Coating film forming 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 solution. [In formula (A), R] 11 Represents a single bond or a divalent group with 1 to 4 carbon atoms. R 12 Indicates a hydrogen atom, hydroxyl group, or methyl group. * Indicates a bond connection site.

Description

Technical Field

[0001] The present invention relates to a coating composition for removing foreign matter that can easily prevent foreign matter residue 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 fabrication, etc. are performed, and then the support substrate is peeled off to obtain the desired semiconductor substrate.

[0003] In such processes, foreign matter may sometimes be generated, which needs to be removed. Therefore, for example, Patent Documents 1 and 2 disclose a substrate processing film forming composition and a substrate processing method that can efficiently remove tiny particles from the substrate surface and easily remove the formed substrate processing film from the substrate surface in a process for forming a substrate processing film on the surface of a semiconductor substrate 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 polymer-containing liquid composition, 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 is used. Then, a process of peeling 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 residue is particularly significant when the adhesive layer is formed directly on the surface of a semiconductor substrate on which wiring or the like 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, bonding agents, 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 removability, and a method for manufacturing a coating film for removing foreign matter using the composition, a semiconductor substrate, and a processed semiconductor substrate.

[0013] Methods for solving problems

[0014] The inventors conducted in-depth research to solve the above-mentioned problems and found that the above-mentioned problems could be solved, thus completing 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 solution. The polymer has a partial structure as shown in formula (A).

[0017]

[0018] In formula (A), R 11 Represents a single bond or a divalent group with 1 to 4 carbon atoms. R 12 Indicates a hydrogen atom, hydroxyl group, or methyl group. * Indicates a bond connection site.

[0019] [2] According to the composition described in [1], R in formula (A) 11 The divalent group represents a carbon group having 1 to 4 carbon atoms, and the divalent group has a hydroxyl group.

[0020] [3] According to the composition described in [1] or [2], R in formula (A) 11 Represents -CH(OH)-, R 12 It represents a hydrogen atom.

[0021] The composition of any one of [4] [1] to [3], wherein the polymer has a structural unit as shown in the following formula (A-1).

[0022]

[0023] (In formula (A-1), A) 1 A 2 A 3 A4 A 5 and A 6 Each can independently represent a hydrogen atom, a methyl group, or an ethyl group; Q represents a divalent organic group. R 11 Represents a single bond or a divalent group with 1 to 4 carbon atoms. R 12 (This indicates a hydrogen atom, hydroxyl group, or methyl group.)

[0024] [5] According to the composition described in [4], Q in the formula (A-1) is represented by either of the following formulas (A-11) and (A-12).

[0025]

[0026] (In formula (A-11), X) 1 This represents the divalent group shown in formula (A-11-1), formula (A-11-2), or formula (A-11-3). 1 and Z 2 Each can independently represent a single bond or a divalent group as shown in the following formula (A-11-4). * indicates a bond connection site.

[0027] In equation (A-12), Q 1 This indicates a divalent group having an aromatic or aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. * indicates a bond connection site.

[0028] (In formulas (A-11-1) to (A-11-3), R) 1 ~R 5 Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from alkyl groups having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R 1 With R 2 They can combine to form rings with 3 to 6 carbon atoms. 3 With R 4 They can combine to form rings with 3 to 6 carbon atoms. * indicates a bond connection site. *1 indicates a bond connection site with a carbon atom. *2 indicates a bond connection site with a nitrogen atom.

[0029] (In formula (A-11-4), m1 is an integer from 1 to 4, and m2 is 0 or 1. *3 indicates the bond connection site with a nitrogen atom. *4 indicates the bond connection site with a carbon atom.)

[0030] [6] According to the composition described in [5], Q in the formula (A-12) 1 Expressed by any of the following formulas (A-12-1) to (A-12-4).

[0031]

[0032] (In formulas (A-12-1) to (A-12-4), R) 31 ~R 36 Each of these groups independently represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkenyloxy group with 2 to 6 carbon atoms, alkynyloxy group with 2 to 6 carbon atoms, acyl group with 2 to 6 carbon atoms, aryloxy group with 6 to 12 carbon atoms, arylcarbonyl group with 7 to 13 carbon atoms, or aralkyl group with 7 to 13 carbon atoms. * indicates a bond connection site.

[0033] In equation (A-12-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. When R 31 When there are two or more R's 31 They can be the same or different.

[0034] In formula (A-12-2), Z 1 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n12 and n13 each independently represent integers from 0 to 4. When R 32 When there are two or more R's 32 They can be the same or different. When R 33 When there are two or more R's 33 They can be the same or different.

[0035] In formula (A-12-3), Y 1 and Y 2 Each independently represents a single bond or an alkylene group with 1 to 6 carbon atoms. n14 represents an integer from 0 to 4. When R 34 When there are two or more R's 34 They can be the same or different.

[0036] In formula (A-12-4), Z 2This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n15 and n16 each independently represent integers from 0 to 4. When R 35 When there are two or more R's 35 They can be the same or different. When R 36 When there are two or more R's 36 They can be the same or different.

[0037] [7] The composition according to any one of [1] to [6], wherein the removal liquid is an alkaline removal liquid.

[0038] [8] The composition according to any one of [1] to [7], wherein the removal liquid is a removal liquid containing 50% by mass or more of an organic solvent.

[0039] [9] The composition according to [1] comprises at least one of a crosslinking agent and an additive.

[0040]

[10] A coating for removing foreign matter formed from the composition of any one of [1] to [9].

[0041]

[11] A semiconductor substrate having the coating for removing foreign matter as described in

[10] .

[0042]

[12] A method for manufacturing a processed semiconductor substrate, comprising: The first step involves bonding the semiconductor substrate described in

[11] to the support substrate through the coating used for removing foreign matter, thereby manufacturing a laminate. The second process for processing the 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 to remove the coating used for removing foreign matter.

[0043]

[13] In the method for manufacturing the processed semiconductor substrate according to

[12] , in the fourth step, foreign matter is removed together with the coating for removing foreign matter.

[0044]

[14] According to the method for manufacturing a processed semiconductor substrate as described in

[12] , the first step is to bond the semiconductor substrate and the support substrate through the coating and adhesive layer for removing foreign matter, thereby manufacturing a laminate.

[0045]

[15] According to the semiconductor substrate manufacturing method described in

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

[0046]

[16] The method for manufacturing the processed semiconductor substrate according to

[12] includes connecting the semiconductor substrate to a second semiconductor substrate.

[0047] The effects of the invention

[0048] In addition, according to the present invention, a coating film forming composition for removing foreign matter that can produce a coating film for removing foreign matter with solvent resistance and easy removability can be provided, as well as a method for manufacturing a coating film for removing foreign matter using the composition, a semiconductor substrate, and a processed semiconductor substrate. Attached Figure Description

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

[0050] Figure 1B This is a schematic cross-sectional view (2) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0051] Figure 1C This is a schematic cross-sectional view (3) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0052] Figure 1D This is a schematic cross-sectional view (4) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0053] Figure 1E This is a schematic cross-sectional view (5) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0054] Figure 1F This is a schematic cross-sectional view (6) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0055] Figure 1G This is a schematic cross-sectional view (7) illustrating an example of a method for manufacturing a processed semiconductor substrate.

[0056] Figure 2A This is a schematic cross-sectional view (1) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0057] Figure 2B This is a schematic cross-sectional view (2) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0058] Figure 2C This is a schematic cross-sectional view (3) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0059] Figure 2D This is a schematic cross-sectional view (4) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0060] Figure 2E This is a schematic cross-sectional view (5) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0061] Figure 2F This is a schematic cross-sectional view (6) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0062] Figure 2G This is a schematic cross-sectional view (7) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0063] Figure 2H This is a schematic cross-sectional view (8) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0064] Figure 2I This is a schematic cross-sectional view (9) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0065] Figure 2J This is a schematic cross-sectional view (10) illustrating another example of a method for manufacturing a processed semiconductor substrate.

