JP2023125710A - Adhesive composition for light-irradiation peeling, laminate, method for producing laminate, and method for producing processed semiconductor substrate - Google Patents

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

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.

Semiconductor wafers have conventionally been integrated in a two-dimensional planar direction, but for the purpose of further integration, there is a need for a semiconductor integration technology in which the planar surfaces are further integrated (stacked) in a three-dimensional direction. This three-dimensional stacking is a technology in which devices are integrated into multiple layers while being connected using through silicon vias (TSV). When integrating multiple layers, each wafer to be integrated is thinned by polishing on the side opposite to the circuit surface on which it is formed (ie, the back surface), and the thinned semiconductor wafers are stacked.

An unthinned semiconductor wafer (also referred to herein simply as a wafer) is adhered to a support for polishing in a polishing device. Since the adhesion at that time must be easily peeled off after polishing, it is called temporary adhesion. This temporary bond must be easily removed from the support, and the thinned semiconductor wafer may be cut or deformed if large forces are applied during removal, so care must be taken to prevent this from occurring. can be easily removed. However, it is undesirable for the polishing member to come off or shift due to polishing stress during backside polishing of the semiconductor wafer. Therefore, the performance required for temporary bonding is that it can withstand stress during polishing and be easily removed after polishing.

For example, performance is required to have high stress (strong adhesive force) in the planar direction during polishing and low stress (weak adhesive force) in the vertical direction during removal.
A method using laser irradiation has been disclosed for such adhesion and separation processes (see, for example, Patent Documents 1 and 2), but with recent progress in the semiconductor field, peeling by irradiation with light such as a laser has become more effective. New technologies related to this are always in demand.

Further, a temporary adhesive layer for temporary (temporary) adhesion that also functions as a laser releasable layer, and a laser releasable adhesive composition for forming the temporary adhesive layer are disclosed (for example, (See Patent Document 3)

JP2004-64040A Japanese Patent Application Publication No. 2012-106486 Special Publication No. 2021-508168

However, the laser releasable adhesive composition described in Patent Document 3 is formed from a polyhydroxy ether containing a copolymer of diglycidyl ether and a dihydroxy dye. In the laser releasable adhesive composition described in Patent Document 3, the type of polymer contained in the composition is limited to a specific one, and in Patent Document 3, a copolymer with a dye is Since it has to be formed, it is necessary to carry out operations for 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 both as an adhesive layer for temporary adhesion and as a laser peeling layer by a simpler method, it is described in Patent Document 3 mentioned above. The adhesive composition was not satisfactory and there was room for improvement.

An object of the present invention is to provide an adhesive composition for light irradiation peeling that can be obtained by a simple method.
The present invention also provides a laminate having an adhesive layer formed of the adhesive composition for light irradiation peeling, wherein the semiconductor substrate and the support substrate in the laminate can be easily peeled off by light irradiation. The purpose is to provide a laminate that can.
A further object of the present invention is to provide a method for manufacturing the laminate and a method for manufacturing a processed semiconductor substrate using the laminate.

In order to solve the above-mentioned problems, the present inventors conducted intensive studies, and as a result found that the above-mentioned problems could be solved, and completed the present invention having the following gist.

That is, the present invention includes the following.
[1] An adhesive composition for light irradiation peeling that is removable by light irradiation and includes 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 either the following formula (AI) or the following formula (A-II).
(In formula (AI), Ar ¹ and Ar ² are each independently 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 Represents a benzene ring or naphthalene ring which may be substituted with a vinyl group, R ^a represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents a benzene ring in which Ar ² is substituted or unsubstituted. When it is a ring, it represents an integer from 1 to 5, and when Ar ² is a substituted or unsubstituted naphthalene ring, it represents an integer from 1 to 7. R ^a and Ar ² are bonded to each other to form a ring. structure, and when p is an integer from 2 to 7, multiple ^Ras may be different from each other.)

(In formula (A-II), Ar ³ to Ar ⁵ are each independently 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 Represents a benzene ring or naphthalene ring which may be substituted with a vinyl group, R ^b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and q represents benzene in which Ar ⁵ is substituted or unsubstituted. When it is a ring, it represents an integer from 1 to 5, and when Ar ⁵ is a substituted or unsubstituted naphthalene ring, it represents an integer from 1 to 7. R ^b and Ar ⁵ are bonded to each other to form a ring. structure, and when q is an integer from 2 to 7, a plurality of R ^b 's may be different from each other, and a plurality of R ^b 's, which may be different, are mutually bonded to Ar ⁵ . (May 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 is cured by a hydrosilylation reaction.
[5] The adhesive composition according to [4], wherein the component that is cured by a hydrosilylation reaction contains a polyorganosiloxane component that is cured by a hydrosilylation reaction.
[6] The polyorganosiloxane component that is cured by a hydrosilylation reaction is
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,
A platinum group metal catalyst (A2),
The adhesive composition according to [5], comprising:
[7] The adhesive composition according to [3], wherein the styrene resin is a polystyrene elastomer.
[8] From [2], R ^a and R ^b in the formula (AI) and the formula (A-II) are selected from an amino group, an alkylamino group, and a dialkylamino group; 7].
[9] The adhesive composition according to [8], wherein the azo dye (X) is a compound represented by the following formula (X-I).

[10] The mixing ratio of the adhesive component (S) and the azo dye (X) is 85:15 to 99.9:0.1 in mass ratio (adhesive component (S): azo dye (X)) The adhesive composition according to any one of [1] to [8].
[11] A semiconductor substrate;
a light-transmissive support substrate;
an adhesive layer provided between the semiconductor substrate and the support substrate;
A laminate used for peeling off the semiconductor substrate and the support substrate after the adhesive layer absorbs light irradiated from the support substrate side,
A laminate, wherein the adhesive layer is formed from the adhesive composition according to any one of [1] to [10].
[12] A first step of applying the adhesive composition according to any one of [1] to [10] to the surface of either the semiconductor substrate or the support substrate to form an adhesive coating layer; ,
The semiconductor substrate and the supporting substrate are combined via the adhesive coating layer, and the semiconductor substrate, the adhesive coating layer, and the supporting substrate are bonded together while performing at least one of heat treatment and reduced pressure treatment. a second step;
A method for producing a laminate comprising:
[13] A method for manufacturing a processed semiconductor substrate, comprising:
a third step in which the semiconductor substrate of the laminate according to [11] is processed;
a fourth step in which the semiconductor substrate processed in the third step and the support substrate are separated;
A method for manufacturing a processed semiconductor substrate, including:
[14] The method for manufacturing a processed semiconductor substrate according to [13], wherein the fourth step includes a step of irradiating the laminate according to [11] with a laser from the supporting 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.

