Semiconductor substrate cleaning method, processed semiconductor substrate manufacturing method, and separation and solution composition

Abstract

Provided are a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate comprising such a cleaning method, and a composition used in such a cleaning method, the method for cleaning a semiconductor substrate is capable of removing (cleaning) an adhesive layer obtained using, for example, a siloxane-based adhesive from a semiconductor substrate having the adhesive layer on the surface thereof by a simple operation, in a shorter time and more cleanly. A method for cleaning a semiconductor substrate, characterized by comprising: a step for peeling and dissolving an adhesive layer on the semiconductor substrate using a composition for peeling and dissolving, the composition for peeling and dissolving comprising the following components: component [I]: a quaternary ammonium salt; component [II]: an amide-based solvent; and component [III]: a solvent represented by formula (G). (In the formula, L11 and L12 each independently represent an alkyl group having 1-6 carbon atoms, and the total of the number of carbon atoms in the alkyl group of L11 and the number of carbon atoms in the alkyl group of L12 is 7 or less. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate, and a composition for stripping and dissolving. Background Art

[0002] With regard to semiconductor wafers that were previously integrated in a two-dimensional plane direction, a semiconductor integration technology that further integrates (stacks) the plane in a three-dimensional direction is pursued for the purpose of further integration. This three-dimensional stacking is a technology that integrates into multiple layers while wiring through silicon vias (TSV). When integrating into multiple layers, the side opposite to the circuit surface formed (i.e., the back side) of each wafer to be integrated is thinned by grinding, and the thinned semiconductor wafers are stacked.

[0003] The semiconductor wafer before thinning (also referred to as the wafer here) is bonded to a support body in order to be ground using a grinding device. The bonding at this time must be easy to peel off after grinding, so it is called temporary bonding. The temporary bonding must be easy to remove from the support body. When a large force is applied to the disassembly, the thinned semiconductor wafer is sometimes cut or deformed. In order to avoid such a situation, it is easy to disassemble. However, when the back of the semiconductor wafer is ground, it is not preferred that it is detached or offset due to the grinding stress. Therefore, the performance pursued by temporary bonding is: to withstand the stress during grinding and to be easy to disassemble after grinding. For example, the following performance is pursued: high stress (strong bonding force) relative to the plane direction during grinding, and low stress (weak bonding force) relative to the direction intersecting the plane direction during disassembly, that is, the longitudinal direction. In addition, sometimes the temperature reaches above 150°C during the processing step, and heat resistance is also required.

[0004] Under such circumstances, in the semiconductor field, polysiloxane adhesives having these properties are mainly used as temporary adhesives. In addition, in polysiloxane bonding using polysiloxane adhesives, adhesive residues often remain on the substrate surface after the thinned substrate is peeled off. In order to avoid adverse conditions in subsequent processes, cleaning agent compositions for removing the residues and cleaning the surface of the semiconductor substrate have been developed (for example, refer to patent documents 1 and 2). Patent document 1 discloses a remover for siloxane resins containing a polar aprotic solvent and quaternary ammonium hydroxide, and patent document 2 discloses a curing resin remover containing alkyl ammonium fluoride. However, in the recent semiconductor field, there is always a desire for new cleaning agent compositions, and there is always a desire for effective cleaning agent compositions and cleaning methods.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2014 / 092022

[0008] Patent Document 2: U.S. Patent No. 6818608 Summary of the invention

[0009] Problems to be solved by the invention

[0010] It is known that the cleaning compositions described in Patent Documents 1 and 2 are intended to remove the adhesive residue from the substrate surface by dissolving the adhesive residue on the substrate surface. However, if the adhesive residue is to be removed from the substrate surface by dissolving in this manner, it takes a long time to remove the adhesive residue.

[0011] Furthermore, the present inventors have studied cleaning agent compositions and found that when a composition containing specific ingredients is used, the adhesive layer can be swollen and peeled off from the substrate. When the composition containing the specific ingredients is used, the adhesive layer can be removed from the substrate in a short time.

[0012] However, from the viewpoint of removing adhesive residues from the substrate surface more cleanly in a shorter time with simple operation, there is room for improvement, and more effective cleaning methods are required. Therefore, the development of new cleaning methods and compositions used in the cleaning methods is being promoted.

[0013] The present invention has been completed in view of the above situation, and its purpose is to provide a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate including such a cleaning method, and a composition used in such a cleaning method, wherein the method for cleaning a semiconductor substrate can remove (clean) an adhesive layer obtained, for example, using a silicone adhesive from a semiconductor substrate having the adhesive layer on its surface with simple operation, in a shorter time and more cleanly.

[0014] Solutions for solving problems

[0015] The present inventors have conducted intensive studies to solve the above-mentioned technical problems and have found that the above-mentioned technical problems can be solved by the following method, thereby completing the present invention, that is, using a composition containing specific components to clean an adhesive layer on a semiconductor substrate, especially an adhesive layer that is a cured film obtained from a siloxane-based adhesive, wherein the siloxane-based adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction, thereby swelling, peeling and dissolving the adhesive layer in one cleaning operation, thereby removing the adhesive layer from the semiconductor substrate.

[0016] That is, the present invention includes the following aspects.

[0017] [1] A method for cleaning a semiconductor substrate, characterized in that it includes: a step of stripping and dissolving an adhesive layer on the semiconductor substrate using a stripping and dissolving composition, wherein the stripping and dissolving composition contains the following components: [I] component: a quaternary ammonium salt; [II] component: an amide solvent; and [III] component: a solvent represented by the following formula (G).

[0018]

[0019] (Where L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms in the alkyl group is 7 or less.)

[0020] [2] The semiconductor substrate cleaning method according to [1], wherein the stripping and dissolving composition further comprises the following component: [IV] Component: a solvent represented by the following formula (T) or the following formula (L).

[0021]

[0022] (Where X 1 and X 3 Each independently represents an alkyl group or an acyl group (X 4 -C(=O)-), X 2 represents an alkylene group, and n represents 2 or 3. 4 represents an alkyl group. )

[0023] L 1 -L 3 -L 2 (L)

[0024] (Where L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S. )

[0025] [3] The semiconductor substrate cleaning method according to [1] or [2], wherein in the formula (G), L 11 It is methyl.

[0026] [4] The semiconductor substrate cleaning method according to [3], wherein in the formula (G), L 12 It is butyl or pentyl.

[0027] [5] The semiconductor substrate cleaning method according to any one of [1] to [4], wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

[0028] [6] The semiconductor substrate cleaning method according to any one of [1] to [5], wherein the amide solvent is an amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y).

[0029]

[0030] (Where R 0 represents ethyl, propyl or isopropyl, R A and R B Each independently represents an alkyl group having 1 to 4 carbon atoms. )

[0031]

[0032] (Where R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).

[0033]

[0034] (Where R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 104 represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond to a carbon atom in formula (Y), and *2 represents a bond to a nitrogen atom in formula (Y).

[0035] [7] A method for cleaning a semiconductor substrate according to any one of [1] to [6], wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), and the adhesive component (S) contains at least one selected from a silicone adhesive, an acrylic resin adhesive, an epoxy resin adhesive, a polyamide adhesive, a polystyrene adhesive, a polyimide adhesive and a phenolic resin adhesive.

[0036] [8] The semiconductor substrate cleaning method according to [7], wherein the adhesive component (S) contains a silicone-based adhesive.

[0037] [9] The semiconductor substrate cleaning method according to [8], wherein the siloxane-based adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

[0038]

[10] The semiconductor substrate cleaning method according to any one of [1] to [9], wherein the peeling and dissolving steps include a step of removing the peeled adhesive layer.

[0039]

[11] A method for manufacturing a processed semiconductor substrate, characterized in that it comprises: a first step of manufacturing a laminate having a semiconductor substrate, a supporting substrate and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of separating the semiconductor substrate and the adhesive layer from the supporting substrate; and a fourth step of removing the adhesive layer on the semiconductor substrate by peeling and dissolving it using a peeling and dissolving composition, wherein the peeling and dissolving composition comprises the following components: [I] component: quaternary ammonium salt; [II] component: amide solvent; and [III] component: a solvent represented by the following formula (G).

[0040]

[0041] (Where L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms in the alkyl group is 7 or less.)

[0042]

[12] The method for manufacturing a processed semiconductor substrate according to

[11] , wherein the stripping and dissolving composition further comprises the following components: [IV] Component: a solvent represented by the following formula (T) or the following formula (L).

[0043]

[0044] (Where X 1 and X 3 Each independently represents an alkyl group or an acyl group (X 4 -C(=O)-), X 2 represents an alkylene group, and n represents 2 or 3. 4 represents an alkyl group. )

[0045] L 1 -L 3 -L 2 (L)

[0046] (Where L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S. )

[0047]

[13] The semiconductor substrate cleaning method according to

[11] or

[12] , wherein in the formula (G), L 11 It is methyl.

[0048]

[14] The semiconductor substrate cleaning method according to

[13] , wherein in the formula (G), L 12 It is butyl or pentyl.

[0049]

[15] The method for producing a processed semiconductor substrate according to any one of

[11] to

[14] , wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

[0050]

[16] The method for producing a processed semiconductor substrate according to any one of

[11] to

[15] , wherein the amide solvent is an amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y).

[0051]

[0052] (Where R 0 represents ethyl, propyl or isopropyl, R A and R B Each independently represents an alkyl group having 1 to 4 carbon atoms. )

[0053]

[0054] (Where R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).

[0055]

[0056] (Where R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 104 represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond to a carbon atom in formula (Y), and *2 represents a bond to a nitrogen atom in formula (Y).

[0057]

[17] A method for manufacturing a processed semiconductor substrate according to any one of

[11] to

[16] , wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), and the adhesive component (S) contains at least one selected from a silicone adhesive, an acrylic resin adhesive, an epoxy resin adhesive, a polyamide adhesive, a polystyrene adhesive, a polyimide adhesive and a phenolic resin adhesive.

