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

Abstract

This adhesive composition is a curable adhesive composition for forming an adhesive layer of a laminate having: a semiconductor substrate or an electronic device layer; a support substrate; and the adhesive layer is provided between the semiconductor substrate or the electronic device layer and the support substrate, and the adhesive composition contains a compound that does not have a siloxane bond and has a linear or branched alkyl chain having 5 or more carbon atoms.

Description

Technical Field

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

[0002] Semiconductor wafers, previously integrated in two dimensions, are now being pursued for further integration by integrating (stacking) these wafers in three dimensions. This three-dimensional stacking technique involves integrating multiple layers using through silicon vias (TSVs) while connecting them. During multi-layer integration, the backside of each wafer, opposite to the circuitry, is thinned by grinding, and the thinned semiconductor wafers are then stacked.

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

[0004] As temporary adhesives used for such temporary bonding, adhesives containing polydimethylsiloxane have been proposed (Patent Documents 1 and 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2017 / 221772 Pamphlet

[0008] Patent Document 2: International Publication No. 2022 / 202153 Pamphlet Summary of the Invention

[0009] Problems to be solved by the invention

[0010] As semiconductor integration technology diversifies, the types of adherends that adhesive layers formed of temporary adhesives contact also diversify, and adhesive layers are also used in contact with sealing resins, etc. Therefore, the adhesive layer is required to have good adhesion to adherends other than semiconductor wafers.

[0011] The present invention has been made in view of the above circumstances, and an object thereof is to provide an adhesive composition capable of forming an adhesive layer having excellent adhesiveness, a laminate using the adhesive composition, and a method for producing a processed semiconductor substrate or electronic device layer using the laminate.

[0012] Solutions for solving problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned technical problems and, as a result, have found that the above-mentioned technical problems can be solved, thereby completing the present invention having the following gist.

[0014] That is, the present invention includes the following contents.

[0015] [1] An adhesive composition, which is a curable adhesive composition for forming an adhesive layer of a laminate, wherein the laminate comprises: a semiconductor substrate or an electronic device layer; a supporting substrate; and the adhesive layer is provided between the semiconductor substrate or the electronic device layer and the supporting substrate, wherein the adhesive composition contains: a compound having no siloxane bond and having a linear or branched alkyl chain having 5 or more carbon atoms.

[0016] [2] The adhesive composition according to [1], wherein the molecular weight of the compound is 150 or more and 600 or less.

[0017] [3] The adhesive composition according to [1] or [2], wherein the content of the compound is 0.1% by mass or more and 5% by mass or less relative to the film-forming component.

[0018] [4] The adhesive composition according to any one of [1] to [3], wherein the total number of oxygen atoms and nitrogen atoms in the compound is 0 to 3.

[0019] [5] The adhesive composition according to any one of [1] to [4], wherein the adhesive composition is an adhesive composition that is cured by a hydrosilylation reaction.

[0020] [6] The adhesive composition according to [5], wherein the adhesive composition contains: a component (A-1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom; and a component (A-2) having a Si—H group.

[0021] [7] The adhesive composition according to [6], wherein the component (A-1) contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom.

[0022] [8] The adhesive composition according to [6] or [7], wherein the component (A-2) contains a polyorganosiloxane having a Si—H group.

[0023] [9] The adhesive composition according to any one of [5] to [8], wherein the adhesive composition contains a polyorganosiloxane as a component that does not undergo a hydrosilylation reaction.

[0024]

[10] A laminate comprising: a semiconductor substrate or an electronic device layer; a supporting substrate; and an adhesive layer disposed between the semiconductor substrate or the electronic device layer and the supporting substrate, the adhesive layer being an adhesive layer formed from the adhesive composition described in any one of [1] to [9].

[0025]

[11] The laminate according to

[10] , further comprising a release agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0026]

[12] A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: step 5A of processing the semiconductor substrate of the stacked body as described in

[10] ; or step 5B of processing the electronic device layer of the stacked body as described in

[10] ; and step 6A of separating the semiconductor substrate processed by step 5A from the supporting substrate; or step 6B of separating the electronic device layer processed by step 5B from the supporting substrate.

[0027] Effects of the Invention

[0028] According to the present invention, there are provided an adhesive composition capable of forming an adhesive layer having excellent adhesiveness, a laminate using the adhesive composition, and a method for producing a processed semiconductor substrate or electronic device layer using the laminate. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic cross-sectional view of an example of the laminated body according to the first embodiment.

[0030] Figure 2 This is a schematic cross-sectional view of another example of the laminated body according to the first embodiment.

[0031] Figure 3 This is a schematic cross-sectional view of another example of the laminated body according to the first embodiment.

[0032] Figure 4A This is a schematic cross-sectional view (part 1) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0033] Figure 4B This is a schematic cross-sectional view (part 2) for explaining a method for producing a laminated body showing an example of the first embodiment.

[0034] Figure 5 This is a schematic cross-sectional view of an example of a laminated body according to the second embodiment.

[0035] Figure 6 This is a schematic cross-sectional view of another example of the laminated body according to the second embodiment.

[0036] Figure 7A This is a schematic cross-sectional view (part 1) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0037] Figure 7B This is a schematic cross-sectional view (part 2) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0038] Figure 7C This is a schematic cross-sectional view (part 3) for explaining a method for producing a laminated body showing an example of the second embodiment.

[0039] Figure 8A This is a schematic cross-sectional view (part 1) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0040] Figure 8B This is a schematic cross-sectional view (part 2) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0041] Figure 8C This is a schematic cross-sectional view (part 3) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0042] Figure 8D This is a schematic cross-sectional view (part 4) for explaining a method for processing a laminated body showing an example of the first embodiment.

[0043] Figure 9A This is a schematic cross-sectional view (part 1) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0044] Figure 9B This is a schematic cross-sectional view (part 2) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0045] Figure 9C This is a schematic cross-sectional view (part 3) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0046] Figure 9D This is a schematic cross-sectional view (Part 4) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0047] Figure 9E This is a schematic cross-sectional view (No. 5) for explaining a method for processing a laminated body showing an example of the second embodiment.

[0048] Figure 9F This is a schematic cross-sectional view (No. 6) for explaining a method for processing a laminated body showing an example of the second embodiment. DETAILED DESCRIPTION

[0049] (Adhesive composition)

[0050] The adhesive composition of the present invention is a curable adhesive composition for forming an adhesive layer of a laminate comprising: a semiconductor substrate or an electronic device layer; a supporting substrate; and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the supporting substrate.

[0051] The adhesive composition contains a compound having no siloxane bond and having a linear or branched alkyl chain having 5 or more carbon atoms (hereinafter sometimes referred to as an "alkyl chain-containing compound").

[0052] The present inventors have conducted intensive studies to provide an adhesive composition capable of forming an adhesive layer having excellent adhesiveness.

[0053] The present inventors conducted studies and obtained the following findings.

[0054] When the adhesive composition contains an alkyl chain-containing compound, good adhesion can be obtained not only on a semiconductor wafer but also when the adhesive layer in an electronic device layer formed by sealing with a sealing resin contacts the sealing resin, thereby completing the present invention.

[0055] Examples of curable adhesive compositions include, but are not limited to, silicone adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives.

[0056] Among them, silicone adhesives are preferred as adhesive compositions because they exhibit suitable adhesion during processing of semiconductor substrates and can be appropriately peeled off after processing, have excellent heat resistance, and can be appropriately removed with a cleaning composition.

[0057] <Alkyl chain-containing compounds>

[0058] The compound containing an alkyl chain does not have a siloxane bond.

[0059] The alkyl chain-containing compound has a linear or branched alkyl chain having 5 or more carbon atoms.

[0060] The alkyl chain-containing compound may be a linear or branched alkyl chain having 5 or more carbon atoms, or may have a linear or branched alkyl chain having 5 or more carbon atoms at any position in its molecular chain.

[0061] The alkyl chain-containing compound is represented by, for example, the following formula (X).

[0062] R1-C n H 2n -R2 (X)

[0063] (In formula (X), R1 and R2 each independently represent a hydrogen atom or a monovalent group having no siloxane bond. -C n H 2n - represents a linear or branched alkyl chain having 5 or more carbon atoms. n represents an integer of 5 or more.

[0064] The molecular weight of the alkyl chain-containing compound is not particularly limited, but is preferably 150 to 1000, more preferably 150 to 800, and particularly preferably 150 to 600, from the viewpoint of preferably obtaining the effects of the present invention.

[0065] There is no particular limitation on the types of atoms constituting the alkyl chain-containing compound.

[0066] The alkyl chain-containing compound has carbon atoms and hydrogen atoms, and may further have oxygen atoms and nitrogen atoms.

[0067] The total number of oxygen atoms and nitrogen atoms in the alkyl chain-containing compound is not particularly limited, but is preferably 0 to 3.

[0068] The compound containing an alkyl chain may also be a saturated hydrocarbon compound.

[0069] The alkyl chain-containing compound may or may not have an aromatic ring.

[0070] The alkyl chain-containing compound may have one, two or more chains having a carbon-carbon unsaturated bond as a hydrocarbon chain other than a linear or branched alkyl chain having 5 or more carbon atoms, or may have no chain having a carbon-carbon unsaturated bond.

[0071] The alkyl chain-containing compound may have a cyclic alkyl structure as a hydrocarbon structure other than a linear or branched alkyl chain having 5 or more carbon atoms, or may not have a cyclic alkyl structure.

[0072] The alkyl chain-containing compound may have one linear or branched alkyl group having 5 or more carbon atoms, or may have two or more linear or branched alkyl groups having 5 or more carbon atoms.

[0073] The alkyl chain-containing compound preferably does not have both an alkynyl group and a hydroxyl group.

[0074] The alkyl chain-containing compound preferably does not have an α-acetylene alcohol structure.

[0075] Examples of the alkyl chain-containing compound include the following compounds.

[0076]

[0077] The above compound has a C 28 H 37 Based compounds.

[0078]

[0079] The above compound is a compound having two CH3(CH2)7 groups.

[0080]

[0081] The above compounds are saturated hydrocarbon compounds.

[0082]

[0083] The above compound is a compound having two CH3(CH2)8 groups.

[0084]

[0085] The above compound has a C 17 H 35 Based compounds.

[0086] The content of the alkyl chain-containing compound in the adhesive composition is not particularly limited, but from the viewpoint of preferably achieving the effects of the present invention, it is preferably 0.01% to 10% by mass, more preferably 0.05% to 8% by mass, and particularly preferably 0.1% to 5% by mass relative to the film-forming component.

[0087] The film-forming component refers to the component obtained by removing the solvent from the adhesive composition. When the adhesive composition does not contain a solvent, the adhesive composition itself is the film-forming component.

[0088] Adhesive ingredients

[0089] The adhesive composition preferably cures by a hydrosilylation reaction. In other words, the adhesive composition preferably contains a component that cures by a hydrosilylation reaction.

[0090] The component that cures by the hydrosilylation reaction is the adhesive component.

[0091] The component that is cured by the 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)"), a platinum group metal catalyst (A-3), and a crosslinking inhibitor (A-4).

[0092] <<Component (A-1) and component (A-2)>>

[0093] The adhesive composition preferably contains component (A-1).

[0094] The adhesive composition preferably contains component (A-2).

[0095] Hereinafter, the combination of component (A-1), component (A-2), platinum group metal catalyst (A-3), and crosslinking inhibitor (A-4) may be referred to as "cured component (A)" or "component (A)".

[0096] From the viewpoint of preferably obtaining the effects of the present invention, the component (A-1) preferably contains a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom.

[0097] From the viewpoint of preferably obtaining the effects of the present invention, the component (A-2) preferably contains a polyorganosiloxane (a2) having a Si—H group.

[0098] Here, the alkenyl group having 2 to 40 carbon atoms may be optionally substituted. 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.

[0099] In another preferred embodiment, the adhesive composition cured by hydrosilylation reaction comprises polysiloxane (A1) and a platinum group metal catalyst (A-3), wherein the polysiloxane (A1) comprises a siloxane unit (Q unit) selected from SiO2, R 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit), R 4 R 5 SiO 2 / 2 The siloxane units (D units) and R 6 SiO 3 / 2The polysiloxane (A1) comprises a polyorganosiloxane (a1') and a polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises a siloxane unit (Q' unit) represented by SiO2, a polyorganosiloxane unit (Q' unit), ... 1 'R 2 'R 3 'SiO 1 / 2 The siloxane units (M' units), R 4 'R 5 'SiO 2 / 2 The siloxane units (D' units) and R 6 'SiO 3 / 2 The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T' units) represented by SiO2, and at least one unit selected from the group consisting of M' units, D' units and T' units, wherein the polyorganosiloxane (a2') comprises a siloxane unit (Q' unit) represented by SiO2, R 1 ”R 2 ”R 3 "SiO 1 / 2 The siloxane units (M" units), R 4 ”R 5 "SiO 2 / 2 The siloxane units (D" units) and R 6 "SiO 3 / 2 The siloxane units (T" units) shown in the embodiment of the present invention are one or more units selected from the group consisting of the siloxane units (T" units), and contain at least one selected from the group consisting of M" units, D" units and T" units.

[0100] It should be noted that (a1′) is an example of (a1), and (a2′) is an example of (a2).

[0101] R 1 ~R 6 is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0102] R 1 '~R 6 ' is a group bonded to a silicon atom, each independently representing an optionally substituted alkyl group or an optionally substituted alkenyl group, R 1 '~R 6 At least one of ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0103] R 1 ”~R 6 " is a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl group or a hydrogen atom, R 1 ”~R 6 " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0104] The alkyl group may be linear, branched, or cyclic, preferably linear or branched. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0105] Specific examples of the optionally substituted linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1- Examples include, but are not limited to, 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. The number of carbon atoms in these groups is generally 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among these, methyl is particularly preferred.

[0106] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, and 2,4-dimethylcyclobutyl. Cycloalkyl groups such as cyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl, and 2-ethyl-3-methylcyclopropyl; bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, bicyclononyl, and dicyclodecyl, but are not limited thereto, and the number of carbon atoms thereof is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0107] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and further preferably 10 or less.

