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

Abstract

The invention relates to a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate, and a composition for peeling and dissolving. 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 a quaternary ammonium salt as component [I], an amide solvent as component [II], and a solvent as component [III] represented by formula (L). In formula (L), L1 and L2 each independently represent an alkyl group having 2-5 carbon atoms, and L3 represents O or S. L1-L3-L2 (L)

Description

[0001] This application is a divisional application of the following application:

[0002] Title of Invention: Cleaning method for semiconductor substrate, manufacturing method for processed semiconductor substrate, and stripping and dissolving composition

[0003] International filing date: September 13, 2022

[0004] International application number: PCT / JP2022 / 034143

[0005] National application number: 202280007459.7 Technical Field

[0006] The present invention relates to a cleaning method for a semiconductor substrate, a manufacturing method for a processed semiconductor substrate, and a stripping and dissolving composition Background Art

[0007] Regarding conventional semiconductor wafers integrated in the two-dimensional plane direction, for the purpose of further integration, semiconductor integration technologies that further integrate the plane in the three-dimensional direction (stacking) are pursued. This three-dimensional stacking is a technology in which multiple layers are integrated while wiring through silicon vias (TSVs: through silicon via). When integrating into multiple layers, each integrated wafer is thinned on the side opposite to the formed circuit surface (i.e., the back surface) by grinding, and the thinned semiconductor wafers are stacked

[0008] Before thinning, a semiconductor wafer (also simply referred to as a wafer here) is bonded to a support for grinding using a grinding device. The bonding at this time must be easily peeled off after grinding, so it is called temporary bonding. This temporary bonding must be easily disassembled from the support. When a large force is applied for disassembly, sometimes the thinned semiconductor wafer is cut or deformed, and it is necessary to be easily disassembled to avoid such a situation. However, during the back grinding of the semiconductor wafer, it may come off or shift due to grinding stress, which is not preferable. Therefore, the performance required for temporary bonding is: resistance to stress during grinding and easy disassembly after grinding. For example, the following performance is pursued: high stress (strong bonding force) in the plane direction during grinding, and low stress (weak bonding force) in the longitudinal direction, which is the direction crossing the plane direction during disassembly. In addition, the temperature sometimes reaches 150°C or higher in the processing process, and heat resistance is also required

[0009] Under such circumstances, in the semiconductor field, polysiloxane-based adhesives capable of having these properties are mainly used as temporary adhesives. Moreover, in polysiloxane-based adhesion using a polysiloxane-based adhesive, adhesive residues often remain on the substrate surface after the thinned substrate is peeled off. However, in order to avoid adverse conditions in subsequent processes, a cleaning agent composition for removing such residues and cleaning the surface of the semiconductor substrate has been developed (for example, Patent Documents 1 and 2). In Patent Document 1, a remover for a silicone resin containing a polar aprotic solvent and a quaternary ammonium hydroxide is disclosed. In Patent Document 2, a cured resin remover containing a fluorinated alkyl / ammonium is disclosed. However, in the recent semiconductor field, there has always been a need for a new cleaning agent composition, and there has always been a need for an effective cleaning agent composition and a cleaning method.

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: International Publication No. 2014 / 092022

[0013] Patent Document 2: U.S. Patent No. 6818608 Summary of the Invention

[0014] Problems to be Solved by the Invention

[0015] The cleaning agent compositions described in Patent Documents 1 and 2 above attempt to remove the adhesive residues from the substrate surface by dissolving the adhesive residues on the substrate surface. However, it is known that when attempting to remove the adhesive residues from the substrate surface in this way by dissolution, the removal takes a long time.

[0016] Furthermore, the inventors of the present invention conducted research on the cleaning agent composition and found that when using a composition containing a specific component, the adhesive layer can be swollen and the adhesive layer can be peeled off from the substrate. When using a composition containing the specific component, the adhesive layer can be removed from the substrate in a short time.

[0017] However, from the viewpoint of removing the adhesive residues from the substrate surface more cleanly in a shorter time by a simple operation, there is room for improvement, a more effective cleaning method is required, and new cleaning methods and compositions for such cleaning methods are being developed.

[0018] The present invention has been completed in view of the above circumstances, and an object thereof 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 for such a cleaning method. The method for cleaning a semiconductor substrate can remove (clean) the adhesive layer from the semiconductor substrate having an adhesive layer obtained by using, for example, a siloxane-based adhesive on its surface more cleanly and in a shorter time through a simple operation.

[0019] Solution to the problem

[0020] The inventors of the present invention repeatedly conducted in-depth research to solve the above problems, and as a result, found that the above problems can be solved by the following method, thereby completing the present invention. That is, a composition containing specific components is used to clean the adhesive layer on the semiconductor substrate, particularly an adhesive layer that is a cured film obtained from a siloxane-based adhesive containing a polyorganosiloxane component (A') cured by a hydrosilylation reaction, so that the adhesive layer is swollen, peeled off, and dissolved together through a single cleaning operation, and the adhesive layer is removed from the semiconductor substrate.

[0021] That is, the present invention includes the following aspects.

[0022] [1] A method for cleaning a semiconductor substrate, comprising a step of using a stripping and dissolving composition to strip and dissolve an adhesive layer on the semiconductor substrate, wherein the stripping and dissolving composition contains: [I] component: a quaternary ammonium salt, [II] component: an amide-based solvent, and [III] component: a solvent represented by the following formula (L).

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

[0024] (In the formula, L 1 and L 2 each independently represents an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.)

[0025] [2] The method for cleaning a semiconductor substrate according to [1], wherein the stripping and dissolving composition further contains [IV] component: a solvent represented by the following formula (T) or the following formula (G).

[0026]

[0027] (In the formula, 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. X 4represents an alkyl group.)

[0028]

[0029] (In the formula, L 11 and L 12 each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the alkyl group of L 11 and the alkyl group of L 12 is 7 or less.)

[0030] [3] The method for cleaning a semiconductor substrate according to [1] or [2], wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.)

[0031] [4] The method for cleaning a semiconductor substrate according to any one of [1] to [3], wherein the amide-based solvent is an acid amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y).

[0032]

[0033] (In the formula, R 0 represents ethyl, propyl or isopropyl, and R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms.)

[0034]

[0035] (In the formula, R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)

[0036]

[0037] (In the formula, 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 bonding bond bonded to a carbon atom in the formula (Y), and *2 represents a bonding bond bonded to a nitrogen atom in the formula (Y).)

[0038] [5] The method for cleaning a semiconductor substrate according to any one of [1] to [4], wherein the above L 1 and L 2 are the same group.)

[0039] [6] The cleaning method of the semiconductor substrate according to any one of [1] to [5], wherein the adhesive layer is a film obtained by using an adhesive composition containing an adhesive component (S), and the adhesive component (S) contains at least one selected from a silicone-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive.

[0040] [7] The cleaning method of the semiconductor substrate according to [6], wherein the adhesive component (S) contains a silicone-based adhesive.

[0041] [8] The cleaning method of the semiconductor substrate according to [7], wherein the silicone-based adhesive contains a polyorganosiloxane component (A') cured by a hydrosilylation reaction.

[0042] [9] The cleaning method of the semiconductor substrate according to any one of [1] to [8], wherein the step of peeling and dissolving includes a step of removing the peeled adhesive layer.

[0043]

[10] A method for manufacturing a processed semiconductor substrate, characterized by comprising: a first step of manufacturing a laminate including a semiconductor substrate, a support 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 support substrate; and a fourth step of peeling and dissolving with a peeling and dissolving composition to remove the adhesive layer on the semiconductor substrate, wherein the peeling and dissolving composition contains: [I] component: a quaternary ammonium salt, [II] component: an amide-based solvent, and [III] component: a solvent represented by the following formula (L).

[0044] L 1 -L 3 -L 2 (L)

[0045] (In the formula, L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.)

[0046]

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

[10] , wherein the peeling and dissolving composition further contains [IV] component: a solvent represented by the following formula (T) or the following formula (G).

[0047]

[0048] (In the formula, X 1 and X 3Each 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. X 4 represents an alkyl group.)

[0049]

[0050] (In the formula, L 11 and L 12 each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the alkyl group of L 11 and the total number of carbon atoms of the alkyl group of L 12 is 7 or less.)

[0051]

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

[10] or

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

[0052]

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

[10] to

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

[0053]

[0054] (In the formula, R 0 represents an ethyl group, a propyl group or an isopropyl group, and R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms.)

[0055]

[0056] (In the formula, R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)

[0057]

[0058] (In the formula, 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 bonding bond bonded to a carbon atom in the formula (Y), and *2 represents a bonding bond bonded to a nitrogen atom in the formula (Y).)

[0059]

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

[10] to

[13] , wherein the above L 1 and L 2 are the same group.

[0060]

[15] The manufacturing method of the processed semiconductor substrate according to any one of

[10] to

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

[0061]

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

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

[0062]

[17] The manufacturing method of the processed semiconductor substrate according to

[16] , wherein the silicone-based adhesive contains a polyorganosiloxane component (A') cured by a hydrosilylation reaction.

[0063]

[18] The manufacturing method of the processed semiconductor substrate according to any one of

[10] to

[17] , wherein the fourth step of removing by peeling and dissolving includes a step of removing the peeled adhesive layer.

[0064]

[19] A composition for peeling and dissolving, characterized in that it is used to peel and dissolve and remove the adhesive layer on the semiconductor substrate when cleaning the semiconductor substrate, and the composition for peeling and dissolving contains [I] component: quaternary ammonium salt, [II] component: amide-based solvent, and [III] component: a solvent represented by the following formula (L), and in the composition for peeling and dissolving, the content of the [III] component in 100% by mass of the aprotic solvent is 30% by mass or more.

[0065] L 1 -L 3 -L 2 (L)

[0066] (In the formula, L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.)

[0067]

[20] The composition for peeling and dissolving according to

[19] , wherein the composition for peeling and dissolving further contains [IV] component: a solvent represented by the following formula (T) or the following formula (G).

[0068]

[0069] (In the formula, X 1 and X 3each 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. X 4 represents an alkyl group.)

[0070]

[0071] (In the formula, L 11 and L 12 each independently represents an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the alkyl group of L 11 and the total number of carbon atoms of the alkyl group of L 12 is 7 or less.)

