Adhesive composition for light-irradiation peeling, laminate, method for manufacturing the laminate, and method for manufacturing a processed semiconductor substrate

Abstract

To provide an adhesive composition for light-irradiation peeling that can be produced by a simple process.SOLUTION: An adhesive composition for light-irradiation peeling includes an adhesive component (S) and an azo dye (X) and can be peeled by light irradiation. Specifically, the azo dye (X) is a compound represented by the following formula (A-I) or the following formula (A-II).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition for light irradiation peeling, a laminate, a method for manufacturing a laminate, and a method for manufacturing a processed semiconductor substrate. [Background technology]

[0002] Conventionally, semiconductor wafers have been integrated in a two-dimensional planar direction. To achieve even greater integration, there is a need for semiconductor integration technology that integrates (stacks) in a three-dimensional direction as well. This three-dimensional stacking is a technology that integrates multiple layers while connecting them with through silicon vias (TSVs). When integrating multiple layers, the side opposite to the circuit surface (i.e., the back surface) of each wafer to be integrated is thinned by polishing, and the thinned semiconductor wafers are stacked.

[0003] Before thinning, the semiconductor wafer (also simply called a wafer here) is bonded to a support in order to be polished using a polishing device. This bonding is called temporary bonding because it must be easily removed after polishing. This temporary bonding must be easily removed from the support, as applying too much force during removal can cause the thinned semiconductor wafer to cut or deform. To prevent this, it must be easily removed. However, it is undesirable for the temporary bonding to detach or shift due to polishing stress during back-side polishing of the semiconductor wafer. Therefore, the performance required of temporary bonding is to withstand the stress during polishing and to be easily removed after polishing.

[0004] For example, the required properties include high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the longitudinal direction during removal. While laser irradiation methods have been disclosed for such bonding and separation processes (see, for example, Patent Documents 1 and 2), with the recent advancements in the semiconductor field, there is a constant demand for new technologies related to delamination using light irradiation, such as lasers.

[0005] Furthermore, a temporary adhesive layer for temporary (provisional) bonding that also functions as a laser release layer, and a laser-release adhesive composition for forming the temporary adhesive layer are disclosed (see, for example, Patent Document 3). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2004-64040 [Patent Document 2] Japanese Patent Publication No. 2012-106486 [Patent Document 3] Special Publication No. 2021-508168 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, the laser-release adhesive composition described in Patent Document 3 is formed from a polyhydroxy ether containing a copolymer of diglycidyl ether and a dihydroxy dye. The laser-release adhesive composition described in Patent Document 3 is limited to a specific type of polymer contained in the composition, and in Patent Document 3, since it is necessary to form a copolymer with the dye, it is necessary to perform operations to cause crosslinking, such as adding a catalyst, and it is also necessary to control the conditions for copolymerization. From the viewpoint of obtaining an adhesive composition for forming an adhesive layer for light irradiation peeling that functions as both a temporary bonding layer and a laser peeling layer, by a simpler method, the adhesive composition described in Patent Document 3 above is not sufficient and there is room for improvement.

[0008] The present invention aims to provide an adhesive composition for light-irradiation peeling that can be obtained by a simple method. Furthermore, the present invention aims to provide a laminate having an adhesive layer formed with the light-irradiation peelable adhesive composition, wherein the semiconductor substrate and support substrate in the laminate can be easily peeled off by light irradiation. Furthermore, the present invention aims to provide a method for manufacturing the laminate and a method for manufacturing a processed semiconductor substrate using the laminate.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved and have completed the present invention having the following gist.

[0010] That is, the present invention includes the following. [1] An adhesive composition for photoirradiation peeling that can be peeled by photoirradiation, containing an adhesive component (S) and an azo dye (X). [2] The adhesive composition according to [1], wherein the azo dye (X) is a compound represented by any one of the following formula (A-I) and the following formula (A-II). [Chemical formula] (In formula (A-I), Ar 1 and Ar 2 each independently represents a benzene ring or a naphthalene ring which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a halogen atom, a cyano group, or a vinyl group, and R a represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents an integer of 1 to 5 when Ar 2 is a substituted or unsubstituted benzene ring, and represents an integer of 1 to 7 when Ar 2 is a substituted or unsubstituted naphthalene ring. R a and Ar 2 may be bonded to each other to form a ring structure, and when p is an integer of 2 to 7, a plurality of R a may be different from each other.) [Chemical formula] (In formula (A-II), Ar 3 ~Ar 5Each independently represents a benzene ring or naphthalene ring which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, a cyano group, or a vinyl group, R b represents a hydroxyl group, amino group, alkylamino group, or dialkylamino group, and q is Ar 5 If it is a substituted or unsubstituted benzene ring, it represents an integer from 1 to 5, and Ar 5 If it is a substituted or unsubstituted naphthalene ring, it represents an integer from 1 to 7. b and Ar 5 These may be linked together to form a ring structure, and if q is an integer from 2 to 7, multiple R b R can be mutually different, or multiple different elements can be present. b is Ar 5 They may also bond to each other to form a ring structure. [3] The adhesive composition according to [1] or [2], wherein the adhesive component (S) is a siloxane resin or a styrene resin. [4] The adhesive composition according to [3], wherein the siloxane resin contains a component that hardens by a hydrosilylation reaction. [5] The adhesive composition according to [4], wherein the component that hardens by the hydrosilylation reaction contains a polyorganosiloxane component that hardens by the hydrosilylation reaction. [6] Polyorganosiloxane components that harden by hydrosilylation reaction, A polyorganosiloxane (a1) having alkenyl groups with 2 to 40 carbon atoms bonded to a silicon atom, A polyorganosiloxane (a2) having a Si-H group, Platinum group metal catalyst (A2), The adhesive composition according to [5], containing the following. [7] The adhesive composition according to [3], wherein the styrene resin is a polystyrene elastomer. [8] R in formula (AI) and formula (A-II) a and R bThe adhesive composition according to any one of [2] to [7], wherein the adhesive is selected from an amino group, an alkylamino group, and a dialkylamino group. [9] The adhesive composition according to [8], wherein the azo dye (X) is a compound represented by the following formula (XI). [ka]

[10] The adhesive composition according to any one of [1] to [8], wherein the mixing ratio of the adhesive component (S) to the azo dye (X) is 85:15 to 99.9:0.1 by mass (adhesive component (S): azo dye (X)).

[11] Semiconductor substrate and A light-transmitting support substrate, The semiconductor substrate and the support substrate are provided with an adhesive layer, A laminate used in which the semiconductor substrate and the support substrate are separated after the adhesive layer absorbs light irradiated from the support substrate side, A laminate in which the adhesive layer is formed from any of the adhesive compositions described in [1] to

[10] .

[12] A first step of applying an adhesive composition according to any of [1] to

[10] to the surface of either the semiconductor substrate or the support substrate to form an adhesive coating layer, A second step involves joining the semiconductor substrate and the support substrate via the adhesive coating layer, and bonding the semiconductor substrate, the adhesive coating layer, and the support substrate while performing at least one of a heat treatment and a vacuum treatment. A method for manufacturing a laminate containing a laminate.

