WO2024010007A1 - Substrate layered body manufacturing method 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°C or higher after said step B.

Description

Manufacturing method of substrate laminate and substrate laminate

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

As electronic devices become smaller, lighter, and more sophisticated, there is a demand for higher integration of semiconductor chips, etc. However, it is difficult to fully meet this demand with miniaturization of circuits. Therefore, in recent years, a method has been proposed in which a plurality of semiconductor substrates (wafers), semiconductor chips, etc. are vertically stacked to form a multilayer three-dimensional structure to achieve high integration. As methods for stacking semiconductor substrates (wafers), semiconductor chips, etc. (hereinafter sometimes referred to as "semiconductor substrates, etc."), methods such as direct bonding of the substrates and methods using adhesives have been proposed (e.g. , Patent Documents 1 to 3).

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

Direct bonding has the problem that voids are likely to occur due to fine irregularities and particles caused by wiring on the surface of the substrate. As a method of stacking semiconductor substrates and the like, a method of bonding inorganic materials such as silicon oxide provided on the substrates is also considered. However, the method of bonding inorganic materials of the substrates has the same problem as direct bonding that voids are likely to occur.

On the other hand, in the case of bonding using an adhesive, the adhesive is applied to the surface of the substrate, and then dried to a semi-cured state, and then the substrates are bonded together. At this time, in order to suppress the generation of voids, it is conceivable to apply an adhesive to the bonding surfaces of the substrates to form an adhesive layer and bond the adhesive layers to each other. Furthermore, in order to increase the bonding strength when bonding the bonding surfaces of the substrates together, it is preferable to subject the bonding surfaces of the substrates to a surface activation treatment such as plasma treatment or FAB (Fast Atom Bombardment) treatment.

However, when surface activation treatment is performed on the adhesive layer, the surface activation treatment may affect the resin contained in the adhesive layer, causing deterioration of the adhesive layer, which may affect reliability. Alternatively, the bonding surface of the substrate may be cleaned in order to remove particles and the like on the bonding surface, but if an adhesive layer is provided on the bonding surface, there is a problem in that cleaning methods are limited. In view of the above, even when a resin layer is provided on the bonding surfaces of the substrates, it is desirable to have a method for manufacturing a substrate stack in which restrictions on the method of surface activation treatment and cleaning treatment of the bonding surfaces of the substrates are suppressed.

One aspect of the present invention has been made in view of the above problems, and includes providing a resin layer on the bonding surface of the substrate, and suppressing restrictions on the method of surface activation treatment and cleaning treatment of the bonding surface of the substrate. An object of the present invention is to provide a method for manufacturing a substrate laminate and a laminate that can be used in this manufacturing method.

Specific means for solving the above problem are as follows.
<1> A first resin layer, a first substrate, and a first inorganic material layer are laminated in this order, the first resin layer is disposed on one surface, and the first inorganic material layer is laminated in this order. A first laminate having a layer disposed on the other surface, a second resin layer, a second substrate, and a second inorganic material layer are laminated in this order, and the second resin layer is a second laminate that is disposed on one surface and the second inorganic material layer is disposed on the other surface;
Laminating the first laminate and the second laminate by bringing the first resin layer of the first laminate into contact with the second inorganic layer of the second laminate. B and
A method for manufacturing a substrate laminate, including a step C of heating the first laminate and the second laminate at 100° C. or higher after the step B.
<2> The first laminate includes an electrode on a part of the surface of the first resin layer and a part of the surface of the first inorganic material layer,
The method for manufacturing a substrate laminate according to <1>, wherein the second laminate includes an electrode on a part of the surface of the second resin layer and a part of the surface of the second inorganic material layer.
<3> The method for manufacturing a substrate laminate according to <2>, including a step of subjecting the second inorganic material layer to a surface activation treatment before the step B.
<4> After the step C, a through hole is provided in the first laminate and the second laminate from the first inorganic layer side surface to the second resin layer side surface. , the method for manufacturing a substrate laminate according to <1>, including the step of forming an electrode penetrating the first laminate and the second laminate in the through hole.
<5> The method for manufacturing a substrate laminate according to any one of <1> to <4>, including a step of cleaning the second inorganic material layer before the step B.
<6> The method for manufacturing a substrate laminate according to any one of <1> to <5>, including the step of providing a surface protective layer on the second inorganic material layer before the step B.
<7> Before the first resin layer and the second inorganic layer are brought into contact in the step B, the composite modulus of elasticity of the first resin layer at 23° C. is 0.1 GPa or more and 20 GPa or less. The method for manufacturing a substrate laminate according to any one of <1> to <6>.
<8> Before the first resin layer and the second inorganic layer are brought into contact in the step B, the curing rate of the first resin layer is 70% or more and 100% or less, < The method for manufacturing a substrate laminate according to any one of items 1> to <7>.
<9> Before the first resin layer and the second inorganic layer are brought into contact in the step B, the surface roughness (Ra) of the first resin layer is 0.01 nm or more and 1. The method for manufacturing a substrate laminate according to any one of <1> to <8>, which has a thickness of 2 nm or less.
<10> The surface of the first resin layer has at least one functional group selected from the group consisting of a silanol group, an amino group, an epoxy group, a hydroxyl group, and a functional group having an unsaturated bond, <1> to <9>.The method for manufacturing a substrate laminate according to any one of 9>.
<11> The first resin layer is
siloxane bond,
The method for producing a substrate laminate according to any one of <1> to <10>, including at least one selected from the group consisting of an ester bond, an ether bond, an amide bond, and an imide bond.
<12> The substrate according to any one of <1> to <11>, wherein the second inorganic layer contains at least one element selected from the group consisting of Si, Ga, Ge, and As. Method for manufacturing a laminate.
<13> The first resin layer, the first substrate, and the first inorganic layer are arranged in this order, the first resin layer is disposed on one surface, and the first inorganic layer is disposed on the other surface of the first laminate;
It has a second resin layer, a second substrate, and a second inorganic material layer in this order, the second resin layer being disposed on one surface, and the second inorganic material layer being disposed on the other surface. a second laminate placed on the surface of the
has
The first laminate and the second laminate are laminated via the first resin layer of the first laminate and the second inorganic layer of the second laminate. , substrate laminate.
<14> The first laminate includes an electrode on a part of the surface of the first resin layer and a part of the surface of the first inorganic material layer,
The second laminate is a substrate laminate according to <13>, wherein the second laminate includes an electrode on a part of the surface of the second resin layer and a part of the surface of the second inorganic material layer.

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

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

In the present disclosure, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In the present disclosure, a "substrate laminate" refers to a laminate having a structure in which two substrates, that is, a first substrate and a second substrate are joined via a first resin layer and a second inorganic material layer. means. Note that the substrate laminate may have three or more substrates, and two of the three or more substrates are bonded via the first resin layer and the second inorganic material layer. It may have a structure.
In the present disclosure, a "substrate" refers to "at least one of a first substrate and a second substrate," and a "resin layer" refers to "at least one of a first resin layer and a second resin layer." The term "inorganic layer" refers to "at least one of the first inorganic layer and the second inorganic layer."

[Method for manufacturing substrate laminate]
In the method for manufacturing a substrate laminate of the present disclosure, a first resin layer, a first substrate, and a first inorganic material layer are laminated in this order, and the first resin layer is disposed on one surface. A first laminate in which the first inorganic material layer is disposed on the other surface, a second resin layer, a second substrate, and a second inorganic material layer are laminated in this order. , a step A of preparing a second laminate in which the second resin layer is disposed on one surface and the second inorganic material layer is disposed on the other surface; 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 layer of the second laminate; , after the step B, includes a step C of heating the first laminate and the second laminate at 100° C. or higher.

In the method for manufacturing a substrate laminate of the present disclosure, at least two laminates in which a resin layer, a substrate, and an inorganic material layer are laminated in this order are prepared in step A. 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. Laminate. Then, in step C, the two laminated bodies are heated at 100°C or higher to join them through the resin layer (first resin layer) and inorganic layer (second inorganic layer). A substrate laminate having a structure is obtained. In the present disclosure, after surface activation treatment, cleaning treatment, etc. are performed on the surface of the inorganic material layer, two substrates can be bonded via the resin layer and the inorganic material layer. This makes it possible to increase the bonding strength of the bonding surface and remove particles attached to the surface of the inorganic layer without performing surface activation treatment, cleaning treatment, etc. on the surface of the resin layer. . Therefore, there is provided a method for manufacturing a substrate stack in which a resin layer is provided on the bonding surfaces of the substrates, and limitations on the method of surface activation treatment and cleaning treatment of the bonding surfaces of the substrates are suppressed.

[Process A]
The method for manufacturing a substrate laminate according to the present disclosure includes a 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 this order, the first resin layer is disposed on one surface, and the first inorganic material layer is arranged on one surface. A layer is placed on the other surface. Similarly, the second laminate includes a second resin layer, a second substrate, and a second inorganic material layer in this order, the second resin layer is disposed on one surface, and the second an inorganic layer is disposed on the other surface.

(First substrate and second substrate)
The materials of the first substrate and the second substrate are not particularly limited, and may be any commonly used material. Note that the materials of the first substrate and the second substrate may be the same or different.
The first substrate and the second substrate include Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and It is preferable that at least one element selected from the group consisting of Nb is included. The materials of the first substrate and the second substrate include, for example, semiconductors: Si, InP, GaN, GaAs, InGaAs, InGaAlAs, SiC, oxides, carbides, nitrides: borosilicate glass (for example, Pyrex (registered trademark) )), quartz glass (SiO ₂ ), sapphire, ZrO ₂ , Si ₃ N ₄ , AlN, piezoelectric, dielectric: BaTiO ₃ , LiNbO ₃ , SrTiO ₃ , diamond, metal: Al, Ti, Fe, Cu, Ag , Au, Pt, Pd, Ta, Nb, etc.

The first substrate and the second substrate may be made of other resins such as polydimethylsiloxane (PDMS), epoxy resin, phenol resin, polyimide, benzocyclobutene resin, and polybenzoxazole.

