Laminate, semiconductor element, and MEMS element

Abstract

There has been a problem of low bonding strength in conventional insulating layers, i.e., SiO2. In addition, there is a problem of poor conduction of the electrode or a decrease in reliability of the obtained laminate due to a void generated when a minute foreign matter is sandwiched in the bonding interface. The invention provides a laminated body. A-1 in at least a portion of a first substrate including an exposed (A-1) metal electrode and an exposed (B-1) resin layer on the same surface of a substrate main body, and a second substrate including an exposed (A-2) metal electrode and an exposed (B-2) resin layer, or an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer on the same surface of the substrate main body the metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer and the (B-2) resin layer, or at least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer and (C) an inorganic insulating layer are bonded together directly, respectively; at least one of the (B-1) resin layer and the (B-2) resin layer contains one or more resins selected from the group consisting of a carbonyl group, a hydroxyl group, an alkylene oxide group, a group having a siloxane bond, and a nitrogen-containing heterocyclic ring.

Description

Technical Field

[0001] The present invention relates to a laminate, a semiconductor element, and a MEMS element. More specifically, it relates to a technology for mounting an element by directly bonding a metal electrode and an insulating film. Background Art

[0002] Previously, when a semiconductor or micro-electromechanical system (MEMS) chip was electrically connected to the outside, a protruding electrode (bump) of gold or copper or the like was formed, and a connection to a connection substrate or the like was made via solder. In order to maintain insulation between electrodes, methods such as bottom filling have been established. In recent years, in the process of greatly increasing the number of electrodes connected to the outside and improving the electrode density due to the high integration of chips, hybrid bonding technology that forms the electrodes and the insulating film into the same plane without forming bumps and connects to the outside by direct bonding has attracted much attention (Patent Document 1). As a result, high-density mounting with an electrode spacing of less than 10 μm can be achieved. In addition, hybrid bonding includes wafer-to-wafer (W2W) bonding of wafers to each other, and chip-to-wafer (C2W) bonding of chips to wafers.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Publication No. 2006-517344

[0006] Non-patent literature

[0007] Non-Patent Document 1: Y. Kagawa et al. “Novel stacked CMOS image sensor with advanced Cu2Cu hybrid bonding,” 2016 IEEE International Electron Devices Meeting (IEDM), DOI: 10.1109 / IEDM.2016.7838375. Summary of the Invention

[0008] Problems to be solved by the invention

[0009] Hybrid bonding has the problem of low bonding strength in the existing insulating layer, SiO2. Furthermore, when bonding semiconductor elements using C2W, tiny foreign particles generated during chip dicing can be trapped at the bonding interface, creating voids that can lead to poor electrode conductivity and reduced reliability of the resulting laminate.

[0010] Technical means to solve the problem

[0011] In order to solve the above-mentioned problems, the present invention has the following configuration.

[0012] [1] A laminate comprising a first substrate including an exposed (A-1) metal electrode and an exposed (B-1) resin layer on the same surface of a substrate body,

[0013] a second substrate including, on the same surface as the substrate body, an exposed (A-2) metal electrode and an exposed (B-2) resin layer, or an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer,

[0014] At least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer and the (B-2) resin layer, or

[0015] At least a portion of the (A-1) metal electrode and the (A-2) metal electrode, and at least a portion of the (B-1) resin layer and the (C) inorganic insulating layer are directly bonded to each other, wherein the laminated body

[0016] At least one of the (B-1) resin layer and the (B-2) resin layer includes one or more resins selected from the group consisting of a carbonyl group, a hydroxyl group, an alkylene oxide group, a group having a siloxane bond, and a nitrogen-containing heterocycle.

[0017] [2] The laminate according to [1], wherein the second substrate includes an exposed (A-2) metal electrode and an exposed (B-2) resin layer on the same surface of the substrate body.

[0018] [3] The laminate according to [1] or [2], wherein the alkylene oxide group is a group represented by formula (1).

[0019] [Chemistry 1]

[0020]

[0021] (In formula (1), R 1 ~R 4 Each independently represents an alkylene group having 1 to 6 carbon atoms; R 5 ~R 12 (a) each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms; wherein the structures represented in the brackets are different; g, h, and i each independently represent an integer from 0 to 35, g+h+i>0; * represents a bonding portion)

[0022] [4] The laminate according to any one of [1] to [3], wherein the group having a siloxane bond is a group represented by formula (2).

[0023] [Chemistry 2]

[0024]

[0025] (In formula (2), j is a natural number from 1 to 50; R 13 and R 14 R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or a phenylene group having 6 to 20 carbon atoms; 15 ~R 18 Each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group; * represents a bonding portion)

[0026] [5] The laminate according to [3] or [4], wherein at least one of the resin layer (B-1) and the resin layer (B-2) comprises one or more resins having a group represented by the formula (1) or the formula (2) and selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide (excluding polyimide precursor and polybenzoxazole precursor) and copolymers thereof.

[0027] [6] The laminate according to any one of [1] to [5], characterized in that the resin contained in at least one of the (B-1) resin layer and the (B-2) resin layer contains two or more structural units represented by formula (9).

[0028] [Chemistry 3]

[0029]

[0030] (* indicates a bond; R 42 ~R 53 Each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group, or a hydrocarbon group having 1 to 6 carbon atoms (partially or entirely substituted with one or more of a fluorine atom, a hydroxyl group, or a carboxyl group)

[0031] [7] The laminate according to any one of [1] to [6], wherein the thermal expansion coefficient of at least one of the (B-1) resin layer and the (B-2) resin layer in the temperature range of 50°C to 150°C is greater than or equal to 10 ppm / K and less than or equal to 40 ppm / K.

[0032] [8] The laminate according to any one of [1] to [7], wherein at least one of the (B-1) resin layer and the (B-2) resin layer further contains an antioxidant.

[0033] [9] The laminate according to any one of [1] to [8], wherein at least one of the (B-1) resin layer and the (B-2) resin layer forms a cross-linked structure.

[0034]

[10] The laminate according to any one of [1] to [9], wherein the elastic modulus of at least one of the (B-1) resin layer and the (B-2) resin layer is 1.5 GPa or more and 7 GPa or less.

[0035]

[11] The laminate according to any one of [1] to

[10] , wherein a plurality of individualized first substrates are directly bonded to the same surface of the second substrate.

[0036]

[12] The laminate according to any one of [1] to

[11] , wherein the bonding strength between the first substrate and the second substrate in a die shear test is 10 MPa or more.

[0037]

[13] A stacked body according to any one of [1] to

[12] , wherein at least one of the substrate bodies of the first substrate and the second substrate comprises one or more selected from the group consisting of silicon, lithium niobate, lithium tantalum oxide, gallium nitride, silicon carbide, gallium arsenide, and indium phosphide.

[0038]

[14] A semiconductor element comprising the laminate according to any one of [1] to

[13] .

[0039]

[15] A micro-electromechanical system component comprising the laminate according to any one of [1] to

[14] .

[0040] Effects of the Invention

[0041] The laminate of the present invention has high bonding strength and few voids on the bonding surface, and therefore has high reliability. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] [ Figure 1 ] is a cross-sectional view of a laminate made using W2W

[0043] [ Figure 2 ] is a cross-sectional view of a laminate made using C2W

[0044] [ Figure 3 ] is a production process diagram of a W2W-based laminate

[0045] [ Figure 4 ] is a production process diagram of a C2W-based laminate DETAILED DESCRIPTION

[0046] The laminate of the present invention is formed by forming a first substrate including an exposed (A-1) metal electrode and an exposed (B-1) resin layer on the same surface of a substrate body.

[0047] a second substrate including, on the same surface as the substrate body, an exposed (A-2) metal electrode and an exposed (B-2) resin layer, or an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer,

[0048] At least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer and the (B-2) resin layer, or

[0049] At least a portion of the (A-1) metal electrode and the (A-2) metal electrode, and at least a portion of the (B-1) resin layer and the (C) inorganic insulating layer are bonded together so as to be directly bonded.

[0050] Here, direct bonding refers to joining two surfaces without the use of adhesives or other auxiliary bonding materials. For example, conductive bonding agents such as solder are commonly used to bond electrodes together. Direct bonding refers to bonding methods that do not use these materials. The following describes the materials and manufacturing process for the laminate.

[0051] The laminate of the present invention has a (A-1) metal electrode and a (A-2) metal electrode (hereinafter, sometimes described as "(A) metal electrode" as a general term for these two). In addition, the (A-1) metal electrode and the (A-2) metal electrode are preferably the same metal, but can also be different metals. As the (A) metal electrode, metals such as copper, gold, silver, aluminum, platinum, titanium, chromium, molybdenum, zinc, nickel, and magnesium can be used. In addition, alloys and laminates of these can also be used. In addition, conductive metal oxides such as ITO and ZnO can also be used. Among these, from the viewpoints of electrical conductivity, thermal conductivity and economy (cost), copper electrodes and copper electrodes including barrier metals are preferred. As barrier metals, nickel, chromium, molybdenum, etc. can be listed. In the case where the (A) metal electrode is a copper electrode, if the film thickness of the oxide film at the bonding interface of the electrode is greater than 0 nm and less than 200 nm, the resistance of the electrode decreases and is preferred.

[0052] The laminate of the present invention has a (B-1) resin layer and a (B-2) resin layer (hereinafter, sometimes described as "(B) resin layer" as a general term for these two). Alternatively, the laminate of the present invention has a (B-1) resin layer and a (C) inorganic insulating layer. The laminate of the present invention preferably has a (B-1) resin layer and a (B-2) resin layer. That is, the second substrate includes an exposed (A-2) metal electrode and an exposed (B-2) resin layer, or an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer, and the second substrate preferably includes an exposed (A-2) metal electrode and an exposed (B-2) resin layer on the same side of the substrate body. The (B-1) resin layer and the (B-2) resin layer are preferably the same type of resin, but may also be different types.

[0053] At least one of the resin layers (B-1) and (B-2) contains a resin containing at least one of a carbonyl group, a hydroxyl group, an alkylene oxide group, a group containing a siloxane bond, and a nitrogen-containing heterocycle. These chemical structures enhance chemical interactions at the interface, resulting in high adhesive strength.