[0066] Figure 2K This is a schematic cross-sectional view (11) illustrating another example of a method for manufacturing a processed semiconductor substrate. Detailed Implementation

[0067] (A coating-forming composition for removing foreign matter)

[0068] The coating composition for removing foreign matter of the present invention contains a polymer and a solvent.

[0069] The coating-forming composition for removing foreign matter is preferably capable of forming a coating that can be removed by a removal solution.

[0070] <Polymer>

[0071] The polymer has a partial structure as shown in formula (A).

[0072]

[0073] In formula (A), R 11 Represents a single bond, or a divalent group with 1 to 4 carbon atoms. R 12 Indicates a hydrogen atom, hydroxyl group, or methyl group. * Indicates a bond connection site.

[0074] By having a partial structure as shown in formula (A) by means of a polymer, a coating obtained from a coating-forming composition for removing foreign matter is endowed with solvent resistance and easy removability.

[0075] The polymer preferably has the structural unit shown in formula (A-1) below. Furthermore, for example, the partial structure shown in formula (A) is a part of the structural unit shown in formula (A-1) below.

[0076]

[0077] (In formula (A-1), A) 1 A 2 A 3 A 4 A 5 and A 6 Each is an independent hydrogen atom, methyl or ethyl group, and Q represents a divalent organic group. R 11 Represents a single bond or a divalent group with 1 to 4 carbon atoms. R 12 (This indicates a hydrogen atom, hydroxyl group, or methyl group.)

[0078] <<R 11 >>

[0079] In equations (A) and (A-1), R 11 It represents a single bond or a divalent group with 1 to 4 carbon atoms.

[0080] R 11 It has 1 to 4 carbon atoms, which can be 1 to 3, 1 or 2, or 1.

[0081] As R 11 Examples include divalent hydrocarbon groups with 1 to 4 carbon atoms that can be replaced by hydroxyl groups.

[0082] In R 11 In the case of a hydroxyl group, R 11 The number of hydroxyl groups it possesses is, for example, R 11 It has fewer than 100 carbon atoms.

[0083] As R 11 From the viewpoint of properly obtaining the effects of the present invention, it is preferable to have a divalent group representing 1 to 4 carbon atoms, and the divalent group preferably has a hydroxyl group.

[0084] As R 11 From the viewpoint of properly obtaining the effects of the present invention, it is more preferable to represent -CH(OH)-.

[0085] <<R 12 >>

[0086] In equations (A) and (A-1), R12 It represents a hydrogen atom, a hydroxyl group, or a methyl group, preferably a hydrogen atom or a hydroxyl group.

[0087] As part of the structure shown in equation (A), the following structures can be listed as examples.

[0088]

[0089] * indicates the key connection point.

[0090] <<Q>>

[0091] In formula (A-1), Q represents a divalent organic group. The divalent organic group is not particularly limited, but a divalent organic group having a heteroatom is preferred, and a divalent organic group having a nitrogen atom and an oxygen atom is more preferred. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, etc.

[0092] The number of carbon atoms in the divalent organic group is not particularly limited, but it is preferred to have 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms.

[0093] As for Q, from the viewpoint of properly obtaining the effects of the present invention, it is preferred to express it as either of the following formulas (A-11) and (A-12).

[0094]

[0095] (In formula (A-11), X) 1 This represents the divalent group shown in formula (A-11-1), formula (A-11-2), or formula (A-11-3). 1 and Z 2 Each can independently represent a single bond or a divalent group as shown in the following formula (A-11-4). * indicates a bond connection site.

[0096] In equation (A-12), Q 1 This indicates a divalent group having an aromatic or aliphatic hydrocarbon ring. n1 and n2 each independently represent 0 or 1. * indicates a bond connection site.

[0097] (In formulas (A-11-1) to (A-11-3), R) 1 ~R 5Each of the following groups independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group having 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from alkyl groups having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. R 1 With R 2 They can combine to form rings with 3 to 6 carbon atoms. 3 With R 4 They can combine to form rings with 3 to 6 carbon atoms. * indicates a bond connection site. *1 indicates a bond connection site with a carbon atom. *2 indicates a bond connection site with a nitrogen atom.

[0098] (In formula (A-11-4), m1 is an integer from 1 to 4, and m2 is 0 or 1. *3 represents the bond connection site with a nitrogen atom. *4 represents the bond connection site with a carbon atom.)

[0099] Q in equation (A-12) 1 It is preferred to express it using any of the following formulas (A-12-1) to (A-12-4).

[0100]

[0101] (In formulas (A-12-1) to (A-12-4), R) 31 ~R 36 Each of these groups independently represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkenyloxy group with 2 to 6 carbon atoms, alkynyloxy group with 2 to 6 carbon atoms, acyl group with 2 to 6 carbon atoms, aryloxy group with 6 to 12 carbon atoms, arylcarbonyl group with 7 to 13 carbon atoms, or aralkyl group with 7 to 13 carbon atoms. * indicates a bond connection site.

[0102] In equation (A-12-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. When R 31 When there are two or more R's 31 They can be the same or different.

[0103] In formula (A-12-2), Z 1 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n12 and n13 each independently represent integers from 0 to 4. When R32 When there are two or more R's 32 They can be the same or different. When R 33 When there are two or more R's 33 They can be the same or different.

[0104] In formula (A-12-3), Y 1 and Y 2 Each independently represents a single bond or an alkylene group with 1 to 6 carbon atoms. n14 represents an integer from 0 to 4. When R 34 When there are two or more R's 34 They can be the same or different.

[0105] In formula (A-12-4), Z 2 This indicates a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms. n15 and n16 each independently represent integers from 0 to 4. When R 35 When there are two or more R's 35 They can be the same or different. When R 36 When there are two or more R's 36 They can be the same or different.

[0106] As Q in equation (A-11), examples of the following structures can be cited.

[0107]

[0108] * indicates the key connection point.

[0109] When the polymer has the structural unit shown in formula (A-1), the mass ratio of the structural unit shown in formula (A-1) in the polymer is not particularly limited, but is preferably 50% to 100% by mass, more preferably 75% to 100% by mass, and particularly preferably 90% to 100% by mass.

[0110] The method for manufacturing the polymer is not particularly limited, but examples include, for instance, reacting a dicarboxylic acid represented by formula (A1) with a dialkoxy compound represented by formula (A2). In this case, a polymer having the structural unit represented by formula (A-1) is obtained.

[0111] Catalysts for activating alkoxy groups include, for example, quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected from 0.1% to 10% by mass relative to the total mass of the polymer feedstock used in the reaction. The optimal conditions for the polymerization reaction can be selected from, for example, a range of 80–160°C and 2–50 hours.

[0112]

[0113] (In formula (A1), R) 11 and R 12 respectively with R in equation (A-1) 11 and R12 The meaning is the same.

[0114] Examples of dicarboxylic acids represented by formula (A1) include tartaric acid, malic acid, hydroxymalonic acid, citrate, dihydroxymalonic acid, and mucilage.

[0115]

[0116] (In formula (A2), A) 1 A 2 A 3 A 4 A 5 A 6 Q and A in equation (A-1) are respectively 1 A 2 A 3 A 4 A 5 A 6 (Same meaning as Q.)

[0117] The weight-average molecular weight of the polymer is not particularly limited, but is preferably 700 to 15,000, more preferably 900 to 10,000. Furthermore, the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0118] 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.