[0058]

[18] The method for producing a processed semiconductor substrate according to

[17] , wherein the adhesive component (S) contains a silicone-based adhesive.

[0059]

[19] The method for producing a processed semiconductor substrate according to

[18] , wherein the siloxane-based adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

[0060]

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

[11] to

[19] , wherein the fourth step of peeling off and dissolving and removing includes a step of removing the adhesive layer after peeling off.

[0061]

[21] A stripping and dissolving composition, characterized in that it is used to strip and dissolve an adhesive layer on a semiconductor substrate to remove it when cleaning the semiconductor substrate, and the stripping and dissolving composition meets at least any one of the following conditions (i) to (iv).

[0062] (i) The peeling and dissolving composition comprises the following component [I], the following component [II] and the following component [III], wherein the content of the component [II] in 100% by mass of the aprotic solvent is 20% by mass or less, and the content of the component [III] is 60% by mass or more.

[0063] (ii): The peeling and dissolving composition comprises the following component [I], the following component [II], and the following component [III], wherein the content of the component [III] in 100% by mass of the aprotic solvent is 70% by mass or more.

[0064] (iii): The peeling and dissolving composition comprises the following component [I], the following component [II], the following component [III] and the following component [IV], wherein the component [IV] comprises a solvent represented by the following formula (L), and when the aprotic solvent is set to 100% by mass, the content of the component [III] is greater than 31% by mass, and the content of the component [IV] is less than 30% by mass.

[0065] (iv) The peeling and dissolving composition comprises the following component [I], the following component [II], the following component [III] and the following component [IV], wherein the component [IV] comprises a solvent represented by the following formula (T), and when the aprotic solvent is set to 100 mass%, the content of the component [III] is greater than 31 mass%, the content of the component [IV] is less than 30 mass%, and the content of the component [II] is less than 20 mass%.

[0066] Here, component [I] represents a quaternary ammonium salt, component [II] represents an amide solvent, component [III] represents a solvent represented by the following formula (G), and component [IV] represents a solvent represented by the following formula (T) or the following formula (L).

[0067]

[0068] (Where L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms in the alkyl group is 7 or less.)

[0069]

[0070] (Where X 1 and X 3 Each independently represents an alkyl group or an acyl group (X 4 -C(=O)-), X 2 represents an alkylene group, and n represents 2 or 3. 4 represents an alkyl group. )

[0071] L 1 -L 3 -L 2 (L)

[0072] (Where L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S. )

[0073]

[22] The peeling and dissolving composition according to

[21] , wherein in the formula (G), L 11 It is methyl.

[0074]

[23] The peeling and dissolving composition according to

[22] , wherein in the formula (G), L 12 It is butyl or pentyl.

[0075]

[24] The peeling and dissolving composition according to any one of

[21] to

[23] , wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

[0076]

[25] The peeling and dissolving composition according to any one of

[21] to

[24] , wherein the amide solvent is an amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y).

[0077]

[0078] (Where R 0 represents ethyl, propyl or isopropyl, R A and R B Each independently represents an alkyl group having 1 to 4 carbon atoms. )

[0079]

[0080] (Where R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).

[0081]

[0082] (Where R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 104 represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond to a carbon atom in formula (Y), and *2 represents a bond to a nitrogen atom in formula (Y).

[0083]

[26] A peeling and dissolving composition according to any one of

[21] to

[25] , wherein the adhesive layer is a film obtained using an adhesive composition containing an adhesive component (S), and the adhesive component (S) contains at least one selected from a silicone adhesive, an acrylic resin adhesive, an epoxy resin adhesive, a polyamide adhesive, a polystyrene adhesive, a polyimide adhesive and a phenolic resin adhesive.

[0084]

[27] The processed peeling and dissolving composition according to

[26] , wherein the adhesive component (S) contains a silicone-based adhesive.

[0085]

[28] The peeling and dissolving composition according to

[27] , wherein the silicone adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

[0086]

[29] The peeling and dissolving composition according to

[21] , wherein, in the case of (ii), the content of the component [III] is more than 35% by mass.

[0087] Effects of the Invention

[0088] According to the present invention, a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate including such a cleaning method, and a composition used in such a cleaning method can be provided, wherein the method for cleaning a semiconductor substrate can remove (clean) an adhesive layer from a semiconductor substrate having the adhesive layer on its surface with simple operation, in a shorter time and more cleanly. DETAILED DESCRIPTION

[0089] Hereinafter, the present invention will be described in detail. It should be noted that the description of the constituent requirements described below is an example for explaining the present invention, and the present invention is not limited to these contents.

[0090] (Semiconductor substrate cleaning method)

[0091] The semiconductor substrate cleaning method of the present invention includes the step of peeling and dissolving an adhesive layer on the semiconductor substrate using a peeling and dissolving composition.

[0092] The peeling and dissolving composition contains the following components: [I] component: a quaternary ammonium salt; [II] component: an amide solvent; and [III] component: a solvent represented by the following formula (G).

[0093]

[0094] (Where L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms in the alkyl group is 7 or less.)

[0095] The peeling and dissolving composition may further contain the following components: [IV] Component: a solvent represented by the following formula (T) or the following formula (L).

[0096]

[0097] (Where X 1 and X 3 Each independently represents an alkyl group or an acyl group (X 4 -C(=O)-), X 2 represents an alkylene group, and n represents 2 or 3. 4 represents an alkyl group. )

[0098] L 1 -L 3 -L 2 (L)

[0099] (Where L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S. )

[0100] <Semiconductor substrate>

[0101] The main material constituting the entire semiconductor substrate is not particularly limited as long as it can be used for such an application, and examples thereof include silicon, silicon carbide, and compound semiconductors.

[0102] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc-shaped semiconductor substrate. It should be noted that the disc-shaped semiconductor substrate does not need to have a completely circular surface shape, and for example, the periphery of the semiconductor substrate may have a straight portion called an orientation flat, or may have a cutout called a notch.

[0103] The thickness of the disk-shaped semiconductor substrate may be appropriately determined according to the intended use of the semiconductor substrate, and is not particularly limited, but is, for example, 500 to 1000 μm.

[0104] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and the like. For example, the diameter is 100 to 1000 mm.

[0105] The semiconductor substrate is, for example, a wafer. Specific examples thereof include a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm, but the present invention is not limited thereto.

[0106] <Adhesive layer>

[0107] The adhesive layer on the semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S).

[0108] Such adhesive component (S) is not particularly limited as long as it is used for such an application, and examples thereof include silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

[0109] Among them, silicone-based adhesives are preferred as the adhesive component (S) because they exhibit appropriate adhesive properties during processing of wafers and the like, can be appropriately peeled off after processing, and have excellent heat resistance.

[0110] <<Adhesive composition>>

[0111] In a preferred embodiment, the adhesive composition used in the present invention contains a component (A) that cures by a hydrosilylation reaction as an adhesive component.

[0112] Furthermore, the adhesive composition used in the present invention contains polyorganosiloxane in a preferred embodiment.

[0113] The component (A) may be a component that is cured by a hydrosilylation reaction, or may be a polyorganosiloxane component (A′) that is cured by a hydrosilylation reaction.

[0114] In another preferred embodiment, component (A) contains, as an example of component (A'), a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal catalyst (A2). The alkenyl group having 2 to 40 carbon atoms may be optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0115] In another preferred embodiment, the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises a siloxane unit (Q unit) selected from the group consisting of SiO2, R 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit), R 4 R 5 SiO 2 / 2 The siloxane units (D units) and R 6 SiO 3 / 2 The polysiloxane (A1) comprises a polyorganosiloxane (a1') and a polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises a siloxane unit (Q' unit) represented by SiO2, a R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane units (M' units), R 4 'R 5 'SiO 2 / 2 The siloxane units (D' units) and R 6 'SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T' units) represented by SiO2, and at least one unit selected from the group consisting of M' units, D' units and T' units, wherein the polyorganosiloxane (a2') comprises a siloxane unit (Q" unit) represented by SiO2, R 1 ”R 2 ”R 3 "SiO 1 / 2 The siloxane units (M" units), R 4 ”R 5 "SiO 2 / 2 The siloxane units (D" units) and R 6 "SiO 3 / 2The siloxane units (T" units) shown in the figure contain one or more units selected from the group consisting of M" units, D" units and T" units.

[0116] It should be noted that (a1′) is an example of (a1), and (a2′) is an example of (a2).

[0117] R 1 ~R 6 is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0118] R 1 '~R 6 ' is a group bonded to a silicon atom, each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6 At least one of ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0119] R 1 ”~R 6 " is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, or a hydrogen atom, R 1 ”~R 6 " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, and the like.

[0120] The alkyl group may be any of linear, branched, and cyclic, preferably linear or branched. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0121] Specific examples of the optionally substituted linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4-methyl n-pentyl, 1,1 The present invention is not limited to 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among them, methyl is particularly preferred.

[0122] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl The cycloalkyl groups include, but are not limited to, cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl; and bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl and dicyclodecyl. The number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0123] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0124] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, vinyl, allyl, butenyl, pentenyl, etc., and the number of carbon atoms thereof is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0125] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms in the cyclic alkenyl group is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0126] As described above, the polysiloxane (A1) includes the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl groups contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a crosslinked structure by a hydrosilylation reaction using a platinum group metal catalyst (A2) and cure. As a result, a cured film is formed.

[0127] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and comprises at least one selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0128] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit).

[0129] In addition, when the polyorganosiloxane (a1') includes two or more polyorganosiloxanes, the combination of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, but not limited to these.

[0130] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units and T" units, and contains at least one selected from the group consisting of M" units, D" units and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0131] Preferred combinations of two or more selected from the group consisting of "Q" units, "M" units, "D" units and "T" units include, but are not limited to: (M" units and "D" units), (Q" units and "M" units), (Q" units, "T" units and "M" units).

[0132] The polyorganosiloxane (a1′) is composed of siloxane units formed by bonding silicon atoms to alkyl and / or alkenyl groups. 1 '~R 6 The ratio of alkenyl groups in all substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R 1 '~R 6 ' can be set to an alkyl group.