According to the present invention, it is possible to provide an adhesive composition for light irradiation and peeling that can be obtained by a simple method.
Further, according to the present invention, there is provided a laminate having an adhesive layer formed of the adhesive composition for peeling by light irradiation, in which the semiconductor substrate and the support substrate in the laminate can be easily peeled off by light irradiation. It is possible to provide a laminate that can.
Furthermore, the present invention can provide a method for manufacturing the laminate and a method for manufacturing a processed semiconductor substrate using the laminate.

It is a schematic sectional view of an example of a layered product.

(Adhesive composition for light irradiation peeling)
The adhesive composition of the present invention is an adhesive composition for light irradiation and peeling 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 for processing semiconductor substrates.
The adhesive composition of the present invention includes an adhesive component (S) and an azo dye (X).
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 in order to adjust the viscosity of the adhesive composition. But that's fine.
The adhesive composition of the present invention can be obtained simply by mixing the adhesive component (S) and the azo dye (X). , it is possible to satisfactorily form an adhesive layer for light irradiation peeling that functions effectively both as an adhesive layer for temporary adhesion and as a laser peeling layer.

<Azo dye (X)>
The type of azo dye (X) according to the present invention is not particularly limited among dyes having an azo group as long as it does not impair the effects of the present invention, and can be appropriately selected depending on the purpose. For example, it is preferably a compound represented by either the following formula (AI) or the following formula (A-II).

In formula (AI), Ar ¹ and Ar ² each independently represent 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. represents a benzene ring or naphthalene ring which may be substituted with a group, R ^a represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents a benzene ring in which Ar ² is substituted or unsubstituted. , it represents an integer of 1 to 5, and when Ar ² is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7. 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, the plurality of R ^a may be different from each other.

In formula (A-II), Ar ³ to Ar ⁵ each independently represent 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. represents a benzene ring or naphthalene ring which may be substituted with a group, R ^b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and q represents a benzene ring in which Ar ⁵ is substituted or unsubstituted When Ar ⁵ is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 5. R ^b and Ar ⁵ may be bonded to each other to form a ring structure, and when q is an integer of 2 to 7, a plurality of R ^b may be different from each other, and a plurality of different R ^b may be mutually bonded to Ar ⁵ to form a ring structure.

Examples of the compound represented by the above formula (AI) include the following compound No. 1~No. 4 can be mentioned.

Further, as the compound represented by the above formula (A-II), for example, the following compound No. 5~No. I can list 7.

Among the compounds represented by the above formula (AI) and the above formula (A-II), they can be well dispersed in the adhesive component (S) regardless of the type of the adhesive component (S), and as a result, From the viewpoint of forming an adhesive layer in good condition and obtaining a laminate having excellent adhesion and releasability, it is preferable that R ^a and R ^b have an amino group. More specifically, R ^a and R ^b are preferably compounds selected from an amino group, an alkylamino group, and a dialkylamino group.

Among the compounds represented by the above formula (AI) and the above formula (A-II), the compound represented by the above formula (A-II) is particularly preferred, and more Specifically, a compound represented by the following formula (XI) (corresponding to the above-mentioned compound No. 5) is preferable.

<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, and various compounds used as adhesive components in this type of composition can be applied, and adhesive components Examples thereof include siloxane resins, styrene resins, acrylic resins, epoxy resins, amide resins, imide resins, phenol resins, and combinations thereof.
The adhesive component (S) may be a thermosetting adhesive component or a thermoplastic adhesive component.
Among these, in consideration of dispersibility, compatibility, etc. with the azo dye (X), siloxane-based resins or styrene-based resins are preferable.
The siloxane resin and styrene resin will be explained below.

<<Siloxane resin>>
In a preferred embodiment of the present invention, when the adhesive component (S) is a siloxane resin, the siloxane resin preferably contains a component (A) that is cured by a hydrosilylation reaction.
Furthermore, it is preferable that the component (A) that is cured by the hydrosilylation reaction contains a polyorganosiloxane component (A') that is cured by the hydrosilylation reaction.

In a more preferred embodiment of the present invention, the component (A) is, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, as an example of the component (A'). , a polyorganosiloxane (a2) having a Si—H group, and a platinum group metal catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

In another more preferred embodiment of the present invention, the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction has a siloxane unit (Q unit) represented by SiO ₂ , R ¹ R ² R ³ SiO _1/ A group consisting of siloxane units (M units) represented by ₂ , siloxane units (D units) represented by R ⁴ R ⁵ SiO _2/2 , and siloxane units (T units) represented by R ⁶ SiO _3/2 The polysiloxane (A1) contains one or more units selected from the following, and a platinum group metal catalyst (A2). The polysiloxane ( _A1 ) contains a siloxane unit (Q' unit), a ^siloxane unit (M' unit ⁾ represented by ^R1'R2'R3'SiO _1/2 , a siloxane unit (D' unit) represented by ^R4'R5'SiO2 _/2 ^, and Contains one or more units selected from the group consisting of siloxane units (T' units) represented by ^R6'SiO _3/2 , and a group consisting of M' units, D' units, and T' units. A polyorganosiloxane (a1') containing at least one selected from the group consisting of a siloxane unit (Q" unit) represented by SiO ₂ and a siloxane unit represented by R ¹ "R ² "R ³ "SiO _1/2 . (M” units), from the group consisting of siloxane units (D” units) represented by R ⁴ ”R ⁵ ”SiO _2/2 and siloxane units (T” units) represented by R ⁶ ”SiO _3/2 A polyorganosiloxane (a2') containing one or more selected units and at least one 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).

R ¹ to R ⁶ are groups or atoms bonded to a silicon atom, and each independently represents 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 hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

R ^{1 ′} to R ⁶ ′ are groups bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, but R ¹ ′ to 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 hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

R ¹ ” to R ⁶ ” are groups or atoms bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but at least one of R ¹ ” to R ⁶ ” One is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

The alkyl group may be linear, branched, or cyclic, but a linear or branched alkyl group is preferable, and the number of carbon atoms thereof is not particularly limited, but is usually 1 to 40. It is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less.

Specific examples of optionally 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. group, tertiary 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, 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, 1-ethyl-2 Examples include, but are not limited to, -methyl-n-propyl group, and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among these, methyl group is particularly preferred.

Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, and a 2-methyl-cyclopropyl group. 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 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, 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 Cycloalkyl groups such as -2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, Examples include, but are not limited to, bicycloalkyl groups such as bicyclodecyl groups, and the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

The alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more Preferably it is 10 or less.