[0119] <<Removal Solution>>

[0120] As a removal liquid, there are no particular limitations as long as it can remove the coating formed by the coating-forming composition for removing foreign matter.

[0121] The coating is formed, for example, on a semiconductor substrate. Removal here refers to removal from the semiconductor substrate.

[0122] 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.

[0123] The removal solution may contain water or organic solvents.

[0124] The removal solution can be a removal solution containing more than 50% by mass of organic solvent.

[0125] 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.

[0126] Examples of removal solutions include alkaline removal solutions and acidic removal solutions.

[0127] Alkaline removal solutions contain alkalis. Examples of alkalis include ammonia, inorganic alkaline compounds, quaternary ammonium hydroxide, amines, and hydrazine.

[0128] Alkaline removal solutions can be developing solutions or cleaning solutions used in semiconductor manufacturing processes, and they are also alkaline. For example, NMD-3 (2.38% tetramethylammonium hydroxide aqueous solution, manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be listed as a developing solution.

[0129] 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, and potassium borate.

[0130] Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, and choline.

[0131] Examples of amines include ethanolamine, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methyl diethylamine, dimethylethanolamine, triethanolamine, ethylenediamine, etc.

[0132] Examples of hydrazine include hydrazine monohydrate.

[0133] In addition, the alkaline removal solution can also be SC-1 (ammonia-hydrogen peroxide solution).

[0134] The acid removal solution contains acid. 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.

[0135] Acid removal solutions can be, for example, aqueous solutions containing dilute hydrofluoric acid.

[0136] 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.

[0137] <Solvent>

[0138] 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.

[0139] These solvents can be used alone or in combination of two or more.

[0140] Furthermore, it can be used in combination with high-boiling-point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate.

[0141] A film-forming composition for removing foreign matter can be easily prepared, for example, by uniformly mixing the components, and can be dissolved in a suitable solvent for use in solution form.

[0142] The coating-forming composition for removing foreign matter prepared in this way is preferably used after filtration using a filter with a pore size of about 0.2 μm. The coating-forming composition for removing foreign matter prepared in this way also exhibits excellent long-term storage stability at room temperature.

[0143] The proportion of solid components in the film-forming composition for removing foreign matter is not particularly limited as long as all components are uniformly dissolved, for example, 0.5% to 50% by mass, or, for example, 1% to 30% by mass. The solid components referred to here are those after removing the solvent components from all the components of the film-forming composition for removing foreign matter.

[0144] 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.

[0145] 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, in which 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 bonding and peeling process of the wafers is removed.

[0146] The coating used for removing foreign matter can also be used to remove foreign matter that is already present on a semiconductor substrate.

[0147] The term "coating for removing foreign matter dissolves in the removal solution" means that when the coating is immersed or cleaned with the removal solution, it dissolves in the solution and becomes non-existent on the substrate or other adherent material. In this invention, "dissolution" refers to the removal of at least 90% (i.e., the remaining film thickness is less than 10% of the initial film thickness), or at least 95% (i.e., the remaining film thickness is less than 5% of the initial film thickness), or at least 99% (i.e., the remaining film thickness is less than 1% of the initial film thickness), and most preferably 100% (i.e., the remaining film thickness is 0% of the initial film thickness (no remaining film)).

[0148] The composition preferably contains at least one of a crosslinking agent and an additive.

[0149] <Cross-linking agent>

[0150] As a crosslinking agent, it is not particularly limited.

[0151] Crosslinking agents have a different structure from polymers.

[0152] As a crosslinking agent, amino plastic crosslinking agents and phenolic plastic crosslinking agents are preferred.

[0153] Amino plastic crosslinking agents are addition condensation products of amino compounds such as melamine or guanidine with formaldehyde.

[0154] Phenolic plastic crosslinking agents refer to the addition condensation products of compounds with phenolic hydroxyl groups and formaldehyde.

[0155] Examples of crosslinking agents include compounds having two or more of the following structures.

[0156]

[0157] (In the structure, R) 101 This indicates a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxyalkyl group with 2 to 6 carbon atoms. * indicates a bond connection site.

[0158] The bond connection site is, for example, a nitrogen atom or a carbon atom that forms an aromatic hydrocarbon ring.

[0159] As R 101 Preferably, it contains hydrogen atoms, methyl, ethyl or groups represented by the following structures.

[0160]

[0161] (In the structure, R) 102 * Indicates a hydrogen atom, methyl group, or ethyl group. * Indicates a bond connection site.

[0162] Preferred crosslinking agents include melamine compounds, guanidine compounds, glycourea compounds, urea compounds, and compounds with phenolic hydroxyl groups. These compounds can be used alone or in combination of two or more.

[0163] Examples of melamine compounds include, for example, 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.

[0164] Examples of guanidine compounds include, for example, 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.

[0165] Examples of glycourea compounds include, for example, 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.

[0166] Alternatively, as a glycourea compound, it may be, for example, a glycourea derivative as shown in the following formula (1E).

[0167]

[0168] (In formula (1E), each of the four R1s independently represents a methyl or ethyl group, and each of the R2 and R3 independently represents an alkyl or phenyl group with 1 to 4 carbon atoms.)

[0169] Examples of glycourea derivatives represented by formula (1E) include compounds represented by formulas (1E-1) to (1E-6) below.

[0170]

[0171] The glycourea derivative shown in formula (1E) can be obtained, for example, by reacting the glycourea derivative shown in formula (2E) with at least one compound shown in formula (3d).

[0172]

[0173] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0174] (In formula (3d), R1 represents methyl or ethyl.)

[0175] Examples of compounds that are glycourea derivatives represented by formula (2E) include, for example, compounds represented by formulas (2E-1) to (2E-4). Furthermore, examples of compounds that are compounds represented by formula (3d) include, for example, compounds represented by formulas (3d-1) and (3d-2).

[0176]

[0177] Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds of tetrahydroxymethylurea in which one to four hydroxymethyl groups are methoxymethylated, or mixtures thereof, and tetramethoxyethylurea.

[0178] Examples of compounds having phenolic hydroxyl groups include, for example, compounds represented by formula (G-1) or formula (G-2) below.

[0179]

[0180] In equations (G-1) and (G-2), Q 1 It represents a single bond or an m1-valent organic group.

[0181] R 1 and R 4 They respectively 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.

[0182] R 2 and R 5 These represent hydrogen atoms or methyl groups, respectively.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] m1 represents an integer from 2 to 10.

[0187] Furthermore, as compounds having phenolic hydroxyl groups, examples include compounds shown in formula (G-3) or formula (G-4) below.

[0188] The compound represented by formula (G-1) or (G-2) can be obtained by reacting the compound represented by formula (G-3) or (G-4) below with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0189]

[0190] In equations (G-3) and (G-4), Q 2 It represents a single bond or an m2 valence organic group.

[0191] R 8 R 9 R 11 and R 12These represent hydrogen atoms or methyl groups, respectively.

[0192] 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.

[0193] 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.

[0194] n 13 For 1≤n 13 Integers ≤3, n 14 For 1≤n 14 Integers ≤ 4, n 15 For 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.

[0195] m2 represents an integer from 2 to 10.

[0196] As Q 2 Examples of m2-valent organic groups include, for example, m2-valent organic groups with 1 to 4 carbon atoms.

[0197] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0198]

[0199] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0200]

[0201] The above-mentioned compounds are available as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, Asahi Organic Materials Co., Ltd.'s trade name TMOM-BP can be cited as an example of such a product.

[0202] Among these, glycourea compounds are 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, and more preferably tetramethoxymethylglycourea.

[0203] The molecular weight of the crosslinking agent is not particularly limited, but is preferably 500 or less.