[0054] That is, when the second substrate includes the exposed (A-2) metal electrode and the exposed (B-2) resin layer, the laminate includes the (B-1) resin layer and the (B-2) resin layer, and at least one of the (B-1) resin layer and the (B-2) resin layer includes a resin including at least one selected from the group consisting of a carbonyl group, a hydroxyl group, an alkylene oxide group, a group having a siloxane bond, and a nitrogen-containing heterocycle.

[0055] The case where the second substrate includes an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer is a case where the laminate does not include a (B-2) resin layer, and the (B-1) resin layer includes one or more resins selected from the group consisting of a carbonyl group, a hydroxyl group, an epoxyalkyl group, a group having a siloxane bond, and a nitrogen-containing heterocycle.

[0056] As described above, the term “at least one of the (B-1) resin layer and the (B-2) resin layer” refers to at least one of the (B-1) resin layer and the (B-2) resin layer when the laminate includes the (B-1) resin layer and the (B-2) resin layer, and refers to the (B-1) resin layer when the laminate does not include the (B-2) resin layer.

[0057] Examples of the functional group containing the carbonyl group include amides, esters, ketones, aldehydes, carbamates, ureas, and imides. Examples of the resin containing the carbonyl group include acrylic resins, polyimides, polyimide precursors, polybenzoxazole precursors, polyamides, polyureas, polyurethanes, polyesters, maleimides, and maleic acid resins. Unless otherwise specified, the term "polyamide" herein refers to polyamides other than polyimide precursors and polybenzoxazole precursors.

[0058] Examples of the hydroxyl group include alcoholic hydroxyl groups, phenolic hydroxyl groups, and silanol hydroxyl groups, which can be introduced as functional groups of various resins. Representative examples include phenolic resins, polyvinyl alcohol, and polysiloxane. 1 ~R 4 Preferred examples include ethylene, propylene, and butylene. 5 ~R 12 Preferred examples include a hydrogen atom, a methyl group and an ethyl group.

[0059] Examples of the alkylene oxide group include ethylene oxide, propylene oxide, butylene oxide, epoxy, and oxetane groups. From the perspective of adhesive strength and resin reliability, it is preferred that the resin contained in at least one of the resin layer (B-1) and the resin layer (B-2) contain a group represented by the following formula (1) containing these groups in a complex manner.

[0060] [Chemistry 4]

[0061]

[0062] In formula (1), R 1 ~R 4 R each independently represents an alkylene group having 1 to 6 carbon atoms. 5 ~R 12 Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms. The structures in parentheses are different. g, h, and i each independently represent an integer from 0 to 35, and g+h+i>0. * represents a bonding moiety.

[0063] Examples of the resin having an alkylene oxide group include polyalkylene oxides and epoxy resins, and condensation-based resins such as polyimides and polyamides having an alkylene oxide group.

[0064] Examples of the group having a siloxane bond include (Si(R)2-O)(D2 unit), (Si(R)-O) 3 / 2 (T3 unit) and (Si-O)2 (Q4 unit) (R is an organic group having carbon bonded to silicon). Among these, from the viewpoint of adhesive strength during direct bonding, the D2 unit is preferred, and the group represented by formula (2) is more preferred.

[0065] [Chemistry 5]

[0066]

[0067] In formula (2), j is a natural number from 1 to 50. 13 and R 14 R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or a phenylene group having 6 to 20 carbon atoms. 15 ~R 18 Each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. * represents a bonding portion.

[0068] As R 13 and R 14 Preferred examples include propylene, butylene, vinylene, and phenylene. 15 ~R 18 Preferred examples include methyl and phenyl.

[0069] As the nitrogen-containing heterocyclic ring, a group having a nitrogen-containing heterocyclic structure can be arbitrarily selected, and examples thereof include a cyclic imide group, an oxazole group, an imidazole group, an oxazine group, etc. Examples of resins containing these include polyimide, polybenzoxazole, polybenzimidazole, and polybenzoxazine.

[0070] Specific examples of the resin containing a group having a siloxane bond include polysiloxane, dimethyl silicone, polyimidesiloxane, and siloxane-modified benzocyclobutene. Among these, resins containing a group represented by formula (2) are preferred. Among these, polyimidesiloxane and siloxane-modified benzocyclobutene containing a group represented by formula (2) are more preferred from the perspective of adhesion and reliability.

[0071] Next, the details of the various resins are described below.

[0072] Examples of acrylic resins include those obtained by free radical polymerization of (meth)acrylic acid and (meth)acrylate esters. Of these, carboxyl-containing acrylic resins are preferred for adhesion during direct bonding, and those containing at least a portion of an ethylenically unsaturated double bond group are preferred for chemical resistance. (Meth)acrylic acid herein refers to methacrylic acid or acrylic acid. This applies to similar descriptions hereinafter.

[0073] Acrylic resins can be synthesized by free radical polymerization of (meth)acrylic acid compounds. Examples of (meth)acrylic acid compounds include (meth)acrylic acid compounds containing carboxyl groups and / or anhydride groups, or other (meth)acrylates. Catalysts for free radical polymerization are typically azo compounds such as azobisisobutyronitrile or organic peroxides such as benzoyl peroxide.

[0074] As the (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, etc. can be used.

[0075] Alternatively, the acrylic resin may be a copolymer of a (meth)acrylic acid compound and other monomers containing unsaturated double bonds. Examples of other monomers containing unsaturated double bonds include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, p-hydroxystyrene, maleic anhydride, norbornene, norbornene dicarboxylic acid, norbornene dicarboxylic anhydride, cyclohexene, butyl vinyl ether, butyl allyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, cyclohexane vinyl ether, cyclohexane allyl ether, and 4-hydroxybutyl vinyl ether.

[0076] The acrylic resin having an ethylenically unsaturated bond is preferably obtained by free radical polymerization of a (meth)acrylic acid compound, (meth)acrylate, and / or other unsaturated double bond-containing monomer containing a carboxyl group and / or anhydride group, followed by an addition reaction of an epoxy compound having an ethylenically unsaturated double bond group. Examples of the catalyst used in the addition reaction include amino-based catalysts such as dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, or dimethylbenzylamine; phosphorus-based catalysts such as triphenylphosphine; ammonium-based catalysts such as tetrabutylammonium acetate; and chromium-based catalysts such as chromium acetylacetonate or chromium chloride.

[0077] Examples of the epoxy compound having an ethylenically unsaturated double bond group include glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, butyl vinyl ether, butyl allyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, cyclohexane vinyl ether, cyclohexane allyl ether, o-vinylbenzyl glycidyl ether, and m-vinylbenzyl glycidyl ether.

[0078] Examples of the polysiloxane include hydrolysis condensates using at least one organic silane compound. Examples of the organic silane compound include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, trifluoromethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-cyclohexyl)ethyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthryltrimethoxysilane, 9-anthryltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-naphthyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthryltrimethoxysilane, 1-anthryltrimethoxysilane, 1-fluorenyltrimethoxysilane, 2-naphthyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-fluorenyltrimethoxysilane, 1-naphth ... Trifunctional silanes such as fluorenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, and di(1-naphthyl)dimethoxysilane, and monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane. Two or more of these organosilanes may be used.

[0079] The conditions for the hydrolysis reaction of the organosilane compound can be appropriately set. For example, it is preferred to add an acid catalyst and water to the organosilane compound in a solvent over a period of 1 to 180 minutes, followed by a reaction at room temperature to 110°C for 1 to 180 minutes. By carrying out the hydrolysis reaction under these conditions, a rapid reaction can be suppressed. The reaction temperature is preferably 30°C to 105°C.

[0080] In addition, the hydrolysis reaction is preferably carried out in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution comprising formic acid, acetic acid or phosphoric acid is preferably used. Relative to 100 parts by mass of all organosilane compounds used during the hydrolysis reaction, the content of these acid catalysts is preferably 0.1 to 5 parts by mass. By setting the content of the acid catalyst to the range, the hydrolysis reaction can be easily controlled so that it is necessary and fully carried out. In addition, a certain amount of silanol groups may also remain.

[0081] The condensation reaction conditions are preferably to heat the reaction mixture at 50°C to the boiling point of the solvent for 1 to 100 hours after obtaining the silanol compound through the hydrolysis reaction of the organosilane compound. Further heating or the addition of an alkaline catalyst may be employed to increase the degree of polymerization of the polysiloxane. Alternatively, after the hydrolysis reaction, the generated alcohol may be distilled off and removed in appropriate amounts by heating and / or reducing pressure, and then any solvent may be added.

[0082] Siloxane-modified benzocyclobutene resins can be produced, for example, by reacting a brominated arylcyclobutene compound with a compound containing an unsaturated alkyl group in the presence of a palladium catalyst. Specifically, examples include the benzocyclobutene having a siloxane structure described in formula (2), preferably divinylsiloxane bisbenzocyclobutene. Commercially available benzocyclobutene compounds include Cyclotene 3022-63 or 4026-46 (trade names, manufactured by Dow Chemical).

[0083] Examples of polyimidesiloxane include polyimides obtained by using at least one of an acid dianhydride having a siloxane structure and a diamine having a siloxane structure as a monomer. Specific examples of the monomer are given in the description of the polyimide precursor described below.

[0084] As the epoxy resin, there can be mentioned a resin obtained by hardening a known epoxy compound. As the epoxy compound, there can be mentioned bisphenol A diglycidyl ether, cresol novolac resin type multifunctional glycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, etc. Specifically, there can be mentioned Epolight (registered trademark) 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 70P, Epolight 200P, Epolight 400P, Epolight 1500NP, Epolight 80 MF, Epolight 4000, Epolight 3002 (the above are trade names, manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L (the above are trade names, manufactured by Nagase Chemical Co., Ltd. ChemteX Corporation), Epikote 828, Epikote 1002, Epikote 1750, Epikote 1007, YX8100-BH30, E1256, E4250, E4275 (trade names, manufactured by Nippon Epoxy Resins Co., Ltd.), Epiclon EXA-9583, Epiclon N666, Epiclon N695, Epiclon HP4032, Epiclon HP7200 (trade names, manufactured by DIC Corporation) , Techmore VG3101L (trade name, manufactured by Printec), Tepic S, Tepic G, Tepic P (the above are trade names, manufactured by Nissan Chemical Industries, Ltd.), Epotot YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), GAN, GOT, EPPN502H, NC3000 or NC6000 (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), YDPN-638, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A (trade names, manufactured by Nippon Steel Chemicals & Materials Co., Ltd.), etc.