[0072]

[21] The stripping and dissolving composition according to

[19] or

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

[0073]

[22] The stripping and dissolving composition according to any one of

[19] to

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

[0074]

[0075] (In the formula, R 0 represents an ethyl group, a propyl group or an isopropyl group, and R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0076]

[0077] (In the formula, R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)

[0078]

[0079] (In the formula, 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 bonding bond bonded to the carbon atom in the formula (Y), and *2 represents a bonding bond bonded to the nitrogen atom in the formula (Y).)

[0080]

[23] The stripping and dissolving composition according to any one of

[19] to

[22] , wherein the above L 1 and L 2 are the same group.

[0081]

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

[19] to

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

[0082]

[25] The composition for peeling and dissolving according to

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

[0083]

[26] The composition for peeling and dissolving according to

[25] , wherein the silicone-based adhesive contains a polyorganosiloxane component (A') cured by a hydrosilylation reaction.

[0084] Advantages of the Invention

[0085] According to the present invention, there can be provided a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate including such a cleaning method, and a composition for such a cleaning method. The method for cleaning a semiconductor substrate can remove (clean) the adhesive layer on the semiconductor substrate having the adhesive layer on its surface more cleanly and in a shorter time through a simple operation. Detailed Description of the Invention

[0086] Hereinafter, the present invention will be described in detail. It should be noted that the description of the constituent elements described below is an example for explaining the present invention, and the present invention is not limited to these contents.

[0087] (Method for Cleaning a Semiconductor Substrate)

[0088] The method for cleaning a semiconductor substrate of the present invention includes a step of peeling and dissolving an adhesive layer on the semiconductor substrate using a composition for peeling and dissolving.

[0089] The composition for peeling and dissolving contains: Component [I]: a quaternary ammonium salt, Component [II]: an amide-based solvent, and Component [III]: a solvent represented by the following formula (L).

[0090] L 1 -L 3 -L 2 (L)

[0091] (In the formula, L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.)

[0092] The composition for stripping and dissolving may further contain a [IV] component: a solvent represented by the following formula (T) or the following formula (G).

[0093]

[0094] (In the formula, 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. X 4 represents an alkyl group.)

[0095]

[0096] (In the formula, L 11 and L 12 each independently represents an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the alkyl group of L 11 and the alkyl group of L 12 is 7 or less.)

[0097] <Semiconductor Substrate>

[0098] As the main material constituting the entire semiconductor substrate, there is no particular limitation as long as it is a material for such a use. For example, silicon, silicon carbide, compound semiconductors, etc. can be cited.

[0099] The shape of the semiconductor substrate is not particularly limited. For example, it is disk-shaped. It should be noted that the shape of the surface of the disk-shaped semiconductor substrate does not need to be a complete circle. For example, the outer periphery of the semiconductor substrate may have a straight portion called a flat plane, or may have a notch called a groove.

[0100] The thickness of the disk-shaped semiconductor substrate can be appropriately determined according to the use purpose of the semiconductor substrate, etc., and there is no particular limitation. For example, it is 500 μm to 1000 μm.

[0101] As the diameter of the disk-shaped semiconductor substrate, it can be appropriately determined according to the use purpose of the semiconductor substrate, etc., and there is no particular limitation. For example, 100 mm to 1000 mm can be cited.

[0102] The semiconductor substrate is, for example, a wafer. As a specific example, a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm can be cited, but it is not limited thereto.

[0103] <Adhesive Layer>

[0104] The adhesive layer on the semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S).

[0105] The adhesive component (S) as such is not particularly limited as long as it is an adhesive component for such use. For example, silicone-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, etc. can be cited.

[0106] Among them, from the aspects of showing appropriate adhesive ability during processing of wafers, etc., being able to be appropriately peeled off after processing, and also having excellent heat resistance, as the adhesive component (S), a silicone-based adhesive is preferred.

[0107] <<Adhesive Composition>>

[0108] 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.

[0109] In addition, the adhesive composition used in the present invention preferably contains a polyorganosiloxane in a preferred embodiment.

[0110] The component (A) may be a component that cures by a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.

[0111] In another preferred embodiment, the component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group with 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having an Si-H group, and a platinum group metal-based catalyst (A2) as an example of the component (A'). Here, the alkenyl group with 2 to 40 carbon atoms is optionally substituted. As substituents, for example, halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc. can be cited.

[0112] In another preferred embodiment, the polyorganosiloxane component (A') that cures by a hydrosilylation reaction contains a polysiloxane (A1) and a platinum group metal-based catalyst (A2), and the above polysiloxane (A1) contains a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 represented siloxane unit (M unit), R 4 R 5 SiO 2 / 2 represented siloxane unit (D unit), and R 6 SiO 3 / 2One or more units in the group consisting of the siloxane units (T units) shown, the polysiloxane (A1) contains a polyorganosiloxane (a1') and a polyorganosiloxane (a2'), and the above polyorganosiloxane (a1') contains a siloxane unit (Q' unit) selected from SiO2, R 1 ’R 2 ’R 3 ’SiO 1 / 2 shown siloxane unit (M' unit), R 4 ’R 5 ’SiO 2 / 2 shown siloxane unit (D' unit), and R 6 ’SiO 3 / 2 shown siloxane unit (T' unit) in the group consisting of one or more units, and contains at least one selected from the group consisting of M' unit, D' unit, and T' unit. The above polyorganosiloxane (a2') contains a siloxane unit (Q" unit) selected from SiO2, R 1 ”R 2 ”R 3 ”SiO 1 / 2 shown siloxane unit (M" unit), R 4 ”R 5 ”SiO 2 / 2 shown siloxane unit (D" unit), and R 6 ”SiO 3 / 2 shown siloxane unit (T" unit) in the group consisting of one or more units, and contains at least one selected from the group consisting of M" unit, D" unit, and T" unit.

[0113] It should be noted that (a1') is an example of (a1), and (a2') is an example of (a2).

[0114] R 1 ~R 6 is a group or atom bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. As substituents, for example, halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc. can be mentioned.

[0115] R 1 ’~R 6 ’ is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, but at least one of R 1 ’~R 6 ’ is an optionally substituted alkenyl group. As substituents, for example, halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc. can be mentioned.

[0116] 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, provided that at least one of 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, etc.

[0117] The alkyl group may be linear, branched, or cyclic, but a linear or branched alkyl group is preferred. Its carbon number is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0118] 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-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, 1-ethyl-2-methyl-n-propyl, etc., but are not limited thereto. Its carbon number is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among them, methyl is particularly preferred.

[0119] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, 2-ethyl-3-methylcyclopropyl and other cycloalkyl groups, dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl and other bicyclic alkyl groups, etc., but are not limited thereto. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, more preferably 5 to 6.

[0120] The alkenyl group can be either 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 even more preferably 10 or less.

[0121] Specific examples of the optionally substituted linear or branched alkenyl group include vinyl, allyl, butenyl, pentenyl, etc., but are not limited thereto. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, more preferably 1 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0122] Specific examples of the optionally substituted cyclic alkenyl group include cyclopentenyl, cyclohexenyl, etc., but are not limited thereto. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, more preferably 5 to 6.

[0123] As described above, the polysiloxane (A1) contains a polyorganosiloxane (a1') and a polyorganosiloxane (a2'). The alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2') form a crosslinked structure and are cured through a hydrosilylation reaction based on a platinum group metal-based catalyst (A2). As a result, a cured film is formed.

[0124] The polyorganosiloxane (a1') 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 (a1'), two or more polyorganosiloxanes satisfying such conditions may also be used in combination.

[0125] As preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units, and T' units, examples include: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit, and M' unit), but are not limited thereto.

[0126] In addition, in the case of containing polyorganosiloxanes included in two or more polyorganosiloxanes (a1'), the combinations 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 are not limited thereto.

[0127] 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 also be used in combination.

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

[0129] The polyorganosiloxane (a1') is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to its silicon atom, but the proportion of the alkenyl group in all the substituents represented by R 1 ' to R 6 ' is preferably 0.1 mol% to 50.0 mol%, more preferably 0.5 mol% to 30.0 mol%, and the remaining R 1 ' to R 6 ' may be an alkyl group.

[0130] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to its silicon atom, but R 1 ” to R 6The proportion of hydrogen atoms among all substituents and substituted atoms shown by “” is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, and the remaining R 1 ” to R 6 ” may be an alkyl group.

[0131] When the component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl group contained in the polyorganosiloxane (a1) to the hydrogen atom constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0132] The weight-average molecular weight of polyorganosiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000 respectively. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 5000 to 50,000.

[0133] It should be noted that in the present invention, the weight-average molecular weight, number-average molecular weight, and dispersity of polyorganosiloxane can be measured, for example, using a GPC device (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and GPC columns (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by Tosoh Corporation), setting the column temperature to 40 °C, using tetrahydrofuran as the eluent (dissolution solvent), setting the flow rate (flow velocity) to 0.35 mL / minute, and using polystyrene (manufactured by Showa Denko K.K., Shodex) as the standard sample.

[0134] The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa·s) respectively. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 50 to 20,000 (mPa·s). It should be noted that the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values measured with an E-type rotational viscometer at 25 °C.

[0135] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other through a hydrosilylation reaction to form a film. Therefore, the curing mechanism thereof is different from, for example, the mechanism via a silanol group. Therefore, any siloxane does not need to contain a silanol group or a functional group that forms a silanol group by hydrolysis such as an alkyloxy group.

[0136] In a preferred embodiment of the present invention, the adhesive composition further contains a polyorganosiloxane component (A') and a platinum group metal-based catalyst (A2).

[0137] Such a platinum-group metal catalyst is a catalyst for promoting the hydrosilylation reaction of the alkenyl group of the polyorganosiloxane (a1) and the Si-H group of the polyorganosiloxane (a2).

[0138] Specific examples of the platinum-group metal catalyst include, but are not limited to, platinum black, platinum tetrachloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, the complex of chloroplatinic acid and an olefin, platinum bis(acetoacetate), and other platinum-based catalysts.

[0139] Examples of the complex of platinum and an olefin include, but are not limited to, the complex of divinyltetramethyldisiloxane and platinum.