[0108] Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl. The number of carbon atoms in the alkenyl group is generally 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0109] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms in the cyclic alkenyl group is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0110] As described above, polysiloxane (A1) comprises polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl groups contained in polyorganosiloxane (a1') and the hydrogen atoms (Si—H groups) contained in polyorganosiloxane (a2') form a crosslinked structure through a hydrosilylation reaction using a platinum group metal catalyst (A-3), thereby curing. As a result, a cured film is formed.

[0111] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also comprises 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 that satisfy these conditions may be used in combination.

[0112] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units, and T' units include: (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units, and M' units), but are not limited to these.

[0113] When the polyorganosiloxane (a1′) contains two or more polyorganosiloxanes, the combination of (Q′ unit and M′ unit) and (D′ unit and M′ unit), the combination of (T′ unit and M′ unit) and (D′ unit and M′ unit), and the combination of (Q′ unit, T′ unit, and M′ unit) and (T′ unit and M′ unit) are preferred, but are not limited to these.

[0114] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and contains at least one unit selected from the group consisting of M" units, D" units, and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes that satisfy these conditions may be used in combination.

[0115] 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.

[0116] The polyorganosiloxane (a1′) is composed of siloxane units in which an alkyl group and / or an alkenyl group is bonded to the silicon atom thereof. 1 '~R 6 The ratio of alkenyl groups in all substituents represented by ' is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R 1 '~R 6 ' can be set to an alkyl group.

[0117] 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 6The ratio of all substituents and hydrogen atoms in the substituent atoms represented by " is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R 1 ”~R 6 " can be set to an alkyl group.

[0118] Preferred examples of the polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom include polyorganosiloxanes represented by the following formula (V) and polyorganosiloxanes represented by the following formula (W).

[0119]

[0120] (In formula (V), n represents the number of repeating units and is a positive integer.)

[0121]

[0122] (In formula (W), n and m represent the number of repeating units and are each independently a positive integer.)

[0123] When the adhesive composition contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in the polyorganosiloxane (a1) to hydrogen atoms constituting Si—H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0124] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is generally 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility.

[0125] It should be noted that in the present invention, the weight-average molecular weight, number-average molecular weight and dispersity of the polyorganosiloxane 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), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) used as a standard sample.

[0126] The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is generally 10 to 1,000,000 (mPa·s) each. From the perspective of achieving the effects of the present invention with good reproducibility, it is preferably 50 to 10,000 (mPa·s). The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values measured at 25°C using an E-type rotational viscometer.

[0127] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction. Therefore, their curing mechanism differs from, for example, a mechanism involving silanol groups. Therefore, neither siloxane needs to contain a silanol group or a functional group such as an alkoxy group that forms a silanol group upon hydrolysis.

[0128] <<Platinum Group Metal Catalyst (A-3)>>

[0129] Platinum group metal catalysts are metal catalysts of the platinum group.

[0130] Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between an alkenyl group and a Si—H group.

[0131] As specific examples of the platinum-based metal catalyst, substances known as platinum-based compounds (platinum or compounds containing platinum) can be used.

[0132] Specific examples thereof include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid and dienes, platinum-olefin complexes, platinum-carbonyl complexes (such as bis(acetylacetate)platinum and bis(acetylacetonate)platinum), chloroplatinic acid-alkenylsiloxane complexes (such as chloroplatinic acid-divinyltetramethyldisiloxane complex and chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex), platinum-alkenylsiloxane complexes (such as platinum-divinyltetramethyldisiloxane complex and platinum-tetravinyltetramethylcyclotetrasiloxane complex), and complexes of chloroplatinic acid and acetylenic alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high effect of promoting the hydrosilylation reaction.

[0133] These hydrosilylation reaction catalysts may be used alone or in combination of two or more.

[0134] The alkenylsiloxane used in the platinum-alkenylsiloxane complex is not particularly limited. 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 a portion of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, or the like, and alkenylsiloxane oligomers in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups, or the like. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred due to the excellent stability of the resulting platinum-alkenylsiloxane complex.

[0135] 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 the components (A-1) and (A-2).

[0136] <<Cross-linking inhibitor (A-4)>>

[0137] The crosslinking inhibitor (A-4) (also referred to as a polymerization inhibitor) is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction. Specific examples thereof include, but are not limited to, alkynyl alkyl alcohols optionally substituted with an aryl group, such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0138] The content of the crosslinking inhibitor (A-4) is usually 1000.0 ppm or more relative to the total mass of the component (A-1) and the component (A-2) in order to obtain the effect thereof, and is usually 10000.0 ppm or less in order to prevent excessive inhibition of the hydrosilylation reaction.

[0139] <Removal Agent Ingredients>

[0140] The adhesive composition may also contain a component that does not undergo a hydrosilylation reaction (hereinafter sometimes referred to as component (B)) as a release agent. Component (B) includes, for example, polyorganosiloxane. By including such a component (B) in the adhesive composition, the resulting adhesive layer can be properly and reproducibly released.

[0141] Typical examples of the component (B) include polyorganosiloxanes. Specific examples thereof include epoxy-containing polyorganosiloxanes, methyl-containing polyorganosiloxanes, and phenyl-containing polyorganosiloxanes, but the present invention is not limited thereto.

[0142] In addition, component (B) includes polydimethylsiloxane. The polydimethylsiloxane may be optionally modified. Examples of the optionally modified polydimethylsiloxane include, but are not limited to, epoxy-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl-containing polydimethylsiloxane.

[0143] Preferred examples of the polyorganosiloxane as the component (B) include epoxy-containing polyorganosiloxane, methyl-containing polyorganosiloxane, and phenyl-containing polyorganosiloxane, but are not limited thereto.

[0144] The weight-average molecular weight of the polyorganosiloxane as component (B) is not particularly limited, but is typically 100,000 to 2,000,000. From the perspective of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but is typically 1.0 to 10.0. From the perspective of achieving appropriate peeling with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight-average molecular weight and dispersity can be measured by the methods described above for polyorganosiloxanes.

[0145] The viscosity of the polyorganosiloxane as component (B) is not particularly limited, but is usually 1,000 to 2,000,000 mm 2 / s. It should be noted that the viscosity of the polyorganosiloxane as component (B) is represented by kinematic viscosity, which is centistokes (cSt) = mm 2 / s. It can also be calculated by dividing the viscosity (mPa·s) by the density (g / cm 3 That is, its value can be obtained from the viscosity and density measured at 25°C using an E-type rotational viscometer, or from the kinematic viscosity (mm 2 / s) = viscosity (mPa·s) / density (g / cm 3 ) is calculated using this formula.

[0146] Examples of epoxy group-containing polyorganosiloxanes include those containing R 11 R 12 SiO 2 / 2 The siloxane units (D 10 units) of polyorganosiloxane.

[0147] R 11 is a group bonded to a silicon atom, representing an alkyl group, R 12 It is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group include those described above.

[0148] The epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings such as 1,2-epoxycyclohexyl group.

[0149] Specific examples of the organic group containing an epoxy group include a 3-glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)ethyl group, but are not limited to these.

[0150] In the present invention, a preferred example of the epoxy-containing polyorganosiloxane is epoxy-containing polydimethylsiloxane, but the present invention is not limited thereto.

[0151] The epoxy-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 10 Unit), but except for D 10 In addition to the Q unit, the Q unit, the M unit and / or the T unit may be contained.

[0152] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: 10 Polyorganosiloxane composed of units; containing D 10 Unit and Q unit polyorganosiloxane; containing D 10 Unit and M unit polyorganosiloxane; containing D 10 Units and T units of polyorganosiloxane; containing D 10 Unit, Q unit and M unit polyorganosiloxane; containing D 10 Unit, M unit and T unit polyorganosiloxane; containing D 10 unit, Q unit, M unit and T unit polyorganosiloxane, etc.

[0153] The epoxy-containing polyorganosiloxane is preferably an epoxy-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight thereof is not particularly limited but is usually 1,500 to 500,000, and is preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0154] Specific examples of the epoxy-containing polyorganosiloxane include polyorganosiloxanes represented by formulae (E1) to (E3), but are not limited thereto.

[0155]

[0156] (m1 and n1 represent the number of repeating units and are positive integers.)

[0157]

[0158] (m2 and n2 represent the number of repeating units and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0159]

[0160] (m3, n3, and o3 represent the number of repeating units and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0161] Examples of the methyl group-containing polyorganosiloxane include: 210 R 220 SiO 2 / 2 The siloxane units (D 200 Units), preferably comprising R 21 R 21 SiO 2 / 2 The siloxane units (D 20 units) of polyorganosiloxane.

[0162] R 210 and R 220 is a group bonded to a silicon atom, each independently represents an alkyl group, but at least one of them is a methyl group. Specific examples of the alkyl group include those described above.

[0163] R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include the above examples. 21 , preferably methyl.

[0164] In the present invention, polydimethylsiloxane can be cited as a preferred example of the methyl group-containing polyorganosiloxane, but the present invention is not limited thereto.

[0165] The methyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 200 Unit or D 20 Unit), but except for D 200 Unit and D 20 In addition to the Q unit, the Q unit, the M unit and / or the T unit may be contained.

[0166] In one embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 200 Polyorganosiloxane composed of units; containing D 200 Unit and Q unit polyorganosiloxane; containing D 200 Unit and M unit polyorganosiloxane; containing D 200 Units and T units of polyorganosiloxane; containing D 200 Unit, Q unit and M unit polyorganosiloxane; containing D 200Unit, M unit and T unit polyorganosiloxane; containing D 200 unit, Q unit, M unit and T unit of the polyorganosiloxane.

[0167] In a preferred embodiment of the present invention, specific examples of methyl-containing polyorganosiloxanes include: 20 Polyorganosiloxane composed of units; containing D 20 Unit and Q unit polyorganosiloxane; containing D 20 Unit and M unit polyorganosiloxane; containing D 20 Units and T units of polyorganosiloxane; containing D 20 Unit, Q unit and M unit polyorganosiloxane; containing D 20 Unit, M unit and T unit polyorganosiloxane; containing D 20 unit, Q unit, M unit and T unit of the polyorganosiloxane.

[0168] Specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxane represented by formula (M1), but the present invention is not limited thereto.

[0169]

[0170] (n4 represents the number of repeating units, which is a positive integer.)

[0171] Examples of the phenyl group-containing polyorganosiloxane include: 31 R 32 SiO 2 / 2 The siloxane units (D 30 units) of polyorganosiloxane.

[0172] R 31 is a group bonded to a silicon atom, representing a phenyl group or an alkyl group, R 32 It is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those mentioned above, and a methyl group is preferred.

[0173] The phenyl-containing polyorganosiloxane comprises the above-mentioned siloxane units (D 30 Unit), but except for D 30 In addition to the Q unit, the Q unit, the M unit and / or the T unit may be contained.

[0174] In a preferred embodiment of the present invention, specific examples of phenyl-containing polyorganosiloxanes include: 30 Polyorganosiloxane composed of units; containing D 30 Unit and Q unit polyorganosiloxane; containing D 30 Unit and M unit polyorganosiloxane; containing D30 Units and T units of polyorganosiloxane; containing D 30 Unit, Q unit and M unit polyorganosiloxane; containing D 30 Unit, M unit and T unit polyorganosiloxane; containing D 30 unit, Q unit, M unit and T unit of the polyorganosiloxane.

[0175] Specific examples of the phenyl group-containing polyorganosiloxane include polyorganosiloxanes represented by formula (P1) or (P2), but are not limited thereto.

[0176]

[0177] (m5 and n5 represent the number of repeating units and are positive integers.)

[0178]

[0179] (m6 and n6 represent the number of repeating units and are positive integers.)

[0180] The polyorganosiloxane as the release agent component (B) may be a commercially available product or a synthesized polyorganosiloxane.

[0181] Examples of commercially available polyorganosiloxanes include Wacker Chemie's WACKERSILICONE FLUID AK series (AK 50, AK 350, AK 1000, AK 10000, AK 1000000), GENIOPLAST GUM, Shin-Etsu Chemical's dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), and cyclic dimethyl silicone oil (KF-995); Gelest's epoxy-containing polyorganosiloxanes (trade names CMS-227 and ECMS-327); Shin-Etsu Chemical's epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, and X-22-343); and Dow Chemical's Epoxy-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, and X-22-343). Epoxy-containing polyorganosiloxane manufactured by Corning (BY16-839); phenyl-containing polyorganosiloxane manufactured by Gelest (PMM-1043, PMM-1025, PDM-0421, PDM-0821), phenyl-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (KF50-3000CS), phenyl-containing polyorganosiloxane manufactured by Momentive (TSF431, TSF433), etc., but not limited to these.

[0182] In one embodiment, the adhesive composition used in the present invention contains both a curable component (A) and a non-curing component (B). In another embodiment, the adhesive composition contains a polyorganosiloxane as the component (B).

[0183] An example of the adhesive composition used in the present invention may contain component (A) and component (B) in any ratio. Taking into account the balance between adhesion and releasability, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25, in terms of mass ratio [(A):(B)].

[0184] Specifically, when the polyorganosiloxane component (A') that cures by a hydrosilylation reaction is included, the ratio of component (A') to component (B) is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25, in terms of mass ratio [(A'):(B)].

[0185] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s at 25° C., and preferably 1,000 to 10,000 mPa·s.

[0186] One example of the adhesive composition used in the present invention can be produced by mixing the component (A), the component (B) when used, and a solvent.

[0187] The order of mixing is not particularly limited. Examples of methods for easily and reproducibly producing the adhesive composition include: dissolving component (A) and component (B) in a solvent; and dissolving a portion of component (A) and component (B) in a solvent and the remaining portion in a solvent, and mixing the resulting solutions. The adhesive composition may be heated appropriately during preparation, as long as the components do not decompose or deteriorate.

[0188] In the present invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all the components are mixed.

[0189] (Laminated body)

[0190] The laminated body of the present invention includes a semiconductor substrate or an electronic device layer, a supporting substrate, and an adhesive layer.