[0133] The polyorganosiloxane (a2') is composed of siloxane units formed by bonding silicon atoms with alkyl groups and / or hydrogen atoms. 1 ”~R 6 The ratio of all substituents and hydrogen atoms in the substituent atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 ”~R 6 " can be set to an alkyl group.

[0134] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si—H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0135] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0136] It should be noted that in the present invention, the weight average molecular weight, number average molecular weight and dispersity of the polyorganosiloxane can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH (Co., Ltd.)) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgelSuperMultiporeHZ-H manufactured by TOSOH (Co., Ltd.), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko (Co., Ltd.)) used as a standard sample.

[0137] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and each is usually 10 to 1,000,000 (mPa·s), and preferably 50 to 20,000 (mPa·s) from the viewpoint of achieving the effects of the present invention with good reproducibility. It should be noted that the viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured at 25° C. using an E-type rotational viscometer.

[0138] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other to form a film by a hydrosilylation reaction. Therefore, the curing mechanism is different from the mechanism via a silanol group, and therefore, any siloxane does not need to contain a silanol group or a functional group such as an alkoxy group that forms a silanol group by hydrolysis.

[0139] In a preferred embodiment of the present invention, the adhesive composition contains the polyorganosiloxane component (A') and a platinum group metal catalyst (A2).

[0140] Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si—H group of the polyorganosiloxane (a2).

[0141] Specific examples of the platinum-based metal catalyst include platinum-based catalysts such as platinum black, platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and bisacetoacetate platinum, but are not limited thereto.

[0142] Examples of the complex of platinum and olefins include a complex of divinyltetramethyldisiloxane and platinum, but the complex is not limited thereto.

[0143] The amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually within a range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0144] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.

[0145] The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0146] The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect thereof and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0147] The adhesive composition used in the present invention may contain a release agent component (B). When the adhesive composition used in the present invention contains such a release agent component (B), the obtained adhesive layer can be appropriately released with good reproducibility.

[0148] Such a release agent component (B) is typically polyorganosiloxane, and in a preferred embodiment, specific examples thereof include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, and phenyl-containing polyorganosiloxane, but are not limited thereto.

[0149] In another preferred embodiment, as the release agent component (B), polydimethylsiloxane may be listed, and the polydimethylsiloxane may be optionally modified. As the optionally modified polydimethylsiloxane, for example, epoxy-containing polydimethylsiloxane, unmodified polydimethylsiloxane, phenyl-containing polydimethylsiloxane, etc. may be listed, but it is not limited thereto.

[0150] The weight average molecular weight of the polyorganosiloxane as the release agent component (B) is not particularly limited, but is generally 100,000 to 2,000,000. From the perspective of achieving the effect of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. In addition, the dispersity thereof is not particularly limited, but is generally 1.0 to 10.0. From the perspective of achieving appropriate release with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight average molecular weight and dispersity can be measured by the method described in relation to polysiloxane.

[0151] The complex viscosity of the polyorganosiloxane as the release agent component (B) can be measured at 25° C. using a rheometer (for example, a rheometer MCR-302 manufactured by Anton Paar Co., Ltd.).

[0152] Examples of the epoxy-containing polyorganosiloxane include: 11 R 12 SiO 2 / 2 The siloxane units (D 10 Units) of polyorganosiloxane.

[0153] R 11 is a group bonded to a silicon atom, represents an alkyl group, and R12 It is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group include those described above.

[0154] The epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as 1,2-epoxycyclohexyl group.

[0155] Specific examples of the organic group containing an epoxy group include a 3-glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)ethyl group, but are not limited thereto.

[0156] In the present invention, a preferred example of the epoxy-containing polyorganosiloxane is an epoxy-containing polydimethylsiloxane, but the present invention is not limited thereto.

[0157] The epoxy-containing polyorganosiloxane comprises the siloxane unit (D 10 Unit), but except for D 10 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0158] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: 10 Polyorganosiloxane composed of units; containing D 10 Units and Q units of polyorganosiloxane; containing D 10 Units and M units of polyorganosiloxane; containing D 10 Units and T units of polyorganosiloxane; containing D 10 Unit, Q unit and M unit of polyorganosiloxane; containing D 10 Unit, M unit and T unit of polyorganosiloxane; containing D 10 Unit, Q unit, M unit and T unit of polyorganosiloxane, etc.

[0159] The epoxy-containing polyorganosiloxane is preferably an epoxy-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight is not particularly limited but is usually 1,500 to 500,000, and is preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive.

[0160] Specific examples of the epoxy-containing polyorganosiloxane include polyorganosiloxanes represented by formulae (E1) to (E3), but are not limited thereto.

[0161]

[0162] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0163]

[0164] (m2 and n2 represent the number of repeating units and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0165]

[0166] (m3, n3 and o3 represent the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0167] Examples of the methyl group-containing polyorganosiloxane include: 210 R 220 SiO 2 / 2 The siloxane units (D 200 Units), preferably comprising R 21 R 21 SiO 2 / 2 The siloxane units (D 20 Units) of polyorganosiloxane.

[0168] R 210 and R 220 is a group bonded to a silicon atom, each independently represents an alkyl group, at least one of which is a methyl group, and specific examples of the alkyl group include the above-mentioned examples.

[0169] R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include the above examples. 21 , preferably methyl.

[0170] In the present invention, polydimethylsiloxane is mentioned as a preferred example of the methyl group-containing polyorganosiloxane, but the present invention is not limited to this.

[0171] The methyl-containing polyorganosiloxane comprises the siloxane unit (D 200 Unit or D 20 Unit), but except for D 200 Unit and D 20 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0172] In one embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 200 Polyorganosiloxane composed of units; containing D 200 Units and Q units of polyorganosiloxane; containing D 200 Units and M units of polyorganosiloxane; containing D 200Units and T units of polyorganosiloxane; containing D 200 Unit, Q unit and M unit of polyorganosiloxane; containing D 200 Unit, M unit and T unit of polyorganosiloxane; containing D 200 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0173] In a preferred embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 20 Polyorganosiloxane composed of units; containing D 20 Units and Q units of polyorganosiloxane; containing D 20 Units and M units of polyorganosiloxane; containing D 20 Units and T units of polyorganosiloxane; containing D 20 Unit, Q unit and M unit of polyorganosiloxane; containing D 20 Unit, M unit and T unit of polyorganosiloxane; containing D 20 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0174] Specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane represented by formula (M1), but the present invention is not limited thereto.

[0175]

[0176] (n4 represents the number of repeating units, which is a positive integer.)

[0177] Examples of the phenyl group-containing polyorganosiloxane include: 31 R 32 SiO 2 / 2 The siloxane units (D 30 Units) of polyorganosiloxane.

[0178] R 31 is a group bonded to a silicon atom, representing a phenyl group or an alkyl group, R 32 It is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those described above, and a methyl group is preferred.

[0179] The phenyl-containing polyorganosiloxane comprises the siloxane unit (D 30 Unit), but except for D 30 In addition to the T unit, Q unit, M unit and / or T unit may be included.

[0180] In a preferred embodiment of the present invention, specific examples of phenyl-containing polyorganosiloxanes include: 30Polyorganosiloxane composed of units; containing D 30 Units and Q units of polyorganosiloxane; containing D 30 Units and M units of polyorganosiloxane; containing D 30 Units and T units of polyorganosiloxane; containing D 30 Unit, Q unit and M unit of polyorganosiloxane; containing D 30 Unit, M unit and T unit of polyorganosiloxane; containing D 30 A polyorganosiloxane containing A unit, Q unit, M unit and T unit.

[0181] Specific examples of the phenyl group-containing polyorganosiloxane include polyorganosiloxanes represented by the formula (P1) or (P2), but are not limited thereto.

[0182]

[0183] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0184]

[0185] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0186] The polyorganosiloxane as the release agent component (B) may be a commercially available product or a synthesized polyorganosiloxane.

[0187] Examples of commercially available polyorganosiloxanes include Wacker Chemie products such as the Wackersilicon Fluid AK series (AK 50, AK 350, AK 1000, AK 10000, AK 1000000), GENIOPLAST GUM, Shin-Etsu Chemical Co., Ltd. dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), and cyclic dimethyl silicone oil (KF-995); Gelest Co., Ltd. epoxy-containing polyorganosiloxanes (trade names: CMS-227, ECMS-327); Shin-Etsu Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343); and Dow Chemical Co., Ltd. epoxy-containing polyorganosiloxanes (KF-102, KF-103, KF-104, KF-1056, X-22-347). Epoxy-containing polyorganosiloxane manufactured by Corning (BY16-839); phenyl-containing polyorganosiloxane manufactured by Gelest (PMM-1043, PMM-1025, PDM-0421, PDM-0821), phenyl-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (KF50-3000CS), phenyl-containing polyorganosiloxane manufactured by Momentive (TSF431, TSF433), etc., but not limited to these.

[0188] The adhesive composition used in the present invention contains both a cured component (A) and a release agent component (B), and in a more preferred embodiment, contains polyorganosiloxane as the release agent component (B).

[0189] An example of the adhesive composition used in the present invention may contain a curable component (A) and a release agent component (B) in an arbitrary ratio. If the balance between adhesion and release properties is taken into consideration, the ratio of the curable component (A) to the release agent component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A):(B)].

[0190] That is, when the polyorganosiloxane component (A') that cures by hydrosilylation reaction is included, the ratio of the component (A') to the release agent component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25 in terms of mass ratio [(A'):(B)].

[0191] The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting viscosity, etc. Specific examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited thereto.

[0192] More specifically, examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone. Such solvents may be used alone or in combination of two or more.

[0193] When the adhesive composition used in the present invention contains a solvent, its content is appropriately set in consideration of the desired viscosity of the composition, the coating method to be used, the thickness of the film to be produced, etc., and is within a range of about 10 to 90% by mass based on the entire composition.

