Method for producing laminate and laminate

Abstract

To provide a method of manufacturing a laminate including two silicon substrates, the method including a novel method of bonding the two silicon substrates.SOLUTION: A method for producing a laminate comprising two silicon substrates, the method comprising (a) preparing a first silicon substrate having a first bonding part and a second silicon substrate having a second bonding part, wherein the first bonding part and the second bonding part are portions containing a silicon oxide, and (b) using an organic material capable of reacting with a hydrosilyl group and / or a silanol group to bond the first bonding part and the second bonding part with a reaction product derived from the organic material.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for manufacturing a stack including two silicon substrates (hereinafter also simply referred to as a "stack"), and the stack. [Background technology]

[0002] In the field of semiconductor technology, the silicon direct bonding (SDB) method has been known as a method for bonding two silicon substrates. In the conventional SDB method, first, the two silicon substrates are cleaned, and then OH is applied to the bonding surfaces. - , H + A thin film consisting of ions / molecules such as HO, H2O, and O2 is formed, and then these silicon substrates are brought into close contact with each other, temporarily bonding them together through the van der Waals forces between the ions / molecules. After that, they are subjected to a heat treatment at approximately 1000°C, which causes interatomic diffusion and firmly bonds the silicon substrates.

[0003] However, in conventional SDB methods, gas is generated between the silicon substrates during the heat treatment, and this gas is not completely discharged but remains, which can cause the formation of voids. To solve this problem, Patent Document 1 describes that the generation of voids can be suppressed by forming a trench and a gas exhaust port in at least one of the two silicon substrates and discharging the gas generated by the heat treatment through the trench and the gas exhaust port. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-184546 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the method described in Patent Document 1 requires the formation of a trench and a gas outlet in at least one of the silicon substrates, making the manufacturing process of the stacked body complicated. Furthermore, in recent years, in the field of semiconductor technology, research and development has been conducted on three-dimensional integration techniques that involve bonding (stacking) two or more silicon substrates, and a new method for bonding silicon substrates is desired.

[0006] An object of the present disclosure is to provide a method for manufacturing a stack comprising two silicon substrates, the method comprising a novel method for bonding the two silicon substrates. [Means for solving the problem]

[0007] [1] A method for manufacturing a stack including two silicon substrates, comprising: (a) preparing a first silicon substrate having a first bonding portion and a second silicon substrate having a second bonding portion, the first bonding portion and the second bonding portion being portions containing silicon oxide; and (b) using an organic material capable of reacting with a hydrosilyl group and / or a silanol group, the first bonding portion and the second bonding portion are bonded together with a reaction product derived from the organic material; A manufacturing method comprising:

[0008] [2] The method for producing a laminate according to [1] above, wherein the organic material has at least one selected from the group consisting of an alkenyl group, a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, an acid anhydride group, and a siloxane bond.

[0009] [3] After (a) and before (b), subjecting at least one of the first bonding portion and the second bonding portion to a surface treatment that generates hydrosilyl groups and / or silanol groups; The method for producing the laminate according to [1] or [2] above, further comprising:

[0010] [4] The method for producing a laminate according to [3] above, wherein the surface treatment includes at least one selected from the group consisting of a hydrogen atom treatment, a heat treatment in a hydrogen-containing atmosphere, a sputtering treatment, a chemical vapor deposition treatment, and a termination treatment using a chemical solution.

[0011] [5] The organic material is (i) a substituted or unsubstituted hydrocarbon compound having alkenyl groups at two terminal ends; and (ii) a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one end and a group selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, and an acid anhydride group at the other end; The method for producing a laminate according to the above item 3 or 4, which includes at least one selected from the group consisting of:

[0012] [6] The organic material is (iii) a substituted or unsubstituted hydrocarbon compound having at its two terminal ends any one group independently selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, and an acid anhydride group; (iv) silsesquioxanes and their derivatives; (v) a combination of a hydrolyzable hydrosilane or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end, and a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkenyl group at the other end; and (vi) Substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group at one end and an alkyl group at the other end. The method for producing a laminate according to any one of the above [1] to [5], which includes at least one selected from the group consisting of:

[0013] [7] The organic material is (vii) A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end. Including, The method for producing a laminate according to any one of [1] to [6] above, wherein (b) uses the organic material and an organic binder having two groups capable of bonding to the reactive functional group of the hydrocarbon compound of (vii) of the organic material to bond the first bonding portion and the second bonding portion with a reaction product derived from the organic material and the organic binder.

[0014] [8] The method for producing a laminate according to any one of the above [1] to [7], wherein (b) comprises maintaining the first silicon substrate and the second silicon substrate at a temperature of 200° C. or less.

[0015] [9] (b) bonding the first silicon substrate and the second silicon substrate together with the organic material interposed between the first bonding portion and the second bonding portion; -8 Pa or more 10 5 The method for producing a laminate according to any one of the above [1] to [8], comprising maintaining the pressure at or below 1 Pa.

[0016]

[10] A method for manufacturing a stack including two silicon substrates, comprising: (c) preparing a first silicon substrate having a first base portion and a first bonding portion formed thereon, and a second silicon substrate having a second base portion and a second bonding portion formed thereon, wherein the first base portion and the second base portion are portions containing silicon oxide, and the first bonding portion and the second bonding portion are silicon layers; and (d) directly bonding the first bonding portion and the second bonding portion, or bonding them using a hydrosilyl group present on the surface of at least one of the first bonding portion and the second bonding portion. A manufacturing method comprising:

[0017]

[11] A stack including two silicon substrates, a first silicon substrate having a first junction; a second silicon substrate having a second bond; a bonding layer that bonds the first bonding portion and the second bonding portion together; wherein the first bonding portion and the second bonding portion are portions containing silicon oxide, and the bonding layer contains an organic substance chemically bonded to Si atoms of the first bonding portion and Si atoms of the second bonding portion.

[0018]

[12] A stack including two silicon substrates, a first silicon substrate having a first junction; a second silicon substrate having a second bond; a bonding layer that bonds the first bonding portion and the second bonding portion together; wherein the first bonding portion and the second bonding portion are portions containing silicon oxide, and the bonding layer contains an organic substance and has a thickness of 10 nm or less.

[0019]

[13] The laminate according to the above

[11] or

[12] , wherein the organic substance contains a residue of an organic material capable of reacting with a hydrosilyl group and / or a silanol group.

[0020]

[14] A stack including two silicon substrates, a first silicon substrate having a first junction; a second silicon substrate having a second bonding portion; wherein the first bonding portion and the second bonding portion are silicon layers formed on a portion containing silicon oxide, and the first bonding portion and the second bonding portion are bonded directly or by using hydrosilyl groups present on a surface of at least one of the first bonding portion and the second bonding portion. [Effects of the Invention]

[0021] According to the present disclosure, a method for manufacturing a stack comprising two silicon substrates is provided, the method comprising a novel method for bonding the two silicon substrates. [Brief explanation of the drawings]

[0022] [Figure 1] 1 shows a schematic cross-sectional view of a laminate according to one embodiment of the present disclosure. [Figure 2] FIG. 2 shows a schematic cross-sectional view of a laminate according to another embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0023] Embodiments of the present disclosure will be described in detail below with reference to the drawings, but the present disclosure is not limited to these embodiments.

[0024] (Embodiment 1) This embodiment relates to an embodiment in which the bonding portions of two silicon substrates are portions containing silicon oxide, and these bonding portions are bonded by an organic material.

[0025] Referring to FIG. 1, the laminate 40 of this embodiment is a first silicon substrate 10 having a first bonding portion 13; a second silicon substrate 20 having a second bonding portion 23; a bonding layer 30 that bonds the first bonding portion 13 and the second bonding portion 23; Includes.

[0026] The first silicon substrate 10 and the second silicon substrate 20 (hereinafter collectively referred to as "silicon substrates") are not particularly limited as long as they respectively have a first bonding portion 13 and a second bonding portion 23 (hereinafter collectively referred to as "bonding portions") to be bonded to each other.

[0027] 1, the first bonding portion 13 may be a film formed on the entire surface of one side of the main body portion 11 of the first silicon substrate 10, and the second bonding portion 23 may be a film formed on the entire surface of one side of the main body portion 21 of the second silicon substrate 20, but this embodiment is not limited to this. For example, the bonding portion may be a portion provided adjacent to a metal portion on one surface of the silicon substrate, more specifically, a portion provided between two metal portions, in which case hybrid bonding may be performed between the first silicon substrate and the second silicon substrate.