[0085] Examples of the phenolic resin include novolac resins and resol resins, which can be obtained by polycondensing various phenols alone or mixtures thereof with aldehydes such as formaldehyde.

[0086] Examples of the phenols constituting the novolac resin and the resol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebisphenol, and methylenebisphenol. Bis-p-cresol, resorcinol, o-catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, p-phenylphenol, α-naphthol, β-naphthol, etc., and these can be used alone or as a mixture.

[0087] Examples of aldehydes used for polycondensation with the novolac resin or resol resin include, in addition to formaldehyde, polyoxymethylene, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, and these may be used alone or as a mixture.

[0088] The phenol resin may also have a structure in which a portion of the hydrogen atoms attached to the aromatic ring are substituted with one or more of an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, a hydroxyl group, an alkoxy group, an alkoxymethyl group, a hydroxymethyl group, a carboxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

[0089] Particularly with regard to the viewpoint of low dielectric constant, more preferably novolac resin or the resol resin with rigid naphthalene structure or biphenyl structure, specifically, are preferably used p-phenylphenol, α-naphthol or β-naphthol as phenol.In addition, as the phenolic resin of commercially available product, PN-80, PN-100, GPH-65, GPH-103 (are more than trade name, Japanese chemical medicine (stock) manufacture, XLC-3L (trade name, Mitsui Chemicals (stock) manufacture), MEHC-7851SS (trade name, Minghe Huacheng (stock) manufacture) etc. are enumerated, particularly preferably GPH-65, GPH-103 and MEHC-7851SS etc. with rigid structure.

[0090] As maleic resin, for example, can be manufactured by copolymerizing maleic anhydride or maleate with the compound containing unsaturated alkyl under free radical polymerization catalyst.Specifically, styrene maleic anhydride copolymer or maleic anhydride modified polyethylene etc. can be enumerated.In addition, as the maleic resin of commercially available product, " Xiran (XIRAN) " 1000, " Xiran (XIRAN) " 1440, " Xiran (XIRAN) " 2000, " Xiran (XIRAN) " 2500, " Xiran (XIRAN) " 3000, " Xiran (XIRAN) " 3500, " Xiran (XIRAN) " 4000, " Xiran (XIRAN) " 6000 and " Xiran (XIRAN) " 9000 (above is trade name, Pakistan Industry (stock) manufactures) etc. can be enumerated.

[0091] As a polyimide precursor, what is obtained by making tetracarboxylic acid and its derivatives react with diamine and its derivatives is mentioned, for example. As a polyimide precursor, polyamic acid, polyamic acid ester, polyamic acid amide or polyisoimide is mentioned, for example.

[0092] Examples of tetracarboxylic acids and their derivatives include 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,3,3',4 ...1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1, , 2',3,3'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2'-bis[4-(3,4-dicarboxyphenyl)oxy]-1,1-bis(2,3-dicarboxyphenyl)ethane phenyl]propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 2,3,5,6-pyridinetetracarboxylic acid or 3,4,9,10-perylenetetracarboxylic acid, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis( 3,4-dicarboxybenzoic acid amide), bicyclo[2.2.2]octane-7-ene-2,3,5,6-tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid or 2,3,4,5-tetrahydrofurantetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid or tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides or tetracarboxylic acid active diesters thereof. These compounds may be used alone or in combination of two or more.

[0093] Furthermore, the use of a tetracarboxylic acid or acid dianhydride having a siloxane structure is preferred because direct bonding is possible at low temperatures ranging from room temperature to approximately 100° C. Examples of the acid dianhydride having a siloxane structure include X-22-168AS, X-22-168A, X-22-168B, and X-22-168-P5-B.

[0094] Examples of diamines and their derivatives include m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl, bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, dimercaptophenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,10-anthracenediamine, 4,4'- '-Diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, 2,7- diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(3-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-6-aminobenzoxazole, 2-(3-aminophenyl)-6-aminobenzoxazole, 1,4-bis(5-amino-2-benzoxazolyl)benzene, 1,4-bis(6-amino-2-benzoxazolyl)benzene, 1,3-bis(5-amino-2-benzoxazolyl)benzene, 1,3-bis(6-amino-2-benzoxazolyl)benzene, 2,6-bis(4-aminophenyl)benzobisoxazole, 2,6-bis(3-aminophenyl)benzobisoxazole, Bis[(3-aminophenyl)-5-benzoxazolyl], bis[(4-aminophenyl)-5-benzoxazolyl], bis[(3-aminophenyl)-6-benzoxazolyl], bis[(4-aminophenyl)-6-benzoxazolyl], 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4-aminobenzoic acid, 4-aminophenyl ester, 1,3-bis(4-anilino)tetramethyldisiloxane, ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane or dimerized diamine, etc.

[0095] In addition, by having a phenolic hydroxyl group, the adhesive force during direct bonding is improved, and when the metal electrode is copper or silver, corrosion can be reduced, so a bisaminophenol compound is preferred. Examples of the bisaminophenol compound include bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis[N-( 3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, N,N'- Bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl) -3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'-diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane, etc.

[0096] Furthermore, the use of a diamine having an alkylene oxide or siloxane structure is preferred because direct bonding is possible at low temperatures ranging from room temperature to about 100° C. The alkylene oxide is preferably a diamine having a structure represented by formula (1). Examples of commercially available products include ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, and HT-1700 (all trade names, manufactured by Huntsman Co., Ltd.). As the siloxane structure, a diamine having a structure represented by the above formula (2) is preferred. Specific examples include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and X-22-9409 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0097] The polyamine compound may be used as it is or as a compound obtained by isocyanating or trimethylsilylating the amine moiety. In addition, two or more polyamine compounds may be used in combination.

[0098] Furthermore, by capping the resin terminals with monoamine, acid anhydride, acid chloride, or monocarboxylic acid, the weight average molecular weight of the resin can be adjusted, or a functional group different from that in the molecule can be introduced.

[0099] Preferred examples of monoamines include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used.

[0100] Preferred examples of acid anhydrides, acid chlorides, and monocarboxylic acids include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and the like; 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene and the like. Monocarboxylic acids and monochloride compounds formed by chlorinating the carboxyl groups of these; monochloride compounds formed by chlorinating only one carboxyl group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene; and active ester compounds obtained by reacting a monochloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide. Two or more of these may also be used.

[0101] As a polyimide precursor, polyamic acid or polyamic acid ester is preferable, For example, the polyimide precursor containing the structural unit represented by Formula (3) is mentioned.

[0102] [Chemistry 6]

[0103]

[0104] In formula (3), R 19 represents a 4- to 6-valent organic group, R 20 represents a 2- to 10-valent organic group. 22 Each independently represents an organic group having 1 to 10 carbon atoms or a hydroxyl group, and n represents an integer from 0 to 8. 21 They may be the same or different and represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. m represents an integer of 2 to 4.

[0105] R 19 -(COOR 21 ) m R represents the above-mentioned tetracarboxylic acid and / or its derivative residue. 20 -(R 22 ) n Represents the diamine and / or its derivative residues described above. * represents the bonding point. 21 The organic group having 1 to 30 carbon atoms includes, for example, a hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, a sec-hexyl group, an n-heptyl group, an n-octyl group, and a sec-octyl group; an alkylene oxide such as a 2-methoxyethyl group, a 2-methoxypropyl group, a diethylene glycol methyl group, a dipropylene glycol methyl group; an organic group containing an unsaturated bond such as an ethyl 2-(meth)acrylate group, a propyl 2-(meth)acrylate group, a butyl 2-(meth)acrylate group, an allyl group, a butenyl group, and the like.

[0106] Examples of polyimides include polyimides obtained by dehydrating and ring-closing the polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide described above by heating or reacting with an acid or base, and having tetracarboxylic acid and / or its derivative residues, and diamine and / or its derivative residues. In order to form a polyimide as the (B) resin layer on the first substrate or the second substrate, the most convenient and preferred method is to apply a polyimide precursor solution to the substrate, dry it, and then heat it to a temperature above the imidization temperature.

[0107] As a polyimide, the thing containing the structural unit represented by following formula (4) is mentioned, for example.

[0108] [Chemistry 7]

[0109]

[0110] In formula (4), R 23 represents a 4- to 10-valent organic group, R 24 represents a 2- to 8-valent organic group. 25 and R 26 represents a hydroxyl group or an organic group having 1 to 20 carbon atoms, and may be a single group or a mixture of different groups. k and l represent integers of 0 to 6. 23 -(R 25 ) k R represents the above-mentioned tetracarboxylic acid and / or its derivative residue. 24 -(R 26 ) l represents the diamine and / or its derivative residue described above. Among them, an alkylene oxide or a diamine residue having a siloxane bond is preferred from the viewpoint of adhesive strength during direct bonding. * represents a bonding point.

[0111] Examples of the polybenzoxazole precursor include polyhydroxyamides obtained by reacting dicarboxylic acid and its derivatives with a bisaminophenol compound or the like as a diamine.

[0112] As the example of dicarboxylic acids, terephthalic acid, isophthalic acid, dimer acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid etc. can be enumerated; as the example of tricarboxylic acids, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid etc. can be enumerated. These compounds can be used alone or in combination of two or more. Particularly with regard to the viewpoint of reducing dielectric loss tangent, dimer acid is preferably used.

[0113] Examples of the bisaminophenol include the bisaminophenol compounds exemplified for the polyimide precursor.

[0114] Examples of the polybenzoxazole precursor used in the present invention include those containing a structural unit represented by the following formula (5).