[0204] The content of the crosslinking agent, relative to 100 parts by weight of the polymer, is, for example, 5 to 70 parts by weight, or 5 to 60 parts by weight, preferably 5 to 45 parts by weight. Regarding the content of the crosslinking agent, from the viewpoint of the degree of curing of the coating and prevention of intermingling with the adhesive layer, it 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.

[0205] <Additives>

[0206] 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.

[0207] The solidification catalyst can use either thermally generated acid-generating agents or photo-generating acid-generating agents, with thermally generated acid-generating agents being preferred.

[0208] Examples of heat-generating acid agents include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium p-toluenesulfonate), pyridinium hydroxybenzenesulfonate, pyridinium p-hydroxybenzenesulfonate (pyridinium p-hydroxybenzenesulfonate salt), pyridinium trifluoromethanesulfonate, 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, N-methylmorpholine-5-sulfosalicylic acid, and other sulfonic acid and carboxylic acid compounds.

[0209] Examples of photoacid-generating agents include, for example, onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0210] Examples of ononium salt compounds include, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butyl sulfonate, diphenyliodonium perfluoron-octyl sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butyl sulfonate, triphenylsulfonium camphor sulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0211] Examples of sulfonylimide compounds include, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0212] Examples of disulfonyldiazomethane compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0213] The curing catalyst can be used alone or in combination of two or more.

[0214] 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.

[0215] As a light-absorbing compound, there are no particular limitations as long as the compound absorbs the light-absorbing 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 used for removing foreign matter in the removal solution, compounds with phenolic hydroxyl groups, carboxyl groups, or sulfonic acid groups are preferred.

[0216] 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-aminonaphthol, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 6-bromo-2-hydroxynaphthoic acid, 1,2-naphthoic acid, 1,3-naphthoic acid, 1,4-naphthoic acid, 1,5-naphthoic acid, 1,6-naphthoic acid, 1,7-naphthoic acid, 1,8-naphthoic acid, and 1,8-naphthoic acid. -Naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 1-bromo-2-naphthoic acid 1-Hydroxy-3-naphthoic acid, 1-bromo-4-hydroxy-3-naphthoic acid, 1,6-dibromo-2-hydroxy-3-naphthoic acid, 3-hydroxy-7-methoxy-2-naphthoic acid, 1-amino-2-naphthol, 1,5-dimercaptonaphthalene, 1,4,5,8-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-naphthoic acid Methyl naphthanoate, methyl 3-hydroxy-7-methoxy-2-naphthanoate, methyl 3,7-dihydroxy-2-naphthanoate, 2,4-dibromo-1-naphthol, 1-bromo-2-naphthol, 2-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.

[0217] 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, benzoyltetracycline, 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.

[0218] In addition, in order to suppress sublimation during firing of the coating used to remove foreign matter, these light-absorbing compounds can be used in combination with polymers or compounds having one or more reactive groups.

[0219] For example, in the case of light-absorbing compounds having carboxyl or phenolic hydroxyl groups, compounds obtained by reacting with multifunctional epoxy compounds such as tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris(p-(2,3-epoxypropoxy)phenyl)propane, 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, as well as polymers containing structures having epoxy groups such as glycidyl methacrylate, can be used.

[0220] 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 mass of the polymer is, for example, 1 to 300 parts by mass, or 1 to 200 parts by mass, or, for example, 1 to 100 parts by mass, or 5 to 100 parts by mass. When the content of the light-absorbing compound is 300 parts by mass or less relative to 100 parts by mass of the polymer, the coating for removing foreign matter has excellent solubility in the removal liquid, or the coating for removing foreign matter is less likely to cause miscibility with the adhesive layer.

[0221] In coating-forming compositions for removing foreign matter, polyphenolic compounds and carboxyl-containing compounds may be added to promote dissolution in the removal solution. Such compounds are not particularly limited, but examples include tris(hydroxyphenyl)ethane, bisphenol-A, bisphenol-S, 4,4'-isopropylidene di-o-cresol, 5-tert-butylpyrogallol, hexafluorobisphenol-A, 3,3,3',3'-tetramethyl-1,1'-spirobinodinium-5,5',6,6'-tetraol, 4,4'-(9-fluoreneyl)diphenol, bisphenol-AP, and bisphenol-P. 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. Polycarboxylic acids such as dicarboxylic acid, 3,4-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,2,3,4-cyclohexane tetracarboxylic acid, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthous succinic acid; and polymers containing carboxylic acids or carboxylic anhydrides such as polyacrylic acid, polymethacrylic acid, polyamic acid, and polymaleic anhydride. As the amount of the above-mentioned compound added, it is used as needed in the solid components of the coating film forming composition for removing foreign matter, for example, in an amount of 20% by mass or less, preferably 10% by mass or less.

[0222] In addition, in the coating composition for removing foreign matter, in order to adjust the dissolution rate in the removal liquid, a compound having a carboxyl 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.

[0223] 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.

[0224] These compounds can readily generate carboxyl or phenolic hydroxyl groups in the presence of acid, enabling compounds with improved solubility in alkaline removal solutions.

[0225] Therefore, these compounds are preferably added together with a photoacid generator to 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 the above-mentioned compounds having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid and a photoacid generator, in the exposed portions, the acid generated from the photoacid generator through exposure regenerates the carboxyl or phenolic hydroxyl groups of the compounds having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid. As a result, the solubility of the exposed portions of the coating for removing foreign matter in an alkaline removal solution is improved.

[0226] When using the above-mentioned compounds having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid, the content of such compounds relative to 100 parts by mass of the polymer is, for example, 50 to 1 part by mass, or 30 to 5 parts by mass, or even, for example, 20 to 10 parts by mass. When used in combination with a photoacid-generating agent, the content of such compounds relative to 100 parts by mass of the compound having carboxyl or phenolic hydroxyl groups protected by groups that are easily decomposed in the presence of acid is, for example, 0.1 to 30 parts by mass, or 0.5 to 20 parts by mass, or even, for example, 1 to 10 parts by mass.

[0227] The coating-forming composition for removing foreign matter may contain a surfactant. Examples of surfactants include, for instance, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; and sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, and sorbitol monostearate. Nonionic surfactants including sorbitol fatty acid esters such as sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate. Fluorinated surfactants such as Eftop 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.

[0228] The coating-forming composition for removing foreign matter may contain silica particles. Examples of silica particles include, for instance, organosilicon powder having a specified average particle size, or silica sol containing silica having a specified average particle size.

[0229] Specific examples of silicone powders include, but are not limited to, the KMP series of silicone powders manufactured by Shin-Etsu Chemical Industry Co., Ltd., such as KMP-600, KMP-601, KMP-602, KMP-605, and X-52-7030.

[0230] 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.

[0231] (Coating for removing foreign matter)

[0232] 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.

[0233] The coating for removing foreign matter according to the present invention can be formed, for example, as follows.

[0234] 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, a coater, or an immersion coater, 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.

[0235] The thickness of the coating used to remove foreign matter is typically 5 nm to 1 μm, preferably 10 nm to 500 nm, and most preferably 15 nm to 300 nm.

[0236] The rate at which the coating film used for removing foreign matter dissolves in the removal solution 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. When the dissolution rate is less than this range, the time required to remove the coating film for removing foreign matter becomes longer, resulting in reduced productivity.

[0237] The coating for removing foreign matter formed by the coating film forming composition of the present invention can have its dissolution rate in the removal liquid controlled by changing the firing conditions during formation. Under a given firing time, a higher firing temperature results in a coating for removing foreign matter with a lower dissolution rate in the removal liquid.

[0238] 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 using 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.

[0239] (Semiconductor substrate)

[0240] The semiconductor substrate of the present invention has a coating thereon for removing foreign matter.