Specific examples of linear or branched alkenyl groups that may be substituted include, but are not limited to, vinyl groups, allyl groups, butenyl groups, pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, more preferably 1 to 6. Among these, ethenyl group and 2-propenyl group are particularly preferred.
Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl, cyclohexenyl, etc., and the number of carbon atoms thereof is usually 4 to 14, preferably 5 to 10, More preferably 5 to 6.

As mentioned above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), but the alkenyl group contained in polyorganosiloxane (a1') and polyorganosiloxane (a2') ) and the hydrogen atoms (Si—H group) contained in the compound form a crosslinked structure through a hydrosilylation reaction using a platinum group metal catalyst (A2) and are cured. As a result, a cured film is formed.

The polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, as well as M' units, D' units, and It contains at least one type selected from the group consisting of T' units. As the polyorganosiloxane (a1'), a combination of two or more polyorganosiloxanes that satisfy such conditions may be used.

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

In addition, when the polyorganosiloxane (a1') contains two or more types of polyorganosiloxanes, a combination of (Q' unit and M' unit) and (D' unit and M' unit), (T' Combinations of (unit and M' unit) and (D' unit and M' unit), combinations of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, Not limited to these.

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

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

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

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

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

The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but each is usually 500 to 1,000,000, and the effects of the present invention can be achieved with good reproducibility. From the viewpoint of this, it is preferably 5,000 to 50,000.
In the present invention, the weight average molecular weight, number average molecular weight, and dispersion degree of the polyorganosiloxane (excluding the organosiloxane polymers mentioned above) are determined using, for example, a GPC device (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column ( Tosoh Corporation TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H) was used, the column temperature was 40°C, tetrahydrofuran was used as the eluent (elution solvent), the flow rate was 0.35mL/min, and the standard sample was It can be measured using polystyrene (Shodex, manufactured by Showa Denko K.K.).

The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but each is usually 10 to 1,000,000 (mPa s) and achieves the effects of the present invention with good reproducibility. From this point of view, it is preferably 50 to 200,000 (mPa·s). In addition, the viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured with an E-type rotational viscometer at 25°C.

The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other through a hydrosilylation reaction to form a cured film. Therefore, the mechanism of curing is different from that via, for example, silanol groups, and therefore it is not necessary for any siloxane to contain silanol groups or functional groups that form silanol groups by hydrolysis, such as alkyloxy groups. None.

In one preferred embodiment of the present invention, the adhesive component (S) contains a platinum group metal catalyst (A2) together with the polyorganosiloxane component (A').
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).

Specific examples of platinum-based metal catalysts include platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Examples include, but are not limited to, platinum-based catalysts.
Examples of complexes of platinum and olefins include, but are not limited to, complexes of 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 based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2). .

The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.
The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. and other alkynyl alcohols.
The amount of the polymerization inhibitor is not particularly limited, but it 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, and it is necessary to prevent the hydrosilylation reaction. The content is 10,000.0 ppm or less from the viewpoint of preventing excessive suppression of

<<Styrenic resin>>
In a preferred embodiment of the present invention, when the adhesive component (S) is a styrene resin, the styrenic resin is a thermoplastic elastomer (hereinafter also referred to as "polystyrene elastomer" in this specification) containing a styrene structure. ) is preferable. Elastomer refers to a polymer compound that exhibits elastic deformation.

The polystyrene elastomer is not particularly limited and can be appropriately selected depending on the purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butylene-styrene Examples include copolymers (SBBS) and hydrogenated products thereof, styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers, and the like.

The weight average molecular weight of the polystyrene elastomer is preferably from 2,000 to 200,000, more preferably from 10,000 to 200,000, even more preferably from 50,000 to 100,000. Within this range, the polystyrene elastomer has excellent solubility in a solvent, and coating properties are improved. In addition, even when removing the remaining adhesive layer after peeling the semiconductor substrate from the support substrate, there is an advantage that no residue is left on the processed substrate or carrier substrate because of its excellent solubility in solvents.

In the present invention, the polystyrene-based elastomer includes block copolymers, random copolymers, and graft copolymers, with block copolymers being preferred, and one or both ends being a block copolymer with styrene. is more preferable, and a block copolymer having styrene at both ends is particularly preferable. When a styrene block copolymer (a repeating unit derived from styrene) is used at both ends of the polystyrene elastomer, thermal stability tends to be further improved. This is because repeating units derived from styrene, which has high heat resistance, are present at the ends. In particular, it is preferable that the block portion of the repeating unit derived from styrene is a reactive polystyrene hard block, as this tends to have better heat resistance and chemical resistance. Moreover, if these are made into a block copolymer, it is thought that phase separation between hard blocks and soft blocks occurs at 200° C. or higher. It is thought that the shape of the phase separation contributes to suppressing the occurrence of unevenness 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.

In the present invention, the polystyrene elastomer is preferably a hydrogenated product. When the polystyrene elastomer is a hydrogenated product, thermal stability and storage stability are improved. Furthermore, the releasability and the cleaning removability of the adhesive layer after peeling are improved. Note that the term "hydrogenated product" means a polymer having a structure in which an elastomer is hydrogenated.

The 5% thermal mass loss temperature of the polystyrene elastomer when heated from 25°C at a rate of 20°C/min is preferably 250°C or higher, more preferably 300°C or higher, and 350°C or higher. is more preferable, and it is particularly preferable that the temperature is 400°C or higher. Further, the upper limit is not particularly limited, but is preferably, for example, 1000°C or less, more preferably 800°C or less. According to this aspect, it is easy to form an adhesive layer with excellent heat resistance.
Polystyrene elastomers can be deformed up to 200% with a small external force at room temperature (20°C), and can be deformed to 130% or less in a short time when the external force is removed, assuming the original size is 100%. It is preferable to have the property of returning.

The amount of unsaturated double bonds in the polystyrene elastomer is preferably less than 15 mmol/g, more preferably 7 mmol/g or less, and less than 5 mmol/g from the viewpoint of peelability after the heating step. More preferably, it is less than 0.5 mmol/g. The lower limit is not particularly determined, but may be, for example, 0.001 mmol/g or more.
Note that the amount of unsaturated double bonds mentioned here does not include unsaturated double bonds in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by nuclear magnetic resonance (NMR) measurement.

In addition, in this specification, the "styrene-derived repeating unit" is a styrene-derived structural unit contained in a polymer when styrene or a styrene derivative is polymerized, and may have a substituent. Examples of styrene derivatives include α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 2 to 5 carbon atoms, an acetoxy group, a carboxyl group, and the like.