[13] A method for manufacturing a processed semiconductor substrate, A third step in which the semiconductor substrate of the laminate described in

[11] is processed, A fourth step involves separating the semiconductor substrate and the support substrate processed in the third step, A method for manufacturing a processed semiconductor substrate, including the method described above.

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

[13] , wherein the fourth step is to irradiate the laminate described in

[11] with a laser from the support substrate side.

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

[14] , wherein the wavelength of the laser is 250 nm to 600 nm. [Effects of the Invention]

[0011] According to the present invention, an adhesive composition for light-irradiation peeling can be obtained by a simple method. Furthermore, according to the present invention, it is possible to provide a laminate having an adhesive layer formed with the light-irradiation peeling adhesive composition, wherein the semiconductor substrate and the support substrate in the laminate can be easily peeled off by light irradiation. Furthermore, the present invention can provide a method for manufacturing the laminate and a method for manufacturing a processed semiconductor substrate using the laminate. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic cross-sectional view of an example of a laminate. [Modes for carrying out the invention]

[0013] (Adhesive composition for light-induced peeling) The adhesive composition of the present invention is a light-irradiation peelable adhesive composition that can be peeled off by light irradiation. 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 semiconductor substrates. The adhesive composition of the present invention comprises an adhesive component (S) and an azo dye (X). Furthermore, in addition to the adhesive component (S) and the azo dye (X), the adhesive composition of the present invention may also contain other components, such as a solvent, to adjust the viscosity of the adhesive composition. The adhesive composition of the present invention can be obtained by a simple method of mixing an adhesive component (S) and an azo dye (X), and as shown in the following examples, the adhesive composition can form a good adhesive layer for light irradiation peeling that functions effectively as both a temporary adhesive layer and a laser peeling layer.

[0014] <Azo dye (X)> The type of azo dye (X) according to the present invention is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected according to the purpose. However, for example, it is preferable that it is a compound represented by either the following formula (AI) or the following formula (A-II).

[0015] [ka]

[0016] In formula (AI), Ar 1 and Ar 2 Each independently represents a benzene ring or naphthalene ring which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, a cyano group, or a vinyl group, R a represents a hydroxyl group, amino group, alkylamino group, or dialkylamino group, and p represents Ar 2 If it is a substituted or unsubstituted benzene ring, it represents an integer from 1 to 5, and Ar 2 If it is a substituted or unsubstituted naphthalene ring, it represents an integer from 1 to 7. a and Ar 2 These may be linked together to form a ring structure, and if p is an integer from 2 to 7, multiple R a They may be different from one another.

[0017] [ka]

[0018] In formula (A-II), Ar 3 ~Ar5 Each independently represents a benzene ring or naphthalene ring which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, a cyano group, or a vinyl group, R b represents a hydroxyl group, amino group, alkylamino group, or dialkylamino group, and q is Ar 5 If it is a substituted or unsubstituted benzene ring, it represents an integer from 1 to 5, and Ar 5 If it is a substituted or unsubstituted naphthalene ring, it represents an integer from 1 to 7. b and Ar 5 These may be linked together to form a ring structure, and if q is an integer from 2 to 7, multiple R b R can be mutually different, or multiple different elements can be present. b is Ar 5 They may also bond to each other to form a ring structure.

[0019] Examples of compounds represented by the above formula (AI) include the following compounds No. 1 to No. 4.

[0020] [ka]

[0021] Furthermore, examples of compounds represented by the above formula (A-II) include compounds No. 5 to No. 7 listed below.

[0022] [ka]

[0023] Of the compounds represented by the above formulas (AI) and (A-II), R can be well dispersed in the adhesive component (S) regardless of the type of adhesive component (S), and as a result, a good adhesive layer can be formed, and a laminate with excellent adhesion and release properties can be obtained. a and R b However, it is preferable that it has an amino group. More specifically, Ra and R b However, it is preferable that the compound is selected from an amino group, an alkylamino group, and a dialkylamino group.

[0024] In particular, among the compounds represented by the above formula (AI) and the above formula (A-II), the compound represented by formula (A-II) is preferred in terms of exhibiting excellent peelability, and more specifically, the compound represented by the following formula (XI) (corresponding to the compound No. 5 above) is preferred.

[0025] [ka]

[0026] <Adhesive component (S)> The adhesive component (S) according to the present invention is not particularly limited as long as it does not impair the effects of the present invention. Various compounds used as adhesive components in this type of composition are applicable, as long as they have adhesive properties. Examples include siloxane resins, styrene resins, acrylic resins, epoxy resins, amide resins, imide resins, phenolic resins, etc., or combinations thereof. The adhesive component (S) may be a thermosetting adhesive component or a thermoplastic adhesive component. In particular, considering dispersibility and compatibility with azo dye (X), siloxane-based resins or styrene-based resins are preferred. The following describes siloxane-based resins and styrene-based resins.

[0027] <<Siloxane-based resin>> In one preferred embodiment of the present invention, when the adhesive component (S) is a siloxane-based resin, it is preferable that the siloxane-based resin contains a component (A) that hardens by a hydrosilylation reaction. Furthermore, it is preferable that the component (A) that hardens by the hydrosilylation reaction contains a polyorganosiloxane component (A') that hardens by the hydrosilylation reaction.

[0028] In a more preferred embodiment of the present invention, component (A) includes, for example, a polyorganosiloxane (a1) having a C2-C40 alkenyl group bonded to a silicon atom, a polyorganosiloxane (a2) having a Si-H group, and a platinum group metal catalyst (A2), as an example of component (A'). Here, the C2-C40 alkenyl group may be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0029] In another more preferred embodiment of the present invention, the polyorganosiloxane component (A') that hardens by a hydrosilylation reaction is a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 Siloxane units (M units) are expressed as R 4 R 5 SiO 2 / 2 Siloxane units (D units) and R are represented by these units. 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units selected from the group consisting of siloxane units (T units) represented by SiO2, and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) comprises siloxane units (Q' units) represented by SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 Siloxane units (M' units) are represented as R 4 'R 5 'SiO 2 / 2 Siloxane units (D' units) and R are represented by these units. 6 'SiO 3 / 2 A polyorganosiloxane (a1') containing one or more units selected from the group consisting of siloxane units (T' units) represented by , and at least one unit selected from the group consisting of M' units, D' units and T' units, and a siloxane unit (Q'' unit) represented by SiO2, R 1 "R 2 "R 3 SiO1 / 2 Siloxane units (M'' units) are expressed as R 4 "R 5 SiO 2 / 2 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 , and at least one unit selected from the group consisting of M'' units, D'' units, and T'' units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0030] R 1 ~R 6 This group or atom is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, and the like.

[0031] R 1 '~R 6 ' represents a group that bonds to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6 At least one of the ' groups is an alkenyl group which may be substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0032] R 1 "~R 6 " represents a group or atom bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or hydrogen atom, but R 1 "~R 6At least one of the atoms is a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0033] The alkyl group may be linear, branched, or cyclic, but linear or branched alkyl groups are preferred. 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 even more preferably 10 or less.

[0034] Specific examples of substituted linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group Examples of suitable groups include the methyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group, but are not limited to these. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among these, the methyl group is particularly preferred.

