Adhesive composition, laminate, and method for manufacturing processed semiconductor substrate

Abstract

The present invention provides an adhesive composition and the like capable of forming an adhesive layer excellent in peelability.　The adhesive composition, which is for forming an adhesive layer used for temporarily bonding a semiconductor substrate or an electronic device layer and a support substrate, contains an adhesive component and a (meth)acrylic acid ester-based polymer having a repeating unit represented by formula (1).

Description

Adhesive composition, laminate, and method for producing processed semiconductor substrate

[0001] The present invention relates to adhesive compositions, laminates, and methods for producing processed semiconductor substrates.

[0002] Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but for the purpose of further integration, semiconductor integration technology is required that integrates (stacks) the plane in a three-dimensional plane as well. This three-dimensional stacking is a technology that integrates multiple layers while connecting them using through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the backside), and the thinned semiconductor wafers are stacked.

[0003] Semiconductor wafers (herein simply referred to as wafers) before thinning are bonded to a support in preparation for polishing with a polishing device. This bond must be easily peeled off after polishing, and is therefore called a temporary bond. This temporary bond must be easily removed from the support; applying a large force to remove it can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this from happening. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during polishing of the backside of the semiconductor wafer. Therefore, the performance required of the temporary bond is to withstand the stress during polishing and be easily removed after polishing.

[0004] As temporary adhesives used for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed.

[0005] International Publication No. 2017 / 221772 Pamphlet International Publication No. 2018 / 216732 Pamphlet

[0006] There is a constant demand for adhesive compositions that can further improve the performance required for the temporary adhesion.The present invention aims to provide an adhesive composition that can form an adhesive layer with excellent releasability, a laminate using the adhesive composition, and a method for producing a processed semiconductor substrate or electronic device layer using the laminate.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0008] That is, the present invention includes the following: [1] An adhesive composition for forming an adhesive layer used for temporarily bonding a semiconductor substrate or an electronic device layer to a support substrate, the adhesive composition containing an adhesive component and a (meth)acrylic acid ester-based polymer having a repeating unit represented by the following formula (1): (In formula (1), R １ represents a hydrogen atom or a methyl group, R ２represents an alkyl group having 1 to 20 carbon atoms.) [2] The adhesive composition according to [1], wherein the alkyl group having 1 to 20 carbon atoms is a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. [3] The adhesive composition according to [1] or [2], wherein the content of the (meth)acrylic acid ester-based polymer in the adhesive composition is 0.01% by mass to 30% by mass, based on the non-volatile content of the adhesive composition. [4] The adhesive composition according to any one of [1] to [3], wherein the adhesive component is a component that cures by a hydrosilylation reaction. [5] The adhesive composition according to [4], wherein the component that cures by a hydrosilylation reaction contains: a component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom; a component (A-2) having a Si—H group; and a platinum group metal-based catalyst (A-3). [6] The adhesive composition according to [5], wherein the component (A-1) contains a polyorganosiloxane (a1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms. [7] The adhesive composition according to [5] or [6], wherein the component (A-2) contains a polyorganosiloxane having a Si—H group. [8] A laminate comprising: a semiconductor substrate or an electronic device layer; a light-transmitting support substrate; and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, wherein the adhesive layer is an adhesive layer formed from the adhesive composition according to any one of [1] to [7]. [9] A method for producing a processed semiconductor substrate or electronic device layer, comprising: a step 5A in which the semiconductor substrate of the laminate described in [8] is processed, or a step 5B in which the electronic device layer of the laminate described in [8] is processed; and a step 6A in which the semiconductor substrate processed in the step 5A is separated from the support substrate, or a step 6B in which the electronic device layer processed in the step 5B is separated from the support substrate.

[0009] According to the present invention, it is possible to provide an adhesive composition capable of forming an adhesive layer with excellent peelability, a laminate using the adhesive composition, and a method for producing a processed semiconductor substrate or electronic device layer using the laminate.

[0010] FIG. 1 is a schematic cross-sectional view of an example of a laminate in the first embodiment. FIG. 2 is a schematic cross-sectional view of another example of a laminate in the first embodiment. FIG. 3A is a schematic cross-sectional view (part 1) for explaining a method for manufacturing a laminate showing an example of the first embodiment. FIG. 3B is a schematic cross-sectional view (part 2) for explaining a method for manufacturing a laminate showing an example of the first embodiment. FIG. 4 is a schematic cross-sectional view of an example of a laminate in the second embodiment. FIG. 5 is a schematic cross-sectional view of another example of a laminate in the second embodiment. FIG. 6A is a schematic cross-sectional view (part 1) for explaining a method for manufacturing a laminate showing an example of the second embodiment. FIG. 6B is a schematic cross-sectional view (part 2) for explaining a method for manufacturing a laminate showing an example of the second embodiment. FIG. 6C is a schematic cross-sectional view (part 3) for explaining a method for manufacturing a laminate showing an example of the second embodiment. FIG. 7A is a schematic cross-sectional view (part 1) for explaining a method for processing a laminate showing an example of the first embodiment. FIG. 7B is a schematic cross-sectional view (part 2) for explaining a method for processing a laminate showing an example of the first embodiment. 7C is a schematic cross-sectional view (part 3) illustrating a method for processing a laminate showing an example of the first embodiment. FIG. 7D is a schematic cross-sectional view (part 4) illustrating a method for processing a laminate showing an example of the first embodiment. FIG. 8A is a schematic cross-sectional view (part 1) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 8B is a schematic cross-sectional view (part 2) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 8C is a schematic cross-sectional view (part 3) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 8D is a schematic cross-sectional view (part 4) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 8E is a schematic cross-sectional view (part 5) illustrating a method for processing a laminate showing an example of the second embodiment. FIG. 8F is a schematic cross-sectional view (part 6) illustrating a method for processing a laminate showing an example of the second embodiment.

[0011] (Adhesive composition) The adhesive composition of the present invention is an adhesive composition for forming an adhesive layer used to temporarily bond a semiconductor substrate or an electronic device layer to a support substrate. The adhesive composition of the present invention contains an adhesive component and a (meth)acrylic acid ester-based polymer having a repeating unit represented by the following formula (1). The adhesive composition may contain other components.

[0012] In formula (1), R １ represents a hydrogen atom or a methyl group, R ２ represents an alkyl group having 1 to 20 carbon atoms.

[0013] Examples of adhesive compositions include, but are not limited to, polysiloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, etc. Among these, polysiloxane-based adhesives are preferred as the adhesive composition because they exhibit suitable adhesive properties during processing of semiconductor substrates, etc., are suitable for peeling after processing, have excellent heat resistance, and can be suitably removed with a cleaning composition.

[0014] <Adhesive Component> The adhesive component is not particularly limited, but is preferably a component that cures, and more preferably a component that cures by a hydrosilylation reaction. The component that cures by a hydrosilylation reaction is not particularly limited, but preferably contains a component having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom (hereinafter sometimes referred to as "component (A-1)"), a component having a Si—H group (hereinafter sometimes referred to as "component (A-2)"), and a platinum group metal catalyst (A-3).

[0015] <<Component (A-1) and Component (A-2)>> The adhesive composition preferably contains component (A-1). The adhesive composition preferably contains component (A-2). Hereinafter, the combination of component (A-1), component (A-2), and platinum group metal catalyst (A-3) may be referred to as "curable component (A)" or "component (A)."

[0016] From the viewpoint of optimally achieving the effects of the present invention, component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom. From the viewpoint of optimally achieving the effects of the present invention, component (A-2) preferably contains a polyorganosiloxane (a2) having a Si—H group. 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.

[0017] In another preferred embodiment, the adhesive composition that cures by a hydrosilylation reaction is ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５ SiO ２／２ Siloxane units (D units) represented by the formula: and R ６ SiO ３／２ and a platinum group metal catalyst (A-3), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (T units) represented by the following formula: ２ Siloxane units (Q′ units) represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by R ４ 'R ５ 'SiO ２／２ Siloxane units (D′ units) represented by the formula: ６ 'SiO ３／２ and a polyorganosiloxane (a1') containing at least one unit selected from the group consisting of M' units, D' units, and T' units, and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２"R ３ "SiO １／２ Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by the formula: ６ "SiO ３／２ and a polyorganosiloxane (a2') containing one or more units selected from the group consisting of siloxane units (T" units) represented by the following formula: and containing 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).

[0018] R １ ~R ６ are groups or atoms bonded to the 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 hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0019] R １ '~R ６ R ′ is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group. １ '~R ６ At least one of the groups ' is an alkenyl group which 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.

[0020] R １ "~R ６ " are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but R １ "~R ６ At least one of " 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.

[0021] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. 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.

[0022] Specific examples of the optionally substituted straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, and a 4-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

[0023] Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a cyclopropyl ... Examples of such cycloalkyl groups include cycloalkyl groups such as 1-n-propyl-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; and 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 in the cycloalkyl groups is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0024] The alkenyl group may be either linear or branched, and the number of carbon atoms therein 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.

[0025] Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, ethenyl and 2-propenyl groups are particularly preferred. Specific examples of optionally substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0026] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2') form a crosslinked structure through a hydrosilylation reaction with the platinum group metal catalyst (A-3), and the crosslinked structure is cured. As a result, a cured film is formed.

[0027] The 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 the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0028] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).

[0029] In addition, when two or more types of polyorganosiloxanes are included in the polyorganosiloxane (a1'), a combination of (Q' units and M' units) and (D' units and M' units), a combination of (T' units and M' units) and (D' units and M' units), a combination of (Q' units, T' units and M' units) and (T' units and M' units) is preferred, but is not limited to these.

[0030] 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 at least one unit selected from the group consisting of M" units, D" units, and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0031] Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units and M" units).

[0032] The polyorganosiloxane (a1') is composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof. １ '~R ６ The proportion of alkenyl groups in all the substituents represented by R ′ 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.

[0033] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. １ "~R ６ The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R １ "~R ６ " can be an alkyl group.

[0034] When the adhesive composition contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si—H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0035] 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 from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0036] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa s), and from the viewpoint of realizing the effects of the present invention with good reproducibility, are preferably 50 to 10,000 (mPa s). The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are values ​​measured at 25 ° C. using an E-type rotational viscometer.

[0037] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a silanol group or a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0038] <<Platinum Group Metal Catalyst (A-3)>> The platinum group metal catalyst is a platinum-based metal catalyst that promotes the hydrosilylation reaction between an alkenyl group and a Si—H group.

[0039] Specific examples of platinum-based metal catalysts that can be used include known platinum-based compounds (platinum or compounds containing platinum). Specific examples include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and diolefins, platinum-olefin complexes, platinum-carbonyl complexes (platinum bis(acetoacetate), platinum bis(acetylacetonate), etc.), chloroplatinic acid-alkenylsiloxane complexes (chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex, etc.), platinum-alkenylsiloxane complexes (platinum-divinyltetramethyldisiloxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane complex, etc.), and complexes of chloroplatinic acid and acetylene alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high hydrosilylation reaction-accelerating effect. These hydrosilylation reaction catalysts may be used either individually or in combination of two or more.