Commercially available polystyrene elastomers include, for example, Tufprene A, Tufprene 125, Tufprene 126S, Solprene T, Asaprene T-411, Asaprene T-432, Asaprene T-437, Asaprene T-438, Asaprene T-439, and Tuftec H1272. , Tuftec P1500, Tuftec H1052, Tuftec H1062, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec P2000, Tuftec H1043 (product names, 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 (trade names, manufactured by Aron Kasei), Clayton D1111, Clayton D1113, Clayton D1114, Clayton D1117, Clayton D1119, 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, Cali Flex 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 D1 189, Clayton D1191, Clayton D1192, Clayton DX405, Clayton DX408, Clayton DX410, Clayton DX414, Clayton DX415, Clayton A1535, Clayton A1536, Clayton FG1901, Clayton FG1924, Clayton G1640, Clayton G1641, Clayton G1642, Clayton G1643, Clayton G1645 , Clayton G1633, Clayton G1650 , Kraton G1651, Kraton G1652, Kraton G1654, Kraton G1657, Kraton G1660, Kraton G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 (all product names, manufactured by Kraton), TR2000, TR2001, TR2003, TR2250, TR2500, TR2601, TR2630, TR2787, TR2827, TR1086, TR1600, SIS5002, SIS5200, SIS5250, SIS5405, SIS5505, Dynaron 6 100P, Dynaron 4600P, Dynaron 6200P, Dynaron 4630P, Dynaron 8601P, Dynaron 8630P, Dynalon 8600P, Dynalon 8903P, Dynalon 6201B, Dynalon 1321P, Dynalon 1320P, Dynalon 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 (all product names, manufactured by Sumitomo Chemical Co., Ltd.), Lavalon series (all above) , product name, manufactured by Mitsubishi Chemical Corporation), Septon 1001, Septon 8004, Septon 4033, Septon 2104, Septon 8007, Septon 2007, 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, Hyblar 5125 (product name, manufactured by Kuraray) ), Sumiflex (trade name, manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (trade name, manufactured by Riken Vinyl Industries, Ltd.), and the like.

An example of the adhesive composition of the present invention can contain the adhesive component (S) and the azo dye (X) in any ratio, but considering the balance between adhesiveness and releasability, the adhesive component The ratio of (S) to azo dye (X) is preferably 85:15 to 99.9:0.1, and 90:10 to 99. 5:0.5 is more preferable, and 95:5 to 99:1 is even more preferable.

<Other ingredients>
The adhesive composition of the present invention may contain a solvent for purposes such as adjusting viscosity and for satisfactorily dissolving film constituents.

Specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, and the like.
More specifically, the solvent includes hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl Examples include, but are not limited to, ketone, 2-octanone, 2-nonanone, 5-nonanone, and the like.
Also, 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 ether Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, Also included are ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and the like.
Such solvents can be used alone or in combination of two or more.

In certain embodiments of the present invention, there are aspects of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition that provides a highly uniform film with good reproducibility. For this reason, it is preferable that the adhesive composition contains a glycol solvent. The term "glycol solvent" as used herein is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

In the adhesive composition, a preferable combination of the adhesive component (S) and the solvent used is, for example, when a silicone resin is used as the adhesive component (S), propylene glycol monomethyl ether acetate ( PGMEA) is more preferably used, and when a styrene resin is used as the adhesive component (S), it is more preferable to use mesitylene as the solvent.

When the adhesive composition of the present invention contains a solvent, the content thereof is determined as appropriate in consideration of the viscosity of the desired composition, the coating method employed, the thickness of the film to be produced, etc. The amount ranges from about 10 to 90% by mass based on the entire product.

The viscosity of the adhesive composition of the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, preferably 1,000 to 6,000 mPa·s at 25°C. The viscosity of the adhesive composition of the present invention can be adjusted by changing the types of solvents used, their ratios, the concentrations of film constituents, etc., taking into consideration various factors such as the application method used and the desired film thickness. be.
In the present invention, the membrane constituent component means a component other than the solvent contained in the composition.

<Method for manufacturing adhesive composition>
As a preferred embodiment of the method for producing an adhesive composition, for example, the adhesive composition of the present invention is produced by mixing the adhesive component (S), the azo dye (X), and, if used, a solvent. can.
The mixing order is not particularly limited, but as an example of a method that can easily and reproducibly produce the adhesive composition of the present invention, for example, the adhesive component (S) and the azo dye (X) are mixed together. Examples include a method of dissolving the adhesive component (S) and azo dye (X) in a solvent, a method of dissolving a part of the adhesive component (S) and the azo dye (X), dissolving the remainder in the solvent, and mixing the resulting solution. Not limited. In addition, when preparing the adhesive composition, heating may be carried out as appropriate within a range where the components do not decompose or change in quality.
In the present invention, in order to remove foreign substances, the adhesive composition may be filtered using a filter or the like during the production of the adhesive composition or after all the components are mixed.

(laminate)
The laminate of the present invention includes a semiconductor substrate, a support substrate, and an adhesive layer for light irradiation and peeling.
The support substrate has optical transparency.
The adhesive layer for light irradiation and peeling is provided between the semiconductor substrate and the support substrate.
The laminate is used when the semiconductor substrate and the support substrate are peeled off 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 above-described adhesive composition for light irradiation peeling of the present invention.

The laminate of the present invention is used for temporary bonding for processing semiconductor substrates, and can be suitably used for processing such as thinning of semiconductor substrates.
While the semiconductor substrate is undergoing processing such as thinning, the semiconductor substrate is supported by the support substrate via the adhesive layer. On the other hand, after processing the semiconductor substrate, the adhesive layer is irradiated with light, and then the support substrate and the semiconductor substrate are separated.
The adhesive layer according to the present invention allows the semiconductor substrate and the support substrate to be easily peeled off after being irradiated with light. Further, residues of the adhesive layer remaining on the semiconductor substrate or the support substrate after the semiconductor substrate and the support substrate are separated can be easily removed with a cleaning composition for cleaning the semiconductor substrate.

The wavelength of the light used for peeling is, for example, preferably 250 to 600 nm, more preferably 250 to 370 nm. More preferred wavelengths are 308nm, 343nm, 355nm, 365nm, or 532nm. The amount of light irradiation required for exfoliation is the amount of irradiation that can cause a suitable alteration, such as decomposition, of the particular 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.

