Method for manufacturing a stacked body including two silicon substrates and said stacked body

Abstract

To provide a method for manufacturing a laminate and a laminate for increasing the bonding strength between silicon substrates.SOLUTION: A method includes: a step for preparing a first composition in which a first junction portion 13 of a first silicon substrate 10 and a second junction portion 23 of a second silicon substrate 20 comprise a portion containing silicon oxide, and the composition contains at least one of an organic material capable of reacting with hydrosilyl groups and / or silanol groups and an inorganic material capable of bonding with silicon oxide, and the particle count is 3,000 particles / mL or less; and a step for bonding or adhering the first junction portion and the second junction portion using at least one of an organic material and an inorganic material, using the organic material and / or reaction products derived from the organic material, or providing an adhesive layer 30, and the adhesive layer includes a first adhesive portion 31 provided on the first junction portion, and the number of particle clusters contained on the surface opposite the first junction portion of the first adhesive portion is 5 particles / cm2 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a stack including two silicon substrates, and to the stack. [Background technology]

[0002] In the field of semiconductor technology, for example, Patent Document 1 has considered providing an adhesive layer between two silicon substrates as a method for bonding the silicon substrates. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2023 / 276638 Summary of the Invention [Problem to be solved by the invention]

[0004] In bonding silicon substrates as described above, it is necessary to increase the bonding strength between the silicon substrates. Therefore, an object of the present invention is to provide a manufacturing method for increasing the bonding strength between silicon substrates and a laminate formed by the method. [Means for solving the problem]

[0005] In order to solve the above problems, the present disclosure provides the following [1] to

[17] . [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; (b) preparing a first composition containing at least one of an organic material capable of reacting with a hydrosilyl group and / or a silanol group and an inorganic material capable of bonding with silicon oxide, and having a particle amount of 3,000 particles / mL or less; (c) providing an adhesive layer using at least one of the organic material and the inorganic material to bond the first bonding portion and the second bonding portion with the organic material and / or a reaction product derived from the organic material, or to bond the first bonding portion and the second bonding portion with the inorganic material and / or a reaction product derived from the inorganic material; Including, the adhesive layer includes a first adhesive portion provided on the first bonding portion, The number of particle clusters contained on the surface of the first adhesive portion opposite to the first bonding portion is 5 / cm 2 The manufacturing method is as follows. [2] 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; [1] The manufacturing method described in [1]. [3] The organic material is (i) A hydrocarbon compound having two terminal alkenyl groups; (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 a plurality of terminal ends, at least two of which have, independently, one group selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, a phosphoric acid group, and an acid anhydride group; and (iv) silsesquioxanes and their derivatives; The method for producing a laminate according to [1] or [2], comprising at least one selected from the group consisting of: [4] The production method according to any one of [1] to [3], wherein the reaction product is derived from the inorganic material. [5] The manufacturing method according to [4], wherein the reaction product contains at least one selected from the group consisting of SiO2, SiOC, SiOF, SiN, SiCN, HfO2, and La2O3. [6] The production method according to any one of [1] to [5], comprising filtering the second composition to purify it into the first composition. [7] The method for producing a filter according to [6], wherein the filtering is performed using a membrane with an effective diameter of 50 nm or less. [8] The manufacturing method according to [6] or [7], wherein the amount of particles in the second composition is more than 3,000 particles / mL. [9] The bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m 2 The manufacturing method according to any one of [1] to [8] above.

[10] The manufacturing method according to any one of [1] to [9], wherein the first adhesive portion is formed from two or more layers.

[11] The adhesive layer further includes a second adhesive portion bonded to the first adhesive portion, the second adhesive portion is provided on the second joining portion, The number of particle clusters contained on the surface of the second adhesive portion opposite to the second bonding portion is 5 / cm 2 Below is the The manufacturing method according to any one of [1] to

[10] .

[12] The manufacturing method according to

[11] , wherein the second adhesive portion is formed from two or more layers.