[0191] The laminate of the present invention may further include a release agent layer. In this case, the laminate of the present invention has a structure including a semiconductor substrate or an electronic device layer, a supporting substrate, a release agent layer, and an adhesive layer.

[0192] The laminate of the present invention may further include an inorganic material layer and a release agent layer. In this case, the laminate of the present invention has a structure including a semiconductor substrate or electronic device layer, a supporting substrate, a release agent layer, an adhesive layer, and an inorganic material layer.

[0193] The adhesive layer is provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0194] 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 the semiconductor substrate or the electronic device layer.

[0195] The semiconductor substrate is supported by the support substrate while the semiconductor substrate is being processed, such as thinning. After the semiconductor substrate is processed, the support substrate is separated from the semiconductor substrate.

[0196] Furthermore, the electronic device layer is supported by the support substrate while the electronic device layer is being processed, such as being thinned. On the other hand, after the electronic device layer is processed, the support substrate is separated from the electronic device layer.

[0197] After the semiconductor substrate or electronic device layer is separated from the support substrate, the residue of the release agent layer or adhesive layer remaining on the semiconductor substrate, electronic device layer or support substrate can be removed by, for example, a cleaning composition used for cleaning the semiconductor substrate.

[0198] The following describes each of the cases where the laminate includes a semiconductor substrate and the case where the laminate includes an electronic device layer in detail.

[0199] A case where the laminate includes a semiconductor substrate will be described in the following <First Embodiment>, and a case where the laminate includes an electronic device layer will be described in the following <Second Embodiment>.

[0200] <First Implementation Plan>

[0201] A laminated body including a semiconductor substrate is used for processing the semiconductor substrate. During processing of the semiconductor substrate, the semiconductor substrate is bonded to a support substrate. After processing of the semiconductor substrate, the semiconductor substrate is separated from the support substrate.

[0202] <<Semiconductor substrate>>

[0203] The main material constituting the entire semiconductor substrate is not particularly limited as long as it can be used for such applications, and examples thereof include silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins.

[0204] The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disc-shaped semiconductor substrate. It should be noted that the disc-shaped semiconductor substrate does not need to have a completely circular surface. For example, the outer periphery of the semiconductor substrate may have a straight portion called an orientation flat or a notch called a groove.

[0205] The thickness of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate. For example, it is 500 to 1000 μm.

[0206] The diameter of the disk-shaped semiconductor substrate is not particularly limited and may be appropriately determined depending on the intended use of the semiconductor substrate. For example, it is 100 to 1000 mm.

[0207] The semiconductor substrate may also have bumps. A bump is a protruding terminal.

[0208] In the laminated body, when the semiconductor substrate has the bump, the semiconductor substrate has the bump on the support substrate side.

[0209] In a semiconductor substrate, bumps are usually formed on the surface where the circuit is formed. The circuit can be single-layer or multi-layer. There are no particular restrictions on the shape of the circuit.

[0210] In the semiconductor substrate, the surface (back surface) opposite to the surface having the bumps is a surface to be processed.

[0211] The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited.

[0212] Examples of the bumps include ball bumps, printed bumps, stud bumps, and plated bumps.

[0213] Generally, the bump height, radius, and pitch are appropriately determined 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.

[0214] Examples of materials for the bumps include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bumps may be composed of a single component or multiple components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other Sn-based alloy plating.

[0215] Furthermore, the bump may have a stacked structure including a metal layer composed of at least any one of these components.

[0216] An example of a semiconductor substrate is a silicon wafer having a diameter of 300 mm and a thickness of approximately 770 μm.

[0217] <<Support substrate>>

[0218] The support substrate is not particularly limited as long as it can support the semiconductor substrate during processing, and examples thereof include a glass support substrate and a silicon support substrate.

[0219] The shape of the support substrate is not particularly limited, and a disc-shaped support substrate may be mentioned, for example. It should be noted that the disc-shaped support substrate does not need to have a completely circular surface. For example, the outer periphery of the support substrate may have a straight portion called an orientation flat or a cutout called a groove.

[0220] The thickness of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 500 to 1000 μm.

[0221] The diameter of the disk-shaped support substrate is not particularly limited and may be appropriately determined according to the size of the semiconductor substrate, etc., but is, for example, 100 to 1000 mm.

[0222] An example of the supporting substrate is a glass wafer having a diameter of 300 mm and a thickness of about 700 μm.

[0223] In addition, when the peeling in the laminated body is performed by light irradiation, a substrate having light-transmitting properties to the light used is used as the supporting substrate, for example.

[0224] <<Adhesive layer>>

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

[0226] The adhesive layer is in contact with, for example, a semiconductor substrate. The adhesive layer may also be in contact with, for example, a supporting substrate.

[0227] The adhesive layer is formed of an adhesive composition.

[0228] The thickness of the adhesive layer possessed by the laminate of the present invention is not particularly limited and is generally 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more. From the viewpoint of avoiding unevenness caused by a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, further preferably 120 μm or less, and further preferably 100 μm or less.

[0229] The method for forming the adhesive layer from the adhesive composition will be described in detail in the description of "Method for producing an example of the laminated body according to the first embodiment" described below.

[0230] <<Release agent layer>>

[0231] The laminate may have a release agent layer.

[0232] In a laminate having a release agent layer, the semiconductor substrate and the support substrate are separated by, for example, irradiating the release agent layer with light.

[0233] The release agent layer is formed of, for example, a release agent composition.

[0234] <<<Removal agent composition>>>

[0235] The stripping agent composition contains, for example, at least an organic resin or a polynuclear phenol derivative, and further contains other components as needed.

[0236] The organic resin is preferably an organic resin that exhibits appropriate peeling ability and absorbs light to appropriately undergo modification, such as decomposition, required for improving the peeling ability when the semiconductor substrate and the support substrate are separated by irradiating the release agent layer with light.

[0237] A laminate having a release agent layer formed of a release agent composition can be peeled without applying an excessive load for peeling by irradiating the release agent layer with laser light, for example.

[0238] The release agent layer included in the laminate is reduced in adhesive strength by, for example, laser irradiation compared to before irradiation. Specifically, in the laminate, for example, during thinning of a semiconductor substrate, the semiconductor substrate is appropriately supported by a laser-transmissive support substrate via the adhesive layer and the release agent layer. After the processing is completed, laser irradiation is performed from the support substrate side, and the laser light transmitted through the support substrate is absorbed by the release agent layer, causing deterioration (e.g., separation) of the release agent layer 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 within the release agent layer. As a result, appropriate peeling (separation) can be achieved without applying excessive load for peeling.

[0239] Examples of the organic resin include novolac resins, etc. Details of these resins will be described later.

[0240] As a preferred embodiment, the stripping agent composition contains at least a novolac resin, and further contains other components such as a cross-linking agent, an acid generator, an acid, a surfactant, and a solvent as needed.

[0241] As another preferred embodiment, the stripping agent composition contains at least a polynuclear phenol derivative and a crosslinking agent, and further contains other components such as an acid generator, an acid, a surfactant, and a solvent as needed.

[0242] As another preferred embodiment, the release agent composition contains at least an organic resin and a branched polysilane, and further contains other components such as a crosslinking agent, an acid generator, an acid, a surfactant, and a solvent as needed.

[0243] <<<<Novolac resin>>>>

[0244] The novolac resin is a resin obtained by condensing 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.

[0245] Examples of phenolic compounds include phenols, naphthols, anthracenes, 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 anthracenes include 9-anthracenol. Examples of hydroxypyrenes include 1-hydroxypyrene and 2-hydroxypyrene.

[0246] 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-(1 (H-benzotriazol-1-ylmethyl)-9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-dicarbaldehyde, 9-benzylcarbazole-3-carbaldehyde, 9-methylcarbazole, 9-phenylcarbazole, 9-vinylcarbazole, potassium carbazole, carbazole-N-carbonyl chloride, N-ethylcarbazole-3-carbaldehyde, N-((9-ethylcarbazole-3-yl)methylene)-2-methyl-1-dihydroindoleamine, and the like.

[0247] Examples of the aromatic amine compound include diphenylamine and N-phenyl-1-naphthylamine.

[0248] These can be used alone or in combination of two or more.

[0249] These may have a substituent. For example, they may have a substituent on the aromatic ring.

[0250] Examples of the aldehyde compound include saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexanal, 2-methylbutyraldehyde, hexanal, undecanal, 7-methoxy-3,7-dimethyloctanal, cyclohexanecarboxaldehyde, 3-methyl-2-butyraldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and adipaldehyde; unsaturated aliphatic aldehydes such as acrolein and methacrolein; heterocyclic aldehydes such as furfural and pyridinecarboxaldehyde; and aromatic aldehydes such as benzaldehyde, naphthalenecarboxaldehyde, anthracenecarboxaldehyde, phenanthraldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, tolualdehyde, (N,N-dimethylamino)benzaldehyde, and acetoxybenzaldehyde. Among these, aromatic aldehydes are preferred.

[0251] Examples of the ketone compound include diaryl ketone compounds such as diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, and xylyl ketone.

[0252] Examples of the divinyl compound include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene, divinylpyrene, limonene, and 5-vinylnorbornadiene.

[0253] These can be used alone or in combination of two or more.

[0254] The novolac resin is, for example, a novolac resin that absorbs light irradiated from the support substrate side and deteriorates, and the deterioration is, for example, photodecomposition.

[0255] The novolac resin includes, for example, at least any 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).

[0256]

[0257] Where C 1 represents a group derived from an aromatic compound containing a nitrogen atom, C 2 represents a group containing a tertiary carbon atom, wherein the side chain has at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring, 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.

[0258] That is, the novolac resin contains, for example, one or two or more of the following structural units.

[0259] 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 selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring as a side chain.

[0260] 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)).

[0261] A structural unit having a bond between 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 and a group having a tertiary carbon atom-containing group having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring as a side chain (Formula (C1-3)).

[0262] In a preferred embodiment, the novolac resin contains either or both 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, the side chain of which has at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring (Formula (C1-1)); and 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)).

[0263] C 1 Specifically, the group derived from an aromatic compound containing a nitrogen atom may be, for example, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, a group derived from N-phenyl-2-naphthylamine, etc., but is not limited thereto.

[0264] C 2 That is, the side chain has at least one group selected from the group consisting of secondary carbon atoms, quaternary carbon atoms and aromatic rings, and the group containing tertiary carbon atoms can be, for example, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from acetaldehyde, etc., but is not limited to these.

[0265] C 3 That is, the group derived from the aliphatic polycyclic compound may be a group derived from dicyclopentadiene, but is not limited thereto.

[0266] C 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.

[0267] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-1-1) as the structural unit represented by the formula (C1-1).

[0268]

[0269] In formula (C1-1-1), R 901 and R 902 The substituents substituted on the ring each independently represent a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.

[0270] R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.

[0271] R 904 represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0272] R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0273] R 904 The group and R 905 The groups are optionally bonded to each other to form a divalent group.

[0274] Examples of the substituents of the alkyl group and the alkenyl group 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.

[0275] Examples of the substituents for the aryl group and the heteroaryl group include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an alkyl group, and an alkenyl group.

[0276] h 1 and h 2 Each independently represents an integer from 0 to 3.

[0277] The number of carbon atoms of the optionally substituted alkyl group and the optionally substituted alkenyl group is usually 40 or less, preferably 30 or less, and more preferably 20 or less from the viewpoint of solubility.

[0278] The number of carbon atoms of the optionally substituted aryl group and heteroaryl group is usually 40 or less, preferably 30 or less, more preferably 20 or less from the viewpoint of solubility.

[0279] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0280] Specific examples of the optionally substituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, Examples include, but are not limited to, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl.

[0281] Specific examples of the optionally substituted alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl- 3-Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 1,2-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3- 1-Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2 1-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, etc., but are not limited to these.

[0282] Specific examples of the optionally substituted aryl group include, but are not limited to, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 1-naphthyl, 2-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, and 9-phenanthrenyl.

[0283] Specific examples of the optionally substituted heteroaryl group include, but are not limited to, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, and 5-isothiazolyl.

[0284] Specific examples of the structural unit represented by formula (C1-1-1) are listed below, but the present invention is not limited thereto.

[0285]

[0286] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-1-2) as the structural unit represented by the formula (C1-1).

[0287]

[0288] 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 h1 and h 2 Means the same as above.

[0289] Specific examples of the structural unit represented by formula (C1-1-2) are listed below, but the present invention is not limited thereto.

[0290]

[0291] In a preferred embodiment, the novolac resin includes, for example, a structural unit represented by the following formula (C1-2-1) or (C1-2-2) as the structural unit represented by the formula (C1-2).

[0292]

[0293] In the above formula, R 906 ~R 909 is a substituent bonded to the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group. Specific examples of the halogen atom, the optionally substituted alkyl group, the optionally substituted alkenyl group and the optionally substituted aryl group and preferred carbon atom numbers thereof are the same as those mentioned above. 3 ~h 6 Each independently represents an integer from 0 to 3, R 901 ~R 903 and h 1 and h 2 Means the same as above.

[0294] Specific examples of the structural units represented by formulae (C1-2-1) and (C1-2-2) are listed below, but the present invention is not limited thereto.

[0295]

[0296] Specific examples of the structural unit represented by formula (C1-3) are listed below, but the present invention is not limited thereto.

[0297]

[0298] As described above, the novolac resin is a resin obtained by condensing 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.

[0299] In the condensation reaction, for example, the aldehyde compound or the ketone compound is usually used in a ratio of 0.1 to 10 equivalents relative to 1 equivalent of the benzene ring constituting the carbazole compound.

[0300] In the above condensation reaction, an acid catalyst is usually used.

[0301] Examples of the acid catalyst include, but are not limited to, inorganic 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.

[0302] The amount of the acid catalyst is appropriately determined depending on the type of acid used, etc., and therefore cannot be generally specified, but is usually appropriately determined within the range of 0.001 to 10,000 parts by mass relative to 100 parts by mass of the carbazole compound.