[0241] 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.

[0242] 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 it may have a notch.

[0243] The thickness of the disc-shaped semiconductor substrate can be appropriately specified according to the intended use of the semiconductor substrate, and is not particularly limited, for example, 500 to 1,000 μm.

[0244] The diameter 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 100 to 1,000 mm.

[0245] Semiconductor substrates can also have bumps. A bump is a protruding terminal.

[0246] In the case where the semiconductor substrate has bumps, the semiconductor substrate has bumps on the support substrate side.

[0247] In semiconductor substrates, bumps are typically formed on the surfaces where circuits are formed. The circuits can be single-layered or multi-layered. The shape of the circuit is not particularly limited.

[0248] In a semiconductor substrate, the side opposite to the side with bumps (the back side) is the side to be processed.

[0249] There are no particular limitations on the material, size, shape, structure, or density of bumps used as semiconductor substrates.

[0250] Examples of bumps include spherical bumps, printed bumps, stud bumps, and plated bumps.

[0251] The height, radius, and spacing of the bumps are usually determined appropriately from conditions such as bump height of about 1 to 200 μm, bump radius of 1 to 200 μm, and bump spacing of 1 to 500 μm.

[0252] Examples of materials that can be used for bumps include 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 alloy plating with Sn as the main component.

[0253] In addition, the bump may also have a stacked structure comprising a metal layer consisting of at least any of these components.

[0254] An example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

[0255] (Method for manufacturing processed semiconductor substrates)

[0256] 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.

[0257] The first step is to bond 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 to manufacture a laminate.

[0258] The second step is to process the laminated body.

[0259] The third step is to peel the supporting substrate from the laminate.

[0260] 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.

[0261] In the first embodiment, the coating for removing foreign matter according to the present invention, which has heat resistance, is used as the coating for removing foreign matter.

[0262] <Step 1>

[0263] The first step is to bond 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 to manufacture a laminate.

[0264] As a support substrate, there are no particular limitations as long as it is a component that can support the semiconductor substrate when the laminate (e.g., semiconductor substrate) is processed. Examples include flexible support substrates and glass support substrates.

[0265] The shape of the supporting substrate is not particularly limited, and examples include a disc shape.

[0266] The thickness of the disc-shaped support substrate can be appropriately specified according to the size of the semiconductor substrate, and is not particularly limited, for example, 500 to 1,000 μm.

[0267] The diameter of the disc-shaped support substrate can be appropriately specified according to the size of the semiconductor substrate, and is not particularly limited, for example, 100 to 1,000 mm.

[0268] One example of a supporting substrate is a glass wafer with a diameter of 300 mm and a thickness of about 700 μm.

[0269] The first step is preferably a step of bonding a semiconductor substrate and a support substrate together through a coating and an adhesive layer for removing foreign matter, thereby manufacturing a laminate.

[0270] 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.

[0271] The adhesive layer can be formed using known adhesives and methods. Examples of adhesives that can be used 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, HT-10.10 (manufactured by Brewer Science), and tape-type adhesives (e.g., back-grinding tapes (e.g., 3MTM temporary fixing adhesive tape ATT-4025 (manufactured by 3M Japan Co., Ltd.), E series, P series, S series (manufactured by Lintec Corporation, trade name), Icros tape (registered trademark) (manufactured by Mitsui Chemicals TOHCELLO Co., Ltd.)), dicing tapes (e.g., solvent-resistant dicing tape (manufactured by Nitto Denko Co., Ltd., trade name), temperature-sensitive adhesive sheet Intelimer (registered trademark) tape). (Manufactured by Anchor Techno Co., Ltd.), Intelimer (registered trademark) tape (manufactured by Anchor Techno Co., Ltd.), etc.

[0272] It can also be a wafer adhesive used in specific wafer operating systems (such as Zero Newton (registered trademark) (manufactured by Tokyo Ohka Kogyo Co., Ltd.)).

[0273] Furthermore, as an adhesive layer, a layer referred to as an adhesive layer, adhesive tape, or temporary fixing material can be used. Examples of such layers include, for instance, 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.

[0274] For example, back-side abrasive tape consists of a substrate film, an adhesive layer, and a release film. Previously, soft thermoplastic films such as ethylene-vinyl acetate copolymer (EVA) were used as substrate films, but rigid stretch films such as polyethylene terephthalate (PET) were also explored to improve wafer support. Further improvements were made, with reports of laminated designs using two films with different elastic moduli, such as laminates of PET and ethylene-based copolymers, or laminates of polypropylene (PP) and ethylene-based copolymers.

[0275] The adhesive is generally acrylic-based. Acrylic adhesives are known to be designed to crosslink 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 the tape is peeled off. Therefore, designs using emulsion-based adhesives have been reported that envision remove adhesive residue by washing with water, but complete removal is difficult. Therefore, the coating for removing foreign matter of this application, after being formed on the circuit surface, forms an adhesive layer, allowing for the complete removal of foreign matter (adhesive layer residue) from subsequent peeling processes by washing with a removal solution, without causing damage to the wiring areas of the circuit, etc.

[0276] 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.

[0277] 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.

[0278] In the absence of an adhesive layer, the support substrate preferably has an adhesive layer. The support substrate may, for example, have a flexible support and an adhesive layer. Examples of flexible supports include, for example, polyimide films. The adhesive layer is not particularly limited and may include layers formed from the adhesive.

[0279] Bonding, for example, is performed under heat and pressure.

[0280] There is no particular limitation on the heating temperature as long as it is above room temperature (25°C), but it is usually above 50°C. From the point of view to avoid overheating, it is usually below 220°C, and in one form it is below 170°C.

[0281] The load is not particularly limited as long as it can adhere to the substrate or layer and does not damage the substrate or layer; for example, it can be 0.5 to 50 kN.

[0282] In addition, the pressure used during bonding can be, for example, 0.1 to 20 N / mm. 2 Furthermore, pressure refers to the pressure per unit area (mm²) of the substrate contacted by the fixture applying the load. 2 ) force (load).

[0283] There are no particular limitations on the pressure reduction as long as it can fit the substrate and the layer without causing damage to the substrate or the layer, for example, 10 to 10,000 Pa.

[0284] When using an adhesive layer, in order to remove foreign matter, which is the peeling residue of the adhesive layer, together with the coating for removing foreign matter 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 can also be semiconductor substrate / coating for removing foreign matter / adhesive layer / support substrate.

[0285] Furthermore, when using an adhesive layer, in order to remove foreign matter, which is the peeling residue of the adhesive layer, together with the coating for removing foreign matter 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 also be semiconductor substrate / adhesive layer / coating for removing foreign matter / support substrate. In this case, the reuse of the support substrate becomes easier.

[0286] In addition, to ensure 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.

[0287] 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 has laser transmittance.

[0288] In the case where the laminate has a laser release layer, in order to remove foreign matter, which is the release residue of the laser release layer and the adhesive layer, together with the coating for removing foreign matter 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 also be, for example, semiconductor substrate / coating for removing foreign matter / laser release layer / adhesive layer / support substrate.

[0289] When the laminate has a laser release layer, in order to remove foreign matter, which is the release residue of the laser release layer and adhesive layer, together with the coating for removing foreign matter 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 also be, for example, semiconductor substrate / adhesive layer / laser release layer / coating for removing foreign matter / support substrate. In this case, the reuse of the support substrate becomes easier.

[0290] Furthermore, after the support substrate is peeled off from the laminate by irradiating the laser release layer with a laser, if there are still laser release layer residues 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, with the aim of removing laser release layer residues from the adhesive layer, can also 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.

[0291] <Second Process>

[0292] The second step is to process the laminated body.