[0115] [Chemistry 8]

[0116]

[0117] In formula (5), R 27 represents a 2- to 6-valent organic group, R 28 represents a single bond or a 2- to 6-valent organic group. 29 and R 30 represents an organic group having 1 to 10 carbon atoms or a hydroxyl group. q and r represent integers of 0 to 4. 27 -(R 29 ) q R represents the above-mentioned dicarboxylic acid and / or its derivative residue. In particular, from the viewpoint of reducing the dielectric loss tangent, it is preferably a dimer acid residue. 28 -(R 30 ) r represents the residue of the bisaminophenol compound and / or its derivative described above. * represents a bonding point.

[0118] Examples of the polybenzoxazole include those obtained by dehydration ring closure of a dicarboxylic acid and a bisaminophenol compound as a diamine by a reaction using polyphosphoric acid, and examples of the polybenzoxazole precursor include those obtained by dehydration ring closure of the polyhydroxyamide by heating or a reaction using phosphoric anhydride, a base, or a carbodiimide compound.

[0119] Examples of polybenzoxazoles include those containing a structural unit represented by formula (6).

[0120] [Chemistry 9]

[0121]

[0122] In formula (6), R 31 represents a 2- to 6-valent organic group, R 32 represents a 4- to 6-valent organic group. 33 and R 34 Each independently represents an organic group having 1 to 10 carbon atoms or a hydroxyl group. o represents an integer of 0 to 4, and p represents an integer of 0 to 2. 31 -(R 33 ) o R represents the above-mentioned dicarboxylic acid and / or its derivative residue. In particular, from the viewpoint of reducing the dielectric loss tangent, it is preferably a dimer acid residue. 32 -(R 34 ) prepresents the residue of the bisaminophenol compound and / or its derivative described above. * represents a bonding point.

[0123] Examples of the polyamide include polyamides obtained by dehydration condensation of dicarboxylic acid and a diamine compound using a reaction using polyphosphoric acid.

[0124] Examples of the polyamide include polyamides containing a structural unit represented by the following formula (7).

[0125] [Chemistry 10]

[0126]

[0127] In formula (7), R 35 and R 36 represents a divalent to hexavalent organic group. 37 and R 38 Each independently represents an organic group having 1 to 10 carbon atoms or a hydroxyl group. s represents an integer of 0 to 4, and t represents an integer of 0 to 4. 35 -(R 37 ) s represents the dicarboxylic acid and / or its derivative residue as described above, R 36 -(R 38 ) t represents a diamine compound other than the bisaminophenol compound described above and / or its derivative residue. * represents a bonding point.

[0128] Furthermore, the resin layer (B) may include a copolymer including two or more selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, polyamide, polyurethane, and polyurea.

[0129] Examples of polyureas include polyureas obtained by addition polymerization of diamine and polyfunctional isocyanate.

[0130] Examples of the diamine include the compounds exemplified for polyimide, polybenzoxazole, and polyamide, and the same applies to preferred examples.

[0131] Examples of the polyfunctional isocyanate include hexamethylene diisocyanate, 1,3-bis(isocyanatemethyl)benzene, 1,3-bis(isocyanatemethyl)cyclohexane, norbornene diisocyanate, naphthalene-1,5-diisocyanate, diphenylmethane-4,4′-diisocyanate, and toluene-2,4-diisocyanate. Examples of the polyol include ethylene glycol, propylene glycol, pentaerythritol, dipentaerythritol, 1,4-bis(2-hydroxyethoxy)benzene, 1,3-bis(2-hydroxyethoxy)benzene, 4,4′-bis(2-hydroxyethoxy)biphenyl, 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, and bis(4-(2-hydroxyethoxy)phenyl)methane.

[0132] The addition polymerization product of diamine and polyfunctional isocyanate can be obtained even without a catalyst, but a catalyst can also be used. Examples of the catalyst include tin compounds such as dibutyltin dilaurate and tertiary amines such as 1,4-diazabicyclo[2.2.2]octane.

[0133] Polyesters obtained by a polyaddition reaction of a polyol compound and an acid dianhydride are preferred because they are easy to synthesize and have few side reactions. Polyol compounds obtained by a reaction of a polyfunctional epoxy compound with a monobasic acid compound containing a free radical polymerizable group, such as (meth)acrylic acid, are preferred because they facilitate the introduction of free radical polymerizable groups and aromatic rings.

[0134] Examples of the polyfunctional epoxy compound include, but are not limited to, aliphatic epoxy compounds such as ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether, and aromatic epoxy compounds such as 9,9-bis(4-glycidyloxyphenyl)fluorene.

[0135] Examples of other polyol compounds include aliphatic alcohol compounds such as ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, and pentaerythritol, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene.

[0136] Examples of the acid dianhydride include the tetracarboxylic dianhydride exemplified in the description of the polyimide precursor.

[0137] Examples of polyurethanes include those obtained by a polyaddition reaction between a polyol compound and a polyfunctional isocyanate. Examples of polyol compounds include the compounds exemplified for polyesters. Examples of polyfunctional isocyanates include the compounds exemplified for polyureas. A catalyst may also be used in the polyaddition reaction, and examples of the catalyst include the compounds exemplified for polyureas.

[0138] The laminate of the present invention may also have an inorganic insulating layer (C). That is, the second substrate may also include an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer. As the inorganic insulating layer (C), inorganic insulating layers such as silicon oxide (SiO2), silicon nitride (SiN), silicon carbide nitride (SiCN), silicon oxynitride (SiON), titanium oxide (TiO2), zirconium oxide (ZrO2), and aluminum oxide (Al2O3) can be used. In addition, the inorganic insulating layer (C) may also be a laminate of these. Among these, from the perspective of insulation and economy (cost), it is preferred to include an inorganic insulating layer of SiO2, SiN, or SiCN.

[0139] In the examples described above, the resin layer (B) also preferably contains a resin having a group represented by the formula (1) or the formula (2). That is, it is preferred that at least one of the resin layer (B-1) and the resin layer (B-2) contains a resin having an alkylene oxide group, wherein the alkylene oxide group is a group represented by the formula (1). In addition, it is preferred that at least one of the resin layer (B-1) and the resin layer (B-2) contains a resin including a group having a siloxane bond, wherein the group having a siloxane bond is a group represented by the formula (2).

[0140] In the above-described example, from the viewpoints of substrate adhesion, bonding strength, and processability, the (B) resin layer preferably comprises one or more resins having a group represented by the formula (1) or the formula (2) selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, a polyamide (excluding polyimide precursors and polybenzoxazole precursors), and copolymers thereof. That is, at least one of the (B-1) resin layer and the (B-2) resin layer preferably comprises one or more resins having a group represented by the formula (1) or the formula (2) selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, a polyamide (excluding polyimide precursors and polybenzoxazole precursors), and copolymers thereof.

[0141] The resin contained in at least one of the resin layer (B-1) and the resin layer (B-2) preferably contains two or more structures represented by formula (9) because the thermal expansion coefficient can be suppressed low.

[0142] [Chemistry 11]

[0143]

[0144] (* indicates a bond; R 42 ~R 53 Each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group, or a hydrocarbon group having 1 to 6 carbon atoms (partially or entirely substituted with any one or more of a fluorine atom, a hydroxyl group, and a carboxyl group)

[0145] Examples of the acid dianhydride that provides the acid dianhydride residue represented by formula (9) include pyromellitic dianhydride and 3,3′,4,4′-biphenyltetracarboxylic dianhydride.

[0146] Examples of diamines that provide the diamine residue represented by formula (9) include p-phenylenediamine, benzidine, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)]bis(3-methylaniline), and 4,4'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)]bis[3-(trifluoromethyl)aniline].

[0147] The acid dianhydride providing the acid dianhydride residue represented by formula (9) or the diamine providing the diamine residue may have a substituent. Examples of the acid dianhydride providing the acid dianhydride residue represented by formula (9) or the diamine providing the diamine residue include 2,5-diaminotoluene, 2,5-dimethyl-1,4-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl 4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 2,2',5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, 3,3'-dihydroxybenzidine, 1,4-diamino-5-dicarboxybenzene, etc.

[0148] The coefficient of thermal expansion of at least one of the resin layer (B-1) and the resin layer (B-2) in the temperature range of 50°C to 150°C is preferably 10 ppm / K or higher and 40 ppm / K or lower, more preferably 15 ppm / K or higher and 30 ppm / K or lower, and even more preferably 20 ppm / K or higher and 25 ppm / K or lower. By being within this range, the difference in thermal expansion coefficient from copper is minimized, thereby facilitating the reliability of the laminated body after bonding.

[0149] Preferably, at least one of the resin layer (B-1) and the resin layer (B-2) further contains an antioxidant. The inclusion of an antioxidant suppresses oxidative degradation of the mixed resin. Furthermore, by providing an anti-rust effect on metal materials, it suppresses metal oxidation caused by external moisture and the associated loss of adhesion and delamination. These effects enhance the long-term reliability of the laminate.

[0150] As the antioxidant, a hindered phenol-based antioxidant or a hindered amine-based antioxidant is preferred. Furthermore, the number of phenolic groups or amino groups in one molecule is preferably 2 or more, more preferably 4 or more, from the perspective of easily achieving an antioxidant effect. Among these, a compound represented by the following formula (8) is preferred. By containing a compound represented by formula (8), mechanical properties of the cured film after reliability tests such as high-temperature storage tests, or peeling from metal materials, can be suppressed.

[0151] [Chemistry 12]

[0152]

[0153] In formula (8), R 39represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R 40 represents an alkylene group having 2 or more carbon atoms. 41 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and a N atom. u represents an integer of 1 to 4.

[0154] About R 41 Preferred monovalent organic groups include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, allyl, vinyl, and heterocyclic groups. Preferred divalent organic groups include carbonyl, -O-, -NH-, -NHNH-, -NHCO-, and -COO-. 41 Preferred trivalent or tetravalent organic groups include groups in which hydrogen atoms of the monovalent or divalent organic groups mentioned above are substituted as bonding points, etc. In addition, combinations of these groups are also possible, and the organic groups may further have substituents.

[0155] Examples of the compound represented by formula (8) include the following, but are not limited thereto.