[0194] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is generally 500 to 20,000 mPa·s, preferably 1,000 to 5,000 mPa·s at 25° C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the type of solvent used, their ratio, the concentration of film constituent components, etc., taking into account various factors such as the coating method used and the desired film thickness.

[0195] In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0196] One example of the adhesive composition used in the present invention can be produced by mixing the component (A), the release agent component (B), and a solvent when used.

[0197] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing a peeling adhesive composition, for example, there can be cited: a method of dissolving component (A) and peeling agent component (B) in a solvent; a method of dissolving a part of component (A) and peeling agent component (B) in a solvent, dissolving the rest in a solvent, and mixing the resulting solutions, but the present invention is not limited thereto. It should be noted that when preparing the adhesive composition, it can also be heated appropriately within a range in which the components are not decomposed or deteriorated.

[0198] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the preparation of the adhesive composition or after all the components are mixed.

[0199] The thickness of the adhesive layer is not particularly limited, but is preferably 10 to 100 μm, more preferably 20 to 50 μm, from the viewpoint of obtaining a good peeling effect with good reproducibility.

[0200] <Composition for peeling and dissolving>

[0201] The peeling and dissolving composition is a composition used in a method of cleaning a semiconductor substrate in order to remove an adhesive layer from the semiconductor substrate.

[0202] The peeling and dissolving composition contains a component for swelling the adhesive layer to peel the adhesive layer from the semiconductor substrate and a component for dissolving the adhesive layer.

[0203] Specifically, the peeling and dissolving composition contains the following components: component [I]: a quaternary ammonium salt; component [II]: an amide solvent; and component [III]: a solvent represented by the following formula (G).

[0204]

[0205] (Where L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms in the alkyl group is 7 or less.)

[0206] The peeling and dissolving composition may further contain the following components: [IV] Component: a solvent represented by the following formula (T) or the following formula (L).

[0207]

[0208] (Where X 1 and X 3 Each independently represents an alkyl group or an acyl group (X 4 -C(=O)-), X 2 represents an alkylene group, and n represents 2 or 3. 4 represents an alkyl group. )

[0209] L 1 -L 3 -L 2 (L)(where L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S. )

[0210] <<[I] Ingredient: Quaternary ammonium salt>>

[0211] The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for such a purpose.

[0212] The quaternary ammonium salt is effective as a component for dissolving the adhesive layer.

[0213] As such quaternary ammonium cations, tetra(alkyl)ammonium cations are typically mentioned. On the other hand, as anions forming a pair with them, hydroxide ions (OH － );Fluoride ion (F － ), chloride ion (Cl － ), bromide ion (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ion (BF4 － );PF6 － ), etc., but not limited to these.

[0214] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.

[0215] In the quaternary ammonium salt, the halogen atom may be contained in the cation or in the anion, but is preferably contained in the anion.

[0216] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0217] Specific examples of the hydrocarbon group in tetrahydrocarbyl ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.

[0218] In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.

[0219] Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride). Among them, tetrabutylammonium fluoride is preferred.

[0220] A quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used in the form of a hydrate. In addition, a quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used alone or in combination of two or more.

[0221] The amount of the quaternary ammonium salt is not particularly limited as long as it is dissolved in the solvent contained in the stripping and dissolving composition, but a small amount of the quaternary ammonium salt can effectively prevent the problem of damage to the dicing tape in the cleaning process described later, so it is preferred. Specifically, for example, it is usually 0.1 to 5% by mass relative to the stripping and dissolving composition.

[0222] <<[II] Component: Amide-based solvent>>

[0223] The amide solvent is effective as a component for dissolving the quaternary ammonium salt well and obtaining a peeling and dissolving composition having excellent uniformity.

[0224] The amide solvent is preferably an N-substituted amide compound having 4 or more carbon atoms and having no active hydrogen on the nitrogen atom.

[0225] As a preferred example of the amide solvent, there is mentioned an amide derivative represented by the following formula (Z).

[0226]

[0227] In the formula, R 0 R represents ethyl, propyl or isopropyl, preferably ethyl or isopropyl, more preferably ethyl. A and R B Each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be any of linear, branched, and cyclic, and specific examples thereof include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclobutyl. A and R B , preferably methyl or ethyl, more preferably both are methyl or ethyl, further preferably both are methyl.

[0228] Examples of the amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutanamide, N,N-diethylbutanamide, N-ethyl-N-methylbutanamide, N,N-dimethylisobutanamide, N,N-diethylisobutanamide, and N-ethyl-N-methylisobutanamide. Among them, N,N-dimethylpropanamide and N,N-dimethylisobutanamide are particularly preferred, and N,N-dimethylpropanamide is more preferred.

[0229] The amide derivative represented by the formula (Z) can be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product can be used.

[0230] Another example of a preferred amide solvent includes a compound represented by formula (Y) including a lactam compound.

[0231]

[0232] In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 It represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).

[0233]

[0234] As R 102Specific examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, n-butyl, etc. Specific examples of the alkylene group having 1 to 6 carbon atoms include: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited to these.

[0235] In formula (Y1), R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 104 represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond to a carbon atom in formula (Y), and *2 represents a bond to a nitrogen atom in formula (Y).

[0236] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, and the like, and these may be used alone or in combination of two or more.

[0237] In a preferred embodiment, the lactam compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, contains N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment, contains N-methylpyrrolidone (NMP).

[0238] Furthermore, as a preferred embodiment of the compound represented by formula (Y), for example, 1,3-dimethyl-2-imidazolidinone can also be mentioned.

[0239] Among the components [II], in consideration of operational restrictions based on regulations related to use in chemical substances, it is more preferable to use an amide derivative represented by formula (Z).

[0240] The content of the amide solvent in the peeling and dissolving composition can be 50% by mass or less when the aprotic solvent is 100% by mass in the peeling and dissolving composition.

[0241] In addition, the content of the amide solvent is preferably 5 mass % or more, more preferably 10 mass % or more, preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 30 mass % or less, and particularly preferably 20 mass % or less, when the aprotic solvent is set to 100 mass %.

[0242] In addition, in the present invention, the content of the mixed solvent is specified as a ratio when the aprotic solvent is taken as 100 mass %, and the aprotic solvent is a solvent having no hydroxyl group (—OH).

[0243] Therefore, protic solvents such as water, methanol, and 1-methoxy-2-propanol are not included in the criteria of the content ratio.

[0244] In the present invention, the aprotic solvent refers to, for example, N,N-dimethylpropionamide, butyl acetate, dipropylene glycol dimethyl ether, dibutyl ether, and the like, and the mixing ratio can be determined based on the total amount thereof.

[0245] <<[III] Component: a solvent represented by formula (G)>>

[0246] The solvent represented by the following formula (G) is effective as a component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.

[0247]

[0248] In formula (G), L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms of the alkyl group is 7 or less.

[0249] In the above formula (G), L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms of the alkyl group is not more than 7. By setting the number of carbon atoms to such a level, the adhesive layer can be peeled off in a short time with good reproducibility.

[0250] The alkyl group may be linear, branched, or cyclic, and is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

[0251] Specific examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, The present invention includes, but is not limited to, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl.

[0252] Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, Cycloalkyl groups such as 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl are also included, but are not limited thereto.

[0253] From the viewpoint of achieving peeling of the adhesive layer in a shorter time with good reproducibility, the above L 11 Preferably, methyl group, in addition, the above L 12 Preferred is butyl or pentyl.

[0254] From the viewpoint of achieving peeling of the adhesive layer in a shorter time with good reproducibility and the viewpoint of easy availability of the compound, preferred examples of the organic solvent represented by formula (G) include butyl acetate and amyl acetate.

[0255] The content of the solvent represented by the formula (G) in the peeling and dissolving composition may be more than 31% by mass when the aprotic solvent in the peeling and dissolving composition is 100% by mass.

[0256] The content of the solvent represented by formula (G) in the stripping and dissolving composition is preferably more than 31% by mass, more preferably more than 35% by mass, further preferably 40% by mass or more, further preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less, when the aprotic solvent is 100% by mass in the stripping and dissolving composition. These upper and lower limits may be combined arbitrarily.

[0257] It should be noted that the peeling and dissolving composition may contain an arbitrary amount of a solvent for the component [IV] represented by the following formula (T) or the following formula (L) and may be mixed with a solvent for the component [III] represented by the following formula (G). In this case, the total content of the components [III] and [IV] is preferably 30 to 90% by mass when the aprotic solvent is taken as 100% by mass.

[0258] <<[IV] Component: a solvent represented by formula (T) or formula (L)>>

[0259] The solvent represented by the following formula (T) or the following formula (L) is effective as an adjusting component for improving the compatibility and peeling properties of the above-mentioned component [II], i.e., the amide solvent, and the above-mentioned component [III], i.e., the solvent represented by the above-mentioned formula (G), in the peeling and dissolving composition containing the above-mentioned component [I], i.e., the quaternary ammonium salt.

[0260] In particular, when the component [IV] is a solvent represented by formula (L), it has good compatibility with the component [III], i.e., the solvent represented by formula (G), and can form a peeling and dissolving composition that well exhibits the effects of the present invention.

[0261]

[0262] In formula (T), X 1 and X 3 Each independently represents an alkyl group or an acyl group (X 4 -C(=O)-), X 2 represents an alkylene group, and n represents 2 or 3. 4 represents an alkyl group.

[0263] Examples of the alkyl group represented by X1 and X3 include alkyl groups having 1 to 4 carbon atoms, and more specifically, include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.

[0264] Examples of the alkylene group represented by X2 include a methylene group, an ethylene group, a 1,3-propylene group, and a 1,2-propylene group.

[0265] Examples of the alkyl group represented by X4 include alkyl groups having 1 to 4 carbon atoms, and examples thereof include the same alkyl groups as those for X1 and X3.

[0266] Preferred examples of the solvent represented by formula (T) include dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0267] L 1 -L 3 -L 2 (L)

[0268] In the above formula (L), L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S.