[0303] When any of the raw material compound and the acid catalyst used is a liquid, the condensation reaction may be carried out without using a solvent, but is usually carried out using a solvent.

[0304] 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.

[0305] The reaction temperature is usually appropriately determined within the range of 40° C. to 200° C. The reaction time varies depending on the reaction temperature and cannot be generally specified, but is usually appropriately determined within the range of 30 minutes to 50 hours.

[0306] After the reaction is completed, purification and separation are performed according to conventional methods if necessary, and the obtained novolac resin is used to prepare a stripper composition.

[0307] A person skilled in the art can determine the production conditions of the novolac resin without undue burden based on the above description and common technical knowledge, and thus can produce the novolac resin.

[0308] The weight-average molecular weight of an organic resin such as a novolac resin is generally 500 to 200,000. From the viewpoint of ensuring solubility in a solvent and from the viewpoint of obtaining a uniform film by good mixing with a branched polysilane when forming a film, the weight-average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, further preferably 5,000 or less, and even 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, further preferably 800 or more, further preferably 900 or more, and even more preferably 1,000 or more.

[0309] It should be noted that in the present invention, the weight-average molecular weight, number-average molecular weight, and dispersity of an organic resin such as a novolac resin as a polymer can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by TOSOH Corporation) and a GPC column (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by TOSOH Corporation), with the column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow velocity) set to 0.35 mL / min, and polystyrene (manufactured by Sigma Aldrich) used as a standard sample.

[0310] The organic resin contained in the stripper composition is preferably a novolac resin. Therefore, the stripper composition preferably contains a novolac resin alone as the organic resin. For the purpose of adjusting film properties, the novolac resin and other polymers may also be contained.

[0311] As a preferred example of the organic resin, a combination of a novolac resin and a (meth)acrylate polymer can be mentioned.

[0312] The (meth)acrylate polymer is a polymer containing a repeating unit derived from an alkyl (meth)acrylate.

[0313] Alkyl (meth)acrylate is a general term for alkyl acrylate and alkyl methacrylate.

[0314] The number of carbon atoms in the alkyl (meth)acrylate is not particularly limited, but is preferably 4 to 20, more preferably 4 to 10.

[0315] Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and decyl acrylate.

[0316] Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and decyl methacrylate.

[0317] These can be used alone or in combination of two or more.

[0318] Among them, methyl methacrylate is preferred.

[0319] (Meth)acrylate polymers may also contain repeating units other than repeating units derived from alkyl (meth)acrylates. Examples of monomers constituting such repeating units include monomers other than (meth)acrylate polymers that contain polymerizable unsaturated groups. Examples of such monomers include carboxyl-containing monomers, hydroxyl-containing monomers, (meth)acrylamide-based monomers, and styrene-based monomers.

[0320] The (meth)acrylate polymer may be a homopolymer or a copolymer.

[0321] As the (meth)acrylate polymer, polymethylmethacrylate is preferably contained.

[0322] The molar ratio of the repeating unit derived from the alkyl (meth)acrylate in all repeating units of the (meth)acrylate polymer is not particularly limited, but is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, and particularly preferably 90 to 100 mol%.

[0323] A preferred example of the organic resin is a combination of a novolac resin and a polyimide or a polyimide precursor. An example of the polyimide precursor is polyamic acid.

[0324] The polyamic acid contains, for example, one or more structural units selected from the group consisting of structural units represented by the following formula (5) and formula (6).

[0325]

[0326] (In the formula, X1 and X2 are each independently a tetravalent organic group having 4 to 32 carbon atoms.)

[0327] Examples of polyimide precursors include those having an absorbance of 0.1 to 0.8 at 308 nm when heated at 350° C. for 1 hour to form a 0.1 μm thick polyimide resin film. Examples of such polyimide precursors include those described in Japanese Patent No. 6732871.

[0328] 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 the polymer contained in the release agent composition.

[0329] The content of the novolac resin in the stripping agent composition is not particularly limited, but is preferably 50 to 100% by mass relative to the film-constituting components. In the present invention, the film-constituting components refer to components other than the solvent contained in the composition.

[0330] <<<<Polynuclear phenol derivatives>>>>

[0331] The polynuclear phenol derivative is represented by, for example, the following formula (P).

[0332]

[0333] In formula (P), Ar represents an arylene group, and the number of carbon atoms thereof is not particularly limited, but is usually 6 to 60. From the viewpoint of preparing a release agent composition with excellent uniformity and obtaining a release agent layer with higher flatness with good reproducibility, it is preferably 30 or less, more preferably 20 or less, further preferably 18 or less, and further preferably 12 or less.

[0334] Specific examples of such arylene groups include, but are not limited to, groups derived from condensed-ring aromatic hydrocarbon compounds such as 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene; groups derived from condensed-ring aromatic hydrocarbon compounds such as 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, 2,3-anthracenediyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl; and groups derived from ring-linked aromatic hydrocarbon compounds such as biphenyl-4,4'-diyl and p-terphenyl-4,4"-diyl.

[0335] From the perspective of producing a peeling agent layer showing good peeling properties and reproducibly obtaining a laminate that can be well separated from the supporting substrate, 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).

[0336]

[0337] The content of the polynuclear phenol derivative in the release agent composition is not particularly limited, but is preferably 50 to 100% by mass based on the film constituent components.

[0338] <<<<Branched polysilane>>>>

[0339] The release agent composition may contain branched polysilane.

[0340] Branched polysilane has Si-Si bonds and a branched structure. By including the branched polysilane in the stripper composition, the stripper layer formed from the resulting film cannot be properly removed by any of organic solvents, acids, and chemical solutions used in semiconductor device manufacturing (e.g., alkaline developers, hydrogen peroxide solutions), but can be properly removed by a cleaning composition. Consequently, by separating the semiconductor substrate and the supporting substrate of the stack and then cleaning each substrate with the cleaning composition, the stripper layer residue on the substrate can be properly removed. The reason for this is not clear, but it is speculated as follows: depending on the type of the terminal group (terminal substituent (atom)) of the polysilane, the polysilane can react with the organic resin to form a crosslink. In addition, since branched polysilane has more terminal groups (terminal substituents (atom)) than linear polysilane, it is believed that branched polysilane has more crosslinking points than linear polysilane. By moderately and appropriately curing through such a large number of crosslinking points in the branched polysilane, it is possible to achieve a balance between the property of being unable to be properly removed by organic solvents, acids, and chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide solution, etc.) and the property of being properly removed by a cleaning composition.

[0341] The branched polysilane preferably includes a structural unit represented by formula (B).

[0342]

[0343] In formula (B), R B " represents a hydrogen atom, a hydroxyl group, a silyl group, or an organic group. 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). These organic groups are generally hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. Furthermore, hydrogen atoms, hydroxyl groups, alkoxy groups, and silyl groups are often substituted at the terminals.

[0344] The optionally substituted alkyl group may be linear, branched, or cyclic.

[0345] Specific examples of the optionally substituted linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1 The present invention also includes, but is not limited to, 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. The number of carbon atoms in the present invention is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.

[0346] Specific examples of the optionally substituted cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl The cycloalkyl groups include, but are not limited to, cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl; and bicycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, bicyclononyl, and dicyclodecyl. The number of carbon atoms in the cycloalkyl groups is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0347] The alkenyl group may be linear, branched, or cyclic.

[0348] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, vinyl, allyl, butenyl, and pentenyl. The number of carbon atoms in the alkenyl group is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6.

[0349] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl and cyclohexenyl. The number of carbon atoms in the cyclic alkenyl group is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0350] Specific examples of the optionally substituted aryl group include, but are not limited to, phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 3,5-dimethylphenyl, 1-naphthyl, and 2-naphthyl. The number of carbon atoms in the aryl group is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 12.

[0351] Specific examples of the optionally substituted aralkyl group include, but are not limited to, benzyl, phenethyl, and phenylpropyl. 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.

[0352] The alkyl portion of the optionally substituted alkoxy group may be linear, branched, or cyclic.

[0353] Specific examples of the optionally substituted linear or branched alkoxy group include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, and pentyloxy. The number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6.

[0354] Specific examples of the optionally substituted cyclic alkoxy group include, but are not limited to, cyclopentyloxy and cyclohexyloxy groups. The number of carbon atoms in the cycloalkoxy group is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0355] Specific examples of the optionally substituted aryloxy group include, but are not limited to, phenoxy, 1-naphthyloxy, and 2-naphthyloxy. The number of carbon atoms thereof is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10.

[0356] Specific examples of optionally substituted aralkyloxy groups include, but are not limited to, benzyloxy, phenethyloxy, and phenylpropyloxy groups. An optionally substituted aralkyloxy group is preferably a group in which one hydrogen atom of an alkoxy group having 1 to 4 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms.

[0357] Specific examples of the silyl group include, but are not limited to, a monosilyl group, a disilyl group, and a trisilyl group. The number of silicon atoms in the silyl group is usually 1 to 10, preferably 1 to 6.

[0358] In R BIn the case of the above-mentioned organic group or silyl group, at least one of the hydrogen atoms thereof may be substituted with a substituent. Specific examples of such a substituent include a hydroxyl group, an alkyl group, an aryl group, and an alkoxy group.

[0359] From the perspective of suppressing unintended peeling when the laminate is brought into contact with any of organic solvents, acids, and chemical solutions used in the manufacture of semiconductor devices (alkaline developer, hydrogen peroxide solution, etc.); and from the perspective of appropriately removing the residue of the release agent layer on the substrate when the semiconductor substrate and the supporting substrate of the laminate are separated and each substrate is cleaned with a cleaning composition, etc., R B It is preferably an alkyl group or an aryl group, more preferably an aryl group, still more preferably a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and still more preferably a phenyl group.

[0360] The branched polysilane may also contain a structural unit represented by formula (B) together with a structural unit represented by the following formula (S) and a structural unit represented by the following formula (N). From the viewpoint of suppressing unintended peeling when the laminate is brought into contact with any of organic solvents, acids, and chemical solutions used in the manufacture of semiconductor devices (such as alkaline developers and aqueous hydrogen peroxide); and from the viewpoint of appropriately removing the residue of the release agent layer on the substrates when the semiconductor substrate and the supporting substrate of the laminate are washed with a cleaning composition after separation, the content of the structural unit represented by formula (B) in the branched polysilane is generally 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90% or more, and even more preferably 95 mol% or more, based on all the structural units.

[0361]

[0362] (R S1 and R S2 With R B have the same meaning.)

[0363] The terminal group (terminal substituent (atom)) of the branched polysilane can generally be a hydrogen atom, a hydroxyl group, a halogen atom (chlorine atom, etc.), an alkyl group, an aryl group, an alkoxy group, a silyl group, etc. Among them, hydroxyl group, methyl group, and phenyl group are most common, with methyl group being preferred. The terminal group can also be a trimethylsilyl group.

[0364] In one embodiment, the average polymerization degree of the branched polysilane is usually 2-100, preferably 3-80, more preferably 5-50, and even more preferably 10-30, in terms of silicon atoms (ie, the average number of silicon atoms per molecule).

[0365] In one embodiment, the upper limit of the weight average molecular weight of the branched polysilane is usually 30,000, preferably 20,000, more preferably 10,000, further preferably 5,000, further preferably 2,000, and further preferably 1,500, and the lower limit is usually 50, preferably 100, more preferably 150, further preferably 200, further preferably 300, and further preferably 500.

[0366] 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 (Showa Denko K.K., Shodex KF-803L, KF-802, and KF-801, respectively), with the column temperature set to 40° C., tetrahydrofuran used as an eluent (elution solvent), the flow rate (flow rate) set to 1.00 mL / min, and polystyrene (manufactured by Sigma Aldrich) used as a standard sample.

[0367] If the degree of polymerization and weight-average molecular weight of the branched polysilane used are too low, the branched polysilane may be vaporized by heating during formation of a film serving as a release agent layer or during processing of a laminate having the resulting release agent layer, or problems may occur due to poor film strength. If the degree of polymerization and molecular weight of the branched polysilane used are too high, sufficient solubility may not be ensured depending on the type of solvent used in the preparation of the release agent composition, resulting in precipitation in the composition, or insufficient mixing with the resin, making it impossible to reproducibly obtain a highly uniform film.

[0368] Therefore, from the viewpoint of obtaining a laminate including a release agent layer that contributes to appropriate production of a semiconductor element with greater reproducibility, the degree of polymerization and weight-average molecular weight of the branched polysilane preferably satisfy the above-mentioned ranges.

[0369] From the viewpoint of obtaining a release agent layer having excellent heat resistance with good reproducibility, the 5% weight loss temperature of the branched polysilane is usually 300°C or higher, preferably 350°C or higher, more preferably 365°C or higher, further preferably 380°C or higher, further preferably 395°C or higher, and even more preferably 400°C or higher.

[0370] The 5% weight loss temperature of the branched polysilane can be measured, for example, by using 2010SR manufactured by NETZSCH GmbH and heating the sample from room temperature (25° C.) to 400° C. at a rate of 10° C. / min in air.

[0371] From the perspectives of properly removing the residue of the stripping agent layer on the substrates when the semiconductor substrate and the supporting substrate of the stack are separated and each substrate is cleaned with a cleaning agent composition; and from the perspectives of reproducibly preparing a stripping agent composition with excellent uniformity, the branched polysilane is preferably soluble in any 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. It should be noted that dissolution in this case means that dissolution can be visually confirmed within 1 hour when attempting to dissolve the polysilane using a shaker at room temperature (25°C) to form a 10% by mass solution.

[0372] The branched polysilane may be in a solid or liquid state at room temperature.

[0373] Branched polysilanes can be produced by referring to known methods described in, for example, Japanese Patent Application Laid-Open Nos. 2011-208054, 2007-106894, 2007-145879, and WO 2005 / 113648, or can be obtained as commercial products. Specific examples of commercial products include, but are not limited to, silicon material polysilanes OGSOL SI-20-10 and SI-20-14 manufactured by OSAKAGAS CHEMICALS.