[0156] [Chemistry 13]

[0157]

[0158] [Chemistry 14]

[0159]

[0160] There is no particular limitation on the method for forming the (B) resin layer. For example, it can be formed by a resin composition comprising at least one of a carbonyl group, a hydroxyl group, an epoxyalkyl group, a group having a siloxane bond, and a nitrogen-containing heterocycle, and a solvent. The resin composition is preferably in liquid or sheet form. In the case of a liquid, the (B) resin layer can be obtained by a drying process in which the coating is dried by heating with a hot plate, an oven, infrared rays, etc. after being applied on the substrate body by known methods such as spin coating, slit die coating, spray coating, and inkjet coating. In the case of a sheet, it can be formed by lamination. In addition, it can also be subjected to a drying process in the same manner after lamination. In addition, it can also be cured by at least one of light and heat as needed within the range that does not damage the characteristics of the (B) resin layer. In the case of curing in heat, the curing temperature can be appropriately selected within the range of 100°C to 400°C, and the time can be selected from 3 minutes to 3 hours according to the purpose. Among them, annealing within the range of 150°C to 250°C is less burdensome on the substrate body and is preferred. Moreover, when the resin composition has photosensitivity, a pattern such as through holes can be formed in the (B) resin layer through exposure and development steps as needed.

[0161] The elastic modulus of at least one of the resin layer (B-1) and the resin layer (B-2) is preferably 1.5 GPa to 7 GPa, and more preferably 2.5 GPa to 5 GPa. By being within this range, high bonding strength and reliability are easily achieved while suppressing the formation of voids caused by tiny foreign matter during cutting.

[0162] At least one of the resin layer (B-1) and the resin layer (B-2) may form a cross-linked structure. Formation of the cross-linked structure may increase the elastic modulus. The cross-linked structure may be formed by adding a cross-linking agent to the resin composition and performing a curing treatment. Examples of the cross-linking agent include, but are not limited to, methylol compounds, epoxy compounds, and oxetane compounds.

[0163] As the epoxy compound, known ones may be contained, and specifically, the ones exemplified in the description of the epoxy resin may be mentioned.

[0164] The oxetane compound may include known ones, for example, OXT-101, OXT-121, OXT-212, OXT-221 (these are trade names, manufactured by Toagosei Co., Ltd.), ETERNACOLL EHO, ETERNACOLL OXBP, ETERNACOLL OXTP, ETERNACOLL OXMA, ETERNACOLL OXIPA (these are trade names, manufactured by Ube Industries, Ltd.), or oxetane-containing phenol novolacs.

[0165] The hydroxymethyl compound may contain known ones. Examples thereof include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, and TML-BPAF. , TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (these are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0166] At least one of the (B-1) resin layer and the (B-2) resin layer may be formed of a resin composition having a photosensitive agent. By forming the resin layer using a photosensitive material, the method for manufacturing the first substrate and the second substrate can be simplified, and the elastic modulus can be controlled by promoting the reaction of the cross-linking agent. As a photosensitive agent, a photopolymerization initiator or a photoacid generator is preferred. Among them, in terms of resolution, a material containing a photoacid generator is preferred. Specific examples of photopolymerization initiators and photoacid generators include those identical to those described in Japanese Patent Laid-Open No. 2018-165819. The same is true for preferred examples.

[0167] The first substrate and the second substrate of the laminate of the present invention each have a substrate body. The so-called substrate body refers to, for example, a plate-shaped item other than the (A-1) metal electrode and the (B-1) resin layer in the first substrate. At least one of the substrate body of the first substrate and the substrate body of the second substrate preferably includes one or more selected from the group consisting of silicon, lithium niobate, lithium tantalum, gallium nitride, silicon carbide, gallium arsenide and indium phosphide. Silicon is preferably used for semiconductor elements with functions such as calculation processing, information storage, and power control functions. Lithium niobate and lithium tantalum are preferably used for MEMS elements with a filtering function for electrical signals. Gallium nitride and silicon carbide are preferably used for semiconductor elements with a power control function, and gallium arsenide and indium phosphide are preferably used for semiconductor elements with light receiving and light emitting functions.

[0168] The laminate of the present invention can be used if the bonding strength between the first substrate and the second substrate in a die shear test is 5 MPa or more. From the viewpoint of reliability, it is preferably 10 MPa or more, more preferably 20 MPa or more.

[0169] The method for producing the laminate of the present invention will be described. Regarding the production method, for example, a known technique in the industry for directly bonding wafers with SiO2 and copper on the same surface can be used (Materials 2022, 15(5), 1888, etc.). This technique involves smoothing the surfaces of the two wafers at the atomic level by chemical mechanical polishing (CMP) before direct bonding, then activating the surfaces by plasma treatment, and performing direct bonding through a bonding process. This known technique can also be applied to the direct bonding in the present invention.

[0170] Before forming the laminate, the first and second substrates may be substrates having circuits of passive and / or active components formed thereon as the substrate bodies. By using such substrate bodies, the obtained laminate can function as a semiconductor and / or MEMS.

[0171] The semiconductor element of the present invention is a semiconductor element comprising a laminate of the present invention. In addition, the MEMS element of the present invention is a MEMS element comprising a laminate of the present invention. In addition, it can also be a composite element in which two substrate bodies each comprise a laminate having semiconductor and MEMS functions. (A) A metal electrode and (B) A resin layer are formed on the substrate body and then smoothed to obtain a first substrate and a second substrate. (A) The metal electrode can be formed using a known method, such as a subtractive method and a semi-additive method. The formation of a copper electrode using a semi-additive method will be described as a specific example. A seed layer of Ti, Ni, etc. is formed on the substrate body by sputtering, a dry film resist pattern is processed, a copper electrode pattern is formed by electrolytic plating, and the resist is removed and the seed layer is subsequently removed to form the substrate. The resin layer is then formed by the (B) resin layer forming method. Thus, a substrate comprising (A) a metal electrode and (B) a resin layer on the same surface can be obtained.

[0172] By smoothing the substrate comprising (A) the metal electrode and (B) the resin layer, each can be exposed. Thus, the first substrate and the second substrate can be obtained. The smoothing process preferably uses CMP or a surface planer using a diamond tool. CMP can reduce surface roughness and improve bonding strength, and is therefore preferred. In addition, from the perspective of shortening the process time, it is preferred to perform CMP after performing the surface planer.

[0173] The smoothed first substrate and the second substrate are preferably activated by plasma treatment to form a surface including (A) a metal electrode and (B) a resin layer. The bonding strength can be improved by activation. Plasma treatment is performed using an inert gas in plasma, and the oxygen volume concentration is preferably less than 1%, more preferably less than 0.1%, and more preferably less than 0.01%. By setting the oxygen volume concentration to less than 1%, the oxidation of the outermost metal electrode can be suppressed and the conductivity can be maintained. In addition, the oxidation of the resin layer can be suppressed and the reduction in bonding strength can be suppressed. As the inert gas used in plasma treatment, argon and helium can be listed. In order to maintain the activated state after treatment for a long time, it is preferred that helium be contained as the inert gas to be plasma-treated. Since helium has low activation energy, the activation energy state of the resin layer activated by helium plasma is low, thereby becoming a relatively stable state. Therefore, the activation state becomes longer, the time margin from plasma treatment to direct bonding is ensured, and the process tolerance is improved. As an example of plasma treatment for direct bonding with helium, this method was shown in the presentation at the Wafer Level Package Symposium 2022 “Atmospheric Plasma System for In-Line Surface Activation of Die-to-Wafer Direct and Hybrid Bonding”, and can also be used in the present invention.

[0174] As a method for joining the first substrate and the second substrate, it can be wafer to wafer (W2W) in which wafers are joined using a wafer bonder, or chip to wafer (C2W) in which a chip is joined to a wafer, or chip to chip (C2C) in which chips are joined to each other. Among them, C2W is preferred from the viewpoints of joining accuracy, ease of circuit design, etc. A flip chip bonder or the like is used for joining the chip. The chip is obtained by a singulation process of a wafer that has been cut. As a method for making a C2W stack, for example, a plurality of singulated first substrates can be prepared by cutting, and the plurality of first substrates can be directly joined to the second substrate in a horizontal arrangement. That is, it is preferred that a plurality of singulated first substrates are directly joined to the same surface of the second substrate. Alternatively, after joining the singulated first substrate to the second substrate, exposed metal electrodes and a resin layer can be formed on the surface opposite the joining surface (or exposed metal electrodes and resin layers can be formed on both surfaces of the first substrate in advance), and then joined to another first substrate in a longitudinal arrangement. This allows for high-density stacking of many chips. Furthermore, the multiple first substrates can be of the same or different sizes.

[0175] Furthermore, the temperature of the bonding stage during bonding and the temperature of the bonding head holding the other substrate are both preferably 20°C to 40°C. Figure 1 , which is a cross-sectional view of a laminate obtained by W2W, Figure 2 ] A cross-sectional view of a laminate obtained by C2W is shown in FIG.

[0176] After bonding, annealing is preferably performed. Annealing improves bonding strength and the reliability of the resulting laminate due to softening of the resin layer and diffusion of the metal electrodes. The annealing temperature can be suitably selected from 100°C to 350°C, and the duration can be selected from 3 minutes to 3 hours depending on the intended purpose. Annealing at a temperature of 150°C to 250°C is preferred, as it minimizes the burden on the substrate.

[0177] In addition, when using a photosensitive resin composition in the formation of (B) resin layer, (A) metal wiring and (B) resin layer can be formed by using different processes. First, the substrate body is coated with a photosensitive resin composition, dried, exposed, developed, and hardened to form a patterned (B) resin layer. Then, a seed layer of Ti, Ni, etc. is formed by sputtering, and the dry film resist is patterned so that the same position opening as the opening of the (B) resin layer of the bottom layer is formed, and a copper electrode pattern is formed by electrolytic plating. Then, the substrate comprising the exposed (A) metal electrode and (B) resin layer on the same side is obtained by removing the resist and removing the seed layer. Later, the smoothing process and the activation process can be used for bonding. In addition, since (A) metal electrode and (B) resin layer are exposed, they can also be directly bonded.

[0178] Example

[0179] Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

[0180] First, the method for producing the laminate, and the method for measuring the physical properties of the resin layer and the resin composition are described. Figure 3 and Figure 4 middle.