[0028] Such a laminate can be manufactured by the following manufacturing method. (a) providing a first silicon substrate 10 having a first bonding portion 13 and a second silicon substrate 20 having a second bonding portion 23; and (b) An organic material capable of reacting with a hydrosilyl group and / or a silanol group is supplied between the first bonding portion 13 and the second bonding portion 23, and the first bonding portion 13 and the second bonding portion 23 are bonded together by a reaction product derived from the organic material. Each step is described in detail below.

[0029] ·Process (a) First, a first silicon substrate having a first bonding portion and a second silicon substrate having a second bonding portion are prepared.

[0030] The silicon substrate may be any silicon-based substrate (or base material), and may consist of silicon or may contain any other suitable material in addition to silicon, such as dopants, impurities that may be unavoidably mixed in, metals (e.g., electrodes, wiring, vias, etc.), and oxides, nitrides, and / or carbides of silicon or the like (e.g., dielectric layers, insulator layers, protective layers, etc.).

[0031] The surface of the bonding portion (bonding surface) may be the entire surface of the silicon substrate (typically one of the two opposing surfaces of the silicon substrate), or may be a partial region thereof. The thickness of the bonding portion is not particularly limited as long as desired or acceptable properties are achieved in the final laminate.

[0032] In this embodiment, the junction may be a portion containing silicon oxide (hereinafter also referred to as a "silicon oxide portion"). The silicon oxide portion may consist of silicon oxide or may contain any other appropriate substance in addition to silicon oxide. Such other substances include, for example, dopants and impurities that may be unavoidably mixed in.

[0033] In this embodiment, the thickness of the junction portion, which is the silicon oxide portion, can be, for example, 1 nm or more and 1 μm or less, particularly 10 nm or less.

[0034] The bond may be applied to the silicon substrate in any suitable manner.

[0035] Although not essential to this embodiment, the surface of the silicon substrate (main body in the embodiment shown in FIG. 1) before forming the bonding portion may be subjected to chemical mechanical polishing (CMP), which allows the surface to be flattened / smoothed.

[0036] Furthermore, although not essential to this embodiment, the surface of the silicon substrate (main body in the embodiment shown in FIG. 1) before forming the bonding portion may be subjected to cleaning after CMP or without CMP, which makes it possible to clean the surface and remove unwanted substances such as organic matter, particles, metals / metal ions, etc.

[0037] Cleaning may be performed by a method known in the field of semiconductor technology, but is not limited to this. Cleaning may include rinsing and drying. Cleaning may be performed using any one or a combination of any two or more cleaning solutions (which may be standard or modified compositions), such as SPM (H2SO4 + HO2 + HO: piranha solution), APM (NH4OH + HO2 + HO: SC-1, RCA-1), HPM (HCl + HO2 + HO: SC-2, RCA-2), DHF (HF + HO), and BHF (NH4F + HF + HO). Cleaning may be performed by adding any one or more of trichloroethylene, alcohol, acetone, deionized water, ultrasound, etc., as appropriate. Furthermore, spin drying, isopropanol (IPA) vapor drying, IPA direct displacement drying, etc. may be applied.

[0038] Depending on the chemical solution and conditions used for cleaning, for example, OH is applied to the surface of the silicon substrate (main body in the embodiment shown in FIG. 1) before the bonding portion is provided. - , H + Ions / molecules such as , H2O, H2 and O2 may be introduced, which may result in hydrosilyl and / or silanol groups on such surfaces.

[0039] The bonded portion, which is a silicon oxide portion, can be formed, for example, by oxidizing the entire surface or a partial region of the surface of the silicon substrate (typically, one of the two opposing surfaces of the silicon substrate). Oxidation of silicon can be achieved by heating in an oxygen-containing atmosphere (so-called thermal oxidation) and / or natural oxidation. For example, the bonded portion of this embodiment can be formed by depositing silicon oxide on the entire surface or a partial region of the surface of the silicon substrate (typically, one of the two opposing surfaces of the silicon substrate). The deposition of silicon oxide may be performed by any one of sputtering, chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), evaporation, etc., or by a combination of any two or more of these. The oxidation of silicon and the deposition of silicon oxide may also be performed in combination. However, the present invention is not limited to these methods, and the bonded portion, which is a silicon oxide portion, can be formed by any appropriate method.

[0040] A small number of silanol groups (-Si-OH) are always present on the surface of the bonding portion, which is the silicon oxide portion.

[0041] Although not essential to this embodiment, it is preferable to subject at least one of the first and second bonding portions to a surface treatment that generates hydrosilyl groups and / or silanol groups after step (a) and before step (b). This allows hydrosilyl groups (-Si-H) and / or silanol groups (-Si-OH) to be present at a higher density on the surface of the bonding portion. The surface treatment only needs to be performed on the surface (bonding surface) of the bonding portion, and may be performed on only the surface of the bonding portion or on a wider surface including the surface of the bonding portion.

[0042] The surface treatment that generates hydrosilyl groups and / or silanol groups may be at least one selected from the group consisting of hydrogen atom treatment, heat treatment in a hydrogen-containing atmosphere, sputtering treatment, chemical vapor deposition (CVD), and termination treatment using a chemical solution. Hydrogen atoms can be introduced into the surface of the bonded portion by hydrogen atom treatment, heat treatment in a hydrogen-containing atmosphere, sputtering treatment, CVD, or termination treatment using a chemical solution to generate hydrosilyl groups (-Si-H). Hydroxyl groups can be introduced into the surface of the bonded portion by termination treatment using a chemical solution to generate silanol groups (-Si-OH).

[0043] The hydrogen atom treatment is carried out, for example, in an ultra-high vacuum (1×10 -6 A vacuum chamber (less than 1×10 Pa) was filled with hydrogen gas at 1×10 -4 This may be carried out by supplying a pressure of about Pa, dissociating hydrogen molecules into hydrogen atoms by thermal electrons or plasma, and adsorbing the hydrogen atoms onto the surface of the joint.

[0044] Heat treatment in a hydrogen-containing atmosphere may be performed, for example, by replacing the atmosphere in the chamber with hydrogen gas by flowing hydrogen as a carrier gas during evacuation, creating a vacuum state of a hydrogen atmosphere (specifically, a hydrogen atmosphere of 10 Pa or less), heating the substrates in this atmosphere to about 100 to 400°C, and allowing hydrogen to be adsorbed onto the surface of the bonding portion.

[0045] The sputtering process may be carried out, for example, by using silicon as a sputtering source to supply hydrogen and allow the hydrogen to be adsorbed on the surface of the joint.

[0046] The CVD process may be carried out, for example, by using silane as a CVD gas and adjusting the hydrogen gas pressure to adsorb hydrogen atoms onto the surface of the joint.

[0047] Termination treatment using a chemical solution may be performed by, for example, immersing the silicon substrate with at least the bonded portion exposed in a chemical solution such as an aqueous solution of hydrofluoric acid (hydrofluoric acid) or ammonium fluoride, and bonding hydrogen ions and / or hydroxide ions to the surface of the bonded portion depending on the chemical solution used.

[0048] Although not essential to this embodiment, after step (a) and before step (b), at least one of the first bonding portion and the second bonding portion may be subjected to a surface treatment that generates a fluorosilyl group.

[0049] The surface treatment to generate fluorosilyl groups may be at least one selected from the group consisting of CVD, discharge treatment, ion implantation, and termination treatment using a chemical solution. The surface treatment to generate fluorosilyl groups may be performed separately from or simultaneously with the surface treatment to generate hydrosilyl groups and / or silanol groups. When performed separately, either of these surface treatments may be performed first.

[0050] The CVD process may be performed, for example, by using CF4 and / or SF6 as a CVD gas to adsorb fluorine atoms onto the surface of the joint.

[0051] The discharge treatment may be carried out by, for example, performing plasma discharge or corona discharge in an atmosphere containing CF4 and / or SF6, etc., to adsorb fluorine radicals onto the surface of the joint.

[0052] The ion implantation may involve implanting fluorine ions into the junction in any suitable manner.

[0053] Termination using a chemical solution may be performed by immersing the silicon substrate with at least the bonded portion exposed in a chemical solution such as hydrofluoric acid (hydrofluoric acid) or ammonium fluoride, and bonding fluorine ions to the bonded portion surface depending on the chemical solution used. In particular, termination using a hydrofluoric acid solution can generate hydrosilyl groups (-Si-H), silanol groups (-Si-OH), and fluorosilyl groups (-Si-F).