[0035] Specific examples of cyclic alkyl groups that may be substituted include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group Examples of cycloalkyl groups include cycloalkyl groups such as ethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group, as well as bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0036] The alkenyl group may be linear or branched, and its carbon number 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.

[0037] Specific examples of substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, buttenyl, and pentenyl groups. Their carbon number is typically 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, ethenyl and 2-propenyl groups are particularly preferred. Specific examples of substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0038] As described above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl groups in polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) in polyorganosiloxane (a2') form a cross-linked structure through a hydrosilylation reaction with a platinum group metal catalyst (A2), resulting in hardening. As a result, a hardened film is formed.

[0039] Polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. As polyorganosiloxane (a1'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0040] Two or more preferred combinations selected from the group consisting of Q' units, M' units, D' units, and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units, and M' units).

[0041] Furthermore, when polyorganosiloxane (a1') contains two or more polyorganosiloxanes, the combinations of (Q' units and M' units) and (D' units and M' units), (T' units and M' units) and (D' units and M' units), and (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

[0042] Polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q'' units, M'' units, D'' units, and T'' units, and also contains at least one unit selected from the group consisting of M'' units, D'' units, and T'' units. As polyorganosiloxane (a2'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0043] Two or more preferred combinations 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), and (Q" units, T" units, and M" units).

[0044] Polyorganosiloxane (a1') is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom, R 1 '~R 6 The proportion of alkenyl groups in the total 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 an alkyl group.

[0045] Polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom are bonded to the silicon atom, R 1 "~R 6 The proportion of hydrogen atoms in all substituents and substituted atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 "~R6 " can be an alkyl group.

[0046] 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 the Si-H bond contained in polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0047] 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 is preferably 5,000 to 50,000 from the viewpoint of reproducibly realizing the effects of the present invention. In this invention, the weight-average molecular weight, number-average molecular weight, and degree of dispersion of polyorganosiloxanes (excluding the organosiloxane polymers mentioned above) can be measured, for example, using a GPC instrument (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex, manufactured by Showa Denko K.K.) as the standard sample.

[0048] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 10 to 1,000,000 (mPa·s), and preferably 50 to 200,000 (mPa·s) from the viewpoint of reproducibly realizing the effects of the present invention. The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is the value measured with an E-type rotational viscometer at 25°C.

[0049] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via hydrosilylation to form a cured film. Therefore, the curing mechanism is different from that mediated by silanol groups, for example, and consequently, neither siloxane needs to contain silanol groups or functional groups that form silanol groups through hydrolysis, such as alkyloxy groups.

[0050] In a preferred embodiment of the present invention, the adhesive component (S) comprises a platinum group metal catalyst (A2) together with a polyorganosiloxane component (A'). Such platinum-based metal catalysts are catalysts for promoting the hydrosilylation reaction between the alkenyl group of polyorganosiloxane (a1) and the Si-H group of polyorganosiloxane (a2).

[0051] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum-based catalysts such as platinum black, platinum-dic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetate. Examples of complexes between platinum and olefins include, but are not limited to, complexes between divinyltetramethyldisiloxane and platinum. The amount of platinum group metal catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

[0052] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction. Polymerization inhibitors are not particularly limited as long as they can suppress the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. The amount of polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), from the viewpoint of obtaining its effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0053] <<Styrene resin>> In a preferred embodiment of the present invention, when the adhesive component (S) is a styrene-based resin, it is preferable that the styrene-based resin is a thermoplastic elastomer containing a styrene structure (hereinafter also referred to as "polystyrene elastomer" in this specification). An elastomer refers to a polymer compound that exhibits elastic deformation.

[0054] There are no particular restrictions on the polystyrene elastomer, and it can be appropriately selected depending on the purpose. Examples include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene-styrene copolymer (SBBS) and their hydrogenated products, styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer, and the like.

[0055] The weight-average molecular weight of the polystyrene elastomer is preferably 2,000 to 200,000, more preferably 10,000 to 200,000, and even more preferably 50,000 to 100,000. Being within this range results in excellent solubility of the polystyrene elastomer in solvents, improving coatability. Furthermore, when removing the remaining adhesive layer after peeling the semiconductor substrate from the support substrate, the excellent solubility in solvents has the advantage of leaving no residue on the processed substrate or carrier substrate.

[0056] In the present invention, polystyrene-based elastomers include block copolymers, random copolymers, and graft copolymers, with block copolymers being preferred, more preferably having one or both ends as a styrene block copolymer, and particularly preferred having both ends as a styrene block copolymer. When both ends of the polystyrene-based elastomer are made of styrene block copolymers (styrene-derived repeating units), thermal stability tends to be further improved. This is because highly heat-resistant styrene-derived repeating units are present at the ends. In particular, when the block portion of the styrene-derived repeating units is a reactive polystyrene-based hard block, it tends to have superior heat resistance and chemical resistance, which is preferable. Furthermore, when these are made as block copolymers, it is thought that phase separation between hard blocks and soft blocks occurs at temperatures above 200°C. The shape of this phase separation is thought to contribute to suppressing the occurrence of irregularities on the surface of the processed substrate of the device wafer. In addition, such resins are more preferable from the viewpoint of solubility in solvents.

[0057] In the present invention, the polystyrene elastomer is preferably a hydrogenated polystyrene elastomer. When the polystyrene elastomer is a hydrogenated polystyrene elastomer, its thermal stability and storage stability are improved. Furthermore, its release properties and the ease of cleaning and removing the adhesive layer after release are improved. Note that a hydrogenated polystyrene elastomer refers to a polymer in which the elastomer has been hydrogenated.

[0058] The polystyrene elastomer preferably has a 5% thermal mass loss temperature of 250°C or higher when heated from 25°C at a rate of 20°C / min, more preferably 300°C or higher, even more preferably 350°C or higher, and particularly preferably 400°C or higher. There is no particular upper limit, but for example, 1000°C or lower is preferred, and 800°C or lower is more preferred. According to this embodiment, it is easy to form an adhesive layer with excellent heat resistance. Preferably, the polystyrene elastomer can be deformed up to 200% of its original size with a small external force at room temperature (20°C), and returns to 130% or less in a short time when the external force is removed.

[0059] The amount of unsaturated double bonds in the polystyrene elastomer is preferably less than 15 mmol / g, more preferably 7 mmol / g or less, even more preferably less than 5 mmol / g, and even more preferably less than 0.5 mmol / g, from the viewpoint of peelability after the heating process. There is no particular lower limit, but for example, it can be 0.001 mmol / g or more. Note that the amount of unsaturated double bonds referred to here does not include the unsaturated double bonds within the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (NMR) measurement.

[0060] In this specification, "styrene-derived repeating units" refer to styrene-derived structural units contained in a polymer when styrene or a styrene derivative is polymerized, and may have substituents. Examples of styrene derivatives include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. Examples of substituents include C1-C5 alkyl groups, C1-C5 alkoxy groups, C2-C5 alkoxyalkyl groups, acetoxy groups, and carboxyl groups.