[13] The organic material is (i) a substituted or unsubstituted hydrocarbon compound having multiple terminal groups, at least two of which have alkenyl groups; (ii) a substituted or unsubstituted hydrocarbon compound having a plurality of terminal portions, at least one of which has an alkenyl group at one terminal portion and at least one of which has any one 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 one terminal portion; (iii) a substituted or unsubstituted hydrocarbon compound having a plurality of terminal ends, at least two of which independently have a group selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, a phosphoric acid 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 according to

[11] or

[12] , comprising at least one selected from the group consisting of:

[14] a first silicon substrate having a first junction; a second silicon substrate having a second bonding portion located on the first bonding portion side; an adhesive layer located between the first bonding portion and the second bonding portion and adhering the first bonding portion and the second bonding portion; and the first bonding portion and the second bonding portion have a hydrosilyl group and / or a silanol group derived from silicon oxide, or a region bonding to an inorganic material, the adhesive layer includes a reaction product of the hydrosilyl group and / or the silanol group, or a region that bonds with the inorganic material; The number of particle clusters on the surface of the adhesive layer is 5 / cm 2 is as follows: The bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m 2 That's all. Laminate.

[15] The laminate according to

[14] , wherein the adhesive layer is composed of two or more layers.

[16] The material includes at least one of an organic material and an inorganic material, A composition having a particle amount of 3,000 particles / mL or less.

[17] The composition according to

[16] , which is used in the manufacturing method according to claim 1. [Effects of the Invention]

[0006] According to the present disclosure, it is possible to provide a manufacturing method for increasing the bonding strength between silicon substrates and a stacked body formed by the method. [Brief explanation of the drawings]

[0007] [Figure 1] 1 shows a schematic cross-sectional view of a laminate according to a first embodiment. [Figure 2] FIG. 10 is a schematic cross-sectional view of a laminate according to a second embodiment. [Figure 3] FIG. 10 is a schematic cross-sectional view of a laminate according to a modified example. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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.

[0009] First Embodiment FIG. 1 is an explanatory diagram that schematically shows a cross-sectional view of a stacked body 40 of the first embodiment. As shown in FIG. 1, the stacked body 40 has a first silicon substrate 10 and a second silicon substrate 20, with an adhesive layer 30 located between the first silicon substrate 10 and the second silicon substrate 20. The first silicon substrate 10 has a first main body portion 11 and a first bonding portion 13. The second silicon substrate 20 has a second main body portion 21 and a second bonding portion 23. The first bonding portion 13 and the second bonding portion 23 are bonded via the adhesive layer 30.

[0010] The laminate 40 can be obtained by a manufacturing method including the following steps. (a) preparing a first silicon substrate 10 having a first bonding portion 13 and a second silicon substrate 20 having a second bonding portion 23, the first bonding portion 13 and the second bonding portion 23 being portions containing silicon oxide; and (b) preparing a first composition containing at least one of an organic material capable of reacting with a hydrosilyl group and / or a silanol group and an inorganic material capable of bonding to silicon oxide, and having a particle amount of 3,000 particles / mL or less; and (c) Using at least one of the organic material and the inorganic material, the first bonding portion 13 and the second bonding portion 23 are bonded together with the organic material and / or a reaction product derived from the organic material, or an adhesive layer 30 is provided that bonds the first bonding portion 13 and the second bonding portion 23 together with the inorganic material. Including, The adhesive layer 30 includes a first adhesive portion 31 provided on the first bonding portion 13, The number of particle clusters contained on the surface of the first adhesive portion 31 opposite to the first joining portion 13 is 5 particles / cm 2 The following is the result. Use of the above manufacturing method can increase the bonding strength between the first and second silicon substrates 10, 20. In this specification, "organic material and / or reaction product derived from the organic material" may be referred to as "reaction product derived from the organic material."

[0011] Each step will be explained below. In the following, unless otherwise specified, "on the first silicon substrate 10" may refer to a state in direct contact with the first silicon substrate 10, or a state in which other layers are included on the first silicon substrate 10. The same applies to other substrates, layers, and regions.

[0012] [Step a] First, a first silicon substrate 10 having a first bonding portion 13 and a second silicon substrate 20 having a second bonding portion 23 are prepared. The first bonding portion 13 and the second bonding portion 23 are portions containing silicon oxide.