[0040] The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited, and examples thereof include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers in which some of the methyl groups of these alkenylsiloxanes have been substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes have been substituted with allyl groups, hexenyl groups, etc. 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is particularly preferred because the resulting platinum-alkenylsiloxane complex has good stability.

[0041] The content of the platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, but is, for example, in the range of 0.1 to 50.0 ppm relative to the total mass of component (A-1) and component (A-2).

[0042] <(Meth)acrylic acid ester-based polymer> When the adhesive composition contains a (meth)acrylic acid ester-based polymer having a repeating unit represented by the following formula (1), the adhesive layer formed from the adhesive composition has excellent releasability. The (meth)acrylic acid ester-based polymer having a repeating unit represented by the following formula (1) is a release agent component (note that in this specification, the (meth)acrylic acid ester-based polymer having the repeating unit represented by formula (1) is also referred to as release agent component (B)). A small amount of the (meth)acrylic acid ester-based polymer having the repeating unit represented by formula (1) can impart good releasability to the adhesive layer formed from the adhesive composition.

[0043] In formula (1), R １ represents a hydrogen atom or a methyl group, R ２ represents an alkyl group having 1 to 20 carbon atoms.

[0044] (Meth)acrylic acid ester is a general term for acrylic acid ester and methacrylic acid ester. The (meth)acrylic acid ester-based polymer may have a repeating unit other than the repeating unit derived from the (meth)acrylic acid alkyl ester. The (meth)acrylic acid ester-based polymer may be a homopolymer or a copolymer. The mass proportion of the repeating unit represented by formula (1) in the (meth)acrylic acid ester-based polymer is not particularly limited, but is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 80 mass% or more.

[0045] (Meth)acrylic acid ester polymers generally do not undergo hydrosilylation reactions.

[0046] In the above formula (1), the alkyl group having 1 to 20 carbon atoms refers to, for example, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. The compatibility between component (A), which is an adhesive component, and the (meth)acrylic acid-based polymer is not so good, but in formula (1), R ２As shown in the formula (1), the presence of an alkyl chain can improve compatibility with component (A). In other words, when a (meth)acrylic acid ester-based polymer having a repeating unit represented by formula (1) is used as the release agent component (B), it is possible to satisfy both good compatibility with component (A), which is an adhesive component, and good releasability of the adhesive layer.

[0047] R of the (meth)acrylic acid ester polymer having a repeating unit represented by the above formula (1) ２ Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an isooctyl group, a 2-ethylhexyl group, a dodecyl group, and a decyl group.

[0048] Preferred specific examples of the (meth)acrylic acid ester-based polymer having a repeating unit represented by the above formula (1) include (meth)acrylic acid ester-based polymers having at least one of the repeating units described below.

[0049]

[0050] The content of the (meth)acrylic acid ester-based polymer in the adhesive composition is not particularly limited, but from the viewpoint of optimally achieving the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile content of the adhesive composition. The upper limit is not particularly limited, but is, for example, preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. In particular, a (meth)acrylic acid ester-based polymer having a repeating unit represented by formula (1) can form an adhesive layer with excellent releasability even at a content as low as 0.1% by mass to 0.5% by mass, relative to the non-volatile content of the adhesive composition. The non-volatile content of the adhesive composition refers to components other than the solvent in the adhesive composition.

[0051] The Tg of the (meth)acrylic acid ester-based polymer is not particularly limited, but is preferably 30° C. to 150° C., and more preferably 40° C. to 120° C. The Tg of the (meth)acrylic acid ester-based polymer can be determined, for example, by differential scanning calorimetry.

[0052] The molecular weight of the (meth)acrylic acid ester-based polymer is not particularly limited, but the weight average molecular weight of the (meth)acrylic acid ester-based polymer is preferably 10,000 to 200,000, and more preferably 10,000 to 30,000. The molecular weight of the (meth)acrylic acid ester-based polymer can be determined, for example, by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0053] A (meth)acrylic acid ester-based polymer having a repeating unit represented by formula (1) can be obtained, for example, by mixing an alkyl (meth)acrylate, an initiator, and a solvent such as tetrahydrofuran, stirring the mixture under a nitrogen atmosphere at a temperature of 40 to 90° C., and, after the reaction is complete, drying under reduced pressure at 40 to 60° C. Examples of initiators that can be used here include 2,2′-azodiisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 4,4′-azobis(4-cyanovaleric acid), tert-butyl peroxide, benzoyl peroxide, and dicumyl peroxide.

[0054] The adhesive composition of the present invention may contain a solvent for the purpose of adjusting viscosity, etc., and specific examples of such a solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0055] More specifically, examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. These solvents may be used alone or in combination of two or more.

[0056] When the adhesive composition of the present invention contains a solvent, the content of the solvent is determined appropriately taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the film to be produced, and the like, but is generally in the range of about 10 to 90 mass % based on the total mass of the composition.

[0057] The viscosity of the adhesive composition of the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s at 25° C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of solvents used, their ratios, the concentrations of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0058] An example of the adhesive composition used in the present invention can be produced by mixing component (A), release agent component (B), and a solvent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving component (A) and release agent component (B) in a solvent, a method of dissolving a portion of component (A) and release agent component (B) in a solvent and the remainder in a solvent, and mixing the resulting solutions, and a method of dissolving component (A) in a solvent and dissolving release agent component (B) in a solvent, and mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after mixing all of the components in order to remove foreign matter.

[0059] (Laminate) The laminate according to the present invention comprises a semiconductor substrate or electronic device layer, a support substrate, and an adhesive layer. The laminate according to the present invention may further comprise a release agent layer, in which case the laminate comprises a semiconductor substrate or electronic device layer, a support substrate, a release agent layer, and an adhesive layer.

[0060] The adhesive layer is disposed between the semiconductor substrate or electronic device layer and the support substrate.

[0061] The laminate of the present invention is used for temporary bonding when processing a semiconductor substrate or an electronic device layer, and can be suitably used for processing such as thinning of a semiconductor substrate or an electronic device layer. While the semiconductor substrate is being processed such as thinning, the semiconductor substrate is supported by a support substrate. On the other hand, after processing of the semiconductor substrate, the support substrate and the semiconductor substrate are separated. Also, while the electronic device layer is being processed such as thinning, the electronic device layer is supported by a support substrate. On the other hand, after processing of the electronic device layer, the support substrate and the electronic device layer are subsequently separated. Residues of the release agent layer or adhesive layer remaining on the semiconductor substrate, electronic device layer, or support substrate after separation of the semiconductor substrate or electronic device layer from the support substrate can be removed, for example, with a cleaning composition for cleaning semiconductor substrates, etc.

[0062] The laminate will be described in detail below, with respect to cases where the laminate has a semiconductor substrate and cases where the laminate has an electronic device layer. The case where the laminate has a semiconductor substrate will be described in the following <First embodiment>, and the case where the laminate has an electronic device layer will be described in the following <Second embodiment>.

[0063] <First embodiment> A stacked body having a semiconductor substrate is used for processing the semiconductor substrate. While the semiconductor substrate is being processed, the semiconductor substrate is adhered to a support substrate. After the semiconductor substrate is processed, the semiconductor substrate is separated from the support substrate.

[0064] <<Semiconductor Substrate>> The main material constituting the entire semiconductor substrate is not particularly limited as long as it is suitable for this type of application, and examples thereof include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins. The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disk. Note that the surface of a disk-shaped semiconductor substrate does not need to be perfectly circular; for example, the outer periphery of the semiconductor substrate may have a straight line portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 100 to 1,000 mm.

[0065] The semiconductor substrate may have bumps. Bumps are protruding terminals. In a laminate, when the semiconductor substrate has bumps, the bumps are located on the support substrate side. In a semiconductor substrate, the bumps are typically formed on the surface on which the circuit is formed. The circuit may be single-layered or multi-layered. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface having the bumps (the back surface) is the surface used for 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. The height, radius, and pitch of the bumps are typically determined appropriately based on the following conditions: a bump height of approximately 1 to 200 μm, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm. Examples of bump materials 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 multiple components. More specifically, examples include alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bump may also have a laminate structure including a metal layer composed of at least one of these components.

[0066] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0067] <<Support Substrate>> The support substrate is not particularly limited as long as it is a member that can support a semiconductor substrate when the semiconductor substrate is processed, and examples thereof include a glass support substrate and a silicon support substrate.

[0068] The shape of the support substrate is not particularly limited, but may be, for example, a disk shape. The disk-shaped support substrate does not need to have a perfectly circular surface; for example, the outer periphery of the support substrate may have a straight line portion called an orientation flat, or a notch. The thickness of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., and is not particularly limited, but is, for example, 500 to 1,000 μm. The diameter of the disk-shaped support substrate may be determined appropriately depending on the size of the semiconductor substrate, etc., and is not particularly limited, but is, for example, 100 to 1,000 mm.

[0069] An example of the support substrate is a glass wafer having a diameter of about 300 mm and a thickness of about 700 μm.

[0070] When the peeling of the laminate is performed by light irradiation, for example, a substrate that is optically transparent to the light used is used as the support substrate.

[0071] <<Adhesive Layer>> The adhesive layer is provided between the support substrate and the semiconductor substrate. The adhesive layer is in contact with, for example, the semiconductor substrate. The adhesive layer may be in contact with, for example, the support substrate. The adhesive layer is an adhesive layer formed from an adhesive composition.

[0072] The thickness of the adhesive layer provided in the laminate of the present invention 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 due to a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 100 μm or less.

[0073] The method for forming the adhesive layer from the adhesive composition will be described in detail below in the section entitled "Example of method for producing the laminate in the first embodiment."

[0074] <<Release Agent Layer>> The laminate may have a release agent layer. In a laminate having a release agent layer, the semiconductor substrate and the support substrate are separated, for example, by irradiating the release agent layer with light. The release agent layer is formed, for example, from a release agent composition.

[0075] <<<Release Agent Composition>>> The release agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and further contains other components as necessary. The organic resin is preferably one that can exhibit suitable release ability, and when the semiconductor substrate and the support substrate are separated by irradiating the release agent layer with light, the organic resin is one that absorbs light and suitably undergoes a change in quality, such as decomposition, required to improve the release ability.

[0076] A laminate having a release agent layer formed from the release agent composition can be peeled off without applying an excessive load for peeling, for example, by irradiating the release agent layer with a laser. The release agent layer provided in the laminate has an adhesive strength that is reduced by, for example, laser irradiation compared to before irradiation. That is, in the laminate, for example, while a semiconductor substrate is being processed, such as thinned, the semiconductor substrate is suitably supported on a laser-transparent support substrate via an adhesive layer and a release agent layer. After processing is completed, by irradiating a laser from the support substrate side, the laser that has transmitted through the support substrate is absorbed by the release agent layer, and alteration (e.g., separation) of the release agent layer occurs at the interface between the release agent layer and the adhesive layer, at the interface between the release agent layer and the support substrate, or inside the release agent layer. As a result, suitable peeling (separation) can be achieved without applying an excessive load for peeling.