The first substrate and the second substrate may have a multilayer structure. For example, a structure in which an inorganic layer such as silicon oxide, silicon nitride, or SiCN (silicon carbonitride) is formed on the surface of a silicon substrate, etc., or a structure in which an inorganic layer such as silicon oxide, silicon nitride, SiCN (silicon carbonitride), etc. , Chem), imide cross-linked siloxane resin, epoxy-modified siloxane, porous silica, organic cross-linked siloxane, organic-inorganic composite low-k such as black diamond (Applied Materials), etc., on a silicon substrate. Another example is a structure in which a complex of inorganic and organic substances is formed.

Each material is mainly used for the following:
Si is used in semiconductor memories, LSI stacks, CMOS image sensors, MEMS encapsulation, optical devices, LEDs, etc.;
SiO ₂ can be used for semiconductor memory, LSI stacking, MEMS sealing, microchannels, CMOS image sensors, optical devices, LEDs, etc.;
PDMS is a microchannel;
InGaAlAs, InGaAs, InP are optical devices;
InGaAlAs, GaAs, GaN, LED, etc.

The thickness of the first substrate and the second substrate is 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 also not particularly limited. For example, when the first substrate and the second substrate are silicon substrates, they may be silicon substrates on which an interlayer insulating layer (low-k film) is formed. ), fine through holes, etc. may be formed.

In the method for manufacturing a substrate laminate of the present disclosure, from the viewpoint of bonding strength, the surface of the first substrate that contacts the first resin layer and the surface of the second substrate that contacts the second resin layer. You may perform surface treatment on at least one of them. For example, by performing the above-mentioned surface treatment, at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, a carboxy group, an amino group, and a mercapto group may be formed.

Examples of the above-mentioned surface treatment include plasma treatment, chemical treatment, and ozone treatment such as ultraviolet (UV) ozone treatment.

Hydroxyl groups can be provided on the surfaces of the first substrate and the second substrate by subjecting the surfaces to a surface treatment such as plasma treatment, chemical treatment, or ozone treatment such as UV ozone treatment.
The hydroxyl groups include Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, Preferably, it exists in a bonded state with at least one element selected from the group consisting of In, Ta, and Nb. It is preferable that 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 have silanol groups containing hydroxyl groups.

The epoxy group can be provided on each of the surfaces of the first substrate and the second substrate by performing surface treatment such as silane coupling with epoxy silane.

A carboxyl group can be provided on each of the surfaces of the first substrate and the second substrate by performing surface treatment such as silane coupling with carboxysilane.

The amino group can be provided on each of the surfaces of the first substrate and the second substrate by performing surface treatment such as silane coupling with aminosilane.

The mercapto group can be provided on each of the surfaces of the first substrate and the second substrate by performing surface treatment such as silane coupling with mercaptosilane.

Furthermore, in order to increase 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 placed on one surface of the first substrate, and the second resin layer is a layer placed on one surface of the second substrate. For example, the first resin layer and the second resin layer are 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. It is formed by curing the respective layers.

The resin material contained in the resin composition is not particularly limited, and examples thereof include materials whose bond or structure is formed by crosslinking, such as polyimide, polyamide, polyamideimide, parylene, polyarylene ether, tetrahydronaphthalene, and octahydroanthracene. Examples include materials in which a nitrogen ring-containing structure is formed such as polybenzoxazal, polybenzoxazine, etc., materials in which a bond or structure is formed by crosslinking such as Si--O, and 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 structures having Si—O bonds (siloxane bonds) include structures represented by formulas (1) to (3) shown below.

In a structure having a Si-O bond (siloxane bond), the group bonding to Si may be substituted with an alkylene group, a phenylene group, etc. For example, (-O-) _x (R ₁ ) _y Si- (R ₂ )-Si(R ₁ ) _y (-O-) A structure having _x , etc. (R ₁ represents a methyl group, etc., R ₂ represents an alkylene group, a phenylene group, etc. is an integer greater than or equal to 0, and x+y is 3).

Examples of materials in which Si—O bonds are formed by crosslinking include compounds represented by the following formulas (4) and (5). Further, the structures represented by formulas (1) and (2) can be produced, for example, by heating and reacting the compounds represented by formulas (4) and (5).

For example, when the resin material includes a material such as polyimide, polyamide, polyamideimide, etc. whose bond or structure is formed by crosslinking, the resin material has a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. , a compound (A) having a weight average molecular weight of 90 to 400,000, and 3 -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule. A crosslinking agent having at least three -C(=O)OX groups, one or more of which are -C(=O)OH groups, and a weight average molecular weight of 200 or more and 2000 or less. It is preferable to include (B).

(Compound (A))
Compound (A) has a cationic functional group containing 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. The cationic functional group is not particularly limited as long as it can be positively charged 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, a "primary nitrogen atom" refers to a nitrogen atom that is bonded to only two hydrogen atoms and one atom other than hydrogen atoms (for example, nitrogen contained in a primary amino group ( _-NH2 group)). or a nitrogen atom (cation) bonded to only three hydrogen atoms and one non-hydrogen atom.
In addition, "secondary nitrogen atom" refers to a nitrogen atom that is bonded to only 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) bonded only to two hydrogen atoms and two atoms other than hydrogen atoms.
Furthermore, a "tertiary nitrogen atom" refers to a nitrogen atom that is bonded to only three atoms other than hydrogen atoms (i.e., a nitrogen atom that is a functional group represented by the following formula (b)), or a hydrogen atom. Refers to a nitrogen atom (cation) that is bonded to only one and three atoms other than hydrogen atoms.

In formulas (a) and (b), * indicates a bonding position with an atom other than a hydrogen atom.
Here, the functional group represented by the formula (a) may be a functional group that constitutes a part of a secondary amino group (-NHR ^a group; here, R ^a represents an alkyl group). However, it may also be a divalent linking group contained in the backbone of the polymer.
In addition, the functional group (i.e., tertiary nitrogen atom) represented by the formula (b) is a tertiary amino group (-NR ^b R ^c group; where R ^b and R ^c each independently represent an alkyl It may be a functional group constituting a part of (representing a group), or it may be a trivalent linking group contained in the skeleton of the polymer.

The weight average molecular weight of compound (A) is 90 or more and 400,000 or less. Examples of the compound (A) include aliphatic amines, compounds having a siloxane bond (Si-O bond) and an amino group, and amine compounds having a ring structure without having an Si-O bond in the molecule. It will be done. When compound (A) is an aliphatic amine, the weight average molecular weight is preferably 10,000 or more and 200,000 or less. When the compound (A) is a compound having a siloxane bond (Si-O bond) and an amino group, the weight average molecular weight is preferably 130 or more and 10,000 or less, more preferably 130 or more and 5,000 or less, and 130 or more. More preferably, it is 2000 or less. When the compound (A) is an amine compound that does not have a Si—O bond in its molecule and has a ring structure, the weight average molecular weight is preferably 90 or more and 600 or less.

Note that in the present disclosure, the weight average molecular weight refers to the weight average molecular weight in terms of polyethylene glycol measured by GPC (Gel Permeation Chromatography) method for other than monomers.
Specifically, the weight average molecular weight was determined using an aqueous solution with a sodium nitrate concentration of 0.1 mol/L as a developing solvent, an analyzer Shodex DET RI-101, and two types of analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL- manufactured by Tosoh). CP) at a flow rate of 1.0 mL/min, and the refractive index is calculated using analysis software (Empower 3 manufactured by Waters) using polyethylene glycol/polyethylene oxide as a standard product.

Moreover, the compound (A) may further have an anionic functional group, a nonionic functional group, etc. as necessary.
The nonionic functional group may be a hydrogen bond accepting group or a hydrogen bond donating group. Examples of the nonionic functional group include a hydroxy group, a carbonyl group, an ether group (-O-), and the like.
The anionic functional group is not particularly limited as long as it can be negatively charged. Examples of the anionic functional group include a carboxylic acid group, a sulfonic acid group, and a sulfuric acid group.

Compound (A) includes aliphatic amines, more specifically ethyleneimine, propyleneimine, butyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine, trimethyleneimine, tetramethyleneimine, Examples include polyalkyleneimine, which is a polymer of alkyleneimine such as pentamethyleneimine, hexamethyleneimine, and octamethyleneimine; polyallylamine; and polyacrylamide.

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

It is also preferable that the compound (A) is a derivative of the above-mentioned polyalkyleneimine (polyalkyleneimine derivative; particularly preferably polyethyleneimine derivative). The polyalkylene imine derivative is not particularly limited as long as it is a compound that can be produced using the above polyalkylene imine. Specifically, polyalkyleneimine derivatives are obtained by introducing an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), an aryl group, etc. into polyalkyleneimine, and polyalkyleneimine derivatives obtained by introducing a crosslinkable group such as a hydroxyl group into polyalkyleneimine. Examples include polyalkyleneimine derivatives.
These polyalkylene imine derivatives can be produced by a conventional method using the above polyalkylene imine. Specifically, it can be produced, for example, in accordance with the method described in JP-A-6-016809.

Further, as the polyalkylene imine derivative, a highly branched polyalkylene imine obtained by increasing the degree of branching of the polyalkylene imine by reacting the polyalkylene imine with a monomer containing a cationic functional group is also preferable.
As a method for obtaining a highly branched polyalkylene imine, for example, a polyalkylene imine having a plurality of secondary nitrogen atoms in its skeleton is reacted with a cationic functional group-containing monomer, and the plurality of secondary nitrogen atoms are A method of substituting at least one of them with a cationic functional group-containing monomer, a method in which a polyalkylene imine having a plurality of primary nitrogen atoms at the terminal is reacted with a cationic functional group-containing monomer, and the plurality of primary nitrogen atoms Examples include a method of replacing at least one of them with a cationic functional group-containing monomer.
Examples of the cationic functional group introduced to improve the degree of branching include aminoethyl group, aminopropyl group, diaminopropyl group, aminobutyl group, diaminobutyl group, triaminobutyl group, etc. An aminoethyl group is preferred from the viewpoint of reducing the functional group equivalent weight and increasing the cationic functional group density.

