Adhesive composition for light irradiation peeling, laminate, and method for producing processed semiconductor substrate

Abstract

Provided are: a laminate having an adhesive layer which has both an adhesive function and a peeling function in one layer and which can be peeled off by irradiation with light; an adhesive composition which forms an adhesive layer which can be peeled off by irradiation with light; and a method for manufacturing a processed semiconductor substrate using the laminate. The present invention relates to a laminate which can firmly bond a support substrate and a semiconductor substrate during polishing of the semiconductor substrate and can easily separate the support substrate and the semiconductor substrate by light irradiation after polishing. The adhesive composition for light irradiation peeling is used to form the following adhesive layer of a laminate having a semiconductor substrate, a support substrate, and an adhesive layer provided between the semiconductor substrate and the support substrate, the adhesive composition contains an adhesive component (S) and a release agent component (R), the adhesive component (S) containing a polysiloxane resin, the release agent component (R) containing a polysiloxane resin, the release agent component (R) containing a polysiloxane resin, the release agent component (R) containing a polysiloxane resin, the release agent component (R) containing a polysiloxane resin, the release agent component (R) containing a polysiloxane resin, the release agent component (R) containing a polysiloxane resin, and the release agent component (R) containing a polysiloxane resin. The stripping agent component (R) contains a (meth) acrylic polymer, and the (meth) acrylic polymer contains a first unit of an organic silicon system and a second unit of a light-absorbing structure.

Description

Technical Field

[0001] The present invention relates to an adhesive composition for photo-irradiation peeling, a laminate, and a method for producing a processed semiconductor substrate. Background Art

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

[0003] The semiconductor wafer before thinning (also referred to as wafer here) is bonded to a support body in order to be ground using a grinding device. The bonding at this time must be easy to peel off after grinding, so it is called temporary bonding. The temporary bonding must be easy to disassemble from the support body. When a large force is applied to the disassembly, the thinned semiconductor wafer is sometimes cut or deformed. In order to avoid such a situation, it is easy to disassemble. However, when the back of the semiconductor wafer is ground, it is not preferred that it is detached or offset due to the grinding stress. Therefore, the performance pursued by temporary bonding is: to withstand the stress during grinding and to be easy to disassemble after grinding.

[0004] For example, the following properties are sought: high stress (strong adhesive force) with respect to the planar direction during grinding, and low stress (weak adhesive force) with respect to the longitudinal direction during removal.

[0005] For such bonding and separation processes, methods using laser irradiation have been disclosed (see, for example, Patent Documents 1 and 2). However, with further progress in the semiconductor field in recent years, new technologies related to peeling by irradiation with light such as laser have been sought.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2004-64040

[0009] Patent Document 2: Japanese Patent Application Publication No. 2012-106486 Summary of the invention

[0010] Problems to be solved by the invention

[0011] The above-mentioned patent documents 1 and 2 describe a laminated body, wherein two layers, a bonding layer (adhesive layer) and a light conversion layer (also called a separation layer) containing a light absorber, are laminated between the substrate and the support in order to peel off the substrate corresponding to the above-mentioned semiconductor chip and the support by laser irradiation.

[0012] Furthermore, if a layer having both the bonding function of the adhesive layer and the peeling function of peeling the substrate of the separation layer from the support body can be formed in the form of a single layer, the two-layer structure of the adhesive layer and the separation layer can be made into a single layer structure, thereby reducing the number of layers. Therefore, from the perspective of producing a laminated body with a simpler structure, this is ideal.

[0013] Therefore, it is desired to provide a laminate having an adhesive layer which has both an adhesive function and a peeling function using light and can be peeled by light irradiation.

[0014] The present invention has been completed in view of the above situation, and its purpose is to provide a laminate, an adhesive composition for forming the following peelable adhesive layer, and a method for manufacturing a processed semiconductor substrate using the following laminate, wherein the laminate has an adhesive layer in one layer that has both bonding and peeling functions and can be peeled by light irradiation, and the laminate can firmly bond a supporting substrate to the semiconductor substrate when the semiconductor substrate is polished, and after polishing, the supporting substrate and the semiconductor substrate can be easily separated by light irradiation.

[0015] Solutions for solving problems

[0016] The present inventors have conducted intensive studies to solve the above-mentioned technical problems, and as a result, have found that the above-mentioned technical problems can be solved, and have completed the present invention having the following gist.

[0017] That is, the present invention includes the following contents.

[0018] [1] An adhesive composition for photoirradiation peeling, wherein the adhesive layer is used to form the following laminated body, the laminated body comprising: a semiconductor substrate, a supporting substrate, and an adhesive layer provided between the semiconductor substrate and the supporting substrate, and the laminated body is used to peel the semiconductor substrate and the supporting substrate after the adhesive layer absorbs light irradiated from the supporting substrate side, the adhesive composition comprising an adhesive component (S) and a peeling agent component (R), the adhesive component (S) containing a polysiloxane resin, and the peeling agent component (R) containing a (meth)acrylic polymer, the (meth)acrylic polymer containing a first unit of an organosilicon system and a second unit of a structure that absorbs light.

[0019] [2] The adhesive composition according to [1], wherein the first silicone-based unit is represented by any of the following formulas (A-1) and (A-2).

[0020]

[0021] (In formula (A-1) and formula (A-2), Rb represents a hydrogen atom or a methyl group. Rc and Rd each independently represent a hydrogen atom, an alkyl group or a phenyl group. m and p each independently represent an integer greater than or equal to 0.)

[0022] [3] The adhesive composition according to [1], wherein the second unit of the light-absorbing structure has a structure selected from the group consisting of a benzophenone structure, a diphenylamine structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure, an azobenzene structure, a dibenzofuran structure, a fluorenone structure, a carbazole structure, an anthraquinone structure, a 9,9-diphenyl-9H-fluorene structure, a naphthalene structure, an anthracene structure, a phenanthrene structure, an acridine structure, a pyrene structure, a phenylbenzotriazole structure, an acenaphthene structure, and a structure derived from cinnamic acid.

[0023] [4] The adhesive composition according to [3], wherein the second unit having the light absorbing structure has a structure represented by any of the following formulae (1) to (9).

[0024]

[0025]

[0026] (In formulas (1) to (9), R1 to R 13 Each independently represents a halogen atom or a monovalent group.

[0027] X represents a single bond, -O-, -CO-, or -NR 31 -(R 31 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group), -SO-, -SO2- or -N=N-.

[0028] Y1 represents a single bond or -CO-. When Y1 is a single bond, Y2 represents -O-, -CO- or -NR 32 -(R 32 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group). When Y1 is -CO-, Y2 represents -CO-.

[0029] n1 is an integer from 0 to 4.

[0030] n2 is an integer from 0 to 5.

[0031] n3 is an integer from 0 to 3.

[0032] n4 is an integer from 0 to 4.

[0033] n5 is an integer from 0 to 4.

[0034] n6 is an integer from 0 to 5.

[0035] n7 is an integer from 0 to 4.

[0036] n8 is an integer from 0 to 4.

[0037] n9 is an integer from 0 to 7.

[0038] n10 is an integer from 0 to 9.

[0039] n11 is an integer from 0 to 9.

[0040] n12 is an integer from 0 to 4.

[0041] n13 is an integer from 0 to 4.

[0042] * indicates a bonding key.

[0043] In R1~R 13 When there are multiple R1 to R 13 Optionally the same or different. )

[0044] [5] The adhesive composition according to [4], wherein the second unit of the light absorbing structure is represented by any of the following formulas (B-1) to (B-5).

