TW202421441A - Method of manufacturing substrate layered body and substrate layered body - Google Patents

Abstract

This substrate layered body manufacturing method includes: a step A for preparing a first layered body in which a first resin layer, a first substrate, and a first organic material layer are layered in that order, the first resin layer is disposed on one surface, and the first inorganic material layer is disposed on the other surface, and a second layered body in which a second resin layer, a second substrate, and a second inorganic material layer are layered in that order, the second resin layer is disposed on one surface, and the second inorganic material layer is disposed on the other surface; a step B for layering the first layered body and the second layered body by bringing into contact the first resin layer of the first layered body and the second inorganic material layer of the second layered body; and a step C for heating the first layered body and the second layered body at 100 DEG C or higher after said step B.

Description

Method for manufacturing substrate laminate and substrate laminate

The present disclosure relates to a method for manufacturing a substrate laminate and the substrate laminate.

As electronic devices are being miniaturized, lightweighted, and highly functionalized, there is a demand for high integration of semiconductor chips, etc. However, it is difficult to fully meet the above requirements with the miniaturization of circuits. Therefore, in recent years, the following method has been proposed: high integration is achieved by vertically stacking multiple semiconductor substrates (wafers), semiconductor chips, etc. to form a multi-layer three-dimensional structure. As a method for stacking semiconductor substrates (wafers), semiconductor chips, etc. (hereinafter sometimes referred to as "semiconductor substrates, etc."), a method of directly bonding substrates to each other, a method of using an adhesive, etc. have been proposed (for example, refer to Patent Documents 1 to 3).

Patent document 1: Japanese Patent Publication No. 4-132258 Patent document 2: Japanese Patent Publication No. 2010-226060 Patent document 3: Japanese Patent Publication No. 2016-47895

[Problems to be solved by the invention] In direct bonding, there is a problem that voids are easily generated due to fine unevenness and particles caused by wiring on the surface of the substrate. Regarding methods such as stacking semiconductor substrates, there are also methods that are conceived to bond inorganic materials such as silicon oxide provided on the substrate. However, in the method of bonding inorganic materials of the substrate, there is a problem that voids are easily generated, just like direct bonding.

On the other hand, when bonding is performed using an adhesive, the adhesive is applied to the substrate surface, and then, after drying and setting to a semi-hardened state, the substrates are bonded together. At this time, in terms of suppressing the generation of voids, it is considered to apply the adhesive to the bonding surface of the substrate to form a bonding layer, and bond the bonding layers together. Furthermore, in terms of improving the bonding strength when bonding the bonding surfaces of the substrates together, it is preferred to perform surface activation treatment such as plasma treatment and fast atom bombardment (FAB) treatment on the bonding surface of the substrate.

However, when the bonding layer is subjected to a surface activation treatment, the resin contained in the bonding layer is affected by the surface activation treatment, and there is a concern that the reliability may be affected by the degradation of the bonding layer. Alternatively, in order to remove particles from the bonding surface of the substrate, the bonding surface is sometimes cleaned, but if a bonding layer is provided on the bonding surface, there are problems such as restrictions on the cleaning method. In view of the above aspects, it is ideal to have a method for manufacturing a substrate laminate in which the restrictions on the surface activation treatment and cleaning treatment methods of the bonding surface of the substrate are suppressed even when a resin layer is provided on the bonding surface of the substrate.

One aspect of the present invention is made in view of the above-mentioned problem, and its purpose is to provide a method for manufacturing a substrate laminated body in which a resin layer is provided on the bonding surface of the substrate and the limitation of the method of surface activation treatment and cleaning treatment of the bonding surface of the substrate is suppressed, and a laminated body that can be used in the manufacturing method. [Means for solving the problem]

The specific method for solving the above-mentioned problem is as follows. ＜1＞ A method for manufacturing a substrate laminate, comprising: step A, preparing a first laminate and a second laminate, wherein the first laminate is laminated in the order of a first resin layer, a first substrate, and a first inorganic material layer, wherein the first resin layer is arranged on one surface, and the first inorganic material layer is arranged on the other surface, and the second laminate is laminated in the order of a second resin layer, a second substrate, and a second inorganic material layer, wherein the second resin layer is arranged on one surface, and the second inorganic material layer is arranged on the other surface; Step B, making the first resin layer of the first laminate contact the second inorganic material layer of the second laminate to laminate the first laminate and the second laminate; and Step C, heating the first laminate and the second laminate at a temperature above 100°C after step B. <2> The method for manufacturing a substrate laminate as described in <1>, wherein the first laminate includes an electrode on a portion of the surface of the first resin layer and a portion of the surface of the first inorganic material layer, and the second laminate includes an electrode on a portion of the surface of the second resin layer and a portion of the surface of the second inorganic material layer. <3> The method for manufacturing a substrate laminate as described in <2> includes the following step, namely, the step of performing a surface activation treatment on the second inorganic material layer before the step B. <4> The method for manufacturing a substrate laminate as described in <1> includes the following step, namely, after the step C, the step of providing a through hole in the first laminate and the second laminate from the surface of the first inorganic material layer side toward the surface of the second resin layer side, and forming an electrode penetrating the first laminate and the second laminate in the through hole. <5> The method for manufacturing a substrate laminate as described in any one of <1> to <4>, comprising the step of cleaning the second inorganic material layer before the step B. <6> The method for manufacturing a substrate laminate as described in any one of <1> to <5>, comprising the step of providing a surface protective layer on the second inorganic material layer before the step B. <7> The method for manufacturing a substrate laminate as described in any one of <1> to <6>, wherein, before the first resin layer is brought into contact with the second inorganic material layer in the step B, the composite elastic modulus of the first resin layer at 23°C is greater than 0.1 GPa and less than 20 GPa. <8> A method for manufacturing a substrate laminate as described in any one of <1> to <7>, wherein before the first resin layer and the second inorganic material layer are brought into contact in the step B, the curing rate of the first resin layer is greater than 70% and less than 100%. <9> A method for manufacturing a substrate laminate as described in any one of <1> to <8>, wherein before the first resin layer and the second inorganic material layer are brought into contact in the step B, the surface roughness (Ra) of the first resin layer is greater than 0.01 nm and less than 1.2 nm. <10> A method for manufacturing a substrate laminate as described in any one of <1> to <9>, wherein the surface of the first resin layer has at least one functional group selected from the group consisting of silanol groups, amine groups, epoxy groups, hydroxyl groups, and functional groups containing unsaturated bonds. <11> A method for manufacturing a substrate laminate as described in any one of <1> to <10>, wherein the first resin layer contains: Siloxane bonds; and At least one selected from the group consisting of ester bonds, ether bonds, amide bonds, and imide bonds. <12> A method for manufacturing a substrate laminate as described in any one of <1> to <11>, wherein the second inorganic material layer contains at least one element selected from the group consisting of Si, Ga, Ge and As. <13> A substrate laminate, comprising: A first laminate, which sequentially comprises a first resin layer, a first substrate, and a first inorganic material layer, wherein the first resin layer is disposed on one surface and the first inorganic material layer is disposed on the other surface; and A second laminate, which sequentially comprises a second resin layer, a second substrate, and a second inorganic material layer, wherein the second resin layer is disposed on one surface and the second inorganic material layer is disposed on the other surface, The first laminate and the second laminate are laminated via the first resin layer of the first laminate and the second inorganic material layer of the second laminate. <14> The substrate laminate as described in <13>, wherein the first laminate includes an electrode on a portion of the surface of the first resin layer and a portion of the surface of the first inorganic material layer, and the second laminate includes an electrode on a portion of the surface of the second resin layer and a portion of the surface of the second inorganic material layer. [Effect of the invention]

One aspect of the present invention can provide a method for manufacturing a substrate laminate in which a resin layer is provided on a bonding surface of a substrate and restrictions on methods of surface activation treatment and cleaning treatment of the bonding surface of the substrate are suppressed, and a laminate that can be used in the manufacturing method.

In the present disclosure, the numerical range represented by "～" refers to a range that includes the numerical values recorded before and after "～" as the lower limit and upper limit. In the numerical range recorded in stages in the present disclosure, the upper limit or lower limit recorded in one numerical range can be replaced with the upper limit or lower limit of another numerical range recorded in stages. In addition, in the numerical range recorded in the present disclosure, the upper limit or lower limit of the numerical range can also be replaced with the value shown in the embodiment. In the present disclosure, "substrate laminate" refers to a laminate having a structure in which two substrates, namely a first substrate and a second substrate, are bonded via a first resin layer and a second inorganic material layer. Furthermore, the substrate laminate may have more than three substrates, or may have a structure in which two of the three or more substrates are joined via a first resin layer and a second inorganic material layer. In the present disclosure, the so-called "substrate" refers to "at least one of the first substrate and the second substrate", the so-called "resin layer" refers to "at least one of the first resin layer and the second resin layer", and the so-called "inorganic material layer" refers to "at least one of the first inorganic material layer and the second inorganic material layer".

[Method for manufacturing substrate laminate] The method for manufacturing substrate laminate disclosed herein includes: step A, preparing a first laminate and a second laminate, wherein the first laminate is laminated in the order of a first resin layer, a first substrate, and a first inorganic material layer, wherein the first resin layer is disposed on one surface, and the first inorganic material layer is disposed on the other surface, and the second laminate is laminated in the order of a second resin layer, a second substrate, and a second inorganic material layer, wherein the first resin layer is disposed on one surface, and the first inorganic material layer is disposed on the other surface. The second resin layer is arranged on one of the surfaces, and the second inorganic material layer is arranged on the other surface; step B, making the first resin layer of the first laminate body contact the second inorganic material layer of the second laminate body to laminate the first laminate body and the second laminate body; and step C, after step B, heating the first laminate body and the second laminate body at a temperature above 100°C.

In the manufacturing method of the substrate laminate disclosed in the present invention, at least two laminates are prepared in the order of a resin layer, a substrate, and an inorganic material layer. For the two prepared laminates, in step B, the resin layer (first resin layer) of one laminate is brought into contact with the inorganic material layer (second inorganic material layer) of the other laminate and laminated. Thereafter, in step C, the two laminated bodies are heated at a temperature of 100° C. or higher, thereby obtaining a substrate laminate having a structure bonded via a resin layer (first resin layer) and an inorganic material layer (second inorganic material layer). In the present disclosure, the two substrates can be bonded via the resin layer and the inorganic material layer after the surface of the inorganic material layer is subjected to a surface activation treatment, a cleaning treatment, etc. In this way, the bonding strength of the bonding surface can be increased, or particles attached to the surface of the inorganic material layer can be removed without subjecting the surface of the resin layer to a surface activation treatment, a cleaning treatment, etc. Therefore, a method for manufacturing a substrate laminate is provided in which a resin layer is provided on a bonding surface of a substrate and restrictions on methods of surface activation treatment and cleaning treatment of the bonding surface of the substrate are suppressed.

[Step A] The manufacturing method of the substrate laminate disclosed in the present invention includes step A of preparing a first laminate and a second laminate. The first laminate includes a first resin layer, a first substrate, and a first inorganic material layer in sequence, the first resin layer is arranged on one surface, and the first inorganic material layer is arranged on the other surface. Similarly, the second laminate includes a second resin layer, a second substrate, and a second inorganic material layer in sequence, the second resin layer is arranged on one surface, and the second inorganic material layer is arranged on the other surface.