[0269] L 1 and L 2 The groups may be the same or different, but are preferably the same from the viewpoint of availability.

[0270] The alkyl group having 2 to 5 carbon atoms may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear, from the viewpoint of achieving peeling of the adhesive layer in a short time with good reproducibility.

[0271] Specific examples of the linear or branched alkyl group include, but are not limited to, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl.

[0272] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, and the like, but are not limited thereto.

[0273] From the viewpoint of achieving peeling of the adhesive layer in a short time with good reproducibility, the alkyl group having 2 to 5 carbon atoms is preferably ethyl, n-propyl, n-butyl or n-pentyl, and more preferably ethyl, n-propyl or n-butyl.

[0274] From the perspective of achieving peeling of the adhesive layer in a shorter time with good reproducibility and the ease of obtaining the compound, L 1 and L 2 The same groups are preferred.

[0275] From the perspective of achieving peeling of the adhesive layer in a shorter time with good reproducibility and the perspective of easy availability of the compound, preferred examples of the organic solvent represented by formula (L) include di(n-butyl) ether, diethyl ether, di(n-pentyl) ether, di(n-propyl) sulfide, and the like.

[0276] The content of the solvent represented by formula (T) or (L) in the peeling and dissolving composition is preferably less than 30% by mass when the aprotic solvent in the peeling and dissolving composition is 100% by mass.

[0277] The content of the solvent represented by formula (T) or (L) in the stripping and dissolving composition is preferably less than 30% by mass, more preferably 25% by mass or less, and further preferably 20% by mass or less, when the aprotic solvent is set to 100% by mass in the stripping and dissolving composition.

[0278] In particular, when the solvent represented by formula (L) is contained as component IV, the content of the solvent represented by formula (L) in the peeling and dissolving composition is more preferably less than 30% by mass when the aprotic solvent is 100% by mass in the peeling and dissolving composition.

[0279] <<Peeling and dissolving process>>

[0280] In the present invention, the peeling and dissolving composition is continuously in contact with the adhesive layer on the semiconductor substrate. By performing the cleaning operation, the adhesive layer is swollen and peeled, and the adhesive layer is dissolved. By a cleaning operation using a cleaning composition, the swelling, peeling and dissolution of the adhesive layer are performed at the same time, thereby the adhesive layer can be removed (cleaned) from the semiconductor substrate in a shorter time and more cleanly with a simple cleaning operation.

[0281] It should be noted that in the present invention, removal (cleaning) refers to removing the adhesive layer from the semiconductor substrate. The situation where the adhesive layer swells and peels off from the semiconductor substrate and the situation where the adhesive layer dissolves, dissolves in the solution, and disappears from the semiconductor substrate are all included in "removal (cleaning)".

[0282] As for the method of making the adhesive layer on the semiconductor substrate continuously contact with the stripping and dissolving composition, there is no particular limitation as long as the adhesive layer on the semiconductor substrate is in contact with the stripping and dissolving composition in a manner with temporal continuity. The temporal continuity not only includes the case where the adhesive layer is always in contact with the stripping and dissolving composition, but also includes, for example, the case where the adhesive layer is in contact with the organic solvent for a certain period of time, the contact is temporarily stopped, and the contact is performed again; the case where the above operation is repeated, in addition, not only the case where the entire adhesive layer on the semiconductor substrate is in contact with the stripping and dissolving composition, but also the case where a part of the adhesive layer is in contact with the stripping and dissolving composition. From the perspective of achieving more effective cleaning with good reproducibility, it is preferred that the adhesive layer on the semiconductor substrate is always in contact with the stripping and dissolving composition. In addition, it is preferred that the adhesive layer on the semiconductor substrate is in contact with the stripping and dissolving composition as a whole.

[0283] Therefore, in a preferred embodiment of the present invention, the adhesive layer on the semiconductor substrate is made to swell and dissolve by immersing the above-mentioned adhesive layer in a stripping and dissolving composition, and is removed from the semiconductor substrate; or the adhesive layer on the semiconductor substrate is made to swell and dissolve by continuously supplying the stripping and dissolving composition to the above-mentioned adhesive layer, and is removed from the semiconductor substrate.

[0284] In order to immerse the adhesive layer on the semiconductor substrate in the peeling and dissolving composition, for example, the semiconductor substrate with the adhesive layer may be immersed in the peeling and dissolving composition.

[0285] The immersion time is set to the time until the adhesive layer swells and dissolves and is peeled off from the semiconductor substrate. It is not particularly limited, but is 5 seconds or more from the perspective of achieving more effective cleaning with good reproducibility, and 5 minutes or less from the perspective of process throughput.

[0286] When the adhesive layer on the semiconductor substrate is immersed in the stripping and dissolving composition, the removal (cleaning) of the adhesive layer can be promoted by moving the semiconductor substrate with the adhesive layer in the stripping and dissolving composition, convection of the stripping and dissolving composition, vibrating the stripping and dissolving composition using ultrasound, etc.

[0287] In order to move the semiconductor substrate with an adhesive layer in the stripping and dissolving composition, for example, an oscillating cleaning machine, a paddle cleaning machine, etc. can be used. If such a cleaning machine is used, the table carrying the semiconductor substrate with an adhesive layer is moved up and down or left and right or rotated, so that the adhesive layer on the semiconductor substrate is relatively subjected to convection; or the adhesive layer on the semiconductor substrate is subjected to the convection generated by the movement or rotation, which not only promotes the swelling and dissolution of the adhesive layer on the semiconductor substrate, but also promotes the stripping and dissolution of the adhesive layer from the semiconductor substrate.

[0288] In order to make the stripping and dissolving composition convect, in addition to using the above-mentioned oscillating cleaning machine and paddle cleaning machine, for example, typically, it is sufficient to use the following convection cleaning machine: a convection cleaning machine in which, when a semiconductor substrate with an adhesive layer is fixed to a table, etc., the stripping and dissolving composition around it can be convected by a stirrer.

[0289] In order to vibrate the peeling and dissolving composition by ultrasonic wave, an ultrasonic cleaning machine and an ultrasonic probe may be used, and the conditions are usually 20 kHz to 5 MHz.

[0290] In order to continuously supply the stripping and dissolving composition to the adhesive layer on the semiconductor substrate, it is sufficient to continuously collide the stripping and dissolving composition with the adhesive layer on the semiconductor substrate. If an example is given, if the adhesive layer on the semiconductor substrate is facing upward, then, for example, from above the adhesive layer on the semiconductor substrate (including obliquely upward), a rod-shaped or mist-shaped, preferably rod-shaped, stripping and dissolving composition is supplied to the adhesive layer on the semiconductor substrate through the nozzle of the cleaning device, etc. in a manner with temporal continuity. The temporal continuity in this case also includes not only the situation that the stripping and dissolving composition is always supplied to the adhesive layer on the semiconductor substrate, but also includes, for example, after a certain period of time of supplying the stripping and dissolving composition, the supply is temporarily stopped and the supply is performed again; the situation of repeatedly performing the above operation, from the viewpoint of achieving more effective cleaning with good reproducibility, it is preferred that the stripping and dissolving composition is always supplied to the adhesive layer on the semiconductor substrate.

[0291] When the peeling and dissolving composition is supplied in a rod shape onto the adhesive layer on the semiconductor substrate, the flow rate thereof is usually 200 to 500 mL / min.

[0292] In one embodiment of the present invention, in order to achieve a state of constant contact with the peeling and dissolving composition, for example, a vapor cleaner may be used to bring the adhesive layer on the semiconductor substrate into contact with vapor of the peeling and dissolving composition.

[0293] If the semiconductor cleaning method of the present invention is used, the swelling, peeling and dissolution of the adhesive layer are performed together as described above, thereby making it possible to remove (clean) the adhesive layer from the semiconductor substrate in a shorter time and more cleanly with a simple cleaning operation. It should be noted that in addition to this effect, if the semiconductor cleaning method of the present invention is used, it is also possible to prevent damage to the dicing tape during the cleaning process.

[0294] For example, after the semiconductor wafer is ground and thinned, the thinned semiconductor wafer is mounted on a dicing tape, and then the semiconductor wafer is separated (peeled off) from the support. After the support is separated (peeled off), the adhesive layer remaining on the semiconductor wafer side is cleaned using a cleaning agent composition in order to be removed from the semiconductor wafer. At this time, if a cleaning agent composition of the type that attempts to dissolve and remove adhesive residues, such as the cleaning agent compositions of the above-mentioned patent documents 1 and 2, is used as the cleaning agent composition, the surface of the dicing tape changes and the dicing tape is damaged.

[0295] However, if the stripping and dissolving composition of the present invention is used to clean a semiconductor substrate with an adhesive layer, most of the adhesive layer can be stripped in a short time, and the small amount of adhesive layer remaining after stripping is also dissolved by the soluble components in the stripping and dissolving composition, so the overall removal (cleaning) time of removing the adhesive layer is short, which can effectively prevent damage to the dicing tape in the cleaning process. In addition, the stripping and dissolving composition of the present invention contains not only a component for dissolving the adhesive layer, but also a component for swelling and stripping the adhesive layer, so that the proportion of the soluble component in the composition, i.e., component [I] (quaternary ammonium salt), is small, and it effectively helps to prevent damage to the dicing tape.

[0296] When the adhesive layer removal step is performed using the peeling and dissolving composition of the present invention, damage to the dicing tape can be effectively prevented.

[0297] The semiconductor substrate cleaning method of the present invention may include a step of removing the peeled adhesive layer.

[0298] The method of removing the adhesive layer after peeling is not particularly limited as long as the adhesive layer after peeling is removed from the semiconductor substrate. When the semiconductor substrate with the adhesive layer is immersed in the peeling and dissolving composition, the adhesive layer after peeling present in the peeling and dissolving composition can be removed without taking the semiconductor substrate out of the peeling and dissolving composition. Alternatively, the adhesive layer after peeling can be removed by taking the semiconductor substrate out of the peeling and dissolving composition and separating the semiconductor substrate from the adhesive layer after peeling. At this time, by only taking the semiconductor substrate out of the peeling and dissolving composition, the adhesive layer after peeling sometimes naturally remains in the peeling and dissolving composition, and most of it can be removed.