[0045]

[0046] [6] The adhesive composition according to [1], wherein the polysiloxane resin contained in the adhesive component (S) contains a cured component (A).

[0047] [7] The adhesive composition according to [6], wherein the curable component (A) is a component that cures by a hydrosilylation reaction.

[0048] [8] The adhesive composition according to [7], wherein the curing component (A) contains: a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having a Si—H group, and a platinum group metal catalyst (A2).

[0049] [9] The adhesive composition according to [1], wherein the (meth)acrylic polymer contained in the release agent component (R) further comprises a third unit represented by the following formula (C-1) or the following formula (C-2).

[0050]

[0051] (In formula (C-1) and formula (C-2), Rp represents a hydrogen atom or a methyl group. Rq represents a chain saturated hydrocarbon group having 3 or more carbon atoms. Rr represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group having 6 or more carbon atoms. r represents an integer greater than 0.)

[0052]

[10] The adhesive composition according to [9], wherein the third unit is represented by any of the following formulas (C-3) to (C-7).

[0053]

[0054]

[11] A laminate comprising: a semiconductor substrate, a light-transmitting supporting substrate, and an adhesive layer provided between the semiconductor substrate and the supporting substrate, wherein the laminate is used for peeling the semiconductor substrate and the supporting substrate after the adhesive layer absorbs light irradiated from the supporting substrate side, and the adhesive layer is formed by the adhesive composition described in any one of [1] to

[10] .

[0055]

[12] A method for manufacturing a processed semiconductor substrate, comprising: a third step of processing the semiconductor substrate of the stacked body described in

[11] ; and a fourth step of separating the semiconductor substrate processed by the third step from the support substrate.

[0056]

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

[12] , wherein the fourth step includes: irradiating the stacked body with a laser from the support substrate side.

[0057] Effects of the Invention

[0058] According to the present invention, there can be provided a laminate, an adhesive composition for forming a peelable adhesive layer, and a method for manufacturing a processed semiconductor substrate using the laminate, wherein the laminate has an adhesive layer in one layer that has both bonding and peeling functions and can be peeled off by light irradiation, and the laminate can firmly bond a supporting substrate to the semiconductor substrate when the semiconductor substrate is polished, and after polishing, the supporting substrate can be easily separated from the semiconductor substrate by light irradiation. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 This is a schematic cross-sectional view of an example of a laminate. DETAILED DESCRIPTION

[0060] (Adhesive composition for light irradiation peeling)

[0061] The adhesive composition of the present invention is an adhesive composition for peeling by light irradiation that can be peeled by light irradiation.

[0062] The adhesive composition of the present invention is a composition that can be suitably used to form an adhesive layer for temporary bonding in order to process a semiconductor substrate.

[0063] The adhesive composition of the present invention contains an adhesive component (S) and a release agent component (R).

[0064] Furthermore, the adhesive composition of the present invention may contain other components such as a solvent in addition to the adhesive component (S) and the release agent component (R) for the purpose of adjusting the viscosity of the adhesive composition.

[0065] The adhesive composition of the present invention can be obtained by a simple method of simply mixing an adhesive component (S) and a release agent component (R). As shown in the following embodiments, the adhesive composition can well form an adhesive layer for light irradiation release that effectively functions as a temporary adhesive layer and also effectively functions as a laser release agent layer.

[0066] <Adhesive component (S)>

[0067] The adhesive component (S) of the present invention contains a polysiloxane-based resin.

[0068] The polysiloxane-based resin contains, for example, a cured component (A) that becomes an adhesive component.

[0069] Preferred embodiments of the component (A) that cures include components (A) that cure by a hydrosilylation reaction, and more preferably include polyorganosiloxane components (A′) that cure by a hydrosilylation reaction.

[0070] In a more preferred embodiment of the present invention, component (A) contains, as an example of component (A'), a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal catalyst (A2). The alkenyl group having 2 to 40 carbon atoms may be optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0071] In another more preferred embodiment of the present invention, the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises a siloxane unit (Q unit) selected from the group consisting of SiO2, R 1 R 2 R 3SiO 1 / 2 The siloxane unit (M unit), R 4 R 5 SiO 2 / 2 The siloxane units (D units) and R 6 SiO 3 / 2 The polysiloxane (A1) comprises a polyorganosiloxane (a1') and a polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises a siloxane unit (Q' unit) represented by SiO2, a R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane units (M' units), R 4 'R 5 'SiO 2 / 2 The siloxane units (D' units) and R 6 'SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T' units) represented by SiO2, and at least one unit selected from the group consisting of M' units, D' units and T' units, wherein the polyorganosiloxane (a2') comprises a siloxane unit (Q" unit) represented by SiO2, R 1 ”R 2 ”R 3 "SiO 1 / 2 The siloxane units (M" units), R 4 ”R 5 "SiO 2 / 2 The siloxane units (D" units) and R 6 "SiO 3 / 2 The siloxane units (T" units) shown in the figure contain one or more units selected from the group consisting of M" units, D" units and T" units.

[0072] It should be noted that (a1′) is an example of (a1), and (a2′) is an example of (a2).

[0073] R 1 ~R 6 is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0074] R 1 '~R 6' is a group bonded to a silicon atom, each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6 At least one of ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0075] R 1 ”~R 6 " is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, or a hydrogen atom, R 1 ”~R 6 " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, and the like.

[0076] The alkyl group may be any of linear, branched, or cyclic, preferably linear or branched. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0077] Specific examples of the optionally substituted linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl n-butyl, 2-methyl n-butyl, 3-methyl n-butyl, 1,1-dimethyl n-propyl, 1,2-dimethyl n-propyl, 2,2-dimethyl n-propyl, 1-ethyl n-propyl, n-hexyl, 1-methyl n-pentyl, 2-methyl n-pentyl, 3-methyl n-pentyl, 4-methyl n-pentyl, 1,1 The present invention is not limited to 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among them, methyl is particularly preferred.

[0078] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl The cycloalkyl groups include, but are not limited to, cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl; and bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl and dicyclodecyl. The number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0079] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0080] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, vinyl, allyl, butenyl, pentenyl, etc., and the number of carbon atoms thereof is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0081] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms in the cyclic alkenyl group is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0082] As described above, the polysiloxane (A1) includes the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl groups contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a crosslinked structure by a hydrosilylation reaction using a platinum group metal catalyst (A2) and cure. As a result, a cured film is formed.

[0083] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and comprises at least one selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0084] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit).

[0085] In addition, when the polyorganosiloxane (a1') includes two or more polyorganosiloxanes, the combination of (Q' unit and M' unit) and (D' unit and M' unit), the combination of (T' unit and M' unit) and (D' unit and M' unit), and the combination of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, but not limited to these.

[0086] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units and T" units, and contains at least one selected from the group consisting of M" units, D" units and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may be used in combination.

[0087] Preferred combinations of two or more selected from the group consisting of "Q" units, "M" units, "D" units and "T" units include, but are not limited to: (M" units and "D" units), (Q" units and "M" units), (Q" units, "T" units and "M" units).

[0088] The polyorganosiloxane (a1′) is composed of siloxane units formed by bonding silicon atoms to alkyl and / or alkenyl groups. 1 '~R 6 The ratio of alkenyl groups in all substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R 1 '~R 6 ' can be set to an alkyl group.

[0089] The polyorganosiloxane (a2') is composed of siloxane units formed by bonding silicon atoms with alkyl groups and / or hydrogen atoms. 1 ”~R 6The ratio of all substituents and hydrogen atoms in the substituent atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 ”~R 6 " can be set to an alkyl group.