(First substrate and second substrate) The materials of the first substrate and the second substrate are not particularly limited and can be those of ordinary users. Furthermore, the materials of the first substrate and the second substrate can be the same or different. The first substrate and the second substrate preferably contain at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta and Nb. Materials for the first substrate and the second substrate include, for example, semiconductors: Si, InP, GaN, GaAs, InGaAs, InGaAlAs, SiC; oxides, carbides, nitrides: borosilicate glass (e.g., Pyrex (registered trademark)), quartz glass ( _SiO2 ), sapphire, _ZrO2 , _Si3N4 , AlN _; piezoelectrics, dielectrics: _BaTiO3 , _LiNbO3 , _SrTiO3 , diamond; metals: Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, Nb, etc.

The materials of the first substrate and the second substrate may be resins other than those mentioned above: polydimethylsiloxane (PDMS), epoxy resin, phenol resin, polyimide, benzocyclobutene resin, polybenzoxazole, etc.

The first substrate and the second substrate may be a multi-layer structure. For example, there may be a structure in which an inorganic layer such as silicon oxide, silicon nitride, SiCN (silicon carbonitride) is formed on the surface of a silicon substrate; a structure in which an organic layer such as polyimide resin, polybenzoxazole resin, epoxy resin, methyl cyclopentenol ketone (cyclotene) (Dow Chemical (Dow, Chem)), amide cross-linked siloxane resin, epoxy-modified siloxane or porous silica, organic cross-linked siloxane, black diamond (Applied Materials) company) is formed on the surface of a silicon substrate; a structure in which a composite of inorganic and organic substances is formed on a silicon substrate.

Regarding each material, as the main use, it can be used for the following. Si is used for semiconductor memory, large scale integrated circuit (LSI) lamination, complementary metal oxide semiconductor (CMOS) image sensor, microelectro mechanical system (MEMS) sealing, optical device, light emitting diode (LED), etc.; _SiO2 is used for semiconductor memory, LSI lamination, MEMS sealing, micro flow path, CMOS image sensor, optical device, LED, etc.; PDMS is used for micro flow path; InGaAlAs, InGaAs, InP are used for optical devices; InGaAlAs, GaAs, GaN are used for LED, etc.

The thickness of the first substrate and the second substrate are independently preferably 0.5 μm to 1 mm, more preferably 1 μm to 900 μm, and even more preferably 2 μm to 900 μm.

The shapes of the first substrate and the second substrate are not particularly limited. For example, when the first substrate and the second substrate are silicon substrates, they may be silicon substrates having interlayer insulating layers (low-k films), and may also have fine grooves (recesses), fine through holes, etc. formed on the silicon substrates.

In the method for manufacturing the substrate laminate disclosed herein, in terms of bonding strength, at least one of the surface of the first substrate in contact with the first resin layer and the surface of the second substrate in contact with the second resin layer may be subjected to surface treatment. For example, at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group, an amine group, and a hydroxyl group may be formed by performing the surface treatment.

Examples of the surface treatment include plasma treatment, chemical treatment, ultraviolet (UV) ozone treatment, and the like.

The hydroxyl group can be disposed on the surfaces of the first substrate and the second substrate by subjecting the surfaces of the substrate to plasma treatment, chemical treatment, UV ozone treatment or other ozone treatment. The hydroxyl group preferably exists in a state of bonding with at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta and Nb contained in the first substrate or the second substrate. The surface of the first substrate in contact with the first resin layer and the surface of the second substrate in contact with the second resin layer preferably have a silanol group containing a hydroxyl group.

The epoxy groups can be provided on the surfaces of the first substrate and the second substrate respectively by performing surface treatment such as silane coupling using epoxysilane on the surfaces of the substrate.

The carboxyl groups can be provided on the surfaces of the first substrate and the second substrate respectively by subjecting the surfaces of the substrate to surface treatment such as silane coupling using carboxyl silane.

The amine groups can be disposed on the surfaces of the first substrate and the second substrate respectively by performing surface treatment such as silane coupling using aminosilane on the surfaces of the substrate.

The phenyl groups can be disposed on the surfaces of the first substrate and the second substrate respectively by performing surface treatment such as silane coupling using phenylsilane.

In order to improve the bonding strength, a primer such as a silane coupling agent may be formed on the surface of at least one of the first substrate and the second substrate to which the resin material is applied.

(First resin layer and second resin layer) The first resin layer is a layer disposed on one surface of the first substrate, and the second resin layer is a layer disposed on one surface of the second substrate. For example, the first resin layer and the second resin layer can be formed by applying a resin composition containing a resin material to one surface of the first substrate and one surface of the second substrate, respectively, and hardening the formed resin composition layers, respectively.

The resin material contained in the resin composition is not particularly limited, and examples thereof include: materials that form bonds or structures such as polyimide, polyamide, polyamide imide, parylene, polyarylene ether, tetrahydronaphthalene, octahydroanthracene, etc. by crosslinking; materials that form nitrogen-containing ring structures such as polybenzoxazole and polybenzoxazine; materials that form bonds or structures such as Si-O by crosslinking; organic materials such as siloxane modified compounds. The resin material used to form the first resin layer and the resin material used to form the second resin layer may be the same or different.

Examples of the structure having a Si—O bond (siloxane bond) include structures represented by the following formulas (1) to (3).

[Chemistry 1]

In a structure having a Si-O bond (siloxane bond), the group bonded to Si may be substituted by an alkylene group, a phenylene group, etc. For example, it may be a structure having (-O-) _x (R ₁ ) _y Si-(R ₂ )-Si(R ₁ ) _y (-O-) _x , etc. (R ₁ represents a methyl group, etc., R ₂ represents an alkylene group, a phenylene group, etc.; x and y are each independently an integer greater than 0, and x+y is 3).

As materials that form Si-O bonds by crosslinking, for example, compounds represented by the following formulas (4) and (5) can be listed. In addition, the structures represented by formulas (1) and (2) can be generated by, for example, heating and reacting the compounds represented by formulas (4) and (5).

[Chemistry 2]

For example, when the resin material includes a material that forms a bond or structure of polyimide, polyamide, polyamide imide, etc. by crosslinking, it is preferred that the material includes a compound (A) and a crosslinking agent (B), wherein the compound (A) has a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom and has a weight average molecular weight of 90 to 400,000, and the crosslinking agent (B) has three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, and among the three or more -C(=O)OX groups, one or more and six or less are -C(=O)OH groups, and the weight average molecular weight is 200 to 2000.

(Compound (A)) Compound (A) is a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and having a weight average molecular weight of 90 or more and 400,000 or less. The cationic functional group is not particularly limited as long as it is a functional group that can carry a positive charge and contains at least one of a primary nitrogen atom and a secondary nitrogen atom.

Furthermore, the compound (A) may contain a tertiary nitrogen atom in addition to the primary nitrogen atom and the secondary nitrogen atom.

In the present disclosure, the so-called "primary nitrogen atom" refers to a nitrogen atom that is bonded only to two hydrogen atoms and one atom other than hydrogen atoms (e.g., a nitrogen atom contained in a primary amine group ( _-NH2 group)) or a nitrogen atom (cation) that is bonded only to three hydrogen atoms and one atom other than hydrogen atoms. In addition, the so-called "secondary nitrogen atom" refers to a nitrogen atom that is bonded only to one hydrogen atom and two atoms other than hydrogen atoms (i.e., a nitrogen atom contained in a functional group represented by the following formula (a)) or a nitrogen atom (cation) that is bonded only to two hydrogen atoms and two atoms other than hydrogen atoms. The term "tertiary nitrogen atom" refers to a nitrogen atom bonded to only three atoms other than hydrogen atoms (i.e., a nitrogen atom serving as a functional group represented by the following formula (b)) or a nitrogen atom bonded to only one hydrogen atom and three atoms other than hydrogen atoms (cations).

[Chemistry 3]

In formula (a) and formula (b), * represents a bonding position to an atom other than a hydrogen atom. Here, the functional group represented by the formula (a) may be a functional group constituting a part of a diamine group (-NHR ^a group; here, R ^a represents an alkyl group), or a divalent linking group contained in the polymer skeleton. In addition, the functional group represented by the formula (b) (i.e., a tertiary nitrogen atom) may be a functional group constituting a part of a tertiary amine group (-NR ^b R ^c group; here, R ^b and R ^c each independently represent an alkyl group), or a trivalent linking group contained in the polymer skeleton.

The weight average molecular weight of compound (A) is 90 to 400,000. Examples of compound (A) include aliphatic amines, compounds having a siloxane bond (Si-O bond) and an amine group, and amine compounds having a ring structure without an Si-O bond in the molecule. When compound (A) is an aliphatic amine, the weight average molecular weight is preferably 10,000 to 200,000. When compound (A) is a compound having a siloxane bond (Si-O bond) and an amine group, the weight average molecular weight is preferably 130 to 10,000, more preferably 130 to 5,000, and even more preferably 130 to 2,000. When the compound (A) is an amine compound having no Si—O bond in the molecule and having a ring structure, the weight average molecular weight is preferably 90 or more and 600 or less.

Furthermore, in this disclosure, the weight average molecular weight for substances other than monomers refers to the weight average molecular weight converted to polyethylene glycol measured by gel permeation chromatography (GPC). Specifically, an aqueous solution of sodium nitrate at a concentration of 0.1 mol/L was used as a developing solvent, and an analytical device Shodex DET RI-101 and two analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP manufactured by Tosoh) were used to detect the refractive index at a flow rate of 1.0 mL/min, and polyethylene glycol/polyethylene oxide was used as a standard, and the weight average molecular weight was calculated using analytical software (Empower3 manufactured by Waters).

In addition, the compound (A) may further have anionic functional groups, nonionic functional groups, etc. as needed. The nonionic functional group may be a hydrogen bond accepting group or a hydrogen bond donating group. Examples of the nonionic functional group include: hydroxyl group, carbonyl group, ether group (-O-), etc. The anionic functional group is not particularly limited as long as it is a functional group that can carry a negative charge. Examples of the anionic functional group include: carboxylic acid group, sulfonic acid group, sulfate group, etc.

Examples of the compound (A) include aliphatic amines, and more specifically include polyalkyleneimines which are polymers of alkyleneimines such as ethylenimine, propylenimine, butylenimine, pentylenimine, hexylenimine, heptylenimine, octylenimine, trimethyleneimine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, and octamethyleneimine; polyallylamine; and polyacrylamide.

Polyethyleneimine (PEI) can be produced by a known method described in Japanese Patent Publication No. 43-8828, Japanese Patent Publication No. 49-33120, Japanese Patent Publication No. 2001-213958, International Publication No. 2010/137711, etc. Polyalkyleneimine other than polyethyleneimine can also be produced by the same method as polyethyleneimine.

Compound (A) is also preferably a derivative of the polyalkyleneimine (polyalkyleneimine derivative; particularly preferably a polyethyleneimine derivative). As a polyalkyleneimine derivative, there is no particular limitation as long as it is a compound that can be produced using the polyalkyleneimine. Specifically, there can be listed: polyalkyleneimine derivatives in which an alkyl group (preferably an alkyl group with 1 to 10 carbon atoms), an aryl group, etc. are introduced into the polyalkyleneimine, and polyalkyleneimine derivatives obtained by introducing a cross-linking group such as a hydroxyl group into the polyalkyleneimine. These polyalkyleneimine derivatives can be produced using the polyalkyleneimine and by a commonly used method. Specifically, for example, they can be produced according to the method described in Japanese Patent Publication No. 6-016809.