[0181] <Substrate Preparation>

[0182] (1) Fabrication of Cu pads and substrates with resin layers

[0183] (1-1) Formation of Metal Electrodes

[0184] A Ti / Cu seed layer was formed on an 8-inch silicon wafer by sputtering, and a commercially available dry film resist for electroplating was laminated and patterned to form through-holes (5×5 rows) with a diameter of 5 μm and a pitch of 10 μm. Then, Cu was formed with a height of 3 μm by electrolytic plating. The resist was then removed by a stripping solution, and the seed layer was further removed by an etchant, thereby forming a Cu pad with a diameter of 5 μm and a height of 3 μm on the 8-inch silicon wafer (see Figure 3 b. Figure 4 b).

[0185] (1-2) Formation of Resin Layer

[0186] The resin composition obtained in the adjustment example described below was spin-coated (1000 rpm, 30 seconds) on the wafer with the Cu pad, pre-baked (120°C for 3 minutes), and cured (230°C for 1 hour, O2 concentration: 20 volume ppm) to obtain a resin layer with a thickness of 4 μm. In the case of using a polyimide precursor, the curing was carried out at 300°C. (See Figure 3 c. Figure 4 c)

[0187] (2) Planarization of the substrate

[0188] The Cu pads and the substrate with the resin layer prepared in (1-2) were subjected to chemical mechanical polishing (CMP) using silica slurry and urethane polishing pads. (See Figure 3 d、 Figure 4 d)

[0189] Through the above steps, the first substrate and the second substrate including the exposed (A) metal electrode and the exposed (B) resin layer on the same surface of the substrate body are obtained.

[0190] (3) Monolithic substrate

[0191] The first substrate was singulated into pieces (1 mm square) using a DAD3240 dicing saw (manufactured by DISCO Corporation). (See Figure 4 e)

[0192] (4) Activation of substrate

[0193] Plasma treatment of the first and second substrates was performed using an atmospheric plasma system (manufactured by Ontos Equipment Systems) with a N₂ concentration of 98 vol% and a He concentration of 2 vol%. The total gas flow rate was set to 15 slpm, the power was set to 80 W, the spacing between the plasma device and the substrate surface was set to 1 mm, and the plasma device speed was set to 1 mm / second.

[0194] (5) Preparation of laminated body

[0195] (5-1) Preparation of W2W Laminated Body

[0196] The exposed surfaces of the metal electrode (A) and the resin layer (B) of the first substrate and the second substrate (wherein the first substrate has not been singulated) subjected to the plasma treatment in (4) are placed facing each other, and W2W bonding is performed at room temperature, a pressure of 8 MPa, for 3 minutes, and a vacuum degree of 50 Pa using a vacuum pressing device VACUUMSTAR (manufactured by Mikado-Technos Co., Ltd.). Then, annealing treatment is performed at 250°C for 1 hour in a nitrogen environment. (See Figure 3 e)

[0197] (5-2) Preparation of C2W Laminated Body

[0198] Prepare the chip (first substrate) singulated in (3) and activated in (4) and the wafer (second substrate) flattened in (2) and activated in (4), and use a flip chip bonder FC-3000S (manufactured by Toray Engineering Co., Ltd.) to bond the chip to the wafer at room temperature, 10N, and 3 seconds. Then, perform annealing at 250°C for 1 hour. (See Figure 4 f)

[0199] (6) Measurement of adhesion of laminated body

[0200] (6-1) Measurement of Adhesion Strength of W2W Laminate

[0201] Use a DAD3240 dicing saw (manufactured by DISCO Co., Ltd.) to cut only the first substrate portion of the stack produced in (5-1) in such a way that five 1 mm square monolithic chips can be obtained (the second substrate retains the shape of the original substrate). Insert a razor blade from the end of the stack and peel the first substrate from the second substrate in such a way that only the monolithic chips remain. For each chip remaining on the second substrate, a die shear measuring device (manufactured by DAGE, Series 4000) is used to apply a lateral force to the chip and measure the force when the chip is peeled off. The adhesive force per unit area obtained by converting the measured value divided by the area of ​​the chip is converted, and the five average values ​​are set as the adhesive force of the W2W stack. Furthermore, for the same samples, a pressure cooker test (PCT) was performed for 100 hours using a pressure cooker test apparatus (HAST CHAMBER EHS-211MD manufactured by Tabai Espec Co., Ltd.) under the conditions of 121°C, 2 atmospheres, and RH 100%, and then a grain shear test was performed.

[0202] (6-2) Adhesion strength measurement of C2W laminate

[0203] For each of the five chips (=first substrate) located in the C2W stack produced in (4), a force was applied to the chip from the lateral direction using a die shear measuring device (Series 4000, manufactured by DAGE), and the force applied when the chip was peeled off was measured. The adhesive force per unit area was converted by dividing the measured value by the area of ​​the chip, and the average value of the five was set as the adhesive force of the C2W stack. Furthermore, for the same sample, a pressure cooker test (PCT) was performed for 100 hours using a pressure cooker test device (HAST CHAMBER EHS-211MD manufactured by Tabai Espec Co., Ltd.) under the conditions of 121°C, 2 atmospheres, and RH 100%, and then a die shear test was performed.

[0204] (7) Reliability test of laminate

[0205] (7-1) High Temperature Storage (HTS) test

[0206] The laminated body produced in (5-1) or (5-2) was treated in a hot air oven at 175° C. for 200 hours.

[0207] The treated laminate was sectioned using an ion milling device (IM4000, manufactured by Hitachi High-Technologies Corporation) and observed using a scanning electron microscope (SEM, S-3000N, manufactured by Hitachi High-Technologies Corporation) to confirm the occurrence of delamination. The degree of metal wiring delamination was evaluated, with 0% delamination being rated as 4, more than 0% to less than 25% delamination being rated as 3, 25% to less than 50% delamination being rated as 2, and 50% or more delamination being rated as 1. Delaminations of 2 or higher were considered acceptable.

[0208] (7-2) Thermal Cycle (TC) Test

[0209] The laminate prepared in (5-1) or (5-2) was treated using a thermal cycle tester (hereinafter referred to as TC device) (manufactured by Tabai Espec Co., Ltd.) for 500 cycles of 15 minutes at -45°C and 15 minutes at 125°C.

[0210] The treated laminate was cut into sections using an ion milling device and observed using a scanning electron microscope to confirm the presence of cracks. The degree of cracking in the resin layer was evaluated, with 0 cracks being rated as 4, 1 or more to 3 or less cracks as 3, 4 or more to 10 or less cracks as 2, 11 or more cracks as 1, and 2 or more cracks as acceptable.

[0211] (8) Determination of elastic modulus

[0212] The resin composition was applied to a 6-inch silicon wafer by spin coating using a Mark-7 coating and developing device so that the film thickness would be 5 μm after pre-baking at 120°C for 3 minutes. After pre-baking, if the resin composition contained a photosensitive component (photoacid generator), the entire surface was exposed to 300 mJ / cm2 of polylactic acid (PLA). 2 In the case of a resin composition that does not contain a photosensitive component (photoacid generator), a heat treatment was performed directly using an inert oven CLH-21CD-S (manufactured by Koyo Thermoelectric Systems Co., Ltd.) at a temperature of 3.5°C / min to 220°C at an oxygen concentration below 20 ppm for 1 hour. The heat-cured wafer was cut into 5 cm squares and the elastic modulus was measured using a nanoindenter (manufactured by Hysitron, in-situ nanomechanical testing system (Triboindenter) TI950). The obtained value was set as the elastic modulus of the resin layer.

[0213] (9) Determination of the coefficient of thermal expansion (CTE)

[0214] The resin composition was applied to a 6-inch silicon wafer by spin coating using a Mark-7 coating and developing device so that the film thickness would be 10 μm after pre-baking at 120° C. for 3 minutes. After pre-baking, the entire surface of the wafer was exposed to 300 mJ / cm2 of PLA if the resin composition contained a photosensitive component (photoacid generator). 2In the case of a resin composition that does not contain a photosensitive component (photoacid generator), an inert oven CLH-21CD-S (manufactured by Koyo Thermoelectric Systems) was directly used, and the temperature was raised to 220°C at 3.5°C / min at an oxygen concentration below 20ppm for 1 hour. The wafer was taken out when the temperature became below 50°C and immersed in 45% hydrofluoric acid for 1 minute to peel off the cured product from the wafer. The film was cut into strips 1.5cm wide and 3cm long, and the measurement was carried out using a thermomechanical analyzer (EXSTAR6000TMA / SS6000 manufactured by SII Nanotechnology). In the first stage, the temperature was raised to 150°C at a heating rate of 5°C / min and the adsorbed water of the sample was removed. In the second stage, the sample was air-cooled to room temperature at a cooling rate of 5°C / min. In the third stage, the formal measurement was carried out at a heating rate of 5°C / min. The thermal expansion coefficient of the target polyimide film was averaged in the officially measured temperature range of 50° C. to 150° C. The thermal expansion coefficient values ​​were used to perform the following evaluations of A, B, and C, with A being considered good, B being considered acceptable, and C being considered unacceptable.

[0215] A: The thermal expansion coefficient is 20ppm / K or more and less than 25ppm / K

[0216] B: Linear expansion coefficient is 10 ppm / K or more and less than 20 ppm / K, or 25 ppm / K or more and less than 40 ppm / K

[0217] C: The linear expansion coefficient is less than 10 ppm / K and greater than 40 ppm / K.

[0218] Next, the resin composition used for forming the resin layer (B) will be described. All the obtained resin compositions were filtered using a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) before evaluation.

[0219] Hereinafter, the abbreviations of the compounds used in Synthesis Examples and Examples are described.

[0220] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

[0221] BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0222] PDA: p-phenylenediamine

[0223] 4,4'-ODA: 4,4'-diaminodiphenyl ether

[0224] ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

[0225] PMDA: pyromellitic dianhydride

[0226] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[0227] DFA: dimethylformamide dimethyl acetal

[0228] HA: 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane

[0229] NA: 5-Norbornene-2,3-dicarboxylic anhydride

[0230] MAP: meta-aminophenol

[0231] RT-1000: a diamine having a structure of formula (1) (trade name, manufactured by HUNTSMAN Co., Ltd.)