[0061] Examples of commercially available polystyrene elastomers include Toughprene A, Toughprene 125, Toughprene 126S, Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, ToughTec H1272, ToughTec P1500, ToughTec H1052, ToughTec H1062, ToughTec M1943, ToughTec M1911, ToughTec H1041, ToughTec MP10, ToughTec M1913, ToughTec H1051, ToughTec H1053, ToughTec P2000, and ToughTec... H1043 (product name, manufactured by Asahi Kasei Corporation), Elastomer AR-850C, Elastomer AR-815C, Elastomer AR-840C, Elastomer AR-830C, Elastomer AR-860C, Elastomer AR-875C, Elastomer AR-885C, Elastomer AR-SC-15, Elastomer AR-SC-0, Elastomer AR-SC-5, Elastomer AR-710, Elastomer AR-SC-65, Elastomer AR-SC-30, Elastomer AR-SC-75, Elastomer AR-SC-45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR-760, Elastomer AR-770, Elastomer AR-781, Elastomer AR-791, Elastomer AR-FL-75N, Elastomer AR-FL-85N, Elastomer AR-FL-60N, Elastomer AR-1050, Elastomer AR-1060, Elastomer AR-1040 (all product names, manufactured by Aron Kasei), Kraton D1111, Kraton D1113, Kraton D1114, Kraton D1117, Kraton D111 9. Clayton D1124, Clayton D1126, Clayton D1161, Clayton D1162, Clayton D1163, Clayton D1164, Clayton D1165, Clayton D1183, Clayton D1193, Clayton DX406, Clayton D4141, Clayton D4150, Clayton D4153, Clayton D4158, Clayton D4270, Clayton D4271, Clayton D4433, Clayton D1170, Clayton D1171, Clayton D1173, Califlex IR0307, ​​Califlex IR0310,Califlex IR0401, Clayton D0242, Clayton D1101, Clayton D1102, Clayton D1116, Clayton D1118, Clayton D1133, Clayton D1152, Clayton D1153, Clayton D1155, Clayton D1184, Clayton D1186, Clayton D1189, Clayton D1191, Clayton D1192, Clayton DX405, Clayton DX408, Clayton DX410, Clayton DX414, Clayton DX415, Clayton A1535, Clayton A1536, Clay Clayton FG1901, Clayton FG1924, Clayton G1640, Clayton G1641, Clayton G1642, Clayton G1643, Clayton G1645, Clayton G1633, Clayton G1650, Clayton G1651, Clayton G1652, Clayton G1654, Clayton G1657, Clayton G1660, Clayton G1726, Clayton G1701, Clayton G1702, Clayton G1730, Clayton G1750, Clayton G1765, Clayton G4609, Clayton G4610 (The above are product names, K (manufactured by Raton), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynalon 6100P, Dynalon 4600P, Dynalon 6200P, Dynalon 4630P, Dynalon 8601P, Dynalon 8630P, Dynalon 8600P, Dynalon 8903P, Dynalon 6201B, Dynalon 1321P, Dynalon 1320P, Da Inalon 2324P, Dynalon 9901P (product names, manufactured by JSR Corporation), Denka STR series (product names, manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac 3520, Quintac 3433N, Quintac 3421, Quintac 3620, Quintac 3450, Quintac 3460 (manufactured by Nippon Zeon), TPESB series (product names, manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (product names, manufactured by Mitsubishi Chemical Corporation), Septon 1001, Septon 8004, Septon 4033, Septon 2104, Septon 8007, Septon 2007,Examples include Septon 2004, Septon 2063, Septon HG252, Septon 8076, Septon 2002, Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077, Septon 4099, Septon 8006, Septon V9461, Septon V9475, Septon V9827, Hybler 7311, Hybler 7125, Hybler 5127, Hybler 5125 (all product names, manufactured by Kuraray), Sumiflex (all product names, manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimmer (all product names, manufactured by Riken Vinyl Industry Co., Ltd.).

[0062] An example of the adhesive composition of the present invention may contain an adhesive component (S) and an azo dye (X) in any ratio. However, considering the balance between adhesion and release properties, the ratio of adhesive component (S): azo dye (X) is preferably 85:15 to 99.9:0.1 by mass ratio (adhesive component (S): azo dye (X)), more preferably 90:10 to 99.5:0.5, and even more preferably 95:5 to 99:1.

[0063] <Other ingredients> The adhesive composition of the present invention may contain a solvent for purposes such as adjusting viscosity or for good dissolution of film components.

[0064] Specific examples of solvents include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones. More specifically, examples of solvents include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, and 5-nonanone. Other examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether (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 ethoxypropyl ether, ethyl hydroxypropyl ether, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl ethyl acetate, butyl lactate, butyl lactate, etc. Such solvents can be used individually or in combination of two or more.

[0065] In one aspect of the present invention, the adhesive composition is preferably a glycol-based solvent, from the viewpoint of obtaining a highly uniform composition with good reproducibility, a composition with good storage stability with good reproducibility, and a composition that provides a highly uniform film with good reproducibility. The term "glycol-based solvent" as used herein refers to glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0066] In adhesive compositions, preferred combinations of adhesive component (S) and solvent include, for example, when a silicone-based resin is used as the adhesive component (S), it is more preferable to use propylene glycol monomethyl ether acetate (PGMEA) as the solvent, and when a styrene-based resin is used as the adhesive component (S), it is more preferable to use mesitylene as the solvent.

[0067] If the adhesive composition of the present invention contains a solvent, its content is appropriately determined considering the viscosity of the desired composition, the application method used, the thickness of the film to be produced, etc., but is in the range of approximately 10 to 90% by mass of the entire composition.

[0068] The viscosity of the adhesive composition of the present invention is not particularly limited, but is typically 500 to 20,000 mPa·s at 25°C, and preferably 1,000 to 6,000 mPa·s. The viscosity of the adhesive composition of the present invention can be adjusted by changing the type of solvent used, their ratios, the concentration of film components, etc., taking into consideration various factors such as the application method used and the desired film thickness. In this invention, "film component" refers to components other than the solvent contained in the composition.

[0069] <Method for manufacturing adhesive composition> As a preferred embodiment of the method for producing the adhesive composition, for example, the adhesive composition of the present invention can be produced by mixing an adhesive component (S), an azo dye (X), and a solvent, if used. The mixing order is not particularly limited, but examples of methods for easily and reproducibly producing the adhesive composition of the present invention include, for example, dissolving the adhesive component (S) and the azo dye (X) in a solvent, or dissolving a portion of the adhesive component (S) and the azo dye (X) in a solvent, dissolving the remainder in a solvent, and then mixing the resulting solutions. However, the method is not limited to these. When preparing the adhesive composition, heating may be used as appropriate, as long as the components do not decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the adhesive composition may be filtered using a filter or the like during the manufacturing process or after all components have been mixed.

[0070] (Laminated structure) The laminate of the present invention comprises a semiconductor substrate, a support substrate, and an adhesive layer for light irradiation peeling. The support substrate is light-transmitting. The adhesive layer for light-induced peeling is provided between the semiconductor substrate and the support substrate. The laminate is used in a system where the semiconductor substrate and the support substrate are separated after the adhesive layer absorbs light irradiated from the support substrate side. The adhesive layer for light-irradiation peeling is a layer formed from the light-irradiation peeling adhesive composition of the present invention described above.