<Semiconductor substrate>
The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, and examples thereof include silicon, silicon carbide, and compound semiconductors.
Although the shape of the semiconductor substrate is not particularly limited, it is, for example, disc-shaped. Note that the surface of a disk-shaped semiconductor substrate does not need to have a completely circular shape; for example, the outer periphery of the semiconductor substrate may have a straight part called an orientation flat, or a straight part called a notch. It may have a notch.
The thickness of the disk-shaped semiconductor substrate may be determined as appropriate depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1,000 μm, although it is not particularly limited.
The diameter of the disk-shaped semiconductor substrate may be determined as appropriate depending on the intended use of the semiconductor substrate, and is, for example, 100 to 1,000 mm, although it is not particularly limited.

The semiconductor substrate may have bumps. A bump is a protruding terminal.
In the stacked body, when the semiconductor substrate has bumps, the semiconductor substrate has the bumps on the support substrate side.
In a semiconductor substrate, bumps are usually formed on a surface on which a circuit is formed. The circuit may be single layer or multilayer. The shape of the circuit is not particularly limited.
In a semiconductor substrate, a surface (back surface) opposite to a surface having bumps is a surface to be processed.
The material, size, shape, structure, and density of the bumps included in the semiconductor substrate are not particularly limited.
Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps.
Usually, 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.
Examples of the material for the bumps include low melting point solder, high melting point solder, tin, indium, gold, silver, and copper. The bump may be composed of only a single component, or may be composed of a plurality of components. More specifically, examples include Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps.
Further, the bump may have a laminated structure including a metal layer made of at least one of these components.

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

<Support board>
The support substrate is not particularly limited as long as it is a member that is transparent to the light irradiated to the adhesive layer and can support the semiconductor substrate when the semiconductor substrate is processed, but for example, it may be made of glass. Examples include a support substrate.

The shape of the support substrate is not particularly limited, but may be, for example, disc-shaped.
The thickness of the disk-shaped support substrate may be determined as appropriate depending on the size of the semiconductor substrate, and is, for example, 500 to 1,000 μm, although it is not particularly limited.
The diameter of the disc-shaped support substrate may be determined as appropriate depending on the size of the semiconductor substrate, and is, for example, 100 to 1,000 mm, although it is not particularly limited.

An example of the support substrate is a glass wafer with a diameter of about 300 mm and a thickness of about 700 μmm.

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

The adhesive layer is formed using the above-mentioned adhesive composition for light irradiation peeling of the present invention.
The adhesive composition of the present invention can be suitably used to form an 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. I can do it. The laminate is used when the semiconductor substrate and the support substrate are peeled off after the adhesive layer absorbs light irradiated from the support substrate side.
One of the characteristics of the adhesive layer obtained from the adhesive composition of the present invention is that after light irradiation, the residue of the adhesive layer remaining on the semiconductor substrate or the supporting substrate after the semiconductor substrate and the supporting substrate are peeled off is removed by the cleaning agent. It can be suitably removed by the composition.

The thickness of the adhesive layer is not particularly limited, but is usually 5 to 500 μm, and 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 a thick film, the thickness 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 the adhesive layer from the adhesive composition will be described in detail in the <Method for manufacturing laminate> section below.

The laminate of the present invention is suitably manufactured, for example, by the following method for manufacturing a laminate of the present invention.

An example of a laminate will be described below with reference to figures.
FIG. 1 is a schematic cross-sectional view of an example of a laminate.
The laminate shown in FIG. 1 includes a semiconductor substrate 1, an adhesive layer 2, and a support substrate 3 in this order.
Adhesive layer 2 is provided between semiconductor substrate 1 and support substrate 3 . Adhesive layer 2 is in contact with semiconductor substrate 1 and support substrate 3 .

<Method for manufacturing laminate>
For example, the laminate of the present invention may include 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 bonding the semiconductor substrate, the adhesive coating layer, and the supporting substrate together by bonding the semiconductor substrate and the supporting substrate via the adhesive coating layer, and performing at least one of heat treatment and reduced pressure treatment. It can be manufactured by a method including.
A more detailed description of the second step includes the steps of the embodiment (i) below or the embodiment (ii) below.
(i) When the adhesive composition is applied to the surface of the semiconductor substrate, the adhesive coating layer of the semiconductor substrate and the supporting substrate are heated and reduced while performing at least one of heat treatment and reduced pressure treatment. Then, a load is applied in the thickness direction of the support substrate to bring them into close contact with each other, and then a post-heating treatment is performed to form a laminate.
(ii) When 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 heated while performing at least one of heat treatment and reduced pressure treatment. Then, a load is applied in the thickness direction of the support substrate to bring them into close contact with each other, and then a post-heating treatment is performed to form a laminate.

The coating method is not particularly limited, but is usually a spin coating method. Note that a method may be adopted in which a coating film is separately formed by a spin coating method or the like, and a sheet-like coating film is attached as an adhesive coating layer.

The heating temperature of the applied adhesive composition depends on the type and amount of the adhesive component 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. Although it cannot be specified unconditionally because it varies, it is usually 80 to 150°C and the heating time is usually 30 seconds to 5 minutes.
When the adhesive composition contains a solvent, the applied adhesive composition is usually heated.

Heating can be performed using a hot plate, oven, or the like.

The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is usually about 5 to 500 μm, and the final thickness of the adhesive layer is within the above-mentioned range. shall be determined as appropriate.

In the present invention, a semiconductor substrate and a support substrate are brought together so as to be in contact with an adhesive layer, and a load is applied in the thickness direction of the semiconductor substrate and support substrate while performing heat treatment, depressurization treatment, or both. The laminate of the present invention can be obtained by bringing the layers into close contact and then performing a post-heat treatment. Note that whether to use heat treatment, reduced pressure treatment, or a combination of both depends on the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the film obtained from both compositions, and the film thickness. , is determined as appropriate after taking into consideration various circumstances such as the required adhesive strength.

The heat treatment is usually carried out at a temperature of 20 to 150°C from the viewpoint of removing the solvent when the composition contains a solvent, and from the viewpoint of softening the adhesive coating layer to achieve suitable bonding with the release agent coating layer. It is determined as appropriate from the range of . In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component (S), the heating temperature is preferably 130°C or lower, more preferably 90°C or lower, and the heating time is determined by the heating temperature and the temperature of the adhesive. Although it is determined as appropriate depending on the type, from the viewpoint of ensuring proper adhesion, the time is usually 30 seconds or more, preferably 1 minute or more, but it is recommended to avoid deterioration of the adhesive layer and other parts. From the viewpoint of suppression, the time is usually 10 minutes or less, preferably 5 minutes or less.