[0077] Examples of organic resins include novolac resins, etc. Details of these will be described later.

[0078] In a preferred embodiment, the release agent composition contains at least a novolac resin, and further contains other components such as a crosslinker, an acid generator, an acid, a surfactant, a solvent, etc., as needed. In another preferred embodiment, the release agent composition contains at least a polynuclear phenol derivative and a crosslinker, and further contains other components such as an acid generator, an acid, a surfactant, a solvent, etc. In another preferred embodiment, the release agent composition contains at least an organic resin and a branched-chain polysilane, and further contains other components such as a crosslinker, an acid generator, an acid, a surfactant, a solvent, etc., as needed.

[0079] <<<<<Novolac Resin>>>> Novolac resins are resins obtained by, for example, subjecting at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound to a condensation reaction with at least one of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst.

[0080] Examples of phenolic compounds include phenols, naphthols, anthrols, and hydroxypyrenes. Examples of phenols include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of naphthols include 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 9,9-bis(6-hydroxynaphthyl)fluorene. Examples of anthrols include 9-anthrole. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene. Examples of the carbazole compound include carbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6-dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'-bis(9H-carbazol-9-yl)biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9-(1H-benzotriazol-1-yl)methylcarbazole, 4 ... Examples of aromatic amine compounds include diphenylamine and N-phenyl-1-naphthylamine. These compounds may be used alone or in combination of two or more. These compounds may have a substituent.For example, they may have a substituent on the aromatic ring.

[0081] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, capronaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanoic aldehyde, 7-methoxy-3,7-dimethyloctyl aldehyde, cyclohexane aldehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and adipic acid. Examples of the ketone compound include saturated aliphatic aldehydes such as benzoic acid aldehyde, unsaturated aliphatic aldehydes such as acrolein and methacrolein, heterocyclic aldehydes such as furfural and pyridine aldehyde, and aromatic aldehydes such as benzaldehyde, naphthyl aldehyde, anthryl aldehyde, phenanthryl aldehyde, salicyl aldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolyl aldehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, aromatic aldehydes are preferred. Examples of the ketone compound include diaryl ketone compounds such as diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, and ditolyl ketone. Examples of divinyl compounds include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborna-2-ene, divinylpyrene, limonene, 5-vinylnorbornadiene, etc. These can be used alone or in combination of two or more.

[0082] The novolac resin is, for example, a novolac resin that absorbs light irradiated from the support substrate side and changes in quality, for example, by photolysis.

[0083] The novolac resin contains, for example, at least one of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3).

[0084]

[0085] In the formula, C １ represents a group derived from an aromatic compound containing a nitrogen atom, C ２ represents a group containing a tertiary carbon atom having at least one member selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain, and C ３ represents a group derived from an aliphatic polycyclic compound, C ４ represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0086] That is, the novolac resin contains, for example, one or more of the following structural units: A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one carbon atom selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain (formula (C1-1)); A structural unit having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound (formula (C1-2)); A structural unit having a bond between a group derived from a phenol, a group derived from a bisphenol, a group derived from a naphthol, a group derived from a biphenyl, or a group derived from a biphenol and a group containing a tertiary carbon atom having at least one carbon atom selected from the group consisting of a quaternary carbon atom and an aromatic ring in its side chain (formula (C1-3)).

[0087] In a preferred embodiment, the novolak resin contains either or both of a structural unit (formula (C1-1)) having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom having at least one kind selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in its side chain, and a structural unit (formula (C1-2)) having a bond between a group derived from an aromatic compound containing a nitrogen atom and a group derived from an aliphatic polycyclic compound.

[0088] C １ Examples of the group derived from an aromatic compound containing a nitrogen atom include, but are not limited to, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, and a group derived from N-phenyl-2-naphthylamine.２ Examples of the group containing a tertiary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in a side chain include, but are not limited to, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, and a group derived from acetaldehyde. ３ The group derived from an aliphatic polycyclic compound of can be, but is not limited to, a group derived from dicyclopentadiene. ４ is a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0089] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-1), for example, a structural unit represented by formula (C1-1-1) below.

[0090]

[0091] In formula (C1-1-1), R ９０１ and R ９０２ represents a substituent substituted on the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０３ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ９０４ represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０５ represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ９０４ and R ９０５The groups may be bonded to each other to form a divalent group. Examples of substituents on the alkyl and alkenyl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxy groups, aryl groups, and heteroaryl groups. Examples of substituents on the aryl and heteroaryl groups include halogen atoms, nitro groups, cyano groups, amino groups, hydroxy groups, carboxy groups, alkyl groups, and alkenyl groups. １ and h ２ each independently represents an integer of 0 to 3.

[0092] The number of carbon atoms in the optionally substituted alkyl group and the optionally substituted alkenyl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less. The number of carbon atoms in the optionally substituted aryl group and heteroaryl group is usually 40 or less, and from the viewpoint of solubility, it is preferably 30 or less, more preferably 20 or less.

[0093] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0094] Specific examples of the optionally substituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, and a 3-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.

[0095] Specific examples of the optionally substituted alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, and 1-methyl-3-butenyl. nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-tert-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group , 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, and the like.

[0096] Specific examples of the optionally substituted aryl group include, but are not limited to, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-nitrophenyl group, a 4-cyanophenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl-4-yl group, a biphenyl-3-yl group, a biphenyl-2-yl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0097] Specific examples of the optionally substituted heteroaryl group include, but are not limited to, a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, a 3-furanyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 3-isoxazolyl group, a 4-isoxazolyl group, a 5-isoxazolyl group, a 2-thiazolyl group, a 4-thiazolyl group, a 5-thiazolyl group, a 3-isothiazolyl group, a 4-isothiazolyl group, a 5-isothiazolyl group, and the like.

[0098] Specific examples of the structural unit represented by formula (C1-1-1) are listed below, but the present invention is not limited to these.

[0099]

[0100] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-1), for example, a structural unit represented by the following formula (C1-1-2).

[0101]

[0102] In formula (C1-1-2), Ar ９０１ and Ar ９０２ each independently represents an aromatic ring such as a benzene ring or a naphthalene ring, and R ９０１ ~R ９０５ and h １ and h ２ has the same meaning as above.

[0103] Specific examples of the structural unit represented by formula (C1-1-2) are listed below, but the present invention is not limited to these.

[0104]

[0105] In a preferred embodiment, the novolak resin contains, as the structural unit represented by formula (C1-2), for example, a structural unit represented by the following formula (C1-2-1) or (C1-2-2).

[0106]

[0107] In the above formula, R ９０６ ~R ９０９ are substituents bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and specific examples and suitable numbers of carbon atoms of the halogen atom, the optionally substituted alkyl group, the optionally substituted alkenyl group, and the optionally substituted aryl group are the same as those described above, and h ３ ~h ６ each independently represents an integer of 0 to 3; R ９０１ ~R ９０３ and h １ and h ２ has the same meaning as above.

[0108] Specific examples of the structural units represented by formulae (C1-2-1) and (C1-2-2) are listed below, but are not limited to these.

[0109]

[0110] Specific examples of the structural unit represented by formula (C1-3) are listed below, but the present invention is not limited to these.

[0111]

[0112] As described above, novolac resins are resins obtained by, for example, condensation reaction of at least one of a phenolic compound, a carbazole compound, and an aromatic amine compound with at least one of an aldehyde compound, a ketone compound, and a divinyl compound in the presence of an acid catalyst. In this condensation reaction, for example, 0.1 to 10 equivalents of the aldehyde compound or ketone compound are typically used per equivalent of the benzene ring constituting the ring of the carbazole compound.

[0113] In the condensation reaction, an acid catalyst is usually used. Examples of the acid catalyst include, but are not limited to, mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of the acid catalyst cannot be generally specified because it is determined appropriately depending on the type of acid used, etc., but is usually determined appropriately in the range of 0.001 to 10,000 parts by mass per 100 parts by mass of the carbazole compound.

[0114] The condensation reaction can be carried out without a solvent if either the starting compounds or the acid catalyst used are liquid, but is usually carried out using a solvent. Such a solvent is not particularly limited as long as it does not inhibit the reaction, and typical examples include ether compounds such as cyclic ether compounds such as tetrahydrofuran and dioxane.

[0115] The reaction temperature is usually appropriately set within the range of 40° C. to 200° C. The reaction time cannot be generally defined since it varies depending on the reaction temperature, but is usually appropriately set within the range of 30 minutes to 50 hours.

[0116] After the reaction is completed, if necessary, purification and isolation are carried out according to a standard method, and the obtained novolak resin is used for preparing a release agent composition. A person skilled in the art can determine the production conditions of the novolak resin without undue burden based on the above explanation and technical common sense, and therefore can produce the novolak resin.

[0117] The weight-average molecular weight of the organic resin such as a novolac resin is usually 500 to 200,000. From the viewpoint of ensuring solubility in a solvent, mixing well with the branched-chain polysilane when formed into a film, and obtaining a uniform film, the weight-average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, still more preferably 5,000 or less, and still more preferably 3,000 or less. From the viewpoint of improving the strength of the film, the weight-average molecular weight is preferably 600 or more, more preferably 700 or more, even more preferably 800 or more, still more preferably 900 or more, and still more preferably 1,000 or more. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of an organic resin such as a polymer novolac resin can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent), at a flow rate (flow rate) of 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0118] The organic resin contained in the release agent composition is preferably a novolac resin, and therefore, the release agent composition preferably contains only a novolac resin as the organic resin, but may contain other polymers together with the novolac resin for the purpose of adjusting the film properties, etc. Examples of such other polymers include polyacrylic acid ester compounds, polymethacrylic acid ester compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydrides, polyacrylonitrile compounds, etc.

[0119] The content of the novolac resin in the release agent composition is not particularly limited, but is preferably 70% by mass or more based on the total amount of polymers contained in the release agent composition. The content of the novolac resin in the release agent composition is not particularly limited, but is preferably 50 to 100% by mass based on the film-constituting components. In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0120] <<<<<Polynuclear Phenol Derivative>>>> The polynuclear phenol derivative is represented, for example, by formula (P) below.

[0121] In formula (P), Ar represents an arylene group, and the number of carbon atoms therein is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition having excellent uniformity and reproducibly obtaining a release agent layer having higher flatness, the number of carbon atoms therein is preferably 30 or less, more preferably 20 or less, even more preferably 18 or less, and still more preferably 12 or less.