[0071] The laminate of the present invention is used for temporary bonding in order to process semiconductor substrates, and can be suitably used for processing semiconductor substrates such as thinning. While the semiconductor substrate is being processed, such as thinning, it is supported by a support substrate via an adhesive layer. After the semiconductor substrate is processed, the adhesive layer is irradiated with light, and thereafter, the support substrate and the semiconductor substrate are separated. The adhesive layer according to the present invention makes it easier to separate the semiconductor substrate and the support substrate after irradiation with light. Furthermore, any residue of the adhesive layer remaining on the semiconductor substrate or the support substrate after the semiconductor substrate and the support substrate have been separated can be easily removed with a cleaning agent composition for cleaning the semiconductor substrate.

[0072] The wavelength of light used for peeling is preferably, for example, 250 to 600 nm, and more preferably 250 to 370 nm. More preferred wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light irradiation required for peeling is an irradiation dose that can cause a suitable alteration, such as decomposition, of a specific light-absorbing compound. The light used for peeling may be laser light, or non-laser light emitted from a light source such as an ultraviolet lamp.

[0073] <Semiconductor substrates> The main materials that make up the entire semiconductor substrate are not particularly limited as long as they are used in this type of application, but examples include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited, but for example, it is disc-shaped. The disc-shaped semiconductor substrate does not need to have a perfectly circular surface; for example, the outer edge of the semiconductor substrate may have a straight section called an orientation flat, or a notch. The thickness of the disc-shaped semiconductor substrate can be determined appropriately depending on the intended use of the semiconductor substrate and is not particularly limited, but for example, it is 500 to 1,000 μm. The diameter of the disc-shaped semiconductor substrate can be determined appropriately depending on the intended use of the semiconductor substrate and is not particularly limited, but for example, it is 100 to 1,000 mm.

[0074] The semiconductor substrate may have bumps. Bumps are protruding terminals. In a laminate, if the semiconductor substrate has bumps, the semiconductor substrate has bumps on the support substrate side. In semiconductor substrates, bumps are typically formed on the surface on which circuits are formed. Circuits may be single-layer or multi-layer. The shape of the circuits is not particularly limited. In a semiconductor substrate, the side opposite to the side with bumps (the back surface) is the side that is subjected to processing. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. Typically, the bump height, radius, and pitch are determined appropriately based on conditions such as a bump height of approximately 1-200 μm, a bump radius of 1-200 μm, and a bump pitch of 1-500 μm. Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, examples include Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. Furthermore, the bump may have a laminated structure that includes a metal layer made of at least one of these components.

[0075] An example of a semiconductor substrate is a silicon wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm.

[0076] <Support substrate> The support substrate is not particularly limited as long as it is a material that is light-transmitting to light irradiated onto the adhesive layer and can support the semiconductor substrate when the semiconductor substrate is being processed, but examples include glass support substrates.

[0077] The shape of the support substrate is not particularly limited, but for example, it can be disc-shaped. The thickness of the disc-shaped support substrate can be determined appropriately according to the size of the semiconductor substrate and is not particularly limited, but for example, it is 500 to 1,000 μm. The diameter of the disc-shaped support substrate can be determined appropriately according to the size of the semiconductor substrate, etc., and is not particularly limited, but for example, it is 100 to 1,000 mm.

[0078] An example of a support substrate is a glass wafer with a diameter of approximately 300 mm and a thickness of approximately 700 μm.

[0079] <Adhesive layer> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer, for example, is in contact with the semiconductor substrate and the support substrate.

[0080] The adhesive layer is formed using the light-irradiation peelable adhesive composition of the present invention described above. The adhesive composition of the present invention can be suitably used to form an adhesive layer in a laminate having a semiconductor substrate, a support substrate, and an adhesive layer provided between the semiconductor substrate and the support substrate. The laminate is used in a manner in which the semiconductor substrate and the support substrate are separated after the adhesive layer absorbs light irradiated from the support substrate side. One of the features of the adhesive layer obtained from the adhesive composition of the present invention is that, after light irradiation and the separation of the semiconductor substrate and the support substrate, any residue of the adhesive layer remaining on the semiconductor substrate or the support substrate can be suitably removed by the cleaning agent composition.

[0081] The thickness of the adhesive layer is not particularly limited, but is usually 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 even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by thick films, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and still more preferably 70 μm or less. The method for forming an adhesive layer from an adhesive composition will be described in detail in the section on <Method for Manufacturing Laminates> below.

[0082] The laminate of the present invention can be suitably manufactured, for example, by the following method for manufacturing the laminate of the present invention.

[0083] An example of a laminate is explained below using a diagram. Figure 1 is a schematic cross-sectional view of an example of a laminate. The laminate in Figure 1 comprises a semiconductor substrate 1, an adhesive layer 2, and a support substrate 3 in that order. The adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 3. The adhesive layer 2 is in contact with both the semiconductor substrate 1 and the support substrate 3.

[0084] <Method for manufacturing laminates> The laminate of the present invention can be manufactured by a method comprising, for example, a first step of applying an adhesive composition to the surface of either the semiconductor substrate or the support substrate and heating it if necessary to form an adhesive coating layer, and a second step of joining the semiconductor substrate and the support substrate via the adhesive coating layer and bonding the semiconductor substrate, the adhesive coating layer and the support substrate together while performing at least one of a heat treatment and a reduced pressure treatment. The second step can be described in more detail as follows: the step of the embodiment described in (i) or the embodiment described in (ii) below. (i) When the adhesive composition is applied to the surface of a semiconductor substrate, the adhesive coating layer of the semiconductor substrate and the support substrate are bonded together by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a vacuum treatment, and then a post-heat treatment is performed to form a laminate. (ii) If the adhesive composition is applied to the surface of the support substrate, the adhesive coating layer of the support substrate and the semiconductor substrate are brought into close contact by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a vacuum treatment, and then a post-heat treatment is performed to form a laminate.

[0085] The coating method is not particularly limited, but it is usually the spin coating method. Alternatively, a method can be adopted in which a coating film is formed separately by the spin coating method or the like, and the sheet-like coating film is attached as an adhesive coating layer.

[0086] The heating temperature of the applied adhesive composition cannot be specified in general terms, as it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc. However, it is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes. If the adhesive composition contains a solvent, the applied adhesive composition is usually heated.

[0087] Heating can be done using a hot plate, oven, etc.

[0088] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is typically around 5 to 500 μm, and is ultimately determined as appropriate so that it falls within the aforementioned range of adhesive layer thickness.

[0089] In the present invention, a laminate can be obtained by bringing a semiconductor substrate and a support substrate together so that they are in contact with an adhesive layer, applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment, a vacuum treatment, or both, to bring the two layers into close contact, and then performing a post-heat treatment. The choice of which treatment conditions to adopt—heat treatment, vacuum treatment, or a combination of both—is determined appropriately after considering various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from both compositions, the film thickness, and the desired adhesive strength.