[0090] When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si—H bonds contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0091] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0092] It should be noted that in the present invention, the weight average molecular weight, number average molecular weight and dispersity of polyorganosiloxane (excluding the above-mentioned organosiloxane polymer) can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH Co., Ltd.) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgelSuperMultiporeHZ-H manufactured by TOSOH Co., Ltd.), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) used as a standard sample.

[0093] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and each is usually 10 to 1,000,000 (mPa·s), and preferably 50 to 200,000 (mPa·s) from the viewpoint of achieving the effects of the present invention with good reproducibility. It should be noted that the viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured at 25° C. using an E-type rotational viscometer.

[0094] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other through a hydrosilylation reaction to form a cured film. Therefore, the curing mechanism is different from the mechanism via a silanol group, and therefore, any siloxane does not need to contain a silanol group or a functional group such as an alkoxy group that forms a silanol group through hydrolysis.

[0095] In a preferred embodiment of the present invention, the adhesive component (S) contains the polyorganosiloxane component (A') and also contains a platinum group metal catalyst (A2).

[0096] Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si—H group of the polyorganosiloxane (a2).

[0097] Specific examples of the platinum-based metal catalyst include platinum-based catalysts such as platinum black, platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and bisacetoacetate platinum, but are not limited thereto.

[0098] Examples of the complex of platinum and olefins include a complex of divinyltetramethyldisiloxane and platinum, but the complex is not limited thereto.

[0099] The amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually within a range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0100] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.

[0101] The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0102] The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect thereof and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0103] <Removal agent component (R)>

[0104] The release agent component (R) of the present invention contains a (meth)acrylic polymer. The (meth)acrylic polymer includes a silicone-based first unit and a second unit having a structure that absorbs light.

[0105] The adhesive composition of the present invention, which uses the polysiloxane resin of the above-mentioned adhesive component (S) and the (meth)acrylic polymer containing the first unit and the second unit as the release agent component (R), can well form an adhesive layer for light irradiation release that effectively functions as a temporary adhesive layer and also effectively functions as a laser release agent layer.

[0106] Furthermore, the (meth)acrylic polymer preferably includes a third unit in addition to the first unit and the second unit in order to improve the compatibility between the first unit and the second unit.

[0107] Hereinafter, each unit of the (meth)acrylic polymer will be described in detail.

[0108] In addition, "(meth)acrylic polymer" means a methacrylic polymer and / or an acrylic polymer.

[0109] <<Unit 1>>

[0110] The (meth)acrylic polymer of the present invention includes a silicone-based first unit.

[0111] The first unit is a unit effective for improving the solubility with the adhesive component (S) when the adhesive component (S) and the release agent component (R) are mixed.

[0112] The silicone-based first unit is preferably a unit represented by any of the following formula (A-1) and the following formula (A-2).

[0113]

[0114] In formula (A-1) and formula (A-2), Rb represents a hydrogen atom or a methyl group. Rc and Rd each independently represent a hydrogen atom, an alkyl group or a phenyl group. m and p each independently represent an integer greater than or equal to 0.

[0115] As Rc, a methyl group is preferred.

[0116] Examples of the alkyl group for Rd include alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, and butyl.

[0117] Examples of m include 1 to 10, and preferably 2 to 5.

[0118] In order to obtain the first unit of the silicone system, for example, a monomer represented by the following formula (A-1-1) or the following formula (A-2-1) can be used and polymerized. Examples of the monomer represented by the following formula (A-1-1) or the following formula (A-2-1) include X-22-174ASX, X-22-2426, X-22-2475, KF-2012 manufactured by Shin-Etsu Chemical Co., Ltd., and FM-0711, FM-0721, and FM-0725 manufactured by JNC Corporation.

[0119]

[0120] The symbols in the formula (A-1-1) and the formula (A-2-1) are the same as those in the above-mentioned formula (A-1) and the formula (A-2).

[0121] <<Unit 2>>

[0122] The (meth)acrylic polymer of the present invention includes a second unit having a structure that absorbs light.

[0123] The second unit has a structure that absorbs light and facilitates separation of the semiconductor substrate and the support substrate by absorbing light.

[0124] The structure included in the second unit absorbs light and changes in quality, so that the adhesive layer changes in quality. As a result, when the adhesive layer is irradiated with light, the semiconductor substrate and the support substrate are easily separated.

[0125] From the viewpoint of achieving good peeling properties between the semiconductor substrate and the supporting substrate by utilizing excellent light absorption, the light-absorbing structure preferably has a structure selected from the group consisting of a benzophenone structure, a diphenylamine structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure, an azobenzene structure, a dibenzofuran structure, a fluorenone structure, a carbazole structure, anthraquinone structure, 9,9-diphenyl-9H-fluorene structure, a naphthalene structure, anthracene structure, phenanthrene structure, acridine structure, pyrene structure, phenylbenzotriazole structure, acenaphthene structure, and a structure derived from cinnamic acid.

[0126] The light-absorbing structure may also have a substituent. Examples of the substituent in the light-absorbing structure include an alkyl group, an alkoxy group, an aryl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amide group, a sulfonamide group, an imide group, a carboxyl group, a carboxylate group, a sulfone group, a sulfonate group, an alkylamino group, and an arylamino group.

[0127] From the viewpoint of achieving good releasability between the semiconductor substrate and the support substrate by utilizing excellent light absorption, the light absorbing structure is preferably a structure represented by any of the following formulas (1) to (9).

[0128]

[0129]

[0130] (In formulas (1) to (7), R1 to R 13 Each independently represents a halogen atom or a monovalent group.

[0131] X represents a single bond, -O-, -CO-, or -NR 31 -(R 31 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group), -SO-, -SO2- or -N=N-.

[0132] Y1 represents a single bond or -CO-. When Y1 is a single bond, Y2 represents -O-, -CO- or -NR 32 -(R 32represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group). When Y1 is -CO-, Y2 represents -CO-.

[0133] n1 is an integer from 0 to 4.

[0134] n2 is an integer from 0 to 5.

[0135] n3 is an integer from 0 to 3.

[0136] n4 is an integer from 0 to 4.

[0137] n5 is an integer from 0 to 4.

[0138] n6 is an integer from 0 to 5.

[0139] n7 is an integer from 0 to 4.

[0140] n8 is an integer from 0 to 4.

[0141] n9 is an integer from 0 to 7.

[0142] n10 is an integer from 0 to 9.

[0143] n11 is an integer from 0 to 9.

[0144] n12 is an integer from 0 to 4.

[0145] n13 is an integer from 0 to 4.

[0146] * indicates a bonding key.

[0147] In R1~R 13 When there are multiple R1 to R 13 Optionally the same or different. )

[0148] As R1~R 13 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0149] As R1~R 13 The monovalent group in the group may be, for example, an atomic group consisting of two or more atoms, specifically, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, -N(R 21 )(R 22 )(R 21 and R 22 Each independently represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group) or the like.

[0150] As R1~R 13Specific examples of the optionally substituted alkyl group include optionally substituted alkyl groups having 1 to 20 carbon atoms. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, and an alkoxy group.

[0151] As R1~R 13 Specific examples of the optionally substituted alkoxy group include optionally substituted alkoxy groups having 1 to 20 carbon atoms. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, and an alkyl group.

[0152] As R1~R 13 Specific examples of the optionally substituted aryl group include optionally substituted aryl groups having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, an alkyl group, and an alkoxy group.