[0122] Specific examples of such an arylene group include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, and 2,3-anthracenediyl. Examples of the anthracene-4,4′-diyl group include, but are not limited to, groups derived by removing two hydrogen atoms on the aromatic ring of a fused-ring aromatic hydrocarbon compound, such as anthracene-4,6-diyl, 2,7-anthracene-4,9-diyl, 2,10-anthracene-4,10-diyl, and 9,10-anthracene-4,4′-diyl group, and groups derived by removing two hydrogen atoms on the aromatic ring of a biphenyl-4,4′-diyl group and para-terphenyl-4,4″-diyl group.

[0123] From the viewpoint of providing a release agent layer exhibiting good releasability and reproducibly obtaining a laminate from which the support substrate can be easily separated, the polynuclear phenol derivative represented by formula (P) is preferably a polynuclear phenol derivative represented by formula (P-1), more preferably a polynuclear phenol derivative represented by formula (P-1-1), and even more preferably a polynuclear phenol derivative represented by formula (P1).

[0124]

[0125] The content of the polynuclear phenol derivative in the stripping composition is not particularly limited, but is preferably 50 to 100% by mass based on the film-constituting components.

[0126] <<<<<Branched Polysilane>>>> The release agent composition may contain a branched polysilane. The branched polysilane has a Si—Si bond and a branched structure. When the release agent composition contains a branched polysilane, the release agent layer formed from the obtained film cannot be suitably removed by any of organic solvents, acids, and chemical solutions used in the production of semiconductor elements (such as alkaline developer and hydrogen peroxide solution), but can be suitably removed by the cleaning composition. As a result, by separating the semiconductor substrate and support substrate of the laminate and then cleaning each substrate with the cleaning composition, the residue of the release agent layer on the substrate can be suitably removed. Although the reason for this is not clear, depending on the type of polysilane terminal group (terminal substituent (atom)), the polysilane can react with an organic resin to form crosslinks. Furthermore, since branched-chain polysilanes have more terminal groups (terminal substituent (atom)) than linear polysilanes, branched-chain polysilanes are thought to have more crosslinking points than linear polysilanes. It is speculated that moderate and suitable curing via such more crosslinking points in the branched-chain polysilanes can achieve both the property of being resistant to removal by organic solvents, acids, and chemical solutions used in the production of semiconductor devices (such as alkaline developers and hydrogen peroxide solutions), and the property of being easily removed by cleaning compositions.

[0127] The branched polysilane preferably contains a structural unit represented by formula (B).

[0128]

[0129] In formula (B), R Ｂ represents a hydrogen atom, a hydroxy group, a silyl group, or an organic group, and specific examples of such organic groups include hydrocarbon groups (optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted aryl groups, and optionally substituted aralkyl groups), and ether groups corresponding to these hydrocarbon groups (optionally substituted alkoxy groups, optionally substituted aryloxy groups, and optionally substituted aralkyloxy groups), and the organic group is usually often a hydrocarbon group such as an alkyl group, alkenyl group, aryl group, or aralkyl group. Furthermore, a hydrogen atom, a hydroxy group, an alkoxy group, a silyl group, or the like is often substituted at the terminal.

[0130] The optionally substituted alkyl group may be linear, branched, or cyclic. Specific examples of the optionally substituted linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 5-methyl-n-pentyl group, a 6-methyl-n-pentyl group, a 7-methyl-n-pentyl group, a 8-methyl-n-pentyl group, a 9-methyl-n-pentyl group, a 10-methyl-n-pentyl group, a 11-methyl-n-pentyl group, a 12-methyl-n-pentyl group, a 13-methyl-n-pentyl group, a 14-methyl-n-pentyl group, a 15-methyl-n-pentyl group, a 16-methyl-n-pentyl group, a 17-methyl-n-pentyl group, a 18-methyl-n-pentyl group, a 19-methyl-n-pentyl group, a 20-methyl-n-pentyl group, a 21-methyl-n-pentyl group, a 22-methyl-n-pentyl group, a 23-methyl-n-pentyl group, a 24-methyl-n-pentyl group, a 25-methyl-n-pentyl group, a 26-methyl-n-pentyl group, a 2 Examples of alkyl groups include, but are not limited to, ethyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3- Examples of cycloalkyl groups include 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-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and 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.

[0131] The alkenyl group may be linear, branched, or cyclic. Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Specific examples of optionally substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0132] Specific examples of the optionally substituted aryl group include, but are not limited to, a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 3,5-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group, and the number of carbon atoms thereof is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 12.

[0133] Specific examples of the optionally substituted aralkyl group include, but are not limited to, a benzyl group, a phenethyl group, a phenylpropyl group, etc. The optionally substituted aralkyl group is preferably a group in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0134] The alkyl moiety of the optionally substituted alkoxy group may be linear, branched, or cyclic. Specific examples of the optionally substituted linear or branched alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a t-butoxy group, and a pentyloxy group, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Specific examples of the optionally substituted cyclic alkoxy group include, but are not limited to, cyclopentyloxy and cyclohexyloxy, and the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0135] Specific examples of the optionally substituted aryloxy group include, but are not limited to, phenoxy, 1-naphthyloxy, and 2-naphthyloxy, and the number of carbon atoms thereof is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10.

[0136] Specific examples of the optionally substituted aralkyloxy group include, but are not limited to, benzyloxy, phenethyloxy, phenylpropyloxy, etc. The optionally substituted aralkyloxy group is preferably a group in which one hydrogen atom of an alkyloxy group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0137] Specific examples of the silyl group include, but are not limited to, a silyl group, a disilanyl group, a trisilanyl group, and the like. The number of silicon atoms is usually 1 to 10, preferably 1 to 6.

[0138] R Ｂ When is the organic group or silyl group, at least one of the hydrogen atoms may be substituted with a substituent, specific examples of which include a hydroxy group, an alkyl group, an aryl group, and an alkoxy group.

[0139] From the viewpoint of preventing unintended peeling when the laminate is brought into contact with an organic solvent, an acid, or a chemical solution used in the manufacture of semiconductor elements (such as an alkaline developer or hydrogen peroxide solution), and from the viewpoint of suitably removing residues of the release agent layer on the substrate when the semiconductor substrate and the support substrate of the laminate are separated and then washed with the cleaning agent composition, R Ｂ is preferably an alkyl group or an aryl group, more preferably an aryl group, even more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and even more preferably a phenyl group.

[0140] The branched-chain polysilane may contain, in addition to the structural unit represented by formula (B), a structural unit represented by formula (S) below or a structural unit represented by formula (N) below. However, from the viewpoint of suppressing unintended peeling when the laminate is brought into contact with any of an organic solvent, an acid, or a chemical solution used in the production of semiconductor devices (such as an alkaline developer or hydrogen peroxide solution), and from the viewpoint of suitably removing residue of the release agent layer on the substrate when the semiconductor substrate and the support substrate of the laminate are separated and then each substrate is washed with a cleaning composition, the content of the structural unit represented by formula (B) in the branched-chain polysilane is usually 50 mol % or more, preferably 60 mol % or more, more preferably 70 mol % or more, still more preferably 80 mol % or more, even more preferably 90 mol % or more, and still more preferably 95 mol % or more, of all structural units.

[0141] (R Ｓ１ and Ｓ２ is R Ｂ It has the same meaning as

[0142] The terminal group (terminal substituent (atom)) of the branched chain polysilane may usually be a hydrogen atom, a hydroxy group, a halogen atom (such as a chlorine atom), an alkyl group, an aryl group, an alkoxy group, a silyl group, etc. Among these, a hydroxy group, a methyl group, or a phenyl group is often used, and a methyl group is particularly preferred, and the terminal group may also be a trimethylsilyl group.

[0143] In one embodiment, the average degree of polymerization of the branched-chain polysilane, in terms of silicon atoms (i.e., the average number of silicon atoms per molecule), is usually 2 to 100, preferably 3 to 80, more preferably 5 to 50, and even more preferably 10 to 30. In one embodiment, the upper limit of the weight-average molecular weight of the branched-chain polysilane is usually 30,000, preferably 20,000, more preferably 10,000, even more preferably 5,000, even more preferably 2,000, and even more preferably 1,500, and the lower limit is usually 50, preferably 100, more preferably 150, even more preferably 200, even more preferably 300, and even more preferably 500. The average degree of polymerization and weight-average molecular weight of the branched polysilane can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and GPC columns (Shodex KF-803L, KF-802, and KF-801 manufactured by Showa Denko K.K., used in this order), at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent), at a flow rate (flow rate) of 1.00 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample. If the degree of polymerization and weight-average molecular weight of the branched-chain polysilane used are too small, the branched-chain polysilane may be vaporized by heating when forming a film that serves as a release agent layer or when processing the resulting laminate comprising the release agent layer, or problems may occur due to poor film strength. On the other hand, if the degree of polymerization and molecular weight of the branched-chain polysilane used are too large, sufficient solubility may not be ensured depending on the type of solvent used in preparing the release agent composition, causing precipitation in the composition, or mixing with the resin may be insufficient, making it difficult to reproducibly obtain a highly uniform film. Therefore, from the viewpoint of more reproducibly obtaining a laminate comprising a release agent layer that contributes to the favorable production of semiconductor elements, it is desirable that the degree of polymerization and weight-average molecular weight of the branched-chain polysilane satisfy the above-mentioned ranges.

[0144] From the viewpoint of reproducibly obtaining a release agent layer having excellent heat resistance, the 5% weight loss temperature of the branched chain polysilane is usually 300° C. or higher, preferably 350° C. or higher, more preferably 365° C. or higher, even more preferably 380° C. or higher, even more preferably 395° C. or higher, and even more preferably 400° C. or higher. The 5% weight loss temperature of the branched chain polysilane can be measured, for example, by using a NETZSCH 2010SR thermometer in air, by increasing the temperature from room temperature (25° C.) to 400° C. at a rate of 10° C. / min.

[0145] When the semiconductor substrate and the support substrate of the laminate are separated and then each substrate is washed with a cleaning composition, from the viewpoint of suitably removing the residue of the release agent layer on the substrate and from the viewpoint of reproducibly preparing a release agent composition with excellent uniformity, the branched-chain polysilane is preferably soluble in any one of ether compounds such as tetrahydrofuran, aromatic compounds such as toluene, glycol ether ester compounds such as propylene glycol monomethyl ether acetate, ketone compounds such as cyclohexanone and methyl ethyl ketone, and glycol ether compounds such as propylene glycol monomethyl ether. In this case, "dissolution" means that when dissolution is attempted using a shaker at room temperature (25°C) to give a 10% by mass solution, dissolution can be visually confirmed within 1 hour.

[0146] The branched chain polysilane may be in either a solid or liquid state at room temperature.

[0147] Branched chain polysilanes can be produced by reference to known methods described in, for example, JP 2011-208054 A, JP 2007-106894 A, JP 2007-145879 A, ​​WO 2005 / 113648 A, etc., or can be obtained as commercially available products. Specific examples of commercially available products include, but are not limited to, silicon-based polysilanes OGSOL SI-20-10 and SI-20-14 manufactured by Osaka Gas Chemicals Co., Ltd.