[0013] (First and second silicon substrates 10 and 20) The first and second silicon substrates 10 and 20 (hereinafter collectively referred to as "silicon substrates") may be silicon-based substrates (or base materials), and may consist of silicon or may contain any other suitable material in addition to silicon. Such other materials include, for example, dopants, impurities that may be inevitably 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.).

[0014] The first silicon substrate 10 and the second silicon substrate 20 may have the same configuration or different configurations. In one embodiment, the first silicon substrate 10 and the second silicon substrate have the same configuration. In another embodiment, the first silicon substrate 10 and the second silicon substrate have different configurations.

[0015] The first silicon substrate 10 has a first main body portion 11 and a first bonding portion 13. The first main body portion 11 is an unprocessed silicon substrate, and the first bonding portion 13 is provided on the surface of the first main body portion 11. The first bonding portion 13 may form the entire surface of the first silicon substrate 10 (typically, one of the two opposing surfaces of the first silicon substrate 10), or may form a partial region thereof.

[0016] The second silicon substrate 20 has a second main body portion 21 and a second bonding portion 23. The second main body portion 21 is an unprocessed silicon substrate, and the second bonding portion 23 is provided on the surface of the second main body portion 21. The second bonding portion 23 may form the entire surface of the second silicon substrate 20 (typically, one of the two opposing surfaces of the second silicon substrate 20), or may form a partial region thereof.

[0017] (1st and 2nd joint parts 13, 23) In this embodiment, the first and second bonding portions 13 and 23 (hereinafter also referred to as "bonding portions") may be portions containing silicon oxide (hereinafter also referred to as "silicon oxide portions"). The silicon oxide portions 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.

[0018] The bonding 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). That is, the first bonding portion 13 may form the entire surface of the first silicon substrate 10 (typically, one of the two opposing surfaces of the first silicon substrate 10), or a partial region thereof. The second bonding portion 23 may form the entire surface of the second silicon substrate 20 (typically, one of the two opposing surfaces of the second silicon substrate 20), or a partial region thereof.

[0019] 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). Silicon oxide deposition may be performed by any one of sputtering, chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), evaporation, or a combination of any two or more of these. Oxidation of silicon and 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, may be formed by any appropriate method.

[0020] The surface of the bonding portion, which is the silicon oxide portion, contains silanol groups (-Si-OH).

[0021] The thickness of the bonded portion is not particularly limited as long as the desired or acceptable properties are achieved in the final laminate. For example, the thickness of the bonded portion, which is a silicon oxide portion, can be 1 nm or more and 1 μm or less, particularly 10 nm or less. The thickness of the bonded portion can be measured, for example, using a transmission electron microscope. Furthermore, before bonding, the thickness of the bonded portion can be measured, for example, by ellipsometry. Preferably, the thickness of the bonded portion (both before and after bonding) is measured by ellipsometry.

[0022] Although not essential to this embodiment, it is preferable to subject at least one of the first bonding portion 13 and the second bonding portion 23 to a surface treatment to generate hydrosilyl groups and / or silanol groups after step (a) and before step (c). This allows for a higher density of hydrosilyl groups (-Si-H) and / or silanol groups (-Si-OH) on the surface of the bonding portion. The surface treatment only needs to be performed on the surface (bonding surface) of the bonding portion. It may be performed on only the surface of the bonding portion or on a wider surface including the surface of the bonding portion. The proportion of hydrosilyl groups and silanol groups on the surface of the bonding portion can be measured, for example, using time-of-flight secondary ion mass spectrometry (TOF-SIMS). For example, the proportion of silanol groups (-Si-OH) can be measured by calculating the ratio of -Si-OH to -CH. Here, the ratio of -Si-OH to -CH refers to the ratio of the number of fragment ions.

[0023] 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) treatment, plasma treatment, 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, plasma treatment, 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).

[0024] The hydrogen atom treatment is carried out 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] The plasma treatment may be carried out, for example, by subjecting a silicon substrate to plasma treatment and then reacting the substrate surface with water molecules in the atmosphere or in a water bath.

[0029] 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 hydrofluoric acid solution (hydrofluoric acid), ammonium fluoride, or formic acid, and bonding hydrogen ions and / or hydroxide ions to the surface of the bonded portion depending on the chemical solution used.