The reduced pressure treatment may be performed by exposing the adhesive coating layer to an atmospheric pressure of 10 to 10,000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

The load in the thickness direction of the semiconductor substrate and the supporting substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the supporting substrate and the two layers between them, and can firmly adhere them. , usually within the range of 10 to 1000N.

The temperature of the post-heating 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 realizing suitable bonding of the substrates and layers that constitute the laminate, to suppress or avoid adverse effects on each layer due to excessive heating. From the viewpoint of this, it is usually 180 minutes or less, preferably 120 minutes or less.
Heating can be performed using a hot plate, oven, or the like. When performing post-heating using a hot plate, heating may be performed with either the semiconductor substrate or the supporting substrate of the laminate facing down, but from the viewpoint of realizing suitable peeling with good reproducibility, it is preferable to heat with the semiconductor substrate facing down. Post-heating is preferred.
Note that one purpose of the post-heat treatment is to realize an adhesive layer that is a more suitable self-supporting film, and in particular, to appropriately realize curing by a hydrosilylation reaction.

(Method for manufacturing processed semiconductor substrate)
The method for manufacturing a processed semiconductor substrate of the present invention includes a third step and a fourth step.
The method for manufacturing a processed semiconductor substrate of the present invention may further include a fifth step.
The third step is a step in which the semiconductor substrate of the laminate of the present invention is processed.
The fourth step is a step in which the semiconductor substrate processed in the third step and the support substrate are separated.
The fifth step is a step in which at least one of the separated semiconductor substrate and support substrate is cleaned with a cleaning composition.

The processing performed on the semiconductor substrate in the third step is, for example, processing on the opposite side of the wafer from the circuit surface, and includes thinning the wafer by polishing the back surface of the wafer. Thereafter, through-silicon vias (TSV) and the like are formed, and then the thinned wafer is peeled off from the support substrate to form a stack of wafers and three-dimensionally packaged. Also, before and after this, the formation of wafer backside electrodes and the like is also performed. In thinning the wafer and in the TSV process, heat of about 250 to 350° C. is applied while the wafer is bonded to a support substrate. The laminate of the present invention usually includes an adhesive layer and has heat resistance against the load.
Note that the processing is not limited to those described above, and includes, for example, implementation of a mounting process for semiconductor components in the case of temporary bonding with a support substrate to support a base material for mounting semiconductor components.

In the fourth step, the method for separating (peeling) the semiconductor substrate and the supporting substrate includes irradiating the adhesive layer with light, mechanically peeling it off using a piece of equipment with a sharp part, and separating the supporting substrate and the wafer. Examples include, but are not limited to, peeling off and the like.
By irradiating the adhesive layer with light from the support substrate side, the adhesive layer is altered as described above (e.g., separation or decomposition of the adhesive layer), and then, for example, one of the substrates is pulled up. Therefore, the semiconductor substrate and the support substrate can be easily separated.

The adhesive layer does not necessarily need to be irradiated with light over the entire area of the adhesive layer. Even if there are areas irradiated with light and areas that are not irradiated, if the peelability of the adhesive layer as a whole is sufficiently improved, the semiconductor substrate can be separated by a slight external force such as pulling up the support substrate. Support substrate can be separated. The ratio and positional relationship between the areas irradiated with light and the areas not irradiated will depend on the type of adhesive used, its specific composition, the thickness of the adhesive layer, the intensity of the irradiated light, etc. Although the conditions are different, those skilled in the art can set the conditions as appropriate without requiring excessive testing. Due to these circumstances, according to the method for manufacturing a processed semiconductor substrate of the present invention, for example, when the supporting substrate of the laminate used has optical transparency, when peeling is performed by light irradiation from the supporting substrate side, As a result, it is possible to shorten the light irradiation time, and as a result, not only can it be expected to improve throughput, but also the semiconductor substrate and supporting substrate can be bonded together by light irradiation alone, avoiding physical stress for peeling. Can be separated easily and efficiently.
Usually, the amount of light irradiation for peeling is 50 to 3,000 mJ/cm ² . The irradiation time is appropriately determined depending on the wavelength and the irradiation amount.

As mentioned above, the wavelength of the light used for peeling is preferably, for example, 250 to 600 nm, more preferably 250 to 370 nm. More preferred wavelengths are 308nm, 343nm, 355nm, 365nm, or 532nm. The amount of light irradiation required for exfoliation is the amount of irradiation that can cause a suitable alteration, such as decomposition, of the particular 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.

In the fifth step, the surface of at least one of the separated semiconductor substrate and the support substrate was cleaned by spraying a cleaning composition or by immersing the separated semiconductor substrate or the support substrate in the cleaning composition. After that, rinsing with a solvent and drying are usually performed. In addition, examples of cleaning compositions include the following.

<Cleaning composition>
After light irradiation, the residue of the adhesive layer remaining on the semiconductor substrate or the support substrate after the semiconductor substrate and the support substrate are peeled off can be suitably removed by a cleaning composition, and such a cleaning composition , usually containing a solvent.

Examples of the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, 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 having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, etc. Derivatives of polyhydric alcohols include, for example, the above-mentioned polyhydric alcohols or Examples of the above compounds having an ester bond include monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether, or compounds having an ether bond such as monophenyl ether. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.
Examples of the cyclic ethers include dioxane.
Examples of the 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, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene. Examples include.
These can be used alone or in combination of two or more.
Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

A mixed solvent of PGMEA and a polar solvent is also preferred. The blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility between PGMEA and the polar solvent, but is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. It is preferable to keep it within this range.
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. Further, 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: It is 3. In addition, 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.

The cleaning composition may or may not contain salt.

An example of a case where the cleaning composition contains a salt is a cleaning composition containing a quaternary ammonium salt and a solvent.
The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for this type of use.
Such quaternary ammonium cations typically include tetra(hydrocarbon) ammonium cations. On the other hand, anions that form a pair with it include hydroxide ion (OH ^- ); halogen ions such as fluorine ion (F ^- ), chloride ion (Cl ^- ), bromine ion (Br ^- ), and iodine ion (I ^- ). ; tetrafluoroborate ion (BF ₄ ⁻ ); hexafluorophosphate ion (PF ₆ ⁻ ), and the like, but are not limited to these.

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.

In one preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon) ammonium fluoride.
Specific examples of hydrocarbon groups in tetra(hydrocarbon) ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. Examples include aryl groups.
In a more preferred embodiment, the tetra(hydrocarbon) ammonium fluoride comprises tetraalkylammonium fluoride.
Specific examples of tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride). Not limited. Among them, tetrabutylammonium fluoride is preferred.