[0140] The amount of the platinum-group metal-based catalyst (A2) is not particularly limited, and is usually in the range of 1.0 ppm to 50.0 ppm relative to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0141] The polyorganosiloxane component (A') may also contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.

[0142] The polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction. Specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0143] The amount of the polymerization inhibitor is not particularly limited. From the viewpoint of obtaining its effect, it is usually 1000.0 ppm or more relative to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2), and from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction, it is 10000.0 ppm or less.

[0144] The adhesive composition used in the present invention may also contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in the present invention, the obtained adhesive layer can be appropriately released with good reproducibility.

[0145] Typical examples of such a release agent component (B) include polyorganosiloxanes. In a preferred embodiment, specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, phenyl group-containing polyorganosiloxanes, and the like.

[0146] In addition, in another preferred embodiment, as the release agent component (B), polydimethylsiloxane can be cited, and the polydimethylsiloxane is optionally modified. Examples of the optionally modified polydimethylsiloxane include epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, phenyl group-containing polydimethylsiloxane, etc., but are not limited thereto.

[0147] Although the weight average molecular weight of the polyorganosiloxane as the release agent component (B) is not particularly limited, it is generally 100,000 to 2,000,000, and from the viewpoint of achieving the effects 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, although its dispersity is not particularly limited, it is generally 1.0 to 10.0, and from the viewpoints of achieving appropriate release with good reproducibility, etc., 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 above-mentioned methods related to polysiloxane.

[0148] The complex viscosity of the polyorganosiloxane as the release agent component (B) can be measured at 25 °C using a rheometer (for example, Rheometer MCR-302 manufactured by Anton Paar Co., Ltd.).

[0149] As the epoxy group-containing polyorganosiloxane, for example, it can be cited that which contains the siloxane unit (D 11 R 12 SiO 2 / 2 shown. 10 unit) of the polyorganosiloxane.

[0150] R 11 is a group bonded to a silicon atom, representing an alkyl group, and R 12 is a group bonded to a silicon atom, representing an epoxy group or an organic group containing an epoxy group. As specific examples of the alkyl group, the above examples can be cited.

[0151] The epoxy group in the organic group containing an epoxy group can be an epoxy group independent of other rings, or an epoxy group that forms a condensed ring with other rings, such as 1,2-epoxycyclohexyl.

[0152] As specific examples of the organic group containing an epoxy group, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, etc. can be cited, but are not limited thereto.

[0153] In the present invention, as a preferred example of the epoxy group-containing polyorganosiloxane, epoxy group-containing polydimethylsiloxane can be cited, but is not limited thereto.

[0154] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 10 unit), but in addition to the D 10 unit, it may also contain Q units, M units, and / or T units.

[0155] In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include: a polyorganosiloxane composed only of D 10 units, a polyorganosiloxane containing D 10 units and Q units, a polyorganosiloxane containing D 10 units and M units, a polyorganosiloxane containing D 10 units and T units, a polyorganosiloxane containing D 10 units, Q units, and M units, a polyorganosiloxane containing D 10 units, M units, and T units, a polyorganosiloxane containing D 10 units, Q units, M units, and T units, etc.

[0156] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. In addition, although its weight average molecular weight is not particularly limited, it is usually 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive.

[0157] Specific examples of the epoxy group-containing polyorganosiloxane include, but are not limited to, polyorganosiloxanes represented by formulas (E1) to (E3).

[0158]

[0159] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0160]

[0161] (m2 and n2 represent the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0162]

[0163] (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.)

[0164] Examples of the methyl group-containing polyorganosiloxane include those containing R 210 R 220 SiO 2 / 2 shown siloxane unit (D 200a polyorganosiloxane of the unit), preferably containing R 21 R 21 SiO 2 / 2 the siloxane unit (D 20 unit) of the polyorganosiloxane.

[0165] R 210 and R 220 are groups bonded to the silicon atom, each independently representing an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those exemplified above.

[0166] R 21 is a group bonded to the silicon atom, representing an alkyl group. Specific examples of the alkyl group include those exemplified above. Among them, as R 21 , it is preferably a methyl group.

[0167] In the present invention, as a preferred example of the methyl-containing polyorganosiloxane, polydimethylsiloxane can be cited, but it is not limited thereto.

[0168] The methyl-containing polyorganosiloxane contains the above siloxane unit (D 200 unit or D 20 unit), but in addition to the D 200 unit and D 20 unit, it may also contain Q units, M units, and / or T units.

[0169] In one aspect of the present invention, as specific examples of the methyl-containing polyorganosiloxane, there can be cited a polyorganosiloxane composed only of D 200 units, a polyorganosiloxane containing D 200 units and Q units, a polyorganosiloxane containing D 200 units and M units, a polyorganosiloxane containing D 200 units and T units, a polyorganosiloxane containing D 200 units, Q units, and M units, a polyorganosiloxane containing D 200 units, M units, and T units, a polyorganosiloxane containing D 200 units, Q units, M units, and T units.

[0170] In a preferred aspect of the present invention, as specific examples of the methyl-containing polyorganosiloxane, there can be cited a polyorganosiloxane composed only of D 20 units, a polyorganosiloxane containing D 20 units and Q units, a polyorganosiloxane containing D 20 units and M units, a polyorganosiloxane containing D 20 units and T units, a polyorganosiloxane containing D 20Polysiloxanes of unit, Q unit, and M unit, containing D 20 Polysiloxanes of D unit, M unit, and T unit, containing D 20 Polysiloxanes of D unit, Q unit, M unit, and T unit.

[0171] As a specific example of the methyl-containing polysiloxane, the polysiloxane represented by the formula (M1) can be cited, but it is not limited thereto.

[0172]

[0173] (n4 represents the number of repeating units and is a positive integer.)

[0174] As the phenyl-containing polysiloxane, for example, the polysiloxane containing R 31 R 32 SiO 2 / 2 The polysiloxane of the siloxane unit (D 30 unit) shown.

[0175] R 31 Is a group bonded to a silicon atom, representing a phenyl group or an alkyl group, and R 32 Is a group bonded to a silicon atom, representing a phenyl group. As specific examples of the alkyl group, the above examples can be cited, but methyl is preferred.

[0176] The phenyl-containing polysiloxane contains the above siloxane unit (D 30 unit), but in addition to the D 30 unit, it may also contain Q unit, M unit, and / or T unit.

[0177] In a preferred embodiment of the present invention, as specific examples of the phenyl-containing polysiloxane, the polysiloxane composed only of D 30 unit, the polysiloxane containing D 30 unit and Q unit, the polysiloxane containing D 30 unit and M unit, the polysiloxane containing D 30 unit and T unit, the polysiloxane containing D 30 unit, Q unit, and M unit, the polysiloxane containing D 30 unit, M unit, and T unit, the polysiloxane containing D 30 unit, Q unit, M unit, and T unit.

[0178] As specific examples of the phenyl-containing polysiloxane, the polysiloxane represented by the formula (P1) or (P2) can be cited, but it is not limited thereto.

[0179]

[0180] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0181]

[0182] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0183] The polyorganosiloxane as the release agent component (B) can be a commercially available product or a synthetic polyorganosiloxane.

[0184] Examples of commercially available polyorganosiloxanes include: WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM manufactured by Wacker Chemie; dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxanes (trade names CMS-227, ECMS-327) manufactured by Gelest, epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd., epoxy group-containing polyorganosiloxane (BY16-839) manufactured by Dow Corning; phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE, etc., but are not limited thereto.

[0185] The adhesive composition used in the present invention contains both the cured component (A) and the release agent component (B). In a more preferred embodiment, the release agent component (B) contains a polyorganosiloxane.

[0186] An example of the adhesive composition used in the present invention can contain the cured component (A) and the release agent component (B) at any ratio. However, considering the balance between adhesiveness and peelability, the ratio of the cured component (A) to the release agent component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, by mass ratio [(A):(B)].

[0187] That is, when the polyorganosiloxane component (A') cured 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 in terms of mass ratio [(A'):(B)], more preferably 99.9:0.1 to 75:25.

[0188] The adhesive composition used in the present invention may also 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.

[0189] More specifically, examples of the solvent include: 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, 5-nonanone, etc., but are not limited thereto. Such solvents may be used alone or in combination of two or more.

[0190] When the adhesive composition used in the present invention contains a solvent, its content is appropriately set in consideration of the viscosity of the desired composition, the coating method employed, the thickness of the film produced, etc., but is in the range of about 10% by mass to 90% by mass relative to the whole composition.

[0191] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 mPa·s to 20000 mPa·s at 25°C, preferably 1000 mPa·s to 5000 mPa·s. 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 the film constituent components, etc. in consideration of various factors such as the coating method used and the desired film thickness.

[0192] In the present invention, the film constituent components refer to the components other than the solvent contained in the composition.

[0193] An example of the adhesive composition used in the present invention can be produced by mixing the component (A), the release agent component (B), and the solvent when used.

[0194] The mixing order is not particularly limited. As an example of a method capable of easily and reproducibly producing the release adhesive composition, for example, a method of dissolving the component (A) and the release agent component (B) in a solvent; a method of dissolving a part of the component (A) and the release agent component (B) in a solvent, dissolving the remaining part in a solvent, and mixing the resulting solutions, etc. are exemplified, but are not limited thereto. It should be noted that when preparing the adhesive composition, it may be appropriately heated within the range where the components do not decompose or deteriorate.

[0195] In the present invention, for the purpose of removing foreign matters, a filter or the like may be used to filter the solvents, solutions, etc. used during the production of the adhesive composition or after mixing all the components.

[0196] The thickness of the adhesive layer is not particularly limited, and from the viewpoint of obtaining a good peeling effect with good reproducibility, it is preferably 10 μm to 100 μm, more preferably 20 μm to 50 μm.

[0197] <Peeling and dissolving composition>

[0198] The peeling and dissolving composition is a composition for a cleaning method of a semiconductor substrate for removing the adhesive layer from the semiconductor substrate.

[0199] 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.

[0200] Specifically, the peeling and dissolving composition contains: [I] component: quaternary ammonium salt; [II] component: amide-based solvent; and [III] component: a solvent represented by the following formula (L).

[0201] L 1 -L 3 -L 2 (L)

[0202] (In the formula, L 1 and L 2 each independently represents an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.)