[0299] Specific examples of methods for removing the adhesive layer after peeling include: removing the adhesive layer after peeling by adsorption or suction using a device, removing the adhesive layer after peeling by blowing away gas using an air gun, etc., removing the adhesive layer after peeling by using centrifugal force generated by moving or rotating the semiconductor substrate up and down or left and right, etc., but the invention is not limited to these.

[0300] After the peeled adhesive layer is removed from the semiconductor substrate, the semiconductor substrate is dried or the like according to a conventional method as necessary.

[0301] (Composition for peeling and dissolving)

[0302] The peeling and dissolving composition used in the semiconductor substrate cleaning method of the present invention is also an object of the present invention.

[0303] The composition for stripping and dissolving of the present invention is used to remove (clean) the adhesive layer on the semiconductor substrate from the semiconductor substrate, and the preferred embodiments and conditions are as described above. The composition for stripping and dissolving of the present invention can be prepared by mixing the solvents constituting the composition in any order as required. At this time, filtration etc. can also be performed as required.

[0304] As a preferred embodiment of the peeling and dissolving composition of the present invention, there can be mentioned a peeling and dissolving composition that satisfies at least any one of the following (i) to (iv).

[0305] (i): The peeling and dissolving composition comprises components [I], [II] and [III], wherein the content of component [II] in 100% by mass of the aprotic solvent is 20% by mass or less, and the content of component [III] is 60% by mass or more.

[0306] (ii): The peeling and dissolving composition comprises the components [I], [II] and [III], wherein the content of the component [III] in 100% by mass of the aprotic solvent is 70% by mass or more.

[0307] (iii): The peeling and dissolving composition comprises component [I], component [II], component [III] and component [IV], wherein the component [IV] comprises a solvent represented by the above formula (L), and when the aprotic solvent is taken as 100% by mass, the content of the component [III] is more than 31% by mass, and the content of the component [IV] is less than 30% by mass.

[0308] In addition, as another preferred embodiment of (iii), the following composition can be listed: the peeling and dissolving composition comprises component [I], component [II], component [III] and component [IV], wherein the component [IV] comprises the solvent represented by the above formula (L), and when the aprotic solvent is set to 100 mass%, the content of the component [III] is more than 35 mass%, and the content of the component [IV] is less than 30 mass%.

[0309] (iv): The peeling and dissolving composition comprises component [I], component [II], component [III] and component [IV], wherein the component [IV] comprises a solvent represented by the above formula (T), and when the aprotic solvent is set to 100 mass%, the content of the component [III] is more than 31 mass%, the content of the component [IV] is less than 30 mass%, and the content of the component [II] is less than 20 mass%.

[0310] In particular, the following composition also showed good results: when the peeling and dissolving composition contains component [I], component [II], component [III] and component [IV], and the component [IV] is a solvent represented by the above formula (L), when the aprotic solvent is set to 100 mass%, for example, the component [II] is 30 mass% or more and 50 mass% or less, and the component [III] is more than 31 mass% and 50 mass% or less, and the component [IV] is 10 mass% or more and less than 30 mass%.

[0311] (Method for manufacturing processed semiconductor substrate)

[0312] By using the semiconductor substrate cleaning method of the present invention described above, the adhesive layer on the semiconductor substrate, especially the adhesive layer in the form of a cured film obtained from the following siloxane-based adhesive, can be efficiently removed, and it can be expected that a highly efficient and good semiconductor element can be manufactured, wherein the siloxane-based adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

[0313] The method for manufacturing a processed semiconductor substrate of the present invention can, for example, manufacture a processed semiconductor substrate with a clean surface and no residual adhesive layer in the following manner: after the semiconductor wafer is polished and thinned, the support body is separated (peeled off) from the processed thinned semiconductor wafer, and then the semiconductor substrate cleaning method of the present invention is used to remove (clean) the adhesive layer remaining on the semiconductor wafer side.

[0314] As described above, examples of the use of the semiconductor substrate cleaning method of the present invention in semiconductor processes include use in a method for manufacturing a semiconductor substrate that has been processed by thinning or the like for semiconductor packaging technology such as TSV.

[0315] The semiconductor substrates that are cleaned by the cleaning method of the present invention include, in addition to the above-mentioned silicon semiconductor substrates such as the silicon wafer, various substrates such as germanium substrates, gallium-arsenic substrates, gallium-phosphorus substrates, gallium-arsenic-aluminum substrates, aluminum-coated silicon substrates, copper-coated silicon substrates, silver-coated silicon substrates, gold-coated silicon substrates, titanium-coated silicon substrates, silicon nitride film-formed silicon substrates, silicon oxide film-formed silicon substrates, polyimide film-formed silicon substrates, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.

[0316] As a preferred embodiment of the method for manufacturing a processed semiconductor substrate of the present invention, the following method for manufacturing a processed semiconductor substrate can be listed, which includes: a first step: a step of manufacturing a stack comprising a semiconductor substrate, a supporting substrate and an adhesive layer obtained from an adhesive composition; a second step: a step of processing the semiconductor substrate of the obtained stack; a third step: a step of separating the semiconductor substrate and the adhesive layer from the supporting substrate; and a fourth step: a step of removing the adhesive layer on the semiconductor substrate by peeling and dissolving it using a peeling and dissolving composition.

[0317] Here, the peeling and dissolving composition is as described in the above-mentioned column of <Peeling and dissolving composition>.

[0318] In the fourth step, the semiconductor substrate cleaning method of the present invention is used.

[0319] Hereinafter, each step will be described in detail.

[0320] <First step>

[0321] As the adhesive composition for forming the adhesive layer in the first step, the various adhesives mentioned above can be used. The semiconductor substrate cleaning method of the present invention is effective for removing the adhesive layer obtained from the polysiloxane adhesive, and is more effective for removing the adhesive layer obtained from the polysiloxane adhesive containing component (A) cured by a hydrosilylation reaction.

[0322] Therefore, the following describes an example in which, when a processed semiconductor substrate is manufactured using an adhesive layer obtained using a polysiloxane-based adhesive (adhesive composition), the adhesive layer is removed by the cleaning method of the present invention, but the present invention is not limited thereto.

[0323] Hereinafter, the first step of producing a laminate including a semiconductor substrate, a supporting substrate, and an adhesive layer obtained from an adhesive composition will be described.

[0324] In a certain embodiment, the first step includes: a step of applying an adhesive composition on the surface of a semiconductor substrate or a supporting substrate to form an adhesive coating layer; and a step of laminating the semiconductor substrate and the supporting substrate together via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the supporting substrate to make them fit together while performing at least one of a heating treatment and a decompression treatment, and then performing a post-heating treatment to thereby form a laminated body.

[0325] In another embodiment, the first process includes, for example, a process of applying an adhesive composition to the circuit surface of a wafer of a semiconductor substrate, heating it, and forming an adhesive coating layer; a process of applying a stripper composition to the surface of a supporting substrate, heating it, and forming a stripper coating layer; and a process of applying a load in the thickness direction of the semiconductor substrate and the supporting substrate to the adhesive coating layer of the semiconductor substrate and the stripper coating layer of the supporting substrate while performing at least one of a heating treatment and a decompression treatment, and then performing a post-heating treatment to form a laminate. It should be noted that the adhesive composition is applied to the semiconductor substrate, and the stripper composition is applied to the supporting substrate, and heated, but the adhesive composition and the stripper composition can also be applied and heated in sequence on either substrate.

[0326] In each of the above schemes, the treatment conditions of heating treatment, reduced pressure treatment, or a combination of the two are determined based on various circumstances such as the type of adhesive composition, the specific composition of the release agent composition, the phase properties of the films obtained from the two compositions, the film thickness, the required bonding strength, etc.

[0327] Here, for example, the semiconductor substrate is a wafer, and the supporting substrate is a support. The target to which the adhesive composition is applied may be either or both of the semiconductor substrate and the supporting substrate.

[0328] Examples of the wafer include a silicon wafer or a glass wafer having a diameter of about 300 mm and a thickness of about 770 μm, but the wafer is not limited thereto.

[0329] In particular, the semiconductor substrate cleaning method of the present invention can effectively clean a semiconductor substrate having bumps.

[0330] Specific examples of such semiconductor substrates with bumps include silicon wafers having bumps such as spherical bumps, printed bumps, columnar bumps (stud bumps), and plated bumps, which are usually appropriately selected from the conditions of a bump height of about 1 to 200 μm, a bump diameter of 1 to 200 μm, and a bump pitch of 1 to 500 μm.

[0331] Specific examples of the plated bump include alloy plating mainly containing Sn, such as SnAg bump, SnBi bump, Sn bump, and AuSn bump, but the present invention is not limited thereto.

[0332] The support (carrier) is not particularly limited, and examples thereof include a silicon wafer having a diameter of 300 mm and a thickness of about 700 μm, but the support is not limited thereto.

[0333] Examples of the release agent composition include compositions containing a release agent component for such applications.

[0334] The coating method is not particularly limited, but is usually a spin coating method. It should be noted that a coating film may be formed separately by a spin coating method or the like, and a sheet-like coating film may be attached, which is also referred to as coating or coating film.

[0335] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive components contained in the adhesive composition, whether a solvent is contained, the desired thickness of the adhesive layer, etc., and therefore cannot be generally specified, but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0336] The heating temperature of the stripping agent composition after coating varies depending on the type and amount of the crosslinking agent, acid generator, acid, etc.; whether a solvent is contained; the thickness of the desired stripping layer, etc., and therefore cannot be generally specified. From the viewpoint of achieving appropriate curing, it is 120° C. or higher, and from the viewpoint of preventing excessive curing, it is preferably 260° C. or lower, and the heating time is generally 1 to 10 minutes.

[0337] Heating can be performed using a hot plate, an oven, or the like.