In addition, as a polyalkyleneimine derivative, it is also preferred to be a highly branched polyalkyleneimine obtained by reacting a polyalkyleneimine with a monomer containing a cationic functional group to increase the branching degree of the polyalkyleneimine. As a method for obtaining a highly branched polyalkyleneimine, for example, there can be listed: a method in which a polyalkyleneimine having a plurality of secondary nitrogen atoms in the skeleton is reacted with a monomer containing a cationic functional group, and at least one of the plurality of secondary nitrogen atoms is replaced by a monomer containing a cationic functional group; a method in which a polyalkyleneimine having a plurality of primary nitrogen atoms at the end is reacted with a monomer containing a cationic functional group, and at least one of the plurality of primary nitrogen atoms is replaced by a monomer containing a cationic functional group, etc. As cationic functional groups introduced to increase the branching degree, aminoethyl, aminopropyl, diaminopropyl, aminobutyl, diaminobutyl, triaminobutyl, etc. can be listed. In terms of reducing the cationic functional group equivalent and increasing the cationic functional group density, aminoethyl is preferred.

In addition, the polyethyleneimine and its derivatives may be commercially available. For example, polyethyleneimine and its derivatives commercially available from Nippon Catalyst Co., Ltd., BASF, MP-Biomedicals, etc. may be appropriately selected and used.

As compound (A), in addition to the above-mentioned aliphatic amines, compounds having Si-O bonds and amine groups can also be listed. As compounds having Si-O bonds and amine groups, for example, siloxane diamine, silane coupling agents having amine groups, siloxane polymers of silane coupling agents having amine groups, etc. can be listed. As silane coupling agents having amine groups, for example, compounds represented by the following formula (A-3) can be listed.

[Chemistry 4]

In formula (A-3), ^R1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted. ^R2 and ^R3 each independently represent an alkylene group having 1 to 12 carbon atoms which may be substituted (may include a carbonyl group, an ether group, etc. in the skeleton), an ether group, or a carbonyl group. ^R4 and ^R5 each independently represent an alkylene group having 1 to 4 carbon atoms which may be substituted or a single bond. Ar represents a divalent or trivalent aromatic ring. ^X1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms which may be substituted. ^X2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an alkyl group having 1 to 5 carbon atoms which may be substituted (may include a carbonyl group, an ether group, etc. in the skeleton). A plurality of ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , and ^X1 may be the same or different. Examples of the substituents of the alkyl and alkylene groups in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X ¹ and X ² include amino, hydroxyl, alkoxy, cyano, carboxylic acid, sulfonic acid, and halogen. Examples of the divalent or trivalent aromatic ring in Ar include divalent or trivalent benzene ring. Examples of the aryl group in X ² include phenyl, methylbenzyl, and vinylbenzyl.

Specific examples of the silane coupling agent represented by formula (A-3) include N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, -(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxy Silane, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, tri Methoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane and hydrolyzates thereof.

Examples of silane coupling agents containing an amino group other than those of formula (A-3) include N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, piperazinylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis( methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-(4-(methoxydimethylsilyl)phenyl)benzamide, 3,5-diamino-N-(4-(triethoxysilyl)phenyl)benzamide, 5-(ethoxydimethylsilyl)benzene-1,3-diamine and their hydrolyzates.

The silane coupling agent having an amine group may be used alone or in combination of two or more. In addition, a silane coupling agent having an amine group and a silane coupling agent not having an amine group may be used in combination. For example, a silane coupling agent having a hydroxyl group may be used to improve adhesion to metal.

In addition, polymers (siloxane polymers) formed from these silane coupling agents via siloxane bonds (Si-O-Si) can also be used. For example, polymers having a linear siloxane structure, polymers having a branched siloxane structure, polymers having a cyclic siloxane structure, polymers having a cage-like siloxane structure, etc. can be obtained from the hydrolyzate of 3-aminopropyltrimethoxysilane. The cage-like siloxane structure is represented by the following formula (A-1), for example.

[Chemistry 5]

Examples of the siloxane diamine include compounds represented by the following formula (A-2): In formula (A-2), i is an integer of 0 to 4, j is an integer of 1 to 3, and Me is a methyl group.

[Chemistry 6]

In addition, examples of the siloxane diamine include 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in formula (A-2), i=0, j=1), and 1,3-bis(2-aminoethylamino)propyltetramethyldisiloxane (in formula (A-2), i=1, j=1).

As compound (A), in addition to the above-mentioned aliphatic amines and compounds having Si-O bonds and amine groups, amine compounds having no Si-O bonds in the molecule but having a ring structure can also be listed. Among them, amine compounds having no Si-O bonds in the molecule but having a ring structure with a weight average molecular weight of 90 or more and 600 or less are preferred. As amine compounds having no Si-O bonds in the molecule but having a ring structure with a weight average molecular weight of 90 or more and 600 or less, alicyclic amines, aromatic cyclic amines, heterocyclic amines, etc. can be listed. There can be multiple ring structures in the molecule, and the multiple ring structures can be the same or different. As amine compounds having a ring structure, compounds having an aromatic ring are more preferred because it is easy to obtain compounds that are more stable to heat. In addition, as an amine compound having a weight average molecular weight of 90 or more and 600 or less and having a ring structure without Si-O bonds in the molecule, a compound having a primary amine group is preferred in terms of easily forming a thermal crosslinking structure such as amide, amide imide, and imide with a crosslinking agent (B) and improving heat resistance. Furthermore, as the amine compound, a diamine compound having two primary amine groups, a triamine compound having three primary amine groups, etc. are preferred in terms of easily increasing the number of thermal crosslinking structures such as amide, amide imide, and imide with a crosslinking agent (B) and further improving heat resistance.

Examples of alicyclic amines include cyclohexylamine, dimethylaminocyclohexane, etc. Examples of aromatic cyclic amines include diaminodiphenyl ether, xylene diamine (preferably p-xylene diamine), diaminobenzene, diaminotoluene, methylene dianiline, dimethyl diamino biphenyl, bis(trifluoromethyl) diamino biphenyl, diamino benzophenone, diamino benzyl aniline, bis(aminophenyl) fluorene, bis(aminophenoxy) benzene, bis(aminophenoxy) biphenyl, dicarboxy diamino diphenyl methane, diamino resorcinol, dihydroxy benzidine, diamino benzidine, 1,3,5-triaminophenoxy benzene, 2,2'-dimethyl benzidine, tri(4-aminophenyl) amine, 2,7-diaminofluorene, 1,9-diaminofluorene, dibenzylamine, etc. Examples of the heterocyclic ring of the heterocyclic amine include a heterocyclic ring containing a sulfur atom as a heterocyclic atom (e.g., a thiophene ring) or a heterocyclic ring containing a nitrogen atom as a heterocyclic atom (e.g., a five-membered ring such as a pyrrole ring, a pyrrolidinyl ring, a pyrazole ring, an imidazole ring, and a triazole ring; a six-membered ring such as an isocyanuric acid ring, a pyridine ring, a oxazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, and a triazine ring; and a condensed ring such as an indole ring, an indoleline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, a purine ring, and a quinoxaline ring). For example, as heterocyclic amines having a heterocyclic ring containing nitrogen, there are melamine, ammeline, melam, melem, tris(4-aminophenyl)amine, etc. Furthermore, as amine compounds having both a heterocyclic ring and an aromatic ring, there are N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine, etc.

The compound (A) has a primary or secondary amine group, and thus can strongly bond the substrates to each other by electrostatic interaction with functional groups such as hydroxyl groups, epoxy groups, carboxyl groups, amine groups, and hydroxyl groups that may exist on the surfaces of the first substrate and the second substrate, or by densely forming covalent bonds with the functional groups. In addition, the compound (A) has a primary or secondary amine group, and thus is easily dissolved in the polar solvent (D) described below. By using a compound (A) that is easily soluble in a polar solvent (D), the affinity with the hydrophilic surface of a substrate such as a silicon substrate becomes higher, so that a smooth film can be easily formed and the thickness of the first resin layer and the second resin layer can be reduced.

As the compound (A), an aliphatic amine or a compound having a Si—O bond and an amine group is preferred from the viewpoint of forming a smooth thin film, and a compound having a Si—O bond and an amine group is more preferred from the viewpoint of heat resistance.

When compound (A) includes a compound having a Si—O bond and an amine group, it is preferable in terms of forming a smooth thin film if the ratio of the total number of primary nitrogen atoms and secondary nitrogen atoms to the number of silicon atoms in compound (A) (total number of primary nitrogen atoms and secondary nitrogen atoms/number of silicon atoms) is greater than 0.2 and less than 5.

When the compound (A) includes a compound having a Si-O bond and an amine group, in terms of adhesion between substrates, it is preferred that, in the compound having a Si-O bond and an amine group, the non-crosslinking group such as a methyl group bonded to Si satisfies the relationship of (non-crosslinking group)/Si<2 in terms of molar ratio. It is speculated that by satisfying this relationship, the crosslinking density (crosslinking of Si-O-Si bonds and amide bonds, imide bonds, etc.) of the formed film is increased, the substrates have sufficient adhesion, and the peeling of the substrates can be suppressed.

As described above, the compound (A) has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. Here, when the compound (A) contains a primary nitrogen atom, the ratio of the primary nitrogen atom to all nitrogen atoms in the compound (A) is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more. In addition, the compound (A) may also have a cationic functional group containing a primary nitrogen atom and not containing a nitrogen atom other than the primary nitrogen atom (e.g., a secondary nitrogen atom, a tertiary nitrogen atom).

When compound (A) contains secondary nitrogen atoms, the ratio of the secondary nitrogen atoms to all nitrogen atoms in compound (A) is preferably 5 mol% to 50 mol%, more preferably 10 mol% to 45 mol%.

In addition, compound (A) may contain tertiary nitrogen atoms in addition to primary nitrogen atoms and secondary nitrogen atoms. When compound (A) contains tertiary nitrogen atoms, the ratio of tertiary nitrogen atoms to all nitrogen atoms in compound (A) is preferably greater than 20 mol % and less than 50 mol %, and more preferably greater than 25 mol % and less than 45 mol %.

In the present disclosure, the content of the component derived from the compound (A) in the first resin layer or the second resin layer is not particularly limited. For example, it can be set to 1 mass % or more and 82 mass % or less, preferably 5 mass % or more and 82 mass % or less, and more preferably 13 mass % or more and 82 mass % or less, relative to the entire first resin layer or the entire second resin layer.

(Crosslinking agent (B)) Crosslinking agent (B) is a compound having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in the molecule, one or more and six or less of the three or more -C(=O)OX groups (hereinafter also referred to as "COOX") are -C(=O)OH groups (hereinafter also referred to as "COOH"), and having a weight average molecular weight of 200 or more and 2000 or less.

The crosslinking agent (B) is a compound having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, preferably a compound having three or more to six -C(=O)OX groups in the molecule, and more preferably a compound having three or four -C(=O)OX groups in the molecule.

In the crosslinking agent (B), X in the -C(=O)OX group may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. Furthermore, X in the -C(=O)OX group may be the same or different.

The crosslinking agent (B) is a compound having one or more and six or less -C(=O)OH groups in which X is a hydrogen atom in the molecule, preferably a compound having one or more and four or less -C(=O)OH groups in the molecule, more preferably a compound having two or more and four or less -C(=O)OH groups in the molecule, and still more preferably a compound having two or three -C(=O)OH groups in the molecule.

The crosslinking agent (B) is a compound having a weight average molecular weight of 200 to 2000. The weight average molecular weight of the crosslinking agent (B) is preferably 200 to 1000, more preferably 200 to 600, and even more preferably 200 to 400.

The crosslinking agent (B) preferably has a ring structure in the molecule. Examples of the ring structure include an aliphatic ring structure and an aromatic ring structure. In addition, the crosslinking agent (B) may have multiple ring structures in the molecule, and the multiple ring structures may be the same or different.

Examples of the alicyclic structure include an alicyclic structure having 3 or more and 8 or less carbon atoms, preferably an alicyclic structure having 4 or more and 6 or less carbon atoms, and the ring structure may be saturated or unsaturated. More specifically, examples of the alicyclic structure include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.

