer.

[0304] Adhesives are generally acrylic-based. Acrylic adhesives are known to be cross-linked by reacting acrylic copolymers, primarily composed of monomers with low glass transition temperatures such as butyl acrylate, with a curing agent. Since back-grinding tapes are used to adhere to the circuit surface of a wafer, there is a risk of contamination from the adhesive after tape peeling. Therefore, it has been reported that emulsion-based adhesives are designed to remove adhesive residue even if it is left behind by water washing, but complete removal is difficult. Therefore, the coating for removing foreign matter in this application, after being formed on the circuit surface, forms an adhesive layer, allowing for complete removal of foreign matter (adhesive layer residue) from subsequent peeling processes by cleaning with a removal solution, without causing damage to wiring areas such as circuits.

[0305] The thickness of the adhesive layer is not particularly limited, for example, it is 5μm to 500μm, preferably 10μm to 300μm, more preferably 20μm to 200μm, and particularly preferably 30μm to 150μm.

[0306] Before the first step, the adhesive layer may be formed on a coating for removing foreign matter, on a support substrate, or on a semiconductor substrate.

[0307] When an adhesive layer is not used, the support substrate preferably has an adhesive layer. The support substrate may have, for example, a flexible support and an adhesive layer. Examples of flexible supports include polyimide films. The adhesive layer is not particularly limited and may include layers formed from the aforementioned adhesive.

[0308] Bonding, for example, is performed under heat and pressure.

[0309] There are no special restrictions on the heating temperature as long as it is above room temperature (25°C). Generally, it is above 50°C. However, to avoid overheating, it is usually below 220°C, and in some cases, below 170°C.

[0310] As long as it can be bonded to the substrate or layer without causing damage to the substrate or layer, there is no particular limitation on the load, for example, 0.5~50kN.

[0311] In addition, the pressure applied during bonding can be, for example, 0.1~20 N / mm. 2 Furthermore, pressure refers to the pressure per unit area (mm²) of the substrate contacted by the load-bearing fixture. 2 ) force (load).

[0312] As long as it can adhere to the substrate and the layer without causing damage to the substrate or the layer, there is no particular limitation on the pressure reduction, for example, 10~10,000 Pa.

[0313] When using an adhesive layer, the purpose is to remove the foreign matter from the coating used for removing foreign matter and the foreign matter that is the peeling residue of the adhesive layer in the fourth step, so that there are no foreign matter on the semiconductor substrate; the layer structure of the laminate manufactured in the first step can also be semiconductor substrate / coating for removing foreign matter / adhesive layer / support substrate.

[0314] Furthermore, when using an adhesive layer, the purpose is to remove the foreign matter from the coating used for foreign matter removal along with the foreign matter that serves as the peeling residue of the adhesive layer in the fourth step, ensuring that the support substrate is free of foreign matter. The layer structure of the laminate manufactured in the first step can also be semiconductor substrate / adhesive layer / coating for foreign matter removal / support substrate. In this case, the reuse of the support substrate becomes easier.

[0315] Furthermore, for the purpose of ensuring that the semiconductor substrate and the support substrate are free of foreign matter, the layer structure of the laminate manufactured in the first process may also be semiconductor substrate / coating for removing foreign matter / adhesive layer / coating for removing foreign matter / support substrate.

[0316] The laminate manufactured in the first step may also have a laser release layer between the semiconductor substrate and the support substrate. When the laminate has a laser release layer, in the third step, for example, the support substrate can be peeled off from the laminate by irradiating the laser release layer with a laser. The laser irradiates the laser release layer, for example, from the support substrate side, which is translucent with laser light.

[0317] When the laminate has a laser release layer, its purpose is to remove the foreign matter from the coating used for removing foreign matter along with the foreign matter that is the release residue of the laser release layer and the adhesive layer in the fourth step, so that the semiconductor substrate is free of foreign matter; the layer structure of the laminate manufactured in the first step may be, for example, semiconductor substrate / coating for removing foreign matter / laser release layer / adhesive layer / support substrate.

[0318] When the laminate has a laser release layer, its purpose is to remove the foreign matter from the coating used for removing foreign matter along with the release residue of the laser release layer and adhesive layer in the fourth step, so that the support substrate is free of foreign matter. The layer structure of the laminate manufactured in the first step can be, for example, semiconductor substrate / adhesive layer / laser release layer / coating for removing foreign matter / support substrate. At this time, the reuse of the support substrate becomes easy.