[0338] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating the adhesive composition is usually 5 to 500 μm.

[0339] The film thickness of the release agent coating layer obtained by applying the release agent composition and heating the release agent composition is usually 5 to 500 μm.

[0340] The heat treatment temperature is usually appropriately determined within the range of 20 to 150° C., from the viewpoint of softening the adhesive coating layer to achieve appropriate adhesion with the release coating layer, and from the viewpoint of achieving appropriate curing of the release coating layer. In particular, from the viewpoint of suppressing / avoiding excessive curing and unnecessary deterioration of the adhesive component and the release component, the temperature is preferably 130° C. or less, and more preferably 90° C. or less. From the viewpoint of reliably demonstrating the adhesive ability and the release ability, the heating time is usually 30 seconds or more, and preferably 1 minute or more. From the viewpoint of suppressing the deterioration of the adhesive layer and other members, the heating time is usually 10 minutes or less, and preferably 5 minutes or less.

[0341] The reduced pressure treatment may be performed by exposing the semiconductor substrate, the adhesive coating layer and the supporting substrate or the semiconductor substrate, the adhesive coating layer, the release agent coating layer and the supporting substrate to a gas pressure of 10 to 10000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0342] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are bonded together preferably by a reduced pressure treatment, more preferably by a combination of a heating treatment and a reduced pressure treatment.

[0343] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate and the layers therebetween and allows them to be firmly adhered to each other, and is usually in the range of 10 to 1000N.

[0344] The post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing speed, and is preferably 260° C. or lower from the viewpoint of preventing the deterioration of the substrate, adhesive component, stripping agent component, etc. The heating time is usually 1 minute or more from the viewpoint of achieving appropriate bonding of the wafer based on curing, and is preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive, and is usually 180 minutes or less, preferably 120 minutes or less from the viewpoint of avoiding adverse effects on the adhesive layer caused by excessive heating. Heating can be performed using a hot plate, an oven, etc.

[0345] It should be noted that one of the purposes of the post-heat treatment is to cure the adhesive component (S) more appropriately.

[0346] <Second step>

[0347] Next, a second step of processing the semiconductor substrate of the laminated body obtained by the method described above will be described.

[0348] As an example of processing performed on the laminate used in the present invention, the processing of the back side opposite to the circuit side of the surface of the semiconductor substrate can be cited. Typically, the thinning of the wafer by grinding the back side of the wafer can be cited. Using such a thinned wafer, through silicon vias (TSV) and the like are formed, and then the thinned wafer is peeled off from the support to form a laminate of wafers for three-dimensional mounting. In addition, the formation of the back electrode of the wafer and the like is also performed before and after the three-dimensional mounting. In the thinning and TSV processes of the wafer, heat of 250 to 350°C is applied in a state of being bonded to the support, and the adhesive layer contained in the laminate used in the present invention has heat resistance to the heat.

[0349] For example, in the case of a wafer having a diameter of 300 mm and a thickness of about 770 μm, the back surface opposite to the circuit surface can be polished to be thinned to a thickness of about 80 to 4 μm.

[0350] <Third step>

[0351] The third step of separating the processed semiconductor substrate and adhesive layer from the support substrate will be described.

[0352] In the third step, the processed semiconductor substrate and adhesive layer are separated from the support substrate. At this time, when a release layer is included in the laminate, the release layer is usually removed together with the support substrate.

[0353] The method for separating the processed semiconductor substrate and the adhesive layer from the supporting substrate is to peel off the adhesive layer and the peeling layer or the supporting substrate in contact with the adhesive layer. Examples of such peeling methods include laser peeling, mechanical peeling using a tool with a sharp portion, manual peeling, etc., but are not limited to these.

[0354] <Fourth step>

[0355] Next, the fourth step of removing the adhesive layer on the processed semiconductor substrate and cleaning the processed semiconductor substrate will be described.

[0356] The fourth step is to remove the adhesive layer on the semiconductor substrate by the semiconductor substrate cleaning method of the present invention. Specifically, for example, the adhesive layer on the thinned substrate is removed cleanly in a short time by the cleaning method of the present invention. The conditions at this time are as described above.

[0357] As described above, only by performing the cleaning operation using the peeling and dissolving composition of the present invention, swelling and dissolution act simultaneously on the adhesive layer, so that in the fourth step, the adhesive layer on the semiconductor substrate can be removed more cleanly in a shorter time.

[0358] The method for manufacturing a processed semiconductor substrate of the present invention includes the first to fourth steps described above, and may also include steps other than these steps. In addition, various changes may be made to the above-mentioned constituent elements and method elements related to the first to fourth steps as long as they do not deviate from the scope of the present invention.

[0359] Example

[0360] Hereinafter, the content and effects of the present invention will be described in further detail by way of examples, but the present invention is not limited thereto. It should be noted that the apparatus used is as follows.

[0361] [Device]

[0362] (1) Mixer A: ARE-500, a rotary and revolving mixer manufactured by THINKY Co., Ltd.

[0363] (2) Mixer B: Mixing rotor VMR-5R manufactured by AS ONE Co., Ltd.

[0364] (3) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.

[0365] (4) Optical microscope: MX61L semiconductor / FPD inspection microscope manufactured by Olympus Corporation.

[0366] [1] Preparation of Adhesive Composition 1

[0367] [Example 1]

[0368] Into a 600 mL stirring container dedicated to the stirrer A, 230.01 g of a p-menthane solution (concentration 81.7 mass %) of an MQ resin (manufactured by Wacker Chemie) having a polysiloxane skeleton and a vinyl group as the component (a1), 78.06 g of the polyorganosiloxane represented by the formula (M1) as the component (B) (complex viscosity 6000 Pa·s, weight average molecular weight 642000 (dispersity 2.6), manufactured by Wacker Chemie, trade name GENIOPLAST GUM), 164.62 g of p-menthane (manufactured by Nippon Terpene Chemicals Co., Ltd.) and 23.13 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) were added, and stirring was repeated for a total of 8 times for 5 minutes with a short break, thereby obtaining a mixture (I) (total stirring time 40 minutes).

[0369] To the obtained mixture (I), 37.58 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa·s as the component (a2) and 54.93 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 200 mPa·s as the component (a1) were added to obtain a mixture (II).

[0370] 0.87 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as the component (A3), 0.87 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie Co., Ltd.) as the component (A3), and 1.73 g of p-menthane (manufactured by Nippon Terpene Chemicals Co., Ltd.) were stirred for 60 minutes using a stirrer B to obtain a mixture (III).

[0371] 2.89 g of the obtained mixture (III) was added to the mixture (II), and the mixture was stirred for 5 minutes using a stirrer A to obtain a mixture (IV).

[0372] 0.139 g of the platinum catalyst (manufactured by Wacker Chemie) as the component (A2) and 10.41 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1000 mPa·s as the component (a1) were stirred for 5 minutes using a stirrer A to obtain a mixture (V).

[0373] 8.79 g of the obtained mixture (V) was added to the mixture (IV), and the mixture was stirred for 5 minutes using the stirrer A to obtain a mixture (VI).

[0374] Finally, the obtained mixture (VI) was filtered through a 300-mesh nylon filter to obtain an adhesive composition. The viscosity of the obtained adhesive composition was 2500 mPa·s.

[0375] [2] Preparation of cleaning composition

[0376] [Example 2-1]

[0377] 1.40 g of N-methyl-2-pyrrolidone, 9.80 g of butyl acetate, and 2.80 g of dipropylene glycol dimethyl ether were added to 0.42 g of tetrabutylammonium fluoride trihydrate (produced by Kanto Chemical), and the mixture was stirred to obtain a cleaning composition.

[0378] [Example 2-2] to [Example 2-5], [Comparative Example 1-1] to [Comparative Example 1-8]

[0379] A cleaning composition was obtained by the same procedure as in Example 2-1 except that the compositions were adjusted to be shown in Tables 1 to 3 (Tables 1 to 3 are also collectively referred to as Table 1, etc.).

[0380] [Example 2-6] to [Example 2-8]

[0381] A cleaning composition was obtained by the same procedure as in Example 2-1 except that N-ethyl-2-pyrrolidone was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound of the component II and the composition was adjusted to be as shown in Table 1 and the like.

[0382] [Example 2-9] to [Example 2-11]

[0383] A cleaning composition was obtained by the same procedure as in Example 2-1 except that N,N-dimethylpropionamide was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound of the component II and the composition was adjusted to be as shown in Table 1.

[0384] [Example 2-12] to [Example 2-14]

[0385] A cleaning composition was obtained by the same procedure as in Example 2-1 except that 1,3-dimethyl-2-imidazolidinone was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound of the component II and the composition was adjusted to be as shown in Table 1.

[0386] [Example 2-15] to [Example 2-16]

[0387] A cleaning composition was obtained by the same procedure as in Example 2-1 except that dibutyl ether was used as the IV component instead of dipropylene glycol dimethyl ether to adjust the composition to be as shown in Table 1 and the like.

[0388] [3] Preparation of evaluation substrate

[0389] [Production Example 1]

[0390] The adhesive composition obtained in Example 1 was applied to a 4 cm × 4 cm silicon wafer (775 μm thick) serving as the device side chip by spin coating, and then heated at 110°C for 1.5 minutes (pre-heating treatment), and then heated at 200°C for 10 minutes to remove the residual solvent on the chip, thereby forming a thin film with a thickness of about 40 μm on the chip, thereby obtaining a chip with an adhesive layer.

[0391] [4] Measurement of peeling time

[0392] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 7 mL of each cleaning composition obtained in Examples 2-1 to 2-16 and Comparative Examples 1-1 to 1-8. The time until the adhesive layer is completely peeled off from the wafer is referred to as the peeling time. The results are shown in Tables 1 to 3 below. It should be noted that in the test of [4] above, Comparative Examples 1-1 and 1-2 became turbid after adding TBAF, so the test of [4] was not carried out (represented as "NA" in the table).