[0203] The peeling and dissolving composition may further contain [IV] component: a solvent represented by the following formula (T) or the following formula (G).

[0204]

[0205] (In the formula, 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. X 4 represents an alkyl group.)

[0206]

[0207] (In the formula, L 11 and L 12 each independently represents an alkyl group having 1 to 6 carbon atoms, and the number of carbon atoms of the alkyl group of L 11 is the same as that of L 12The total number of carbon atoms of the alkyl group is 7 or less.

[0208] <<[I] Component: Quaternary ammonium salt>>

[0209] The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and there is no particular limitation as long as it is a substance used for this purpose.

[0210] The quaternary ammonium salt is effective as a component for dissolving the adhesive layer.

[0211] Typical examples of such quaternary ammonium cations include tetra(hydrocarbyl)ammonium cations. On the other hand, examples of the anion paired with it include hydroxide ion (OH － ); fluoride ion (F － ), chloride ion (Cl － ), bromide ion (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ion (BF4 － ); hexafluorophosphate ion (PF6 － ), etc., but are not limited thereto.

[0212] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.

[0213] 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.

[0214] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbyl)ammonium fluoride.

[0215] Specific examples of the hydrocarbyl group in tetra(hydrocarbyl)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, aryl groups having 6 to 20 carbon atoms, etc.

[0216] In a more preferred embodiment, tetra(hydrocarbyl)ammonium fluoride contains tetraalkylammonium fluoride.

[0217] Specific examples of tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride), etc., but are not limited thereto. Among them, tetrabutylammonium fluoride is preferred.

[0218] Quaternary ammonium salts such as tetra(hydrocarbyl)ammonium fluoride can use hydrates. In addition, quaternary ammonium salts such as tetra(hydrocarbyl)ammonium fluoride can be used alone or in combination of two or more.

[0219] 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, and a small amount is preferably contained because it can effectively prevent the problem of damage to the cutting tape in the subsequent cleaning step. Specifically, for example, it is usually 0.1% by mass to 5% by mass relative to the stripping and dissolving composition.

[0220] <<[II] Component: Amide-based solvent>>

[0221] The amide-based solvent is effective as a component for dissolving the quaternary ammonium salt well to obtain a stripping and dissolving composition with excellent uniformity.

[0222] The amide-based solvent is preferably an N-substituted amide compound having 4 or more carbon atoms and not having an active hydrogen on the nitrogen atom.

[0223] As a preferred example of the amide-based solvent, an acid amide derivative represented by the following formula (Z) can be cited.

[0224]

[0225] In the formula, R 0 represents ethyl, propyl or isopropyl, preferably ethyl or isopropyl, more preferably ethyl. R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms can be any of linear, branched and cyclic types, and specifically, methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, etc. can be cited. Among them, as R A and R B , methyl or ethyl is preferred, both being methyl or ethyl is more preferred, and both being methyl is even more preferred.

[0226] As the acid amide derivative represented by the formula (Z), N,N-dimethylpropanamide, N,N-diethylpropanamide, N-ethyl-N-methylpropanamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, N-ethyl-N-methylisobutyramide, etc. can be cited. Among them, N,N-dimethylpropanamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropanamide is more preferred.

[0227] The acid amide derivative represented by the formula (Z) can be synthesized by the substitution reaction of the corresponding carboxylic acid ester and amine, or a commercially available product can be used.

[0228] As another example of the preferred amide-based solvent, for example, a compound represented by the formula (Y) containing a lactam compound, etc. can be cited.

[0229]

[0230] In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).

[0231]

[0232] As specific examples of the alkyl group having 1 to 6 carbon atoms for R 102 , there may be mentioned: methyl, ethyl, n-propyl, n-butyl, etc. As specific examples of the alkylene group having 1 to 6 carbon atoms, there may be mentioned: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited thereto.

[0233] 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 bonding bond bonded to the carbon atom in formula (Y), and *2 represents a bonding bond bonded to the nitrogen atom in formula (Y).

[0234] As specific examples of the lactam compound represented by formula (Y), there may be mentioned: α-lactam compound, β-lactam compound, γ-lactam compound, δ-lactam compound, etc., and they may be used alone or in combination of two or more.

[0235] In a preferred embodiment, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam). In a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP). In an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0236] In addition, as a preferred embodiment of the compound represented by formula (Y), for example, 1,3-dimethyl-2-imidazolidinone may also be mentioned.

[0237] In the [II] component, considering the operational constraints based on the restrictions related to the use of chemicals, it is more preferable to use the acid amide derivative represented by formula (Z).

[0238] As the content of the amide-based solvent in the stripping and dissolving composition, when the aprotic solvent is set to 100% by mass in the stripping and dissolving composition, it can be set to 70% by mass or less.

[0239] In addition, when the aprotic solvent is 100% by mass, the content of the amide-based solvent is preferably 10% to 55% by mass, more preferably 20% to 50% by mass, still more preferably 20% to 45% by mass, and particularly preferably 20% to 40% by mass.

[0240] It should be noted that in the present invention, the content of the mixed solvents is defined as a ratio when the aprotic solvent, which is a solvent having no hydroxyl group (-OH), is 100% by mass.

[0241] Thus, protic solvents such as water, methanol, and 1-methoxy-2-propanol are not included in the basis of the content ratio.

[0242] In the present invention, aprotic solvents refer to, for example, N,N-dimethylpropanamide, dibutyl ether, dipropylene glycol dimethyl ether, butyl acetate, etc., and the mixing ratio can be calculated based on their total amount.

[0243] <<[III] Component: Solvent Represented by Formula (L)>>

[0244] The solvent represented by the following formula (L) is effective as a component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.

[0245] L 1 -L 3 -L 2 (L)

[0246] In the above formula (L), L 1 and L 2 each independently represents an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.

[0247] L 1 and L 2 may be the same group or different groups, but from the viewpoint of availability, they are preferably the same group.

[0248] The alkyl group having 2 to 5 carbon atoms can be any of linear, branched, and cyclic types. From the viewpoint of achieving good reproducibility and peeling the adhesive layer in a short time, etc., a linear or branched alkyl group is preferred, and a linear alkyl group is more preferred.

[0249] Specific examples of the linear or branched alkyl group include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, etc., but are not limited thereto.

[0250] Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, etc., but are not limited thereto.

[0251] From the viewpoint of achieving good reproducibility of peeling of the adhesive layer in a short time, 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.

[0252] From the viewpoints of achieving good reproducibility of peeling of the adhesive layer in an even shorter time, ease of obtaining the compound, etc., L 1 and L 2 are preferably the same group.

[0253] From the viewpoints of achieving good reproducibility of peeling of the adhesive layer in an even shorter time, ease of obtaining the compound, etc., preferred examples of the organic solvent represented by the formula (L) include: di(n-butyl) ether, diethyl ether, di(n-pentyl) ether, di(n-propyl) sulfide, etc.

[0254] As the content of the solvent represented by the formula (L) in the peeling and dissolving composition, when the aprotic solvent is set to 100% by mass in the peeling and dissolving composition, it can be 30% by mass or more.

[0255] As the content of the solvent represented by the formula (L) in the peeling and dissolving composition, when the aprotic solvent is set to 100% by mass in the peeling and dissolving composition, it is preferably 30% by mass or more, more preferably 31% by mass or more, further preferably 40% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less. These upper and lower limit values can be any combination. Therefore, as the content of the solvent represented by the formula (L), when the aprotic solvent is set to 100% by mass in the peeling and dissolving composition, it is preferably 30% by mass to 90% by mass, and more preferably 40% by mass to 80% by mass.

[0256] It should be noted that the peeling and dissolving composition may contain an arbitrary amount of the solvent of the [IV] component represented by the following formula (T) or the following formula (G), and be mixed with the solvent of the [III] component represented by the formula (L). In this case, when the aprotic solvent is set to 100% by mass, the content obtained by adding the [III] component and the [IV] component is preferably 30% by mass to 90% by mass.

[0257] In addition, when the stripping and dissolving composition contains a solvent of the [IV] component represented by the following formula (T) or the following formula (G), particularly when the [IV] component is the component represented by the formula (G), in addition to the effect of improving the compatibility between the [II] component and the [III] component achieved by containing the [IV] component, the stripping effect of the adhesive can be further improved. Therefore, if the stripping and dissolving composition contains 30% by mass or more of the component represented by the formula (L) as the [III] component, the stripping and dissolving composition containing the [I] component, the [II] component, the [III] component, and the [IV] component represented by the formula (G) becomes a composition that exhibits the effects of the present invention well.

[0258] <<[IV] Component: Solvent Represented by Formula (T) or Formula (G)>>

[0259] The solvent represented by the following formula (T) or the following formula (G) is effective as an adjustment component for improving the compatibility between the amide-based solvent as the above [II] component and the solvent represented by the above formula (L) as the above [III] component in the stripping and dissolving composition containing the quaternary ammonium salt as the above [I] component.

[0260]

[0261] 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. X 4 represents an alkyl group.

[0262] Examples of the alkyl group represented by X1 and X3 include alkyl groups having 1 to 4 carbon atoms. More specifically, examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0263] Examples of the alkylene group represented by X2 include: methylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, etc.

[0264] Examples of the alkyl group represented by X4 include alkyl groups having 1 to 4 carbon atoms, and the same alkyl groups as those of X1 and X3 can be enumerated.

[0265] Preferred examples of the solvent represented by the formula (T) include: dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.

[0266]

[0267] In formula (G), L 11and L 12 each independently represents an alkyl group having 1 to 6 carbon atoms, and the alkyl group of L 11 and the alkyl group of L 12 have a total of 7 or less carbon atoms.

[0268] In the above formula (G), L 11 and L 12 each independently represents an alkyl group having 1 to 6 carbon atoms, and the alkyl group of L 11 and the alkyl group of L 12 have a total of 7 or less carbon atoms. By setting the number of carbon atoms in this way, the peeling of the adhesive layer can be achieved with good reproducibility in a short time.

[0269] The alkyl group can be any of linear, branched, and cyclic types, preferably a linear or branched alkyl group, more preferably a linear alkyl group.

[0270] 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, 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, 1-ethyl-2-methyl-n-propyl, etc., but are not limited thereto.

[0271] Specific examples of the cyclic alkyl group include, but are not limited to, 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-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, 2-ethyl-3-methyl-cyclopropyl, and other cyclic alkyl groups.