[0319] Furthermore, after the support substrate is peeled off from the laminate by irradiating the laser release layer with a laser, if laser release residue remains on the adhesive layer, foreign matter from the laser release layer may sometimes re-adhere to the semiconductor substrate or support substrate, or the cleaning time of the adhesive layer may become longer. To prevent these situations, the layer structure of the laminate manufactured in the first step for the purpose of removing laser release residue from the adhesive layer may be semiconductor substrate / adhesive layer / coating for foreign matter removal / laser release layer / support substrate, or semiconductor substrate / laser release layer / coating for foreign matter removal / adhesive layer / support substrate.

[0320] <Second Process>

[0321] The second step is to process the laminated body.

[0322] The processing in the second step is not particularly limited, and examples include, for instance, the polishing of the semiconductor substrate, the formation of through electrodes on the semiconductor substrate, and the connection processing between the semiconductor substrate and the second semiconductor substrate. The processing in the second step may include one or more of these processes.

[0323] <<Grinding Process>>

[0324] The grinding process of semiconductor substrates is not particularly limited, for example, any process that grinds the side of the semiconductor substrate opposite to the side with the coating used to remove foreign matter, so as to make the semiconductor substrate thinner. Examples include physical grinding using abrasives or grinding stones.

[0325] The polishing process can be performed using general polishing equipment used for polishing semiconductor substrates (such as silicon wafers).

[0326] By grinding, the thickness of the semiconductor substrate is reduced, resulting in a semiconductor substrate that has been thinned to the desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, and can be, for example, 30~300μm or 30~100μm.

[0327] <<Through-Electrode Formation Process>>

[0328] For example, sometimes through electrodes are formed on a polished semiconductor substrate to enable conduction between multiple thinned semiconductor substrates when stacking multiple thinned semiconductor substrates.

[0329] Therefore, a through electrode forming process can be included in the polished semiconductor substrate after the polishing process and before the stripping process.

[0330] There is no particular limitation on the method of forming through electrodes on a semiconductor substrate. Examples include forming through holes and filling the formed through holes with conductive material.

[0331] Through-holes can be formed, for example, by photolithography.

[0332] The through-hole is filled with a conductive material, for example, by plating.

[0333] Furthermore, in the second process, a through-electrode formation process can be performed instead of a grinding process.

[0334] <<Connection Processing>>

[0335] The connection process is, for example, the process of connecting a semiconductor substrate to a second semiconductor substrate.

[0336] The second semiconductor substrate is not particularly limited, and examples such as those listed in the description of the aforementioned semiconductor substrate can be included.

[0337] The connection process is performed, for example, under heating. Alternatively, the connection process is performed, for example, under pressure.

[0338] There are no particular restrictions on the heating temperature; for example, 100℃ to 350℃ can be listed.

[0339] In the connection process, for example, the wiring of the semiconductor substrate is electrically connected to the wiring of the second semiconductor substrate. Such a connection is performed, for example, by connecting the ends of the wiring to each other.

[0340] The material, shape, and structure of wiring in semiconductor substrates are not particularly restricted.

[0341] The material, shape, and structure of the wiring in the second semiconductor substrate are not particularly restricted.

[0342] <Step 3>

[0343] The third step is the process of peeling the support substrate from the laminate. This third step can also be referred to as the process of separating the semiconductor substrate from the support substrate.

[0344] Peeling methods may include, but are not limited to, solvent peeling, peeling by light irradiation (laser light, non-laser light), mechanical peeling by a mechanism with a sharp part (so-called debonding machine), and peeling by manually pulling apart the semiconductor substrate and the support substrate.

[0345] In particular, when the laminate contains an adhesive layer, and the adhesive layer is formed of an organic resin that has undergone modification due to light absorption to improve peelability, the adhesive layer can be peeled off, for example, by irradiating a laser from the support substrate side.

[0346] Laser irradiation can be performed using ultraviolet light with wavelengths of 190nm to 400nm or 190nm to 600nm (e.g., 308nm, 355nm, 532nm).