[0054] In this manner, the first silicon substrate and the second silicon substrate are prepared. Note that the first silicon substrate and the second silicon substrate do not require trenches and gas exhaust ports, but at least one of them may have trenches and / or gas exhaust ports. The trenches and / or gas exhaust ports may be formed at any appropriate time.

[0055] ·Process (b) Next, an organic material capable of reacting with a hydrosilyl group and / or a silanol group is supplied between the first bonding portion and the second bonding portion, and the first bonding portion and the second bonding portion are bonded together by a reaction product derived from the organic material.

[0056] The specific aspects of the method for supplying the organic material and the bonding method may be appropriately selected depending on the organic material used. Generally, after supplying the organic material, the first and second silicon substrates may be maintained under predetermined reaction conditions (particularly, a predetermined temperature) with the organic material interposed between the first and second bonding portions, thereby bonding the first and second bonding portions with a reaction product.

[0057] More specifically, for example, an organic material (which may be a composition) is applied (e.g., by coating, spraying, printing, etc.) to one or both of the surfaces of at least the first bonding portion of the first silicon substrate and at least the surfaces of the second bonding portion of the second silicon substrate. The organic material may be applied in its original form or in the form of a composition mixed with any appropriate component (e.g., a solvent, etc.). When a composition containing an organic material is used, the water content of the composition is substantially zero. By reducing the water content in the composition in this manner, the occurrence of voids can be reduced. Thereafter, washing and / or drying may be performed as necessary. The washing and drying may be similar to those described above. When a fluorine-containing organic material is used, pre-cleaning using a fluorine-based solvent may be performed. Next, the first silicon substrate and the second silicon substrate are aligned so that the first bonding portion and the second bonding portion face each other, and the first silicon substrate and the second silicon substrate are brought into close contact with each other with the organic material interposed between the first bonding portion and the second bonding portion. The first and second silicon substrates that have been brought into close contact are maintained under predetermined reaction conditions (particularly, a predetermined temperature) to allow the reaction to proceed, after which an annealing treatment may be carried out as necessary.

[0058] The reaction conditions may vary depending on the organic material used, but the predetermined temperature may be, for example, 200°C or less, particularly 120°C or less, more particularly 80°C or less, or may simply be room temperature (typically 10°C or more and 40°C or less). According to this embodiment, bonding can be performed at such a relatively low temperature, so that bonding misalignment caused by thermal expansion of the silicon substrate can be reduced, and the first bonding portion and the second bonding portion can be bonded with high precision. The pressure (absolute pressure) is, for example, 10 -8 Pa or higher, especially 10 -5 Pa or more, especially 10 -1 Pa or more, and more particularly 10 2 Pa or higher, and is conveniently set at atmospheric pressure (typically about 1.01 × 10 5 When a reduced pressure is applied, for example, 10 5 Pa or less, especially 10 4 Pa or less, more particularly 10 3 Pa or less.

[0059] The organic material may be, for example, an organic material having at least one selected from the group consisting of an alkenyl group, a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, an acid anhydride group, and a siloxane bond. The alkenyl group can react with a hydrosilyl group (-Si-H), and the hydroxyl group, the hydrolyzable silyl group, the isocyanate group, the epoxy group, the amino group, the acid anhydride group, and the siloxane bond can react with a silanol group (-Si-OH).

[0060] More specifically, the organic material is (i) a substituted or unsubstituted hydrocarbon compound having alkenyl groups at two terminal ends; (ii) a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one end and a group selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, and an acid anhydride group at the other end; (iii) a substituted or unsubstituted hydrocarbon compound having at its two terminal ends any one group independently selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, and an acid anhydride group; (iv) silsesquioxanes and their derivatives; (v) A combination of a hydrolyzable hydrosilane or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end, and a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkenyl group at the other end. (vi) a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end; and (vii) A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end. The organic material may contain at least one selected from the group consisting of: It should be noted that the organic material may be one type of compound or a combination of two or more types of compounds.

[0061] Exemplary embodiments using the organic materials (i) to (vii) are described in detail below.

[0062] (i) Example of using organic materials In this example, the first and second silicon substrates have hydrosilyl groups (-Si-H) on the surfaces of the first and second bonding portions (which are silicon oxide portions in this embodiment). The first and second silicon substrates having hydrosilyl groups on the surfaces of the first and second bonding portions, which are silicon oxide portions, may be obtained, for example, by the surface treatment described above that generates hydrosilyl groups.

[0063] The organic material is a substituted or unsubstituted hydrocarbon compound having alkenyl groups at two terminals. The alkenyl group is a group reactive to a hydrosilyl group. Such a compound may have two or more terminals, and may have alkenyl groups at any two or more terminals. Such a compound may be fluorine-substituted, that is, it may be a fluoroalkyl compound or a fluoropolyether group-containing compound having alkenyl groups at two or more terminals.

[0064] Illustrative fluoroalkyl compounds having two, three, or four terminal alkenyl groups are shown below.

[0065] [ka] Rf represents a fluoroalkyl group (the same applies hereinafter).

[0066] The number of carbon atoms in the portion excluding the terminal reactive groups is not particularly limited, but may be, for example, 1 to 200, particularly 100 or less. The portion excluding the reactive groups may be linear, branched, or cyclic. When the portion excluding the terminal reactive groups is a fluoroalkyl group, the fluorine substitution ratio is not particularly limited, but may be, for example, a perfluoroalkyl group.

[0067] The fluoropolyether group-containing compound having alkenyl groups at two or more terminals is, for example, (A) Formula (1): [ka] [In formula: R F2 is -Rf 2 p -R F -O q - and; Rf 2 C optionally substituted with one or more fluorine atoms 1-20 is an alkylene group; R F independently in each occurrence represent the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - (In the formula, R Fa is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula, provided that all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or greater. is a group represented by the formula: p is 0 or 1; q is 0 or 1; R D is CH2=CH-; X A are each independently a single bond or a divalent to decavalent organic group; Each γ is independently an integer of 1 to 9. or a compound represented by (B) Formula (2): [ka] [In formula: R N teeth, [ka] and; R F2 is -Rf 2 p -R F -O q - and; Rf 2 C optionally substituted with one or more fluorine atoms 1-6 is an alkylene group; R F independently in each occurrence represent the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - (In the formula, R Fa is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula, provided that all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or greater. is a group represented by the formula: p is 0 or 1; q is 0 or 1; X ais, independently in each occurrence, a single bond or a divalent organic group; R A1 are each independently in each occurrence: OR Ac is a group-containing group; R Ac is a (meth)acryloyl group; R B independently in each occurrence, R F1 -X a - or R A1 -X b - and R F1 is Rf 1 -R F -O q - and; Rf 1 C optionally substituted with one or more fluorine atoms 1-16 is an alkyl group, X b is a divalent organic group. The compound may be represented by the formula:

[0068] The organic material is supplied between the first and second bonding portions, and the alkenyl groups of the organic material react (hydrosilylate) with the hydrosilyl groups of the first and second bonding portions. As a result, a reaction product derived from the organic material chemically bonds to the Si atoms of the first and second bonding portions, bonding the first and second bonding portions together with the reaction product derived from the organic material. This reaction does not produce by-products, fundamentally eliminating the problem of void formation due to by-products.

[0069] The reaction may be carried out in one step with the organic material sandwiched between the first and second bonding portions, or in two steps, in which the organic material is applied to one of the first and second bonding portions to allow the reaction to proceed partially, and then the other bonding portion is placed on top of the organic material to allow the reaction to proceed further.

[0070] As an example, the reaction when a fluoroalkyl compound having alkenyl groups at two terminals is used is shown below. (The same applies to the case of a fluoropolyether group-containing compound having alkenyl groups at two terminals.)

[0071] [ka]

[0072] The reaction products derived from the organic material are preferably chemically bonded to both the Si atoms of the first and second bonding portions. However, it is not necessary for all reaction products to be chemically bonded to both the Si atoms of the first and second bonding portions. Some reaction products may be chemically bonded to only one of the Si atoms of the first and second bonding portions, or may be chemically bonded to two or more Si atoms within the same silicon substrate. To obtain higher bonding strength, it is preferable that more reaction products be chemically bonded to both the Si atoms of the first and second bonding portions. From this perspective, the organic material is preferably a linear compound having alkenyl groups at both ends, but is not limited to this.