The aromatic ring structure is not particularly limited as long as it is a ring structure showing aromaticity, and examples thereof include benzene-based aromatic rings such as benzene ring, naphthalene ring, anthracene ring, and perylene ring, aromatic heterocyclic rings such as pyridine ring and thiophene ring, and non-benzene-based aromatic rings such as indene ring and azulene ring.

The ring structure of the crosslinking agent (B) in the molecule is preferably at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring and a naphthalene ring. In terms of further improving the heat resistance of the first resin layer and the second resin layer, at least one of a benzene ring and a naphthalene ring is more preferred.

As described above, the crosslinking agent (B) may have a plurality of ring structures in the molecule. When the ring structure is benzene, the crosslinking agent (B) may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, or the like.

The crosslinking agent (B) preferably has a fluorine atom in the molecule, more preferably has one or more and six or less fluorine atoms in the molecule, and even more preferably has three or more and six or less fluorine atoms in the molecule. For example, the crosslinking agent (B) may have a fluoroalkyl group in the molecule, specifically, a trifluoroalkyl group or a hexafluoroisopropyl group.

Furthermore, as the crosslinking agent (B), there can be listed: carboxylic acid compounds such as alicyclic carboxylic acids, benzene carboxylic acids, naphthalene carboxylic acids, diphthalic acid, and fluorinated aromatic ring carboxylic acids; carboxylic acid ester compounds such as alicyclic carboxylic acid esters, benzene carboxylic acid esters, naphthalene carboxylic acid esters, diphthalic acid esters, and fluorinated aromatic ring carboxylic acid esters. Furthermore, the carboxylic acid ester compound is a compound having a carboxyl group (-C(=O)OH group) in the molecule, and at least one X among three or more -C(=O)OX groups is an alkyl group with a carbon number of 1 or more and 6 or less (i.e., having an ester bond). In the present disclosure, by using the crosslinking agent (B) as a carboxylic acid ester compound, the aggregation caused by the combination of the compound (A) and the crosslinking agent (B) is suppressed, so that the number of aggregates and pits is reduced and the film thickness is easily adjusted.

The carboxylic acid compound is preferably a tetravalent or less carboxylic acid compound containing four or less -C(=O)OH groups, and more preferably a trivalent or tetravalent carboxylic acid compound containing three or four -C(=O)OH groups.

The carboxylate compound is preferably a compound containing three or less carboxyl groups (—C(═O)OH groups) and three or less ester bonds in the molecule, and more preferably a compound containing two or less carboxyl groups and two or less ester bonds in the molecule.

In the carboxylate compound, when X is an alkyl group having 1 to 6 carbon atoms among three or more -C(=O)OX groups, X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, etc., and is preferably an ethyl group or a propyl group in terms of further suppressing the aggregation caused by the combination of the compound (A) and the crosslinking agent (B).

Specific examples of the carboxylic acid compound include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid and the like; 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, 3,4'-diphthalic acid, p-phenylenedicarboxylic acid (trimellitic acid), benzenepentacarboxylic acid, mellitic acid (mellitic acid); acid) and other benzoic acids; 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid and other naphthalenecarboxylic acids; 3,3',5,5'-tetracarboxy diphenylmethane, biphenyl-3,3',5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, biphenyl-3,3',4,4'-tetracarboxylic acid, benzophenone-3,3',4,4'-tetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4'-(ethynyl-1,2-diyl)diphthalic acid (4,4'-(Ethyne-1,2-diyl)diphthalic acid acid), 4,4'-(1,4-phenylenebis(oxy))diphthalic acid), 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid), 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid acid) and other diphthalic acids; perylene-3,4,9,10-tetracarboxylic acid and other perylene carboxylic acids; anthracene carboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid; fluorinated aromatic ring carboxylic acids such as 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthine-2,3,6,7-tetracarboxylic acid and 1,4-di-trifluoromethylpyromellitic acid.

Specific examples of the carboxylic acid ester compound include compounds in which at least one carboxyl group in the specific examples of the carboxylic acid compound is substituted with an ester group. Examples of the carboxylic acid ester compound include half-esterified compounds represented by the following general formulas (B-1) to (B-5).

[Chemistry 7]

R in general formula (B-1) to general formula (B-5) is independently an alkyl group having 1 or more and 6 or less carbon atoms, preferably methyl, ethyl, propyl, or butyl, and more preferably ethyl or propyl. Y in general formula (B-2) is a single bond, O, C=O, or C(CF ₃ ) ₂ .

For example, a carboxylic acid anhydride as the anhydride of the carboxylic acid compound is mixed in an alcohol solvent, and the carboxylic acid anhydride is ring-opened to generate a half-esterified compound.

In the present disclosure, the content of the component derived from the crosslinking agent (B) in the first resin layer and the second resin layer is not particularly limited. For example, the ratio of the number of carbonyl groups (-(C=O)-Y) in the substance derived from the crosslinking agent (B) to the number of all nitrogen atoms in the substance derived from the compound (A) (-(C=O)-Y)/N) is preferably 0.1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and further preferably 0.4 or more and 2.2 or less. Here, in -(C=O)-Y, Y represents a nitrogen atom, OH or ester group crosslinked by imide or amide. When (-(C=O)-Y)/N is 0.1 or more and 3.0 or less, the first resin layer and the second resin layer preferably have a cross-linked structure such as amide, amide imide, or imide, and the heat resistance is further improved.

(Polar solvent (D)) In step A, a resin composition containing a resin material may be applied to the surface of at least one of the first substrate and the second substrate. In this case, the resin composition containing a resin material preferably contains a resin material such as the compound (A), a crosslinking agent (B), and a polar solvent (D). Here, the so-called polar solvent (D) refers to a solvent having a relative dielectric constant of 5 or more at room temperature. As the polar solvent (D), specifically, there can be listed: protic inorganic compounds such as water and heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, isopentanol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, glycerol; ethers such as tetrahydrofuran and dimethoxyethane; furfural, propylene glycol ... Aldehydes/ketones such as ketone, ethyl methyl ketone, and cyclohexane; acid derivatives such as acetic anhydride, ethyl acetate, butyl acetate, ethyl carbonate, propyl carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphamide; nitriles such as acetonitrile and propionitrile; nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide. As the polar solvent (D), it is preferred to include a protic solvent, more preferably water, and even more preferably ultrapure water. The content of the polar solvent (D) in the resin composition is not particularly limited, and is, for example, 1.0 mass % or more and 99.99896 mass % or less, preferably 40 mass % or more and 99.99896 mass % or less, relative to the entire resin composition. The boiling point of the polar solvent (D) is preferably 150°C or less, and more preferably 120°C or less, in terms of volatilizing the polar solvent (D) by heating when forming the first resin layer and the second resin layer and reducing the amount of the residual solvent in the first resin layer and the second resin layer.

(Additive (C)) The resin composition containing the resin material may contain an additive (C) in addition to the resin material such as the compound (A), the crosslinking agent (B), the polar solvent (D), etc. As the additive (C), there can be listed an acid (C-1) having a carboxyl group and a weight average molecular weight of 46 or more and 195 or less, and a base (C-2) having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less and having no ring structure. In addition, the additive (C) is volatilized by heating when forming the first resin layer and the second resin layer, but the first resin layer and the second resin layer in the substrate laminate of the present disclosure may also contain the additive (C).

The acid (C-1) is an acid having a carboxyl group and a weight average molecular weight of 46 or more and 195 or less. By including the acid (C-1) as the additive (C), the amino group in the compound (A) forms an ionic bond with the carboxyl group in the acid (C-1), and it is estimated that aggregation caused by the combination of the compound (A) and the crosslinking agent (B) is suppressed. More specifically, since the interaction (e.g., electrostatic interaction) between the ammonium ions derived from the amino group in the compound (A) and the carboxylate ions derived from the carboxyl group in the acid (C-1) is stronger than the interaction between the ammonium ions derived from the amino group in the compound (A) and the carboxylate ions derived from the carboxyl group in the crosslinking agent (B), it is estimated that aggregation is suppressed. In addition, the present invention is not limited to the above speculation.

The acid (C-1) is not particularly limited as long as it is a compound having a carboxyl group and a weight average molecular weight of 46 or more and 195 or less, and examples thereof include monocarboxylic acid compounds, dicarboxylic acid compounds, oxydicarboxylic acid compounds, etc. More specifically, examples of the acid (C-1) include formic acid, acetic acid, malonic acid, oxalic acid, citric acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, 3,4,5-trihydroxybenzoic acid, etc.

In the present disclosure, the content of the acid (C-1) in the resin composition including the resin material is not particularly limited. For example, the ratio of the number of carboxyl groups in the acid (C-1) to the number of all nitrogen atoms in the compound (A) (COOH/N) is preferably 0.01 or more and 10 or less, more preferably 0.02 or more and 6 or less, and even more preferably 0.5 or more and 3 or less.

The base (C-2) is a base having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less. The resin composition containing the resin material contains the base (C-2) as the additive (C), and the carboxyl group in the crosslinking agent (B) forms an ionic bond with the amine group in the base (C-2), so it is estimated that the aggregation caused by the combination of the compound (A) and the crosslinking agent (B) is suppressed. More specifically, since the interaction between the carboxyl salt ions derived from the carboxyl group in the crosslinking agent (B) and the ammonium ions derived from the amine group in the base (C-2) is stronger than the interaction between the ammonium ions derived from the amine group in the compound (A) and the carboxyl salt ions derived from the carboxyl group in the crosslinking agent (B), it is estimated that the aggregation is suppressed. In addition, the present invention is not limited to the above speculation.

The base (C-2) is not particularly limited as long as it is a compound having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less and having no ring structure, and examples thereof include monoamine compounds and diamine compounds. More specifically, examples of the base (C-2) include ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, and N-(2-aminoethyl)glycine.

In the present disclosure, the content of the base (C-2) in the resin composition including the resin material is not particularly limited. For example, the ratio (N/COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) is preferably 0.5 or more and 5 or less, and more preferably 0.9 or more and 3 or less.

When the first resin layer and the second resin layer of the substrate laminate of the present invention require insulation, in order to improve the insulation or mechanical strength, tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexadecene, or the like may be mixed. Ethoxy-1,3,5-trisilane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxycyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisilethylene, 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilane. Furthermore, in order to improve the hydrophobicity of the first resin layer and the second resin layer having insulation, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, etc. may also be mixed. These compounds may be mixed in order to control etching selectivity.

The resin composition including the resin material may include a solvent other than the polar solvent (D), for example, n-hexane.

In addition, for example, in order to improve electrical properties, the resin composition containing the resin material may also contain phthalic acid, benzoic acid, etc. or their derivatives. In addition, for example, in order to inhibit copper corrosion, the resin composition containing the resin material may also contain benzotriazole or its derivatives.

The pH value of the resin composition including the resin material is not particularly limited, but is preferably 2.0 or more and 12.0 or less.

In addition, when the acid (C-1) is used as the additive (C), it is preferred to mix the mixture of the acid (C-1) and the compound (A) and the crosslinking agent (B). That is, it is preferred to mix the compound (A) and the acid (C-1) in advance before mixing the compound (A) and the crosslinking agent (B). Thereby, when the compound (A) and the crosslinking agent (B) are mixed, the resin composition containing the resin material can be appropriately suppressed from becoming cloudy and gelling (if gelling occurs, it may take time for the resin composition to become transparent, which is not preferred).

In addition, when the base (C-2) is used as the additive (C), it is preferred to mix the mixture of the base (C-2) and the crosslinking agent (B) with the compound (A). That is, it is preferred to mix the crosslinking agent (B) and the base (C-2) in advance before mixing the compound (A) and the crosslinking agent (B). Thereby, when the compound (A) and the crosslinking agent (B) are mixed, the resin composition containing the resin material can be appropriately suppressed from becoming cloudy and gelling (if gelling occurs, it may take time for the resin composition to become transparent, which is not preferred).