[0374] Preferred examples of branched polysilane include the following, but are not limited thereto.

[0375]

[0376] (Ph represents phenyl, R E Each independently represents a terminal substituent, represents an atom or group, n b represents the number of repeating units. )

[0377] The content of the branched polysilane in the above-mentioned stripping agent composition is generally 10 to 90% by weight relative to the film constituent components. From the perspective of reproducibly achieving a film that cannot be properly removed by an organic solvent, acid, or a chemical solution (alkaline developer, hydrogen peroxide solution, etc.) used in the manufacture of semiconductor elements but can be properly removed by a cleaning agent composition, the content is preferably 15 to 80% by weight, more preferably 20 to 70% by weight, further preferably 25 to 60% by weight, and further preferably 30 to 50% by weight.

[0378] <<<<Crosslinking agent>>>>

[0379] The stripper composition may also contain a crosslinking agent.

[0380] The crosslinking agent may also cause a crosslinking reaction based on self-condensation. When a crosslinkable substituent is present in the novolac resin, the crosslinking agent may cause a crosslinking reaction with the crosslinkable substituent.

[0381] Specific examples of cross-linking agents are not particularly limited, but typically include phenolic cross-linking agents, melamine cross-linking agents, urea cross-linking agents, thiourea cross-linking agents, etc., which have cross-linking-forming groups such as hydroxymethyl, methoxymethyl, butoxymethyl, etc. in the molecule. These can be low molecular weight compounds or high molecular weight compounds.

[0382] The crosslinking agent contained in the release agent composition generally has two or more crosslinking groups. From the viewpoint of achieving more appropriate curing with good reproducibility, the number of crosslinking groups contained in the crosslinking agent compound is preferably 2 to 10, more preferably 2 to 6.

[0383] From the viewpoint of achieving higher heat resistance, the crosslinking agent contained in the release agent composition preferably has an aromatic ring (eg, a benzene ring or a naphthalene ring) in the molecule. Typical examples of such crosslinking agents include, but are not limited to, phenolic crosslinking agents.

[0384] The phenolic crosslinking agent having a crosslinking group refers to a compound having a crosslinking group bonded to an aromatic ring and having at least one of a phenolic hydroxyl group and an alkoxy group derived from the phenolic hydroxyl group. Examples of such an alkoxy group derived from a phenolic hydroxyl group include, but are not limited to, a methoxy group and a butoxy group.

[0385] The aromatic ring to which the crosslinking group is bonded and the aromatic ring to which the phenolic hydroxyl group and / or the alkoxy group derived from the phenolic hydroxyl group is bonded are not limited to non-condensed aromatic rings such as benzene rings, but may also be condensed aromatic rings such as naphthalene ring and anthracene ring.

[0386] When a plurality of aromatic rings are present in the phenolic crosslinking agent molecule, the crosslinking group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group may be bonded to the same aromatic ring in the molecule or to different aromatic rings.

[0387] The aromatic ring bonded to the crosslinking group, the phenolic hydroxyl group, and the alkoxy group derived from the phenolic hydroxyl group may be further substituted with a hydrocarbon group such as an alkyl group such as methyl, ethyl, or butyl; an aryl group such as phenyl; or a halogen atom such as a fluorine atom.

[0388] For example, specific examples of the phenolic crosslinking agent having a crosslinking-forming group include compounds represented by any of the formulae (L1) to (L4).

[0389]

[0390] 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 3 It is determined according to q1, represents a single bond, methylene, propane-2,2-diyl, methanetriyl or ethane-1,1,1-triyl, t11, t12 and t13 are integers satisfying 2≤t11≤5, 1≤t12≤4, 0≤t13≤3 and t11+t12+t13≤6, t21, t22 and t23 are integers satisfying 2≤t21≤4, 1≤t22≤3, 0≤t23≤2 and t21+t22+t23≤5, t24, t25 and t26 are integers satisfying 2≤t24≤4, 1≤t25≤3, 0≤t26≤2 and t24+t25+t26≤5, t27, t28 and t29 are integers satisfying 0 ≤t27≤4, 0≤t28≤4, 0≤t29≤4 and t27+t28+t29≤4, t31, t32 and t33 are integers satisfying 2≤t31≤4, 1≤t32≤3, 0≤t33≤2 and t31+t32+t33≤5, t41, t42 and t43 are integers satisfying 2≤t41≤3, 1≤t42≤2, 0≤t43≤1 and t41+t42+t43≤4, q1 is 2 or 3, q2 represents the number of repetitions and is an integer greater than 0, specific examples of the aryl group and the alkyl group include the same groups as the specific examples described below, preferably a phenyl group as the aryl group, and preferably a methyl group or a tert-butyl group as the alkyl group.

[0391] Specific examples of compounds represented by formulae (L1) to (L4) are listed below, but are not limited thereto. It should be noted that these compounds can be synthesized by known methods and can also be obtained as products of, for example, Asahi Organic Materials Industries, Ltd. and Honshu Chemical Industries, Ltd.

[0392]

[0393]

[0394] The melamine-based crosslinking agent having a crosslinking group refers to 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 of the hydrogen atoms of the amino group bonded to the triazine ring is substituted with a crosslinking group, and the triazine ring may further have a substituent such as an aryl group such as a phenyl group.

[0395] Specific examples of melamine-based crosslinking agents having a crosslinking group include, but are not limited to, mono-, di-, tri-, tetra-, penta- or hexa-alkoxymethyl melamines such as N,N,N',N',N",N",-hexa(methoxymethyl)melamine and N,N,N',N',N",N",-hexa(butoxymethyl)melamine; and mono-, di-, tri- or tetra-alkoxymethyl benzoguanamines such as N,N,N',N'-tetra(methoxymethyl)benzoguanamine and N,N,N',N'-tetra(butoxymethyl)benzoguanamine.

[0396] The urea-based crosslinking agent having a crosslinking group refers to a derivative of a urea bond-containing compound having a structure in which at least one of the hydrogen atoms of the NH group constituting the urea bond is substituted with a crosslinking group.

[0397] Specific examples of urea-based crosslinking agents having a crosslinking group include, but are not limited to, mono-, di-, tri-, or tetra-alkoxymethyl glycolurils such as 1,3,4,6-tetrakis(methoxymethyl)glycoluril and 1,3,4,6-tetrakis(butoxymethyl)glycoluril; and mono-, di-, tri-, or tetra-alkoxymethyl ureas such as 1,3-bis(methoxymethyl)urea and 1,1,3,3-tetramethoxymethylurea.

[0398] The thiourea-based crosslinking agent having a crosslinking group refers to a derivative of a thiourea bond-containing compound having a structure in which at least one of the hydrogen atoms of the NH group constituting the thiourea bond is substituted with a crosslinking group.

[0399] Specific examples of the thiourea crosslinking agent having a crosslinking group include mono-, di-, tri-, or tetra-alkoxymethylthiourea such as 1,3-bis(methoxymethyl)thiourea and 1,1,3,3-tetramethoxymethylthiourea, but are not limited thereto.

[0400] The amount of the crosslinking agent contained in the release agent composition varies depending on the coating method used, the desired film thickness, etc., and therefore cannot be generally specified. However, it is generally 0.01 to 50% by mass relative to the organic resin or polynuclear phenol derivative. From the perspective of achieving appropriate curing and reproducibly obtaining a laminate in which the semiconductor substrate and the supporting substrate can be well separated, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0401] <<<<Acid Generators and Acids>>>>

[0402] For the purpose of promoting a cross-linking reaction, the release agent composition may contain an acid generator or an acid.

[0403] Examples of the acid generator include thermal acid generators and photoacid generators.

[0404] The thermal acid generator is not particularly limited as long as it generates an acid by heat. Specific examples thereof include, but are not limited to, 2,4,4,6-tetrabromocyclohexadienonone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, and K-PURE 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.

[0405] Examples of the photoacid generator include onium salt compounds, sulfonyl imide compounds, and disulfonyldiazomethane compounds.

[0406] Specific examples of the onium salt compound include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-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-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0407] Specific examples of the sulfonyl imide compound include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0408] 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, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0409] Specific examples of the acid include: p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid (pyridinium p-toluenesulfonate), pyridinium trifluoromethanesulfonate, pyridinium phenolsulfonic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid and other arylsulfonic acids, pyridinium salts, and salts thereof; salicylic acid, benzoic acid, hydroxybenzoic acid, naphthoic acid and other arylcarboxylic acids, and salts thereof; trifluoromethanesulfonic acid, camphorsulfonic acid and other chain or cyclic alkylsulfonic acids, and salts thereof; citric acid and other chain or cyclic alkylcarboxylic acids, and salts thereof, but are not limited thereto.

[0410] The amounts of the acid generator and acid contained in the release agent composition vary depending on the type of crosslinking agent used, the heating temperature during film formation, etc., and therefore cannot be generally specified, but are generally 0.01 to 5% by mass based on the film constituents.

[0411] <<<<Surfactants>>>>

[0412] The stripper composition may contain a surfactant for the purpose of adjusting the liquid properties of the composition itself, the film properties of the obtained film, and preparing a highly uniform stripper composition with good reproducibility.

[0413] 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 octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; and EFTOP. Fluorochemical surfactants such as EF301, EF303, EF352 (trade names of Tohkem Products Co., Ltd.), MEGAFACE F171, F173, R-30, R-30N (trade names of DIC Corporation), Fluorad FC430, FC431 (trade names of Sumitomo 3M Co., Ltd.), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade names of Asahi Glass Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0414] The surfactant may be used alone or in combination of two or more.

[0415] The amount of the surfactant is usually 2% by mass or less based on the film-constituting components of the release agent composition.

[0416] <<<<Solvent>>>>

[0417] The stripper composition preferably contains a solvent.

[0418] As such a solvent, for example, a high-polarity solvent that can well dissolve the above-mentioned organic resin, polynuclear phenol derivative, branched polysilane, cross-linking agent and other film-forming components can be used. As required, for the purpose of adjusting viscosity, surface tension, etc., a low-polarity solvent can also be used. It should be noted that, in the present invention, a low-polarity solvent refers to a solvent defined as having a relative dielectric constant of less than 7 at a frequency of 100 kHz, and a high-polarity solvent refers to a solvent defined as having a relative dielectric constant of 7 or more at a frequency of 100 kHz. One solvent can be used alone or in combination of two or more.

[0419] 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; polyol 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.

[0420] 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.

[0421] The content of the solvent is appropriately determined taking into account the desired viscosity of the composition, the coating method to be adopted, the thickness of the film to be produced, etc., and is 99% by mass or less of the entire composition, preferably 70 to 99% by mass relative to the entire composition, that is, the amount of the film constituent components in this case is 1 to 30% by mass relative to the entire composition.

[0422] The viscosity and surface tension of the release agent composition can be appropriately adjusted by changing the type of solvent used, their ratio, and the concentration of the film constituent components in consideration of various factors such as the coating method used and the desired film thickness.

[0423] In one embodiment of the present invention, the release agent composition includes a glycol solvent from the perspective of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition having high storage stability, and reproducibly obtaining a composition providing a highly uniform film. It should be noted that the term "glycol solvent" herein refers to a general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0424] An example of a preferred glycol solvent is represented by formula (G).

[0425]

[0426] 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 An integer from 1 to 6.

[0427] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include, but are not limited to, ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, and hexamethylene.

[0428] Among them, from the viewpoints of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition providing a highly uniform film with good reproducibility, etc., a straight-chain or branched alkylene group having 2 to 3 carbon atoms is preferred, and a straight-chain or branched alkylene group having 3 carbon atoms is more preferred.

[0429] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-butyl Examples include, but are not limited to, n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl.

[0430] Among them, from the viewpoints of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition providing a highly uniform film with good reproducibility, etc., a methyl group and an ethyl group are preferred, and a methyl group is more preferred.

[0431] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkylacyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms include the same groups as mentioned above.

[0432] Among them, from the viewpoint of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition providing a highly uniform film with good reproducibility, etc., a methylcarbonyl group and an ethylcarbonyl group are preferred, and a methylcarbonyl group is more preferred.

[0433] From the perspectives of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition providing a highly uniform film with good reproducibility, n g It is preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and most preferably 1.

[0434] From the viewpoints of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition providing a highly uniform film with good reproducibility, in formula (G), R is preferably G2 and R G3 At least one of them is a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably R G2 and R G3One 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 moiety is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0435] From the perspective of obtaining a highly uniform composition with good reproducibility, obtaining a composition with high storage stability with good reproducibility, and obtaining a composition that provides a highly uniform film with good reproducibility, the content of the diol solvent is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, and even more preferably 95% by mass or more relative to the solvent contained in the stripper composition.

[0436] From the perspectives of reproducibly obtaining a highly uniform composition, reproducibly obtaining a composition having high storage stability, and reproducibly obtaining a composition providing a highly uniform film, the film-constituting components in the release agent composition are uniformly dispersed or dissolved, preferably dissolved, in the solvent.

[0437] The release agent composition can be produced by mixing, for example, an organic resin or a polynuclear phenol derivative, a solvent, and, if necessary, a crosslinking agent.

[0438] The order of mixing is not particularly limited. Examples of methods for easily and reproducibly producing a stripper composition include: dissolving the organic resin or polynuclear phenol derivative and the crosslinking agent in a solvent all at once; or dissolving a portion of the organic resin or polynuclear phenol derivative and the crosslinking agent in a solvent and the remaining portion in a separate solvent, and then mixing the resulting solutions. Furthermore, the stripper composition may be heated appropriately during preparation, within a range that does not decompose or deteriorate the components.

[0439] In the present invention, for the purpose of removing 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 all the components are mixed.

[0440] The thickness of the release agent layer is not particularly limited, but is usually 5 nm to 100 μm, 10 nm to 10 μm in one embodiment, 50 nm to 1 μm in another embodiment, and 100 nm to 700 nm in yet another embodiment.

[0441] The method of forming the release agent layer from the release agent composition is not particularly limited, and examples thereof include a method of applying the release agent composition to form the release agent layer.

[0442] The coating method of the release agent composition is not particularly limited, but is usually a spin coating method.