[0073] (ii) Example of using organic materials In this example, the first silicon substrate has silanol groups (-Si-OH) on the surface of the first bonding portion (a silicon oxide portion in this embodiment), and the second silicon substrate has hydrosilyl groups (-Si-H) on the surface of the second bonding portion (a silicon oxide portion in this embodiment). The first silicon substrate having silanol groups on the surface of the first bonding portion, which is a silicon oxide portion, does not require any particular surface treatment, but may be obtained, if necessary, by the above-mentioned surface treatment that generates silanol groups. The second silicon substrate having hydrosilyl groups on the surface of the second bonding portion, which is a silicon oxide portion, may be obtained, for example, by the above-mentioned surface treatment that generates hydrosilyl groups.

[0074] The organic material is a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one end and a hydroxyl group at the other end. The alkenyl group is a group reactive with hydrosilyl groups, and the hydroxyl group is a group reactive with silanol groups. Such a compound may have two or more end groups, and may have an alkenyl group at any one or more end groups and a hydroxyl group at any one or more end groups. Such a compound may be fluorine-substituted, in other words, a fluoroalkyl compound or a fluoropolyether group-containing compound having an alkenyl group at one end and a hydroxyl group at the other end group.

[0075] Unless otherwise specified, the above description may apply. (Other than having a hydroxyl group at at least one terminal, the compound may be the same as the fluoroalkyl compound or fluoropolyether group-containing compound detailed in (i) above.)

[0076] The organic material is supplied between the first and second bonding portions, and the hydroxyl groups of the organic material are reacted with the silanol groups of the first bonding portion (etherification by dehydration), and the alkenyl groups of the organic material are reacted with the hydrosilyl groups of the second bonding portion (hydrosilylation). As a result, the reaction product derived from the organic material chemically bonds to the Si atoms of the first bonding portion and the Si atoms of the second bonding portion, and the first bonding portion and the second bonding portion are bonded together by the reaction product derived from the organic material.

[0077] More specifically, it is preferable to supply an organic material to the first bond, react the hydroxyl groups of the organic material with the silanol groups of the first bond (first step), and then arrange the first bond and the second bond opposite each other to react the alkenyl groups of the organic material with the hydrosilyl groups of the second bond (second step). According to this procedure, water is generated as a by-product in the first step, but this by-product can be removed without being trapped between the first and second bond, and no by-products are generated in the second step, preventing voids from forming due to the by-products.

[0078] As an example, the reaction when a fluoroalkyl compound having an alkenyl group at one end and a hydroxyl group at the other end is used is shown below.

[0079] [ka]

[0080] In order to obtain higher bonding strength, the organic material is preferably a straight-chain compound having an alkenyl group and a hydroxyl group at both ends, but is not limited to this.

[0081] Furthermore, in this example, the first silicon substrate has silanol groups on the surface of the first bonding portion, and the second silicon substrate has hydrosilyl groups on the surface of the second bonding portion. Therefore, when an organic material (preferably linear) having an alkenyl group and a hydroxyl group at both ends is used, it is possible to prevent the reaction product from chemically bonding to two or more Si atoms within the same silicon substrate, thereby achieving even higher bonding strength.

[0082] The above describes an example of using a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one end and a hydroxyl group at the other end as the organic material. However, instead of or in addition to the hydroxyl group, a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, or an acid anhydride group may also be used. Hydroxyl groups, hydrolyzable silyl groups, isocyanate groups, epoxy groups, amino groups, and acid anhydride groups can all function as groups reactive with silanol groups. (Note that a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one end and a hydroxyl group at the other end may be similar to the substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two ends, as described in detail in (iii) below, except that it has an alkenyl group at at least one end.)

[0083] (iii) First example using organic materials In this example, the first and second silicon substrates used have silanol groups (-Si-OH) on the surfaces of the first and second bonding portions (which are silicon oxide portions in this embodiment). The first and second silicon substrates having silanol groups on the surfaces of the first and second bonding portions, which are silicon oxide portions, do not require any particular surface treatment, but may be obtained, if necessary, by the above-mentioned surface treatment that generates silanol groups.

[0084] The organic material is a substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two terminals. Such a compound may have two or more terminals, and may have hydrolyzable silyl groups at any two or more terminals. Such a compound may be fluorine-substituted, in other words, a fluorine-containing silane compound such as a fluoroalkyl compound having hydrolyzable silyl groups at two terminals or a fluoropolyether group-containing compound.

[0085] The fluorine-containing silane compound is, for example, a compound represented by the following formula (11): [ka] [In formula: R F2 is -Rf 2 p -R F r -O q - and; Rf 2 C optionally substituted with one or more fluorine atoms 1-20 is an alkylene group; R F independently in each occurrence represent the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4)e -(OCF2) f - (In the formula, R Fa is independently in each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula, provided that all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or greater. is a group represented by the formula: p is 0 or 1; q is 0 or 1; r is 0 or 1; where either p or r is 1; R Si is each independently in each occurrence a formula (S1), (S2), (S3), (S4) or (S5): [ka] (In the formula: R 11 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 12 is independently in each occurrence a hydrogen atom or a monovalent organic group; n1 is (SiR 11 n1 R 12 3-n1 ) units are each independently an integer of 0 to 3; X 11 is independently in each occurrence a single bond or a divalent organic group; R 13 is independently in each occurrence a hydrogen atom or a monovalent organic group; t, independently in each occurrence, is an integer greater than or equal to 2; R 14is independently in each occurrence a hydrogen atom, a halogen atom or -X 11 -SiR 11 n1 R 12 3-n1 and; R a1 independently in each occurrence -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 and; Z 1 is independently in each occurrence an oxygen atom or a divalent organic group; R 21 independently in each occurrence -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ and; R 22 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 23 is independently in each occurrence a hydrogen atom or a monovalent organic group; p1, in each occurrence, is independently an integer from 0 to 3; q1, in each occurrence, is independently an integer from 0 to 3; r1, in each occurrence, is independently an integer from 0 to 3; Z 1’ is independently in each occurrence an oxygen atom or a divalent organic group; R 21’ independently in each occurrence -Z 1” -SiR 22” q1” R 23” r1” and; R 22’ is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 23’is independently in each occurrence a hydrogen atom or a monovalent organic group; p1' in each occurrence is independently an integer from 0 to 3; q1' is independently in each occurrence an integer from 0 to 3; r1' in each occurrence is independently an integer from 0 to 3; Z 1” is independently in each occurrence an oxygen atom or a divalent organic group; R 22” is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 23” is independently in each occurrence a hydrogen atom or a monovalent organic group; q1″ in each occurrence is independently an integer from 0 to 3; r1″ is independently in each occurrence an integer from 0 to 3; R b1 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R c1 is independently in each occurrence a hydrogen atom or a monovalent organic group; k1, in each occurrence, is independently an integer from 1 to 3; l1, in each occurrence, is independently an integer from 0 to 3; m1 in each occurrence is independently an integer from 0 to 3; R d1 independently in each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 and; Z 2 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R 31 independently in each occurrence -Z 2’ -CR 32’ q2’ R 33’r2’ and; R 32 independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 and; R 33 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2, in each occurrence, is independently an integer from 0 to 3; q2 in each occurrence is independently an integer from 0 to 3; r2, in each occurrence, is independently an integer from 0 to 3; Z 2’ is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R 32’ independently in each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 and; R 33’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is independently in each occurrence an integer from 0 to 3; r2' is independently in each occurrence an integer from 0 to 3; Z 3 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R 34 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 35 is independently in each occurrence a hydrogen atom or a monovalent organic group; n2 in each occurrence is independently an integer from 0 to 3; R e1 independently in each occurrence -Z 3 -SiR 34 n2 R 353-n2 and; R f1 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2, in each occurrence, is independently an integer from 0 to 3; l2, in each occurrence, is independently an integer from 0 to 3; m2 in each occurrence is independently an integer from 0 to 3; R g1 and R h1 independently in each occurrence -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , -Z 4 -CR d1 k2 R e1 l2 R f1 m2 and; Z 4 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; However, in formulae (S1), (S2), (S3), (S4), and (S5), there is at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded.) is a group represented by the formula: X A are each independently a single bond or a divalent to decavalent organic group; Each γ is independently an integer of 1 to 9. The compound may be represented by the formula:

[0086] The hydrolyzable group means a group that can undergo a hydrolysis reaction, and is preferably —OR j , -OCOR j , -ON=CR j 2, -NR j 2, -NHR j, or halogen. j is a substituted or unsubstituted C 1-4 alkyl group, preferably unsubstituted C 1-4 It is an alkyl group. 1-4 The alkyl group is preferably an ethyl group or a methyl group, more preferably a methyl group.