A hydrate of the quaternary ammonium salt such as tetra(hydrocarbon) ammonium fluoride may be used. Further, quaternary ammonium salts such as tetra(hydrocarbon) ammonium fluoride may be used alone or in combination of two or more.
The amount of the quaternary ammonium salt is not particularly limited as long as it is dissolved in the solvent contained in the cleaning composition, but is usually 0.1 to 30% by mass based on the cleaning composition.

When the cleaning 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. From the viewpoint of obtaining a detergent composition with excellent detergency with good reproducibility, and from the viewpoint of obtaining a detergent composition with excellent uniformity by dissolving salts such as quaternary ammonium salts, it is preferable to use the cleaning method. The agent composition contains one or more amide solvents.

A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. 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 specifically includes a methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, n-butyl group, and isobutyl group. , s-butyl group, t-butyl group, cyclobutyl group, etc. Among these, R ^A and R ^B are preferably a methyl group or an ethyl group, both are more preferably a methyl group or an ethyl group, and both are even more preferably a methyl group.

The acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N, Examples include N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, and the like. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

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

Another example of a preferable amide solvent is a lactam compound represented by formula (Y).

In formula (Y), R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, etc. Specific examples of alkylene groups having 1 to 6 carbon atoms include methylene group , ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc., but are not limited thereto.

Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which may be used singly or in combination. More than one species can be used in combination.

In a preferred embodiment of the present invention, the lactam compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), and in a more preferred embodiment, N-methyl pyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, N-methylpyrrolidone (NMP).

Note that the cleaning composition used in the present invention may contain water as a solvent, but from the viewpoint of avoiding corrosion of the substrate, etc., usually only an organic solvent is intentionally used as the solvent. In this case, it is not denied that the hydration water of the salt or the trace amount of water contained in the organic solvent may be included in the cleaning composition. The water content of the cleaning composition used in the present invention is usually 5% by mass or less.

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 with the cleaning agent composition, but the processed semiconductor substrate manufactured through the fifth step is cleaned using a removal tape or the like. This does not preclude further cleaning of the surface of the processed semiconductor substrate, and if necessary, the surface may be further cleaned using a removal tape or the like.

The components and methodological elements related to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be modified in various ways without departing from the gist of the present invention.
The method for manufacturing a processed semiconductor substrate of the present invention may include steps other than those described above.

In the peeling process according to the present invention, when the semiconductor substrate or support substrate of the laminate of the present invention has light transmittance, the adhesive layer is irradiated with light from the semiconductor substrate side or the support substrate side. It separates the semiconductor substrate and the support substrate.
In the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded to each other by the adhesive layer in a suitable removable manner. By irradiating the adhesive layer with light from the side, the semiconductor substrate and the support substrate can be easily separated. Usually, peeling is performed after processing is performed on the semiconductor substrate of the stack.

EXAMPLES 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 equipment used is as follows.

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

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

[1] Preparation of adhesive composition [Preparation Example 1-1]
In a 600 mL stirring container exclusively for an autorotation-revolution mixer, as the above-mentioned component (a1), 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 were added. 150 g of base polymer (manufactured by Wacker Chemi), 15.81 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi) with a viscosity of 100 mPa·s as the above-mentioned component (a2), 1-ethynyl- as the above-mentioned component (A3) 0.17 g of 1-cyclohexanol (manufactured by Wacker Chemi) was added and stirred for 5 minutes using stirrer A to obtain a mixture (I).
In a 50 mL screw tube, 0.33 g of platinum catalyst (manufactured by Wacker Chemi Co., Ltd.) was added as the above-mentioned component (A2), and a vinyl group-containing straightener with a viscosity of 1000 mPa·s expressed by the above formula (W) was added as the above-mentioned component (a1). 9.98 g of linear polydimethylsiloxane (manufactured by Wacker Chemi) (hereinafter referred to as vinyl group-containing linear polydimethylsiloxane v3) was stirred for 5 minutes using stirrer A to obtain a mixture (II).
0.52 g of the obtained mixture (II) was added to mixture (I) and stirred for 5 minutes using stirrer A to obtain mixture (III).
The mixture (III) finally obtained was filtered through a 300 mesh nylon filter to obtain an adhesive composition. The viscosity of the adhesive composition measured using a rotational viscometer was 9900 mPa·s.

[Preparation example 1-2]
20.10 g of the adhesive composition obtained in Preparation Example 1-1 was placed in a 100 mL stirring container exclusively for a rotation-revolution mixer, and 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) 0 .02 g, 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 above formula (X-I) as an azo dye, and stirrer A. The mixture was stirred for 10 minutes to obtain a mixture (I). The obtained mixture (I) was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[Preparation example 1-3]
In a 100 mL stirring vessel dedicated to the rotation-revolution mixer, 10.05 g of thermoplastic resin Septon 4033 (manufactured by Kuraray Co., Ltd.), which is a hydrogenated styrene-isoprene-butadiene copolymer, and Sudan Black B (Tokyo Kasei Kogyo Co., Ltd.) as an azo dye were placed Co., Ltd.) and 30.06 g of mesitylene were added and stirred for 10 minutes using stirrer A, and the resulting mixture was used as an adhesive composition.

[2] Adhesiveness test [2-1] Preparation of laminate [Example 2-1]
The adhesive composition obtained in Preparation Example 1-2 was applied to a 300 mm silicon wafer (thickness: 775 μm) as a device side wafer (semiconductor substrate) by spin coating, and heated at 120°C for 1.5 minutes ( An adhesive coating layer was formed on the circuit surface of the silicon wafer by pre-heating treatment so that the final thickness of the adhesive layer in the laminate was about 40 μm.
Thereafter, in a vacuum bonding device, the semiconductor substrate and a 300 mm glass wafer (thickness: 700 μm) as a supporting substrate were bonded together with the adhesive coating layer sandwiched between them, and heated to 200° C. with the semiconductor substrate side down on a hot plate. A laminate was produced by heating for 10 minutes (post-heat treatment). Note that the bonding was performed at a temperature of 23° C., a degree of vacuum of 1,000 Pa, and a load of 30 N. The finally obtained laminate was cut into 4 cm square pieces using a dicing device.