[0232] KF-8010: a diamine having a structure of formula (2) (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0233] Dicarboxylic acid derivative A: 1,1'-(4,4'-oxybenzoyl)diimidazole

[0234] Dicarboxylic acid derivative B: 1,12-bis(1-imidazole)-1,12-dodecanedione

[0235] Methyl silicate 51: silicate oligomer (trade name, manufactured by COLCOAT Co., Ltd.)

[0236] TBAA: Tetrabutylammonium acetate

[0237] CYCLOTENE 4022-35: A TMB solution containing siloxane-modified benzocyclobutene (trade name, manufactured by Dow Chemical Co., Ltd.) includes a group having a siloxane bond, and the group having a siloxane bond is a group represented by formula (2).

[0238] YDCN-700-10: a cresol novolac-type multifunctional epoxy resin (trade name, manufactured by Nippon Steel Chemicals & Materials Co., Ltd.) having an alkylene oxide group, which is a group represented by formula (1).

[0239] NMP: N-methyl-2-pyrrolidone

[0240] GBL: gamma-butyrolactone

[0241] CHN: Cyclohexanone

[0242] PGMEA: Propylene glycol methyl ether acetate

[0243] TMB: 1,3,5-trimethylbenzene

[0244] MOM: 4-[1,1-bis[4-hydroxy-3,5-bis(methoxymethyl)phenyl]ethyl]-2,6-bis(methoxymethyl)phenol (crosslinking agent)

[0245] DCP: dicumyl peroxide

[0246] PAG-102: Photoacid generator (trade name, manufactured by BASF)

[0247] VG-3101: Monomeric triphenylmethane epoxy resin (trade name, manufactured by Printec Co., Ltd.)

[0248] TP5-280M: 5-naphthoquinonediazidesulfonic acid ester compound of α,α,α,-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (photoacid generator) (trade name, manufactured by Toyo Gosei Co., Ltd.).

[0249] IRGANOX 245: Ethylene bis(oxyethylene) bis-(3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate) (antioxidant) (trade name, manufactured by BASF)

[0250] LN: Lithium niobate (used as the substrate body, manufactured by Mitsui Metals).

[0251] [Synthesis Example 1] Synthesis of polyester (P-1)

[0252] 148 g of 1,1-bis(4-(2,3-epoxypropyloxy)phenyl)-3-phenylindane, 47 g of acrylic acid, 1 g of TBAA, 2.0 g of tert-butylcatechol and 244 g of PGMEA were added and stirred at 120°C for 5 hours. After cooling to room temperature, 30 g of biphenyltetracarboxylic dianhydride and 1 g of TBAA were added and stirred at 110°C for 3 hours. After cooling to room temperature, 15 g of tetrahydrophthalic anhydride was added and stirred at 120°C for 5 hours. After the reaction was completed, 500 g of PGMEA was added, and the reaction solution was subjected to liquid separation and extraction with a 1 equivalent aqueous formic acid solution to remove the addition catalyst. After drying with magnesium sulfate, it was concentrated using a rotary evaporator to a solid content concentration of 40 wt%, thereby obtaining a PGMEA solution of polyester (P-1).

[0253] [Synthesis Example 2] Synthesis of polysiloxane (P-2)

[0254] Under a dry nitrogen stream, a 500 ml three-necked flask was charged with 54.48 g (0.40 mol) of methyltrimethoxysilane, 109.07 g (0.55 mol) of phenyltrimethoxysilane, 5.88 g (equivalent to 0.05 mol of Si atoms) of methyl silicate 51, and 155.04 g of PGMEA. While stirring at room temperature, an aqueous solution of phosphoric acid, prepared by dissolving 0.515 g of phosphoric acid in 54.45 g of water (0.30 parts by mass relative to the monomers charged), was added over 10 minutes. The flask was then immersed in a 40°C oil bath and stirred for 60 minutes. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and the mixture was then heated and stirred for 2 hours (internal temperature at 100°C) to obtain polysiloxane (P-2). The group having a siloxane bond is included, and the group having a siloxane bond is a group represented by formula (2): After stirring, PGMEA was added so that the solid content concentration became 40 wt%.

[0255] [Synthesis Example 3] Synthesis of acrylic resin (P-3)

[0256] A 500ml flask was charged with 3g of 2,2'-azobis(isobutyronitrile) and 50g of PGMEA. Subsequently, 23.0g of methacrylic acid, 31.5g of benzyl methacrylate, and 32.8g of tricyclo[5.2.1.02,6]decan-8-yl methacrylate were added and stirred at room temperature for a while. After thoroughly purging the flask with nitrogen by bubbling, the mixture was heated and stirred at 70°C for 5 hours. Next, 12.7g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90°C for 4 hours to obtain acrylic resin (P-3). After stirring, PGMEA was added to achieve a solids concentration of 40wt%.

[0257] [Synthesis Example 4] Synthesis of polyimide (P-4)

[0258] Under a dry nitrogen flow, 32.96 g (0.090 mol) of BAHF, 2.18 g (0.020 mol) of MAP, and 160 g of NMP were weighed and dissolved in a three-necked flask. A solution of 31.02 g (0.10 mol; 100 mol% relative to the structural units derived from all carboxylic acids and their derivatives) of ODPA dissolved in 100 g of NMP was added thereto, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. Then, 15 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotroping water and xylene. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered to obtain a polyimide (P-4). After washing the obtained solid three times with water, it was dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide (P-4).

[0259] [Synthesis Example 5] Synthesis of polyimide (P-5)

[0260] Under a dry nitrogen flow, 29.30 g (0.080 mol) of BAHF, 10.00 g of RT-1000, 2.18 g (0.020 mol) of MAP, and 190 g of NMP were weighed and dissolved in a three-necked flask. A solution of 31.02 g (0.10 mol; 100 mol% relative to the structural units derived from all carboxylic acids and their derivatives) of ODPA dissolved in 100 g of NMP was added thereto, and the mixture was stirred at 20°C for 1 hour and then at 50°C for 4 hours. Then, 15 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotroping water and xylene. After the reaction was completed, the reaction solution was poured into 3 L of water, and the precipitated solid precipitate was filtered to obtain a polyimide (P-5). After washing the obtained solid three times with water, it was dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide (P-5).

[0261] [Synthesis Example 6] Synthesis of polyimide (P-6)

[0262] Under a dry nitrogen stream, 29.30 g (0.080 mol) of BAHF, 8.6 g of KF-8010, 2.18 g (0.020 mol) of MAP, and 100 g of CHN were weighed and dissolved in a three-necked flask. 31.02 g (0.10 mol; 100 mol% relative to the total structural units derived from carboxylic acids and their derivatives) of ODPA and 50 g of CHN were added to the mixture, and the mixture was stirred at 20°C for 1 hour and then at 50°C for 4 hours. Subsequently, the mixture was stirred at 150°C for 5 hours while azeotropically diluting water with cyclohexanone to obtain a polyimide (P-6).

[0263] [Synthesis Example 7] Synthesis of polyimide precursor (P-7)

[0264] Under a dry nitrogen flow, HA 51.4g (0.085 mol), SiDA 1.24g (0.005 mol), and MAP 2.18g (0.020 mol) as an end sealant were dissolved in NMP 200g. ODPA 31.0g (0.10 mol) was added thereto and stirred at 40°C for 2 hours. Then, a solution obtained by diluting DFA 7.14g (0.06 mol) with NMP 5g was added dropwise over 10 minutes. After the addition, stirring was continued at 40°C for 2 hours. After the stirring was completed, the solution was poured into 2L of water and the precipitate of the polymer solid was collected by filtration. The solution was then washed three times with 2L of water and the collected polymer solid was dried for 72 hours in a vacuum dryer at 50°C to obtain a polyimide precursor (P-7).

[0265] [Synthesis Example 8] Synthesis of polybenzoxazole precursor (P-8)

[0266] Under a dry nitrogen stream, 36.63g (0.100mol) of BAHF was dissolved in 200g of NMP. 28.67g (0.080mol) of dicarboxylic acid derivative A and 20g of NMP were added thereto, and the mixture was reacted at 85°C for 3 hours. Subsequently, 6.57g (0.040mol) of NA and 10g of NMP were added, and the mixture was reacted at 85°C for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature, and 48.02g (0.80mol) of acetic acid and 90g of NMP were added, and the mixture was stirred at room temperature for 1 hour. After the stirring was completed, the solution was poured into 3L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain a powder of a polybenzoxazole precursor (P-8).

[0267] [Synthesis Example 9] Synthesis of polybenzoxazole precursor / polyamide copolymer (P-9)

[0268] Under a dry nitrogen stream, 32.96g (0.090mol) of BAHF and 10.00g (0.010mol) of RT-1000 were dissolved in 200g of NMP. 32.25g (0.090mol) of dicarboxylic acid derivative A and 20g of NMP were added thereto, and the mixture was reacted at 85°C for 3 hours. Subsequently, 3.28g (0.020mol) of NA and 10g of NMP were added, and the mixture was reacted at 85°C for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature, 54.02g (0.90mol) of acetic acid and 90g of NMP were added, and the mixture was stirred at room temperature for 1 hour. After the stirring was completed, the solution was added to 3L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilated dryer at 50°C for three days to obtain a powder of a polybenzoxazole precursor / polyamide copolymer (P-9).

[0269] [Synthesis Example 10] Synthesis of polybenzoxazole precursor / polyimide precursor copolymer (P-10)

[0270] Under a dry nitrogen stream, 32.96 g (0.090 mol) of BAHF and 10.00 g (0.010 mol) of RT-1000 were dissolved in 200 g of NMP. 30.46 g (0.085 mol) of dicarboxylic acid derivative A and 20 g of NMP were added, and the mixture was reacted at 85°C for 3 hours. Subsequently, 1.24 g (0.005 mol) of SiDA, 1.55 g (0.005 mol) of ODPA, 4.92 g (0.030 mol) of NA, and 20 g of NMP were added, and the mixture was reacted at 85°C for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature, and 51.02 g (0.85 mol) of acetic acid and 90 g of NMP were added, followed by stirring at room temperature for 1 hour. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilation dryer at 50° C. for three days to obtain a powder of a polybenzoxazole precursor (P-10).