[0030] Although not essential to this embodiment, after step (a) and before step (c), at least one of the first bonding portion 13 and the second bonding portion 23 may be subjected to a surface treatment that generates fluorosilyl groups.

[0031] The surface treatment that generates fluorosilyl groups may be at least one selected from the group consisting of CVD, discharge treatment, ion implantation, plasma treatment, and termination treatment using a chemical solution. The surface treatment that generates fluorosilyl groups may be performed separately from or simultaneously with the surface treatment that generates hydrosilyl groups and / or silanol groups. When performed separately, either of these surface treatments may be performed first.

[0032] 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.

[0033] 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.

[0034] The ion implantation may involve implanting fluorine ions into the junction in any suitable manner.

[0035] 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).

[0036] Although not essential to this embodiment, the surface of the silicon substrate before forming the bonding portion may be subjected to chemical mechanical polishing (CMP) to make the surface flat or smooth.

[0037] Although not essential to this embodiment, the surface of the silicon substrate before forming the bonding portion may be cleaned after CMP or without CMP, thereby cleaning the surface and removing unwanted substances such as organic matter, particles, metals and / or metal ions.

[0038] 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.

[0039] Depending on the chemicals and conditions used for cleaning, for example, OH may be applied to the surface of the silicon substrate before the bonding section is formed. - , H + Ions and / or molecules such as , H2O, H2 and O2 may be introduced, which may result in hydrosilyl and / or silanol groups on such surfaces.

[0040] In this manner, the first silicon substrate 10 and the second silicon substrate 20 are prepared.

[0041] [Step b] Next, a first composition is prepared, which contains at least one of an organic material capable of reacting with hydrosilyl groups and / or silanol groups and an inorganic material capable of bonding with silicon oxide, and has a particle amount of 3,000 particles / mL or less. The lower limit of the particle amount in the first composition is not particularly limited, but is, for example, 1 particle / mL or more, specifically 0 particle / mL or more.

[0042] (First composition containing organic or inorganic material) At least one of the organic material and the inorganic material is used as a first composition containing, for example, a solvent. The first composition may contain, in addition to the organic material and / or the inorganic material, a solvent, an acid catalyst, a base catalyst, or other reaction accelerator. A commonly used solvent may be used, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, toluene, tetrahydrofuran, or isopropyl alcohol. The water content of the first composition is substantially zero. By reducing the water content in the first composition in this manner, the occurrence of voids can be reduced. The first composition may contain only organic materials or only inorganic materials, or may contain only organic materials and inorganic materials.

[0043] The first composition may be prepared by dissolving, dispersing, or suspending an organic material and / or an inorganic material in a solvent. For example, the first composition may dissolve the organic material and / or the inorganic material.

[0044] The amount of particles in the first composition is, for example, 3,000 particles / mL or less, preferably 2,000 particles / mL or less, more preferably 1,000 particles / mL or less, and may be, for example, 500 particles / mL or less. The lower limit of the amount of particles in the first composition is not particularly limited, but may be, for example, 0 particles / mL or more.

[0045] The particles may be individual particles or aggregates of particles. That is, the particles include primary particles and secondary particles. The particles may be inorganic or organic. Examples of particles include particles present in the environment or particles supplied together with an organic material, which exist in particulate form after the organic material has hardened.

[0046] The amount of particles can be measured using, for example, a syringe sampling system SLS-1040.

[0047] The first composition preferably contains 50% by mass or less of the organic material and / or inorganic material, more preferably 35% by mass or less, and even more preferably 30% by mass or less. The lower limit of the organic material and / or inorganic material is not particularly limited, but may be, for example, 1% by mass or more, 3% by mass or more, or 5% by mass or more. For example, the first composition may contain 1 to 50% by mass of the organic material and / or inorganic material, 3 to 35% by mass or 5 to 30% by mass. Furthermore, the first composition may contain 1 to 30% by mass of the organic material and / or inorganic material, or 3 to 30% by mass. When both the organic material and the inorganic material are contained, the total amount of both materials may be within the above range.

[0048] Preferably, the first composition contains only a solvent and an organic material and / or an inorganic material.