Examples of methods for applying the resin material to the surface of at least one of the first substrate and the second substrate include vapor deposition polymerization, chemical vapor deposition (CVD), atomic layer deposition (ALD) and other vapor phase film forming methods, immersion methods, spraying methods, spin coating methods, rod coating methods and other coating methods. When applying the resin material by coating, it is preferred to apply the resin composition containing the resin material. For example, when forming a film with a film thickness of micrometer size, it is preferable to use a rod coating method, and when forming a film with a film thickness of nanometer size (several nm to several hundred nm), it is preferable to use a spin coating method. In addition, the film thickness of the resin material can be appropriately adjusted according to the target thickness of the first resin layer and the second resin layer.

For example, there is no particular limitation on the method of applying the resin material by spin coating. For example, the following method can be used, that is, while the first substrate is rotated by a spin coater, a resin composition containing a resin material is dripped onto the surface of the first substrate, and then the rotation speed of the first substrate is increased to dry. In the method of applying the resin material by spin coating, there is no particular limitation on the conditions such as the rotation speed of the substrate, the dripping amount and dripping time of the resin composition containing the resin material, and the rotation speed of the substrate during drying, and the conditions can be appropriately adjusted in consideration of the thickness of the formed resin material, etc.

Regarding the substrate provided with the resin material, in order to remove the excess resin material provided, the substrate provided with the resin material may be cleaned. Examples of the cleaning method include wet cleaning using a rinse liquid such as a polar solvent, plasma cleaning, and the like.

In the method for manufacturing a substrate laminate disclosed herein, step A may include hardening the resin material applied to one surface of the first substrate and one surface of the second substrate to form a first resin layer and a second resin layer. For example, the resin material is hardened by heating or the like to form the first resin layer and the second resin layer. At this time, when the resin material includes a thermosetting compound, the resin material is hardened by heating the resin material at a temperature above the hardening temperature.

It is preferred that the resin material applied to one surface of the first substrate and one surface of the second substrate is heated at 100°C to 450°C to harden it. Furthermore, the temperature refers to the surface temperature of the resin material applied to the surface. By heating the resin material, the solvent in the resin composition containing the resin material is removed. In addition, the components in the resin material react to obtain a hardened material, thereby forming a first resin layer and a second resin layer containing the hardened material. From the viewpoint of suppressing heat damage to devices such as semiconductor memory, the temperature is preferably 150°C to 450°C, more preferably 180°C to 400°C, further preferably 180°C to 250°C, and particularly preferably 180°C to 200°C.

In addition, there is no particular restriction on the pressure when the resin material applied to the surface is heated, and it is preferably an absolute pressure exceeding 17 Pa and below atmospheric pressure. The absolute pressure is more preferably 1000 Pa or more and below atmospheric pressure, further preferably 5000 Pa or more and below atmospheric pressure, and particularly preferably 10000 Pa or more and below atmospheric pressure.

The resin material applied to the surface can be heated by a common method using a furnace or a heating plate. As the furnace, for example, SPX-1120 manufactured by APEX, VF-1000LP manufactured by Koyo Thermo Systems, etc. can be used. In addition, the resin material applied to the surface can be heated in an atmospheric environment or in an inert gas (nitrogen, argon, helium, etc.) environment.

There is no particular restriction on the heating time of the resin material applied to the surface, and for example, it is 3 hours or less, preferably 1 hour or less. There is no particular restriction on the lower limit of the heating time, and for example, it can be set to 5 minutes.

In order to shorten the curing time of the resin material applied to the surface, the resin material applied to the surface may be irradiated with ultraviolet light (UV). As ultraviolet light, preferably ultraviolet light with a wavelength of 170 nm to 230 nm, excimer light with a wavelength of 222 nm, excimer light with a wavelength of 172 nm, etc. In addition, it is preferred to perform ultraviolet irradiation in an inert gas environment.

Whether the resin material is hardened can be confirmed by measuring the peak intensity of specific bonds and structures using Fourier Transform Infrared Spectrometry (FT-IR). As specific bonds and structures, bonds and structures generated by crosslinking reactions can be listed. For example, when amide bonds, imide bonds, siloxane bonds, tetrahydronaphthalene structures, oxazole ring structures, etc. are formed, it can be determined that the resin material is hardened, and it can be confirmed by measuring the peak intensity derived from these bonds, structures, etc. using FT-IR. Amide bonds can be confirmed by the presence of vibration peaks at about 1650 cm ^-1 and about 1520 cm ^-1 . An imide bond can be confirmed by the presence of vibration peaks at about 1770 cm ^-1 and about 1720 cm ^-1 . A siloxane bond can be confirmed by the presence of vibration peaks between 1000 cm ^-1 and 1080 cm ^-1 . A tetrahydronaphthalene structure can be confirmed by the presence of vibration peaks between 1500 cm ^-1 . An oxazole ring structure can be confirmed by the presence of vibration peaks at about 1625 cm ^-1 and about 1460 cm ^-1 .

At least one of the first resin layer and the second resin layer formed by curing the resin material preferably has a siloxane bond and at least any one selected from the group consisting of an ester bond, an ether bond, an amide bond, and an imide bond, and more preferably has a siloxane bond and an imide bond.

The first resin layer and the second resin layer formed by curing the resin material preferably contain sodium and potassium in an amount of 10 ppb or less on an element basis. If the sodium or potassium content is 10 ppb or less on an element basis, abnormalities in the electrical characteristics of the semiconductor device, such as malfunction of the transistor, can be suppressed.

The amount of silicon in the surface of the first resin layer and the second resin layer is preferably 20 atomic % or less, more preferably 15 atomic % or less, and further preferably 10 atomic % or less, respectively. The amount of silicon in the surface of the resin layer can be evaluated by atomic ratio measurement using an X-ray photoelectron spectrometer (XPS). Specifically, the atomic ratio can be measured using AXIS-NOVA (manufactured by KRATOS) as an XPS, and based on the peak intensity of the narrow spectrum when the total amount of each element detected in the wide spectrum is set to 100%.

The thickness of the first resin layer and the second resin layer is preferably 0.001 μm to 8.0 μm, more preferably 0.01 μm to 6.0 μm, and further preferably 0.03 μm to 5.0 μm, respectively. By making the thickness of the first resin layer and the second resin layer 0.001 μm or more, the bonding strength with the second inorganic material layer, other layers, etc. can be improved. By making the thickness of the first resin layer and the second resin layer 8.0 μm or less, when the resin layer is formed on a substrate with a large area, the thickness deviation of the resin layer can be suppressed.

When electrodes are provided on a portion of the surface of the first resin layer and a portion of the surface of the second resin layer, in order to improve the bonding strength with the second inorganic material layer, other layers, etc. and suppress the thickness deviation of the first resin layer and the second resin layer, the thickness of the first resin layer and the second resin layer is preferably 0.01 μm to 8.0 μm, more preferably 0.03 μm to 6.0 μm, and further preferably 0.05 μm to 5.0 μm.

When no electrodes are provided on the surfaces of the first resin layer and the second resin layer, in order to improve the bonding strength with the second inorganic material layer, other layers, etc. and to suppress the thickness deviation of the first resin layer and the second resin layer, the thickness of the first resin layer and the second resin layer is preferably greater than 0.001 μm and less than 1.0 μm, more preferably 0.01 μm to 0.8 μm, and further preferably 0.03 μm to 0.6 μm.

In order to facilitate temporary fixing of the first resin layer and the second inorganic material layer described later at low temperature and improve the bonding strength of the first laminate and the second laminate in the substrate laminate, the first resin layer preferably has a functional group capable of forming a chemical bond on the surface of the first resin layer, and more preferably has at least one functional group selected from the group consisting of a silanol group (Si-OH group), an amine group, an epoxy group, a hydroxyl group, and a functional group containing an unsaturated bond. In terms of heat resistance, it is further more preferable to have a silanol group. These functional groups can be formed by surface treatment after forming the first resin layer, or can be formed by silane coupling agent treatment, etc. Alternatively, a compound containing these functional groups may be mixed into the resin composition. Furthermore, as the functional group containing an unsaturated bond, there can be listed: vinyl, allyl, acrylic, methacrylic, styrene, etc. The second resin layer may have the functional group capable of forming a chemical bond on the surface of the second resin layer.

Whether the surface of the resin layer has Si-OH groups can be evaluated by analyzing the surface of the resin layer using Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Specifically, PHI nanoTOFII (Ulvac-Phi Co., Ltd.), which is TOF-SIMS, can be used to evaluate whether the surface of the resin layer has Si-OH groups based on the presence or absence of a peak of mass-to-charge ratio (m/Z) 45.

After forming the first resin layer or the second resin layer, the surface of at least one of the first resin layer and the second resin layer may be planarized. As a planarization method, fly cutting, chemical mechanical polishing (CMP), etc. may be listed. The planarization method may be a single method or a combination of two or more methods.

After forming the first resin layer or the second resin layer, the surface of at least one of the first resin layer and the second resin layer may be cleaned. Examples of the cleaning method include wet cleaning using a rinse solution, dry cleaning using plasma, etc. Examples of wet cleaning include ultrasonic cleaning using pure water, and rotary cleaning using a solvent such as NMP.

(First inorganic material layer and second inorganic material layer) The first inorganic material layer is a layer disposed on the other surface of the first substrate, and the second inorganic material layer is a layer disposed on the other surface of the second substrate. For example, after forming the first resin layer on one side of the first substrate, the first inorganic material layer can be formed on the other side of the first substrate. Conversely, the first resin layer can be formed after forming the first inorganic material layer. The same is true for the second substrate, and the order of forming the second resin layer and the second inorganic material layer is not particularly limited.

The materials of the first inorganic material layer and the second inorganic material layer are not particularly limited, and may be, for example, materials of inorganic materials used when inorganic materials are bonded to each other on a semiconductor substrate. Specifically, the first inorganic material layer and the second inorganic material layer may independently contain at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb, preferably at least one element selected from the group consisting of Si, Ga, Ge, and As. The first inorganic material layer and the second inorganic material layer may contain oxides, carbides, nitrides, etc. of the elements. The materials of the first inorganic material layer and the second inorganic material layer may be the same or different.

The method for forming the inorganic material layer on the surface of the substrate is not particularly limited, and the previously known methods for forming the inorganic material layer may be listed, such as CVD, sputtering, aerosol gas deposition (AGD), sol-gel method, anodic oxidation treatment, thermal decomposition method, etc.

(Electrode) The first laminate may include an electrode on a portion of the surface of the first resin layer and a portion of the surface of the first inorganic material layer, and the second laminate may include an electrode on a portion of the surface of the second resin layer and a portion of the surface of the second inorganic material layer. Preferably, each electrode is configured so that the electrode disposed on the side of the first resin layer in step B contacts the electrode disposed on the second inorganic material layer.

A through hole may be provided from the surface of the first resin layer side of the first laminate toward the surface of the first inorganic material layer side, and an electrode penetrating the first laminate may be provided in the through hole. A through hole may be provided from the surface of the second resin layer side of the second laminate toward the surface of the second inorganic material layer side, and an electrode penetrating the second laminate may be provided in the through hole.

The material of the electrode is not particularly limited, and conventionally known electrode materials can be cited. Specifically, copper, solder, tin, gold, silver, aluminum, indium, cobalt, tungsten, and the like can be cited.