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

Examples of the compound (A) include, in addition to the aforementioned aliphatic amines, compounds having an Si--O bond and an amino group. Examples of the compound having an Si--O bond and an amino group include siloxane diamine, a silane coupling agent having an amino group, and a siloxane polymer of a silane coupling agent having an amino group.
Examples of the silane coupling agent having an amino group include a compound represented by the following formula (A-3).

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

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, N-(2-aminoethyl)- 11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzyl Aminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[ 2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, trimethoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, Examples include N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane, and hydrolysates thereof.

Examples of the silane coupling agent containing an amino group other than formula (A-3) include N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl] silyl)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-( Examples include triethoxysilyl)phenyl)benzamide, 5-(ethoxydimethylsilyl)benzene-1,3-diamine, and hydrolysates thereof.

The aforementioned silane coupling agents having an amino group may be used alone or in combination of two or more. Furthermore, a silane coupling agent having an amino group and a silane coupling agent not having an amino group may be used in combination. For example, a silane coupling agent having a mercapto group may be used to improve adhesion to metals.

Furthermore, a polymer (siloxane polymer) formed from these silane coupling agents via a siloxane bond (Si-O-Si) may be used. For example, from the hydrolyzate of 3-aminopropyltrimethoxysilane, a polymer having a linear siloxane structure, a polymer having a branched siloxane structure, a polymer having a cyclic siloxane structure, a polymer having a cage-shaped siloxane structure, etc. is obtained. The cage-like siloxane structure is represented by the following formula (A-1), for example.

Examples of the siloxane diamine include a compound 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.

Further, as the siloxane diamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in formula (A-2), i=0, j=1), 1,3-bis(2-aminoethyl Examples include amino)propyltetramethyldisiloxane (in formula (A-2), i=1, j=1).

Examples of the compound (A) include, in addition to the aforementioned aliphatic amines and compounds having an Si-O bond and an amino group, amine compounds that do not have a Si-O bond in the molecule and have a ring structure. . Among these, amine compounds having a ring structure and having a weight average molecular weight of 90 or more and 600 or less are preferred, and do not have a Si--O bond in the molecule. Examples of the amine compound having a ring structure and having a weight average molecular weight of 90 or more and 600 or less without having an Si--O bond in the molecule include alicyclic amines, aromatic ring amines, heterocyclic amines, and the like. The molecule may have multiple ring structures, and the multiple ring structures may be the same or different. As the amine compound having a ring structure, a compound having an aromatic ring is more preferable because a more thermally stable compound is easily obtained.
In addition, as an amine compound having a ring structure and having a weight average molecular weight of 90 or more and 600 or less, which does not have a Si-O bond in the molecule, it may form a thermally crosslinked structure such as amide, amide-imide, or imide together with the crosslinking agent (B). Compounds having a primary amino group are preferred because they are easy to use and can improve heat resistance. Furthermore, as for the above-mentioned amine compound, two primary amino groups are used because it is easy to increase the number of thermally crosslinked structures such as amide, amide-imide, imide, etc. together with the crosslinking agent (B), and the heat resistance can be further improved. Diamine compounds having three primary amino groups, triamine compounds having three primary amino groups, and the like are preferred.

Examples of the alicyclic amine include cyclohexylamine and dimethylaminocyclohexane.
Examples of aromatic ring amines include diaminodiphenyl ether, xylene diamine (preferably paraxylene diamine), diaminobenzene, diaminotoluene, methylene dianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl, diaminobenzophenone, and diaminobenzanilide. , bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcin, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2 Examples include '-dimethylbenzidine, tris(4-aminophenyl)amine, 2,7-diaminofluorene, 1,9-diaminofluorene, and dibenzylamine.
The heterocycle of the heterocyclic amine includes a heterocycle containing a sulfur atom as a heteroatom (for example, a thiophene ring), or a heterocycle containing a nitrogen atom as a heteroatom (for example, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring). , 5-membered rings such as triazole ring; 6-membered rings such as isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, triazine ring; indole ring, indoline ring, quinoline ring, acridine ring, fused rings such as a naphthyridine ring, a quinazoline ring, a purine ring, a quinoxaline ring, etc.).
For example, examples of the heterocyclic amine having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, tris(4-aminophenyl)amine, and the like.
Furthermore, examples of amine compounds having both a heterocycle and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine.

Since the compound (A) has a primary or secondary amino group, it does not interact with functional groups such as hydroxyl groups, epoxy groups, carboxy groups, amino groups, and mercapto groups that may exist on the surfaces of the first substrate and the second substrate. The substrates can be strongly bonded to each other by electrical interaction or by forming a close covalent bond with the functional group.
Moreover, since the compound (A) has a primary or secondary amino group, it easily dissolves in the polar solvent (D) described below. By using a compound (A) that is easily soluble in a polar solvent (D), it has a high affinity with the hydrophilic surface of a substrate such as a silicon substrate, making it easier to form a smooth film and making it easier to form a smooth film. And the thickness of the second resin layer can be reduced.

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

When the compound (A) contains a compound having an Si-O bond and an amino group, the ratio of the total number of primary nitrogen atoms and secondary nitrogen atoms to the number of silicon atoms in the compound (A) ( It is preferable that the ratio (total number of primary nitrogen atoms and secondary nitrogen atoms/number of silicon atoms) is 0.2 or more and 5 or less from the viewpoint of forming a smooth thin film.

When the compound (A) contains a compound having an Si-O bond and an amino group, from the viewpoint of adhesion between substrates, the methyl group bonded to Si in the compound having an Si-O bond and an amino group is It is preferable that the molar ratio of non-crosslinkable groups such as (non-crosslinkable group)/Si<2 is satisfied. By satisfying this relationship, the density of crosslinking (crosslinking between Si-O-Si bonds and amide bonds, imide bonds, etc.) of the formed film increases, the substrates have sufficient adhesive strength, and the substrates can be peeled off. It is assumed that this can be suppressed.

As mentioned above, 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 proportion of the primary nitrogen atom in the total nitrogen atoms in the compound (A) is preferably 20 mol% or more, and 25 mol% It is more preferable that it is above, and even more preferable that it is 30 mol% or more. Further, the compound (A) may have a cationic functional group that contains a primary nitrogen atom and does not contain any nitrogen atoms other than the primary nitrogen atom (e.g., a secondary nitrogen atom, a tertiary nitrogen atom). good.

Further, when the compound (A) contains a secondary nitrogen atom, the proportion of the secondary nitrogen atom in the total nitrogen atoms in the compound (A) is preferably 5 mol% or more and 50 mol% or less, More preferably, it is 10 mol% or more and 45 mol% or less.

In addition, the compound (A) may contain a tertiary nitrogen atom in addition to the primary nitrogen atom and the secondary nitrogen atom, and when the compound (A) contains a tertiary nitrogen atom, the compound (A) The proportion of tertiary nitrogen atoms in the total nitrogen atoms in the carbon fiber is preferably 20 mol% or more and 50 mol% or less, and more preferably 25 mol% or more and 45 mol% or less.

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, and for example, the content of the component derived from the compound (A) in the first resin layer or the second resin layer is not particularly limited. The content can be 1% by mass or more and 82% by mass or less, preferably 5% by mass or more and 82% by mass or less, and more preferably 13% by mass or more and 82% by mass or less.

(Crosslinking agent (B))
The crosslinking agent (B) has 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, and has 3 or more -C Among the (=O)OX groups (hereinafter also referred to as "COOX"), one or more and six or less are -C(=O)OH groups (hereinafter also referred to as "COOH"), and the weight average molecular weight is 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, but preferably , a compound having 3 or more and 6 or less -C(=O)OX groups in the molecule, more preferably a compound having 3 or 4 -C(=O)OX groups in the molecule.

In the crosslinking agent (B), examples of X in the -C(=O)OX group include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and among them, a hydrogen atom, a methyl group, an ethyl group, and a propyl group. is preferred. Note that X in the -C(=O)OX group may be the same or different.

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

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

It is preferable that the crosslinking agent (B) has a ring structure within the molecule. Examples of the ring structure include an alicyclic structure and an aromatic ring structure. Further, the crosslinking agent (B) may have a plurality of ring structures within the molecule, and the plurality of ring structures may be the same or different.

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

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

The ring structure that the crosslinking agent (B) has in its 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. At least one of a benzene ring and a naphthalene ring is more preferred in terms of further improving the heat resistance of the second resin layer.

As mentioned above, the crosslinking agent (B) may have a plurality of ring structures in its molecule, and when the ring structure is benzene, it may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, etc.

The crosslinking agent (B) preferably has a fluorine atom in the molecule, more preferably has 1 to 6 fluorine atoms in the molecule, and has 3 to 6 fluorine atoms in the molecule. It is further preferable to have. For example, the crosslinking agent (B) may have a fluoroalkyl group in the molecule, specifically, a trifluoroalkyl group or a hexafluoroisopropyl group.

Further, as the crosslinking agent (B), carboxylic acid compounds such as alicyclic carboxylic acid, benzene carboxylic acid, naphthalene carboxylic acid, diphthalic acid, and fluorinated aromatic ring carboxylic acid; alicyclic carboxylic acid ester, benzene carboxylic acid ester, naphthalene carboxylic acid Examples include carboxylic acid ester compounds such as carboxylic acid ester, diphthalic acid ester, and fluorinated aromatic ring carboxylic acid ester. The carboxylic acid ester compound has a carboxy group (-C(=O)OH group) in the molecule, and in three or more -C(=O)OX groups, at least one X has a carbon number. It is a compound having 1 or more and 6 or less alkyl groups (that is, having an ester bond). In the present disclosure, since the crosslinking agent (B) is a carboxylic acid ester compound, aggregation due to association between the compound (A) and the crosslinking agent (B) is suppressed, aggregates and pits are reduced, and film thickness can be adjusted. becomes easier.

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

The carboxylic acid ester compound is preferably a compound containing three or less carboxy groups (-C(=O)OH groups) and three or less ester bonds in the molecule; It is more preferable that the compound contains two or less ester bonds and contains two or less ester bonds.