[0347] Stripping can be achieved by setting the processing energy density of pulsed laser to 50~500 mJ / cm². 2 Proceed from left to right.

[0348] When a laminate contains an adhesive layer, delamination typically occurs within the adhesive layer or at the interface between the adhesive layer and an adjacent substrate or layer (e.g., a coating for removing foreign matter). Delamination within the adhesive layer means that the adhesive layer cracks.

[0349] <Step 4>

[0350] The fourth step is to clean the semiconductor substrate or support substrate with a cleaning solution and remove the coating used to remove foreign matter.

[0351] On a semiconductor substrate that has been peeled off from a support substrate, for example, there may be a coating film for removing foreign matter. Therefore, this coating film for removing foreign matter is removed with a removal solution.

[0352] In step 4, for example, foreign matter is removed together with a coating used to remove foreign matter.

[0353] In the fourth step, for example, foreign matter that serves as peeling residue of the adhesive layer is removed together with the coating used to remove foreign matter.

[0354] The removal liquid can be exemplified by, for example, the removal liquid listed in the description of the coating film forming composition for removing foreign matter of the present invention.

[0355] The cleaning method is not particularly limited, and examples include immersing a semiconductor substrate with residual coating for removing foreign matter in a cleaning solution, and spraying a cleaning solution onto a semiconductor substrate with residual coating for removing foreign matter.

[0356] There are no particular restrictions on cleaning conditions, such as the temperature of the cleaning solution being 5°C to 50°C. Furthermore, the cleaning time can be appropriately selected from 2 to 500 seconds, or 3 to 400 seconds.

[0357] For example, a coating for removing foreign matter is preferably easily peeled off at room temperature (e.g., 25°C) using a commonly used 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0358] The following diagram illustrates an example of a method for manufacturing a processed semiconductor substrate.

[0359] First, prepare the semiconductor substrate 11 ( Figure 1A ).

[0360] Next, a coating 12 for removing foreign matter is formed on the semiconductor substrate 11. Figure 1B ).

[0361] Next, Figure 1B The semiconductor substrate 11 shown, which has a coating 12 for removing foreign matter, and the support substrate 14 having a flexible support 14A and an adhesive layer 14B, are configured such that the coating 12 for removing foreign matter and the adhesive layer 14B are bonded together facing each other. Figure 1C ).

[0362] Next, the side of the semiconductor substrate 11 opposite to the side of the coating 12 used for removing foreign matter is ground to thin the semiconductor substrate 11. Figure 1D ).

[0363] Next, the support substrate 14 is separated from the semiconductor substrate 11. Figure 1E and Figure 1F ).

[0364] On the separated foreign matter removal coating 12, there is a peeling residue 14C of adhesive layer 14B remaining. Figure 1F Therefore, the coating 12 used for removing foreign matter is removed by a removal solution. Figure 1G In this way, stripping residue 14C, which is a foreign object, can be prevented from remaining on the semiconductor substrate 11.

[0365] The following figure illustrates another example of a method for manufacturing a processed semiconductor substrate.

[0366] First, prepare a semiconductor substrate 1 with wiring 1A. Figure 2A ).

[0367] Next, a coating 2 for removing foreign matter is formed on the semiconductor substrate 1. Figure 2B ).

[0368] On the other hand, a glass substrate 4 on which an adhesive layer 3 is formed is prepared. Figure 2C ).

[0369] Then, Figure 2B The semiconductor substrate 1 shown has a coating 2 for removing foreign matter, and Figure 2C The glass substrate 4 shown, which has an adhesive layer 3, is configured such that the coating 2 for removing foreign matter and the adhesive layer 3 are bonded together facing each other. Figure 2D and Figure 2E ).

[0370] Next, the side of the semiconductor substrate 1 opposite to the side of the coating 2 used for removing foreign matter is ground to thin the semiconductor substrate 1. Figure 2F Then expose wiring 1A.

[0371] Next, Figure 2F The laminate shown, together with the second semiconductor substrate 5 having wiring 5A, is configured such that the side of the semiconductor substrate 1 opposite to the side of the coating 2 for removing foreign matter is bonded to the side of the second semiconductor substrate 5 where the wiring 5A is exposed. Figure 2G and Figure 2H ).