[0049] (Organic material in first composition) The amount of particles in the organic material is, for example, 3,000 particles / mL or less, preferably 2,000 particles / mL or less, more preferably 1,000 particles / mL or less, and may be, for example, 500 particles / mL or less. The lower limit of the amount of particles in the organic material is not particularly limited, but may be, for example, 0 particles / mL or more. The amount of particles in the organic material can be measured, for example, using the same method as that for the amount of particles in the first composition.

[0050] The organic material preferably has at least two functional groups, which are preferably located at both ends of the organic material.

[0051] The organic material can react with the hydrosilyl group and / or silanol group at one terminal functional group to form a reaction product, the composition of which depends on the structure of the organic material.

[0052] The organic material may be capable of reacting with the second activated region 23a at the functional group at the other end thereof, and the first bonding portion 13 and the second bonding portion 23 are bonded together by a reaction product derived from the organic material.

[0053] The functional group may include 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.

[0054] Alkenyl groups can react with hydrosilyl groups (-Si-H), and hydroxyl groups, hydrolyzable silyl groups, isocyanate groups, epoxy groups, amino groups, acid anhydride groups and siloxane bonds can react with silanol groups (-Si-OH).

[0055] More specifically, the organic material may contain at least one selected from the group consisting of the following (i) to (iv): Note that the organic material may be a single compound or a combination of two or more compounds. (i) A substituted or unsubstituted hydrocarbon compound having multiple terminal ends, at least two of which have alkenyl groups. (ii) A substituted or unsubstituted hydrocarbon compound having a plurality of terminal ends, at least one of which has an alkenyl group at the terminal end and at least one of which has any one 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. (iii) A substituted or unsubstituted hydrocarbon compound having a plurality of terminal ends, at least two of which have a group independently selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, a phosphoric acid group, and an acid anhydride group. (iv) Silsesquioxanes and their derivatives. Details of (i) to (iv) will be described later.

[0056] (Inorganic material in first composition) The amount of particles in the inorganic material is, for example, 3,000 particles / mL or less, preferably 2,000 particles / mL or less, more preferably 1,000 particles / mL or less, and may be, for example, 500 particles / mL or less. The lower limit of the amount of particles in the inorganic material is not particularly limited, but may be, for example, 0 particles / mL or more. The amount of particles in the inorganic material can be measured, for example, using the same method as that for the amount of particles in the first composition.

[0057] The inorganic material may react with the hydrosilyl group and / or the silanol group to form a reaction product. The reaction product may contain, for example, at least one selected from the group consisting of SiO2, SiOC, SiOF, SiN, SiCN, HfO2, and La2O3. Note that a layer derived from the inorganic material may be provided on the first silicon substrate 10 or the second silicon substrate 20 without reacting with the inorganic material. In this case, the layer derived from the inorganic material may contain, for example, at least one selected from the group consisting of SiO2, SiOC, SiOF, SiN, SiCN, HfO2, and La2O3. At least one thin film can be formed using the inorganic material. The thickness of the thin film is not particularly limited, but is, for example, 10 nm or less.

[0058] Preferably, the method includes purifying the second composition into the first composition by filtering. This removes particles contained in the second composition, reducing the amount of particles contained in the first adhesive portion 31. The organic material contained in the second composition has the same structure as the organic material contained in the first composition, except for the amount of particles. The amount of particles in the second composition is, for example, more than 3,000 particles / mL.

[0059] Preferably, the filtering is performed using a membrane with an effective diameter of 50 nm or less. The effective diameter of the membrane is more preferably 10 nm or less. The lower limit of the effective diameter of the membrane is not particularly limited, but may be, for example, 1 nm or more. Here, the effective diameter refers to the average effective diameter of the membrane.

[0060] [Process c] Next, at least one of an organic material or an inorganic material is supplied between the first bonding portion 13 and the second bonding portion 23 to bond the first bonding portion 13 and the second bonding portion 23 with a reaction product derived from the organic material, or an adhesive layer 30 is provided to bond the first bonding portion 13 and the second bonding portion 23 with the inorganic material.