[0148] Suitable examples of branched polysilanes include, but are not limited to, the following: (Ph represents a phenyl group, R Ｅeach independently represents a terminal substituent, represents an atom or a group, n ｂ indicates the number of repeating units.)

[0149] The content of the branched-chain polysilane in the stripper composition is usually 10 to 90% by mass relative to the film-constituting components. From the viewpoint of reproducibly realizing a film that cannot be suitably removed by organic solvents, acids, or chemical solutions used in the production of semiconductor elements (such as alkaline developers and hydrogen peroxide solutions) but can be suitably removed by the cleaning composition, the content is preferably 15 to 80% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 60% by mass, and still more preferably 30 to 50% by mass.

[0150] <<<<Crosslinking Agent>>>> The release agent composition may contain a crosslinking agent. The crosslinking agent may undergo a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the novolak resin, the crosslinking agent can undergo a crosslinking reaction with those crosslinkable substituents.

[0151] Specific examples of crosslinking agents are not particularly limited, but typically include phenol-based crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, and thiourea-based crosslinking agents, each of which has a crosslinking group, such as an alkoxymethyl group (e.g., hydroxymethyl group, methoxymethyl group, or butoxymethyl group), in the molecule; these may be low-molecular-weight compounds or high-molecular-weight compounds. The crosslinking agent contained in the release agent composition usually has two or more crosslinking groups, but from the viewpoint of achieving more suitable curing with good reproducibility, the number of crosslinking groups contained in the crosslinking agent compound is preferably 2 to 10, and more preferably 2 to 6. From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule; a typical example of such a crosslinking agent includes, but is not limited to, a phenol-based crosslinking agent.

[0152] A phenolic crosslinking agent having a crosslinking group is a compound having a crosslinking group bonded to an aromatic ring and at least one of a phenolic hydroxy group and an alkoxy group derived from the phenolic hydroxy group. Examples of the alkoxy group derived from the phenolic hydroxy group include, but are not limited to, a methoxy group and a butoxy group. The aromatic ring to which the crosslinking group is bonded and the aromatic ring to which the phenolic hydroxy group and / or the alkoxy group derived from the phenolic hydroxy group are bonded are not limited to non-fused aromatic rings such as benzene rings, but may also be fused aromatic rings such as naphthalene rings and anthracene rings. When multiple aromatic rings are present in the molecule of the phenolic crosslinking agent, the crosslinking group and the phenolic hydroxy group and the alkoxy group derived from the phenolic hydroxy group may be bonded to the same aromatic ring or to different aromatic rings in the molecule. The aromatic ring to which the crosslinking group, the phenolic hydroxy group, and the alkoxy group derived from the phenolic hydroxy group are bonded may be further substituted with a hydrocarbon group such as an alkyl group (e.g., methyl, ethyl, or butyl), an aryl group (e.g., phenyl), or a halogen atom (e.g., fluorine).

[0153] For example, specific examples of phenol-based crosslinking agents having a crosslinking group include compounds represented by any of formulas (L-1) to (L-4).

[0154]

[0155] In each formula, each R' independently represents a fluorine atom, an aryl group, or an alkyl group, each R'' independently represents a hydrogen atom or an alkyl group, and L １ and L ２ each independently represents a single bond, a methylene group, or a propane-2,2-diyl group; L ３is determined depending on q1 and represents a single bond, a methylene group, a propane-2,2-diyl group, a methanetriyl group, or an ethane-1,1,1-triyl group; t11, t12, and t13 are integers that satisfy 2≦t11≦5, 1≦t12≦4, 0≦t13≦3, and t11+t12+t13≦6; t21, t22, and t23 are integers that satisfy 2≦t21≦4, 1≦t22≦3, 0≦t23≦2, and t21+t22+t23≦5; t24, t25, and t26 are integers that satisfy 2≦t24≦4, 1≦t25≦3, 0≦t26≦2, and t24+t25+t26≦5; and t27, t28, and t29 are integers that satisfy 0≦t27≦4, 0≦t28≦ t31, t32, and t33 are integers that satisfy 2≦t31≦4, 1≦t32≦3, 0≦t33≦2, and t31+t32+t33≦5; t41, t42, and t43 are integers that satisfy 2≦t41≦3, 1≦t42≦2, 0≦t43≦1, and t41+t42+t43≦4; q1 is 2 or 3, and q2 represents the number of repetitions and is an integer of 0 or more. Specific examples of the aryl group and alkyl group include the same as those described below, although a phenyl group is preferred as the aryl group, and a methyl group or a t-butyl group is preferred as the alkyl group.

[0156] Specific examples of compounds represented by formulas (L1) to (L4) are listed below, but are not limited to these. These compounds may be synthesized by known methods or are available as products from, for example, Asahi Organic Chemicals Co., Ltd. or Honshu Chemical Industry Co., Ltd.

[0157]

[0158]

[0159]

[0160]

[0161] The melamine-based crosslinking agent having a crosslink-forming group is a melamine derivative, a 2,4-diamino-1,3,5-triazine derivative, or a 2-amino-1,3,5-triazine derivative in which at least one hydrogen atom of an amino group bonded to the triazine ring is substituted with a crosslink-forming group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group. Specific examples of melamine-based crosslinking agents having a crosslinking group include mono-, bis-, tris-, tetrakis-, pentakis- or hexakisalkoxymethylmelamines such as N,N,N',N',N",N"-hexakis(methoxymethyl)melamine and N,N,N',N',N",N"-hexakis(butoxymethyl)melamine; and mono-, bis-, tris- or tetrakisalkoxymethylbenzoguanamines such as N,N,N',N'-tetrakis(methoxymethyl)benzoguanamine and N,N,N',N'-tetrakis(butoxymethyl)benzoguanamine, but are not limited to these.

[0162] A urea-based crosslinking agent having a crosslink-forming group is a derivative of a urea bond-containing compound and has a structure in which at least one hydrogen atom of an NH group constituting a urea bond is substituted with a crosslink-forming group. Specific examples of the urea-based crosslinking agent having a crosslink-forming group include mono-, bis-, tris-, or tetrakisalkoxymethylglycolurils such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril and 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and mono-, bis-, tris-, or tetrakisalkoxymethylureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetrakismethoxymethylurea, but are not limited to these.

[0163] A thiourea-based crosslinking agent having a crosslink-forming group is a derivative of a thiourea bond-containing compound, and has a structure in which at least one hydrogen atom of an NH group constituting a thiourea bond is substituted with a crosslink-forming group. Specific examples of thiourea-based crosslinking agents having a crosslink-forming group include, but are not limited to, mono-, bis-, tris-, or tetrakis-alkoxymethylthioureas such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetrakismethoxymethylthiourea.

[0164] The amount of crosslinking agent contained in the release agent composition cannot be generally defined because it differs depending on the coating method used, the desired film thickness, etc., but is usually 0.01 to 50% by mass relative to the organic resin or polynuclear phenol derivative. From the viewpoint of achieving suitable curing and reproducibly obtaining a laminate from which the semiconductor substrate and the support substrate can be easily separated, the amount is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, still more preferably 5% by mass or more, and is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and still more preferably 30% by mass or less.

[0165] <<<<<Acid Generator and Acid>>>> The stripping composition may contain an acid generator or an acid for the purpose of promoting the crosslinking reaction or the like.

[0166] Examples of the acid generator include thermal acid generators and photoacid generators. The thermal acid generator is not particularly limited as long as it generates an acid by heat, and specific examples include, but are not limited to, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, and TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0167] Examples of the photoacid generator include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

[0168] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium nitrate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate, but are not limited to these.

[0169] Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited to these.

[0170] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0171] Specific examples of acids include arylsulfonic acids and pyridinium salts such as p-toluenesulfonic acid, pyridinium p-toluenesulfonate (pyridinium paratoluenesulfonate), pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid, and salts thereof; arylcarboxylic acids and salts thereof such as salicylic acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid; linear or cyclic alkylsulfonic acids and salts thereof such as trifluoromethanesulfonic acid and camphorsulfonic acid; and linear or cyclic alkylcarboxylic acids and salts thereof such as citric acid, but are not limited to these.

[0172] The amounts of the acid generator and acid contained in the stripping composition cannot be generally defined because they vary depending on the type of crosslinking agent used, the heating temperature during film formation, and the like, but are usually 0.01 to 5 mass % based on the film-constituting components.

[0173] <<<<<Surfactant>>>> The stripping composition may contain a surfactant for the purposes of adjusting the liquid properties of the composition itself and the film properties of the resulting film, preparing a highly uniform stripping composition with good reproducibility, etc. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Examples of suitable surfactants include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30, and R-30N (trade names, manufactured by DIC Corporation), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactant may be used alone or in combination of two or more. The amount of the surfactant is usually 2% by mass or less based on the film-constituting components of the stripping composition.

[0174] <<<<<Solvent>>>> The release agent composition preferably contains a solvent. As such a solvent, for example, a high-polarity solvent that can well dissolve the film-constituting components such as the above-mentioned organic resin, polynuclear phenol derivative, branched-chain polysilane, and crosslinking agent can be used. If necessary, a low-polarity solvent may be used for the purpose of adjusting viscosity, surface tension, etc. In the present invention, a low-polarity solvent is defined as one having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and a high-polarity solvent is defined as one having a relative dielectric constant of 7 or more at a frequency of 100 kHz. The solvents can be used alone or in combination of two or more.

[0175] Examples of highly polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, and cyclohexanone; cyano solvents such as acetonitrile and 3-methoxypropionitrile; polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, and 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, and tetrahydrofurfuryl alcohol; and sulfoxide solvents such as dimethyl sulfoxide.

[0176] Examples of low-polarity solvents include chlorine-based solvents such as chloroform and chlorobenzene; aromatic hydrocarbon-based solvents such as alkylbenzenes such as toluene, xylene, tetralin, cyclohexylbenzene and decylbenzene; aliphatic alcohol-based solvents such as 1-octanol, 1-nonanol and 1-decanol; ether-based solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether and triethylene glycol butyl methyl ether; and ester-based solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isoamyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

[0177] The content of the solvent is determined appropriately taking into consideration the viscosity of the desired composition, the coating method to be used, the thickness of the film to be produced, and the like, but is 99% by mass or less of the entire composition, and preferably 70 to 99% by mass of the entire composition, i.e., the amount of the film-constituting components in this case is 1 to 30% by mass of the entire composition.

[0178] The viscosity and surface tension of the stripping composition are appropriately adjusted by changing the types of solvents used, their ratios, the concentrations of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

[0179] In one embodiment of the present invention, the stripper composition contains a glycol-based solvent from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that gives a highly uniform film, etc. Note that the term "glycol-based solvent" used here is a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0180] An example of a preferred glycol-based solvent is represented by formula (G).