Further, in the carboxylic acid ester compound, when X is an alkyl group having 1 to 6 carbon atoms in three or more -C(=O)OX groups, X is a methyl group, an ethyl group, a propyl group, A butyl group is preferable, but an ethyl group or a propyl group is preferable from the viewpoint of further suppressing aggregation due to association between 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, and 1,3,5-cyclohexane. Alicyclic carboxylic acids such as tricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; 1 , 2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, 3,4'-biphthalic acid, P-phenylenebis(trimellitate acid), benzenepentacarboxylic acid, mellitic acid, etc. Carboxylic acids; Naphthalenecarboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic acid; 3,3',5,5'-tetracarboxydiphenylmethane, 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'-(ethyne-1,2- 4,4'-(Ethyne-1,2-diyl)diphthalic acid, 4,4'-(1,4-phenylenebis(oxy))diphthalic acid 4-phenylenebis(oxy))diphthalic acid), 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid (4,4'-([1,1' -biphenyl]-4,4'-diylbis(oxy))diphthalicacid), 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid(4,4'-((oxybis( Diphthalic acid such as 4,1-phenylene))bis(oxy))diphthalic acid); Perylene carboxylic acid such as perylene-3,4,9,10-tetracarboxylic acid; Anthracene-2,3,6,7-tetra Anthracenecarboxylic acid such as carboxylic acid; 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, 1 , 4-ditrifluoromethylpyromellitic acid and other fluorinated aromatic ring carboxylic acids.

Specific examples of the carboxylic acid ester compounds include compounds in which at least one carboxy group in the specific examples of the carboxylic acid compounds described above 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).

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

A half-esterified compound can be produced, for example, by mixing a carboxylic acid anhydride, which is an anhydride of the aforementioned carboxylic acid compound, with an alcohol solvent and ring-opening the carboxylic acid anhydride.

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, and for example, the content of the component derived from the compound (A) is The ratio of the number of carbonyl groups (-(C=O)-Y) in the substance derived from the crosslinking agent (B) to the number ((-(C=O)-Y)/N) is independently 0. It is preferably 1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and even more preferably 0.4 or more and 2.2 or less. Here, in -(C=O)-Y, Y represents an imide-bridged or amide-bridged nitrogen atom, OH, or an ester group. (-(C=O)-Y)/N is 0.1 or more and 3.0 or less, so that the first resin layer and the second resin layer preferably have a crosslinked structure of amide, amide-imide, imide, etc. , and has superior heat resistance.

(Polar solvent (D))
In step A, a resin composition containing a resin material may be applied onto the surface of at least one of the first substrate and the second substrate. At this time, the resin composition containing the resin material preferably contains a polar solvent (D) together with the resin materials such as the above-mentioned compound (A) and crosslinking agent (B). Here, the polar solvent (D) refers to a solvent having a dielectric constant of 5 or more at room temperature. Specific examples of the polar solvent (D) include protic inorganic compounds such as water and heavy water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, Alcohols such as cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, glycerin; Ethers such as tetrahydrofuran and dimethoxyethane; furfural, acetone, ethyl methyl ketone , aldehydes and ketones such as cyclohexane; acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, Examples include acid derivatives such as N-methyl-2-pyrrolidone and hexamethylphosphoric acid amide; nitriles such as acetonitrile and propionitrile; nitro compounds such as nitromethane and nitrobenzene; and sulfur compounds such as dimethyl sulfoxide. The polar solvent (D) preferably includes a protic solvent, more preferably includes water, and even more preferably includes ultrapure water.
The content of the polar solvent (D) in the resin composition is not particularly limited, and is, for example, 1.0% by mass or more and 99.99896% by mass or less, and 40% by mass or more and 99.9% by mass or less based on the entire resin composition. It is preferably 99896% by mass or less.
The boiling point of the polar solvent (D) is such that the polar solvent (D) is volatilized by heating when forming the first resin layer and the second resin layer, and In terms of reducing the amount of residual solvent, the temperature is preferably 150°C or lower, more preferably 120°C or lower.

(Additive (C))
The resin composition containing the resin material may contain an additive (C) in addition to the above-mentioned compound (A), the resin material such as the crosslinking agent (B), the polar solvent (D), and the like. As the additive (C), an acid having a carboxyl group and having a weight average molecular weight of 46 to 195 (C-1), a base having a nitrogen atom and having a weight average molecular weight of 17 to 120 and not having a ring structure (C-2) can be mentioned. Further, although the additive (C) is vaporized by heating when forming the first resin layer and the second resin layer, the first resin layer and the second resin layer in the substrate laminate of the present disclosure are , an additive (C) may be included.

The acid (C-1) is an acid having a weight average molecular weight of 46 or more and 195 or less and having a carboxy group. By including the acid (C-1) as the additive (C), the amino group in the compound (A) and the carboxy group in the acid (C-1) form an ionic bond, resulting in crosslinking with the compound (A). It is presumed that aggregation due to association with agent (B) is suppressed. More specifically, the interaction between the ammonium ion derived from the amino group in compound (A) and the carboxylate ion derived from the carboxy group in acid (C-1) (for example, electrostatic interaction) ) is stronger than the interaction between the ammonium ion derived from the amino group in the crosslinking agent (B) and the carboxylate ion derived from the carboxy group in the crosslinking agent (B), so it is presumed that aggregation is suppressed. Note that the present invention is not limited in any way by the above speculation.

The acid (C-1) is not particularly limited as long as it has a carboxy group and has 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, the acid (C-1) includes 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, Examples include terephthalic acid, picolinic acid, salicylic acid, and 3,4,5-trihydroxybenzoic acid.

In the present disclosure, the content of the acid (C-1) in the resin composition containing the resin material is not particularly limited, and for example, the content of the acid (C-1) relative to the total number of nitrogen atoms in the compound (A) is The ratio of the number of carboxy groups (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 having a weight average molecular weight of 17 or more and 120 or less. The resin composition containing the resin material includes a base (C-2) as an additive (C), so that the carboxy group in the crosslinking agent (B) and the amino group in the base (C-2) form an ionic bond. It is presumed that by doing so, aggregation due to association between compound (A) and crosslinking agent (B) is suppressed. More specifically, the interaction between the carboxylate ion derived from the carboxy group in the crosslinking agent (B) and the ammonium ion derived from the amino group in the base (C-2) is derived from the amino group in the compound (A). It is assumed that aggregation is suppressed because the interaction is stronger than the interaction between the ammonium ion and the carboxylate ion derived from the carboxy group in the crosslinking agent (B). Note that the present invention is not limited in any way by the above speculation.

The base (C-2) is not particularly limited as long as it has a nitrogen atom and has a weight average molecular weight of 17 or more and 120 or less and does not have a ring structure, and includes monoamine compounds, diamine compounds, and the like. More specifically, the base (C-2) includes ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, N-(2-aminoethyl)ethanolamine, and N-(2-aminoethyl)ethanolamine. Examples include ethyl)glycine.

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

When insulation properties are required for the first resin layer and the second resin layer of the substrate laminate of the present disclosure, tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylethane, bistriethoxysilane, bistriethoxysilane, bistriethoxysilane, bistriethoxysilane, etc. Ethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1 , 3,5,7-tetrahydroxylcyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisylethylene, 1,3,5-trimethyl-1,3,5-trimethyl-1 , 3,5-triethoxy-1,3,5-trisilacyclohexane may be mixed. Furthermore, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, etc. may be mixed in order to improve the hydrophobicity of the first resin layer and the second resin layer having insulating properties. These compounds may be mixed to control etching selectivity.

The resin composition containing the resin material may contain a solvent other than the polar solvent (D), such as normal hexane.

Further, the resin composition containing the resin material may contain phthalic acid, benzoic acid, etc., or derivatives thereof, for example, to improve electrical characteristics.
Further, the resin composition containing the resin material may contain benzotriazole or a derivative thereof, for example, in order to suppress corrosion of copper.

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

Furthermore, when acid (C-1) is used as additive (C), it is preferable to mix a mixture of acid (C-1) and compound (A) with crosslinking agent (B). That is, it is preferable to mix compound (A) and acid (C-1) in advance before mixing compound (A) and crosslinking agent (B). As a result, when compound (A) and crosslinking agent (B) are mixed, cloudiness and gelation of the resin composition containing the resin material (if gelation occurs, it may take time for the resin composition to become transparent; undesirable) can be suitably suppressed.

Furthermore, when using the base (C-2) as the additive (C), it is preferable to mix the mixture of the base (C-2) and the crosslinking agent (B) with the compound (A). That is, it is preferable to mix the crosslinking agent (B) and the base (C-2) in advance before mixing the compound (A) and the crosslinking agent (B). As a result, when compound (A) and crosslinking agent (B) are mixed, cloudiness and gelation of the resin composition containing the resin material (if gelation occurs, it may take time for the resin composition to become transparent; undesirable) can be suitably suppressed.

Examples of methods for applying the resin material on the surface of at least one of the first substrate and the second substrate include vapor deposition polymerization, CVD (chemical vapor deposition), and ALD (atomic layer deposition). Application methods include a film method, a dipping method, a spray method, a spin coating method, and a bar coating method. When applying a resin material by a coating method, it is preferable to apply a resin composition containing the above-mentioned resin material. For example, when forming a film with a micron-sized film thickness, it is preferable to use a bar coating method, and when forming a film with a nano-sized film thickness (several nanometers to several hundred nanometers), a spin coating method is used. It is preferable. Note that the film thickness of the resin material may be adjusted as appropriate depending on the intended thickness of the first resin layer and the second resin layer.

For example, the method of applying the resin material by spin coating is not particularly limited, and for example, a resin composition containing the resin material is dripped onto the surface of the first substrate while rotating the first substrate with a spin coater. Then, a method can be used in which the first substrate is dried by increasing the number of rotations.
In the method of applying a resin material by spin coating, there are no particular restrictions on various conditions such as the number of rotations of the substrate, the amount and time of dropping the resin composition containing the resin material, and the number of rotations of the substrate during drying. It may be adjusted as appropriate while considering the thickness of the resin material used.