[0293] The processing in the second step is not particularly limited, and examples include, for instance, polishing of the semiconductor substrate, forming of through electrodes on the semiconductor substrate, and 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.

[0294] <<Grinding Process>>

[0295] As for the polishing process of semiconductor substrates, there are no particular limitations as long as the process of polishing the side of the semiconductor substrate opposite to the side of the coating used for removing foreign matter, thereby thinning the semiconductor substrate, such as physical polishing using abrasives or polishing stones.

[0296] The polishing process can be performed using general polishing equipment used for polishing semiconductor substrates (such as silicon wafers).

[0297] By grinding, the thickness of the semiconductor substrate is reduced, resulting in a semiconductor substrate thinned to the desired thickness. The thickness of the thinned semiconductor substrate is not particularly limited, and can be, for example, 30–300 μm or 30–100 μm.

[0298] <<Penetrating Electrode Formation Process>>

[0299] 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.

[0300] Therefore, a through electrode formation process, which forms a through electrode on a polished semiconductor substrate, can be included after the polishing process and before the stripping process.

[0301] There are no particular limitations on the method of forming a through electrode on a semiconductor substrate. Examples include forming a through hole and filling the formed through hole with a conductive material.

[0302] The formation of the through-hole is, for example, done by photolithography.

[0303] The filling of the through-holes with conductive materials is achieved, for example, by plating.

[0304] In addition, in the second process, the through electrode formation process can be performed without grinding.

[0305] <<Connection Processing>>

[0306] The connection process is, for example, the process of connecting a semiconductor substrate to a second semiconductor substrate.

[0307] The second semiconductor substrate is not particularly limited, and examples include the substrates listed in the above description of semiconductor substrates.

[0308] The connection process can be performed, for example, under heating. Alternatively, the connection process can be performed, for example, under pressure.

[0309] The heating temperature is not particularly limited, but can be exemplified by, for example, 100℃ to 350℃.

[0310] In the connection process, for example, wiring on a semiconductor substrate is electrically connected to wiring on a second semiconductor substrate. Such a connection is performed, for example, by connecting the ends of the wiring to each other.

[0311] The material, shape, and structure of wiring in a semiconductor substrate are not particularly restricted.

[0312] The material, shape, and structure of the wiring in the second semiconductor substrate are not particularly restricted.

[0313] <Step 3>

[0314] The third step is the process of peeling the support substrate from the laminate. This third step can be referred to as the process of separating the semiconductor substrate from the support substrate.

[0315] Examples of peeling methods include solvent peeling, light-based peeling (laser, non-laser), mechanical peeling using a device with a pointed tip (so-called a peeler), and peeling by manually pulling apart the semiconductor substrate and the support substrate, but are not limited to these.

[0316] In particular, when the laminate contains an adhesive layer, and the adhesive layer is formed of an organic resin that has been modified to improve peelability by absorbing light, the adhesive layer can be peeled off, for example, by irradiating a laser from the support substrate side.

[0317] Laser irradiation can be performed using ultraviolet light with wavelengths of 190nm–400nm or 190nm–600nm (e.g., 308nm, 355nm, 532nm).

[0318] Stripping can be achieved by setting the processing energy density of the pulsed laser to 50–500 mJ / cm². 2 Proceed from left to right.

[0319] In laminates containing adhesive layers, 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 refers to cracking of the adhesive layer.

[0320] <Step 4>

[0321] 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.

[0322] 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.

[0323] In step 4, for example, foreign matter is removed together with a coating used to remove foreign matter.

[0324] 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.

[0325] Examples of removal solutions include, for instance, those listed in the description of the coating-forming composition for removing foreign matter according to the present invention.

[0326] 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.

[0327] There are no particular restrictions on the cleaning conditions; for example, the temperature of the cleaning solution can be between 5°C and 50°C. Furthermore, the cleaning time can be appropriately selected from 2 to 500 seconds, or 3 to 400 seconds.

[0328] For example, a coating used to remove foreign matter can preferably be easily peeled off at room temperature (e.g., 25°C) using a commonly used 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0329] The following diagram illustrates an example of a method for manufacturing a processed semiconductor substrate.

[0330] First, prepare the semiconductor substrate 11 ( Figure 1A ).

[0331] Next, a coating 12 for removing foreign matter is formed on the semiconductor substrate 11. Figure 1B ).

[0332] 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 to bond the coating 12 for removing foreign matter to the adhesive layer 14B. Figure 1C ).

[0333] 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 ).

[0334] Next, the support substrate 14 is separated from the semiconductor substrate 11. Figure 1E and Figure 1F ).

[0335] 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 with a removal solution. Figure 1G This prevents the removal residue 14C, which is a foreign object, from remaining on the semiconductor substrate 11.

[0336] The following figure illustrates another example of a method for manufacturing a processed semiconductor substrate.

[0337] First, prepare a semiconductor substrate 1 with wiring 1A. Figure 2A ).

[0338] Next, a coating 2 for removing foreign matter is formed on the semiconductor substrate 1. Figure 2B ).

[0339] On the other hand, a glass substrate 4 on which an adhesive layer 3 is formed is prepared. Figure 2C ).

[0340] 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 to bond the coating 2 for removing foreign matter to the adhesive layer 3. Figure 2D and Figure 2E ).

[0341] 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 ).

[0342] Then expose wiring 1A.

[0343] Next, Figure 2F The stack shown, and the second semiconductor substrate 5 having wiring 5A, are 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 ).

[0344] 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 adhesive strength of the adhesive layer 3.

[0345] 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 with a removal solution. Figure 2K This prevents stripping residue 3A, which is a foreign object, from remaining on the semiconductor substrate 1.

[0346] The method for manufacturing the processed semiconductor substrate of the present invention is suitable for use in hybrid bonding to connect semiconductor substrates to each other.

[0347] <Other Implementation Methods>

[0348] One embodiment of the present invention can be 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 for removing foreign matter from the surface of a semiconductor substrate by forming a substrate processing film on the surface of the substrate. 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.

[0349] The above example is described in detail below. In this application example, the coating film forming composition for removing foreign matter according to 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 as a so-called full-coverage substrate (planar) in which various films are formed. For the purpose of manufacturing semiconductor devices, it may also be in a state where the shape of wiring, etc., has been processed. Examples of coating methods include, for example, spin coating, casting coating, roll coating, etc. Next, by heating (baking) and / or reducing pressure on the coating film, part or all of the solvent contained in the coating film is efficiently removed, thereby promoting the curing and / or hardening of the solid components contained in the coating film. Here, "curing" refers to solidification, and "curing" refers to the increase in molecular weight due to the linkage of molecules to each other (e.g., crosslinking or polymerization). Thus, a coating film is formed. At this time, for example, particles of circuits attached to the semiconductor substrate are absorbed into the coating film and efficiently separated from the circuits, etc. Next, a coating removal process is performed. That is, by supplying a removal solution that dissolves the coating onto the coating, the coating is completely removed from the semiconductor substrate. As a result, the particles are removed from the semiconductor substrate along with the coating.

[0350] Example

[0351] Next, specific examples and embodiments will be given to illustrate the content of the present invention, but the present invention is not limited to these.

[0352] <Determination of molecular weight>

[0353] The weight-average molecular weights of the polymers shown in Synthetic Examples 1 to 7 below were determined using 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.