[0181]

[0182] In formula (G), R Ｇ１ each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms; R Ｇ２ and R Ｇ３ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms; n ｇ is an integer from 1 to 6.

[0183] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include, but are not limited to, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, a 2-methylpropane-1,3-diyl group, a pentamethylene group, a hexamethylene group, etc. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, linear or branched alkylene groups having 2 to 3 carbon atoms are preferred, and linear or branched alkylene groups having 3 carbon atoms are more preferred.

[0184] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl Examples of the alkyl group include, but are not limited to, a methyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Among these, from the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0185] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms include the same as the specific examples described above. Among these, from the viewpoints of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition having high storage stability, and reproducibly obtaining a composition that gives a highly uniform film, a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0186] n ｇ is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and most preferably 1, from the viewpoint of reproducibly obtaining a highly uniform composition, from the viewpoint of reproducibly obtaining a composition with high storage stability, from the viewpoint of reproducibly obtaining a composition that gives a highly uniform film, etc.

[0187] From the viewpoint of reproducibly obtaining a composition having high uniformity, a composition having high storage stability, and a composition that gives a film having high uniformity, it is preferable that R Ｇ２ and R Ｇ３ At least one of R is a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably R Ｇ２ and R Ｇ３ One of the groups is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkylacyl group in which the alkyl portion is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0188] From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the content of the glycol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more, relative to the solvent contained in the stripper composition. From the viewpoint of reproducibly obtaining a highly uniform composition, a highly storage stable composition, and a composition that gives a highly uniform film, the film constituent components in the stripper composition are uniformly dispersed or dissolved, preferably dissolved, in the solvent.

[0189] The release agent composition can be produced, for example, by mixing an organic resin or a polynuclear phenol derivative, a solvent, and, if necessary, a crosslinker. The order of mixing is not particularly limited, and examples of methods that can easily and reproducibly produce a release agent composition include, but are not limited to, a method in which the organic resin or polynuclear phenol derivative and the crosslinker are dissolved in a solvent at once, or a method in which a portion of the organic resin or polynuclear phenol derivative and the crosslinker are dissolved in a solvent and the remainder is separately dissolved in a solvent, and the resulting solutions are mixed. Furthermore, when preparing the release agent composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, in order to remove foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the release agent composition or after mixing all the components.

[0190] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, in one embodiment 10 nm to 10 μm, in another embodiment 50 nm to 1 μm, and in still another embodiment 100 nm to 700 nm.

[0191] The method for forming a release agent layer from a release agent composition is not particularly limited, but examples include a method of forming a release agent layer by applying the release agent composition. The method for applying the release agent composition is not particularly limited, but is typically spin coating. The heating temperature of the applied release agent composition cannot be generally specified because it varies depending on the type and amount of release agent components contained in the release agent composition, the desired thickness of the release agent layer, etc., but from the perspective of reproducibly achieving a suitable release agent layer, it is 80°C or higher and 300°C or lower, and the heating time is typically determined appropriately within the range of 10 seconds to 10 minutes depending on the heating temperature. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds to 8 minutes, more preferably 1 minute to 5 minutes. Heating can be performed using a hot plate, oven, or the like.

[0192] An example of the configuration of the laminate of the first embodiment will be described below with reference to the drawings. Fig. 1 shows a schematic cross-sectional view of an example of the laminate of the first embodiment. The laminate of Fig. 1 has a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4, in this order. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 contacts the semiconductor substrate 1 and the support substrate 4.

[0193] Another example of the configuration of the laminate of the first embodiment will be described below with reference to the drawings. Figure 2 shows a schematic cross-sectional view of another example of the laminate of the first embodiment. The laminate of Figure 2 has a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4, in this order. The adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0194] <<Manufacturing Method of an Example of the Laminate in the First Embodiment>> A manufacturing method of a laminate will be described below using the laminate shown in Fig. 1 as an example of the laminate in the first embodiment. An example of the laminate of the present invention can be manufactured, for example, by a method including the following first and second steps. First step: A step of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer. Second step: A step of heating the adhesive coating layer to form an adhesive layer.

[0195] The method for applying the adhesive composition is not particularly limited, but is typically spin coating. Alternatively, a method can be employed in which a coating film is formed separately by spin coating or the like, a sheet-like coating film is formed, and the sheet-like coating film is then applied as an adhesive coating layer. The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the boiling point of the solvent used, the desired thickness of the adhesive layer, and other factors. However, it is typically 80 to 150°C, and the heating time is typically 30 seconds to 5 minutes. When the adhesive composition contains a solvent, the applied adhesive composition is typically heated. The thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is typically about 5 to 500 μm, and is appropriately determined so as to ultimately achieve the above-mentioned range of adhesive layer thickness.

[0196] In the present invention, the laminate of the present invention can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment, a decompression treatment, or both, and then performing a post-heat treatment. The treatment conditions to be adopted, whether heat treatment, decompression treatment, or a combination of both, are appropriately determined taking into consideration various factors such as the type of adhesive composition, the film thickness, and the desired adhesive strength.

[0197] The heat treatment temperature is determined appropriately from the viewpoint of removing the solvent from the composition, etc., usually within the range of 20 to 160° C. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component (A), the heat treatment temperature is preferably 150° C. or lower, more preferably 130° C. or lower, and the heating time is determined appropriately depending on the heating temperature and the type of adhesive, but is usually 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of reliably achieving suitable adhesion, and is usually 10 minutes or shorter, preferably 5 minutes or shorter, from the viewpoint of suppressing deterioration of the adhesive layer and other components.

[0198] The reduced pressure treatment can be carried out by exposing the adhesive coated layers in contact with each other to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0199] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the layers therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 50,000 N.

[0200] The post-heating temperature is preferably 120°C or higher from the viewpoint of achieving a sufficient curing rate, 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 longer, preferably 5 minutes or longer, from the viewpoint of achieving suitable bonding of the substrate and layers constituting the laminate, and usually 180 minutes or shorter, preferably 120 minutes or shorter, 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, or the like. When post-heating is performed using a hot plate, either the semiconductor substrate or the support substrate of the laminate may be heated facing down, but from the viewpoint of achieving suitable peeling with good reproducibility, post-heating with the semiconductor substrate facing down is preferred. Note that one purpose of the post-heating treatment is to achieve an adhesive layer that is a more suitable free-standing film, and in particular to achieve suitable curing by a hydrosilylation reaction.

[0201] 3A to 3C are diagrams illustrating one embodiment of manufacturing a laminate. First, a laminate is prepared in which an adhesive coating layer 2a is formed on a semiconductor substrate 1 (FIG. 3A). This laminate can be obtained, for example, by applying an adhesive composition to the semiconductor substrate 1 and heating it. Next, the laminate shown in FIG. 3A is bonded to a support substrate 4 so that the adhesive coating layer 2a contacts the support substrate 4. Then, a load is applied in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure. After that, a heating device (not shown; hot plate) is placed on the surface of the semiconductor substrate 1 opposite the surface where the adhesive coating layer 2a contacts. The heating device heats and hardens the adhesive coating layer 2a, converting it into the adhesive layer 2 (FIG. 3B). The laminate shown in FIG. 1 is obtained by the steps shown in FIGS. 3A and 3B.

[0202] Second Embodiment The laminate having an electronic device layer is used for processing the electronic device layer. While the electronic device layer is being processed, the electronic device layer is adhered to a support substrate. After the electronic device layer is processed, the electronic device layer is separated from the support substrate.

[0203] <<Electronic Device Layer>> The electronic device layer refers to a layer having an electronic device. In the present invention, it refers to a layer in which multiple semiconductor chip substrates are embedded in a sealing resin, that is, a layer consisting of multiple semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates. Here, "electronic device" refers to a member that constitutes at least a part of an electronic component. The electronic device is not particularly limited and can be a semiconductor substrate having various mechanical structures or circuits formed on the surface thereof. The electronic device is preferably a composite of a member made of metal or semiconductor and a resin that seals or insulates the member. The electronic device may have a rewiring layer (described later) and / or a semiconductor element or other element sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.

[0204] <<Support Substrate>> Examples of the support substrate include those similar to those explained in the section <<Support Substrate>> of the <First Embodiment>> above.

[0205] <<Release Agent Layer>> The release agent layer is formed using the release agent composition for photoirradiation peeling of the present invention described above. Details of the release agent layer are as described above in the section <<Release Agent Layer>> of the <First Embodiment>>.

[0206] <<Adhesive Layer>> The adhesive layer is formed using the adhesive composition described above. Details of the adhesive layer are as described above in the <<Adhesive Layer>> section of the <First Embodiment>>.

[0207] An example of the configuration of the laminate of the second embodiment will be described below with reference to the drawings. The laminate of Fig. 4 has a support substrate 24, an adhesive layer 22, and an electronic device layer 26, in this order. The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and sealing resin 25, which is a sealing material, disposed between the semiconductor chip substrates 21. The adhesive layer 22 is provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 contacts the electronic device layer 26 and the support substrate 24.

[0208] Figure 5 shows a schematic cross-sectional view of another example of the laminate of the second embodiment. The laminate of Figure 5 has a support substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26, in this order. The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and sealing resin 25, which serves as a sealing material, disposed between the semiconductor chip substrates 21. The adhesive layer 22 and the release agent layer 23 are provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0209] <<Example of Manufacturing Method of Laminate in Second Embodiment>> A method for manufacturing a laminate will be described below using the laminate shown in Figure 4 as an example of the laminate in the second embodiment. The laminate of the present invention can be manufactured, for example, by a method including the following first to fourth steps. First step: applying an adhesive composition to the surface of the support substrate to form an adhesive coating layer (and, if necessary, further heating to form an adhesive layer). Second step: placing a semiconductor chip substrate on the adhesive coating layer or adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or adhesive layer while performing at least one of a heat treatment and a decompression treatment. Third step: curing the adhesive coating layer by post-heat treatment to form an adhesive layer. Fourth step: sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin. Step 2 will be described in more detail, for example, by step (i) of the following embodiment. (i) A semiconductor chip substrate is placed on the adhesive coating layer or adhesive layer, and while performing at least one of a heat treatment and a decompression treatment, a load is applied in the thickness direction of the semiconductor chip substrate and the support substrate to bring them into close contact, and the semiconductor chip substrate is bonded to the adhesive coating layer or adhesive layer.

[0210] The third step may be performed after bonding the semiconductor chip substrate to the adhesive coating layer in the second step, or may be performed in conjunction with the second step. For example, the semiconductor chip substrate may be placed on the adhesive coating layer, and the adhesive coating layer may be heated and cured while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, thereby simultaneously achieving close contact between the semiconductor chip substrate and the adhesive coating layer and curing the adhesive coating layer to the adhesive layer, thereby bonding the adhesive layer to the semiconductor chip substrate. The third step may also be performed before the second step, in which the semiconductor chip substrate is placed on the adhesive layer, and the adhesive layer may be bonded to the semiconductor chip substrate while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.