[0090] The heat treatment temperature is usually determined appropriately from the range of 20 to 150°C, from the viewpoint of removing the solvent if the composition contains one, and from the viewpoint of softening the adhesive coating layer to achieve suitable bonding with the release agent coating layer. In particular, from the viewpoint of suppressing or avoiding excessive hardening or unwanted deterioration of the adhesive component (S), the temperature is preferably 130°C or lower, more preferably 90°C or lower. The heating time is appropriately determined depending on the heating temperature and the type of adhesive, but from the viewpoint of reliably achieving suitable adhesion, it is usually 30 seconds or more, preferably 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other members, it is usually 10 minutes or less, preferably 5 minutes or less.

[0091] The depressurization process involves exposing the adhesive coating layer to a pressure of 10 to 10,000 Pa. The depressurization time is typically 1 to 30 minutes.

[0092] The load applied in the thickness direction to the semiconductor substrate and the support substrate is not particularly limited, as long as it does not adversely affect the semiconductor substrate, the support substrate, and the two layers between them, and can firmly adhere them to each other; however, it is usually in the range of 10 to 1000 N.

[0093] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing speed, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate and each layer. The post-heating time is usually 1 minute or more, preferably 5 minutes or more, from the viewpoint of achieving suitable bonding of the substrates and layers constituting the laminate, and is usually 180 minutes or less, preferably 120 minutes or less, from the viewpoint of suppressing or avoiding adverse effects on each layer due to excessive heating. Heating can be performed using a hot plate, oven, etc. When post-heating using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be placed facing downwards during heating, but from the viewpoint of achieving suitable delamination with good reproducibility, it is preferable to post-heat with the semiconductor substrate facing downwards. One of the purposes of the post-heat treatment is to create a more suitable self-supporting adhesive layer, and in particular to facilitate curing by hydrosilylation reaction.

[0094] (Method for manufacturing processed semiconductor substrates) The present invention relates to a method for manufacturing a processed semiconductor substrate, comprising a third step and a fourth step. The method for manufacturing a processed semiconductor substrate according to the present invention may further include a fifth step. The third step is the process of processing the semiconductor substrate of the laminate according to the present invention. The fourth step is the process of separating the semiconductor substrate and the support substrate that were processed in the third step. The fifth step is to clean at least one of the separated semiconductor substrate and support substrate with a cleaning agent composition.

[0095] The processing performed on the semiconductor substrate in the third step is, for example, processing on the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface. Subsequently, through-silicon viable (TSV) electrodes are formed, and then the thinned wafer is peeled off the support substrate to form a wafer laminate for 3D mounting. The back surface electrodes of the wafer are also formed before or after this. During the wafer thinning and TSV processes, heat of approximately 250-350°C is applied while the wafer is bonded to the support substrate. The laminate of the present invention typically includes an adhesive layer and possesses heat resistance to this load. Furthermore, the processing is not limited to those described above, and also includes, for example, the implementation of the semiconductor component mounting process when a substrate is temporarily bonded to a support substrate to support the substrate for mounting semiconductor components.

[0096] In the fourth step, methods for separating (peeling) the semiconductor substrate from the support substrate include, but are not limited to, mechanical peeling using equipment with sharp parts after light irradiation of the adhesive layer, or peeling the support from the wafer. By irradiating the adhesive layer with light from the support substrate side, the adhesive layer is altered as described above (for example, separation or decomposition of the adhesive layer), and then, for example, one of the substrates can be easily lifted to separate the semiconductor substrate from the support substrate.

[0097] Irradiation of the adhesive layer with light does not necessarily have to be performed over the entire surface of the adhesive layer. Even if there is a mixture of irradiated and unirradiated areas, if the peelability of the adhesive layer as a whole is sufficiently improved, the semiconductor substrate and the support substrate can be separated by a small external force, such as lifting the support substrate. The ratio and positional relationship between the irradiated and unirradiated areas will vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the intensity of the irradiated light, etc., but those skilled in the art can set the conditions appropriately without requiring excessive testing. For these reasons, according to the manufacturing method of the processed semiconductor substrate of the present invention, for example, when the support substrate of the laminate used is light-transmitting, it is possible to shorten the light irradiation time when peeling by light irradiation from the support substrate side, and as a result, not only is an improvement in throughput expected, but the semiconductor substrate and the support substrate can be easily and efficiently separated by light irradiation alone, avoiding physical stress for peeling. Typically, the light irradiation dose for delamination is 50-3,000 mJ / cm². 2 The irradiation time is determined appropriately according to the wavelength and irradiation dose.

[0098] As mentioned above, the wavelength of light used for peeling is preferably, for example, 250 to 600 nm, and more preferably 250 to 370 nm. More preferable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light irradiation required for peeling is an irradiation amount that can cause a suitable alteration, such as decomposition, of a specific light-absorbing compound. The light used for peeling may be laser light, or non-laser light emitted from a light source such as an ultraviolet lamp.

[0099] In the fifth step, the cleaning agent composition is sprayed onto at least one of the surfaces of the separated semiconductor substrate and the support substrate, or the separated semiconductor substrate or support substrate is immersed in the cleaning agent composition to clean it, and then rinsing with a solvent and drying are usually performed. Examples of cleaning agent compositions include the following:

[0100] <Detergent composition> After light irradiation, any adhesive residue remaining on the semiconductor substrate or support substrate after the semiconductor substrate and support substrate have been separated can be suitably removed by a cleaning agent composition, which typically contains a solvent.

[0101] Examples of solvents include lactones, ketones, polyhydric alcohols, compounds containing ester bonds, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of lactones include γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds containing ester bonds include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include monoalkyl ethers such as monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers, or compounds having ether bonds such as monophenyl ethers, which are monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers, which are monomethyl ethers, or which are monomethyl as mentioned above. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxanes. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. These can be used individually or in combination of two or more types. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0102] Furthermore, a mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined considering the compatibility of PGMEA and the polar solvent, but it is preferably in the range of 1:9 to 9:1, and more preferably in the range of 2:8 to 8:2. For example, when EL is blended as a polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is blended as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are blended as polar solvents, the mass ratio of PGMEA:(PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.

[0103] The cleaning composition may or may not contain a salt.

[0104] As an example of the case where the cleaning composition contains a salt, a cleaning composition containing a quaternary ammonium salt and a solvent can be mentioned. The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application. Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, examples of the anion paired with it include hydroxide ions (OH - ); halogen ions such as fluoride ions (F - ), chloride ions (Cl - ), bromide ions (Br - ), iodide ions (I - ); tetrafluoroborate ions (BF4 - ); hexafluorophosphate ions (PF6 - ), etc., but are not limited to these.

[0105] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in the cation or the anion, but is preferably contained in the anion.

[0106] In one preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of hydrocarbon groups in tetraammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, tetra(hydrocarbon)ammonium fluoride comprises tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Among these, tetrabutylammonium fluoride is preferred.

[0107] Quaternary ammonium salts such as tetraammonium(hydrocarbon)fluoride may be used in hydrate form. Furthermore, quaternary ammonium salts such as tetraammonium(hydrocarbon)fluoride may be used individually or in combination of two or more types. The amount of quaternary ammonium salt is not particularly limited as long as it is soluble in the solvent contained in the detergent composition, but it is usually 0.1 to 30% by mass relative to the detergent composition.