Regarding the substrate to which the resin material has been applied, the substrate to which the resin material has been applied may be cleaned in order to remove the excess resin material applied. Examples of the cleaning method include wet cleaning using a rinsing liquid such as a polar solvent, plasma cleaning, and the like.

In the method for manufacturing a substrate laminate according to the present disclosure, step A includes curing the resin material applied to one surface of the first substrate and one surface of the second substrate to form the first resin layer and the second substrate. The method may include a step of forming a resin layer. For example, the first resin layer and the second resin layer are formed by curing the resin material by heating or the like. At this time, when the resin material contains a thermosetting compound, it is cured by heating the resin material at a temperature equal to or higher than the curing temperature.

Preferably, the resin material applied to one surface of the first substrate and one surface of the second substrate is cured by heating at 100° C. to 450° C.
Note that the above-mentioned temperature refers to the temperature of the surface 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. Further, components in the resin material react to obtain a cured product, and a first resin layer and a second resin layer containing the cured product are formed.
The temperature is preferably 150°C to 450°C, more preferably 180°C to 400°C, even more preferably 180°C to 250°C, and even more preferably 180°C to 200°C, from the viewpoint of suppressing heat damage to devices such as semiconductor memories. C is particularly preferred.

Further, there is no particular restriction on the pressure at which the resin material applied to the surface is heated, and an absolute pressure of 17 Pa or less is preferable.
The absolute pressure is more preferably at least 1000 Pa and at most atmospheric pressure, even more preferably at least 5000 Pa and at most atmospheric pressure, particularly preferably at least 10000 Pa and at most atmospheric pressure.

The resin material applied to the surface can be heated by a conventional method using a furnace or a hot plate. As the furnace, for example, SPX-1120 manufactured by Apex Corporation, VF-1000LP manufactured by Koyo Thermo Systems Co., Ltd., etc. can be used.
Further, the heating of the resin material applied to the surface may be performed in an atmospheric atmosphere or in an inert gas (nitrogen gas, argon gas, helium gas, etc.) atmosphere.

The heating time of the resin material applied to the surface is not particularly limited, and is, for example, 3 hours or less, preferably 1 hour or less. There is no particular restriction on the lower limit of the heating time, and it can be set to, for example, 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 (UV) light. As the ultraviolet light, 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. are preferable. Moreover, it is preferable to perform ultraviolet irradiation under an inert gas atmosphere.

Whether the resin material is cured or not can be confirmed by, for example, measuring the peak intensity of specific bonds and structures using FT-IR (Fourier transform infrared spectroscopy). Specific bonds and structures include bonds and structures generated by crosslinking reactions.
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 cured, and the peak intensities derived from these bonds, structures, etc. are measured by FT - You can confirm by measuring with IR.
The amide bond can be confirmed by the presence of vibrational peaks at about 1650 cm ⁻¹ and about 1520 cm ⁻¹ .
Imide bonds can be confirmed by the presence of vibrational peaks at about 1770 cm ⁻¹ and about 1720 cm ⁻¹ .
Siloxane bonds can be confirmed by the presence of vibrational peaks between 1000 cm ⁻¹ and 1080 cm ⁻¹ .
The tetrahydronaphthalene structure can be confirmed by the presence of vibrational peaks between 1500 cm ⁻¹ .
The oxazole ring structure can be confirmed by the presence of vibrational 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 has at least one selected from the group consisting of a siloxane bond, an ester bond, an ether bond, an amide bond, and an imide bond. It is more preferable to have a siloxane bond and an imide bond.

It is preferable that the first resin layer and the second resin layer formed by curing the resin material each have a content of sodium and potassium of 10 mass ppb or less on an elemental basis. If the content of sodium or potassium is 10 mass ppb or less on an elemental basis, it is possible to suppress the occurrence of inconveniences in the electrical characteristics of the semiconductor device, such as malfunction of the transistor.

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

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 0.03 μm. More preferably, the thickness is 5.0 μm. When the thickness of the first resin layer and the second resin layer is 0.001 μm or more, the bonding strength with the second inorganic material layer, other layers, etc. can be increased. When the thickness of the first resin layer and the second resin layer is 8.0 μm or less, variations in the thickness of the resin layer can be suppressed when the resin layer is formed on a large-area substrate.

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, the thickness of the first resin layer and the second resin layer is the same as that of the second resin layer. From the viewpoint of improving the bonding strength with the equipment layer, other layers, etc. and suppressing variations in the thickness of the first resin layer and the second resin layer, it is preferably 0.01 μm to 8.0 μm, and 0.01 μm to 8.0 μm. It is more preferably 0.03 μm to 6.0 μm, and even more preferably 0.05 μm to 5.0 μm.

When electrodes are not provided on the surface of the first resin layer and the surface of the second resin layer, the thickness of the first resin layer and the second resin layer is the same as that of the second inorganic material layer and the other layers. From the viewpoint of improving the bonding strength with the like and suppressing variations in the thickness of the first resin layer and the second resin layer, it is preferably 0.001 μm or more and less than 1.0 μm, and 0.01 μm to 0.8 μm. More preferably, it is 0.03 μm to 0.6 μm.

The first resin layer facilitates temporarily fixing the first resin layer and the second inorganic material layer, which will be described later, at a low temperature, and also allows the first laminate and the second laminate in the substrate laminate to be easily fixed together. In order to increase the bonding strength of It is more preferable to have at least one functional group selected from the group consisting of functional groups having a bond, and from the viewpoint of heat resistance, it is even more preferable to have a silanol group. These functional groups may be formed by surface treatment after forming the first resin layer, or may be formed by treatment with a silane coupling agent or the like. Alternatively, compounds containing these functional groups may be mixed into the resin composition.
Note that examples of the functional group having an unsaturated bond include a vinyl group, an allyl group, an acrylic group, a methacryl group, and a styryl group.
The second resin layer may have the above-mentioned functional group capable of forming a chemical bond on the surface of the second resin layer.

Whether or not the surface of the resin layer has Si-OH groups can be evaluated by surface analysis of the resin layer using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Specifically, using PHI nanoTOFII (ULVAC-PHI Co., Ltd.), which is a TOF-SIMS, it was determined whether the surface of the resin layer had Si-OH groups based on the presence or absence of a peak at a mass-to-charge ratio (m/Z) of 45. can be evaluated.

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 flattened. Examples of the flattening method include a fly cut method, chemical mechanical polishing (CMP), and the like. As for the flattening method, one method may be used alone, or two or more methods may be used in combination.

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 washed. Examples of the cleaning method include wet cleaning using a rinsing liquid and dry cleaning using plasma or the like. Examples of wet cleaning include ultrasonic cleaning using pure water, spin cleaning using a solvent such as NMP, and the like.

(First inorganic layer and second inorganic 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. be. For example, after forming the first resin layer on one surface of the first substrate, the first inorganic material layer may be formed on the other surface of the first substrate; The first resin layer may be formed after forming the equipment layer. The same applies to the second substrate, and the order in which the second resin layer and the second inorganic material layer are formed is not particularly limited.

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

The method for forming the inorganic layer on the surface of the substrate is not particularly limited, and includes conventionally known methods for forming an inorganic layer. Examples include CVD, sputtering, AGD (aerosolized gas deposition), sol-gel method, anodizing treatment, thermal decomposition method, and the like.

(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 layer, and the second 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 layer. An electrode may be provided on a part of the surface of the second inorganic material layer and a part of the surface of the second inorganic material layer. In step B, it is preferable that each electrode is arranged so that the electrode provided on the first resin layer side is in contact with the electrode provided on the second inorganic material layer.

A through hole is provided in the first laminate from the surface on the first resin layer side to the surface on the first inorganic material layer side, and an electrode passing through the first laminate is provided in the through hole. You can leave it there. A through hole is provided in the second laminate from the surface on the second resin layer side to the surface on the second inorganic material layer side, and an electrode passing through the second laminate is provided in the through hole. You can leave it there.

The material of the electrode is not particularly limited, and conventionally known electrode materials may be used. Specific examples include copper, solder, tin, gold, silver, aluminum, indium, cobalt, and tungsten.

The method of providing electrodes on the first laminate and the second laminate is not particularly limited, and conventionally known methods can be employed.
In the first laminate, an electrode may be formed on the surface to which the resin material is applied before the first resin layer is formed, and an electrode may be formed on the surface to which the resin material is applied before the first resin layer is formed. An electrode may be formed on the surface on which is formed. The same applies to the second laminate.
In the first laminate, an electrode may be formed on the surface on which the inorganic layer is formed before the first inorganic layer is formed; An electrode may be formed on the surface on which the inorganic material layer is formed. The same applies to the second laminate.

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

If the electrode is formed before the resin layer or inorganic layer is formed, removing the resin layer or inorganic layer on the electrode will remove a part of the surface of the resin layer or the inorganic layer. The structure includes an electrode on a part of the surface. Examples of methods for removing the resin layer or inorganic layer on the current-carrying layer include fly-cutting, chemical mechanical polishing (CMP), and plasma dry etching. As for the removal method, one method may be used alone, or two or more methods may be used in combination. For example, in the fly cut method, a surface planer (DFS8910 (manufactured by DISCO Co., Ltd.)) or the like can be used. When using CMP, the slurry may be, for example, a slurry containing silica or alumina, which is generally used for polishing resins, or a slurry containing hydrogen peroxide and silica, which is used for polishing metals. good. When using plasma dry etching, fluorocarbon plasma, oxygen plasma, etc. may be used.

When the resin layer or inorganic layer on the electrode surface is removed to expose the electrode, the oxide on the electrode surface may be reduced if necessary. Examples of reduction treatment methods include a method of heating the substrate at 100° C. to 300° C. in an acid atmosphere such as formic acid, a method of heating the substrate in a hydrogen atmosphere, and the like. These treatments may be performed simultaneously with Step C, which will be described later.