[0153] As R 21 , R 22 , R 31 and R 32 Specific examples of the optionally substituted alkyl group include R1 to R 13 Specific examples of optionally substituted alkyl are shown in the specific examples of .

[0154] As R 21 , R 22 , R 31 and R 32 Specific examples of the optionally substituted aryl group in include R1 to R 13 Specific examples of optionally substituted aryl are described in detail below.

[0155] Examples of the alkyl group as a substituent include alkyl groups having 1 to 6 carbon atoms.

[0156] Examples of the alkoxy group as a substituent include alkoxy groups having 1 to 6 carbon atoms.

[0157] It should be noted that the "carbon number 1 to 20" in the "optionally substituted alkyl group having 1 to 20 carbon atoms" means the number of carbon atoms excluding the number of carbon atoms in the substituent. The same applies to the "optionally substituted aryl group having 6 to 20 carbon atoms" and the "optionally substituted alkoxy group having 1 to 20 carbon atoms".

[0158] In order to obtain the second unit having a structure that absorbs light, for example, a monomer having a structure that absorbs light may be used and polymerized. Examples of monomers having a structure that absorbs light include acenaphthylene, 2-vinylnaphthalene, vinyl cinnamate, 4-benzoylphenyl methacrylate, and 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole.

[0159] The second unit having a structure for absorbing light is preferably a unit represented by any of the following formulas (B-1) to (B-5).

[0160]

[0161] <<Unit 3>>

[0162] The (meth)acrylic polymer of the present invention preferably includes a third unit represented by the following formula (C-1) or the following formula (C-2) in addition to the above-mentioned first unit and the above-mentioned second unit.

[0163]

[0164] (In formula (C-1) and formula (C-2), Rp represents a hydrogen atom or a methyl group. Rq represents a chain saturated hydrocarbon group having 3 or more carbon atoms. Rr represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group having 6 or more carbon atoms. r represents an integer greater than 0.)

[0165] In Rr, the aromatic hydrocarbon group and the aliphatic hydrocarbon group may each be a monocyclic ring or a condensed ring, or a linked ring formed by linking any ring selected from these rings. In addition, the aromatic hydrocarbon group and the aliphatic hydrocarbon group may be linked.

[0166] The third unit is effective as a unit for improving the compatibility between the first unit and the second unit.

[0167] The third unit can be obtained by, for example, using a monomer represented by the following formula (C-1-1) or the following formula (C-2-1) and polymerizing the monomer. Examples of the monomer represented by the following formula (C-1-1) or the following formula (C-2-1) include stearyl methacrylate, hexyl acrylate, behenyl acrylate, benzyl methacrylate, and dicyclopentyl methacrylate.

[0168]

[0169] The third unit is preferably a unit represented by any of the following formulas (C-3) to (C-7).

[0170]

[0171] When the release agent component (R) is mixed with the adhesive component (S), for example, if a polymer having only a second unit having a structure that absorbs light is used for mixing, the compatibility with the adhesive component (S) is poor and the mixture becomes turbid. Therefore, in the present invention, a first unit having good solubility with the adhesive component is used, and a polymer having a first unit and a second unit is mixed with the adhesive component (S), thereby improving the solubility of the polymer and the adhesive component (S) and preventing turbidity of the mixture.

[0172] However, the solubility between the first unit and the second unit is not sufficient, and therefore, in order to prevent turbidity of the polymer having the first unit and the second unit itself, in the present invention, it is more preferable to include a third unit in the polymer for improving the compatibility between the first unit and the second unit.

[0173] That is, as a more preferred embodiment of the present invention, a polymer having the first unit, the second unit, and the third unit is mixed with the adhesive component (S). Thus, even if the polymer is mixed with the adhesive component (S), the mixture will not become turbid, and the turbidity of the polymer itself mixed with the adhesive component (S) can be prevented.

[0174] <<Ratio of each unit in (meth)acrylic acid polymer>>

[0175] In the (meth)acrylic polymer having the first unit and the second unit, the ratio of the first unit to the second unit can be appropriately set without particular limitation as long as the effect of the present invention is achieved. For example, the mass ratio of the first unit to the second unit is preferably 5:5 to 8:2.

[0176] In addition, in the (meth)acrylic polymer having the first unit, the second unit and the third unit, the ratio of the first unit, the second unit and the third unit can be appropriately set without particular limitation as long as the effect of the present invention is achieved. For example, the mass ratio of the first unit: the second unit: the third unit is preferably 1 to 8: 1 to 5: 1 to 2, more preferably 5 to 8: 2 to 5: 1 to 2, and particularly preferably 7: 2: 1.

[0177] <<Production of (meth)acrylic acid polymer>>

[0178] The monomers for preparing the first unit and the second unit (including the third unit if the third unit is included) are mixed. The mixture contains a compound having a (meth)acrylate group that undergoes free radical polymerization. Therefore, if a free radical initiator that generates free radicals by heat is mixed into the mixture and heated, a (meth)acrylic polymer including the first unit and the second unit (including the third unit if the third unit is included) can be prepared by free radical polymerization. It should be noted that a solvent may be further mixed into the above mixture for the purpose of adjusting the viscosity, etc.

[0179] As the thermal free radical initiator that generates free radicals by heat, there can be listed: compounds having a ketone peroxide structure, a peroxyketal structure, a hydroperoxide structure, a dialkyl peroxide structure, a diacyl peroxide structure, a peroxyester structure, a peroxydicarbonate structure or an azo structure, etc. It should be noted that if a thermal free radical initiator that generates gas when generating free radicals is used, voids may be generated, so as the thermal free radical initiator, a compound having a ketone peroxide structure, a peroxyketal structure, a hydroperoxide structure, a dialkyl peroxide structure, a diacyl peroxide structure, a peroxyester structure or a peroxydicarbonate structure is preferred.

[0180] Specifically, the following may be mentioned: diisobutyryl peroxide, isopropyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, di(4-tert-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneoheptanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, disuccinic acid peroxide, and di-isobutyl peroxide. acidperoxide), 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxide)hexane, tert-hexyl peroxide-2-ethylhexanoate, di(4-methylbenzoyl peroxide), tert-butyl peroxide-2-ethylhexanoate, dibenzoyl peroxide, 1,1-di(tert-butylperoxide)-2-methylcyclohexane, 1,1-di(tert-hexylperoxide)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxide)cyclohexane, 1,1-di(tert-butylperoxide)cyclohexane, 2,2-di(4,4-di(tert-butylperoxide)cyclohexyl)propane, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tert-butylperoxyisopropylmonocarbonate, Carbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, tert-butyl peroxyacetate, 2,2-di(tert-butyl peroxy)butane, tert-butyl peroxybenzoate, 4,4-di(tert-butyl peroxy)butyl valerate, di(2-tert-butyl peroxyisopropyl)benzene, diisopropylbenzene peroxide, di-tert-hexyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, tert-butyl peroxideisopropylbenzene, di-tert-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(tert-butyl peroxy)-3-hexyne, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, isopropylbenzene hydroperoxide and tert-butyl hydroperoxide, etc.