[0443] The heating temperature of the applied release agent composition varies depending on the type and amount of the release agent component contained in the release agent composition, the desired release agent layer thickness, and other factors, and therefore cannot be generally specified. However, from the perspective of reproducibly achieving an appropriate release agent layer, it is preferably 80°C to 300°C. The heating time is generally determined within the range of 10 seconds to 10 minutes, depending on the heating temperature. The heating temperature is preferably 100°C to 280°C, more preferably 150°C to 250°C. The heating time is preferably 30 seconds to 8 minutes, more preferably 1 minute to 5 minutes.

[0444] Heating can be performed using a hot plate, an oven, or the like.

[0445] <<Inorganic material layer>>

[0446] The laminate may also have an inorganic material layer.

[0447] The inorganic material layer is usually sandwiched between the release layer and the adhesive layer. The inorganic material layer can prevent the release layer and the adhesive layer from mixing.

[0448] The inorganic material layer is not particularly limited as long as it is composed of an inorganic material. Examples thereof include layers formed of compounds such as oxides, nitrides, and carbides of at least one element selected from the group consisting of silicon, boron, titanium, zirconium, and aluminum, and mixtures thereof.

[0449] Preferably, the inorganic material layer is a layer obtained by plasma polymerization of an organic silicon compound.

[0450] The inorganic material layer is formed by, for example, chemical vapor deposition (CVD) method. The chemical vapor deposition method may be, for example, plasma polymerization coating.

[0451] Examples of materials used for plasma polymerization coating include organosilicon compounds. For example, by plasma polymerization coating an organosilicon compound on a release layer or adhesive layer, a raw material gas containing the organosilicon compound can be decomposed to form an inorganic material layer as a thin film containing Si—O bonds on the release layer or adhesive layer.

[0452] The raw material gas containing the organosilicon compound is preferably blended with an oxygen-containing gas such as O2 or N2O. Furthermore, a rare gas such as argon or helium may be blended into the raw material gas as a carrier gas. In a preferred example of a method for decomposing the raw material gas, a plasma generator is used to decompose the raw material gas under appropriate pressure conditions using the generated plasma. It should be noted that the technique of forming a film (layer) by decomposing the raw material gas using plasma is sometimes generally referred to as plasma polymerization.

[0453] Examples of the organosilicon compound include siloxane compounds, disilazane compounds, and silane compounds.

[0454] Examples of the siloxane compound include 1,1,3,3-tetramethyldisiloxane, pentamethyldisiloxane, hexamethyldisiloxane, 1,1,3,3-tetraphenyl-1,3-dimethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, octamethyltrisiloxane, 1,1,3,3-tetraphenyl-1,3-dimethyldisiloxane, 1,3-divinyltetramethyldisiloxane, Chain siloxanes such as 1,3,5,7,7,7-octamethyltetrasiloxane, decamethyltetrasiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane; cyclic siloxanes such as hexamethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, etc.

[0455] Examples of the disilazane compound include 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, heptamethyldisilazane, hexamethylcyclotrisilazane, and 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane.

[0456] Examples of the silane compound include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, trimethoxysilane, triethylsilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, tetramethoxysilane, trimethoxymethylsilane, ethyltrimethoxysilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, triethoxyethylsilane, diethoxydimethylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethoxydimethylsilane, acetoxytrimethylsilane, allyloxytrimethylsilane, allyltrimethylsilane, butoxytrimethylsilane, butyltrimethoxysilane, diacetoxydimethylsilane, dimethoxydiphenylsilane, Silane, diethoxydiphenylsilane, dimethoxymethylphenylsilane, ethoxydimethylvinylsilane, diphenylsilanediol, triacetoxymethylsilane, triacetoxyethylsilane, 3-glycidoxypropyltrimethoxysilane, hexyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, octadecyltriethoxysilane, triethoxyoctylsilane, triethoxyphenylsilane, trimethylphenylsilane, propoxytrimethylsilane, triethoxypropylsilane, tetraacetoxysilane, tetrabutoxysilane, tetrapropoxysilane, triacetoxyvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, triphenylsilanol, trimethylvinylsilane, tris(2-methoxyethoxy)vinylsilane, etc.

[0457] The thickness of the inorganic material layer is not particularly limited, but is usually 1 to 1000 nm, preferably 100 to 500 nm.

[0458] Hereinafter, an example of the structure of the laminated body according to the first embodiment will be described using the drawings.

[0459] Figure 1 A schematic cross-sectional view showing an example of the laminated body according to the first embodiment.

[0460] Figure 1 The laminated body includes, in this order: a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4. That is, the adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1 and the support substrate 4.

[0461] Hereinafter, another example of the structure of the laminated body according to the first embodiment will be described with reference to the drawings.

[0462] Figure 2 A schematic cross-sectional view showing another example of the laminated body according to the first embodiment.

[0463] Figure 2 The laminated body includes a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4 in this order.

[0464] 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.

[0465] In another example, the adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The release agent layer 3 is in contact with the semiconductor substrate 1. The adhesive layer 2 is in contact with the release agent layer 3 and the support substrate 4.

[0466] Hereinafter, another example of the structure of the laminated body according to the first embodiment will be described with reference to the drawings.

[0467] Figure 3 A schematic cross-sectional view showing another example of the laminated body according to the first embodiment.

[0468] Figure 3 The laminated body includes a semiconductor substrate 1 , an adhesive layer 2 , an inorganic material layer 5 , a release agent layer 3 , and a support substrate 4 in this order.

[0469] Adhesive layer 2, inorganic material layer 5, and release agent layer 3 are provided between semiconductor substrate 1 and support substrate 4. Adhesive layer 2 is in contact with semiconductor substrate 1. Inorganic material layer 5 is in contact with adhesive layer 2 and release agent layer 3. Release agent layer 3 is in contact with inorganic material layer 5 and support substrate 4.

[0470] <<Method for producing an example of the laminated body according to the first embodiment>>

[0471] Hereinafter, the laminated body of the first embodiment Figure 1 Taking the laminate shown in FIG. 1 as an example, a method for producing the laminate will be described.

[0472] An example of the laminate of the present invention can be produced, for example, by a method including the following first and second steps.

[0473] Step 1: A step of applying an adhesive composition on a semiconductor substrate to form an adhesive coating layer.

[0474] Second step: a step of heating the adhesive coating layer to form an adhesive layer.

[0475] The adhesive composition coating method is not particularly limited, but is generally spin coating. Alternatively, a coating film may be formed separately by spin coating or the like to form a sheet-like coating film, and the sheet-like coating film may be attached as the adhesive coating layer.

[0476] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive components contained in the adhesive composition; whether a solvent is contained; the boiling point of the solvent used; the desired thickness of the adhesive layer, etc., and therefore cannot be generally specified, but is generally 80 to 150°C, and the heating time is generally 30 seconds to 5 minutes.

[0477] When the adhesive composition contains a solvent, the adhesive composition after application is usually heated.

[0478] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is generally about 5 to 500 μm, and is appropriately determined so as to ultimately fall within the above-mentioned thickness range of the adhesive layer.

[0479] In the present invention, a load is applied to the semiconductor substrate and the support substrate in the thickness direction while performing a heat treatment or a pressure reduction treatment, or both, followed by a post-heat treatment, thereby obtaining the laminate of the present invention. It should be noted that the treatment conditions for any of the heat treatments, pressure reduction treatments, or a combination of the two should be appropriately determined based on various considerations, such as the type of adhesive composition, film thickness, and the desired bonding strength.

[0480] From the perspective of removing the solvent from the composition, the heat treatment temperature is generally appropriately determined within the range of 20 to 160°C. In particular, from the perspective of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component (A), the temperature is preferably 150°C or lower, more preferably 130°C or lower. The heating time is appropriately determined depending on the heating temperature and the type of adhesive. From the perspective of reliably achieving appropriate adhesion, the heating time is generally 30 seconds or longer, preferably 1 minute or longer. From the perspective of suppressing deterioration of the adhesive layer and other members, the heating time is generally 10 minutes or shorter, preferably 5 minutes or shorter.

[0481] The reduced pressure treatment may be performed by exposing the adhesive coating layers in contact with each other to an air pressure of 10 to 10,000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

[0482] 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 allows for strong adhesion between them, but is generally within the range of 10 to 50,000 N.

[0483] From the viewpoint of achieving a sufficient curing speed, the post-heating temperature is preferably 120° C. or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260° C. or lower.

[0484] From the perspective of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually more than 1 minute, preferably more than 5 minutes. From the perspective of suppressing or avoiding the adverse effects of excessive heating on the layers, the post-heating time is usually less than 180 minutes, preferably less than 120 minutes.

[0485] Heating can be performed using a hot plate, an oven, etc. When post-heating is performed using a hot plate, either the semiconductor substrate or the support substrate of the stack can be heated facing downward. However, from the perspective of achieving appropriate peeling with good reproducibility, post-heating is preferably performed with the semiconductor substrate facing downward.

[0486] It should be noted that one of the purposes of the post-heat treatment is to realize a more suitable self-supporting film of the adhesive layer, and in particular, to appropriately realize curing by the hydrosilylation reaction.

[0487] Figure 4A 4C is a diagram for explaining one method of manufacturing a laminated body.

[0488] First, a laminate ( Figure 4A ). The laminate can be obtained, for example, by applying the adhesive composition on the semiconductor substrate 1 and heating it.

[0489] Next, Figure 4A The laminated body shown is bonded to the support substrate 4 in such a manner that the adhesive coating layer 2a is in contact with the support substrate 4. Then, a load is applied to the semiconductor substrate 1 and the support substrate 4 in the thickness direction under reduced pressure. A heating device (not shown; heating plate) is arranged on the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive coating layer 2a. The heating device heats the adhesive coating layer 2a to cure it and convert it into the adhesive layer 2 ( Figure 4B ).

[0490] pass Figure 4A-4B The process shown can be obtained Figure 1 The stack shown.

[0491] <Second Implementation Plan>

[0492] The laminate having the electronic device layer is used for processing the electronic device layer. During the processing of the electronic device layer, the electronic device layer is bonded to the support substrate. After the processing of the electronic device layer, the electronic device layer is separated from the support substrate.

[0493] <<Electronic device layer>>

[0494] The electronic device layer refers to a layer having electronic devices. In the present invention, it refers to a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, a layer including a plurality of semiconductor chip substrates and a sealing resin arranged between the semiconductor chip substrates.

[0495] Here, "electronic device" refers to a component that constitutes at least a portion of an electronic component. The electronic device is not particularly limited and may be an electronic device having various mechanical structures or circuits formed on the surface of a semiconductor substrate. The electronic device is preferably a composite of a component composed of a metal or semiconductor and a resin that seals or insulates the component. The electronic device may be an electronic device in which the redistribution layer and / or semiconductor element or other element described later is sealed or insulated with a sealing material or insulating material, and may have a single-layer or multi-layer structure.

[0496] <<Support substrate>>

[0497] As the supporting substrate, the same supporting substrate as that described in the column of "Supporting Substrate" in the above-mentioned "First Embodiment" can be exemplified.

[0498] <<Release agent layer>>

[0499] The release agent layer is formed using the above-mentioned release agent composition for light irradiation release of the present invention.

[0500] The release agent layer is described in detail in the section "Release Agent Layer" in the above-mentioned "First Embodiment".

[0501] <<Adhesive layer>>

[0502] The adhesive layer is formed using the above-mentioned adhesive composition.

[0503] The adhesive layer is described in detail in the section "Adhesive layer" in the above-mentioned "First embodiment".

[0504] Hereinafter, an example of the structure of the laminated body according to the second embodiment will be described with reference to the drawings.

[0505] Figure 5 The laminated body includes a support substrate 24 , an adhesive layer 22 , and an electronic device layer 26 in this order.

[0506] The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21 .

[0507] The adhesive layer 22 is 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 and the support substrate 24 .

[0508] Figure 6 A schematic cross-sectional view showing another example of the laminated body according to the second embodiment.

[0509] Figure 6 The laminated body includes a support substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26 in this order.

[0510] The electronic device layer 26 includes a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21 .

[0511] 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.

[0512] <<Method for producing an example of a laminate in the second embodiment>>

[0513] Hereinafter, the laminated body in the second embodiment Figure 5 Taking the laminate shown in FIG. 1 as an example, a method for producing the laminate will be described.

[0514] The laminate of the present invention can be produced, for example, by a method including the following first to fourth steps.

[0515] Step 1: A step of applying an adhesive composition on the surface of the supporting substrate to form an adhesive coating layer (if necessary, further heating to form an adhesive layer).

[0516] Second step: placing a semiconductor chip substrate on the adhesive coating layer or the adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer while performing at least one of a heating treatment and a reduced pressure treatment.

[0517] Step 3: A step of forming an adhesive layer by subjecting the adhesive coating layer to a post-heat treatment to cure the adhesive layer.

[0518] Step 4: The semiconductor chip substrate fixed to the adhesive layer is sealed with a sealing resin.

[0519] When the second step is described in more detail, for example, the step of the embodiment (i) below can be cited.

[0520] (i) placing a semiconductor chip substrate on an adhesive coating layer or an adhesive layer, applying a load in the thickness direction of the semiconductor chip substrate and the supporting substrate to make them close together while performing at least one of a heating treatment and a decompression treatment, and bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer.

[0521] It should be noted that the third step can be performed after the semiconductor chip substrate is bonded to the adhesive coating layer in the second step, or can be performed simultaneously with the second step. For example, the semiconductor chip substrate can be placed on the adhesive coating layer, and while a load in the thickness direction of the semiconductor chip substrate and the support substrate is applied, the adhesive coating layer can be heated to cure. In this way, the semiconductor chip substrate and the adhesive coating layer are bonded together, and the adhesive coating layer is cured from the adhesive coating layer to the adhesive layer, thereby bonding the adhesive layer to the semiconductor chip substrate.

[0522] The third step may be performed before the second step, or the semiconductor chip substrate may be placed on the adhesive layer and the adhesive layer and the semiconductor chip substrate may be bonded together while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.