When an electrode is formed after a resin layer or an inorganic layer is formed, for example, the electrode is placed 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. It is also possible to form a hole in which is formed using a known method, and then form an electrode in the formed hole. Examples of methods for forming the holes include dry etching using gas, laser ablation, and the like.

Examples of methods for forming the electrodes include electroplating, electroless plating, sputtering, and inkjet methods.

When the resin material is photosensitive, holes in which electrodes are formed may be formed by photolithography in the resin material applied to at least one of the first substrate and the second substrate. After the resin material is cured to form at least one of the first resin layer and the second resin layer, electrodes may be formed in the formed holes.

The first laminate and the second laminate may be laminates separated into individual pieces by performing a dicing process, if necessary. For example, in the dicing process, a dicer (DAD6340 (manufactured by DISCO Corporation)) or the like can be used.

[Process B]
The method for manufacturing a substrate laminate of the present disclosure includes contacting the first resin layer of the first laminate and the second inorganic material layer of the second laminate to form the first laminate and the second laminate. It includes step B of laminating the bodies.

In step B, before joining the first laminate and the second laminate via the first resin layer and the second inorganic material layer in step C, which will be described later, the first resin layer and the second laminate are bonded together. This is the step of bringing the inorganic material layer into contact with the inorganic material layer. The first laminate and the second laminate are brought into contact so that a desired positional relationship is achieved when the first laminate and the second laminate are joined.

For example, when the above-mentioned electrodes are provided on the first laminate and the second laminate, the electrode provided on the first resin layer comes into contact with the electrode provided on the second inorganic material layer. It is preferable that the first laminate and the second laminate are brought into contact with each other so that the first laminate and the second laminate are brought into contact with each other.

Before the first resin layer and the second inorganic 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. As a result, the first laminate and the second laminate are firmly bonded in Step C, which will be described later, and there is a tendency for bonding positional deviation (alignment deviation) to be less likely to occur.

The curing rate of the first resin layer is more preferably 80% or more, even more preferably 85% or more, particularly preferably 90% or more, and even more preferably 93% or more. . Further, the curing rate of the first resin layer may be 100%, 99% or less, 95% or less, or 90% or less.
Moreover, the preferable range of the curing rate of the second resin layer is the same as the preferable range of the curing rate of the first resin layer. The curing rate of the second resin layer may be the curing rate before contacting with another layer (for example, another inorganic material layer).

A resin layer containing at least one member 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 (at least of the first resin layer and the second resin layer). The curing rate of (on the other hand) is more preferably 80% or more, even more preferably 85% or more, particularly preferably 90% or more, and even more preferably 93% or more. Curing rate of a resin layer (at least one of the first resin layer and the second resin layer) containing a siloxane bond and at least 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, even more 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 is, for example, the resin material before being applied to the first substrate, the first resin layer and the second inorganic layer in step B being brought into contact with each other. In the previous first resin layer and the first resin layer after step C, the peak intensity of a specific bond and structure (if there are multiple peaks such as imide, amide, etc., the sum of those peak intensities) It may be confirmed by measuring by FT-IR (Fourier transform infrared spectroscopy) and determining the rate of increase or decrease in peak intensity. Note that in the case of a band-like peak that is difficult to separate, such as a siloxane bond, the maximum peak intensity may be used.

Specifically, when specific bonds and structures are generated by the curing reaction, the rate of increase in peak intensity may be calculated using the following formula, and the calculated value may be used as the curing rate of the first resin layer.
Rate of increase in peak intensity (curing rate of the first resin layer) = [(Specific bond and structure of the first resin layer before contacting the first resin layer and the second inorganic layer in step B) peak intensity)/(peak intensity of specific bond and structure of the first resin layer after heating at 300°C for 1 hour in step C)]×100
Note that background signal removal may be performed using a normal method. Further, the FT-IR measurement can be performed by a transmission method or a reflection method, if necessary.

In the above-mentioned rate of increase in peak intensity, if there are multiple bonds and structures that cause an increase in peak intensity, the peak intensity may be read as the total intensity of the multiple peak intensities.

Before the first resin layer and the second inorganic layer are brought into contact in step B, the composite modulus of elasticity of the first resin layer at 23°C is preferably 0.1 GPa or more and 20 GPa or less, and 0. More preferably, it is .1 GPa or more and 10 GPa or less. As a result, the voids formed when the first resin layer and the second inorganic layer are brought into contact in step B are absorbed by the first resin layer in step C, suppressing the generation of voids. There is a tendency to Moreover, this makes it easy to temporarily fix the first resin layer and the second inorganic material layer, which will be described later, at a low temperature.

The composite modulus of elasticity of the first resin layer at 23° C. is preferably 8 GPa or less, more preferably 6 GPa or less, from the viewpoint of suitably suppressing the generation of voids. Further, the composite modulus of elasticity of the first resin layer at 23° C. is preferably 0.1 GPa or more, more preferably 1 GPa or more, from the viewpoint of suitably suppressing misalignment.
Further, the preferable range of the composite modulus of the second resin layer at 23°C is the same as the preferable range of the composite modulus of the first resin layer at 23°C. The composite modulus of elasticity at 23° C. of the second resin layer may be the composite modulus at 23° C. before contacting with another layer (for example, another inorganic material layer).

The composite elastic modulus of the resin layer at 23° C. can be measured by the method described below.
A measurement sample is prepared by preparing a resin composition containing a resin material, spin-coating it on a silicon substrate, and then heating it at 400° C. for 10 minutes. For the prepared measurement sample, the unloading-displacement curve at 23°C was measured at a test depth of 20 nm using a nanoindentator (trade name TI-950 Tribo Indenter, manufactured by Hysitron, Berkovich type indenter), and the unloading-displacement curve was determined as a reference. According to the calculation method in the literature (Handbook of Micro/nano Tribology (second edition), edited by Bharat Bhushan, CRC Press), the composite modulus at 23°C is calculated from the maximum load and maximum displacement.
Note that here, the composite modulus of elasticity is defined by the following formula (1). In formula (1), E _r represents the composite modulus of elasticity, E _i represents the Young's modulus of the indenter and is 1140 GPa, ν _i represents the Poisson's ratio of the indenter and is 0.07, E _s and ν _s represent the Young's modulus and Poisson's ratio of the sample, respectively.

Before the first resin layer and the second inorganic 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. , 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, which will be described later, at a low temperature.
Moreover, the preferable range of the surface roughness (Ra) of the second resin layer is the same as the preferable 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 another layer (for example, another inorganic material layer).
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 SPM SPA400 (manufactured by Hitachi High-Technologies) in dynamic force microscope mode.

The method for manufacturing a substrate laminate of the present disclosure may include various steps described below before the above-mentioned step B. The following various steps are preferably performed after step A and before step B.

The method for manufacturing a substrate laminate according to the present disclosure may include, before step B, a step of subjecting the second inorganic material layer to a surface activation treatment. By performing the surface activation treatment, the bonding strength between the first resin layer and the second inorganic layer can be increased. In particular, when electrodes are provided on the bonding surfaces of the first laminate and the second laminate and the electrodes are bonded together, the viewpoint is to promote the diffusion of metal such as copper contained in the electrodes and to increase the bonding strength between the electrodes. From the viewpoint of reducing the heating temperature during metal diffusion, it is preferable to perform a surface activation treatment.
Furthermore, the first inorganic layer in the first substrate may also be subjected to surface activation treatment, especially when the first inorganic layer is bonded to another layer (for example, another resin layer). , the first inorganic material layer may also be subjected to surface activation treatment before bonding.

Specific examples of the surface activation treatment include plasma treatment, FAB (Fast Atom Bombardment) treatment, and the like.

The method for manufacturing a substrate laminate according to the present disclosure may include, before step B, a step of cleaning the second inorganic material layer in order to remove particles and the like. The above-mentioned cleaning step is preferably performed after the surface treatment step and before step B.
Furthermore, the first inorganic layer on the first substrate may be cleaned. In particular, when the first inorganic layer is bonded to another layer (for example, another resin layer), the first inorganic layer may be cleaned before bonding. You may wash the first inorganic material layer.

The cleaning method is not particularly limited, and may include wet cleaning using a solvent such as alkaline cleaning solution, acidic cleaning solution, hydrofluoric acid-containing cleaning solution, permanganic acid-containing solution (desmear solution), wet cleaning using pure water, etc., UV ozone, plasma. For example, dry cleaning by etc.

The method for manufacturing a substrate laminate of the present disclosure includes, before step B, a second inorganic layer, which prevents foreign matter from adhering to the inorganic layer (for example, from preventing foreign matter from adhering during dicing). The method may include a step of providing a surface protective layer on the surface. The step of providing a surface protective layer is preferably performed before the above-mentioned cleaning step and before step B.

The surface protective layer is not particularly limited as long as it can protect the second inorganic layer, and may include a water-soluble resin, a photoresist that can be cleaned with an organic solvent such as NMP (N-methyl-2-pyrrolidone), etc. Can be mentioned. As the water-soluble resin, Hogomax from Disco may be used.

The second laminate provided with the surface protective layer may be subjected to dicing as necessary, and the surface protective layer may be peeled off after the dicing. In this case, it is preferable that the surface protective layer is peeled off after the dicing process, and the above-mentioned cleaning step and step B are performed in this order after the surface protective layer is peeled off.

The method for manufacturing a substrate laminate of the present disclosure may include a step of temporarily fixing the first laminate and the second laminate after step B and before step C. Temporary fixing of the first laminate and the second laminate is preferably carried out at a low temperature between room temperature and 100°C, more preferably between room temperature and 50°C, and more preferably at room temperature. preferable.