[0354] GPC pillars: Shodex KF803L, Shodex KF802, Shodex KF801 [Registered Trademark] (Showa Denko Co., Ltd.) Column temperature: 40℃ Flow rate: 0.35 ml / min Eluent: Tetrahydrofuran (THF) Standard sample: Polystyrene (Tosoh Corporation) <Synthesis example 1> 3.00 g of EX-201 (resorcinol diglycidyl ether, manufactured by Nagase ChemteX Corporation), 2.02 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.16 g of tetrabutylphosphonium bromide (manufactured by Kitakō Chemical Co., Ltd.) were added to a reaction flask containing propylene glycol monomethyl ether (PME). The resulting mixture was heated and stirred at 120°C for 16 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-1), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 2070.

[0355]

[0356] <Synthesis example 2>

[0357] 3.50 g of EX-721 (manufactured by Nagase ChemteX Corporation), 1.72 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.09 g of tetrabutylphosphonium bromide (manufactured by Kitakō Chemical Co., Ltd.) were added to a reaction flask containing propylene glycol monomethyl ether (PPD). The resulting mixture was heated and stirred at 120 °C for 16 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-2), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 1070.

[0358]

[0359] <Synthesis Example 3>

[0360] 5.00 g of EX-711 (manufactured by Nagase ChemteX Corporation), 2.70 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.21 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) were added to a reaction flask containing 18.49 g of propylene glycol monomethyl ether. The resulting mixture was heated and stirred at 120 °C for 16 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-3), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 2480.

[0361]

[0362] <Synthesis example 4>

[0363] 7.00 g of monoallyl diglycidyl isocyanuric acid (product name: MA-DGIC, manufactured by Shikoku Chemical Industry Co., Ltd.), 3.93 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.21 g of tetrabutylphosphonium bromide (manufactured by Kitakō Chemical Co., Ltd.) were added to a reaction flask containing propylene glycol monomethyl ether. The resulting mixture was heated and stirred at 120°C for 20 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-4), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 2200.

[0364]

[0365] <Synthesis example 5>

[0366] 10.00 g of a propylene glycol monomethyl ether solution of monomethyl diglycidyl isocyanuric acid (product name: Me-DGIC, manufactured by Shikoku Chemical Industry Co., Ltd., solid content 30% by mass), 1.87 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.15 g of tetrabutylphosphonium bromide (manufactured by Kitakō Chemical Co., Ltd.) were added to a reaction flask. The resulting mixture was heated and stirred at 120°C for 14 hours under a nitrogen atmosphere in a reaction flask. The resulting reaction product corresponds to formula (x-5), and the weight-average molecular weight Mw, determined by conversion to polystyrene using GPC, is 950.

[0367]

[0368] <Synthesis Example 6>

[0369] 10.00 g of a propylene glycol monomethyl ether solution of 1,3-diglycidyl-5,5-dimethylhydantoin (30% by mass solids), 1.99 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.13 g of tetrabutylphosphonium bromide (manufactured by Kitakō Chemical Co., Ltd.) were added to a reaction flask. The resulting mixture was heated and stirred at 120°C for 15 hours under a nitrogen atmosphere. The resulting reaction product corresponds to formula (x-6), and its weight-average molecular weight (Mw) determined using GPC for polystyrene is 1100.

[0370]

[0371] <Synthesis Example 7>

[0372] 3.00 g of HP-4032D (manufactured by DIC Corporation), 1.69 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.14 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) were added to a reaction flask containing propylene glycol monomethyl ether (PPD). The resulting mixture was heated and stirred at 105°C for 16 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-7), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 1600.

[0373]

[0374] <Synthesis example 8>

[0375] 3.50 g of EX-711 (manufactured by Nagase ChemteX Corporation), 1.45 g of succinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.10 g of tetrabutylphosphonium bromide (manufactured by Kitakō Chemical Co., Ltd.) were added to a reaction flask containing propylene glycol monomethyl ether (PME). The resulting mixture was heated and stirred at 105 °C for 15 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-8), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 3080.

[0376]

[0377] <Synthesis Example 9>

[0378] 5.00 g of RE-303S-L (manufactured by Nippon Kayaku Co., Ltd.), 2.68 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.19 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) were added to a reaction flask containing propylene glycol monomethyl ether (18.38 g). The resulting mixture was heated and stirred at 120 °C for 15 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-8), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 2480.

[0379]

[0380] <Synthesis Example 10>

[0381] 10.00 g of EXA-850CRP (manufactured by DIC Corporation), 4.44 g of tartaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.37 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.) were added to a reaction flask containing propylene glycol monomethyl ether (PPD). The resulting mixture was heated and stirred at 120°C for 16 hours under a nitrogen atmosphere in the reaction flask. The resulting reaction product corresponds to formula (x-10), and its weight-average molecular weight (Mw) determined using GPC polystyrene conversion is 2980.

[0382]

[0383] <Example 1>

[0384] In Synthesis Example 1, 8.76 g of a propylene glycol monomethyl ether solution (solid content 19.53% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of p-phenolsulfonium pyridinium, and 91.04 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.

[0385] <Example 2>

[0386] In Synthesis Example 2, 8.87 g of a propylene glycol monomethyl ether solution (solid content 19.28% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 90.93 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.

[0387] <Example 3>

[0388] In Synthesis Example 3, 6.23 g of a propylene glycol monomethyl ether solution (solid content 27.44% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 93.57 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.

[0389] <Example 4>

[0390] In Synthesis Example 4, 8.69 g of a propylene glycol monomethyl ether solution (solid content 19.68% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 91.11 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.

[0391] <Example 5>

[0392] In Synthesis Example 5, 8.90 g of a propylene glycol monomethyl ether solution (solid content 19.22% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 90.90 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.

[0393] <Example 6>

[0394] In Synthesis Example 6, 9.09 g of a propylene glycol monomethyl ether solution (solid content 18.82% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 90.71 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.

[0395] <Example 7>

[0396] In Synthesis Example 7, 12.02 g of a propylene glycol monomethyl ether solution (solid content 14.24% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 87.79 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.

[0397] <Example 8>

[0398] In Synthesis Example 9, 6.18 g of a propylene glycol monomethyl ether solution (solid content 27.86% by mass) of the reaction product was added to 0.25 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 93.53 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.

[0399] <Example 9>

[0400] In Synthesis Example 10, 6.34 g of a propylene glycol monomethyl ether solution (solid content 27.19% by mass) of the reaction product was added to 0.25 g of tetramethoxymethyl glycourea, 0.02 g of pyridinium p-phenolsulfonate, and 93.38 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.

[0401] <Comparative Example 1>

[0402] In Synthesis Example 8, 9.53 g of a propylene glycol monomethyl ether solution (solid content 17.95% by mass) of the reaction product was added with 0.17 g of tetramethoxymethyl glycourea, 0.02 g of p-phenolsulfonate pyridinium, and 90.27 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.

[0403] <Comparative Example 2>

[0404] The coating composition for removing foreign matter of Example 1, WO2018 / 159665, was prepared as follows and used as the coating composition for removing foreign matter of Comparative Example 1.

[0405] <<Synthesis of Polyamic Acid>>

[0406] 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].

[0407] Synthesis of Light-Absorbing Compounds

[0408] 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].

[0409] <<Preparation of a Coating Composition for Removing Foreign Matter>>

[0410] 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.

[0411] [Soluble Resistance Test]

[0412] The coating compositions for removing foreign matter prepared in Examples 1 to 9 and Comparative Examples 1 to 2 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 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: Nanospec6100, manufactured by Nanometrics Japan Co., Ltd.).

[0413] The evaluation of solvent resistance is based on the following formula, which calculates the film thickness reduction rate (%) after solvent removal.

[0414] Film thickness reduction rate (%) = ((AB) ÷ A) × 100

[0415] A: Film thickness before solvent impregnation

[0416] B: Film thickness after solvent impregnation

[0417] The results are shown in Table 1. If the absolute value of the film thickness reduction rate is less than approximately 1%, then it can be said to have sufficient solvent resistance.