[0181] More specifically, PEROYL IB, PERCUMYL ND, PEROYL NPP, PEROYL IPP, PEROYL SBP, PEROYL ND, PEROYL TCP, PEROYL OPP, PERHEXYL ND, PERBUTYL ND, PERBUTYLNHP, PERHEXYL PV, PERBUTYL PV, PEROYL 355, PEROYL L, PEROCTA O, PEROYL SA, PERHEXA25O, PERHEXYL O, NYPER PMB, PERBUTYL O, NYPER BMT, NYPER BW, PERHEXA MC, PERHEXATMH, PERHEXA HC, PERHEXA C, PERTETRA A, PERHEXYL I, PERBUTYL MA, PERBUTYL 355, PERBUTYL L, PERBUTYL I, PERBUTYL E.PERHEXYL Z.PERHEXA 25Z, PERBUTYL A, PERHEXA22, PERBUTYL Z, PERHEXA V, PERBUTYL P, PERCUMYL D, PERHEXYL D, PERHEXA 25B, PERBUTYL C, PERBUTYL D, PERMENTA H, PERHEXYNE 25B, PERCUMYL P, PEROCTA H, PERCUMYL H, PERBUTYL H or NOFMER BC (all manufactured by NOF Corporation), etc.

[0182] Among them, from the viewpoint of reactivity and reaction starting temperature, di(4-tert-butylcyclohexyl)peroxydicarbonate (PEROYL TCP / manufactured by NOF Corporation), tert-butyl peroxypivalate (PERBUTYL PV / manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (PEROCTA O / manufactured by NOF Corporation), 1,1-di(tert-hexylperoxy)cyclohexane (PERHEXA HC / manufactured by NOF Corporation), 2,5-dimethyl-2,5-di(benzoylperoxide)hexane (PERHEXA 25Z / manufactured by NOF Corporation), tert-butyl peroxybenzoate (PERBUTYL Z / manufactured by NOF Corporation) and di(2-tert-butylperoxyisopropyl)benzene (PERBUTYL P / manufactured by NOF Corporation) are preferably used.

[0183] Specific examples of the solvent include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.

[0184] 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, and 5-nonanone, but are not limited thereto.

[0185] In addition, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and the like can also be mentioned.

[0186] Such solvents may be used alone or in combination of two or more.

[0187] The adhesive composition of the present invention contains the above-mentioned adhesive component (S) and the above-mentioned release agent component (R).

[0188] The mixing ratio of the adhesive component (S) to the release agent component (R) is not particularly limited as long as the effects of the present invention are achieved, and may be appropriately selected depending on the purpose. For example, the mass ratio is preferably 50:50 to 95:5.

[0189] <Other ingredients>

[0190] The adhesive composition of the present invention may contain a solvent for the purpose of adjusting the viscosity or dissolving the film-constituting components well.

[0191] Specific examples of the solvent are the same as those described in the above section "Preparation of (meth)acrylic polymer".

[0192] (Laminated body)

[0193] The laminated body of the present invention comprises a semiconductor substrate, a supporting substrate, and an adhesive layer for peeling by light irradiation.

[0194] The supporting substrate has light-transmitting properties.

[0195] The adhesive layer for light irradiation peeling is provided between the semiconductor substrate and the supporting substrate.

[0196] The laminate is used to separate the semiconductor substrate and the supporting substrate after the adhesive layer absorbs light irradiated from the supporting substrate side.

[0197] The adhesive layer for removal by light irradiation is a layer formed of the adhesive composition for removal by light irradiation of the present invention described above.

[0198] The laminate of the present invention is used for temporary bonding in order to process a semiconductor substrate, and can be suitably used for processing such as thinning of a semiconductor substrate.

[0199] While the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported by the support substrate via the adhesive layer. On the other hand, after the semiconductor substrate is processed, the adhesive layer is irradiated with light, and then the support substrate is separated from the semiconductor substrate.

[0200] The adhesive layer of the present invention makes it easy to peel off the semiconductor substrate and the supporting substrate after irradiation with light. Moreover, after the semiconductor substrate and the supporting substrate are peeled off, the residue of the adhesive layer remaining on the semiconductor substrate or the supporting substrate can be removed by, for example, a cleaning agent composition for cleaning the semiconductor substrate.

[0201] The wavelength of the light used for stripping is preferably 250 to 600 nm, more preferably 250 to 370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the specific light absorbing compound, such as decomposition.

[0202] The light used for the stripping may be laser light or a non-laser light source such as an ultraviolet lamp.

[0203] <Semiconductor substrate>

[0204] The main material constituting the entire semiconductor substrate is not particularly limited as long as it can be used for such an application, and examples thereof include silicon, silicon carbide, and compound semiconductors.

[0205] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc-shaped semiconductor substrate. It should be noted that the disc-shaped semiconductor substrate does not need to have a completely circular surface shape, and for example, the periphery of the semiconductor substrate may have a straight portion called an orientation flat, or may have a cutout called a notch.

[0206] The thickness of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1000 μm.

[0207] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate, and is, for example, 100 to 1000 mm.

[0208] The semiconductor substrate may have a bump. A bump is a protruding terminal.

[0209] In the laminated body, when the semiconductor substrate has the bump, the semiconductor substrate has the bump on the supporting substrate side.

[0210] In a semiconductor substrate, bumps are usually formed on the surface where a circuit is formed. The circuit may be a single layer or a multilayer. There is no particular limitation on the shape of the circuit.

[0211] In the semiconductor substrate, the surface (back surface) opposite to the surface having the bumps is a surface to be processed.

[0212] The material, size, shape, structure, and density of the bumps included in the semiconductor substrate are not particularly limited.

[0213] Examples of the bump include a ball bump, a printed bump, a stud bump, and a plated bump.

[0214] Generally, the height, radius, and pitch of the bumps are appropriately determined based on the conditions that the bump height is about 1 to 200 μm, the bump radius is 1 to 200 μm, and the bump pitch is 1 to 500 μm.

[0215] Examples of materials for the bumps include low melting point solder, high melting point solder, tin, indium, gold, silver, copper, etc. The bumps may be made of a single component or multiple components. More specifically, SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other alloy platings based on Sn may be included.

[0216] Furthermore, the bump may have a stacked structure including a metal layer composed of at least any one of these components.

[0217] An example of a semiconductor substrate is a silicon wafer having a diameter of 300 mm and a thickness of about 770 μm.

[0218] <Support substrate>

[0219] The supporting substrate is not particularly limited as long as it is a member that is light-transmissive to the light irradiated to the adhesive layer and can support the semiconductor substrate when the semiconductor substrate is processed, and examples thereof include glass supporting substrates.

[0220] The shape of the support substrate is not particularly limited, and an example thereof may be a disk shape.

[0221] The thickness of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 500 to 1000 μm.

[0222] The diameter of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 100 to 1000 mm.

[0223] An example of the supporting substrate is a glass wafer having a diameter of 300 mm and a thickness of about 700 μm.

[0224] <Adhesive layer>

[0225] The adhesive layer is provided between the support substrate and the semiconductor substrate.

[0226] The adhesive layer is in contact with, for example, the semiconductor substrate or the supporting substrate.

[0227] The adhesive layer is formed using the adhesive composition for peeling by light irradiation of the present invention described above.

[0228] The adhesive composition of the present invention can be suitably used to form an adhesive layer of a laminate comprising: a semiconductor substrate, a support substrate, and an adhesive layer provided between the semiconductor substrate and the support substrate. The laminate is used to peel the semiconductor substrate and the support substrate after the adhesive layer absorbs light irradiated from the support substrate side.

[0229] One of the characteristics of the adhesive layer obtained from the adhesive composition of the present invention is that the semiconductor substrate and the supporting substrate can be easily peeled off after light irradiation.

[0230] The thickness of the adhesive layer is not particularly limited and is generally 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more. From the viewpoint of avoiding unevenness caused by a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, further preferably 120 μm or less, and further preferably 70 μm or less.

[0231] The method for forming an adhesive layer from the adhesive composition is described in detail in the description of the <Method for Producing a Laminated Body> described below.