[0272] From the viewpoint of achieving good reproducibility of peeling the adhesive layer in a shorter time, the above L 11 is preferably methyl. In addition, the above L 12 is preferably butyl or pentyl.

[0273] From the viewpoints of achieving good reproducibility of peeling the adhesive layer in a shorter time and easy availability of the compound, etc., preferred examples of the organic solvent represented by the formula (G) include butyl acetate, amyl acetate, etc.

[0274] As the content of the solvent represented by the formula (T) or the formula (G) in the peeling and dissolving composition, when the aprotic solvent is set to 100% by mass in the peeling and dissolving composition, it is preferably 0.1% by mass to 60% by mass, more preferably 5% by mass to 40% by mass, further preferably 5% by mass to 35% by mass, still further preferably 5% by mass to 31% by mass or less, and particularly preferably 5% by mass to 30% by mass or less.

[0275] It should be noted that when the peeling and dissolving composition contains the [IV] component represented by the formula (T) or the formula (G), when the aprotic solvent is set to 100% by mass, the content obtained by adding the [III] component and the [IV] component is preferably 30% by mass to 90% by mass as described above. If further explained, it is more preferably 40% by mass to 90% by mass, further preferably 45% by mass to 90% by mass, still further preferably 50% by mass to 80% by mass, particularly preferably 55% by mass to 80% by mass, and more preferably 60% by mass to 80% by mass.

[0276] <<Process of stripping and dissolution>>

[0277] In the present invention, the stripping and dissolution composition is continuously brought into contact with the adhesive layer on the semiconductor substrate. By performing this cleaning operation, the operations of swelling and stripping the adhesive layer and dissolving the adhesive layer are carried out together. Through a single cleaning operation using the cleaning composition, the swelling, stripping, and dissolution of the adhesive layer are carried out together, whereby the adhesive layer can be removed (cleaned) from the semiconductor substrate more cleanly and in a shorter time by a simple cleaning operation.

[0278] It should be noted that in the present invention, "removing (cleaning)" means removing the adhesive layer from the semiconductor substrate, and both the case where the adhesive layer swells and peels off from the semiconductor substrate and the case where the adhesive layer dissolves in the solution and disappears from the semiconductor substrate are included in "removing (cleaning)".

[0279] Regarding the method of continuously bringing the adhesive layer on the semiconductor substrate into contact with the stripping and dissolution composition, there is no particular limitation as long as the adhesive layer on the semiconductor substrate is in contact with the stripping and dissolution composition in a temporally continuous manner. This temporal continuity includes not only the case where the adhesive layer is always in contact with the stripping and dissolution composition, but also, for example, the case where after the adhesive layer has been in contact with an organic solvent for a certain period of time, the contact is temporarily stopped and then resumed, or the above situation is repeated. In addition, it includes not only the case where the entire adhesive layer on the semiconductor substrate is in contact with the stripping and dissolution composition, but also the case where a part of the adhesive layer is in contact with the stripping and dissolution composition. However, from the viewpoint of achieving more effective cleaning with good reproducibility, a preferred embodiment is that the adhesive layer on the semiconductor substrate is always in contact with the stripping and dissolution composition, and in addition, a preferred embodiment is that the entire adhesive layer on the semiconductor substrate is in contact with the stripping and dissolution composition.

[0280] Therefore, in a preferred embodiment of the present invention, the adhesive layer on the semiconductor substrate is swollen and dissolved by immersing the above-mentioned adhesive layer in the stripping and dissolution composition, and the adhesive layer on the semiconductor substrate is removed from the semiconductor substrate, or the adhesive layer on the semiconductor substrate is swollen and dissolved by continuously supplying the stripping and dissolution composition onto the above-mentioned adhesive layer, and the adhesive layer on the semiconductor substrate is removed from the semiconductor substrate.

[0281] In order to immerse the adhesive layer on the semiconductor substrate in the stripping and dissolution composition, for example, the semiconductor substrate with the adhesive layer can be immersed in the stripping and dissolution composition.

[0282] The dipping time is set to the time until the adhesive layer swells and dissolves and the adhesive layer is peeled off from the semiconductor substrate, and there is no particular limitation. From the viewpoint of achieving more effective cleaning with good reproducibility, it is 5 seconds or more, and from the viewpoint of process throughput, it is 5 minutes or less.

[0283] When dipping the adhesive layer on the semiconductor substrate 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, causing the stripping and dissolving composition to convect, and vibrating the stripping and dissolving composition using ultrasonic waves, etc.

[0284] In order to move the semiconductor substrate with the adhesive layer in the stripping and dissolving composition, for example, a swing cleaner, a paddle cleaner, etc. can be used. If such a cleaner is used, by moving the stage carrying the semiconductor substrate with the adhesive layer up and down, left and right, or rotating, the adhesive layer on the semiconductor substrate is relatively subjected to convection, or the adhesive layer on the semiconductor substrate is subjected to convection generated by its movement or rotation, which not only promotes the swelling and dissolution of the adhesive layer on the semiconductor substrate, but also promotes the peeling and dissolution of the adhesive layer from the semiconductor substrate.

[0285] In order to cause the stripping and dissolving composition to convect, in addition to the above-mentioned swing cleaner and paddle cleaner, for example, typically, the following convection cleaner can be used: a convection cleaner that can achieve a state where the stripping and dissolving composition around it is convected by a stirrer in a state where the semiconductor substrate with the adhesive layer is fixed to a stage or the like.

[0286] In order to vibrate the stripping and dissolving composition using ultrasonic waves, an ultrasonic cleaner or an ultrasonic probe can be used, and the conditions are usually 20 kHz to 5 MHz.

[0287] In order to continuously supply the stripping and dissolving composition to the adhesive layer on the semiconductor substrate, it is only necessary to continuously touch the stripping and dissolving composition to the adhesive layer on the semiconductor substrate. Taking an example, if the adhesive layer on the semiconductor substrate is facing up, for example, from above (including obliquely above) the adhesive layer on the semiconductor substrate, a rod-shaped or mist-shaped, preferably rod-shaped, stripping and dissolving composition is supplied to the adhesive layer on the semiconductor substrate in a time-persistent manner through a nozzle of a cleaning device or the like. The time persistence in this case also includes not only the case where the stripping and dissolving composition is always supplied to the adhesive layer on the semiconductor substrate, but also, for example, the case where after supplying the stripping and dissolving composition for a certain period of time, the supply is temporarily stopped and then the supply is resumed, or the above situation is repeated. From the viewpoint of achieving more effective cleaning with good reproducibility, it is preferred to always supply the stripping and dissolving composition to the adhesive layer on the semiconductor substrate.

[0288] When supplying the composition for peeling and dissolving in a rod shape onto the adhesive layer on the semiconductor substrate, the flow rate is generally 200 to 500 mL / minute.

[0289] In one aspect of the present invention, in order to achieve a state of always being in contact with the composition for peeling and dissolving, for example, a vapor cleaner can be used to bring the adhesive layer on the semiconductor substrate into contact with the vapor of the composition for peeling and dissolving.

[0290] If the cleaning method of the semiconductor of the present invention is used, as described above, by swelling, peeling, and dissolving the adhesive layer together, the adhesive layer can be removed (cleaned) from the semiconductor substrate more cleanly in a shorter time through a simple cleaning operation. However, in addition to this effect, if the cleaning method of the semiconductor of the present invention is used, damage to the dicing tape during the cleaning process can be prevented.

[0291] For example, after the semiconductor wafer is ground and thinned, the thinned semiconductor wafer is mounted on the dicing tape, and then the semiconductor wafer and the support are separated (peeled). After the support is separated (peeled), in order to remove the adhesive layer remaining on the semiconductor wafer side from the semiconductor wafer, the adhesive layer is cleaned with a cleaning agent composition. At this time, as the cleaning agent composition, if a cleaning agent composition of the type that dissolves and removes the adhesive residue, such as the cleaning agent compositions of Patent Documents 1 and 2 described above, is used, the surface of the dicing tape changes and the dicing tape is damaged (refer to the results of [Comparative Example 2-1] described in the following Example section).

[0292] However, if the composition for peeling and dissolving of the present invention is used to clean the semiconductor substrate with an adhesive layer, most of the adhesive layer can be peeled in a short time, and the small amount of adhesive layer remaining after peeling is also dissolved by the dissolving component in the composition for peeling and dissolving. Thus, the overall removal (cleaning) time of the adhesive layer is short, and damage to the dicing tape during the cleaning process can be effectively prevented. In addition, in the composition for peeling and dissolving of the present invention, not only the component for dissolving the adhesive layer is included, but also the component for swelling and peeling the adhesive layer is included. Thus, the proportion of the dissolving component in the composition, that is, the [I] component (quaternary ammonium salt), can be small, which also effectively helps to prevent damage to the dicing tape.

[0293] If the composition for peeling and dissolving of the present invention is used for the removal process of the adhesive layer, damage to the dicing tape can be effectively prevented (refer to the results of [Example 3-1] described in the following Example section).

[0294] The cleaning method of the semiconductor substrate of the present invention may also include a process of removing the peeled adhesive layer.

[0295] The method for removing the peeled adhesive layer is not particularly limited as long as the peeled adhesive layer is removed from the semiconductor substrate. When the semiconductor substrate with the adhesive layer is immersed in the stripping and dissolving composition, the peeled adhesive layer present in the stripping and dissolving composition can be removed without taking out the semiconductor substrate from the stripping and dissolving composition. Alternatively, the peeled adhesive layer can be removed by taking out the semiconductor substrate from the stripping and dissolving composition and separating the semiconductor substrate from the peeled adhesive layer. At this time, sometimes by simply taking out the semiconductor substrate from the stripping and dissolving composition, the peeled adhesive layer can be naturally left in the stripping and dissolving composition and most of it can be removed.

[0296] As specific examples of the method for removing the peeled adhesive layer, for example, methods such as removing by adsorption or suction using a device, removing by gas blowing using an air gun, etc., removing by centrifugal force generated by moving the semiconductor substrate up and down, left and right, or rotating, etc. can be cited, but it is not limited thereto.

[0297] After removing the peeled adhesive layer from the semiconductor substrate, if necessary, drying of the semiconductor substrate and the like are carried out according to conventional methods.