[0372] Next, the adhesive layer 3 and the glass substrate 4 are separated from the semiconductor substrate 1. Figure 2I Separation can be easily achieved, for example, by irradiating the adhesive layer 3 with a laser, thereby reducing the bonding strength of the adhesive layer 3.

[0373] On the separated foreign matter removal coating 2, there is a peeling residue 3A of the adhesive layer 3 remaining. Figure 2I and Figure 2J Therefore, the coating 2 used for removing foreign matter is removed by the removal solution. Figure 2K In this way, stripping residue 3A, which is a foreign object, can be prevented from remaining on the semiconductor substrate 1.

[0374] The method for manufacturing the processed semiconductor substrate of the present invention is suitable for use in hybrid bonding of semiconductor substrates to connect each other.

[0375] <Other Implementation Methods>

[0376] One embodiment of the present invention is a method for removing foreign matter already present on a semiconductor manufacturing substrate. For example, as disclosed in International Publications No. 2017 / 056746 and No. 2020 / 008965, a substrate processing film forming composition and a substrate processing method are disclosed in a process of forming a substrate processing film on the surface of a semiconductor substrate and removing foreign matter from the substrate surface. These methods can efficiently remove small particles from the substrate surface and easily remove the formed substrate processing film from the substrate surface. The coating film forming composition for removing foreign matter of the present invention can also be used in the same methods and applications as described above.

[0377] The above example is described in detail below. In this applicable example, the coating film forming composition for removing foreign matter of the present invention is used as a composition for forming a coating film on a semiconductor substrate. First, a coating film forming process is performed. That is, the coating film forming composition for removing foreign matter is applied to the semiconductor substrate to form a coating film. The semiconductor substrate may be in an unprocessed state or a so-called full-coverage substrate (planar) in which various films are formed. For the purpose of manufacturing semiconductor devices, it may be processed into the shape of wiring, etc. Examples of coating methods include spin coating, casting coating, roll coating, etc. Next, by heating (baking) and / or reducing pressure on the coating film, part or all of the solvent contained in the coating film is efficiently removed, thereby promoting the curing and / or hardening of the solid components contained in the coating film. Here, "curing" means solidification, and "curing" means that molecules are linked together to increase the molecular weight (e.g., crosslinking or polymerization). In this way, a coating film is formed. At this point, particles, such as those attached to circuits on a semiconductor substrate, are absorbed into the coating and efficiently separated from the circuits. Next, a coating removal process is performed. That is, by supplying a removal solution that dissolves the coating onto the coating, the coating is completely removed from the semiconductor substrate. As a result, the particles are removed from the semiconductor substrate along with the coating.

[0378] Example

[0379] Next, examples of synthesis and embodiments are listed to specifically illustrate the content of the present invention, but the present invention is not limited to these.

[0380] <Determination of molecular weight>

[0381] The weight-average molecular weights of the polymers shown in Synthetic Examples 1 to 7 below are determined by gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus manufactured by Tosoh Corporation, and the determination conditions are as follows.

[0382] • GPC tubing: Shodex KF803L, Shodex KF802, Shodex KF801 [Registered Trademark] (Showa Denko Co., Ltd.)

[0383] • Column temperature: 40℃

[0384] • Flow rate: 0.35 ml / min

[0385] • Eluent: Tetrahydrofuran (THF)

[0386] • Standard sample: Polystyrene (Tosoh Corporation)

[0387] <Synthesis example 1>

[0388] A solution of 5.00 g of 1-butoxyethyl methacrylate, 1.59 g of 4-hydroxyphenyl methacrylate (manufactured by Resonac Co., Ltd.), 0.13 g of dimethyl 2,2'-azobis(isobutyrate) (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.), and 21.52 g of methyl ethyl ketone was added dropwise to a dropping funnel and then to a reaction flask containing 5.38 g of methyl ethyl ketone. The mixture was heated and stirred at 80°C under nitrogen atmosphere for 16 hours. The reaction product solution was then added dropwise to a hexane solution. The resulting precipitate was collected by filtration and dried under vacuum at 40°C. The resulting reaction product corresponds to formula (X-1), and its weight-average molecular weight (Mw) determined by GPC to be 23,000 (converted to polystyrene). The values ​​in formula (X-1) represent molar percentages (%).