[0232] The laminated body of the present invention can be suitably produced, for example, by the following method for producing a laminated body of the present invention.

[0233] An example of the laminate will be described below using the drawings.

[0234] Figure 1 This is a schematic cross-sectional view of an example of a laminate.

[0235] Figure 1 The laminated body includes a semiconductor substrate 1, an adhesive layer 2, and a support substrate 3 in this order.

[0236] The adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 3. The adhesive layer 2 is in contact with the semiconductor substrate 1 and the support substrate 3.

[0237] <Method for producing laminate>

[0238] The laminate of the present invention can be manufactured, for example, by the following method, which comprises: a first step, applying the adhesive composition on the surface of any one of the above-mentioned semiconductor substrate and the above-mentioned supporting substrate, and heating it if necessary to form an adhesive coating layer; and a second step, laminating the semiconductor substrate and the supporting substrate together via the adhesive coating layer, while performing at least any one of a heating treatment and a decompression treatment, while laminating the semiconductor substrate, the adhesive coating layer and the supporting substrate.

[0239] When the second step is described in more detail, the steps of the following embodiment (i) or the following embodiment (ii) can be cited.

[0240] (i) When the adhesive composition is coated on the surface of a semiconductor substrate, the adhesive coating layer of the semiconductor substrate and the supporting substrate are subjected to at least one of a heating treatment and a pressure reduction treatment while a load in the thickness direction of the semiconductor substrate and the supporting substrate is applied to make them closely attached, and then a post-heating treatment is performed, thereby forming a laminate.

[0241] (ii) When the adhesive composition is coated on the surface of a supporting substrate, the adhesive coating layer of the supporting substrate and the semiconductor substrate are subjected to at least one of a heating treatment and a pressure reduction treatment while a load in the thickness direction of the semiconductor substrate and the supporting substrate is applied to make them closely attached, and then a post-heating treatment is performed, thereby forming a laminate.

[0242] The coating method is not particularly limited, but is usually a spin coating method. It is also possible to form a coating film separately by a spin coating method or the like, and to attach the coating film in a sheet form as the adhesive coating layer.

[0243] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive components contained in the adhesive composition; whether a solvent is contained; the boiling point of the solvent used; the desired thickness of the adhesive layer, etc., and therefore cannot be generally specified, but is usually 80 to 200°C, and the heating time is usually 30 seconds to 10 minutes.

[0244] When the adhesive composition contains a solvent, the adhesive composition after application is usually heated.

[0245] Heating can be performed using a hot plate, an oven, or the like.

[0246] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is generally about 5 to 500 μm, and is appropriately determined so as to finally be within the above-mentioned thickness range of the adhesive layer.

[0247] In the present invention, the semiconductor substrate and the supporting substrate can be combined in a manner of contacting with the adhesive layer, and a load in the thickness direction of the semiconductor substrate and the supporting substrate is applied to make the two layers close to each other while performing a heating treatment or a decompression treatment or both, and then a post-heating treatment is performed, thereby obtaining the laminate of the present invention. It should be noted that the treatment conditions of any of the heating treatment, the decompression treatment, and the combination of the two are appropriately determined based on various situations such as the type of the adhesive composition, the specific composition of the stripper composition, the phase of the film obtained from the two compositions, the film thickness, and the bonding strength to be obtained.

[0248] The heating treatment is usually appropriately determined within the range of 20 to 150° C. from the viewpoint of removing the solvent when the composition contains a solvent, softening the adhesive coating layer and achieving appropriate bonding with the release agent coating layer, etc. In particular, from the viewpoint of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component (S), it is preferably 130° C. or less, more preferably 90° C. or less, and the heating time is appropriately determined depending on the heating temperature and the type of adhesive, and is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably achieving appropriate bonding, and is usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing deterioration of the adhesive layer and other members.

[0249] The reduced pressure treatment may be carried out by exposing the adhesive coating layer to a gas pressure of 10 to 10000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

[0250] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the two layers therebetween and allows them to be firmly adhered to each other, but is usually in the range of 10 to 1000N.

[0251] From the viewpoint of achieving a sufficient curing speed, the post-heating temperature is preferably 120° C. or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260° C. or lower.

[0252] From the perspective of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually more than 1 minute, preferably more than 5 minutes. From the perspective of suppressing or avoiding the adverse effects of excessive heating on the layers, the post-heating time is usually less than 180 minutes, preferably less than 120 minutes.

[0253] Heating can be performed using a hot plate, an oven, etc. When post-heating is performed using a hot plate, the semiconductor substrate and the support substrate of the stack can be heated with either side facing downward. From the perspective of achieving appropriate peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.

[0254] It should be noted that one of the purposes of the post-heat treatment is to realize a more appropriate adhesive layer as a self-supporting film, and in particular, to appropriately realize curing by a hydrosilylation reaction.

[0255] (Method for manufacturing processed semiconductor substrate)

[0256] The method for manufacturing a processed semiconductor substrate of the present invention includes a third step and a fourth step.

[0257] The third step is a step of processing the semiconductor substrate of the laminated body of the present invention.

[0258] The fourth step is a step of separating the semiconductor substrate processed in the third step from the support substrate.

[0259] In the third step, the processing performed on the semiconductor substrate refers to, for example, the processing on the opposite side of the circuit surface of the wafer, and the thinning of the wafer by grinding the back side of the wafer can be cited. Then, through silicon vias (TSV) and the like are formed, and then the thinned wafer is peeled off from the supporting substrate to form a stack of wafers for three-dimensional mounting. In addition, the formation of the back electrode of the wafer and the like is also performed before and after the three-dimensional mounting. In the thinning and TSV processes of the wafer, heat of about 250 to 350°C is applied in a state bonded to the supporting substrate. The stack of the present invention generally includes an adhesive layer having heat resistance to the load.

[0260] It should be noted that the processing is not limited to the above processing, and includes, for example, a semiconductor component mounting process when temporary bonding with a support substrate is performed in order to support a base material for mounting a semiconductor component.

[0261] In the fourth step, the method of separating (peeling) the semiconductor substrate from the support substrate includes, but is not limited to, mechanical peeling using a tool having a sharp portion after irradiating the adhesive layer with light, peeling by tearing between the support and the wafer, and the like.

[0262] By irradiating the adhesive layer with light from the support substrate side, the adhesive layer is altered (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the semiconductor substrate from the support substrate.

[0263] The irradiation of the adhesive layer with light does not necessarily need to be performed on the entire area of ​​the adhesive layer. Even if the areas irradiated with light and the areas not irradiated with light are mixed, as long as the peeling ability of the adhesive layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the supporting substrate by a slight external force such as pulling up the supporting substrate. The ratio and positional relationship of the areas irradiated with light and the areas not irradiated with light vary depending on the type of adhesive used, its specific composition; the thickness of the adhesive layer; the intensity of the irradiated light, etc., but if a person skilled in the art is skilled in the art, appropriate conditions can be set without excessive experiments. Due to such a situation, according to the method for manufacturing a processed semiconductor substrate of the present invention, for example, when the supporting substrate of the stacked body used is light-transmissive, the light irradiation time can be shortened when peeling is performed by irradiating light from the supporting substrate side. As a result, not only can an improvement in throughput be expected, but also physical stress used for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the supporting substrate only by irradiation with light.

[0264] Generally, the irradiation dose of light used for peeling is 50 to 3000 mJ / cm 2 The irradiation time is appropriately determined according to the wavelength and the irradiation amount.