[0298] (Stripping and dissolving composition)

[0299] The stripping and dissolving composition used in the cleaning method of the semiconductor substrate of the present invention is also an object of the present invention.

[0300] The stripping and dissolving composition of the present invention is used to remove (clean) the adhesive layer on the semiconductor substrate from the semiconductor substrate. Preferred embodiments and various conditions are as described above. For the stripping and dissolving composition of the present invention, if necessary, it can be manufactured by mixing the solvents constituting the composition in any order. At this time, if necessary, filtration and the like can also be carried out.

[0301] The content of the solvent represented by the formula (L) in the stripping and dissolving composition of the present invention is characterized in that it is 30% by mass or more when the aprotic solvent is set to 100% by mass.

[0302] In the stripping and dissolving composition like this, the content ratio of the [III] component (the solvent represented by the formula (L)), which helps to swell and peel the adhesive layer, is high. Thus, when the stripping and dissolving composition of the present invention comes into contact with the adhesive layer, the adhesive layer is swollen, peeled, and dissolved together.

[0303] For example, International Publication No. 2020 / 080060 (hereinafter referred to as Publication A) describes a method for cleaning an adhesive on a semiconductor substrate and a cleaning agent composition used in the cleaning method. However, the adhesive described in Publication A is not the type of adhesive that can be swollen and peeled off by the cleaning composition targeted in the present invention. Therefore, in Publication A, there is no idea of swelling and peeling the adhesive layer as a means for removing the adhesive, and the cleaning agent composition described in Publication A is only intended to dissolve the adhesive layer to remove the adhesive layer. In fact, by preparing a cleaning composition with the solvent ratio described in the examples of Publication A (refer to the cleaning liquid of [Comparative Examples 1-1 to 1-6] described in the column of the following examples), it was found that the adhesive layer would not be peeled off if it did not contain more than a certain amount of component [III] (the solvent represented by formula (L)) (refer to the measurement results of [4] peeling time described in the column of the following examples).

[0304] In the composition for peeling and dissolving of the present invention, the content ratio of component [III] (the solvent represented by formula (L)) is high, and the proportions of component [II] and component [III] (in the case of containing component [IV], the proportions of component [II], component [III] and component [IV]) are high. Therefore, in the composition for peeling and dissolving, the content of component [I] (quaternary ammonium salt) is relatively small. By suppressing the content of component [I], damage to the cutting tape in the cleaning process can be reduced.

[0305] As a preferred embodiment of the composition for peeling and dissolving of the present invention, there can be mentioned: a composition in which, when the composition for peeling and dissolving contains component [I], component [II] and component [III] (optionally containing or not containing component [IV]), and assuming 100% by mass of the aprotic solvent, component [III] contains 35% by mass or more.

[0306] Furthermore, as another preferred embodiment of the composition for peeling and dissolving of the present invention, there can be mentioned: a composition in which, when the composition for peeling and dissolving contains component [I], component [II] and component [III] (optionally containing or not containing component [IV]), and assuming 100% by mass of the aprotic solvent, component [III] contains 40% by mass or more.

[0307] In addition, as another preferred embodiment of the composition for stripping and dissolving of the present invention, the following can be cited: when the composition for stripping and dissolving contains component [I], component [II], component [III], and component [IV], assuming the aprotic solvent is 100% by mass, a composition in which component [III] contains 30% by mass or more, or component [IV] contains 31% by mass or less; or a composition in which component [III] contains 30% by mass or more and component [IV] contains 31% by mass or less.

[0308] In addition, as another preferred embodiment of the composition for stripping and dissolving of the present invention, the following can be cited: when the composition for stripping and dissolving contains component [I], component [II], component [III], and component [IV], assuming the aprotic solvent is 100% by mass, a composition in which component [III] contains 35% by mass or more or component [IV] contains 35% by mass or less; or a composition in which component [III] contains 35% by mass or more and component [IV] contains 35% by mass or less.

[0309] In particular, the following can be preferably cited: when the composition for stripping and dissolving contains component [I], component [II], component [III], and component [IV], and when component [IV] is the solvent represented by formula (G), assuming the aprotic solvent is 100% by mass, a composition in which component [III] contains 30% by mass or more.

[0310] In addition, the following can be preferably cited: when the composition for stripping and dissolving contains component [I], component [II], component [III], and component [IV], and when component [IV] is the solvent represented by formula (G), assuming the aprotic solvent is 100% by mass, a composition in which component [III] contains 30% by mass or more or component [IV] contains 35% by mass or less, or 31% by mass or less, or 30% by mass or less.

[0311] Alternatively, the following can be preferably cited: when the composition for stripping and dissolving contains component [I], component [II], component [III], and component [IV], and when component [IV] is the solvent represented by formula (G), assuming the aprotic solvent is 100% by mass, a composition in which component [III] contains 30% by mass or more and component [IV] contains 35% by mass or less, or 31% by mass or less, or 30% by mass or less.

[0312] (Method for manufacturing a processed semiconductor substrate)

[0313] By using the cleaning method of the semiconductor substrate of the present invention described above, the adhesive layer on the substrate of the semiconductor substrate can be efficiently removed, particularly the adhesive layer which is a cured film obtained from a silicone-based adhesive containing a polyorganosiloxane component (A') cured by a hydrosilylation reaction, and high-efficiency and good manufacturing of semiconductor elements can be expected.

[0314] Regarding the manufacturing method of the processed semiconductor substrate of the present invention, for example, after a semiconductor wafer is ground and thinned, and the support is separated (peeled off) from the processed and thinned semiconductor wafer, the cleaning method of the semiconductor substrate of the present invention is used to remove (clean) the adhesive layer remaining on the semiconductor wafer side, whereby a processed semiconductor substrate with a clean surface without a remaining adhesive layer can be manufactured.

[0315] As an example of the use of the cleaning method of the semiconductor substrate of the present invention in such a semiconductor process, the use in the manufacturing method of a processed semiconductor substrate such as a semiconductor substrate thinned or otherwise processed used in semiconductor packaging technologies such as TSV can be cited.

[0316] The semiconductor substrate to be cleaned by the cleaning method of the present invention includes, in addition to the above-mentioned silicon semiconductor substrates such as silicon wafers, various substrates such as germanium substrates, gallium-arsenide substrates, gallium-phosphorus substrates, gallium-arsenide-aluminum substrates, aluminum-coated silicon substrates, copper-coated silicon substrates, silver-coated silicon substrates, gold-coated silicon substrates, titanium-coated silicon substrates, silicon substrates with a silicon nitride film formed, silicon substrates with a silicon oxide film formed, silicon substrates with a polyimide film formed, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.

[0317] As a preferred embodiment of the manufacturing method of the processed semiconductor substrate of the present invention, the following manufacturing method of the processed semiconductor substrate can be cited, which includes: a first step: a step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step: a step of processing the semiconductor substrate of the obtained laminate; a third step: a step of separating the semiconductor substrate and the adhesive layer from the support substrate; and a fourth step: a step of removing the adhesive layer on the semiconductor substrate by peeling and dissolving using a peeling and dissolving composition.

[0318] Here, the peeling and dissolving composition is as described in the above <Peeling and Dissolving Composition> column.

[0319] In the above fourth step, the cleaning method of the semiconductor substrate of the present invention is used.

[0320] Hereinafter, each step will be described in detail.

[0321] <First Step>

[0322] As the adhesive composition used for forming the adhesive layer in the first step, various adhesives described above can be used. However, the cleaning method of the semiconductor substrate of the present invention is effectively used to remove the adhesive layer obtained from a polysiloxane-based adhesive, and more effectively used to remove the adhesive layer obtained from a polysiloxane-based adhesive containing component (A) cured by a hydrosilylation reaction.

[0323] Therefore, hereinafter, an example of removing the adhesive layer obtained using a polysiloxane-based adhesive (adhesive composition) by the cleaning method of the present invention when manufacturing a processed semiconductor substrate using this adhesive layer will be described, but the present invention is not limited thereto.

[0324] The first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described below.

[0325] In one aspect, the above first step includes: a step of coating the adhesive composition on the surface of the semiconductor substrate or the support substrate to form an adhesive coating layer; and a step of laminating the semiconductor substrate and the support substrate via the adhesive coating layer, while applying at least one of heat treatment and pressure reduction treatment, applying a load in the thickness direction of the semiconductor substrate and the support substrate to make them closely adhere, and then performing post-heat treatment to thereby manufacture a laminate.

[0326] In another aspect, the above first step, for example, includes: a step of coating the adhesive composition on the circuit surface of the wafer of the semiconductor substrate and heating it to form an adhesive coating layer; a step of coating the release agent composition on the surface of the support substrate and heating it to form a release agent coating layer; and a step of making the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate closely adhere while applying at least one of heat treatment and pressure reduction treatment, applying a load in the thickness direction of the semiconductor substrate and the support substrate, and then performing post-heat treatment to thereby manufacture a laminate. It should be noted that the adhesive composition is coated on the semiconductor substrate and the release agent composition is coated on the support substrate, and heating is performed, or the coating and heating of the adhesive composition and the release agent composition can be sequentially performed on either substrate.

[0327] In each of the above aspects, which treatment condition of heat treatment, pressure reduction treatment, or both is used together is determined based on various conditions such as the type of the adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from the two compositions, the film thickness, and the required adhesive strength.

[0328] Here, for example, the semiconductor substrate is a wafer and the support substrate is a support. The object of coating the adhesive composition can be either one or both of the semiconductor substrate and the support substrate.

[0329] As the wafer, for example, a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm, a glass wafer can be cited, but it is not limited thereto.

[0330] In particular, the cleaning method of the semiconductor substrate of the present invention can effectively clean the substrate even for a semiconductor substrate with bumps.

[0331] As a specific example of such a semiconductor substrate with bumps, a silicon wafer having bumps such as ball bumps, printed bumps, columnar bumps, plated bumps, etc. can be cited. Generally, it is appropriately selected from the conditions of a bump height of about 1 μm to 200 μm, a bump diameter of 1 μm to 200 μm, and a bump pitch of 1 μm to 500 μm.

[0332] As a specific example of the plated bump, alloy plating mainly composed of Sn such as SnAg bump, SnBi bump, Sn bump, AuSn bump, etc. can be cited, but it is not limited thereto.