[0418]

[0419] 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 9 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.

[0420] [Alkali solubility test]

[0421] The coating compositions for removing foreign matter prepared in Examples 1 to 9 and Comparative Examples 1 to 2 were each applied onto silicon wafers using a spin coater. 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.).

[0422] Regarding the evaluation of alkali solubility, the film thickness reduction rate (%) after solvent removal is calculated using the following formula.

[0423] Film thickness reduction rate (%) = ((AB) ÷ A) × 100

[0424] A: Film thickness before solvent impregnation

[0425] B: Film thickness after solvent impregnation

[0426] The results are shown in Table 2. A film thickness reduction rate of approximately 99% or higher indicates sufficient alkali solubility.

[0427]

[0428] The above results confirm that the coating film-forming compositions for removing foreign matter in Examples 1 to 9 are resistant to organic solvents and soluble in alkaline solvents. Furthermore, compared to Comparative Examples 1 to 2, they exhibit good solubility in alkaline solvents.

[0429] [Defect Inspection and Evaluation After Development Processing]

[0430] The coating composition for removing foreign matter prepared in Example 3 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 processing adhesive sheet was attached to the coating of this sample using a manual wafer mounter (manufactured by Omiya Industrial Co., Ltd.). Next, the semiconductor wafer processing adhesive sheet was irradiated with ultraviolet light (500 mJ / cm²) using a manual UV irradiation device (manufactured by Omiya Industrial Co., Ltd.). 2The adhesive sheet was peeled off. Further, the entire surface of the silicon wafer was evaluated using a defect inspection device (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 device (KLA-Tencor Corporation, Surfscan SP2XP) to assess the removability of the cleaned coating. In addition, a sample of a silicon wafer prepared using the same procedure but without a coating of the coating-forming composition for removing foreign matter was prepared 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, most defects were detected on the coating after the adhesive sheet was peeled off. However, after dissolving the coating with NMD-3, the defects from the adhesive sheet could be removed. 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.

[0431] Based on the above results, it can be said that by using the coating composition for removing foreign matter of Example 3, defects from the adhesive sheet can be removed.

[0432] Symbol Explanation

[0433] 1: Semiconductor substrate

[0434] 1A: Wiring

[0435] 2: Coating for removing foreign matter

[0436] 3: Adhesive layer

[0437] 4: Glass substrate

[0438] 5: Second semiconductor substrate

[0439] 5A: Wiring

[0440] 11: Semiconductor substrate

[0441] 12: Coating for removing foreign matter

[0442] 14: Supporting substrate

[0443] 14A: Flexible support

[0444] 14B: Adhesive layer

[0445] 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 solution. The polymer has a partial structure as shown in formula (A) below. In formula (A), R 11 R represents a single bond or a divalent group with 1 to 4 carbon atoms. 12 * indicates a hydrogen atom, hydroxyl group, or methyl group; * indicates a bond connection site.

2. The composition according to claim 1, wherein R in formula (A) 11 The divalent group represents a carbon group having 1 to 4 carbon atoms, and the divalent group has a hydroxyl group.

3. The composition according to claim 1, wherein R in formula (A) 11 Represents -CH(OH)-, R 12 It represents a hydrogen atom.

4. The composition according to claim 1, wherein the polymer has a structural unit represented by the following formula (A-1), In equation (A-1), A 1 A 2 A 3 A 4 A 5 and A 6 Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group; Q represents a divalent organic group; R... 11 R represents a single bond or a divalent group with 1 to 4 carbon atoms. 12 It represents a hydrogen atom, a hydroxyl group, or a methyl group.

5. The composition according to claim 4, wherein Q in formula (A-1) is represented by any one of formulas (A-11) and (A-12). In equation (A-11), X 1 Z represents the divalent group shown in formula (A-11-1), formula (A-11-2), or formula (A-11-3) below. 1 and Z 2 Each can independently represent a single bond or a divalent group as shown in the following formula (A-11-4), with * indicating a bond connection site. In equation (A-12), Q 1 This indicates a divalent group having an aromatic or aliphatic hydrocarbon ring; n1 and n2 each independently represent 0 or 1; * indicates a bond connection site. In equations (A-11-1) to (A-11-3), R 1 ~R 5 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkenyl group with 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, an alkynyl group with 2 to 10 carbon atoms that can be interrupted by an oxygen or sulfur atom, a benzyl group, or a phenyl group, wherein the phenyl group may be substituted with at least one monovalent group selected from alkyl groups with 1 to 6 carbon atoms, a halogen atom, an alkoxy group with 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group with 1 to 6 carbon atoms, R 1 With R 2 They can combine to form rings with 3 to 6 carbon atoms, R 3 With R 4 They can combine to form rings with 3 to 6 carbon atoms. * indicates a bond connection site, *1 indicates a bond connection site with a carbon atom, and *2 indicates a bond connection site with a nitrogen atom. In formula (A-11-4), m1 is an integer from 1 to 4, m2 is 0 or 1, *3 represents the bond connection site with nitrogen atom, and *4 represents the bond connection site with carbon atom.

6. The composition according to claim 5, wherein Q in formula (A-12) 1 Expressed by any of the following formulas (A-12-1) to (A-12-4), In equations (A-12-1) to (A-12-4), R 31 ~R 36 Each of these groups independently represents a halogen atom, hydroxyl group, alkyl group with 1 to 6 carbon atoms, alkenyl group with 2 to 6 carbon atoms, alkynyl group with 2 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkenyloxy group with 2 to 6 carbon atoms, alkynyloxy group with 2 to 6 carbon atoms, acyl group with 2 to 6 carbon atoms, aryloxy group with 6 to 12 carbon atoms, arylcarbonyl group with 7 to 13 carbon atoms, or aralkyl group with 7 to 13 carbon atoms. * indicates a bond connection site. In equation (A-12-1), n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6. 31 When there are two or more R's 31 They can be the same or different. In formula (A-12-2), Z 1 Represents a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms; n12 and n13 each independently represent integers from 0 to 4. 32 When there are two or more R's 32 They can be the same or different, when R 33 When there are two or more R's 33 They can be the same or different. In formula (A-12-3), Y 1 and Y 2 Each independently represents a single bond or an alkylene group with 1 to 6 carbon atoms, and n14 represents an integer from 0 to 4. When R 34 When there are two or more R's 34 They can be the same or different. In formula (A-12-4), Z 2 Represents a single bond, oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or alkylene group with 1 to 6 carbon atoms; n15 and n16 each independently represent integers from 0 to 4. 35 When there are two or more R's 35 They can be the same or different, when R 36 When there are two or more R's 36 They can be the same or different.

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

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

9. The composition according to claim 1, comprising at least one of a crosslinking agent and an additive.

10. A coating for removing foreign matter formed from the composition according to any one of claims 1 to 9.

11. A semiconductor substrate having the coating for removing foreign matter as described in claim 10.

12. A method for manufacturing a processed semiconductor substrate, comprising: The first step involves bonding the semiconductor substrate as described in claim 11 to a support substrate through the coating used for removing foreign matter, thereby manufacturing a laminate. The second process for processing the 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 to remove the coating used for removing foreign matter.

13. The method for manufacturing a processed semiconductor substrate according to claim 12, wherein in the fourth step, foreign matter is removed together with the coating used for removing foreign matter.

14. The method for manufacturing a processed semiconductor substrate according to claim 12, 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, thereby manufacturing a laminate.

15. The method for manufacturing a semiconductor substrate according to claim 14, 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.

16. The method of manufacturing a processed semiconductor substrate according to claim 12, wherein the processing includes connecting the semiconductor substrate to a second semiconductor substrate.

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