[0523] The coating method, the heating temperature of the adhesive composition after coating, the heating method, etc. are the same as those described in the above-mentioned <<Method for producing an example of a laminate in the first embodiment>> of the <First embodiment>.

[0524] The manufacturing method of the laminated body of the second embodiment will be described in more detail below using the accompanying drawings. Figure 5 The stack shown.

[0525] like Figure 7A As shown, an adhesive coating layer 22' made of an adhesive composition is formed on a support substrate 24. At this time, the adhesive coating layer 22' may be heated to form the adhesive layer 22.

[0526] Then, if Figure 7B As shown, a semiconductor chip substrate 21 is placed on an adhesive layer 22 or an adhesive coating layer 22'. A load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to achieve close contact while performing at least one of a heating treatment and a pressure reduction treatment. This allows the semiconductor chip substrate 21 to be bonded 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-heated to cure it, thereby forming the adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22.

[0527] Then, if Figure 7C As shown in FIG. 1 , the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed using a sealing resin 25. Figure 7C In the embodiment, a plurality of semiconductor chip substrates 21 temporarily bonded to a support substrate 24 via an adhesive layer 22 are sealed with a sealing resin 25. An electronic device layer 26 is formed on the adhesive layer 22, comprising the semiconductor chip substrates 21 and the sealing resin 25 disposed between the semiconductor chip substrates 21. Thus, the electronic device layer 26 serves as a base layer in which the plurality of semiconductor chip substrates are embedded in the sealing resin.

[0528] <<<Sealing process>>>

[0529] The semiconductor chip substrate 21 is sealed using a sealing material.

[0530] As a sealing material for sealing the semiconductor chip substrate 21 , a member capable of insulating or sealing a member made of metal or semiconductor is used.

[0531] In the present invention, as the sealing material, for example, a resin composition (sealing resin) is used. The type of sealing resin is not particularly limited as long as it can seal and / or insulate a metal or semiconductor, and for example, epoxy resins or silicone resins are preferably used.

[0532] The sealing material may contain other components such as fillers in addition to the resin component. Examples of the filler include spherical silica particles.

[0533] In the sealing process, a sealing resin heated to, for example, 130 to 170°C is supplied to the adhesive layer 22 while maintaining a high viscosity and covering the semiconductor chip substrate 21, and compression molding is performed, thereby forming a layer of sealing resin 25 on the adhesive layer 22. At this time, the temperature condition is, for example, 130 to 170°C. In addition, the pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm 2 .

[0534] (Method for Manufacturing Processed Semiconductor Substrate or Electronic Device Layer)

[0535] By using the laminate of the present invention, a method for producing a processed semiconductor substrate or a method for producing a processed electronic device layer can be provided.

[0536] The "method for producing a processed semiconductor substrate" uses the laminate described in the "First embodiment" of the aforementioned (laminate). Furthermore, the "method for producing a processed electronic device layer" uses the laminate described in the "Second embodiment" of the aforementioned (laminate).

[0537] The “method for producing a processed semiconductor substrate” will be described in the following <Third Embodiment>, and the “method for producing a processed electronic device layer” will be described in the following <Fourth Embodiment>.

[0538] <Third Implementation Plan>

[0539] The method for producing a processed semiconductor substrate of the present invention includes the following step 5A and the following step 6A. The method for producing a processed semiconductor substrate may further include the following step 7A.

[0540] Here, step 5A is a step of processing the semiconductor substrate in the laminate described in the section of the above-mentioned <First Embodiment>.

[0541] In addition, step 6A is a step of separating the semiconductor substrate processed in step 5A from the support substrate.

[0542] In addition, step 7A is a step of cleaning the processed semiconductor substrate after step 6A.

[0543] In the 5A process, the processing performed on the semiconductor substrate refers to, for example, the processing on the opposite side of the circuit surface of the wafer, and the thinning of the wafer by grinding the back side of the wafer can be cited. Then, for example, a through silicon via (TSV) is formed, and then the thinned wafer is peeled off from the supporting substrate to form a stack of wafers for three-dimensional mounting. In addition, for example, the formation of the back electrode of the wafer is also performed before and after the three-dimensional mounting. In addition, in the thinning and TSV processes of the wafer, heat of about 250 to 350°C is applied in a state bonded to the supporting substrate. The stack of the present invention usually includes an adhesive layer and has heat resistance for the load it bears.

[0544] Note that the processing is not limited to the above-mentioned processing, and includes, for example, a semiconductor component mounting process in which temporary bonding to a support substrate is performed in order to support a base material for mounting a semiconductor component.

[0545] In step 6A, the method of separating (peeling off) the semiconductor substrate and the support substrate is not particularly limited.

[0546] For example, a method of mechanical peeling using a tool having a sharp portion (so-called peeling machine) can be mentioned. Specifically, for example, the sharp portion is inserted between the semiconductor substrate and the support substrate to separate the semiconductor substrate and the support substrate.

[0547] In addition, when the laminate has a release agent layer, the method of separating (peeling) the semiconductor substrate from the supporting substrate in step 6A may also be peeling by irradiating the release agent layer with light and then tearing it apart between the semiconductor substrate and the supporting substrate.

[0548] By irradiating the release agent layer with light from the support substrate side, the release agent layer is degraded (eg, separated or decomposed) as described above, and then, for example, one of the substrates is pulled up to easily separate the semiconductor substrate from the support substrate.

[0549] It is not necessary to irradiate the release agent layer with light on the entire area of the release agent layer. Even if there are a mixture of areas irradiated with light and areas not irradiated with light, as long as the peeling ability of the release agent layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the support substrate by a slight external force such as pulling up the support substrate. The ratio and positional relationship of the areas irradiated with light and the areas not irradiated with light vary depending on the type of adhesive used, its specific composition; the thickness of the adhesive layer; the thickness of the adhesive layer; the thickness of the release agent layer; the intensity of the irradiated light, etc., but those skilled in the art can set appropriate conditions without excessive experiments. Due to such circumstances, according to the method for manufacturing a processed semiconductor substrate of the present invention, for example, when the support substrate of the stacked body used has light transmittance, the light irradiation time can be shortened when peeling is performed by irradiating light from the support substrate side. As a result, not only can an improvement in throughput be expected, but also physical stress for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the support substrate only by irradiation with light.

[0550] Generally, the irradiation dose of light used for peeling is 50 to 3000 mJ / cm 2 The irradiation time is appropriately determined according to the wavelength and irradiation dose.

[0551] The wavelength of the light used for stripping is preferably 250 to 600 nm, more preferably 250 to 370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The amount of light required for stripping is an amount that causes appropriate degradation, such as decomposition, of the specific compound or polymer.

[0552] The light used for the peeling may be a laser or a non-laser light source such as an ultraviolet lamp.

[0553] The cleaning composition may be sprayed on the surface of at least any one of the separated semiconductor substrate and the support substrate, or the separated semiconductor substrate or the support substrate may be immersed in the cleaning composition to clean the substrate.

[0554] Alternatively, the surface of a processed semiconductor substrate or the like can be cleaned using a removal tape or the like.

[0555] As an example of substrate cleaning, a step 7A of cleaning the processed semiconductor substrate may be performed after the step 6A.

[0556] Examples of the cleaning composition used for cleaning include the following.

[0557] Cleaner compositions typically contain a solvent.

[0558] Examples of the solvent include lactones, ketones, polyols, compounds having an ester bond, derivatives of polyols, cyclic ethers, esters, and aromatic organic solvents.

[0559] Examples of lactones include γ-butyrolactone.

[0560] Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, and 2-heptanone.

[0561] Examples of the polyols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.

[0562] Examples of the compound having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate.

[0563] Examples of polyol derivatives include monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the aforementioned polyols or compounds having ester bonds, and compounds having ether bonds such as monophenyl ether. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.

[0564] Examples of the cyclic ethers include dioxane and the like.

[0565] Examples of the esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate.

[0566] Examples of the aromatic organic solvent include anisole, benzyl ethyl ether, methyl anisole, diphenyl ether, dibenzyl ether, phenetole, phenbutyl ether, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, isopropyl toluene, and mesitylene.

[0567] These can be used alone or in combination of two or more.

[0568] Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.

[0569] A mixed solvent of PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) can be appropriately determined taking into account the compatibility of PGMEA and the polar solvent, and is preferably within the range of 1:9 to 9:1, and more preferably within the range of 2:8 to 8:2.

[0570] For example, when EL is added as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Furthermore, when PGME is added 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. Furthermore, when PGME and cyclohexanone are added as the polar solvent, 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.

[0571] The cleaning composition may or may not contain a salt, but preferably contains no salt from the viewpoints of increasing versatility in processing semiconductor substrates using the laminate and reducing costs.

[0572] As an example of the case where the cleaning composition contains a salt, there is a cleaning composition containing a quaternary ammonium salt and a solvent.

[0573] The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for such a purpose.

[0574] As such quaternary ammonium cations, tetraalkylammonium cations are typically mentioned. On the other hand, as anions forming a pair with them, hydroxide ions (OH － );Fluoride ion (F － ), chloride ion (Cl － ), bromide ion (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ion (BF4 - ); hexafluorophosphate ion (PF6 － ), but not limited to these.

[0575] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.

[0576] In the quaternary ammonium salt, the halogen atom may be contained in the cation or the anion, but is preferably contained in the anion.

[0577] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0578] Specific examples of the hydrocarbon group in tetrahydrocarbyl 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.

[0579] In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.

[0580] Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride). Among them, tetrabutylammonium fluoride is preferred.

[0581] A quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used in the form of a hydrate. In addition, a quaternary ammonium salt such as tetrahydrocarbyl ammonium fluoride may be used alone or in combination of two or more.

[0582] The amount of the quaternary ammonium salt is not particularly limited as long as it is soluble in the solvent contained in the cleaning composition, but is generally 0.1 to 30% by mass based on the cleaning composition.

[0583] When the cleaning composition contains a salt, the solvent used in combination is not particularly limited as long as it is suitable for such an application and dissolves salts such as quaternary ammonium salts. However, from the perspective of obtaining a cleaning composition with excellent cleaning properties with good reproducibility and from the perspective of obtaining a cleaning composition with excellent uniformity by dissolving salts such as quaternary ammonium salts well, the cleaning composition preferably contains one or more amide solvents.

[0584] A suitable example of the amide solvent includes an amide derivative represented by formula (Z).

[0585]

[0586] Where R 0 represents ethyl, propyl or isopropyl, preferably ethyl or isopropyl, more preferably ethyl. 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 any of linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and cyclobutyl. A and R B , preferably methyl or ethyl, more preferably both are methyl or ethyl, further preferably both are methyl.

[0587] Examples of the amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutanamide, N,N-diethylbutanamide, N-ethyl-N-methylbutanamide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, and N-ethyl-N-methylisobutyramide. Among these, N,N-dimethylpropanamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropanamide is more preferred.

[0588] The amide derivative represented by formula (Z) can be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product can be used.

[0589] Another example of a preferred amide solvent includes a lactam compound represented by formula (Y).

[0590]

[0591] 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. 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 thereto.

[0592] 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.

[0593] In a preferred embodiment, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment, comprises N-methylpyrrolidone (NMP).

[0594] It should be noted that the cleaning composition used in the present invention may also contain water as a solvent, but to avoid corrosion of the substrate, it is generally intended to use only organic solvents as solvents. It should be noted that in this case, the cleaning composition may contain water of hydration of salts and trace amounts of water contained in the organic solvent, but this does not necessarily negate this. The water content of the cleaning composition used in the present invention is generally 5% by mass or less.

[0595] The constituent elements and method elements related to the above-described steps of the method for manufacturing a processed semiconductor substrate of the present invention may be variously modified without departing from the spirit of the present invention.

[0596] The method for producing a processed semiconductor substrate of the present invention may include steps other than the above-mentioned steps.

[0597] In one example of the peeling method of the present invention, when the semiconductor substrate or the supporting substrate of the laminate of the present invention is light-transmissive, the semiconductor substrate and the supporting substrate of the laminate are separated by irradiating the release agent layer with light from the semiconductor substrate side or the supporting substrate side.

[0598] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded appropriately and releasably via an adhesive layer and a release agent layer. Therefore, for example, if the support substrate is light-transmissive, the semiconductor substrate and the support substrate can be easily separated by irradiating the release agent layer with light from the support substrate side of the laminate. Typically, the release is performed after the semiconductor substrate of the laminate has been processed.

[0599] use Figures 8A to 8D An example of the third embodiment will be described, which is an example of manufacturing a thinned semiconductor substrate.

[0600] First, prepare a laminate ( Figure 8A ). The laminate is Figure 1 and Figure 4B The stack shown is the same stack.

[0601] Next, the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2 is polished using a polishing device (not shown) to thin the semiconductor substrate 1 ( Figure 8B ) It should be noted that through-electrodes may be formed on the thinned semiconductor substrate 1 .

[0602] Next, a peeling device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4 ( Figure 8C ).

[0603] In this way, a thinned semiconductor substrate 1 ( Figure 8D ).

[0604] Here, 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 residues of the adhesive layer 2 from the semiconductor substrate 1 .

[0605] <Fourth Implementation Plan>

[0606] The method for producing a processed electronic device layer of the present invention includes the following step 5B and the following step 6B. The method for producing a processed electronic device layer may further include the following step 7B.

[0607] Here, step 5B is a step of processing the electronic device layer of the laminate described in the section of the above-mentioned <Second embodiment>.

[0608] In addition, step 6B is a step of separating the electronic device layer processed in step 5B from the support substrate.

[0609] In addition, step 7B is a step of cleaning the processed electronic device layer after step 6B.

[0610] Below, use Figures 9A to 9F A specific example of the fourth embodiment will be described.

[0611] Examples of the processing performed on the electronic device layer in step 5B include a grinding step and a wiring layer forming step.

[0612] <<Grinding process>>

[0613] The grinding step is a step of grinding the resin portion of the sealing resin 25 layer in the electronic device layer 26 so that a portion of the semiconductor chip substrate 21 is exposed.