[0108] When a detergent composition contains a salt, the solvent used in combination is not particularly limited as long as it is used for this type of application and dissolves salts such as quaternary ammonium salts. However, from the viewpoint of obtaining a detergent composition with excellent cleaning properties with good reproducibility, and from the viewpoint of dissolving salts such as quaternary ammonium salts well to obtain a detergent composition with excellent uniformity, the detergent composition preferably contains one or more amide-based solvents.

[0109] A suitable example of an amide solvent is an acid amide derivative represented by formula (Z). [ka]

[0110] In the formula, R 0 represents an ethyl group, a propyl group or an isopropyl group, with an ethyl group or an isopropyl group being preferred, and an ethyl group being more preferred. 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 may be linear, branched or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, etc. Among these, R A and R B are preferably a methyl group or an ethyl group, more preferably both a methyl group or an ethyl group, and even more preferably both a methyl group.

[0111] Examples of the acid amide derivative represented by the formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, N-ethyl-N-methylisobutyramide, etc. Among these, particularly, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are preferred, and N,N-dimethylpropionamide is more preferred.

[0112] The acid amide derivative represented by the formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0113] Another example of a preferred amide-based solvent includes a lactam compound represented by the formula (Y).

Chemical formula

[0114] In the formula (Y), R101 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 102 The symbol represents an alkylene group having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, and n-butyl groups, while specific examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups, but are not limited to these.

[0115] Specific examples of lactam compounds represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used individually or in combination of two or more.

[0116] In one preferred embodiment of the present invention, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in one more preferred embodiment, comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in one even more preferred embodiment, comprises N-methylpyrrolidone (NMP).

[0117] The cleaning agent composition used in this invention may contain water as a solvent, but from the viewpoint of avoiding corrosion of the substrate, etc., only organic solvents are usually intentionally used as solvents. In this case, however, it is not ruled out that trace amounts of water contained in the salt's hydrated water or in the organic solvent may be included in the cleaning agent composition. The water content of the cleaning agent composition used in this invention is usually 5% by mass or less.

[0118] In the method for manufacturing a processed semiconductor substrate of the present invention, the processed semiconductor substrate manufactured through the fifth step is well cleaned by the cleaning agent composition. However, this does not prevent further cleaning of the surface of the processed semiconductor substrate using a removal tape or the like, and if necessary, the surface may be further cleaned using a removal tape or the like.

[0119] The components and method elements relating to the above-described steps of the method for manufacturing the processed semiconductor substrate of the present invention may be modified in various ways as long as they do not depart from the spirit of the present invention. The method for manufacturing a processed semiconductor substrate according to the present invention may include steps other than those described above.

[0120] The peeling process according to the present invention separates the semiconductor substrate and the support substrate of the laminate by irradiating the adhesive layer with light from the semiconductor substrate side or the support substrate side, when the semiconductor substrate or support substrate of the laminate according to the present invention is light-transmitting. In the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded together by an adhesive layer in a suitably peelable manner. For example, if the support substrate is light-transmitting, 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. Typically, peeling is performed after processing has been carried out on the semiconductor substrate of the laminate. [Examples]

[0121] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The apparatus used is as follows.

[0122] [Device] (1) Mixer A: ARE-500, manufactured by Thinky Co., Ltd. (2) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd. (3) Film thickness gauge (film thickness measurement): BRUKER DEKTAK XT-A (4) Vacuum bonding equipment: Manufactured by Züss Microtech Co., Ltd., manual bonder (5) Dicing machine: SS30 manufactured by Tokyo Seimitsu Co., Ltd. (6) Laser irradiation device: Lambda SX manufactured by Coherent Corporation (7) Measurement of weight-average molecular weight and degree of dispersion: GPC instrument (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation) Column temperature: 40℃ Eluent (elution solvent): Tetrahydrofuran Flow rate (flow rate): 0.35mL / min Standard sample: Polystyrene (manufactured by Sigma-Aldrich)

[0123] The structural formulas of each component used in the examples are shown below.

[0124] [ka]

[0125] [1] Preparation of adhesive composition [Preparation Example 1-1] In a 600 mL stirring container specifically for the rotation-orbit mixer, 150 g of a base polymer (manufactured by Wacker Chem Co., Ltd.) consisting of a vinyl group-containing linear polydimethylsiloxane v2 with a viscosity of 200 mPa·s represented by the above formula (V) and a vinyl group-containing MQ resin was added as component (a1), 15.81 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Co., Ltd.) with a viscosity of 100 mPa·s was added as component (a2), and 0.17 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem Co., Ltd.) was added as component (A3). The mixture was stirred with stirrer A for 5 minutes to obtain mixture (I). Mixture (II) was obtained by stirring a 50 mL screw-cap tube with 0.33 g of platinum catalyst (manufactured by Wacker Chem Ltd.) as component (A2) and 9.98 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem Ltd.) (hereinafter referred to as vinyl group-containing linear polydimethylsiloxane v3) represented by the above formula (W) and having a viscosity of 1000 mPa·s as component (a1) using stirrer A for 5 minutes. 0.52 g of the obtained mixture (II) was added to mixture (I), and the mixture was stirred with stirrer A for 5 minutes to obtain mixture (III). Finally, the resulting mixture (III) was filtered through a 300-mesh nylon filter to obtain the adhesive composition. The viscosity of the adhesive composition, as measured using a rotational viscometer, was 9900 mPa·s.

[0126] [Preparation Examples 1-2] In a 100 mL stirring container specifically for the rotation-orbit mixer, 20.10 g of the adhesive composition obtained in Preparation Example 1-1, 0.02 g of 1,1-diphenyl-2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.50 g of propylene glycol monomethyl ether acetate as a solvent, and 0.50 g of Sudan Black B (manufactured by Tokyo Chemical Industry Co., Ltd.), represented by the aforementioned formula (XI), as an azo dye were added. The mixture was stirred for 10 minutes using stirrer A to obtain mixture (I). The obtained mixture (I) was filtered through a 300 mesh nylon filter to obtain the adhesive composition.

[0127] [Preparation Examples 1-3] In a 100 mL stirring container specifically for the rotation-orbit mixer, 10.05 g of Septon 4033 (manufactured by Kuraray Co., Ltd.), a thermoplastic resin that is a hydrogenated styrene-isoprene-butadiene copolymer, 0.25 g of Sudan Black B (manufactured by Tokyo Chemical Industry Co., Ltd.) as an azo dye, and 30.06 g of mesitylene were added and stirred with stirrer A for 10 minutes to obtain the adhesive composition.

[0128] [2] Adhesion test [2-1] Fabrication of the laminate [Example 2-1] A 300 mm silicon wafer (thickness: 775 μm) was used as the device wafer (semiconductor substrate). The adhesive composition obtained in Preparation Example 1-2 was applied by spin coating and heated at 120°C for 1.5 minutes (preheating treatment) to form an adhesive coating layer on the circuit surface of the silicon wafer such that the final thickness of the adhesive layer in the laminate was approximately 40 μm. Subsequently, a semiconductor substrate and a 300 mm glass wafer (thickness: 700 μm) used as a support substrate were bonded together in a vacuum bonding apparatus, with an adhesive coating layer in between. The laminate was then heated on a hot plate with the semiconductor substrate side down at 200°C for 10 minutes (post-heat treatment) to create a laminate. The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and a load of 30 N. Finally, the resulting laminate was cut into 4 cm squares using a dicing apparatus.