[0087] The hydrolyzable silyl group may be, in its simplest form, an alkoxysilyl group. The number of alkoxy groups in the alkoxysilyl group is 1 to 3, for example, 3. The number of carbon atoms in the alkoxy group may be, for example, 1 to 4, particularly 2 or less, and preferably 1.

[0088] Unless otherwise specified, the above explanations may apply.

[0089] The organic material is supplied between the first and second bonding portions, and the hydrolyzable silyl groups of the organic material react with the silanol groups of the first and second bonding portions (for example, when the hydrolyzable groups are alkoxy groups, siloxane bonds are formed by dealcoholization). This chemically bonds the reaction product derived from the organic material to the Si atoms of the first and second bonding portions, bonding the first and second bonding portions together with the reaction product derived from the organic material. This reaction generates by-products, such as alcohols, which can have a small carbon number as described above and can be effectively removed from between the first and second bonding portions to the outside through the gaps in the reaction product, thereby reducing the formation of voids due to the by-products.

[0090] The reaction may be carried out in one step with the organic material sandwiched between the first and second bonding portions, or in two steps, in which the organic material is applied to one of the first and second bonding portions to allow the reaction to proceed partially, and then the other bonding portion is placed on top of the organic material to allow the reaction to proceed further.

[0091] As an example, the reaction using an alkyl compound having trimethoxysilyl groups at two terminals is shown below. (The following also shows an example in which the reaction is carried out in two separate steps as described above.)

[0092] [ka]

[0093] [ka]

[0094] In order to obtain higher bonding strength, the organic material is preferably a linear compound having hydrolyzable silyl groups at both ends, but is not limited to this.

[0095] (iii) Second example using organic materials In this example, the differences from the first example using an organic material (iii) will be mainly described, and unless otherwise specified, the same description as in the first example above can be applied.

[0096] The organic material used is a substituted or unsubstituted hydrocarbon compound having isocyanate groups at two terminals. Such a compound may have two or more terminals, and may have isocyanate groups at any two or more terminals.

[0097] The organic material is supplied between the first and second bonding portions, and the isocyanate groups of the organic material react with the silanol groups of the first and second bonding portions (forming urethane bonds). This chemically bonds the reaction product derived from the organic material to the Si atoms of the first and second bonding portions, bonding the first and second bonding portions together with the reaction product derived from the organic material. This reaction does not produce by-products, fundamentally eliminating the problem of void formation due to by-products.

[0098] As an example, the reaction when an alkyl compound having isocyanate groups at two terminals is used is shown below.

[0099] [ka]

[0100] (iii) A third example using organic materials In this example, differences from the first example using an organic material (iii) will be mainly described, and unless otherwise specified, the same description as for the first example can be applied.

[0101] The organic material is a substituted or unsubstituted hydrocarbon compound having acid anhydride groups at two terminals. Such a compound may have two or more terminals, and may have acid anhydride groups at any two or more terminals.

[0102] The organic material is supplied between the first and second bonding portions, and the acid anhydride groups of the organic material react with the silanol groups of the first and second bonding portions. As a result, the reaction product derived from the organic material chemically bonds to the Si atoms of the first and second bonding portions, bonding the first and second bonding portions together with the reaction product derived from the organic material. This reaction does not produce by-products, fundamentally eliminating the problem of void formation due to by-products.

[0103] As an example, the reaction when an alkyl compound having acid anhydride groups at two terminals is used is shown below.

[0104] [ka] R represents an alkyl group.

[0105] The above describes the first to third examples of the organic material, which use substituted or unsubstituted hydrocarbon compounds having hydrolyzable silyl groups, isocyanate groups, or acid anhydride groups at two terminal ends. However, instead of or in addition to the hydrolyzable silyl groups, isocyanate groups, or acid anhydride groups, substituted or unsubstituted hydrocarbon compounds having hydroxyl groups, epoxy groups, and / or amino groups may also be used. The hydroxyl groups, hydrolyzable silyl groups, isocyanate groups, epoxy groups, amino groups, and acid anhydride groups can all function as reactive groups with silanol groups. These reactive groups at at least two terminal ends may be the same or different.

[0106] (iv) Example of using organic materials In this example, the differences from the first example using an organic material (iii) will be mainly described, and unless otherwise specified, the same description as in the first example above can be applied.

[0107] Silsesquioxane is used as the organic material. Silsesquioxane refers to a silicon-containing polymer (polysiloxane) whose main chain is composed of siloxane bonds and whose basic structural unit is a T unit. Silsesquioxane is a (R'SiO 1.5 ) n(R' can be any organic group, n is 6 or more), and can have a random structure, a ladder structure, a cage structure (a complete cage structure, an incomplete cage structure), etc. Examples of hydrocarbon groups where R' is a hydrocarbon group include methyl, ethyl, propyl (n-propyl, i-propyl), butyl (n-butyl, i-butyl, t-butyl, sec-butyl), pentyl (n-pentyl, i-pentyl, neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, i-hexyl, cyclohexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl (n-octyl, i-octyl, t-octyl, etc.), nonyl (n-nonyl, i-nonyl, etc.), decyl (n-decyl, i-decyl, etc.), uracil, ...), hexyl (n-pentyl, i-pentyl, neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, i-hexyl, cyclohexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl (n-octyl, i-octyl, Examples of the alkyl group include acyclic or cyclic aliphatic hydrocarbon groups such as undecyl (n-undecyl, i-undecyl, etc.) and dodecyl (n-dodecyl, i-dodecyl, etc.), acyclic and cyclic alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and styrenyl, and aralkyl groups such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl, and aralkyl groups such as PhCH=CH-, aryl groups such as phenyl, tolyl, and xylyl, and substituted aryl groups such as 4-aminophenyl, 4-hydroxyphenyl, 4-methoxyphenyl, and 4-vinylphenyl.

[0108] The organic material is supplied between the first and second bonding portions, and the siloxane bond sites of the organic material react with the silanol groups of the first and second bonding portions (siloxane bond cleavage and addition). As a result, reaction products derived from the organic material chemically bond to the Si atoms of the first and second bonding portions, bonding the first and second bonding portions with the reaction products derived from the organic material. This reaction does not produce by-products, fundamentally eliminating the problem of void formation due to by-products.

[0109] For example, T8 silsesquioxane ((R'SiO)) having a complete cage structure is1.5 The reaction when 8) is used is shown below.

[0110] [ka]

[0111] In order to obtain higher bonding strength, the organic material is preferably a cage silsesquioxane having a clear molecular structure, but is not limited to this.

[0112] Although the above describes an example in which silsesquioxane is used as the organic material, a silsesquioxane derivative may also be used. The silsesquioxane derivative may be any compound derived from silsesquioxane, and may have any substituent, modifying group, functional group, etc.

[0113] (v) Example of using organic materials In this example, the differences from the first example using an organic material (iii) will be mainly described, and unless otherwise specified, the same description as in the first example above can be applied.

[0114] The organic material is a combination of two organic materials: a hydrolyzable hydrosilane or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end; and a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkenyl group at the other end.

[0115] The first organic material may be a hydrolyzable hydrosilane, or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end, or a mixture thereof. The hydrolyzable hydrosilane may be one having an H atom on one Si atom and one or more hydrolyzable groups. The substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end may have two or more ends, and may have a hydrolyzable silyl group at any one or more ends and a hydrosilyl group at any one or more ends. The substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end may be similar to the substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two ends described in detail in (iii) above, except for the presence of a hydrosilyl group at the other end.

[0116] The second organic material is a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkenyl group at the other end. Such a compound may have two or more end portions, and may have a hydrolyzable silyl group at any one or more end portions and an alkenyl group at any one or more end portions. The substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkenyl group at the other end may be similar to the substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two end portions described in detail in (iii) above, except for the presence of an alkenyl group at the other end portion.