[0211] The application method, the heating temperature of the applied adhesive composition, the heating means, etc. are as described above in <<An example of the method for producing the laminate in the first embodiment>> of the <First embodiment>>.

[0212] The procedure for manufacturing a laminate according to the second embodiment will be described in more detail below with reference to the accompanying drawings. This manufacturing method produces the laminate shown in FIG. 4 . As shown in FIG. 6A , an adhesive coating layer 22′ made of an adhesive composition is formed on a support substrate 24. The adhesive coating layer 22′ may be heated to form the adhesive layer 22. Next, as shown in FIG. 6B , a semiconductor chip substrate 21 is placed on the adhesive layer 22 or the adhesive coating layer 22′. While performing at least one of a heat treatment and a decompression treatment, a load is applied in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 to bring them into close contact, bonding the semiconductor chip substrate 21 to the adhesive layer 22 or the adhesive coating layer 22′. When the semiconductor chip substrate 21 is bonded to the adhesive coating layer 22′, the adhesive coating layer 22′ is post-heat treated to harden it into the adhesive layer 22, and the semiconductor chip substrate 21 is then fixed to the adhesive layer 22. Next, as shown in FIG. 6C , the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed with a sealing resin 25. 6C , a plurality of semiconductor chip substrates 21 temporarily adhered to a support substrate 24 via an adhesive layer 22 are sealed with a sealing resin 25. An electronic device layer 26 having semiconductor chip substrates 21 and sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22. In this manner, the electronic device layer 26 is a base layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0213] <<<Encapsulating Step>>> The semiconductor chip substrate 21 is encapsulated using an encapsulant. The encapsulant used for encapsulating the semiconductor chip substrate 21 is a material capable of insulating or encapsulating metal or semiconductor components. In the present invention, for example, a resin composition (encapsulating resin) is used as the encapsulant. The type of encapsulating resin is not particularly limited as long as it is capable of encapsulating and / or insulating metal or semiconductor components. For example, epoxy-based resins or silicone-based resins are preferably used. The encapsulating material may contain other components, such as fillers, in addition to the resin component. Examples of fillers include spherical silica particles. In the encapsulating step, the encapsulating resin, heated to, for example, 130 to 170°C, is supplied onto the adhesive layer 22 while maintaining a high viscosity, covering the semiconductor chip substrate 21. The encapsulating resin is then compression-molded to form a layer of encapsulating resin 25 on the adhesive layer 22. The temperature conditions are, for example, 130 to 170°C. The pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm. ２ is.

[0214] (Method for manufacturing a processed semiconductor substrate or an electronic device layer) Using the laminate of the present invention, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided. The "method for manufacturing a processed semiconductor substrate" uses the laminate described in the <First embodiment> section of the above (Laminate). The "method for manufacturing a processed electronic device layer" uses the laminate described in the <Second embodiment> section of the above (Laminate). The "method for manufacturing a processed semiconductor substrate" will be explained in the <Third embodiment> below, and the "method for manufacturing a processed electronic device layer" will be explained in the <Fourth embodiment> below.

[0215] <Third embodiment> The method for producing a processed semiconductor substrate of the present invention includes the following step 5A and step 6A. The method for producing a processed electronic device layer may further include the following step 7A. Here, step 5A is a step of processing the semiconductor substrate in the stack described in the above <First embodiment> section. Furthermore, step 6A is a step of separating the semiconductor substrate processed in step 5A from the support substrate. Furthermore, step 7A is a step of cleaning the processed semiconductor substrate after step 6A.

[0216] The processing performed on the semiconductor substrate in step 5A is, for example, processing of the side opposite the circuit surface of the wafer, such as thinning the wafer by polishing the back surface of the wafer. Thereafter, for example, through-silicon vias (TSVs) are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally mounted. Also, for example, before or after this, formation of wafer backside electrodes is also performed. During the wafer thinning and TSV process, a heat load of approximately 250 to 350°C is applied while the wafer is adhered to the support substrate. The laminate of the present invention, including the adhesive layer, typically has heat resistance to this load. Note that the processing is not limited to the above-described processing, and also includes, for example, the implementation of a semiconductor component mounting process when the wafer is temporarily adhered to a support substrate to support the substrate for mounting the semiconductor component.

[0217] In Step 6A, the method for separating (peeling) the semiconductor substrate and the support substrate is not particularly limited. For example, a mechanical peeling method using a tool with a sharp portion (a so-called debonder) can be used. Specifically, for example, a sharp portion is inserted between the semiconductor substrate and the support substrate, and then the semiconductor substrate and the support substrate are separated. Furthermore, when the laminate has a release agent layer, the method for separating (peeling) the semiconductor substrate and the support substrate in Step 6A may be, for example, a peeling method in which the release agent layer is irradiated with light and then the semiconductor substrate and the support substrate are peeled off from each other. By irradiating the release agent layer with light from the support substrate side, the release agent layer is altered (e.g., separated or decomposed) as described above, and then, for example, one of the substrates can be lifted up to easily separate the semiconductor substrate and the support substrate.

[0218] The light irradiation of the release agent layer does not necessarily have to be performed on the entire area of ​​the release agent layer. Even if there are regions irradiated with light and regions not irradiated with light, as long as the release ability of the release agent layer as a whole is sufficiently improved, the semiconductor substrate and the support substrate can be separated by a slight external force, such as by lifting up the support substrate. The ratio and positional relationship of the light-irradiated and non-irradiated regions will vary depending on the type and specific composition of the adhesive used, the thickness of the adhesive layer, the thickness of the release agent layer, the intensity of the light irradiated, etc., but those skilled in the art will be able to set appropriate conditions without the need for excessive testing. For these reasons, the method for producing a processed semiconductor substrate of the present invention makes it possible to shorten the light irradiation time when peeling is performed by light irradiation from the support substrate side, for example, when the support substrate of the laminate used is optically transparent. As a result, not only can throughput be improved, but physical stresses and the like required for peeling can be avoided, and the semiconductor substrate and the support substrate can be easily and efficiently separated by light irradiation alone. Typically, the light irradiation dose for peeling is 50 to 3,000 mJ / cm. ２ The irradiation time is appropriately determined depending on the wavelength and the irradiation amount.

[0219] The wavelength of the light used for peeling is, for example, preferably 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 light irradiation amount required for peeling is an irradiation amount that can cause suitable alteration, for example, decomposition, of the specific compound and polymer. The light used for peeling may be laser light or non-laser light emitted from a light source such as an ultraviolet lamp.

[0220] The substrate can be cleaned by spraying the cleaning composition onto the surface of at least one of the separated semiconductor substrate and the support substrate, or by immersing the separated semiconductor substrate or the support substrate in the cleaning composition. The surface of the processed semiconductor substrate or the like may also be cleaned using a removal tape or the like. As an example of cleaning the substrate, after the step 6A, a step 7A of cleaning the processed semiconductor substrate may be performed. Examples of cleaning compositions used for cleaning include the following.

[0221] Detergent compositions usually contain a solvent. Examples of solvents 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, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers (e.g., monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether) or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. 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, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene. These may 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.

[0222] Also preferred are mixed solvents containing PGMEA and a polar solvent. The blending ratio (mass ratio) can be determined appropriately taking into account the compatibility of the PGMEA and the polar solvent, but is preferably within the range of 1:9 to 9:1, and more preferably 2:8 to 8:2. For example, when EL is blended as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2. When PGME is blended as the 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 the 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.

[0223] The cleaning composition may or may not contain a salt; however, the absence of a salt is preferred in terms of increasing versatility in processing semiconductor substrates using the laminate and reducing costs.

[0224] An example of a detergent composition containing a salt is a detergent 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 is used for this type of application. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, the anion paired with the quaternary ammonium cation is a hydroxide ion (OH － ) ; fluorine ion (F － ), chloride ions (Cl － ), bromine ion (Br － ), iodine ion (I － ) and other halogen ions; tetrafluoroborate ion (BF４ － ) ; hexafluorophosphate ion (PF ６ － ) and the like, but are not limited to these.

[0225] 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 either the cation or the anion, but is preferably contained in the anion.

[0226] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group 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 aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Of these, tetrabutylammonium fluoride is preferred.

[0227] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the cleaning composition, but is usually 0.1 to 30 mass% based on the cleaning composition.

[0228] When the cleaning composition contains a salt, the solvent to be used in combination with the salt is not particularly limited as long as it is used for this type of application and dissolves the salt such as a quaternary ammonium salt. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent cleaning properties and from the viewpoint of satisfactorily dissolving the salt such as a quaternary ammonium salt to obtain a cleaning composition having excellent uniformity, the cleaning composition preferably contains one or two or more amide solvents.

[0229] A suitable example of the amide solvent is an acid amide derivative represented by formula (Z).

[0230] 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. Ａ and R Ｂ each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be 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, and a cyclobutyl group. Of these, R Ａ and R Ｂ As the alkyl group, a methyl group or an ethyl group is preferred, and both of them are more preferably methyl groups or ethyl groups, and both of them are even more preferably methyl groups.

[0231] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,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, etc. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0232] 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.

[0233] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0234] In formula (Y), R １０１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R １０２ represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, but are not limited to these.

[0235] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, and these can be used alone or in combination of two or more.

[0236] In a preferred embodiment, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0237] The cleaning composition used in the present invention may contain water as a solvent, but usually only an organic solvent is used as the solvent from the viewpoint of avoiding corrosion of the substrate, etc. In this case, it is not excluded that the cleaning composition may contain water of hydration of salts or trace amounts of water contained in the organic solvent. The water content of the cleaning composition used in the present invention is usually 5 mass% or less.

[0238] The constituent elements and methodological elements of 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 spirit and scope of the present invention. The method for manufacturing a processed semiconductor substrate of the present invention may include steps other than those described above.

[0239] In one example of the peeling method of the present invention, when the semiconductor substrate or support substrate of the laminate of the present invention is optically transparent, the semiconductor substrate and support substrate of the laminate are separated by irradiating the release agent layer with light from the semiconductor substrate side or the support substrate side. In one example of the laminate of the present invention, the semiconductor substrate and support substrate are suitably and releasably temporarily bonded by the adhesive layer and the release agent layer. Therefore, for example, when the support substrate is optically transparent, the semiconductor substrate and support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Usually, peeling is performed after processing the semiconductor substrate of the laminate.

[0240] An example of the third embodiment will be described with reference to FIGS. 7A to 7D. This example is an example of manufacturing a thinned semiconductor substrate. First, a laminate is prepared (FIG. 7A). This laminate is the same as the laminate shown in FIGS. 1 and 3B. Next, a polishing device (not shown) is used to polish the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2, thereby thinning the semiconductor substrate 1 (FIG. 7B). The thinned semiconductor substrate 1 may also be subjected to the formation of through-hole electrodes, etc. Next, a peeling device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4 (FIG. 7C). This results in the thinned semiconductor substrate 1 (FIG. 7D). Residues of the adhesive layer 2 may remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 using a cleaning composition to remove the residue of the adhesive layer 2 from the semiconductor substrate 1.