[Example 2-2]
The adhesive composition obtained in Preparation Example 1-3 was applied to a 300 mm silicon wafer (thickness: 775 μm) as a device side wafer (semiconductor substrate) by spin coating, and heated at 120°C for 1.5 minutes ( An adhesive coating layer was formed on the circuit surface of the silicon wafer by pre-heating treatment so that the final thickness of the adhesive layer in the laminate was about 40 μm.
Thereafter, in a vacuum bonding device, the semiconductor substrate and a 300 mm glass wafer (thickness: 700 μm) as a supporting substrate were bonded together with the adhesive coating layer sandwiched between them, and heated to 200° C. with the semiconductor substrate side down on a hot plate. A laminate was produced by heating for 10 minutes (post-heat treatment). Note that the bonding was performed at a temperature of 90° C., a degree of vacuum of 1,000 Pa, and a load of 500 N.
The finally obtained laminate was cut into 4 cm square pieces using a dicing device.

[Comparative example 1]
The adhesive composition obtained in Preparation Example 1-1 was applied to a 300 mm silicon wafer (thickness: 775 μm) as a device side wafer (semiconductor substrate) by spin coating, and heated at 120°C for 1.5 minutes ( An adhesive coating layer was formed on the circuit surface of the silicon wafer by pre-heating treatment so that the final thickness of the adhesive layer in the laminate was about 40 μm.
Thereafter, in a vacuum bonding device, the semiconductor substrate and a 300 mm glass wafer (thickness: 700 μm) as a supporting substrate were bonded together with the adhesive coating layer sandwiched between them, and heated to 200° C. with the semiconductor substrate side down on a hot plate. A laminate was produced by heating for 10 minutes (post-heat treatment). Note that the bonding was performed at a temperature of 23° C., a degree of vacuum of 1,000 Pa, and a load of 30 N. The finally obtained laminate was cut into 4 cm square pieces using a dicing device.

[2-2] Evaluation of Adhesiveness Evaluation of adhesiveness was performed by visually checking the presence or absence of voids from the glass wafer (support) side of the laminate.
It was evaluated as good if no voids were observed, and bad if any voids were observed.
As a result, no voids were observed in the laminates obtained in Examples 2-1, 2-2, and Comparative Example 1.

[3] Evaluation of laser peelability Using a laser irradiation device, the release layer was irradiated with a laser beam of 308 nm wavelength at 300 mJ/cm ² from the glass wafer side of the fixed laminate. Then, by manually lifting the support substrate, it was confirmed whether or not it could be peeled off. As a result, each of the laminates obtained in Examples 2-1 and 2-2 could be peeled off without any load by lifting the support substrate, but in Preparation Example 1-1, in which no azo dye was added. The laminate of Comparative Example 1 produced using the above-described method could not be peeled off even when force was applied.

1 Semiconductor substrate 2 Adhesive layer 3 Support substrate

Claims (15)

An adhesive composition for light irradiation and peeling that is removable by light irradiation and includes an adhesive component (S) and an azo dye (X). The adhesive composition according to claim 1, wherein the azo dye (X) is a compound represented by either the following formula (AI) or the following formula (A-II).
(In formula (AI), Ar ¹ and Ar ² are each independently 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 Represents a benzene ring or naphthalene ring which may be substituted with a vinyl group, R ^a represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents a benzene ring in which Ar ² is substituted or unsubstituted. When it is a ring, it represents an integer from 1 to 5, and when Ar ² is a substituted or unsubstituted naphthalene ring, it represents an integer from 1 to 7. R ^a and Ar ² are bonded to each other to form a ring. structure, and when p is an integer from 2 to 7, multiple ^Ras may be different from each other.)

(In formula (A-II), Ar ³ to Ar ⁵ are each independently 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 Represents a benzene ring or naphthalene ring which may be substituted with a vinyl group, R ^b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and q represents benzene in which Ar ⁵ is substituted or unsubstituted. When it is a ring, it represents an integer from 1 to 5, and when Ar ⁵ is a substituted or unsubstituted naphthalene ring, it represents an integer from 1 to 7. R ^b and Ar ⁵ are bonded to each other to form a ring. structure, and when q is an integer from 2 to 7, a plurality of R ^b 's may be different from each other, and a plurality of R ^b 's, which may be different, are mutually bonded to Ar ⁵ . (May form a ring structure.) The adhesive composition according to claim 1 or 2, wherein the adhesive component (S) is a siloxane resin or a styrene resin. The adhesive composition according to claim 3, wherein the siloxane resin contains a component that is cured by a hydrosilylation reaction. The adhesive composition according to claim 4, wherein the component that is cured by a hydrosilylation reaction contains a polyorganosiloxane component that is cured by a hydrosilylation reaction. A polyorganosiloxane component that hardens through a hydrosilylation reaction,
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,
A platinum group metal catalyst (A2),
The adhesive composition according to claim 5, comprising: The adhesive composition according to claim 3, wherein the styrene resin is a polystyrene elastomer. Any one of claims 2 to 7, wherein R ^a and R ^b in the formula (AI) and the formula (A-II) are selected from an amino group, an alkylamino group, and a dialkylamino group. The adhesive composition described in . The adhesive composition according to claim 8, wherein the azo dye (X) is a compound represented by the following formula (X-I).
The mixing ratio of the adhesive component (S) and the azo dye (X) is 85:15 to 99.9:0.1 in terms of mass ratio (adhesive component (S): azo dye (X)). The adhesive composition according to any one of claims 1 to 8. a semiconductor substrate;
a light-transmissive support substrate;
an adhesive layer provided between the semiconductor substrate and the support substrate;
A laminate used for peeling off the semiconductor substrate and the support substrate after the adhesive layer absorbs light irradiated from the support substrate side,
A laminate, wherein the adhesive layer is formed from the adhesive composition according to any one of claims 1 to 10. A first step of coating the adhesive composition according to any one of claims 1 to 10 on the surface of either the semiconductor substrate or the supporting substrate to form an adhesive coating layer;
The semiconductor substrate and the supporting substrate are combined via the adhesive coating layer, and the semiconductor substrate, the adhesive coating layer, and the supporting substrate are bonded together while performing at least one of heat treatment and reduced pressure treatment. a second step;
A method for manufacturing a laminate including: A method for manufacturing a processed semiconductor substrate, the method comprising:
a third step in which the semiconductor substrate of the laminate according to claim 11 is processed;
a fourth step in which the semiconductor substrate processed in the third step and the support substrate are separated;
A method for manufacturing a processed semiconductor substrate, including: 14. The method for manufacturing a processed semiconductor substrate according to claim 13, wherein the fourth step includes a step of irradiating the laminate according to claim 11 with a laser from the support substrate side. The method for manufacturing a processed semiconductor substrate according to claim 14, wherein the wavelength of the laser is 250 nm to 600 nm.