[0117] The first organic material is supplied to the first bonding portion, causing the hydrolyzable silyl groups of the first organic material to react with the silanol groups of the first bonding portion (e.g., if the hydrolyzable group is an alkoxy group, forming a siloxane bond by dealcoholization). The second organic material is supplied to the second bonding portion, causing the hydrolyzable silyl groups of the second organic material to react with the silanol groups of the second bonding portion (e.g., if the hydrolyzable group is an alkoxy group, forming a siloxane bond by dealcoholization). The first bonding portion and the second bonding portion are then arranged facing each other, with intermediates derived from the first organic material and intermediates derived from the second organic material positioned between them, and these intermediates are reacted (hydrosilylated). As a result, reaction products derived from the first organic material and the second organic material chemically bond to the Si atoms of the first bonding portion and the Si atoms of the second bonding portion, bonding the first bonding portion and the second bonding portion together with the reaction products derived from the organic materials. Although such a reaction produces an alcohol as a by-product, the number of carbon atoms thereof can be small as described above, and it can be effectively removed before the first bonding portion and the second bonding portion are arranged opposite each other, thereby reducing the formation of voids due to the by-product.

[0118] As an example, the reaction when trimethoxyhydrosilane is used as the first organic material and vinyltrimethoxysilane is used as the second organic material is shown below.

[0119] [ka]

[0120] (vi) Example of using organic materials In this example, the differences from the first example using an organic material (iii) will be mainly described, and unless otherwise specified, the same description as in the first example above can be applied.

[0121] The organic material used is a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end. Such a compound may have two or more end portions, and may have a hydrolyzable silyl group at any one or more end portions and an alkyl group at any one or more end portions. The substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end may be similar to the substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two end portions detailed in (iii) above, except for the alkyl group at the other end portion.

[0122] The organic material is supplied to the first bonding section, where the hydrolyzable silyl groups of the organic material react with the silanol groups of the first bonding section (e.g., if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). The organic material is also supplied to the second bonding section, where the hydrolyzable silyl groups of the organic material react with the silanol groups of the second bonding section (e.g., if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). (The organic material supplied to the first bonding section and the organic material supplied to the second bonding section may be the same or different.) The first bonding section and the second bonding section are then arranged facing each other, with an intermediate derived from the organic material positioned between them, and a reaction (radical reaction) is allowed to occur between the intermediates. The reaction (radical reaction) between the intermediates may be carried out using, for example, ultraviolet irradiation, ion beams, or weak plasma. As a result, a reaction product derived from the organic material chemically bonds to the Si atoms of the first bonding portion and the Si atoms of the second bonding portion, and the first bonding portion and the second bonding portion are bonded by the reaction product derived from the organic material. Although alcohol is generated as a by-product in this reaction, the number of carbon atoms thereof can be small as described above, and it can be effectively removed before the first bonding portion and the second bonding portion are arranged opposite each other, thereby reducing the formation of voids due to the by-product.

[0123] As an example, the reaction when ethyltrimethoxysilane is used is shown below.

[0124] [ka]

[0125] (vii) Example of using organic materials In this example, the differences from the first example using an organic material (iii) will be mainly described, and unless otherwise specified, the same description as in the first example above can be applied.

[0126] The organic material used is a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end. Such a compound may have two or more end portions, and may have a hydrolyzable silyl group at any one or more end portions and a reactive functional group at any one or more end portions. The substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end may be similar to the substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two end portions described in detail in (iii) above, except for the reactive functional group at the other end portion.

[0127] The reactive functional group may typically be at least one selected from the group consisting of an isocyanate group, an amino group, a hydroxyl group, a thiol group (also called a sulfanyl group), and the like, but is not limited to these.

[0128] When a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end is used as the organic material, an organic binder having two groups capable of bonding to the reactive functional group of the hydrocarbon compound is also used. Such an organic binder may have two (or more) of the bondable groups, more specifically, the bondable groups may be at any two (or more) of the end(s). The number of carbon atoms in the organic binder excluding the bondable groups is not particularly limited, but may be, for example, 1 to 20, and particularly 5 or less. The portion excluding the bondable groups may be linear, branched, or cyclic. Typically, the organic binder may be a linear organic compound having the bondable groups at both ends, but is not limited thereto.

[0129] The bondable group is selected depending on the reactive functional group. Examples of combinations of reactive functional groups and groups bondable thereto are shown below, but are not limited to these. The reactive functional group may be one or more types, and the bondable group may be one or more types as long as it can be bonded to the reactive functional group.

[0130] [Table 1]

[0131] The reactive functional groups and bondable groups may be reactive with hydrosilyl groups and / or silanol groups, or may not substantially react with them. When all of the reactive functional groups and bondable groups are reactive with hydrosilyl groups and / or silanol groups, it can be understood that two organic materials (iii) are used, but this need not be taken into consideration when using an organic material (vii).

[0132] Any appropriate method (scheme) may be applied to bond the first bonding portion and the second bonding portion using the organic material and the organic binder, including, but not limited to, the following three methods.

[0133] In the first method, the organic material and the organic binder are mixed (e.g., immediately before use), and the resulting mixture is supplied between the first and second bonding portions. The hydrolyzable silyl groups of the organic material react with the silanol groups of the first and second bonding portions (e.g., when the hydrolyzable groups are alkoxy groups, siloxane bonds are formed by dealcoholization). This chemically bonds the organic material to the Si atoms of the first and second bonding portions. Furthermore, the reactive functional groups of the organic material react with the bondable groups of the organic binder to bond the materials together. This allows the organic material chemically bonded to the Si atoms of the first bonding portion and the organic material chemically bonded to the Si atoms of the second bonding portion to be bonded via the organic binder. The reaction between the hydrolyzable silyl groups of the organic material and the silanol groups of the first and second bonding portions, and the reaction between the reactive functional groups of the organic material and the bondable groups of the organic binder can occur at any time; for example, either reaction can proceed first, or they can proceed simultaneously. As a result, the first and second bonding portions are bonded together by a reaction product derived from the organic material and the organic binder. While the first reaction generates by-products, such as alcohols, their carbon numbers can be small as described above, allowing them to be effectively removed from between the first and second bonding portions through the gaps in the reaction product, thereby reducing the formation of voids due to the by-products. In the second reaction, no by-products are generated, for example, with the combinations shown in Table 1.

[0134] In the second method, the organic material is supplied to the first bonding portion, where the hydrolyzable silyl groups of the organic material react with the silanol groups of the first bonding portion (e.g., if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). The organic material is also supplied to the second bonding portion, where the hydrolyzable silyl groups of the organic material react with the silanol groups of the second bonding portion (e.g., if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). (The organic material supplied to the first bonding portion and the organic material supplied to the second bonding portion may be the same or different.) This chemically bonds the organic material to the Si atoms of the first bonding portion and the Si atoms of the second bonding portion. The first bonding portion and the second bonding portion are then arranged facing each other, with an intermediate derived from the organic material and the organic binder positioned between them. The reactive functional groups of the organic material react with the bondable groups of the organic binder to form bonds. As a result, the organic material chemically bonded to the Si atoms of the first bonding portion and the organic material chemically bonded to the Si atoms of the second bonding portion are bonded via the organic binder. As a result, the first bonding portion and the second bonding portion are bonded together by a reaction product derived from the organic material and the organic binder. While alcohol, for example, is produced as a by-product in the first-stage reaction, its carbon number can be small as described above, and it can be effectively removed before the first bonding portion and the second bonding portion are placed opposite each other, thereby reducing the formation of voids due to the by-product. In the second-stage reaction, for example, with the combinations shown in Table 1, no by-products are produced.

[0135] In the third method, the organic material is supplied to the first bonding portion, where the hydrolyzable silyl groups of the organic material react with the silanol groups of the first bonding portion (for example, if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization), and the organic material is supplied to the second bonding portion, where the hydrolyzable silyl groups of the organic material react with the silanol groups of the second bonding portion (for example, if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). (The organic material supplied to the first bonding portion and the organic material supplied to the second bonding portion may be the same or different.) As a result, the organic material chemically bonds to the Si atoms of the first bonding portion and the Si atoms of the second bonding portion (intermediate X). Then, a first bonding portion is conveniently selected as one of the resulting first and second bonding portions, and the organic binder is supplied to the first bonding portion to react and bond the reactive functional groups of the organic material with the bondable groups of the organic binder (intermediate Y). The resulting first bonding portion and the resulting second bonding portion are then arranged facing each other, with intermediate Y derived from the organic material positioned on the first bonding portion side and intermediate X derived from the organic material and the organic binder positioned on the second bonding portion side, and the reactive functional groups of intermediate X (the organic material) react and bond with the bondable groups of intermediate Y (the organic material + the organic binder). This bonds the organic material chemically bonded to the Si atoms of the first bonding portion and the organic material chemically bonded to the Si atoms of the second bonding portion via the organic binder. As a result, the first and second bonding portions are bonded together by a reaction product derived from the organic material and the organic binder. While alcohol, for example, is produced as a by-product in the preceding reaction, its carbon number can be small as described above, and it can be effectively removed before the first and second bonding portions are placed face-to-face, thereby reducing the formation of voids due to the by-product. Furthermore, this method effectively removes any unreacted organic binder that may remain on the second bonding portion before placing the first and second bonding portions face-to-face. This reduces the amount of unnecessary material (that does not contribute to bonding) remaining between the first and second bonding portions in the final laminate.In the latter reaction, for example, the combinations shown in Table 1 do not produce by-products.