[0271] [Synthesis Example 11] Synthesis of polybenzoxazole precursor / polyimide precursor copolymer (P-11)

[0272] Under a dry nitrogen stream, 32.96 g (0.090 mol) of BAHF and 10.00 g (0.010 mol) of RT-1000 were dissolved in 200 g of NMP. 16.13 g (0.045 mol) of dicarboxylic acid derivative A, 13.22 g (0.040 mol) of dicarboxylic acid derivative B, and 20 g of NMP were added, and the mixture was reacted at 85°C for 3 hours. Subsequently, 1.24 g (0.005 mol) of SiDA, 1.55 g (0.005 mol) of ODPA, 4.92 g (0.030 mol) of NA, and 20 g of NMP were added, and the mixture was reacted at 85°C for 30 minutes. After the reaction was completed, the mixture was cooled to room temperature, and 51.02 g (0.85 mol) of acetic acid and 90 g of NMP were added, followed by stirring at room temperature for 1 hour. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a ventilation dryer at 50° C. for three days to obtain a powder of a polybenzoxazole precursor (P-10).

[0273] [Synthesis Example 12] Polyimide Precursor (P-12)

[0274] Under a dry nitrogen stream, 19.2 g (0.096 mol) of 4,4'-ODA and 0.99 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. To this solution, 16.8 g (0.077 mol) of PMDA and 5.9 g (0.020 mol) of BPDA were added, and the mixture was stirred at 60°C for 5 hours to obtain a polyimide precursor solution (P-12). After stirring, NMP was added to adjust the solids concentration to 16 wt%.

[0275] [Synthesis Example 13] Polyimide Precursor (P-13)

[0276] Under a dry nitrogen stream, 10.4 g (0.096 mol) of PDA and 0.99 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. 28.5 g (0.097 mol) of BPDA was added to the solution, and the mixture was stirred at 60°C for 5 hours to obtain a polyimide precursor solution (P-13). After stirring, NMP was added to adjust the solid content to 16 wt%.

[0277] [Synthesis Example 14] Polyimide Precursor (P-14)

[0278] Under a dry nitrogen stream, 7.8 g (0.072 mol) of PDA, 4.8 g (0.024 mol) of 4,4'-ODA, and 0.99 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. 28.5 g (0.097 mol) of BPDA was added to the solution, and the mixture was stirred at 60°C for 5 hours to obtain a polyimide precursor solution (P-14). After stirring, NMP was added to adjust the solids concentration to 16 wt%.

[0279] [Synthesis Example 15] Polyimide Precursor (P-15)

[0280] Under a dry nitrogen stream, 20.4 g (0.096 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl and 0.99 g (0.004 mol) of SiDA were dissolved in 200 g of NMP. 28.5 g (0.097 mol) of BPDA was added to the solution, and the mixture was stirred at 60°C for 5 hours to obtain a polyimide precursor solution (P-15). After stirring, NMP was added to adjust the solids concentration to 16 wt%.

[0281] [Synthesis Example 16] Polyimide Precursor (P-16)

[0282] Under a dry nitrogen stream, 10.8 g (0.1 mol) of PDA was dissolved in 200 g of NMP. To this solution, 10.7 g (0.049 mol) of PMDA and 26.5 g (0.049 mol) of BPDA were added, and the mixture was stirred at 60°C for 5 hours to obtain a polyimide precursor solution (P-16). After stirring, NMP was added to adjust the solid content concentration to 16 wt%.

[0283] [Comparative Synthesis Example 1] Synthesis of Polystyrene (HP-1)

[0284] A 500ml flask equipped with a reflux tube was charged with 200ml of tetrahydrofuran, 2g of 2,2'-azobis(isobutyronitrile), and 40g of styrene. The mixture was stirred at room temperature for a while, and after thoroughly purging the flask with nitrogen by bubbling, the mixture was heated and stirred at 80°C for 5 hours while refluxing the solvent. After stirring, the solution was poured into 2L of methanol to obtain a white precipitate. The precipitate was collected by filtration, washed twice with methanol, and then dried overnight in a vacuum oven at room temperature to obtain a polystyrene (HP-1) powder.

[0285] [Adjustment Example 1 to Adjustment Example 27] [Comparative Preparation Example 1]

[0286] The resins obtained in the synthesis examples or conventional resins were mixed with solvents and additives at weight ratios and solid content concentrations shown in Table 1 to obtain respective resin compositions.

[0287] [Table 1]

[0288]

[0289]

[0290] [Examples 1 to 48, 51 to 55, 58 to 62] [Comparative Examples 1 and 3]

[0291] Using the resin compositions prepared in the Adjustment Examples and Comparative Preparation Examples and commercially available resin compositions, laminates were prepared using the laminate preparation methods (1) to (5) described above. These were then evaluated using the physical property measurement methods (6) to (8) for the resin layer and the resin composition. The results for each Example and Comparative Example are shown in Tables 2 and 3.

[0292] [Examples 49-50, 56-57] [Comparative Examples 2, 4]

[0293] Except for using tetraethoxysilane instead of the resin layer (1-2) to form the SiO2 film by chemical vapor deposition, a laminate was produced in the same manner as in the laminate production methods (1) to (5) described above, and the physical properties of the resin layer and the resin composition were evaluated by the methods (5) to (8). The examples and comparative examples are shown in Tables 2 and 3.

[0294] [Table 2]

[0295]

[0296]

[0297]

[0298]

[0299] [Preparation Examples 23 to 25, Comparative Preparation Example 1]

[0300] The evaluation was performed by the physical property measurement method (9) for the resin composition. Table 4 shows the respective preparation examples and comparative preparation examples.

[0301] [Table 4]

[0302] [Table 4]

[0303]

[0304] Explanation of Figure Numbers

[0305] 1: Substrate body (silicon wafer, etc.)

[0306] 2: (A-1) Metal electrode (Cu, etc.)

[0307] 3: (B-1) Resin layer

[0308] 4: (B-2) resin layer or (C) inorganic insulating layer

[0309] 5: (A-2) Metal electrode (Cu, etc.)

[0310] 6: Substrate body (silicon wafer, etc.)

[0311] 7: First substrate

[0312] 8: Second substrate.

Claims

1. A laminate comprising a first substrate including an exposed (A-1) metal electrode and an exposed (B-1) resin layer on the same surface of a substrate body, a second substrate including, on the same surface as the substrate body, an exposed (A-2) metal electrode and an exposed (B-2) resin layer, or an exposed (A-2) metal electrode and an exposed (C) inorganic insulating layer, At least a portion of the (A-1) metal electrode and the (A-2) metal electrode and at least a portion of the (B-1) resin layer and the (B-2) resin layer, or At least a portion of the (A-1) metal electrode and the (A-2) metal electrode, and at least a portion of the (B-1) resin layer and the (C) inorganic insulating layer are directly bonded to each other, wherein the laminated body At least one of the (B-1) resin layer and the (B-2) resin layer includes one or more resins selected from the group consisting of a carbonyl group, a hydroxyl group, an alkylene oxide group, a group having a siloxane bond, and a nitrogen-containing heterocycle.

2. The laminate according to claim 1, wherein The second substrate includes an exposed (A-2) metal electrode and an exposed (B-2) resin layer on the same surface of a substrate body.

3. The laminate according to claim 1 or 2, wherein The alkylene oxide group is a group represented by formula (1). [Chemistry 1] (In formula (1), R 1 ~R 4 R each independently represents an alkylene group having 1 to 6 carbon atoms. 5 ~R 12 (g, h, i each independently represent an integer from 0 to 35, g+h+i>0; * represents a bonding portion).

4. The laminate according to claim 1 or 2, wherein The group having a siloxane bond is a group represented by formula (2). [Chemistry 2] (In formula (2), j is a natural number from 1 to 50. 13 and R 14 R each independently represents an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, or a phenylene group having 6 to 20 carbon atoms. 15 ~R 18 (each independently represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group; * represents a bonding portion).

5. The laminate according to claim 3 or 4, wherein At least one of the resin layer (B-1) and the resin layer (B-2) contains a group represented by the formula (1) or the formula (2) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide (wherein, One or more resins selected from the group consisting of polyimide precursors and polybenzoxazole precursors) and copolymers thereof.

6. The laminate according to claim 1 or 2, wherein: The resin contained in at least one of the resin layer (B-1) and the resin layer (B-2) contains two or more structures represented by formula (9). [Chemistry 3] (* indicates a bonding part. 42 ~R 53 Each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group, or a hydrocarbon group having 1 to 6 carbon atoms (a part or all of which may be substituted with one or more of a fluorine atom, a hydroxyl group, and a carboxyl group).

7. The laminate according to claim 1 or 2, wherein At least one of the (B-1) resin layer and the (B-2) resin layer has a thermal expansion coefficient of 10 ppm / K or more and 40 ppm / K or less in a temperature range of 50° C. to 150° C.

8. The laminate according to claim 1 or 2, wherein At least one of the (B-1) resin layer and the (B-2) resin layer further contains an antioxidant.

9. The laminate according to claim 1 or 2, wherein At least one of the (B-1) resin layer and the (B-2) resin layer forms a cross-linked structure.

10. The laminate according to claim 1 or 2, wherein The elastic modulus of at least one of the (B-1) resin layer and the (B-2) resin layer is 1.5 GPa or more and 7 GPa or less.

11. The laminate according to claim 1 or 2, wherein A plurality of singulated first substrates are directly bonded to the same surface of the second substrate.

12. The laminate according to claim 1 or 2, wherein The bonding strength between the first substrate and the second substrate in a die shear test is greater than 10 MPa.

13. The laminate according to claim 1 or 2, wherein At least one of the substrate bodies of the first substrate and the second substrate includes one or more selected from the group consisting of silicon, lithium niobate, lithium tantalum oxide, gallium nitride, silicon carbide, gallium arsenide, and indium phosphide.

14. A semiconductor element comprising the laminate according to claim 1 or 2. 15 . A micro-electromechanical system component comprising the laminated body according to claim 1 or 2 .

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