The method of providing electrodes in the first laminate and the second laminate is not particularly limited, and a previously known method can be adopted. In the first laminate, the electrode can be formed on the surface where the resin material is applied before the first resin layer is formed, or the electrode can be formed on the surface where the first resin layer is formed after the first resin layer is formed. The same is true for the second laminate. In the first laminate, the electrode can be formed on the surface where the inorganic material layer is formed before the first inorganic material layer is formed, or the electrode can be formed on the surface where the first inorganic material layer is formed after the first inorganic material layer is formed. The same is true for the second laminate.

The electrode may be formed in a convex shape on the surface of the first substrate or the second substrate, may be formed in a state of penetrating the first substrate or the second substrate, or may be formed in a state of being buried in the first substrate or the second substrate.

In the case where an electrode is formed before forming a resin layer or before forming an inorganic material layer, the resin layer or inorganic material layer on the electrode is removed to form a structure in which a portion of the surface of the resin layer or a portion of the surface of the inorganic material layer includes the electrode. As a method for removing the resin layer or the inorganic material layer on the current-carrying layer, there can be listed: fly cutting, chemical mechanical polishing (CMP), plasma dry etching, etc. The removal method can be a single method or two or more methods can be used in combination. For example, in the fly cutting method, a plane planer (DFS8910 (manufactured by Disco Co., Ltd.)) can be used. When CMP is used, as the slurry, for example, a slurry containing silica or alumina for polishing resin, a slurry containing hydrogen peroxide and silica for polishing metal, etc. can be generally used. When plasma dry etching is used, fluorocarbon plasma, oxygen plasma, etc. can be used.

When the resin layer or inorganic material layer on the electrode surface is removed to expose the electrode, the oxide on the electrode surface may be reduced as needed. As a reduction treatment method, there are methods of heating the substrate at 100°C to 300°C in an acid environment such as formic acid; methods of heating the substrate in a hydrogen environment, etc. These treatments can be performed simultaneously with step C described later.

When the electrode is formed after the resin layer is formed or after the inorganic material layer is formed, for example, a hole for forming the electrode can be formed on the surface of the substrate on which the resin layer is formed or on the surface of the substrate on which the inorganic material layer is formed by a known method, and the electrode is formed in the formed hole. Examples of hole forming methods include dry etching using gas, laser ablation, and the like.

As a method for forming the electrode, there can be listed: electrolytic plating, electroless plating, sputtering, inkjet method, etc.

When the resin material is photosensitive, holes for forming electrodes can be formed in the resin material applied to at least one of the first substrate and the second substrate by photolithography. After the resin material is hardened to form at least one of the first resin layer and the second resin layer, electrodes can be formed in the formed holes.

The first laminate and the second laminate may be separated into individual pieces by dicing as necessary. For example, a dicer (DAD6340 (manufactured by Disco Co., Ltd.)) or the like may be used for the dicing process.

[Step B] The manufacturing method of the substrate laminate disclosed herein includes step B of laminating the first laminate and the second laminate by bringing the first resin layer of the first laminate into contact with the second inorganic material layer of the second laminate.

Step B is a step of bringing the first resin layer and the second inorganic material layer into contact with each other before joining the first laminate and the second laminate via the first resin layer and the second inorganic material layer in step C described later. The first laminate and the second laminate are brought into contact with each other so as to have a desired positional relationship when joining the first laminate and the second laminate.

For example, when the electrodes are provided on the first laminate and the second laminate, respectively, it is preferred that the first laminate and the second laminate be in contact with each other in such a manner that the electrode provided on the first resin layer side is in contact with the electrode provided on the second inorganic material layer.

Before the first resin layer and the second inorganic material layer are brought into contact in step B, the curing rate of the first resin layer is preferably 70% or more and 100% or less. Thereby, in step C described later, the first laminate and the second laminate are firmly bonded together, and there is a tendency that positional deviation (alignment deviation) of the bonding is less likely to occur.

The curing rate of the first resin layer is preferably 80% or more, more preferably 85% or more, particularly preferably 90% or more, and particularly preferably 93% or more. In addition, the curing rate of the first resin layer may be 100%, or less than 99%, or less than 95%, or less than 90%. In addition, the preferred range of the curing rate of the second resin layer is the same as the preferred range of the curing rate of the first resin layer. The curing rate of the second resin layer may be the curing rate before contact with other layers (such as other inorganic material layers).

The curing rate of the resin layer (at least one of the first resin layer and the second resin layer) containing at least one selected from the group consisting of an amide bond, an imide bond, a siloxane bond, a tetrahydronaphthalene structure, an oxazole ring structure, an ester bond and an ether bond is more preferably 80% or more, further preferably 85% or more, particularly preferably 90% or more, and even more preferably 93% or more. The curing rate of the resin layer (at least one of the first resin layer and the second resin layer) containing a siloxane bond and at least any one selected from the group consisting of an ester bond, an ether bond, an amide bond, and an imide bond is more preferably 80% or more, further preferably 85% or more, particularly preferably 90% or more, and even more preferably 93% or more.

The curing rate of the first resin layer formed by curing the resin material can be confirmed by measuring the peak intensity of a specific bond and structure (the sum of the peak intensities in the case of multiple peaks such as imide and amide) using Fourier transform infrared spectroscopy (FT-IR) in the resin material before being applied to the first substrate, the first resin layer before the first resin layer is brought into contact with the second inorganic material layer in step B, and the first resin layer after step C, and calculating the increase or decrease rate of the peak intensity. In addition, in the case of a band-shaped peak that is difficult to separate, such as a siloxane bond, the maximum peak intensity can be used.

Specifically, when a specific bond and structure are generated by the curing reaction, the increase rate of the peak strength can be calculated by the following formula, and the calculated value is used as the curing rate of the first resin layer. Increase rate of peak strength (curing rate of the first resin layer) = [(peak strength of the specific bond and structure of the first resin layer before the first resin layer and the second inorganic material layer are brought into contact in step B) / (peak strength of the specific bond and structure of the first resin layer after heating at 300°C for 1 hour in step C)] × 100 Furthermore, background signal removal can be performed by a conventional method. In addition, FT-IR measurement can be performed by a transmission method or a reflection method as needed.

In the increase rate of the peak intensity, when there are multiple bonds and structures that cause the increase of the peak intensity, the peak intensity reading can be converted into the total intensity of the multiple peak intensities.

Before the first resin layer and the second inorganic material layer are brought into contact in step B, the composite elastic modulus of the first resin layer at 23°C is preferably 0.1 GPa or more and 20 GPa or less, and more preferably 0.1 GPa or more and 10 GPa or less. Thus, the voids formed when the first resin layer and the second inorganic material layer are brought into contact in step B are absorbed by the first resin layer in step C, and there is a tendency to suppress the generation of voids. In addition, thereby, the first resin layer and the second inorganic material layer described later can be easily temporarily fixed at a low temperature.

In terms of appropriately suppressing the generation of voids, the composite elastic coefficient of the first resin layer at 23°C is preferably 8 GPa or less, and more preferably 6 GPa or less. In addition, in terms of appropriately suppressing the offset of alignment, the composite elastic coefficient of the first resin layer at 23°C is preferably 0.1 GPa or more, and more preferably 1 GPa or more. In addition, the preferred range of the composite elastic coefficient of the second resin layer at 23°C is the same as the preferred range of the composite elastic coefficient of the first resin layer at 23°C. The composite elastic coefficient of the second resin layer at 23°C may be the composite elastic coefficient at 23°C before contact with other layers (such as other inorganic material layers).

The composite elastic modulus of the resin layer at 23°C can be measured by the method described below. A resin composition including a resin material is prepared, spin-coated on a silicon substrate, and then heated at 400°C for 10 minutes to prepare a measurement sample. For the prepared test sample, a nanoindenter (trade name TI-950 Tribo Indenter, manufactured by Hysitron, Berkovich type indenter) was used to measure the load removal-displacement curve at 23°C under the condition of a test depth of 20 nm. The composite elastic coefficient at 23°C was calculated based on the maximum load and maximum displacement according to the calculation method of the reference (Handbook of Micro/nano Tribology (second edition) edited by Bharat Bhushan, CRC Press Co., Ltd.). Here, the composite elastic coefficient is defined by the following formula (1). In formula (1), _Er represents the composite elastic coefficient, _Ei represents the Young's modulus of the pressure head, which is 1140 GPa, _νi represents the Poisson's ratio of the pressure head, which is 0.07, and _Es and _νs represent the Young's modulus and Poisson's ratio of the sample, respectively.

[Formula 1]

Before the first resin layer and the second inorganic material layer are brought into contact in step B, the surface roughness (Ra) of the first resin layer is preferably 0.01 nm or more and 1.2 nm or less, and more preferably 0.1 nm or more and 1.0 nm or less. This makes it easy to temporarily fix the first resin layer and the second inorganic material layer described later at a low temperature. In addition, the preferred range of the surface roughness (Ra) of the second resin layer is the same as the preferred range of the surface roughness (Ra) of the first resin layer. The surface roughness (Ra) of the second resin layer may be the surface roughness (Ra) before contacting with other layers (e.g., other inorganic material layers). The surface roughness of the resin layer can be evaluated by morphological observation using a scanning probe microscope (SPM). Specifically, the surface roughness is determined by measuring a 3 μm×3 μm square area using the SPM SPA400 (manufactured by Hitachi High-technologies) in dynamic force microscopy mode.

The manufacturing method of the substrate laminate of the present disclosure may include the following steps before step B. The following steps are preferably performed after step A and before step B.

The manufacturing method of the substrate laminate disclosed in the present invention may include the step of performing a surface activation treatment on the second inorganic material layer before step B. By performing the surface activation treatment, the bonding strength between the first resin layer and the second inorganic material layer can be improved. In particular, when electrodes are provided on the bonding surfaces of the first laminate and the second laminate and the electrodes are bonded to each other, it is preferred to perform the surface activation treatment from the viewpoint of promoting the diffusion of metals such as copper contained in the electrodes to improve the bonding strength between the electrodes and reducing the heating temperature during metal diffusion. In addition, the first inorganic material layer on the first substrate may be subjected to a surface activation treatment. In particular, when the first inorganic material layer is bonded to other layers (such as other resin layers), the first inorganic material layer may be subjected to a surface activation treatment before bonding.

Specific examples of the surface activation treatment include plasma treatment and fast atom bombardment (FAB) treatment.

In terms of removing particles, etc., the manufacturing method of the substrate laminate disclosed in the present invention may include the following step, that is, the step of cleaning the second inorganic material layer before step B. The cleaning step is preferably performed after the step of performing the surface treatment and before step B. In addition, the first inorganic material layer on the first substrate may also be cleaned, especially when the first inorganic material layer is bonded to other layers (such as other resin layers), the first inorganic material layer may also be cleaned before bonding.

The cleaning method is not particularly limited, and examples thereof include: wet cleaning using solvents such as alkaline cleaning solutions, acidic cleaning solutions, cleaning solutions containing hydrofluoric acid, solutions containing permanganic acid (desmear solutions), etc.; wet cleaning using pure water, etc.; dry cleaning using UV ozone, plasma, etc., etc.

In terms of preventing foreign matter from adhering to the inorganic material layer (for example, preventing foreign matter from adhering to the inorganic material layer during cutting), the method for manufacturing a substrate laminate disclosed herein may include the step of providing a surface protection layer on the second inorganic material layer before step B. The step of providing the surface protection layer is preferably performed before the cleaning step and before step B.

As the surface protection layer, there is no particular limitation as long as it can protect the second inorganic material layer, and examples thereof include: water-soluble resins, photoresists that can be cleaned using organic solvents such as N-methyl-2-pyrrolidone (NMP), etc. As the water-soluble resin, Hogomax from Disco can be used.