[0333] The support (carrier) is not particularly limited. For example, a silicon wafer with a diameter of 300 mm and a thickness of about 700 μm can be cited, but it is not limited thereto.

[0334] As the release agent composition, a composition containing a release agent component for such a use can be cited.

[0335] The coating method is not particularly limited. Generally, it is a spin coating method. It should be noted that a method of forming a coating film separately by a spin coating method or the like and pasting a sheet-like coating film can also be used, which is also called coating or coating film.

[0336] The heating temperature of the adhesive composition after coating varies depending on the type, amount, whether it contains a solvent, the desired thickness of the adhesive layer, etc. of the adhesive component contained in the adhesive composition. Therefore, it cannot be generally specified, but the heating temperature is usually 80°C to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0337] The heating temperature of the release agent composition after coating varies depending on the type, amount, whether it contains a solvent, the desired thickness of the release layer, etc. of the crosslinking agent, acid generator, acid, etc. Therefore, it cannot be generally specified, but from the viewpoint of achieving appropriate curing, the heating temperature is 120°C or higher, and from the viewpoint of preventing excessive curing, the heating temperature is preferably 260°C or lower, and the heating time is usually 1 minute to 10 minutes.

[0338] Heating can be carried out using a hot plate, an oven, etc.

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

[0340] A coating release agent composition, and the film thickness of the release agent coating layer obtained by heating it is generally 5 μm to 500 μm.

[0341] From the viewpoints of softening the adhesive coating layer to achieve proper adhesion to the release agent coating layer and achieving proper curing of the release agent coating layer, etc., the heat treatment is generally appropriately determined within the range of 20°C to 150°C. In particular, from the viewpoints of suppressing / avoiding excessive curing and unwanted deterioration of the adhesive component and the release agent component, the heat treatment is preferably 130°C or lower, more preferably 90°C or lower. From the viewpoints of reliably demonstrating the adhesive ability and the release ability, the heating time is generally 30 seconds or longer, preferably 1 minute or longer. From the viewpoints of suppressing the deterioration of the adhesive layer and other components, the heating time is generally 10 minutes or shorter, preferably 5 minutes or shorter.

[0342] For the pressure reduction treatment, it is only necessary to expose the semiconductor substrate, the adhesive coating layer, and the support substrate, or the semiconductor substrate, the adhesive coating layer, the release agent coating layer, and the support substrate to an air pressure of 10 Pa to 10,000 Pa. The time for the pressure reduction treatment is generally 1 minute to 30 minutes.

[0343] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are preferably adhered by the pressure reduction treatment, and more preferably by the combined use of the heat treatment and the pressure reduction treatment.

[0344] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not cause adverse effects on the semiconductor substrate, the support substrate, and the layers therebetween, and can firmly bond them, and is generally in the range of 10 N to 1000 N.

[0345] From the viewpoint of obtaining a sufficient curing rate, the post-heating temperature is preferably 120°C or higher. From the viewpoints of preventing the deterioration of the substrate, the adhesive component, the release agent component, etc., the post-heating temperature is preferably 260°C or lower. From the viewpoint of achieving proper bonding of the wafer based on curing, the heating time is generally 1 minute or longer. Further, from the viewpoints of stabilizing the physical properties of the adhesive, etc., the heating time is preferably 5 minutes or longer. From the viewpoints of avoiding adverse effects on the adhesive layer caused by excessive heating, etc., the heating time is generally 180 minutes or shorter, preferably 120 minutes or shorter. The heating can be performed using a hot plate, an oven, etc.

[0346] It should be noted that one of the purposes of the post-heating treatment is to more appropriately cure the adhesive component (S).

[0347] <Second process>

[0348] Next, the second process of processing the semiconductor substrate of the laminate obtained by the method described above will be described.

[0349] As an example of the processing performed on the laminate used in the present invention, processing of the back surface of the semiconductor substrate, which is opposite to the circuit surface on the front surface, can be cited. Typically, thinning of the wafer achieved by grinding the back surface of the wafer can be cited. Using such a thinned wafer, formation of through-silicon vias (TSVs) and the like is performed, and then the thinned wafer is peeled off from the support to form a laminate of wafers for three-dimensional mounting. In addition, formation of electrodes on the back surface of the wafer and the like is also performed before and after three-dimensional mounting. Heat of 250°C to 350°C is applied in a state of being bonded to the support during the thinning of the wafer and the TSV process, and the adhesive layer contained in the laminate used in the present invention has heat resistance to this heat.

[0350] For example, a wafer with a diameter of 300 mm and a thickness of about 770 μm can be thinned to a thickness of about 80 μm to 4 μm by grinding the back surface, which is opposite to the circuit surface on the front surface.

[0351] <Third process>

[0352] A description will be given of the third process of separating the processed semiconductor substrate and the adhesive layer from the support substrate.

[0353] In the third process, the processed semiconductor substrate and the adhesive layer are separated from the support substrate. At this time, when the laminate includes a release layer, generally, the release layer is also removed together with the support substrate.

[0354] A method of separating the processed semiconductor substrate and the adhesive layer from the semiconductor substrate may be to peel between the adhesive layer and the release layer or the support substrate in contact therewith. As such a peeling method, laser peeling, mechanical peeling using a mechanical material having a sharp portion, peeling by manual tearing, etc. can be cited, but it is not limited thereto.

[0355] <Fourth process>

[0356] Next, a description will be given of the fourth process of removing the adhesive layer on the processed semiconductor substrate and cleaning the processed semiconductor substrate.

[0357] The fourth process is a process of removing the adhesive layer on the semiconductor substrate by the cleaning method of the semiconductor substrate of the present invention. Specifically, for example, the adhesive layer on the thinned substrate is cleanly removed in a short time by the cleaning method of the present invention. The respective conditions at this time are as described above.

[0358] As described above, only the stripping and dissolving composition of the present invention is used for the cleaning operation, and swelling and dissolution act on the adhesive layer at the same time. Therefore, in the fourth process, the adhesive layer on the semiconductor substrate can be removed more cleanly in a short time.

[0359] The method for manufacturing the processed semiconductor substrate of the present invention includes the above-described first to fourth processes, but may also include processes other than these. In addition, various modifications can be made to the above-described constituent elements and method elements related to the first to fourth processes as long as they do not depart from the gist of the present invention.

[0360] [Examples]

[0361] Hereinafter, the content and effects of the present invention will be further described in detail by way of examples, but the present invention is not limited thereto. It should be noted that the devices used are as follows.

[0362] [Devices]

[0363] (1) Stirrer A: Planetary mixer ARE-500 manufactured by THINKY Corporation.

[0364] (2) Stirrer B: Mix Rotor VMR-5R manufactured by AS ONE Corporation.

[0365] (3) Viscometer: Rotary viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.

[0366] (4) Optical microscope: Semiconductor / FPD inspection microscope MX61L manufactured by Olympus Corporation.

[0367] [1] Preparation of Adhesive Composition 1

[0368] [Example 1]

[0369] Into a 600 mL stirring container dedicated to Stirrer A, 99.12 g of a p-menthane solution (concentration 80.6 mass%) of an MQ resin having a polysiloxane skeleton and vinyl (manufactured by Wacker Chemie AG), which is the above-described component (a1), 22.12 g of the above-described polyorganosiloxane represented by the formula (M1) (complex viscosity 6000 Pa·s, weight average molecular weight 642000 (dispersion degree 2.6), manufactured by Wacker Chemie AG, trade name GENIOPLAST GUM), 48.89 g of p-menthane (manufactured by NIPPON TERPENE CHEMICALS Co., Ltd.), and 5.43 g of n-decane (manufactured by Sankyo Chemical Co., Ltd.) were added, and stirring with Stirrer A for 5 minutes was repeated a total of 8 times with a momentary stop in the middle to obtain a mixture (I) (total stirring time: 40 minutes).

[0370] To the obtained mixture (I), 15.98 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s as the above-mentioned component (a2) and 23.35 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 200 mPa·s as the above-mentioned component (a1) were added to obtain a mixture (II).

[0371] Using a stirrer B, 0.31 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as the above-mentioned component (A3), 0.31 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as the above-mentioned component (A3), and 0.61 g of p-menthane (manufactured by NIPPON TERPENE CHEMICALS Co., Ltd.) were stirred for 60 minutes to obtain a mixture (III).

[0372] 1.23 g of the obtained mixture (III) was added to the mixture (II), and the mixture was stirred with a stirrer A for 5 minutes to obtain a mixture (IV).

[0373] Using a stirrer A, 0.074 g of a platinum catalyst (manufactured by Wacker Chemie) as the above-mentioned component (A2) and 7.37 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1000 mPa·s as the above-mentioned component (a1) were stirred for 5 minutes to obtain a mixture (V).

[0374] 3.72 g of the obtained mixture (V) was added to the mixture (IV), and the mixture was stirred with a stirrer A for 5 minutes to obtain a mixture (VI).

[0375] Finally, the obtained mixture (VI) was filtered through a 300-mesh nylon filter to obtain an adhesive composition. It should be noted that the viscosity of the obtained adhesive composition was 2700 mPa·s.

[0376] [2] Preparation of cleaning composition

[0377] [Example 2-1]

[0378] To 0.59 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical), 8.08 g of N-methyl-2-pyrrolidone, 8.50 g of dibutyl ether, and 2.55 g of dipropylene glycol dimethyl ether were added and stirred to obtain a cleaning composition.

[0379] [Example 2-2] to [Example 2-12], [Example 2-26], [Comparative Example 1-1] to [Comparative Example 1-6]

[0380] It was adjusted to the compositions of Tables 1 to 3 (Tables 1 to 3 are collectively referred to as Table 1 etc.), and in addition, a cleaning composition was obtained in the same order as in Example 2-1.

[0381] [Example 2-13] to [Example 2-17]

[0382] As the N-substituted amide compound as the second component, N-ethyl-2-pyrrolidone was used instead of N-methyl-2-pyrrolidone, and it was adjusted to the compositions of Table 1 etc. In addition, a cleaning composition was obtained in the same order as in Example 2-1.