When the first substrate and the second substrate have silicon substrates, the surface energy of the bonding interface between the first and second laminates is determined by the handling in step C. From the viewpoint of ease of assembly, suppression of misalignment (displacement of bonding position), suppression of foreign matter contamination, etc., it is preferably 0.05 J/m ² or more, more preferably 0.1 J/m ² or more, and 0. More preferably, it is .15 J/m ² or more.
The surface energy (bond strength) of the bond interface mentioned above was determined by a blade insertion test according to the method in the non-patent document MP Maszara, G. Goetz, A. Cavigila, and JBMckitterick, Journal of Applied Physics, 64 (1988) 4943-4950. You can ask for it. A blade with a thickness of 0.1 mm to 0.3 mm is inserted into the joint interface of the temporarily fixed laminate, and the distance at which the laminate separates from the blade edge is measured using an infrared light source and an infrared camera. After that, the surface energy may be determined based on the following formula.
γ=3× ¹⁰⁹ × _tb2 ^{× E2} × ^t6 /(32× ^L4 ×E× ^t3 )
Here, γ is the surface energy (J/m ² ), t _b is the blade thickness (m), E is the Young's modulus (GPa) of the silicon substrate included in the first substrate and the second substrate, and t is the The thicknesses (m) of the first substrate and the second substrate, and L represent the peeling distance (m) of the laminate from the blade edge.

[Process C]
The method for manufacturing a substrate laminate of the present disclosure includes, after step B, step C of heating the first laminate and the second laminate at 100° C. or higher. Thereby, a substrate laminate is obtained in which the first laminate and the second laminate are joined via the first resin layer and the second inorganic material layer.

There is no particular restriction on the pressure at which the first laminate and the second laminate are bonded, and the absolute pressure is preferably 10 ⁻⁴ Pa or less superatmospheric pressure.
The absolute pressure is more preferably at least 10 ⁻³ Pa and at most atmospheric pressure, even more preferably at least 100 Pa and at most atmospheric pressure, particularly preferably at least 1000 Pa and at most atmospheric pressure.
When joining the first laminate and the second laminate, it may be performed in an atmospheric atmosphere or in an inert gas (nitrogen gas, argon gas, helium gas, etc.) atmosphere.

In step C, the first laminate and the second laminate are preferably heated at 100° C. to 450° C. while the first resin layer and the second inorganic layer are in contact with each other.
Note that the above 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, even more preferably 150°C to 250°C, and particularly preferably 150°C to 200°C.

When each electrode is arranged so that the electrode provided on the first resin layer side contacts the electrode provided on the second inorganic material layer in step B, the above-mentioned temperature is 130 ° C. or higher. The temperature is preferably 150°C or higher, more preferably 200°C or higher. As a result, components (for example, copper) contained in the electrodes provided on the first resin layer side and the electrodes provided on the second inorganic material layer tend to diffuse, and the bonding strength between the electrodes tends to increase.

Heating in step C can be performed by a conventional method using a furnace or a hot plate.
Further, the heating in step C may be performed in an atmospheric atmosphere or in an inert gas (nitrogen gas, argon gas, helium gas, etc.) atmosphere.
The heating time in step C is not particularly limited, and is, for example, 3 hours or less, preferably 1 hour or less. There is no particular restriction on the lower limit of the heating time, and it can be set to, for example, 5 minutes.

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

The method for manufacturing a substrate laminate of the present disclosure includes, after step C, penetrating the first laminate and the second laminate from the first inorganic layer side surface to the second resin layer side surface. The method may include a step of providing a hole and forming an electrode that penetrates the first stacked body and the second stacked body in the through hole. When electrodes are not formed in the substrate laminate obtained in step C, by performing the step of forming the electrodes, the electrodes penetrating the first laminate and the second laminate are formed in the through holes. Preferably, it is formed.

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

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

The material of the electrodes penetrating the first laminate and the second laminate is not particularly limited, and conventionally known electrode materials may be used. Specific examples include copper, solder, tin, gold, silver, aluminum, indium, cobalt, and tungsten.

In the method for manufacturing a substrate laminate of the present disclosure, at least one of the first substrate and the second substrate further includes another substrate on a surface on the first inorganic material layer side and a surface on the second resin layer side. Another laminate or the like may be laminated. The preferred material for the other substrate is the same as the preferred material for the first substrate and the second substrate. Preferred embodiments of the other laminate are the same as those of the first laminate and the second laminate.

In the method for manufacturing a substrate laminate of the present disclosure, after step C, the surface of the substrate laminate may be subjected to thinning processing (back grinding or back grinding) if necessary.

(Example of laminated structure of substrate laminate)
Examples of the laminated structure of the substrate laminate for each application are shown below. Note that the bonding layer means a layer in a bonded state consisting of an inorganic material layer/resin layer.
For MEMS packaging; Si/bonding layer/Si, _SiO2 /bonding layer/Si, _SiO2 /bonding layer/ _SiO2 , Cu/bonding layer/Cu,
For microchannel; PDMS/bonding layer/PDMS, PDMS/bonding layer/SiO ₂ ,
For CMOS image sensor; SiO ₂ /bonding layer/SiO ₂ , Si/bonding layer/Si, SiO ₂ /bonding layer/Si,
For through silicon vias (TSV); SiO ₂ (with Cu electrode) / bonding layer / SiO ₂ (with Cu electrode), Si (with Cu electrode) / bonding layer / Si (with Cu electrode),
For optical devices; (InGaAlAs, InGaAs, InP, GaAs)/bonding layer/Si,
For LED; (InGaAlAs, GaAs, GaN)/bonding layer/Si, (InGaAlAs, GaAs, GaN)/bonding layer/SiO ₂ , (InGaAlAs, GaAs, GaN)/bonding layer/(Au, Ag, Al), ( InGaAlAs, GaAs, GaN)/bonding layer/sapphire.

Hereinafter, an example of a method for manufacturing a substrate stack will be described using FIGS. 1a to 1h and FIGS. 2a to 2i. Note that the present disclosure is not limited to the configuration shown in the drawings. Furthermore, the sizes of the members in FIGS. 1a to 1h and 2a to 2i are conceptual, and the relative size relationships between the members are not limited thereto. Further, in each drawing, members having substantially the same function are given the same reference numerals in all drawings, and overlapping explanations may be omitted.

<Example 1 of manufacturing method of substrate laminate>
Hereinafter, Example 1 of the method for manufacturing a substrate stack will be described using FIGS. 1a to 1h. As shown in FIG. 1a, a wafer 3 having a flattened surface and having electrodes 4 extending therethrough is prepared. An inorganic material layer 5 such as an oxide film is formed on the surface of the wafer 3. A wafer 3 provided with an electrode 4 is fixed to a carrier 1 via a temporary fixing material 2.

Next, as shown in FIG. 1b, 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 that includes an inorganic material layer 15, a wafer 13, and a resin layer 16 in this order, and further includes an electrode 14 that penetrates the wafer 13. As shown in FIG. 1c, a surface protection material 6 is disposed on the inorganic material layer 15 side of the laminate.

As shown in FIG. 1d, after dicing the laminate, the surface protection material 6 is peeled off to obtain a singulated laminate. The singulation laminate includes, in this order, an inorganic material layer 15A, a wafer 13A, and a resin layer 16A, each of which has been singulated. Furthermore, the singulated laminate includes an electrode 14A that penetrates the singulated laminate. From the viewpoint of removing foreign matter, the surface of the singulated laminate may be washed with pure water, a solvent, etc. after the surface protection material 6 is peeled off. At this time, a plurality of singulated laminates may be washed all at once while being loaded on the frame.

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

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

According to the procedure shown in FIGS. 1c and 1d, a singulated laminate is obtained, each of which includes the singulated inorganic material layer 15B, the wafer 13B, and the resin layer 16B in this order. The singulated laminate includes an electrode 14B that penetrates the singulated laminate. As shown in FIG. 1g, the inorganic material layer 15A of the singulated laminate temporarily fixed to the wafer 3 and the resin layer 16B of the singulated laminate are brought into contact and temporarily fixed. At this time, a plurality of singulated laminates may be temporarily fixed along the width direction and the length direction.

By repeating the process shown in FIGS. 1f and 1g, the singulated laminates are stacked in a temporarily fixed state in the height direction. After the stacking of the singulated laminates is completed, the laminate of the singulated laminates is heated at 100° C. or higher. As a result, the wafer 3 and the singulated wafer 13B are bonded via the inorganic material layer 5 and the resin layer 16A, and the wafer 3 and the singulated wafer 13B are bonded in the height direction via each of the singulated inorganic material layers and each resin layer. The stacked singulated laminates can be joined. From the viewpoint of increasing the bonding strength between each electrode, it is preferable to heat the laminate of the singulated laminate at 130° C. or higher. As a result, components (for example, copper) contained in each electrode tend to diffuse, and the bonding strength between the electrodes tends to increase.
Through the above steps, a substrate laminate 100 is obtained as shown in FIG. 1h.

<Example 2 of manufacturing method of substrate laminate>
Example 2 of the method for manufacturing a substrate stack will be described below with reference to FIGS. 2a to 2i. In Example 2 of the manufacturing method of a substrate stack, a wafer without electrodes is used, a through hole is finally provided in the substrate stack without electrodes, and an electrode is provided in the through hole, which is the same as described above. This is different from Example 1 of the method for manufacturing a substrate laminate.

As shown in FIG. 2a, a wafer 23 with a flattened 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 the temporary fixing material 2.

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

Further, a laminate including an inorganic material layer 35, a wafer 33, and a resin layer 36 in this order is prepared. As shown in FIG. 2c, a surface protection material 6 is disposed on the inorganic material layer 35 side of the laminate.

As shown in FIG. 2d, after dicing the laminate, the surface protection material 6 is peeled off to obtain a singulated laminate. The singulation laminate includes, in this order, an inorganic material layer 35A, a wafer 33A, and a resin layer 36A, each of which has been singulated. From the viewpoint of removing foreign matter, the surface of the singulated laminate may be washed with pure water, a solvent, etc. after the surface protection material 6 is peeled off. At this time, a plurality of singulated laminates may be washed all at once while being loaded on the frame.

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

As shown in FIG. 2f, the inorganic material layer 35A of the singulated laminate temporarily fixed to the wafer 23 is subjected to the surface activation treatment as described above. After surface activation, the surface of the inorganic layer 35A may be washed with pure water, a solvent, or the like.