[0393] [5] Check whether there is any residue after peeling

[0394] The wafer with the adhesive layer prepared in Manufacturing Example 1 was immersed in 7 mL of each cleaning composition obtained in Examples 2-1 to 2-16 and Comparative Examples 1-1 to 1-8. After being immersed in the cleaning composition, if the adhesive layer peeled off within 1 minute, the peeled adhesive layer was removed with tweezers. After standing for 1 minute from the start of immersion, the substrate was cleaned with isopropyl alcohol and ultrapure water, and the presence or absence of residue on the substrate was confirmed with an optical microscope. The results are shown in Tables 1 to 3 below. It should be noted that Comparative Examples 1-1 and 1-2 became turbid after adding TBAF in the test [4] above, so the test [5] was not carried out (represented as "NA" in the table). In addition, Comparative Examples 1-3 to 1-6 did not peel off after 300 seconds in the test [4] above, so the test [5] was not carried out (represented as "NA" in the table).

[0395] It can be seen that: when the stripping and dissolving composition of the present invention is used to clean a semiconductor substrate with an adhesive layer, as shown in Examples 2-1 to 2-16, the adhesive layer can be removed (cleaned) from the semiconductor substrate in a short time. In the present invention, most of the adhesive layer can be stripped in a short time, so even if a small amount of adhesive layer remains after stripping, the adhesive residue will be dissolved by the soluble components in the stripping and dissolving composition and removed cleanly. This is also shown in the results of Examples 2-1 to 2-16. As shown in Examples 2-1 to 2-16, the adhesive layer on the semiconductor substrate can be cleanly removed in a short time of 1 minute simply by immersing the semiconductor substrate in the stripping and dissolving composition of the present invention.

[0396] That is, when the semiconductor substrate cleaning method of the present invention is used, the adhesive layer can be removed (cleaned) from the semiconductor substrate having the adhesive layer on the surface with a simple operation, in a shorter time, and more cleanly.

[0397] [Table 1]

[0398]

[0399] [Table 2]

[0400]

[0401] [Table 3]

[0402]

Claims

1. A method for cleaning a semiconductor substrate, characterized in that: include: A step of peeling and dissolving an adhesive layer on a semiconductor substrate using a peeling and dissolving composition, wherein: The peeling and dissolving composition comprises the following ingredients: Ingredient I: quaternary ammonium salt; Component II: an amide solvent; and Component III: a solvent represented by the following formula (G), Where, L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms of the alkyl group is 7 or less.

2. The semiconductor substrate cleaning method according to claim 1, wherein: The peeling and dissolving composition further comprises the following ingredients: Component IV: a solvent represented by the following formula (T) or the following formula (L), In formula (T), X 1 and X 3 Each independently represents an alkyl group or an acyl group X 4 -C(=O)-,X 2 represents an alkylene group, n represents 2 or 3; X 4 represents an alkyl group, L 1 -L 3 -L 2 (L) In formula (L), L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S.

3. The semiconductor substrate cleaning method according to claim 1, wherein: In the formula (G), L 11 It is methyl.

4. The semiconductor substrate cleaning method according to claim 3, wherein: In the formula (G), L 12 It is butyl or pentyl.

5. The semiconductor substrate cleaning method according to claim 1, wherein: The quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

6. The method for cleaning a semiconductor substrate according to claim 1, wherein: The amide solvent is an amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y), In formula (Z), R 0 represents ethyl, propyl or isopropyl, R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms, In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1), In formula (Y1), R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 104 represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond to a carbon atom in formula (Y), and *2 represents a bond to a nitrogen atom in formula (Y).

7. The method for cleaning a semiconductor substrate according to claim 1, wherein: The adhesive layer is a film obtained using an adhesive composition containing an adhesive component S, wherein the adhesive component S contains at least one selected from silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives and phenolic resin adhesives.

8. The method for cleaning a semiconductor substrate according to claim 7, wherein: The adhesive component S contains a silicone-based adhesive.

9. The method for cleaning a semiconductor substrate according to claim 8, wherein: The silicone-based adhesive includes a polyorganosiloxane component A' that is cured by a hydrosilylation reaction.

10. The semiconductor substrate cleaning method according to claim 1, wherein: The peeling and dissolving process includes a process of removing the peeled adhesive layer.

11. A method for manufacturing a processed semiconductor substrate, characterized in that: include: The first step is to produce a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; The second step is to process the semiconductor substrate of the obtained stacked body; A third step is to separate the semiconductor substrate and the adhesive layer from the support substrate; as well as In the fourth step, the adhesive layer on the semiconductor substrate is peeled off and dissolved by using a peeling and dissolving composition to remove the adhesive layer. In the method for manufacturing the processed semiconductor substrate, the stripping and dissolving composition comprises the following components: Ingredient I: quaternary ammonium salt; Component II: an amide solvent; and Component III: a solvent represented by the following formula (G), Where, L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms of the alkyl group is 7 or less.

12. The method for manufacturing a processed semiconductor substrate according to claim 11, wherein: The peeling and dissolving composition further comprises the following ingredients: Component IV: a solvent represented by the following formula (T) or the following formula (L), In formula (T), X 1 and X 3 Each independently represents an alkyl group or an acyl group X 4 -C(=O)-,X 2 represents an alkylene group, n represents 2 or 3; X 4 represents an alkyl group, L 1 -L 3 -L 2 (L) In formula (L), L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S.

13. The semiconductor substrate cleaning method according to claim 11, wherein: In the formula (G), L 11 It is methyl.

14. The method for cleaning a semiconductor substrate according to claim 13, wherein: In the formula (G), L 12 It is butyl or pentyl.

15. The method for manufacturing a processed semiconductor substrate according to claim 11, wherein: The quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

16. The method for manufacturing a processed semiconductor substrate according to claim 11, wherein: The amide solvent is an amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y), In formula (Z), R 0 represents ethyl, propyl or isopropyl, R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms, In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1), In formula (Y1), R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 104 represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond to a carbon atom in formula (Y), and *2 represents a bond to a nitrogen atom in formula (Y).

17. The method for manufacturing a processed semiconductor substrate according to claim 11, wherein: The adhesive layer is a film obtained using an adhesive composition containing an adhesive component S, wherein the adhesive component S contains at least one selected from silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives and phenolic resin adhesives.

18. The method for manufacturing a processed semiconductor substrate according to claim 17, wherein: The adhesive component S contains a silicone-based adhesive.

19. The method for manufacturing a processed semiconductor substrate according to claim 18, wherein: The silicone-based adhesive includes a polyorganosiloxane component A' that is cured by a hydrosilylation reaction.

20. The method for manufacturing a processed semiconductor substrate according to claim 11, wherein: The fourth step of peeling and dissolving and removing includes a step of removing the peeled adhesive layer.

21. A composition for peeling and dissolving, characterized in that When cleaning a semiconductor substrate, it is used to peel off and dissolve the adhesive layer on the semiconductor substrate to remove it. The peeling and dissolving composition meets at least any one of the following conditions i to iv, i: The peeling and dissolving composition comprises the following component I, the following component II, and the following component III, The content of the component II in 100% by mass of the aprotic solvent is 20% by mass or less, and the content of the component III is 60% by mass or more; ii: The peeling and dissolving composition comprises the following component I, the following component II and the following component III, The content of the component III in 100% by mass of the aprotic solvent is 70% by mass or more; iii: The peeling and dissolving composition comprises the following component I, the following component II, the following component III and the following component IV, The IV component includes a solvent represented by the following formula (L), When the aprotic solvent is set to 100 mass %, the content of the III component is greater than 31 mass %, and the content of the IV component is less than 30 mass %; iv: The peeling and dissolving composition comprises the following component I, the following component II, the following component III and the following component IV, The IV component comprises a solvent represented by the following formula (T), When the aprotic solvent is set to 100 mass %, the content of the component III is greater than 31 mass %, the content of the component IV is less than 30 mass %, and the content of the component II is 20 mass % or less, Here, component I represents a quaternary ammonium salt, Component II represents an amide solvent, Component III represents a solvent represented by the following formula (G), Component IV represents a solvent represented by the following formula (T) or the following formula (L), In formula (G), L 11 and L 12 Each independently represents an alkyl group having 1 to 6 carbon atoms, L 11 The number of carbon atoms in the alkyl group and L 12 The total number of carbon atoms of the alkyl group is 7 or less, In formula (T), X 1 and X 3 Each independently represents an alkyl group or an acyl group X 4 -C(=O)-,X 2 represents an alkylene group, n represents 2 or 3; X 4 represents an alkyl group, L 1 -L 3 -L 2 (L) In formula (L), L 1 and L 2 Each independently represents an alkyl group having 2 to 5 carbon atoms, L 3 Indicates O or S.

22. The peeling and dissolving composition according to claim 21, wherein In the formula (G), L 11 It is methyl.

23. The peeling and dissolving composition according to claim 22, wherein In the formula (G), L 12 It is butyl or pentyl.

24. The peeling and dissolving composition according to claim 21, wherein The quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

25. The peeling and dissolving composition according to claim 21, wherein The amide solvent is an amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y), In formula (Z), R 0 represents ethyl, propyl or isopropyl, R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms, In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1), In formula (Y1), R 103 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 104 represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond to a carbon atom in formula (Y), and *2 represents a bond to a nitrogen atom in formula (Y).

26. The peeling and dissolving composition according to claim 21, wherein The adhesive layer is a film obtained using an adhesive composition containing an adhesive component S, wherein the adhesive component S contains at least one selected from silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives and phenolic resin adhesives.

27. The processed peeling and dissolving composition according to claim 26, wherein The adhesive component S contains a silicone-based adhesive.

28. The peeling and dissolving composition according to claim 27, wherein The silicone-based adhesive includes a polyorganosiloxane component A' that is cured by a hydrosilylation reaction.

29. The peeling and dissolving composition according to claim 21, wherein In the case of the above-mentioned ii, the content of the above-mentioned component III is more than 35% by mass.

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