[0265] The wavelength of the light used for stripping is preferably 250 to 600 nm, and more preferably 250 to 370 nm, as described above. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for stripping is an irradiation amount that causes appropriate deterioration of the specific light absorbing compound, such as decomposition.

[0266] The light used for the stripping may be laser light or a non-laser light source such as an ultraviolet lamp.

[0267] The cleaning composition may be sprayed on the surface of at least any one of the separated semiconductor substrate and the supporting substrate, or the separated semiconductor substrate or the supporting substrate may be immersed in the cleaning composition to clean the substrate.

[0268] Alternatively, the surface of a processed semiconductor substrate or the like may be cleaned using a removal tape or the like.

[0269] The constituent elements and method elements related to the above-mentioned steps of the method for manufacturing a processed semiconductor substrate of the present invention may be variously modified without departing from the gist of the present invention.

[0270] The method for producing a processed semiconductor substrate of the present invention may include steps other than the above-mentioned steps.

[0271] In the peeling step of the present invention, when the semiconductor substrate or the supporting substrate of the laminate of the present invention is light-transmissive, the semiconductor substrate and the supporting substrate of the laminate are separated by irradiating the adhesive layer with light from the semiconductor substrate side or the supporting substrate side.

[0272] In the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded appropriately and releasably by the adhesive layer, so that, for example, when the support substrate is light-transmissive, the semiconductor substrate and the support substrate can be easily separated by irradiating the adhesive layer with light from the support substrate side of the laminate. Usually, the peeling is performed after the semiconductor substrate of the laminate is processed.

[0273] Example

[0274] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The apparatus used is as follows.

[0275] [Device]

[0276] (1) Mixer: ARE-500, a rotary and revolving mixer manufactured by THINKY Co., Ltd.

[0277] (2) Viscometer: TVE-22H rotary viscometer manufactured by Toki Sangyo Co., Ltd.

[0278] (3) Vacuum bonding device: manual bonding machine manufactured by SUSS MicroTec Co., Ltd.

[0279] (4) Laser irradiation device: NC-LD300-EXC manufactured by OPTEK Corporation.

[0280] [1] Preparation of adhesive composition

[0281] [Preparation Example 1] Preparation of Adhesive Component

[0282] In a 600 mL stirring container for a stirrer, 80 g of an MQ resin containing polysiloxane and a vinyl group (manufactured by Wacker Chemie) as the polyorganosiloxane (a1), 2.52 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa·s as the polyorganosiloxane (a2), 5.89 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 70 mPa·s as the polyorganosiloxane (a2), and 0.22 g of 1-ethynylcyclohexanol (manufactured by Wacker Chemie) as a polymerization inhibitor (A3) were added, and the mixture was stirred for 5 minutes using a stirrer.

[0283] To the obtained mixture, 3.96 g of a mixture obtained by stirring for 5 minutes with a stirrer was added 0.147 g of a platinum catalyst (manufactured by Wacker Chemie) as a platinum group metal catalyst (A2) and 5.81 g of a vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 1000 mPa·s as a polyorganosiloxane (a1), and the mixture was stirred for 5 minutes with a stirrer.

[0284] Finally, the obtained mixture was filtered through a 300-mesh nylon filter to obtain an adhesive component 1. The viscosity of the adhesive measured with a viscometer was 10,000 mPa·s.

[0285] [Preparation Example 2] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0286] 25.7 g of KF-2012 (produced by Shin-Etsu Chemical Co., Ltd.), 12.4 g of acenaphthylene (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of hexyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL glass bottle and stirred to prepare Solution-1. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and the mixture was heated in an oil bath at 100°C while being stirred with a stirrer, and Solution-1 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the same state, and the recovered polymer solution was used as the stripping agent component 1.

[0287] [Preparation Example 3] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0288] In a 100 mL glass bottle, 30.0 g of KF-2012 (produced by Shin-Etsu Chemical Co., Ltd.), 8.5 g of 2-vinylnaphthalene (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of hexyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added and stirred to prepare Solution-2. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and the mixture was heated in an oil bath at 100°C while being stirred with a stirrer, and Solution-2 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the same state, and the recovered polymer solution was used as the stripping agent component 2.

[0289] [Preparation Example 4] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0290] 25.7 g of KF-2012 (produced by Shin-Etsu Chemical Co., Ltd.), 12.4 g of 2-vinylnaphthalene (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of hexyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL glass bottle and stirred to prepare Solution-3. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and the mixture was heated in an oil bath at 100°C while being stirred with a stirrer, and Solution-3 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the same state, and the recovered polymer solution was used as the stripping agent component 3.

[0291] [Preparation Example 5] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0292] 21.2 g of KF-2012 (produced by Shin-Etsu Chemical Co., Ltd.), 10.6 g of acenaphthylene (produced by Tokyo Chemical Industry Co., Ltd.), 10.6 g of stearyl methacrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL glass bottle and stirred to prepare Solution-4. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and the mixture was heated in an oil bath at 100°C while being stirred with a stirrer, and Solution-4 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the same state, and the recovered polymer solution was used as the stripping agent component 4.

[0293] [Preparation Example 6] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0294] In a 100 mL glass bottle, 21.2 g of KF-2012 (produced by Shin-Etsu Chemical Co., Ltd.), 17.1 g of vinyl cinnamate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of hexyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added and stirred to prepare Solution-5. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and the mixture was heated in an oil bath at 100°C while being stirred with a stirrer, and Solution-5 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the same state, and the recovered polymer solution was used as the stripping agent component 5.

[0295] [Preparation Example 7] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0296] 21.2 g of X-22-167C (produced by Shin-Etsu Chemical Co., Ltd.), 21.2 g of 2-vinylnaphthalene (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL glass bottle and stirred to prepare Solution-6. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and heated in a 100°C oil bath while stirring with a stirrer, and Solution-6 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining this state, and the recovered polymer solution was used as the stripping agent component 6.

[0297] [Preparation Example 8] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0298] 21.2 g of X-22-167C (produced by Shin-Etsu Chemical Co., Ltd.), 21.2 g of acenaphthylene (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL glass bottle and stirred to prepare Solution-7. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and heated in an oil bath at 100°C while stirring with a stirrer, and Solution-7 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the state, and the recovered polymer solution was used as the stripping agent component 7.

[0299] [Preparation Example 9] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0300] In a 100 mL glass bottle, 21.2 g of KF-2012 (produced by Shin-Etsu Chemical Co., Ltd.), 17.1 g of 4-benzoylphenyl methacrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of hexyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added and stirred to prepare Solution-8. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and the mixture was heated in an oil bath at 100°C while being stirred with a stirrer, and Solution-8 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the same state, and the recovered polymer solution was used as the stripping agent component 8.

[0301] [Preparation Example 10] Preparation of Release Agent Component - Polymerization of (Meth) Acrylic Acid Polymer

[0302] In a 100 mL glass bottle, 21.2 g of KF-2012 (produced by Shin-Etsu Chemical Co., Ltd.), 17.1 g of 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of hexyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), 4.2 g of PERBUTYL P (produced by NOF Corporation), and 43.2 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) were added and stirred to prepare Solution-9. Separately, 57.5 g of mesitylene (produced by Tokyo Chemical Industry Co., Ltd.) was added to a 300 mL eggplant-shaped flask, and the mixture was heated in an oil bath at 100°C while being stirred with a stirrer, and Solution-9 was added dropwise. After the addition was completed, the solution was heated and stirred for 24 hours while maintaining the same state, and the recovered polymer solution was used as the stripping agent component 9.