[0389]

[0390] <Synthesis example 2>

[0391] A solution of 5.00 g of 1-butoxyethyl methacrylate, 1.59 g of N-(4-hydroxyphenyl)methacrylamide, 0.33 g of dimethyl 2,2'-azobis(isobutyrate) (manufactured by Fujifilm and Kazuko Pure Chemicals Co., Ltd.), and 22.13 g of propylene glycol monomethyl ether was added dropwise to a dropping funnel and then added dropwise to a reaction flask containing 5.53 g of propylene glycol monomethyl ether under nitrogen atmosphere at 100°C, with stirring for 14 hours. Afterward, the reaction product solution was added dropwise to a hexane solution, and the resulting precipitate was separated by filtration and dried under vacuum at 40°C. The resulting reaction product corresponds to formula (X-2), and its weight-average molecular weight (Mw) determined by GPC to be 18000 (converted to polystyrene). The values ​​in formula (X-2) represent molar percentages (%).

[0392]

[0393] <Synthesis Example 3>

[0394] A solution of 5.00 g of 1-butoxyethyl methacrylate, 0.90 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.12 g of dimethyl 2,2'-azobis(isobutyrate) (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.), and 19.24 g of methyl ethyl ketone was added dropwise to a reaction flask containing 4.81 g of methyl ethyl ketone. The mixture was heated and stirred at 80°C under nitrogen atmosphere for 17 hours. The reaction product solution was then added dropwise to a methanol solution. The resulting precipitate was collected by filtration and dried under vacuum at 40°C. The resulting reaction product corresponds to formula (X-3), and its weight-average molecular weight (Mw) determined by GPC (converted to polystyrene) is 32,000. The values ​​in formula (X-3) represent molar percentages (%).

[0395]

[0396] <Synthesis Example 4>

[0397] A solution of 4.00 g of 1-butoxyethyl methacrylate, 1.77 g of 4-hydroxyphenyl methacrylate (manufactured by Resonac Co., Ltd.), 0.23 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.30 g of 2,2'-azobis(isobutyrate) dimethyl ester (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.), and 20.16 g of methyl ethyl ketone was added dropwise to a dropping funnel. The solution was then added dropwise to a reaction flask containing 5.04 g of methyl ethyl ketone under nitrogen atmosphere at 80°C, with stirring for 20 hours. Afterward, the reaction product solution was added dropwise to a hexane solution. The resulting precipitate was separated by filtration and dried under vacuum at 40°C. The resulting reaction product corresponds to formula (X-4), and its weight-average molecular weight (Mw) determined by GPC to be 16500 (converted to polystyrene). The values ​​in formula (X-4) represent molar percentages (%).

[0398]

[0399] <Synthesis example 5>

[0400] A solution of 3.00 g of 1-butoxyethyl methacrylate, 2.87 g of 4-hydroxyphenyl methacrylate (manufactured by Resonac Co., Ltd.), 0.29 g of dimethyl 2,2'-azobis(isobutyrate) (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.), and 19.72 g of methyl ethyl ketone was added dropwise to a reaction flask containing 4.93 g of methyl ethyl ketone. The mixture was heated and stirred at 80°C under nitrogen atmosphere for 16 hours. The reaction product solution was then added dropwise to a hexane solution. The resulting precipitate was collected by filtration and dried under vacuum at 40°C. The resulting reaction product corresponds to formula (X-5), and its weight-average molecular weight (Mw) determined by GPC (converted to polystyrene) is 11000. The values ​​in formula (X-5) represent molar percentages (%).

[0401]

[0402] <Synthesis example 6>

[0403] A solution of 4.00 g of 1-butoxyethyl methacrylate, 0.75 g of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.09 g of dimethyl 2,2'-azobis(isobutyrate) (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.), and 15.49 g of methyl ethyl ketone was added dropwise to a reaction flask containing 3.87 g of methyl ethyl ketone. The mixture was heated and stirred at 80°C under nitrogen atmosphere for 16 hours. The reaction product solution was then added dropwise to a methanol solution. The resulting precipitate was collected by filtration and dried under vacuum at 40°C. The resulting reaction product corresponds to formula (X-6), and its weight-average molecular weight (Mw) determined by GPC (converted to polystyrene) is 18000. The values ​​in formula (X-6) represent molar percentages (%).