[0136] As an example, the reaction when isocyanatomethyltrimethoxysilane is used as the organic material and ethylenediamine (1,2-diaminoethane) is used as the organic binder is shown below. In the following schematic diagram, the upper part conveniently shows only the bonding portion of one of the substrates, the first method corresponds to the scheme indicated by the arrows pointing from the upper left to the lower part, the second method corresponds to the scheme indicated by the arrows pointing from the upper left to the center and from the center to the lower part, and the third method corresponds to the scheme indicated by the arrows pointing from the upper left to the center, from the center to the upper right, and from the upper right to the lower part (the same applies below).

[0137] [ka]

[0138] The reaction when isocyanatomethyltrimethoxysilane is used as the organic material and 1,2-ethanedithiol is used as the organic binder is shown below.

[0139] [ka]

[0140] The reaction when isocyanatomethyltrimethoxysilane is used as the organic material and ethylene glycol (1,2-ethanediol) is used as the organic binder is shown below.

[0141] [ka]

[0142] The reaction when aminomethyltrimethoxysilane is used as the organic material and ethylene diisocyanate (1,2-ethane diisocyanate) is used as the organic binder is shown below.

[0143] [ka]

[0144] Although exemplary embodiments using organic materials (i) to (vii) have been described in detail above, the present embodiment is not limited to these embodiments.

[0145] In the manner described above, the laminate 40 of this embodiment is manufactured. In the laminate 40, the bonding layer 30 contains an organic substance. Such an organic substance can be understood as a residue of an organic material capable of reacting with a hydrosilyl group and / or a silanol group.

[0146] The organic substance may be chemically bonded to the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23 .

[0147] The bonding layer 30 can be made extremely thin. The thickness of the bonding layer 30 can be, for example, 10 nm or less, particularly 8 nm or less, and although there is no particular lower limit, it can be, for example, 1 nm or more.

[0148] According to this embodiment, the laminate can be manufactured at a relatively low temperature, and the occurrence of voids can be effectively suppressed or prevented.

[0149] (Embodiment 2) This embodiment relates to an embodiment in which the bonding portions of two silicon substrates are silicon layers formed on underlying portions that contain silicon oxide, and these bonding portions are directly bonded. This embodiment will be described focusing on the differences from the above-described first embodiment, and unless otherwise specified, the same description as in the above-described first embodiment can be applied.

[0150] Referring to FIG. 2, the laminate 40′ of this embodiment is a first silicon substrate 10' having a first underlayer 15 and a first bonding portion 17 formed thereon; a second silicon substrate 20' having a second underlayer 25 and a second bonding portion 27 formed thereon; Includes.

[0151] The first silicon substrate 10' and the second silicon substrate 20' (hereinafter collectively referred to as "silicon substrates") are not particularly limited as long as they have a first bonding portion 17 and a second bonding portion 27 (hereinafter collectively referred to as "bonding portions") to be bonded to each other on a first base portion 15 and a second base portion 25 (hereinafter collectively referred to as "base portions"), respectively.

[0152] 2, the first bonding portion 17 may be a film on the first base portion 15 formed on the entire surface of one side of the main body portion 11 of the first silicon substrate 10′, and the second bonding portion 27 may be a film on the second base portion 25 formed on the entire surface of one side of the main body portion 21 of the second silicon substrate 20′, but this embodiment is not limited to this. For example, the bonding portion may be a portion on one surface of the silicon substrate that is adjacent to a metal portion and is provided on the base portion, more specifically, a portion between two metal portions and is provided on the base portion, and in this case, hybrid bonding may be performed between the first silicon substrate and the second silicon substrate.

[0153] The laminate 40' of this embodiment differs from the laminate of embodiment 1 in that it does not have a bonding layer containing an organic substance between the first bonding portion 17 and the second bonding portion 27, and the first bonding portion 17 and the second bonding portion 27 are directly bonded together.

[0154] Such a laminate can be manufactured by the following manufacturing method. (c) preparing a first silicon substrate 10' having a first base portion 15 and a first bonding portion 17 formed thereon, and a second silicon substrate 20' having a second base portion 25 and a second bonding portion 27 formed thereon; and (d) Directly joining the first joining portion 17 and the second joining portion 27 Each step is described in detail below.

[0155] ·Process (c) In this embodiment, the base portion may be a portion containing silicon oxide (hereinafter also referred to as a "silicon oxide portion"). The silicon oxide portion may be the same as the silicon oxide portion described above as the bonding portion in the first embodiment.

[0156] In this embodiment, the junction may be a silicon layer. The silicon layer may consist of silicon or may contain any other suitable substance in addition to silicon. Such other substances include, for example, impurities that may be unavoidably mixed in.

[0157] In this embodiment, the thickness of the junction, which is a silicon layer, can be, for example, 100 nm or less, particularly 10 nm or less, and although there is no particular lower limit, can be, for example, 1 nm or more.

[0158] The silicon layer junction can be formed by depositing silicon on an underlayer, such as a silicon oxide portion. The silicon deposition may be performed by any one or a combination of two or more of sputtering, chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), evaporation, etc. However, the silicon layer junction can be formed by any suitable method, without being limited thereto.

[0159] A small number of silanol groups (-Si-OH) are always present on the surface of the bonding portion, which is a silicon layer.

[0160] In this embodiment, after step (c) and before step (d), neither the first bonding portion nor the second bonding portion is subjected to a surface treatment that generates hydrosilyl groups and / or silanol groups.

[0161] Otherwise, step (c) may be the same as step (a) in the production method of embodiment 1.

[0162] ·Process (d) Next, the first bonding portion and the second bonding portion are directly bonded together.

[0163] Direct bonding can be performed, for example, by overlapping the first and second silicon substrates so that the first and second bonding portions face each other, and then heating the substrates while pressing the first and second bonding portions together. The heating temperature is not particularly limited, but can be, for example, 800°C or higher, and the upper limit is not particularly limited, but can be, for example, 1000°C or lower.

[0164] This results in a direct bond between the first and second bonding portions (they are in close contact / bonded to each other). While this embodiment is not bound by any theory, it is believed that the direct bond is achieved by the formation of siloxane bonds (hydrophilic bonding) between silanol groups present on the surface of the first bonding portion and silanol groups present on the surface of the second bonding portion. More specifically, as the temperature increases due to heating, a bond across the interface between the first and second bonding portions is formed by hydrogen bonding of water molecules up to approximately 110°C. Between approximately 110°C and approximately 150°C, water molecules at the interface disappear, and siloxane bonds begin to form. Between approximately 150°C and approximately 800°C, stable siloxane bonds are formed. Above approximately 800°C, a uniform bond is achieved due to the viscous flow of the oxide layer at the interface.

[0165] In this manner, the laminate 40' of this embodiment is manufactured.

[0166] Direct bonding can be confirmed, for example, as follows. The bonded interface is analyzed using a focused ion beam scanning electron microscope (FIB-SEM) and / or transmission electron microscope energy dispersive X-ray spectroscopy (TEM-EDS). In the case of organic molecular bonding, elements derived from the organic molecules (C, F, etc.) are detected, but in the case of direct bonding, elements derived from the organic molecules (C, F, etc.) are not detected. Furthermore, the bonded interface is analyzed using secondary ion mass spectroscopy (SIMS) and / or X-ray photoelectron spectroscopy (XPS) while etching with argon ions or the like from the surface exposed by FIB processing or the like. In the case of organic molecular bonding, ions and elements derived from the organic molecules are detected, but in the case of direct bonding, only Si and O are detected. Therefore, if these analyses show that elements and ions derived from organic molecules are not detected and only Si and O are detected, it can be determined that the bond is direct.

[0167] (Embodiment 3) This embodiment relates to an embodiment in which each bonding portion of two silicon substrates is a silicon layer formed on a base portion that is a portion containing silicon oxide, and these bonding portions are bonded using hydrosilyl groups present on the surface. This embodiment will be described focusing on the differences from the above-mentioned embodiment 2, and unless otherwise specified, the same description as the above-mentioned embodiment 2 can be applied.