The second laminate provided with the surface protection layer may be cut as needed, and the surface protection layer may be peeled off after the cutting process. In this case, it is preferred to peel off the surface protection layer after the cutting process, and then perform the treatment in the order of the cleaning step and step B after peeling off the surface protection layer.

The manufacturing method of the substrate laminate of the present disclosure may include the step of temporarily fixing the first laminate and the second laminate after step B and before step C. The temporary fixing of the first laminate and the second laminate is preferably performed at a low temperature above room temperature and below 100° C., more preferably at a low temperature above room temperature and below 50° C., and even more preferably at room temperature.

When the first substrate and the second substrate have silicon substrates, in terms of ease of operation in step C, suppression of alignment deviation (bonding position deviation), suppression of foreign matter mixing, etc., the surface energy of the bonding interface of the two laminates in a state where the first laminate and the second laminate are temporarily fixed is preferably 0.05 J/m ² or more, more preferably 0.1 J/m ² or more, and further preferably 0.15 J/m ² or more. The surface energy (bonding strength) of the bonding interface can be obtained by a blade insertion test according to the method of the non-patent document MPMaszara, G.Goetz, A.Cavigila, and JB Mckitterick, Journal of Applied Physics, 64 (1988) 4943-4950. A blade with a thickness of 0.1 mm to 0.3 mm is inserted into the bonding interface of the temporarily fixed laminate, and the distance of the laminate peeling from the blade tip is measured using an infrared light source and an infrared camera. The surface energy can then be calculated based on the following formula. γ=3×10 ⁹ ×t _b ² ×E ² ×t ⁶ /(32×L ⁴ ×E×t ³ ) Here, γ represents the surface energy (J/m ² ), t _b represents the blade thickness (m), E represents the Young's modulus of the silicon substrate contained in the first substrate and the second substrate (GPa), t represents the thickness of the first substrate and the second substrate (m), and L represents the distance of the laminate peeling from the blade tip (m).

[Step C] The manufacturing method of the substrate laminate disclosed in the present invention includes step C, which is step C of heating the first laminate and the second laminate at a temperature above 100°C after step B. In this way, a substrate laminate in which the first laminate and the second laminate are bonded via the first resin layer and the second inorganic material layer can be obtained.

The pressure when the first laminate and the second laminate are bonded is not particularly limited, and preferably the absolute pressure is greater than 10 ^-4 Pa and less than atmospheric pressure. The absolute pressure is more preferably greater than 10 ^-3 Pa and less than atmospheric pressure, further preferably greater than 100 Pa and less than atmospheric pressure, and particularly preferably greater than 1000 Pa and less than atmospheric pressure. When the first laminate and the second laminate are bonded, it can be performed in an atmospheric environment or in an inert gas (nitrogen, argon, helium, etc.) environment.

In step C, it is preferred to heat the first laminate and the second laminate at 100°C to 450°C while the first resin layer is in contact with the second inorganic material layer. Furthermore, the temperature refers to the temperature of the surface of the first substrate on which the first resin layer is formed. The temperature is preferably 100°C to 400°C, more preferably 130°C to 350°C, more preferably 150°C to 300°C, further preferably 150°C to 250°C, and particularly preferably 150°C to 200°C.

When the electrodes are arranged so that the electrode disposed on the first resin layer side contacts the electrode disposed on the second inorganic material layer in step B, the temperature is preferably 130° C. or higher, more preferably 150° C. or higher, and even more preferably 200° C. or higher. Thereby, the components (e.g., copper) contained in the electrode disposed on the first resin layer side and the electrode disposed on the second inorganic material layer diffuse, and there is a tendency to increase the bonding strength between the electrodes.

The heating in step C can be performed by a common method using a furnace or a heating plate. In addition, the heating in step C can be performed in an atmospheric environment or in an inert gas environment (nitrogen, argon, helium, etc.). There is no particular restriction on the heating time in step C, for example, it is less than 3 hours, preferably less than 1 hour. There is no particular restriction on the lower limit of the heating time, for example, it can be set to 5 minutes.

In step C, in order to improve the bonding strength between the first laminate and the second laminate, the first laminate and the second laminate can be pressurized while the first resin layer and the second inorganic material layer are in contact. Pressurization can be performed simultaneously with heating. The pressure when the first laminate and the second laminate are pressurized is not particularly limited, and is preferably 0.1 MPa or more and 10 MPa or less, and more preferably 0.1 MPa or more and 5 MPa or less. As a pressurizing device, for example, a test mini press (TEST MINI PRESS) manufactured by Toyo Seiki Seisakusho Co., Ltd. can be used.

The manufacturing method of the substrate laminate disclosed in the present invention may include the following steps, namely, after step C, providing through holes in the first laminate and the second laminate from the surface on the side of the first inorganic material layer to the surface on the side of the second resin layer, and forming electrodes penetrating the first laminate and the second laminate in the through holes. In step C, if the substrate laminate obtained does not have electrodes formed, it is preferred to form electrodes penetrating the first laminate and the second laminate in the through holes by performing the step of forming such electrodes.

For example, a through hole penetrating the first laminate and the second laminate can be formed by a known method, and an electrode can be formed in the formed hole. Examples of the hole forming method include dry etching using a gas, laser etching, and the like.

Examples of methods for forming the electrode penetrating the first laminate and the second laminate include electrolytic plating, electroless plating, sputtering, and inkjet.

The material of the electrode penetrating the first laminate and the second laminate is not particularly limited, and conventionally known electrode materials can be cited, etc. Specifically, copper, solder, tin, gold, silver, aluminum, indium, cobalt, tungsten, etc. can be cited.

In the manufacturing method of the substrate laminate disclosed in the present invention, at least one of the first substrate and the second substrate can be further laminated with other substrates, other laminates, etc. on the surface of the first inorganic material layer side and the surface of the second resin layer side. The preferred material of the other substrate is the same as the preferred material of the first substrate and the second substrate. The preferred embodiment of the other laminate is the same as the preferred embodiment of the first laminate and the second laminate.

In the manufacturing method of the substrate laminate body disclosed in the present invention, after step C, the surface of the substrate laminate body can be thinned (back grinding or back grinding) as needed.

(Examples of laminated structures of substrate laminates) Examples of laminated structures of substrate laminates in various applications are shown below. The so-called bonding layer refers to a layer including a bonding state of an inorganic material layer/resin layer. MEMS packaging applications: Si/junction layer/Si, SiO ₂ /junction layer/Si, SiO ₂ /junction layer/SiO ₂ , Cu/junction layer/Cu, Microflow applications: PDMS/junction layer/PDMS, PDMS/junction layer/SiO ₂ , CMOS image sensor applications: SiO ₂ /junction layer/SiO ₂ , Si/junction layer/Si, SiO ₂ /junction layer/Si, Through Silicon Via (TSV) applications: SiO ₂ (with Cu electrode)/junction layer/SiO ₂ (with Cu electrode), Si (with Cu electrode)/junction layer/Si (with Cu electrode), Optical device applications: (InGaAlAs, InGaAs, InP, GaAs)/junction layer/Si, LED uses: (InGaAlAs, GaAs, GaN)/junction layer/Si, (InGaAlAs, GaAs, GaN)/junction layer/SiO ₂ , (InGaAlAs, GaAs, GaN)/junction layer/(Au, Ag, Al), (InGaAlAs, GaAs, GaN)/junction layer/sapphire.

Hereinafter, an example of a method for manufacturing a substrate laminate is described using FIG. 1a to FIG. 1h and FIG. 2a to FIG. 2i. Furthermore, the present disclosure is not limited to the structures shown in the attached drawings. In addition, the sizes of the components in FIG. 1a to FIG. 1h and FIG. 2a to FIG. 2i are conceptual, and the relative relationship between the sizes of the components is not limited thereto. In addition, in each attached drawing, for components having substantially the same function, the same symbols are marked in all attached drawings, and repeated descriptions are sometimes omitted.

<Example 1 of a method for manufacturing a substrate laminate> Below, Example 1 of a method for manufacturing a substrate laminate is described using FIG. 1a to FIG. 1h. As shown in FIG. 1a, a wafer 3 including a through electrode 4 and having a flattened surface is prepared. An inorganic material layer 5 such as an oxide film is formed on the surface of the wafer 3. The wafer 3 including the electrode 4 is fixed to the carrier 1 via a temporary fixing material 2.

Next, as shown in FIG. 1 b , the inorganic material layer 5 on the surface of the wafer 3 is subjected to the surface activation treatment as described above.

Furthermore, a laminate is prepared which includes an inorganic material layer 15, a wafer 13, and a resin layer 16 in sequence and further includes an electrode 14 penetrating the wafer 13. As shown in FIG1c, a surface protection material 6 is disposed on the side of the inorganic material layer 15 in the laminate.

As shown in FIG1d, after cutting the laminate, the surface protection material 6 is peeled off to obtain a monolithic laminate. The monolithic laminate includes, in sequence, an inorganic material layer 15A, a wafer 13A, and a resin layer 16A that have been singulated. The monolithic laminate further includes an electrode 14A that passes through the monolithic laminate. From the perspective of removing foreign matter, the surface of the monolithic laminate can be cleaned with pure water, a solvent, etc. after the surface protection material 6 is peeled off. At this time, a plurality of monolithic laminates can be cleaned together while being loaded on a frame.

Next, as shown in Fig. 1e, the inorganic material layer 5 on the surface of the wafer 3 is brought into contact with the resin layer 16A of the monolithic laminate and temporarily fixed. At this time, a plurality of monolithic laminates can be temporarily fixed along the width direction and the length direction.

As shown in Fig. 1f, the inorganic material layer 15A of the monolithic laminate temporarily fixed to the wafer 3 is subjected to the surface activation treatment as described above. After the surface activation, the surface of the inorganic material layer 15A can be cleaned with pure water, a solvent, or the like.

According to the procedure shown in FIG. 1c and FIG. 1d, a monolithic laminated body including the inorganic material layer 15B, the wafer 13B and the resin layer 16B which are singulated in sequence is obtained. The monolithic laminated body includes an electrode 14B penetrating the monolithic laminated body. As shown in FIG. 1g, the inorganic material layer 15A of the monolithic laminated body temporarily fixed to the wafer 3 is brought into contact with the resin layer 16B of the monolithic laminated body and temporarily fixed. At this time, multiple monolithic laminated bodies can be temporarily fixed along the width direction and the length direction.

By repeating the processing shown in FIG. 1f and FIG. 1g, the monolithic laminate is laminated in a temporarily fixed state in the height direction. After the lamination of the monolithic laminate is completed, the monolithic laminate is heated at a temperature above 100° C. Thus, the wafer 3 and the monolithic wafer 13B are bonded via the inorganic material layer 5 and the resin layer 16A, and the monolithic laminate laminated in the height direction is bonded via the individual inorganic material layers and the individual resin layers. From the perspective of improving the bonding strength between the electrodes, it is preferable to heat the monolithic laminate at a temperature above 130°C. This allows the components (such as copper) contained in each electrode to diffuse, tending to improve the bonding strength between the electrodes. Through the above, as shown in FIG. 1h, a substrate laminate 100 is obtained.

<Example 2 of the method for manufacturing a substrate laminate> Below, Example 2 of the method for manufacturing a substrate laminate is described using Figures 2a to 2i. In Example 2 of the method for manufacturing a substrate laminate, a wafer not including an electrode is used, a through hole is provided in a substrate laminate that is ultimately not provided with an electrode, and an electrode is provided in the through hole, which is different from Example 1 of the method for manufacturing a substrate laminate.

As shown in FIG. 2a, a wafer 23 with a flat surface is prepared. An inorganic material layer 25 such as an oxide film is formed on the surface of the wafer 23. The wafer 23 is fixed to the carrier 1 via a temporary fixing material 2.