[0404]

[0405] <Synthesis Example 7>

[0406] A solution of 4.00 g of 1-butoxyethyl methacrylate, 1.26 g of benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.11 g of dimethyl 2,2'-azobis(isobutyrate) (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.), and 17.17 g of methyl ethyl ketone was added dropwise to a dropping funnel in a reaction flask containing 4.29 g of methyl ethyl ketone. The mixture was heated and stirred at 80°C under nitrogen atmosphere for 16 hours. The reaction product solution was then added dropwise to a methanol solution. The resulting precipitate was collected by filtration and dried under vacuum at 40°C. The resulting reaction product corresponds to formula (X-7), and its weight-average molecular weight (Mw) determined by GPC (converted to polystyrene) is 20,000. The values ​​in formula (X-7) represent molar percentages (%).

[0407]

[0408] <Example 1>

[0409] In the reaction product obtained in Synthesis Example 1, 7.88 g of propylene glycol monomethyl ether solution (solid content 20 by mass) was mixed with 0.31 g of tetramethoxymethyl glycosuria, 0.01 g of pyridinium p-hydroxybenzenesulfonic acid and 91.79 g of propylene glycol monomethyl ether. The mixture was then filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a coating composition for removing foreign matter.

[0410] <Example 2>

[0411] In Synthesis Example 2, 7.88 g of a propylene glycol monomethyl ether solution (solid content 20 by mass) of the reaction product was mixed with 0.31 g of tetramethoxymethyl glycosuria, 0.01 g of pyridinium p-hydroxybenzenesulfonic acid, and 91.79 g of propylene glycol monomethyl ether. The mixture was then filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a coating-forming composition for removing foreign matter.

[0412] <Example 3>

[0413] In Synthesis Example 3, 7.88 g of a propylene glycol monomethyl ether solution (solid content 20 by mass) of the reaction product was mixed with 0.31 g of tetramethoxymethyl glycosuria, 0.01 g of pyridinium p-hydroxybenzenesulfonic acid, and 91.79 g of propylene glycol monomethyl ether. The mixture was then filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a coating-forming composition for removing foreign matter.

[0414] <Example 4>

[0415] After adding 90.50 g of propylene glycol monomethyl ether to 9.50 g of the propylene glycol monomethyl ether solution (solid content of 20 by mass) obtained in Synthesis Example 4, the mixture was filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a coating film forming composition for removing foreign matter.

[0416] <Example 5>

[0417] In Synthesis Example 5, 7.88 g of a propylene glycol monomethyl ether solution (solid content 20 by mass) of the reaction product was added with 0.31 g of tetramethoxymethyl glycourea, 0.01 g of pyridinium p-hydroxybenzenesulfonic acid, and 91.79 g of propylene glycol monomethyl ether. The solution was then filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a coating-forming composition for removing foreign matter.

[0418] <Example 6>

[0419] In Synthesis Example 6, 7.88 g of a propylene glycol monomethyl ether solution (solid content 20 by mass) of the reaction product was mixed with 0.31 g of tetramethoxymethyl glycosuria, 0.01 g of pyridinium p-hydroxybenzenesulfonic acid, and 91.79 g of propylene glycol monomethyl ether. The mixture was then filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a coating-forming composition for removing foreign matter.

[0420] <Example 7>

[0421] In Synthesis Example 7, 7.88 g of a propylene glycol monomethyl ether solution (solid content 20 by mass) of the reaction product was added with 0.31 g of tetramethoxymethyl glycourea, 0.01 g of pyridinium p-hydroxybenzenesulfonic acid, and 91.79 g of propylene glycol monomethyl ether. The solution was then filtered using a PTFE syringe filter with a pore size of 0.20 μm to prepare a coating-forming composition for removing foreign matter.

[0422] <Comparative Example 1>

[0423] The coating composition for removing foreign matter of Example 1, prepared as follows (WO2018 / 159665), was used as the coating composition for removing foreign matter of Comparative Example 1.

[0424] <<Synthesis of Polyamic Acid>>

[0425] 4.36 g of benzopyrenic acid dianhydride, 1.19 g of diaminobenzoic acid, and 4.26 g of 2,2-bis(3-amino-4-toluamide)hexafluoropropane were reacted in 55.6 g of propylene glycol monomethyl ether at 60 °C for 25 hours to obtain a solution containing polyamic acid [A].