[0168] The stack of this embodiment may have a configuration similar to stack 40' described above with reference to FIG.

[0169] The laminate 40' of this embodiment differs from the laminate of embodiment 2 in that the first bonding portion 17 and the second bonding portion 27 are bonded using hydrosilyl groups present on the surface of the bonding portion instead of being bonded directly.

[0170] Such a laminate can be produced by modifying the production method described above in the second embodiment.

[0171] ·Process (c) In this embodiment, after step (c) and before step (d), at least one of, and preferably both of, the first and second bonding portions, which are silicon layers, are subjected to a surface treatment to generate hydrosilyl groups. This allows hydrosilyl groups (-Si-H) to be present at a higher density on the surfaces of the bonding portions. Note that even after the surface treatment to generate hydrosilyl groups, a small amount of silanol groups (-Si-OH) always remain on the surfaces of the bonding portions, which are silicon layers.

[0172] The surface treatment to generate hydrosilyl groups may be the same as that described above in the first embodiment.

[0173] ·Process (d) Next, the first bonding portion and the second bonding portion are bonded together using the hydrosilyl groups present on the surfaces thereof.

[0174] Bonding using hydrosilyl groups can be performed, for example, by overlapping a first silicon substrate and a second silicon substrate so that the first bonding portion and the second bonding portion face each other, and then heating the first bonding portion and the second bonding portion while pressing them together. The heating temperature is not particularly limited, but can be, for example, 100°C or higher, and the upper limit is not particularly limited, but can be, for example, 800°C or lower.

[0175] As a result, the first and second bonding portions are bonded (adhered / bonded to each other) using the hydrosilyl groups present on their surfaces. While this embodiment is not bound by any theory, it is believed that bonding using hydrosilyl groups occurs due to some reaction and / or electrical interaction (e.g., electroaffinity) occurring between the hydrosilyl groups present on the surface of the first bonding portion and the hydrosilyl groups present on the surface of the second bonding portion when hydrosilyl groups are present on the surfaces of both the first and second bonding portions, or between the hydrosilyl groups present on one surface and the silanol groups present on the other surface when hydrosilyl groups are present on the surface of either the first or second bonding portion. Additionally, it is believed that some reaction and / or electrical interaction (e.g., electroaffinity) may also occur between the silanol groups present on the surface of the first bonding portion and the silanol groups present on the surface of the second bonding portion, thereby reinforcing the bond.

[0176] In the manner described above, the laminate of this embodiment is manufactured.

[0177] Bonding using a hydrosilyl group can be confirmed, for example, as follows: When an analysis similar to that described above in embodiment 2 shows that no elements or ions derived from organic molecules are detected, and only Si, O, and H are detected, it can be determined that bonding is using a hydrosilyl group.

[0178] Although three embodiments of the present disclosure have been described above, the present disclosure is not limited thereto and any appropriate modifications are possible. For example, in the illustrated embodiments 1 to 3, two silicon substrates are bonded together over the entire surface of one side thereof, but the present disclosure is not limited to such an embodiment. For example, two silicon substrates may be bonded in a partial region. Furthermore, three or more silicon substrates may be used, with different silicon substrates bonded to both sides of one silicon substrate over the entire surface / in a partial region, or two or more silicon substrates may be bonded to one side of one silicon substrate in separate regions, or a combination thereof may be used. [Industrial Applicability]

[0179] The laminate manufacturing method and laminate of the present disclosure can be suitably used in bonding silicon substrates and in three-dimensional integration technology for silicon semiconductors. [Explanation of symbols]

[0180] 11 First main body part 13 First junction (silicon oxide part) 15 First base part (silicon oxide part) 17 First bonding part (silicon layer) 10, 10' First silicon substrate 21 Second main body part 23 Second junction (silicon oxide part) 25 Second base part (silicon oxide part) 27 Second bonding part (silicon layer) 20, 20' Second silicon substrate 30 Bonding layer 40, 40' laminate

Claims

1. A method for manufacturing a stack including two silicon substrates, comprising: (a) preparing a first silicon substrate having a first bonding portion and a second silicon substrate having a second bonding portion, the first bonding portion and the second bonding portion being portions including silicon oxide; and (b) using an organic material capable of reacting with a hydrosilyl group and / or a silanol group, bonding the first bonding portion and the second bonding portion with a reaction product derived from the organic material; A manufacturing method comprising:

2. 2. The method for producing a laminate according to claim 1, wherein the organic material has at least one selected from the group consisting of an alkenyl group, a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, an acid anhydride group, and a siloxane bond.

3. After (a) and before (b), subjecting at least one of the first bonding portion and the second bonding portion to a surface treatment that generates hydrosilyl groups and / or silanol groups; The method for producing a laminate according to claim 1 or 2, further comprising:

4. 4. The method for producing a laminate according to claim 3, wherein the surface treatment includes at least one selected from the group consisting of a hydrogen atom treatment, a heat treatment in a hydrogen-containing atmosphere, a sputtering treatment, a chemical vapor deposition treatment, and a termination treatment using a chemical solution.

5. The organic material is (i) a substituted or unsubstituted hydrocarbon compound having alkenyl groups at two terminal ends; and (ii) a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one end and a group selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, and an acid anhydride group at the other end; The method for producing a laminate according to claim 3 or 4, comprising at least one selected from the group consisting of:

6. The organic material is (iii) a substituted or unsubstituted hydrocarbon compound having, at two terminal positions, any group independently selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, and an acid anhydride group; (iv) silsesquioxanes and their derivatives; (v) a combination of a hydrolyzable hydrosilane or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end, and a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkenyl group at the other end; and (vi) a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end The method for producing a laminate according to any one of claims 1 to 5, comprising at least one selected from the group consisting of:

7. The organic material is (vii) a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end Including, The method for producing a laminate according to any one of claims 1 to 6, wherein (b) uses the organic material and an organic binder having two groups capable of bonding to the reactive functional group of the hydrocarbon compound of (vii) of the organic material, and bonds the first bonding portion and the second bonding portion with a reaction product derived from the organic material and the organic binder.

8. 8. The method for manufacturing a stacked body according to claim 1, wherein the step (b) includes maintaining the first silicon substrate and the second silicon substrate at a temperature of 200° C. or less.

9. (b) forming the first silicon substrate and the second silicon substrate by 10 －８ Pa or more 10 ５ The method for producing the laminate according to any one of claims 1 to 8, comprising maintaining the pressure at 0.1 Pa or less.

10. A method for manufacturing a stack including two silicon substrates, comprising: (c) preparing a first silicon substrate having a first base portion and a first bonding portion formed thereon, and a second silicon substrate having a second base portion and a second bonding portion formed thereon, wherein the first base portion and the second base portion are portions containing silicon oxide, and the first bonding portion and the second bonding portion are silicon layers; and (d) The first bonding portion and the second bonding portion are bonded directly to each other, or to each other using a hydrosilyl group present on the surface of at least one of the first bonding portion and the second bonding portion. A manufacturing method comprising:

11. A stack including two silicon substrates, a first silicon substrate having a first bonding portion; a second silicon substrate having a second bonding portion; a bonding layer that bonds the first bonding portion and the second bonding portion together; wherein the first bonding portion and the second bonding portion are portions containing silicon oxide, and the bonding layer contains an organic substance chemically bonded to Si atoms of the first bonding portion and Si atoms of the second bonding portion.

12. A stack including two silicon substrates, a first silicon substrate having a first bonding portion; a second silicon substrate having a second bonding portion; a bonding layer that bonds the first bonding portion and the second bonding portion together; wherein the first bonding portion and the second bonding portion are portions containing silicon oxide, and the bonding layer contains an organic substance and has a thickness of 10 nm or less.

13. 13. The laminate according to claim 11 or 12, wherein the organic substance comprises a residue of an organic material capable of reacting with hydrosilyl groups and / or silanol groups.

14. A stack including two silicon substrates, a first silicon substrate having a first underlayer and a first bonding portion formed thereon; a second silicon substrate having a second underlayer and a second bonding portion formed thereon; wherein the first base portion and the second base portion are portions containing silicon oxide, the first bonding portion and the second bonding portion are silicon layers, and the first bonding portion and the second bonding portion are bonded together directly or by using a hydrosilyl group present on a surface of at least one of the first bonding portion and the second bonding portion.

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