[0129] [Example 2-2] A 300 mm silicon wafer (thickness: 775 μm) was used as the device wafer (semiconductor substrate). The adhesive compositions obtained in Preparation Example 1-3 were applied by spin coating and heated at 120°C for 1.5 minutes (preheating treatment) to form an adhesive coating layer on the circuit surface of the silicon wafer such that the final thickness of the adhesive layer in the laminate was approximately 40 μm. Subsequently, a semiconductor substrate and a 300 mm glass wafer (thickness: 700 μm) used as a support substrate were bonded together in a vacuum bonding apparatus, with an adhesive coating layer in between. The laminate was then heated on a hot plate with the semiconductor substrate side down at 200°C for 10 minutes (post-heat treatment) to create the laminate. The bonding was performed at a temperature of 90°C, a reduced pressure of 1,000 Pa, and a load of 500 N. Finally, the resulting laminate was cut into 4cm squares using a dicing device.

[0130] [Comparative Example 1] A 300 mm silicon wafer (thickness: 775 μm) was used as the device-side wafer (semiconductor substrate). The adhesive composition obtained in Preparation Example 1-1 was applied by spin coating and heated at 120°C for 1.5 minutes (preheating treatment) to form an adhesive coating layer on the circuit surface of the silicon wafer such that the final thickness of the adhesive layer in the laminate was approximately 40 μm. Subsequently, a semiconductor substrate and a 300 mm glass wafer (thickness: 700 μm) used as a support substrate were bonded together in a vacuum bonding apparatus, with an adhesive coating layer in between. The laminate was then heated on a hot plate with the semiconductor substrate side down at 200°C for 10 minutes (post-heat treatment) to create a laminate. The bonding was performed at a temperature of 23°C, a reduced pressure of 1,000 Pa, and a load of 30 N. Finally, the resulting laminate was cut into 4 cm squares using a dicing apparatus.

[0131] [2-2] Evaluation of adhesion Adhesion was evaluated by visually checking for the presence or absence of voids from the glass wafer (support) side of the laminate. If no voids were found, the result was rated as good; if voids were found, it was rated as poor. As a result, no voids were observed in the laminates obtained in Examples 2-1, 2-2, and Comparative Example 1.

[0132] [3] Evaluation of laser peelability Using a laser irradiation device, a 308nm wavelength laser is applied to the delamination layer of the fixed laminate from the glass wafer side at a rate of 300mJ / cm². 2 The laminates were irradiated. Then, the feasibility of peeling was confirmed by manually lifting the support substrate. As a result, in each of the laminates obtained in Examples 2-1 and 2-2, peeling was possible without load by lifting the support substrate. However, in Comparative Example 1, which was prepared using Adjustment Example 1-1 without the addition of azo dye, peeling was not possible even when force was applied. [Explanation of Symbols]

[0133] 1. Semiconductor substrate 2 Adhesive layer 3. Support substrate

Claims

1. An adhesive composition for forming an adhesive layer that is peelably bonded between a support substrate and a semiconductor substrate, The aforementioned adhesive composition is an adhesive composition for light irradiation that can be peeled off by light irradiation, The adhesive composition comprises an adhesive component (S) and an azo dye (X), The azo dye (X) is a compound represented by either the following formula (A-I) or the following formula (A-II), 【Chemistry 1】 (In formula (A-I), Ar1 and Ar2 each independently represent a benzene ring or naphthalene ring which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, a cyano group, or a vinyl group; Ra represents a hydroxyl group, an amino group, an alkylamino group, or a dialkylamino group; p represents an integer from 1 to 5 when Ar2 is a substituted or unsubstituted benzene ring, and an integer from 1 to 7 when Ar2 is a substituted or unsubstituted naphthalene ring. Ra and Ar2 may be bonded to each other to form a ring structure, and if p is an integer from 2 to 7, the multiple Ras may be different from each other.) 【Chemistry 2】 (In formula (A-II), Ar3 to Ar5 each independently represent a benzene ring or naphthalene ring which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a halogen atom, a cyano group, or a vinyl group; Rb represents a hydroxyl group, an amino group, an alkylamino group, or a dialkylamino group; q represents an integer from 1 to 5 when Ar5 is a substituted or unsubstituted benzene ring, and an integer from 1 to 7 when Ar5 is a substituted or unsubstituted naphthalene ring. Rb and Ar5 may bond to each other to form a ring structure, and when q is an integer from 2 to 7, multiple Rb may be different from each other, and multiple different Rb may bond to Ar5 to form a ring structure.) The adhesive component (S) is a siloxane-based resin or a styrene-based resin. The siloxane-based resin contains a component that hardens by a hydrosilylation reaction, The styrene-based resin is a polystyrene elastomer in this adhesive composition.

2. The adhesive composition according to claim 1, wherein the component that hardens by the hydrosilylation reaction contains a polyorganosiloxane component that hardens by the hydrosilylation reaction.

3. Polyorganosiloxane components that harden through a hydrosilylation reaction, A polyorganosiloxane (a1) having alkenyl groups with 2 to 40 carbon atoms bonded to a silicon atom, A polyorganosiloxane (a2) having a Si-H group, Platinum group metal catalyst (A2), The adhesive composition according to claim 2, comprising:

4. In formulas (A-I) and (A-II), R ａ and R ｂ The adhesive composition according to claim 1, wherein the group is selected from an amino group, an alkylamino group, and a dialkylamino group.

5. The adhesive composition according to claim 1, wherein the azo dye (X) is a compound represented by the following formula (X-I). 【Transformation 3】

6. The adhesive composition according to claim 1, wherein the mixing ratio of the adhesive component (S) and the azo dye (X) is 85:15 to 99.9:0.1 by mass (adhesive component (S): azo dye (X)).

7. Semiconductor substrate and A light-transmitting support substrate, The semiconductor substrate and the support substrate are provided with an adhesive layer, A laminate used in which the semiconductor substrate and the support substrate are separated after the adhesive layer absorbs light irradiated from the support substrate side, A laminate in which the adhesive layer is formed from the adhesive composition described in any one of claims 1 to 6.

8. A first step of forming an adhesive coating layer by applying the adhesive composition according to any one of claims 1 to 6 to the surface of either the semiconductor substrate or the support substrate, A second step involves joining the semiconductor substrate and the support substrate via the adhesive coating layer, and bonding the semiconductor substrate, the adhesive coating layer, and the support substrate while performing at least one of a heat treatment and a vacuum treatment. A method for manufacturing a laminate containing a laminate.

9. A method for manufacturing a processed semiconductor substrate, A third step in which the semiconductor substrate of the laminate according to claim 7 is processed, A fourth step involves separating the semiconductor substrate and the support substrate processed in the third step, A method for manufacturing a processed semiconductor substrate, including the method described above.

10. The method for manufacturing a processed semiconductor substrate according to claim 9, wherein the fourth step includes irradiating the laminate according to claim 7 with a laser from the support substrate side.

11. The method for manufacturing a processed semiconductor substrate according to claim 10, wherein the wavelength of the laser is 250 nm to 600 nm.

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