[0426] Synthesis of Light-Absorbing Compounds

[0427] 19.0 g of 3,7-dihydroxy-2-naphthoic acid, 10 g of tris(2,3-epoxypropyl)isocyanurate and 0.552 g of benzyltriethylammonium chloride were reacted in 118 g of cyclohexanone at 130 °C for 24 hours to obtain a solution containing a light-absorbing compound [a].

[0428] <<Preparation of a Coating Composition for Removing Foreign Matter>>

[0429] A composition for removing foreign matter is prepared by adding 4.38 g of a solution [a] containing a light-absorbing compound, 0.630 g of tris(2,3-epoxypropyl)isocyanurate, 52.3 g of propylene glycol monomethyl ether, and 67.5 g of propylene glycol monomethyl ether acetate to a solution [A] containing 14.0 g of polyamic acid, and stirring at room temperature for 30 minutes.

[0430] [Soluble Resistance Test]

[0431] The coating compositions for removing foreign matter prepared in Examples 1 to 7 and Comparative Example 1 were each applied to silicon wafers using a spin coater. The coated silicon wafers were then heated at 205°C for 1 minute on a hot plate to form a coating with a thickness of 40 nm. Next, to confirm the solvent resistance of the coating, the coated silicon wafers were immersed in a mixed solvent obtained by mixing propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA) at a mass ratio of 7:3 (PGME to PEGMEA) for 1 minute, followed by spin drying and baking at 100°C for 30 seconds. The coating thickness before and after immersion in the mixed solvent was measured using an optical interferometer (product name: Nanospec 6100, manufactured by Nanometrics Japan Co., Ltd.).

[0432] Solvent resistance is evaluated by calculating and assessing the reduction rate (%) of the film thickness removed by solvent immersion using the following formula.

[0433] Film thickness reduction rate (%) = ((AB) ÷ A) × 100

[0434] A: Film thickness before solvent impregnation

[0435] B: Film thickness after solvent impregnation

[0436] The results are shown in Table 1. Furthermore, if the absolute value of the film thickness reduction rate is less than about 1%, it can be said to have sufficient solvent resistance.

[0437]

[0438] As can be seen from the above results, the films formed by the coating film forming compositions for removing foreign matter according to Examples 1 to 7 exhibit very small changes in film thickness even after immersion in solvent. Therefore, the films formed by the coating film forming compositions for removing foreign matter according to Examples 1 to 7 have sufficient solvent resistance.

[0439] [Alkali solubility test]

[0440] The coating compositions for removing foreign matter prepared in Examples 1 to 7 and Comparative Example 1 were each applied to silicon wafers using a spin coater (spin coating). The coated silicon wafers were heated at 205°C for 1 minute on a hot plate to form a coating with a thickness of 40 nm. Next, to confirm the alkali solubility of the coating, the coated silicon wafers were immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds. The coating thickness before and after immersion in the alkali solvent was measured using an optical interferometer (product name: Lambda Ace VM-3210, manufactured by SCREEN Control Co., Ltd.).

[0441] The evaluation of alkali solubility is performed by calculating and evaluating the film thickness reduction rate (%) of the coating film removed by solvent impregnation using the following formula.

[0442] Film thickness reduction rate (%) = ((AB) ÷ A) × 100

[0443] A: Film thickness before solvent impregnation

[0444] B: Film thickness after solvent impregnation

[0445] The results are shown in Table 2. Furthermore, if the film thickness reduction rate is more than 99%, it can be said to have sufficient alkali solubility.

[0446]

[0447] The results above confirm that the coating film forming compositions for removing foreign matter in Examples 1 to 7 are resistant to organic solvents and soluble in alkaline solvents.