[0303] [Example 1] Preparation of adhesive composition

[0304] 50.0 g of the adhesive component 1 obtained in Preparation Example 1 was used, 50.0 g of the release agent component 1 obtained in Preparation Example 2 and 0.5 g of 1,1-diphenyl-2-propyn-1-ol (produced by Tokyo Chemical Industry) were added to the adhesive component 1, and stirred for 5 minutes with a stirrer to obtain an adhesive composition (A).

[0305] Next, the same operation was performed by changing the release agent component 1 to the release agent components 2 to 9 to obtain adhesive compositions (B) to (I). In addition, for each adhesive composition, whether or not suspension occurred was visually confirmed.

[0306] [Example 2] Preparation of laminate

[0307] The adhesive composition (A) to (I) was applied to a 100 mm silicon wafer (thickness: 500 μm) as a wafer on the device side using a spin coater, and heated on a 90°C hot plate for 90 seconds to form an adhesive composition layer (A) to (I) of 30 μm. A 100 mm glass wafer (EAGLE-XG, manufactured by Corning, thickness 500 μm) was prepared as a wafer (support) on the carrier side, and the adhesive composition layers (A) to (I) were sandwiched and laminated in a vacuum laminating device to produce a laminate. Then, the device side wafer was heated at 200°C for 10 minutes on a hot plate with the device side wafer facing downward to cure each adhesive composition layer, thereby obtaining a laminate (A) to (I).

[0308] [Comparative Example 1] Preparation of a laminate (without mixing of a release agent component)

[0309] The adhesive composition 1 was applied to a 100 mm silicon wafer (thickness: 500 μm) as a wafer on the device side by a spin coater, and heated on a 90° C. hot plate for 90 seconds to form an adhesive composition layer 1 of 30 μm. A 100 mm glass wafer (EAGLE-XG, manufactured by Corning, thickness 500 μm) was prepared as a wafer (support) on the carrier side, and the adhesive composition layer 1 was sandwiched in a vacuum laminating device to produce a laminate. Then, the device side wafer was heated on a hot plate at 200° C. for 10 minutes to cure the adhesive composition layer, thereby obtaining a laminate (1).

[0310] [Example 3] Laser irradiation test

[0311] A laser irradiation device was used to irradiate the glass wafer at an output of 300 mJ / cm 2 The obtained laminate was irradiated with laser light to check whether the glass wafer could be peeled off. After laser irradiation, the glass wafer was lifted up with tweezers, and the case where it could be easily peeled off was marked as "○", and the case where it could not be peeled off was marked as "×".

[0312] The results of each laminate are shown in Table 1 below.

[0313] [Table 1]

[0314]

[0315] The laminates A to I to which the release agent component was added were able to be peeled after laser irradiation. On the other hand, the laminate 1 to which no release agent component was added was not able to be peeled.

[0316] Furthermore, it was found that when the release agent component contained the third unit, turbidity of the release agent component could be effectively prevented.

[0317] Description of Reference Numerals

[0318] 1: semiconductor substrate; 2: adhesive layer; 3: supporting substrate.

Claims

1. An adhesive composition for light irradiation peeling, wherein: The adhesive layer is used to form a laminated body comprising a semiconductor substrate, a support substrate, and an adhesive layer provided between the semiconductor substrate and the support substrate, and the laminated body is used to peel the semiconductor substrate and the support substrate after the adhesive layer absorbs light irradiated from the support substrate side, The adhesive composition comprises an adhesive component S and a release agent component R, The adhesive component S contains a polysiloxane resin. The release agent component R contains a (meth)acrylic polymer including a first unit of an organosilicon system and a second unit having a structure that absorbs light.

2. The adhesive composition according to claim 1, wherein The first silicone-based unit is represented by any of the following formulas (A-1) and (A-2), In formula (A-1) and formula (A-2), Rb represents a hydrogen atom or a methyl group; Rc and Rd each independently represent a hydrogen atom, an alkyl group or a phenyl group; and m and p each independently represent an integer greater than 0.

3. The adhesive composition according to claim 1, wherein The second unit of the light-absorbing structure has a structure selected from the group consisting of a benzophenone structure, a diphenylamine structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure, an azobenzene structure, a dibenzofuran structure, a fluorenone structure, a carbazole structure, an anthraquinone structure, a 9,9-diphenyl-9H-fluorene structure, a naphthalene structure, anthracene structure, a phenanthrene structure, an acridine structure, a pyrene structure, a phenylbenzotriazole structure, an acenaphthene structure, and a structure derived from cinnamic acid.

4. The adhesive composition according to claim 3, wherein The second unit of the light absorbing structure has a structure represented by any of the following formulas (1) to (9), In formulas (1) to (9), R1 to R 13 each independently represents a halogen atom or a monovalent group; X represents a single bond, -O-, -CO-, or -NR 31 -, -SO-, -SO2- or -N=N-, the -NR 31 - Middle, R 31 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group; Y1 represents a single bond or -CO-; when Y1 is a single bond, Y2 represents -O-, -CO- or -NR 32 -, said -NR 32 - Middle, R 32 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group; when Y1 is -CO-, Y2 represents -CO-, n1 is an integer from 0 to 4; n2 is an integer from 0 to 5; n3 is an integer from 0 to 3; n4 is an integer from 0 to 4; n5 is an integer from 0 to 4; n6 is an integer from 0 to 5; n7 is an integer from 0 to 4; n8 is an integer from 0 to 4; n9 is an integer from 0 to 7; n10 is an integer from 0 to 9; n11 is an integer from 0 to 9; n12 is an integer from 0 to 4; n13 is an integer from 0 to 4, * indicates a bonding key, In R1~R 13 When there are multiple R1 to R 13 Optionally the same or different.

5. The adhesive composition according to claim 4, wherein The second unit of the light absorbing structure is represented by any of the following formulas (B-1) to (B-5), 6. The adhesive composition according to claim 1, wherein The polysiloxane-based resin contained in the adhesive component S contains the component A which is cured.

7. The adhesive composition according to claim 6, wherein The cured component A is a component that is cured by a hydrosilylation reaction.

8. The adhesive composition according to claim 7, wherein The solidified component A contains: polyorganosiloxane a1 having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, polyorganosiloxane a2 having a Si—H group, and Platinum group metal catalyst A2.

9. The adhesive composition according to claim 1, wherein The (meth)acrylic polymer contained in the release agent component R further includes a third unit represented by the following formula (C-1) or the following formula (C-2), In formula (C-1) and formula (C-2), Rp represents a hydrogen atom or a methyl group; Rq represents a chain saturated hydrocarbon group having 3 or more carbon atoms; Rr represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group having 6 or more carbon atoms; and r represents an integer greater than 0.

10. The adhesive composition according to claim 9, wherein The third unit is represented by any of the following formulas (C-3) to (C-7), 11. A laminated body, wherein: The invention comprises: a semiconductor substrate, a light-transmitting support substrate, and an adhesive layer provided between the semiconductor substrate and the support substrate. The laminate is used for: after the adhesive layer absorbs light irradiated from the support substrate side, the semiconductor substrate and the support substrate are peeled off. The adhesive layer is formed from the adhesive composition according to any one of claims 1 to 10.

12. A method for manufacturing a processed semiconductor substrate, wherein: include: A third step is to process the semiconductor substrate of the stacked body according to claim 11; as well as The fourth step is to separate the semiconductor substrate processed in the third step from the support substrate.

13. The method for manufacturing a processed semiconductor substrate according to claim 12, wherein: The fourth step includes the step of irradiating the stacked body with laser light from the support substrate side.

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