Next, as shown in FIG. 2 b , the inorganic material layer 25 on the surface of the wafer 23 is subjected to the surface activation treatment as described above.

Furthermore, a laminate is prepared which sequentially includes an inorganic material layer 35, a wafer 33, and a resin layer 36. As shown in FIG2c, a surface protection material 6 is disposed on the side of the inorganic material layer 35 in the laminate.

As shown in FIG. 2d, after the laminate is cut, the surface protection material 6 is peeled off to obtain a single-chip laminate. The single-chip laminate includes the inorganic material layer 35A, the wafer 33A and the resin layer 36A which are singulated in sequence. From the perspective of removing foreign matter, the surface of the single-chip laminate can be cleaned with pure water, a solvent, etc. after the surface protection material 6 is peeled off. At this time, a plurality of single-chip laminates can be cleaned together in a state where they are loaded on a frame.

Next, as shown in Fig. 2e, the inorganic material layer 25 on the surface of the wafer 23 is brought into contact with the resin layer 36A of the monolithic laminate and temporarily fixed. At this time, a plurality of monolithic laminates can be temporarily fixed along the width direction and the length direction.

As shown in Fig. 2f, the inorganic material layer 35A of the monolithic laminate temporarily fixed to the wafer 23 is subjected to the surface activation treatment as described above. After the surface activation, the surface of the inorganic material layer 35A can be cleaned using pure water, a solvent, or the like.

According to the procedure shown in FIG. 2c and FIG. 2d, a monolithic laminate body including the inorganic material layer 35B, the wafer 33B and the resin layer 36B which are monolithicized in sequence is obtained. As shown in FIG. 2g, the inorganic material layer 35A of the monolithic laminate body temporarily fixed to the wafer 23 is brought into contact with the resin layer 36B of the monolithic laminate body and temporarily fixed. At this time, a plurality of monolithic laminate bodies can be temporarily fixed along the width direction and the length direction.

By repeating the processing shown in FIG. 2f and FIG. 2g, the monolithic laminate is laminated in a temporarily fixed state in the height direction. After the lamination of the monolithic laminate is completed, the monolithic laminate is heated at a temperature above 100°C. In this way, the wafer 23 and the monolithic wafer 33B can be bonded via the inorganic material layer 25 and the resin layer 36A, and the monolithic laminate laminated in the height direction can be bonded via the individual inorganic material layers and the individual resin layers. As a result, as shown in FIG. 2h, a substrate laminate 200 is obtained.

Furthermore, the substrate laminate 200 is provided with a through hole, i.e., a through hole that penetrates the monolithic laminate along the height direction. As a method for forming the through hole, dry etching using gas, laser stripping, etc. can be listed. Then, an electrode 34 that penetrates the monolithic laminate through the laminate is formed in the through hole. Through the above, as shown in FIG. 2i, a substrate laminate 300 including an electrode 34 that penetrates the monolithic laminate is obtained.

[Substrate laminate] The substrate laminate disclosed in the present invention comprises: A first laminate, which sequentially comprises a first resin layer, a first substrate, and a first inorganic material layer, wherein the first resin layer is disposed on one surface and the first inorganic material layer is disposed on the other surface; and A second laminate, which sequentially comprises a second resin layer, a second substrate, and a second inorganic material layer, wherein the second resin layer is disposed on one surface and the second inorganic material layer is disposed on the other surface, The first laminate and the second laminate are laminated via the first resin layer of the first laminate and the second inorganic material layer of the second laminate. The first and second layers in the substrate laminate disclosed in the present invention may be laminates mounted three-dimensionally on a substrate such as a wafer, and the first and second layers used in the manufacturing method of the substrate laminate disclosed in the present invention may be listed. The preferred shapes of the first and second layers in the substrate laminate are the same as the preferred shapes of the first and second layers in the manufacturing method of the substrate laminate disclosed in the present invention. For example, as specific examples of the first and second laminates in the substrate laminate, there can be cited laminates as shown in FIG. 1c or FIG. 2c, and monolithic laminates as shown in FIG. 1d and FIG. 2d. Furthermore, the first or second laminate in the substrate laminate of the present disclosure is preferably a laminate for a three-dimensional semiconductor device.

In the substrate laminate of the present disclosure, it is preferred that: the first laminate includes an electrode on a portion of the surface of the first resin layer and a portion of the surface of the first inorganic material layer, and the second laminate includes an electrode on a portion of the surface of the second resin layer and a portion of the surface of the second inorganic material layer. Furthermore, the preferred form of the electrode is the same as the preferred form of the electrode in the manufacturing method of the substrate laminate of the present disclosure.

<Variation of the method for manufacturing a substrate laminate> In the variation of the method for manufacturing a substrate laminate of the present disclosure, a laminate (third laminate) formed by laminating a first resin layer, a first substrate, and a third resin layer in order is used instead of the first laminate, and a laminate (third laminate) formed by laminating a second resin layer, a first substrate, and a fourth resin layer in order is used instead of the second laminate, which is different from the method for manufacturing a substrate laminate of the present disclosure. That is, in the laminate (third laminate), the first inorganic material layer in the first laminate is replaced by the third resin layer, and in the laminate (fourth laminate), the second inorganic material layer in the second laminate is replaced by the fourth resin layer. Furthermore, the first resin layer and the fourth resin layer are bonded by step C, thereby obtaining a substrate laminate in the variant.

In the modified example, the first resin layer and the fourth resin layer preferably have different resin compositions, and the resin material used to form the first resin layer and the resin material used to form the fourth resin layer preferably have different resin compositions. Thereby, even if the thickness of the third laminate and the fourth laminate is small, there is a tendency to appropriately suppress the warping of the substrate laminate.

As a resin material for forming the first resin layer, it is preferred to be a resin material capable of forming a resin layer having a composite elastic modulus of 0.1 GPa or more and 10 GPa at 23°C. That is, the composite elastic modulus of the first resin layer at 23°C is preferably 0.1 GPa or more and 10 GPa or less. The resin material for forming the first resin layer and the preferred conditions of the first resin layer are the same as those described in the manufacturing method of the substrate laminate of the present disclosure.

The resin material used to form the fourth resin layer is not particularly limited as long as the composition is different from the resin material used to form the first resin layer. For example, the following materials can be listed: materials that form bonds or structures of polyimide, polyamide, polyamide imide, parylene, polyaryl ether, tetrahydronaphthalene, octahydroanthracene, etc. by crosslinking; materials that form nitrogen-containing ring structures such as polybenzoxazole and polybenzoxazine; materials that form bonds or structures such as Si-O by crosslinking; organic materials such as siloxane modified compounds; benzocyclobutene, epoxy compounds, etc.

The resin material used to form the fourth resin layer is preferably a material that forms a polyimide bond by crosslinking, benzocyclobutene, epoxy compounds, siloxane-modified compounds, etc. The material that forms a polyimide bond by crosslinking is preferably a siloxane compound that forms a polyimide bond by crosslinking, and the siloxane-modified compound is preferably epoxy-modified siloxane.

The disclosure of Japanese Patent Application No. 2022-109052 filed on July 6, 2022 is hereby incorporated by reference in its entirety. All documents, patent applications, and technical specifications described in this specification are hereby incorporated by reference to the same extent as if each document, patent application, or technical specification was specifically and individually described as being incorporated by reference.

1: Carrier 2: Temporary fixing material 3, 13, 13A, 13B, 23, 33, 33A, 33B: Wafer 4, 14, 14A, 14B, 34: Electrode 5, 15, 15A, 15B, 25, 35, 35A, 35B: Inorganic material layer 6: Surface protective material 16, 16A, 16B, 36, 36A, 36B: Resin layer 100, 200, 300: Substrate laminate

Figures 1a to 1h are schematic structural diagrams showing Example 1 of the method for manufacturing a substrate laminate of the present disclosure. Figures 2a to 2i are schematic structural diagrams showing Example 2 of the method for manufacturing a substrate laminate of the present disclosure.

Claims (14)

A method for manufacturing a substrate laminate, comprising: Step A, preparing a first laminate and a second laminate, wherein the first laminate is laminated in the order of a first resin layer, a first substrate, and a first inorganic material layer, wherein the first resin layer is disposed on one surface, and the first inorganic material layer is disposed on the other surface, and the second laminate is laminated in the order of a second resin layer, a second substrate, and a second inorganic material layer, wherein the second resin layer is disposed on one surface, and the second inorganic material layer is disposed on the other surface; Step B, making the first resin layer of the first laminate contact with the second inorganic material layer of the second laminate to laminate the first laminate and the second laminate; and Step C, after step B, heating the first laminate and the second laminate at a temperature above 100°C. A method for manufacturing a substrate laminate as described in claim 1, wherein, the first laminate includes an electrode on a portion of the surface of the first resin layer and a portion of the surface of the first inorganic material layer, the second laminate includes an electrode on a portion of the surface of the second resin layer and a portion of the surface of the second inorganic material layer. The method for manufacturing a substrate laminate as described in claim 2 comprises: Before step B, the second inorganic material layer is subjected to a surface activation treatment. The method for manufacturing a substrate laminate as described in claim 1 comprises: After step C, a step of providing a through hole in the first laminate and the second laminate from the surface of the first inorganic material layer side toward the surface of the second resin layer side, and forming an electrode penetrating the first laminate and the second laminate in the through hole. The method for manufacturing a substrate laminate as described in any one of claims 1 to 4 comprises: Before step B, the second inorganic material layer is cleaned. The method for manufacturing a substrate laminate as described in any one of claims 1 to 4 comprises: Before step B, a step of providing a surface protection layer on the second inorganic material layer. A method for manufacturing a substrate laminate as described in any one of claims 1 to 4, wherein, before the first resin layer and the second inorganic material layer are brought into contact in step B, the composite elastic modulus of the first resin layer at 23°C is greater than 0.1 GPa and less than 20 GPa. A method for manufacturing a substrate laminate as described in any one of claims 1 to 4, wherein, before the first resin layer and the second inorganic material layer are brought into contact in step B, the curing rate of the first resin layer is greater than 70% and less than 100%. A method for manufacturing a substrate laminate as described in any one of claims 1 to 4, wherein, before the first resin layer and the second inorganic material layer are brought into contact in step B, the surface roughness (Ra) of the first resin layer is greater than 0.01 nm and less than 1.2 nm. A method for manufacturing a substrate laminate as described in any one of claims 1 to 4, wherein the surface of the first resin layer has at least one functional group selected from the group consisting of silanol groups, amine groups, epoxy groups, hydroxyl groups, and functional groups containing unsaturated bonds. A method for manufacturing a substrate laminate as described in any one of claims 1 to 4, wherein the first resin layer comprises: Siloxane bonds; and At least one selected from the group consisting of ester bonds, ether bonds, amide bonds, and imide bonds. A method for manufacturing a substrate laminate as described in any one of claims 1 to 4, wherein the second inorganic material layer contains at least one element selected from the group consisting of Si, Ga, Ge and As. A substrate laminate has: A first laminate having a first resin layer, a first substrate, and a first inorganic material layer in sequence, wherein the first resin layer is disposed on one surface and the first inorganic material layer is disposed on another surface; and A second laminate having a second resin layer, a second substrate, and a second inorganic material layer in sequence, wherein the second resin layer is disposed on one surface and the second inorganic material layer is disposed on another surface, The first laminate and the second laminate are laminated via the first resin layer of the first laminate and the second inorganic material layer of the second laminate. The substrate laminate as described in claim 13, wherein, the first laminate includes an electrode on a portion of the surface of the first resin layer and a portion of the surface of the first inorganic material layer, the second laminate includes an electrode on a portion of the surface of the second resin layer and a portion of the surface of the second inorganic material layer.