[0383] [Example 2-18] to [Example 2-20]

[0384] As the N-substituted amide compound as the second component, N,N-dimethylpropanamide was used instead of N-methyl-2-pyrrolidone, and it was adjusted to the compositions of Table 1 etc. In addition, a cleaning composition was obtained in the same order as in Example 2-1.

[0385] [Example 2-21] to [Example 2-22]

[0386] As the N-substituted amide compound as the second component, 1,3-dimethyl-2-imidazolidinone was used instead of N-methyl-2-pyrrolidone, and it was adjusted to the compositions of Table 1 etc. In addition, a cleaning composition was obtained in the same order as in Example 2-1.

[0387] [Example 2-23] to [Example 2-25]

[0388] As the fourth component, butyl acetate was used instead of dipropylene glycol dimethyl ether, and it was adjusted to the compositions of Table 1 etc. In addition, a cleaning composition was obtained in the same order as in Example 2-1.

[0389] [Comparative Example 1-7]

[0390] 1.3 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical) was added to 24.70 g of N,N-dimethylpropanamide and stirred to obtain a cleaning composition.

[0391] [3] Preparation of Substrate for Evaluation

[0392] [Production Example 1]

[0393] The adhesive composition obtained in Example 1 was spin-coated onto a 4 cm × 4 cm silicon wafer (thickness 775 μm) of the wafer on the device side, and heated at 110 °C (preheating treatment) for 1.5 minutes to remove the residual solvent on the wafer, and a film with a thickness of about 40 μm was formed on the wafer, thereby obtaining a wafer with an adhesive layer.

[0394] [4] Measurement of peeling time

[0395] The wafer with an adhesive layer produced in Production Example 1 was immersed in 7 mL of each cleaning composition obtained in Examples 2-1 to 2-26 and Comparative Examples 1-1 to 1-7. The time until the adhesive layer was completely peeled off from the wafer was defined as the peeling time. The results are shown in Table 1 to Table 3 below.

[0396] [5] Confirmation of the presence or absence of residue after peeling

[0397] The wafer with an adhesive layer produced in Production Example 1 was immersed in 7 mL of each cleaning composition obtained in Examples 2-1 to 2-26 and Comparative Examples 1-1 to 1-7. When the adhesive layer was peeled off within 1 minute after immersion in the cleaning composition, the peeled adhesive layer was removed with tweezers. After 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 using an optical microscope. The results are shown in Table 1 to Table 3 below. It should be noted that in the tests of Comparative Examples 1-1 to 1-7 in [4] above, peeling did not occur even after 300 seconds, so the test in [5] was not performed (denoted as "N.A." in the table).

[0398] [6] Confirmation of damage

[0399] [Example 3-1]

[0400] As a cutting tape, DU-300 (manufactured by Nitto Denko Corporation) was cut into 4 cm × 4 cm, immersed in 7 mL of the cleaning composition mixture of Example 2-1, and after standing for 5 minutes, the cutting tape was cleaned with isopropyl alcohol and ultrapure water, and the surface of the tape was observed using an optical microscope. As a result, no change was observed on the surface of the tape before and after immersion.

[0401] In addition, the cleaning composition mixture of Example 2-1 was changed to the cleaning composition mixtures of Examples 2-2 to 2-5 respectively, and the same experiment was conducted. The result was the same as that when the cleaning composition mixture of Example 2-1 was used, and no change was observed on the surface of the tape before and after immersion.

[0402] [Comparative Example 2-1]

[0403] As a cutting tape, DU-300 (manufactured by Nitto Denko Corporation) was cut into 4 cm × 4 cm, immersed in 7 mL of the cleaning liquid composition of Comparative Examples 1-7, left for 5 minutes, and then the cutting tape was cleaned with isopropyl alcohol and ultrapure water, and the surface of the tape was observed with an optical microscope. As a result, in the substrate after immersion, uneven shapes were observed on the surface of the tape, and tape damage was confirmed.

[0404] It can be seen that if 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 2-26, 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. Therefore, even if a small amount of the adhesive layer remains after stripping, the adhesive residue will be dissolved by the dissolving component in the stripping and dissolving composition and removed cleanly. This fact is also shown by the results of Examples 2-1 to 2-26. As shown in Examples 2-1 to 2-26, by immersing the semiconductor substrate in the stripping and dissolving composition of the present invention for only 1 minute, which is a short time, the adhesive layer on the semiconductor substrate can be removed cleanly.

[0405] That is to say, if the cleaning method of the semiconductor substrate of the present invention is used, the adhesive layer can be removed (cleaned) from the semiconductor substrate having an adhesive layer on its surface more cleanly and in a shorter time through a simple operation.

[0406] In addition, if the cleaning method of the semiconductor substrate of the present invention is used, as shown in [Example 3-1], no damage to the cutting tape occurs in the adhesive layer removal process.

[0407] [Table 1]

[0408]

[0409] [Table 2]

[0410]

[0411] [Table 3]

[0412]

Claims

1. A cleaning method for a semiconductor substrate, characterized in that, it includes a step of using a stripping and dissolving composition to strip and dissolve the adhesive layer on the semiconductor substrate, the stripping and dissolving composition contains: Component I: a quaternary ammonium salt, Component II: an amide-based solvent, and Component III: a solvent represented by the following formula (L), L 1 —L 3 —L 2 (L) In formula (L), L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.

2. The cleaning method for a semiconductor substrate according to claim 1, wherein, the stripping and dissolving composition further contains Component IV: a solvent represented by the following formula (T) or the following formula (G), 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, In formula (G), L 11 and L 12 each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the alkyl group of L 11 and the total number of carbon atoms of the alkyl group of L 12 is 7 or less.

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

4. The cleaning method for a semiconductor substrate according to claim 1, wherein, the amide-based solvent is an acid 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, and 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, and R 104 represents an alkylene group having 1 to 5 carbon atoms. *1 represents a bonding bond bonded to the carbon atom in formula (Y), and *2 represents a bonding bond bonded to the nitrogen atom in formula (Y).

5. The cleaning method for a semiconductor substrate according to claim 1, wherein, The said L 1 and L 2 are the same group.

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

7. The cleaning method for a semiconductor substrate according to claim 6, wherein, the adhesive component S contains a silicone-based adhesive.

8. The cleaning method for a semiconductor substrate according to claim 7, wherein, the silicone-based adhesive contains a polyorganosiloxane component A' cured by a hydrosilylation reaction.

9. The cleaning method for a semiconductor substrate according to claim 1, wherein, the step of stripping and dissolving includes a step of removing the stripped adhesive layer.

10. A method for manufacturing a processed semiconductor substrate, characterized in that, It includes: The first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; The second step of processing the semiconductor substrate of the obtained laminate; The third step of separating the semiconductor substrate and the adhesive layer from the support substrate; and The fourth step of using the stripping and dissolving composition to strip and dissolve to remove the adhesive layer on the semiconductor substrate, the stripping and dissolving composition contains: Component I: a quaternary ammonium salt, Component II: an amide-based solvent, and Component III: a solvent represented by the following formula (L), L 1 -L 3 -L 2 (L) In formula (L), L 1 and L 2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L 3 represents O or S.

11. The manufacturing method for a processed semiconductor substrate according to claim 10, wherein, the stripping and dissolving composition further contains Component IV: a solvent represented by the following formula (T) or the following formula (G), 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, In formula (G), L 11 and L 12 each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the alkyl group of L 11 and the total number of carbon atoms of the alkyl group of L 12 is 7 or less.

12. The manufacturing method for a processed semiconductor substrate according to claim 10, wherein, the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

13. The manufacturing method for a processed semiconductor substrate according to claim 10, wherein, the amide-based solvent is an acid 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, and 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, and R 104 represents an alkylene group having 1 to 5 carbon atoms. *1 represents a bonding bond bonded to the carbon atom in formula (Y), and *2 represents a bonding bond bonded to the nitrogen atom in formula (Y).

14. The manufacturing method for a processed semiconductor substrate according to claim 10, wherein, The said L 1 and L 2 are the same group.

15. The manufacturing method of the processed semiconductor substrate according to claim 10, wherein, the adhesive layer is a film obtained by using an adhesive composition containing an adhesive component S, and the adhesive component S includes at least one selected from a silicone-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive.

16. The manufacturing method of the processed semiconductor substrate according to claim 15, wherein, the adhesive component S includes a silicone-based adhesive.

17. The manufacturing method of the processed semiconductor substrate according to claim 16, wherein, the silicone-based adhesive includes a polyorganosiloxane component A' cured by a hydrosilylation reaction.

18. The manufacturing method of the processed semiconductor substrate according to claim 10, wherein, the fourth step of peeling and dissolving for removal includes a step of removing the peeled adhesive layer.

19. A composition for stripping and dissolving, characterized in that, For peeling and dissolving to remove the adhesive layer on the semiconductor substrate when cleaning the semiconductor substrate, the peeling and dissolving composition includes: Component I: a quaternary ammonium salt, Component II: an amide-based solvent, and Component III: a solvent represented by the following formula (L), in the peeling and dissolving composition, the content of the Component III in 100% by mass of the aprotic solvent is 30% by mass or more, 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, and L 3 represents O or S.

20. The peeling and dissolving composition according to claim 19, wherein, the peeling and dissolving composition further includes Component IV: a solvent represented by the following formula (T) or the following formula (G), In formula (T), X 1 and X 3 each independently represent 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, In formula (G), L 11 and L 12 each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the alkyl group of L 11 and the alkyl group of L 12 is 7 or less.

21. The peeling and dissolving composition according to claim 19, wherein, the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

22. The peeling and dissolving composition according to claim 19, wherein, the amide-based solvent is an acid 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, and 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, and 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 bonding bond bonded to a carbon atom in formula (Y), and *2 represents a bonding bond bonded to a nitrogen atom in formula (Y).

23. The peeling and dissolving composition according to claim 19, wherein, The L 1 and L 2 are the same group.

24. The peeling and dissolving composition according to claim 19, wherein, the adhesive layer is a film obtained by using an adhesive composition containing an adhesive component S, and the adhesive component S includes at least one selected from a silicone-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive.

25. The peeling and dissolving composition according to claim 24, wherein, the adhesive component S includes a silicone-based adhesive.

26. The peeling and dissolving composition according to claim 25, wherein, the silicone-based adhesive includes a polyorganosiloxane component A' cured by a hydrosilylation reaction.

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