[0241] <Fourth embodiment> The method for producing a processed electronic device layer of the present invention includes the following step 5B and step 6B. The method for producing a processed electronic device layer may further include the following step 7B. Here, step 5B is a step of processing the electronic device layer in the laminate described in the above <Second embodiment> section. Furthermore, step 6B is a step of separating the electronic device layer processed in step 5B from the support substrate. Furthermore, step 7B is a step of cleaning the processed electronic device layer after step 6B. Specific examples of the fourth embodiment will be described below with reference to FIGS. 8A to 8F.

[0242] Examples of the processing performed on the electronic device layer in the step 5B include a grinding step and a wiring layer forming step.

[0243] <<Grinding Process>> The grinding process is a process of grinding the resin portion of the layer of sealing resin 25 in the electronic device layer 26 so as to expose a part of the semiconductor chip substrate 21. Grinding of the sealing resin portion is performed by grinding the layer of sealing resin 25 of the stack shown in Fig. 8A until it has a thickness substantially equal to that of the semiconductor chip substrate 21, as shown in Fig. 8B, for example. The stack shown in Fig. 8A is the same stack as the stacks shown in Figs. 4 and 6C.

[0244] <<Wiring Layer Forming Process>> The wiring layer forming process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the grinding process. In FIG. 8C , a wiring layer 28 is formed on an electronic device layer 26 consisting of the semiconductor chip substrate 21 and a layer of sealing resin 25. The wiring layer 28 is also called an RDL (Redistribution Layer), and is a thin-film wiring body that constitutes wiring connected to the substrate, and can have a single-layer or multi-layer structure. The wiring layer is made of a dielectric (silicon oxide (SiO ｘThe wiring layer 28 may be formed by forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys) and a layer of a sealing resin 25 (for example, a photosensitive resin such as photosensitive epoxy, photosensitive epoxy, etc.). The wiring layer 28 may be formed by, for example, forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys, etc. ...). The wiring layer 28 may be formed by, for example, forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys, etc.). The wiring layer 28 may be formed by, for example, forming wiring between a conductive material (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys, etc.). ｘ ), a dielectric layer made of a photosensitive resin or the like is formed. The dielectric layer made of silicon oxide can be formed by, for example, sputtering, vacuum deposition, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin onto the layer of sealing resin 25 by, for example, spin coating, dipping, roller blade, spray coating, slit coating, or the like. Next, wiring is formed on the dielectric layer using a conductor such as metal. Methods for forming wiring can include, for example, known semiconductor process techniques such as lithography processes such as photolithography (resist lithography) and etching processes. Examples of such lithography processes include lithography processes using a positive resist material and lithography processes using a negative resist material. In the manufacturing method of the laminate according to the fourth embodiment, bumps can be formed on the wiring layer 28, or elements can be mounted on the wiring layer 28. Elements can be mounted on the wiring layer 28 using, for example, a chip mounter. The stack according to the fourth embodiment may be a stack produced in a process based on fan-out technology, in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer extending outside the chip area.

[0245] In Step 6B, methods for separating (peeling) the electronic device layer from the support substrate include, but are not limited to, mechanical peeling using a tool with a sharp part, peeling by pulling the support and the electronic device layer apart, etc. When the laminate has a release agent layer, for example, light can be irradiated onto the release agent layer from the support substrate side to cause alteration of the release agent layer (e.g., separation or decomposition of the release agent layer) as described above, and then the electronic device layer can be easily separated from the support substrate by, for example, lifting up one of the substrates.

[0246] 8D to 8E are schematic cross-sectional views illustrating a method for separating the stack, and Fig. 8F is a schematic cross-sectional view illustrating a cleaning method after separation of the stack. One embodiment of a method for manufacturing a semiconductor package (electronic component) can be explained with reference to Figs. 8D to 8F. The step of separating the stack is a step of separating the electronic device layer 26 and the support substrate 24 using a peeling device (not shown), as shown in Figs. 8D and 8E.

[0247] The substrate can be cleaned by spraying the cleaning composition onto at least one surface of the separated electronic device layer and / or the supporting substrate, or by immersing the separated electronic device layer or the supporting substrate in the cleaning composition. Alternatively, the surface of the processed electronic device layer, etc., may be cleaned using a removal tape or the like. For example, in FIG. 8E , after the separation step, an adhesive layer 22 is attached to the electronic device layer 26. The adhesive layer 22 can be removed by decomposing the adhesive layer 22 using a cleaning composition such as an acid or alkali. By removing the adhesive layer, a processed electronic device layer (electronic component) such as that shown in FIG. 8F can be suitably obtained.

[0248] The constituent elements and methodological elements of the above-described steps of the method for producing a processed electronic device layer of the present invention may be modified in various ways without departing from the spirit and scope of the present invention. The method for producing a processed electronic device layer of the present invention may include steps other than those described above.

[0249] 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.

[0250] [Apparatus] (1) Mixer: ARE-500, a planetary centrifugal mixer manufactured by Thinky Corporation (2) Vacuum bonding device: XBS-300, manufactured by SUSS Microtec Co., Ltd. (3) Substrate peeling device: XBC300, manufactured by SUSS Microtec Co., Ltd.

[0251] [1] Preparation of Release Agent Component [Synthesis Example 1] 4.0 g of hexyl acrylate (Tokyo Chemical Industry Co., Ltd.), 0.2 g of 2,2'-azodiisobutyronitrile (Tokyo Chemical Industry Co., Ltd.), and 4.2 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and stirred at 60°C for 24 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was dried under reduced pressure at 60°C to obtain Release Agent Component 1. The weight average molecular weight measured by GPC in terms of standard polystyrene was 14,000.

[0252] Synthesis Example 2 5.0 g of ethylhexyl acrylate (Tokyo Chemical Industry Co., Ltd.), 0.125 g of 2,2'-azodiisobutyronitrile (Tokyo Chemical Industry Co., Ltd.), and 5.125 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and stirred at 60°C for 24 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was dried under reduced pressure at 60°C to obtain release agent component 2. The weight average molecular weight measured by GPC in terms of standard polystyrene was 11,000.

[0253] Synthesis Example 3 5.0 g of dodecyl acrylate (Tokyo Chemical Industry Co., Ltd.), 0.25 g of 2,2'-azodiisobutyronitrile (Tokyo Chemical Industry Co., Ltd.), and 5.25 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added and stirred at 60°C for 24 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was dried under reduced pressure at 60°C to obtain release agent component 3. The weight average molecular weight measured by GPC in terms of standard polystyrene was 12,000.

[0254] [2] Preparation of adhesive composition [Preparation Example 1] 80 g of MQ resin (manufactured by Wacker Chemie) containing a polysiloxane skeleton and a vinyl group, 2.52 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 100 mPa·s, 5.89 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) having a viscosity of 70 mPa·s, 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie), and 19.83 g of p-menthane (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a 600 mL stirring vessel dedicated to a planetary centrifugal mixer, and the mixture was stirred for 5 minutes with a stirrer to obtain a mixture (1). 0.147 g of platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of vinyl-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1,000 mPa·s were added and stirred with a stirrer for 5 minutes to obtain mixture (2). 3.96 g of the obtained mixture (2) was added to mixture (1) and stirred with a stirrer for 5 minutes to obtain an adhesive component. 0.1 g of release agent component 1 was added to 10 g of the obtained adhesive component and stirred with a stirrer for 5 minutes. Finally, the composition obtained by mixing was filtered through a 300 mesh nylon filter to obtain adhesive composition 1.

[0255] Preparation Examples 2 and 3 Adhesive composition 2 and adhesive composition 3 were obtained in the same manner as in Preparation Example 1 above, except that release agent component 1 was replaced with release agent component 2 or 3, respectively.

[0256] [3] Preparation of Laminate for Evaluation [Example 1] The adhesive composition 1 obtained in Preparation Example 1 was spin-coated onto a 300 mm silicon substrate (thickness 775 μm) so that the film thickness of the final laminate was approximately 60 μm, and heated at 120 °C for 90 seconds to form an adhesive coating layer on the sample substrate, which was a semiconductor substrate. Then, using a bonding device, the silicon substrates were bonded together with the adhesive coating layer sandwiched between them, and then the sample substrate was placed face down and post-heated on a hot plate at 200 °C for 10 minutes to produce a laminate. The bonding was performed at a temperature of 23 °C and a vacuum of 1,500 Pa. A substrate peeling device was used to insert a wedge between the device-side substrate and the carrier-side substrate, and the carrier-side substrate was lifted to perform peeling. When peeling was confirmed, peeling was easily achieved.

[0257] REFERENCE SIGNS LIST 1 semiconductor substrate 2 adhesive layer 2a adhesive coating layer 3 release agent layer 4 support substrate 21 semiconductor chip substrate 22 adhesive layer 22' adhesive coating layer 23 release agent layer 24 support substrate 25 sealing resin 26 electronic device layer 28 wiring layer

Claims

1. An adhesive composition for forming an adhesive layer used to temporarily bond a semiconductor substrate or an electronic device layer to a support substrate, the adhesive composition comprising an adhesive component and a (meth)acrylic acid ester-based polymer having a repeating unit represented by the following formula (1): (In formula (1), R １ represents a hydrogen atom or a methyl group, R ２ represents an alkyl group having 1 to 20 carbon atoms.

2. The adhesive composition according to claim 1, wherein the alkyl group having 1 to 20 carbon atoms is a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms.

3. The adhesive composition according to claim 1, wherein the content of the (meth)acrylic acid ester polymer in the adhesive composition is 0.01% by mass to 30% by mass relative to the non-volatile content of the adhesive composition.

4. The adhesive composition according to claim 1, wherein the adhesive component is a component that cures by a hydrosilylation reaction.

5. The adhesive composition according to claim 4, wherein the components that cure by a hydrosilylation reaction contain: a component (A-1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms; a component (A-2) having a Si—H group; and a platinum group metal catalyst (A-3).

6. The adhesive composition according to claim 5, wherein the component (A-1) contains a polyorganosiloxane (a1) having a silicon-bonded alkenyl group having 2 to 40 carbon atoms.

7. The adhesive composition according to claim 6, wherein the component (A-2) contains a polyorganosiloxane having Si—H groups.

8. A laminate comprising: a semiconductor substrate or an electronic device layer; a light-transmitting support substrate; and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, wherein the adhesive layer is an adhesive layer formed from the adhesive composition according to any one of claims 1 to 7.

9. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: a step 5A in which the semiconductor substrate of the laminate described in claim 8 is processed, or a step 5B in which the electronic device layer of the laminate described in claim 8 is processed; and a step 6A in which the semiconductor substrate processed in step 5A is separated from the support substrate, or a step 6B in which the electronic device layer processed in step 5B is separated from the support substrate.

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