In accordance with the procedure shown in FIGS. 2c and 2d, a singulated laminate is obtained which includes an inorganic material layer 35B, a wafer 33B, and a resin layer 36B, each of which has been singulated, in this order. As shown in FIG. 2g, the inorganic material layer 35A of the singulated laminate temporarily fixed to the wafer 23 and the resin layer 36B of the singulated laminate are brought into contact and temporarily fixed. At this time, a plurality of singulated laminates may be temporarily fixed along the width direction and the length direction.

By repeating the process shown in FIGS. 2f and 2g, the singulated laminates are stacked in a temporarily fixed state in the height direction. After the stacking of the singulated laminates is completed, the laminate of the singulated laminates is heated at 100° C. or higher. As a result, the wafer 23 and the singulated wafer 33B are bonded via the inorganic material layer 25 and the resin layer 36A, and the wafer 23 and the singulated wafer 33B are bonded in the height direction through the inorganic material layer 25 and the resin layer 36A. The stacked singulated laminates can be joined. As a result, a substrate stack 200 is obtained, as shown in FIG. 2h.

Furthermore, a through hole is provided that penetrates the singulated laminate stacked on the substrate laminate 200 along the height direction. Examples of methods for forming the through holes include dry etching using gas, laser ablation, and the like. Next, an electrode 34 is formed that penetrates the singulated laminate stacked against the through hole.
Through the above steps, as shown in FIG. 2i, a substrate stack 300 including electrodes 34 penetrating the singulated stack is obtained.

[Substrate laminate]
The substrate laminate of the present disclosure includes a first resin layer, a first substrate, and a first inorganic material layer in this order, the first resin layer is disposed on one surface, and the first resin layer is arranged on one surface, and a first laminate in which one inorganic layer is disposed on the other surface;
It has a second resin layer, a second substrate, and a second inorganic material layer in this order, the second resin layer being disposed on one surface, and the second inorganic material layer being disposed on the other surface. a second laminate placed on the surface of the
has
The first laminate and the second laminate are laminated via the first resin layer of the first laminate and the second inorganic layer of the second laminate. .
The first laminate and the second laminate in the substrate laminate of the present disclosure may be a laminate three-dimensionally mounted on a substrate such as a wafer, and the substrate laminate of the present disclosure described above may be a laminate that is three-dimensionally mounted on a substrate such as a wafer. Examples include a first laminate, a second laminate, etc. used in the manufacturing method. Preferred forms of the first laminate and the second laminate in the substrate laminate are similar to the preferred forms of the first laminate and the second laminate in the method for manufacturing a substrate laminate of the present disclosure described above. be.
For example, specific examples of the first laminate and the second laminate in the substrate laminate include a laminate as shown in FIG. 1c or 2c, and a singulated laminate as shown in FIGS. 1d and 2d. Examples include laminated bodies.
Note that the first laminate or the 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, the first laminate includes an electrode on a part of the surface of the first resin layer and a part of the surface of the first inorganic material layer,
The second laminate preferably includes electrodes on a part of the surface of the second resin layer and a part of the surface of the second inorganic material layer.
Note that the preferred form of the electrode is the same as the preferred form of the electrode in the method for manufacturing a substrate laminate of the present disclosure described above.

<Modified example of manufacturing method of substrate laminate>
In a modified example of the method for manufacturing a substrate laminate according to the present disclosure, instead of the first laminate, a laminate (third laminate), and instead of the second laminate, a laminate (third laminate) in which the second resin layer, the first substrate, and the fourth resin layer are laminated in this order. This method is different from the method for manufacturing a substrate laminate according to the present disclosure described above in that it is used. That is, in the laminate (third laminate), the first inorganic layer in the first laminate is replaced with the third resin layer, and in the laminate (fourth laminate), the first inorganic layer in the first laminate is replaced with the third resin layer. The second inorganic material layer in the second laminate is replaced with a fourth resin layer. Then, by joining the first resin layer and the fourth resin layer in step C, a substrate laminate is obtained in a modified example.

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 It is preferable that the resin composition is different from that of the resin material. Thereby, even if the thickness of the third laminate and the fourth laminate is small, warping of the substrate laminate tends to be suitably suppressed.

The resin material used for forming the first resin layer is preferably a resin material capable of forming a resin layer having a composite modulus of elasticity of 0.1 GPa or more and 10 GPa at 23°C. That is, the composite modulus of elasticity of the first resin layer at 23° C. is preferably 0.1 GPa or more and 10 GPa or less.
The resin material used to form the first resin layer and the preferable conditions for the first resin layer are the same as the preferable conditions described in the above-mentioned method for manufacturing a substrate laminate of the present disclosure.

The resin material used to form the fourth resin layer is not particularly limited as long as it has a composition different from the resin material used to form the first resin layer, and examples thereof include polyimide, polyamide, polyamideimide, parylene, etc. , materials in which bonds or structures are formed by crosslinking, such as polyarylene ether, tetrahydronaphthalene, octahydroanthracene, etc., materials in which nitrogen ring-containing structures are formed, such as polybenzoxazal, polybenzoxazine, Si-O, etc. Examples include materials whose bonds or structures are formed by crosslinking, organic materials such as siloxane-modified compounds, benzocyclobutene, and epoxy compounds.

The resin material used to form the fourth resin layer is preferably a material in which polyimide bonds are formed by crosslinking, benzocyclobutene, epoxy compounds, siloxane-modified compounds, etc. The material in which polyimide bonds are formed by crosslinking is preferably a siloxane compound in which polyimide bonds are formed by crosslinking, and the siloxane-modified compound is preferably an epoxy-modified siloxane.

-Explanation of symbols-
1: carrier, 2: temporary fixing material, 3: wafer, 4: electrode, 5: inorganic material layer, 6: surface protection material, 13: wafer, 13A: wafer, 13B: wafer, 14: electrode, 14A: electrode, 14B: electrode, 15: inorganic layer, 15A: inorganic layer, 15B: inorganic layer, 16: resin layer, 16A: resin layer, 16B: resin layer, 23: wafer, 25: inorganic layer, 33: wafer , 33A: wafer, 33B: wafer, 34: electrode, 35: inorganic layer, 35A: inorganic layer, 35B: inorganic layer, 36: resin layer, 36A: resin layer, 36B: resin layer, 100: substrate stack body, 200: substrate laminate, 300: substrate laminate

Note that the disclosure of Japanese Patent Application No. 2022-109052 filed on July 6, 2022 is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference. , incorporated herein by reference.

Claims (14)

A first resin layer, a first substrate, and a first inorganic layer are laminated in this order, and the first resin layer is disposed on one surface, and the first inorganic layer is disposed on the other surface. A first laminate disposed on one surface, a second resin layer, a second substrate, and a second inorganic material layer are laminated in this order, and the second resin layer is disposed on one surface. a second laminate, the second inorganic material layer being disposed on the other surface;
Laminating the first laminate and the second laminate by bringing the first resin layer of the first laminate into contact with the second inorganic layer of the second laminate. B and
A method for manufacturing a substrate laminate, including a step C of heating the first laminate and the second laminate at 100° C. or higher after the step B. The first laminate includes an electrode on a part of the surface of the first resin layer and a part of the surface of the first inorganic material layer,
The method for manufacturing a substrate laminate according to claim 1, wherein the second laminate includes electrodes on a part of the surface of the second resin layer and a part of the surface of the second inorganic material layer. The method for manufacturing a substrate laminate according to claim 2, comprising a step of subjecting the second inorganic material layer to a surface activation treatment before the step B. After the step C, a through hole is provided in the first laminate and the second laminate from the first inorganic material layer side surface to the second resin layer side surface, and the through hole 2. The method of manufacturing a substrate laminate according to claim 1, comprising the step of forming an electrode penetrating the first laminate and the second laminate in the hole. The method for manufacturing a substrate laminate according to any one of claims 1 to 4, including a step of cleaning the second inorganic material layer before the step B. The method for manufacturing a substrate laminate according to any one of claims 1 to 4, including the step of providing a surface protective layer on the second inorganic layer before the step B. Before the first resin layer and the second inorganic material layer are brought into contact in the step B, the composite modulus of elasticity of the first resin layer at 23° C. is 0.1 GPa or more and 20 GPa or less, A method for manufacturing a substrate laminate according to any one of claims 1 to 4. The curing rate of the first resin layer is 70% or more and 100% or less before the first resin layer and the second inorganic material layer are brought into contact in the step B. The method for manufacturing a substrate laminate according to claim 4. Before the first resin layer and the second inorganic layer are brought into contact in the step B, the surface roughness (Ra) of the first resin layer is 0.01 nm or more and 1.2 nm or less. The method for manufacturing a substrate laminate according to any one of claims 1 to 4. Claims 1 to 4, wherein the first resin layer has at least one functional group selected from the group consisting of a silanol group, an amino group, an epoxy group, a hydroxyl group, and a functional group having an unsaturated bond on the surface of the first resin layer. A method for manufacturing a substrate laminate according to any one of the items. The first resin layer is
siloxane bond,
The method for manufacturing a substrate laminate according to any one of claims 1 to 4, comprising at least one selected from the group consisting of an ester bond, an ether bond, an amide bond, and an imide bond. The substrate laminate according to any one of claims 1 to 4, wherein the second inorganic layer contains at least one element selected from the group consisting of Si, Ga, Ge, and As. Production method. It has a first resin layer, a first substrate, and a first inorganic material layer in this order, the first resin layer is arranged on one surface, and the first inorganic material layer is arranged on the other surface. a first laminate placed on the surface of the
It has a second resin layer, a second substrate, and a second inorganic material layer in this order, the second resin layer being disposed on one surface, and the second inorganic material layer being disposed on the other surface. a second laminate placed on the surface of the
has
The first laminate and the second laminate are laminated via the first resin layer of the first laminate and the second inorganic layer of the second laminate. , substrate laminate. The first laminate includes an electrode on a part of the surface of the first resin layer and a part of the surface of the first inorganic material layer,
The substrate laminate according to claim 13, wherein the second laminate includes electrodes on a part of the surface of the second resin layer and a part of the surface of the second inorganic material layer.