[0448] [Defect Inspection and Evaluation After Development Processing]

[0449] The coating composition for removing foreign matter prepared in Example 1 was applied to a silicon wafer using a spin coater. The sample was then heated at 205°C for 1 minute to form a coating (40 nm thick). A semiconductor wafer bonding sheet was then attached to the coating of the sample using a manual wafer mounter (manufactured by Omiya Industrial Co., Ltd.). Next, the semiconductor wafer bonding sheet was irradiated with ultraviolet light (500 mJ / cm²) using a manual UV irradiation device (manufactured by Omiya Industrial Co., Ltd.). 2 The adhered film was peeled off. Further, the entire surface of the silicon wafer was evaluated using a defect inspection apparatus (KLA-Tencor Corporation, Surfscan SP2XP). The coating of this sample was then immersed in a 2.38% tetramethylammonium hydroxide aqueous solution (NMD-3, Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds. The silicon wafer, after the coating had completely dissolved in NMD-3, was again evaluated using the defect inspection apparatus (KLA-Tencor Corporation, Surfscan SP2XP) to assess the removability of the cleaned coating. In addition, a sample of a silicon wafer was prepared using the same procedure but without a coating containing the coating-forming composition for removing foreign matter, as a comparative example. Comparing the number of defects with a size of 100 nm or larger, it was found that when using the coating composition for removing foreign matter prepared in Example 1, a large number of defects were detected on the coating after the adhesive sheet was peeled off. However, the defects from the adhesive sheet could be removed after dissolving the coating with NMD-3. On the other hand, in the comparative example, even after impregnation with NMD-3, the number of defects on the silicon wafer remained unchanged after the adhesive sheet was peeled off, and the defects from the adhesive sheet could not be removed.

[0450] Based on the above results, it can be concluded that by using the coating composition for removing foreign matter of Example 1, defects from adhesive sheets can be removed.

[0451] Explanation of symbols in attached drawings

[0452] 1: Semiconductor substrate

[0453] 1A: Wiring

[0454] 2: Coating for removing foreign matter

[0455] 3: Adhesive layer

[0456] 4: Glass substrate

[0457] 5: Second semiconductor substrate

[0458] 5A: Wiring

[0459] 11: Semiconductor substrate

[0460] 12: Coating for removing foreign matter

[0461] 14: Supporting substrate

[0462] 14A: Flexible support

[0463] 14B: Adhesive layer

[0464] 14C: Stripping residue

Claims

1. A coating film forming composition for removing foreign matter, comprising a polymer and a solvent, and capable of forming a coating film removable by a removal liquid. The polymer is a polymer containing structural units represented by the following formula (1). In equation (1), R 1 R represents an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. 2 R represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. 3 R indicates an alkyl group with 1 to 10 carbon atoms that can be substituted, or an aromatic hydrocarbon group that can be substituted. 2 and R 3 It can also be used with R 2 and R 3 The carbon and oxygen atoms together form a ring, which may also contain heteroatoms other than the oxygen atoms.

2. The composition of claim 1, wherein the polymer is a polymer further comprising structural units derived from (meth)acrylate compounds, (meth)acrylamide compounds, or styrene compounds.

3. The composition according to claim 1, wherein the removal liquid is an alkaline removal liquid.

4. The composition of claim 1, wherein the removal liquid is a removal liquid containing 50% by mass or more of an organic solvent.

5. The composition of claim 1, wherein it contains at least one of a crosslinking agent and an additive.

6. A coating for removing foreign matter, formed from the composition of any one of claims 1 to 5.

7. A semiconductor substrate having the coating for removing foreign matter as described in claim 6.

8. A method for manufacturing a processed semiconductor substrate, comprising the following steps: The first step of manufacturing a laminate involves bonding the semiconductor substrate as described in claim 7 to a support substrate through the coating for removing foreign matter. The second process in the fabrication of this laminated body The third step of peeling the support substrate from the laminate, and The fourth step involves cleaning the semiconductor substrate or the support substrate with a removal solution and removing the coating used to remove foreign matter.

9. The method for manufacturing a processed semiconductor substrate as described in claim 8, wherein in the fourth step, foreign matter is removed together with the coating used for removing foreign matter.

10. The method for manufacturing a processed semiconductor substrate as described in claim 8, wherein the first step is a step of bonding the semiconductor substrate and the support substrate through the coating and adhesive layer for removing foreign matter to manufacture a laminate.

11. The method for manufacturing a semiconductor substrate as claimed in claim 10, wherein in the fourth step, foreign matter that serves as peeling residue of the adhesive layer is removed together with the coating used for removing foreign matter.

12. The method of manufacturing a processed semiconductor substrate as claimed in claim 8, wherein the processing includes the step of connecting the semiconductor substrate to a second semiconductor substrate.

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