[0614] Grinding of the sealing resin part, for example Figure 9B As shown, by Figure 9A The sealing resin 25 layer of the laminated body shown is ground to a thickness substantially the same as that of the semiconductor chip substrate 21. Figure 9A The stack shown is Figure 5 and Figure 7C The stack shown is the same stack.

[0615] <<Wiring layer formation process>>

[0616] The wiring layer forming step is a step of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding step.

[0617] exist Figure 9C In the embodiment, a wiring layer 28 is formed on an electronic device layer 26 including a semiconductor chip substrate 21 and a sealing resin 25 .

[0618] The wiring layer 28, also known as the RDL (Redistribution Layer), is a thin-film wiring body that forms wiring connected to the substrate and can have a single-layer or multi-layer structure. The wiring layer can be made of a conductor (such as aluminum, copper, titanium, nickel, gold, silver, and other metals, as well as silver-tin alloys) on a dielectric (silicon oxide (SiO X ), photosensitive resin such as photosensitive epoxy, etc.) to form a layer of wiring, but is not limited to this.

[0619] As a method of forming the wiring layer 28 , for example, the following method can be cited.

[0620] First, silicon oxide (SiO X), a dielectric layer such as a photosensitive resin. The dielectric layer composed of silicon oxide can be formed by, for example, sputtering, vacuum evaporation, etc. The dielectric layer composed of a photosensitive resin can be formed by applying the photosensitive resin onto the layer of the sealing resin 25 by, for example, spin coating, dipping, roller blade coating, spray coating, slit coating, etc.

[0621] Next, wiring is formed on the dielectric layer using a conductor such as metal. Methods for forming wiring can include, for example, photolithography (resist lithography) or other known semiconductor process methods such as etching. Examples of such photolithography include photolithography using positive-type resist materials and photolithography using negative-type resist materials.

[0622] In the method for manufacturing the laminated body of the fourth embodiment, bumps may be further formed or components may be mounted on the wiring layer 28. The components may be mounted on the wiring layer 28 using, for example, a chip mounter.

[0623] The laminated body of the fourth embodiment may be a laminated body produced by a process based on a fan-out technology in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer extending outside the chip region.

[0624] In step 6B, the electronic device layer and the support substrate may be separated (peeled) by mechanical peeling using a tool having a sharp portion or peeling by tearing between the support and the electronic device layer, but the method is not limited thereto.

[0625] In the case where the stack has a release agent layer, the release agent layer can be degraded (for example, separated or decomposed) as described above by, for example, irradiating the release agent layer with light from the supporting substrate side, and then, for example, pulling up either substrate, the electronic device layer can be easily separated from the supporting substrate.

[0626] Figures 9D to 9E is a schematic cross-sectional view for explaining a method for separating a laminated body. Figure 9F This is a schematic cross-sectional view for explaining a method for cleaning a laminate after separation. Figures 9D to 9F , which can illustrate an embodiment of a method for manufacturing a semiconductor package (electronic component).

[0627] like Figure 9D and Figure 9E As shown, the step of separating the laminated body is a step of separating the electronic device layer 26 and the support substrate 24 using a peeling device (not shown).

[0628] The substrate can be cleaned by spraying the cleaning composition on the surface of at least any one of the separated electronic device layer and the supporting substrate, or by immersing the separated electronic device layer or the supporting substrate in the cleaning composition.

[0629] Alternatively, the surface of the processed electronic device layer or the like can be cleaned using a removal tape or the like.

[0630] For example, in Figure 9E In the embodiment, after the separation process, the adhesive layer 22 is attached to the electronic device layer 26. By using a cleaning agent composition such as an acid or an alkali, the adhesive layer 22 is decomposed and removed. By removing the adhesive layer, the following can be appropriately obtained: Figure 9F The processed electronic device layer (electronic component) is shown.

[0631] The constituent elements and method elements related to the above-mentioned steps of the method for producing a processed electronic device layer of the present invention may be variously modified without departing from the spirit of the present invention.

[0632] The method for producing a processed electronic device layer of the present invention may include steps other than the above-mentioned steps.

[0633] Example

[0634] 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.

[0635] [Installation]

[0636] (1) Mixer A: ARE-500, a rotary and revolving mixer manufactured by THINKY Co., Ltd.

[0637] (2) Mixer B: AS ONE Co., Ltd. mixing rotor VMR-5R.

[0638] (3) Spin coating device: Coater manufactured by SUSS MicroTec Co., Ltd.

[0639] (4) Vacuum heating laminating device: VE09-07 manufactured by Ayumi Industry Co., Ltd.

[0640] [Preparation Example 1]

[0641] To a 200 mL glass container with a lid were added 96.2 g of a p-menthane solution (81.7 mass %) of a vinyl-containing MQ resin (manufactured by Wacker Chemie), 1.44 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.), and 12.9 g of a linear SiH group-containing polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 1020 mPa·s. The mixture was stirred using stirrer A until it became homogeneous. Subsequently, 0.005 g of a platinum catalyst (manufactured by Wacker Chemie) was added, and the mixture was stirred again using stirrer A until it became homogeneous. The mixture was then reacted at 40°C for 20 hours using stirrer B to obtain a mixture (I).

[0642] Next, 0.50 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.50 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were added to another container and stirred for 5 minutes using stirrer A to obtain a mixture (II).

[0643] To mixture (I) was added 0.50 g of mixture (II), and the mixture was stirred with stirrer A until the mixture was homogeneous. Then, 6.52 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s was added, and the mixture was again stirred with stirrer A until the mixture was homogeneous, thereby obtaining mixture (III).

[0644] Finally, the obtained mixture (III) was filtered through a 400-mesh nylon filter to obtain an adhesive composition (1).

[0645] [Preparation Example 2]

[0646] To 50 g of the adhesive composition (1) obtained in Preparation Example 1, 0.5 g of 2-dodecylhexadecane-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to obtain an adhesive composition (2).

[0647] In addition, 0.5 g of 2-dodecylhexadecane-1-ol was 1.18 mass % based on the solid content of 50 g of the adhesive composition (1).

[0648] [Preparation Examples 3 to 12]

[0649] Adhesive compositions (3) to (12) were obtained in the same manner as in Preparation Example 2 except that 0.5 g of 2-dodecylhexadecane-1-ol was replaced with 0.5 g of the additives described in Table 1.

[0650] Note that 0.5 g of the additives accounted for 1.18% by mass relative to 50 g of the solid content of the adhesive composition (1).

[0651] [Table 1]

[0652] Adhesive composition additive Preparation Example 2 Adhesive composition (2) 2-Dodecylhexadecane-1-ol Preparation Example 3 Adhesive composition (3) 9,9'-di-n-octylfluorene Preparation Example 4 Adhesive composition (4) Squalane Preparation Example 5 Adhesive composition (5) 4,4'-Dinonyl-2,2'-bipyridine Preparation Example 6 Adhesive composition (6) FOLDI-E101 Preparation Example 7 Adhesive composition (7) KF4917 Preparation Example 8 Adhesive composition (8) KF3935 Preparation Example 9 Adhesive composition (9) KF2201 Preparation Example 10 Adhesive composition (10) KF6003 Preparation Example 11 Adhesive composition (11) KF9701 Preparation Example 12 Adhesive composition (12) KF8008

[0653] The additives in Table 1 are described below.

[0654] · 2-Dodecylhexadecane-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) (structural formula shown below).

[0655]

[0656] 9,9'-di-n-octylfluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) (structural formula shown below).

[0657]

[0658] Squalane (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0659]

[0660] 4,4'-Dinonyl-2,2'-bipyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) (structural formula shown below).

[0661]

[0662] FOLDI-E101 (manufactured by Nissan Chemical Co., Ltd., 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoate, 2,3-epoxypropyl) (structural formula shown below).

[0663]

[0664] KF4917 (manufactured by Shin-Etsu Chemical Co., Ltd., side chain type / long chain alkyl modified silicone oil).

[0665] KF3935 (manufactured by Shin-Etsu Chemical Co., Ltd., side chain type / higher fatty acid amide-modified silicone oil).

[0666] KF2201 (manufactured by Shin-Etsu Chemical Co., Ltd., dual-end type / phenol-modified silicone oil).

[0667] KF6003 (manufactured by Shin-Etsu Chemical Co., Ltd., dual-end type / methanol-modified silicone oil).

[0668] KF9701 (manufactured by Shin-Etsu Chemical Co., Ltd., dual-end type / silanol-modified silicone oil).

[0669] KF8008 (manufactured by Shin-Etsu Chemical Co., Ltd., dual-end type / amino-modified silicone oil).

[0670] <Preparation of Laminated Body and Adhesion Evaluation>

[0671] [Example 1]

[0672] The adhesive composition (2) obtained in Preparation Example 2 was spin-coated on a 5 cm square glass substrate (thickness: 700 μm), and heated at 90°C for 3 minutes (pre-heating treatment) to form an adhesive coating layer on the glass surface in such a manner that the thickness of the adhesive layer in the final laminate was about 60 μm.

[0673] Next, in a vacuum heating laminating apparatus, the glass substrate with the adhesive coating layer was laminated to a separately prepared 5 cm square glass substrate with a molded resin, with the adhesive coating layer sandwiched between them, to produce a laminate. Lamination was performed at a temperature of 50°C, a reduced pressure of 700 Pa, and a load of 150 kg for 60 seconds.

[0674] [Examples 2 to 5, Comparative Examples 1 to 7]

[0675] Laminated bodies were obtained by the same method as in Example 1 except that the adhesive compositions described in the following Table 2 were used instead of the adhesive composition (2).

[0676] <<Evaluation of Adhesion>>

[0677] Adhesion was evaluated by visually checking the presence of voids from the glass substrate (support) side of the laminate. Clearly observed voids were marked as "×," slight but non-problematic voids were marked as "○," and virtually no voids were marked as "◎." The results of the adhesion evaluation are shown in Table 2.

[0678] [Table 2]

[0679] Adhesive composition additive Adhesion Example 1 Adhesive composition (2) 2-Dodecylhexadecane-1-ol ◎ Example 2 Adhesive composition (3) 9,9'-di-n-octylfluorene 〇 Example 3 Adhesive composition (4) Squalane ◎ Example 4 Adhesive composition (5) 4,4'-Dinonyl-2,2'-bipyridine ◎ Example 5 Adhesive composition (6) FOLDI-E101 ◎ Comparative Example 1 Adhesive composition (1) - × Comparative Example 2 Adhesive composition (7) KF4917 × Comparative Example 3 Adhesive composition (8) KF3935 × Comparative Example 4 Adhesive composition (9) KF2201 × Comparative Example 5 Adhesive composition (10) KF6003 × Comparative Example 6 Adhesive composition (11) KF9701 × Comparative Example 7 Adhesive composition (12) KF8008 ×

[0680] As shown in Table 2, a large number of voids were observed in Comparative Examples 1 to 7, whereas in Examples 1 to 5, no voids were observed or the voids were significantly improved, indicating good adhesion.

[0681] This confirmed that Examples 1 to 5, which are adhesive compositions of the present invention, are less likely to generate voids and exhibit good adhesiveness due to the addition of the adhesion improver of the present invention.

[0682] Industrial applicability

[0683] The adhesive composition of the present invention can form a uniform adhesive layer without voids when laminating substrates containing structures or multiple substrates. Therefore, it is useful for laminating two substrates in an environment where it is desired to avoid undesirable conditions such as uneven wafer thickness during the semiconductor substrate processing step (back grinding), damage to the wafer due to uneven pressure applied during the peeling step (during debonding), and the generation of adhesive layer residue.

[0684] Description of Reference Numerals

[0685] 1: semiconductor substrate; 2: adhesive layer; 2a: adhesive coating layer; 3: release agent layer; 4: supporting substrate; 5: inorganic material layer; 21: semiconductor chip substrate; 22: adhesive layer; 22': adhesive coating layer; 23: release agent layer; 24: supporting substrate; 25: sealing resin; 26: electronic device layer; 28: wiring layer.

Claims

1. An adhesive composition, which is a curable adhesive composition for forming an adhesive layer of a laminate, wherein the laminate comprises: a semiconductor substrate or an electronic device layer; a supporting substrate; and the adhesive layer is provided between the semiconductor substrate or the electronic device layer and the supporting substrate. The adhesive composition contains a compound having no siloxane bond and having a linear or branched alkyl chain having 5 or more carbon atoms.

2. The adhesive composition according to claim 1, wherein The molecular weight of the compound is 150 or more and 600 or less.

3. The adhesive composition according to claim 1, wherein The content of the compound is 0.1% by mass or more and 5% by mass or less relative to the film-forming components.

4. The adhesive composition according to claim 1, wherein The total number of oxygen atoms and nitrogen atoms in the compound is 0 to 3.

5. The adhesive composition according to claim 1, wherein The adhesive composition is an adhesive composition that is cured by a hydrosilylation reaction.

6. The adhesive composition according to claim 5, wherein The adhesive composition contains: a component A-1 having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom; and a component A-2 having a Si—H group.

7. The adhesive composition according to claim 6, wherein The component A-1 contains a polyorganosiloxane a1 having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom.

8. The adhesive composition according to claim 6, wherein The component A-2 contains polyorganosiloxane having Si—H groups.

9. The adhesive composition according to claim 5, wherein The adhesive composition contains polyorganosiloxane as a component that does not undergo a hydrosilylation reaction.

10. A laminated body, wherein: The laminated body has: Semiconductor substrate or electronic device layer; support base plate; as well as an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, The adhesive layer is an adhesive layer formed from the adhesive composition according to any one of claims 1 to 9. The laminate according to claim 10 , wherein: have: A release agent layer is provided between the semiconductor substrate or the electronic device layer and the support substrate.

12. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: Step 5A, processing the semiconductor substrate of the laminate according to claim 10; or step 5B, processing the electronic device layer of the laminate according to claim 10; as well as Step 6A is to separate the semiconductor substrate processed in step 5A from the support substrate; or Step 6B is to separate the electronic device layer processed in step 5B from the support substrate.

Images