[0061] (adhesive layer 30) The adhesive layer 30 includes a first adhesive portion 31 provided on the first bonding portion 13. In this embodiment, the first silicon substrate 10 and the second silicon substrate 20 are bonded together by the first adhesive portion 31. The number of particle clusters contained on the surface of the first adhesive portion 31 opposite to the first bonding portion 13 is 5 clusters / cm. 2 The lower limit of the number of particle clusters on the surface of the adhesive layer 30 is not particularly limited, but for example, it is 1 cluster / cm 2 Specifically, 0 pieces / cm 2 The number of particle clusters may be measured by placing at least one of an organic material (or a composition containing an organic material) and an inorganic material (or a composition containing an inorganic material) on a separately prepared substrate (for example, the surface of the first silicon substrate 10 on the side of the first bonding portion 13), drying the organic material (or the composition containing an organic material) and the inorganic material (or the composition containing an inorganic material), and then measuring the number of particle clusters on the surface after drying.

[0062] A cluster refers to an aggregate of particles present on a surface (also called "surface particles"). For example, a cluster may contain a single particle, or two or more particles clumped together. The number of particles contained in a cluster is not particularly limited, but may be, for example, 30 or less.

[0063] The number of clusters can be measured using a surface foreign matter inspection device. A device commonly used in front-end inspections can be used as the surface foreign matter inspection device, and measurements can be performed on, for example, a 300 mm wafer. For example, when the thickness of the adhesive layer 30 is small, the particle diameter may be larger than the thickness of the adhesive layer 30. In this case, measurement using a surface foreign matter inspection device can be particularly useful.

[0064] When the number of particle clusters on the surface of the adhesive layer 30 is within the above range, the bonding strength between the first silicon substrate 10 and the second silicon substrate 20 is good. Furthermore, the laminate 40 can be manufactured at a relatively low temperature, which effectively suppresses or prevents the occurrence of voids in the adhesive layer 30. The bonding strength can be measured, for example, by a blade test. For example, a razor blade is inserted between the wafers and the peel distance is observed with an infrared microscope. The bonding strength γ is expressed by the following formula: γ = (3Ed 3 y 2 ) / (32L 4 ) where E is the Young's modulus of the wafer, y is the blade thickness, d is the wafer thickness, and L is the peel distance.

[0065] The lower limit of the number of particle clusters in the adhesive layer 30 is not particularly limited, but for example, it is 0 clusters / cm 3 That's all.

[0066] The number of particle clusters on the surface of adhesive layer 30 may be, for example, 3,000 clusters / wafer or less, 2,000 clusters / wafer or less, or 1,000 clusters / wafer or less. The lower limit of the number of clusters on the surface of adhesive layer 30 is not particularly limited, but may be 0 clusters / wafer or more, or 1 cluster / wafer or more. The wafer is a 300 mm wafer, i.e., a wafer with a diameter of 300 mm, and the area of ​​the wafer is 706.8 cm. 2 is.

[0067] The particle size of the particles in the adhesive layer may be, for example, 60 nm or more, or may be 200 nm or more. There is no particular upper limit to the particle size, but it may be, for example, 6 μm or less.

[0068] The particle size of a particle refers to the light scattering equivalent diameter that can be quantified using a measuring device. The particle size can be measured, for example, using a surface foreign matter inspection device or a liquid particle counter. The particle size can be measured, for example, using a surface foreign matter inspection device for particle diameters of 60 nm or more.

[0069] The particle amount on the surface of the adhesive layer 30 is, for example, 3,000 particles / cm 2 It may be less than 2,000 pieces / cm 2 It may be less than 1,000 pieces / cm 2 The lower limit of the particle amount on the surface of the adhesive layer 30 is not particularly limited, but may be 0 particles / cm 2 May be more than 1 piece / cm 2 It may be more than that.

[0070] In the first embodiment, the first adhesive portion 31 is provided on the first bonding portion 13, but the first adhesive portion 31 may be provided on the second bonding portion 23. In this case, the "first bonding portion 13" is read as the "second bonding portion 23," and the "first bonding portion 13" is read as the "second bonding portion 23."

[0071] The adhesive layer 30 (first adhesive portion 31) may be formed of two or more layers. That is, a first adhesive portion layer may be provided on the first silicon substrate 10, dried and / or heated as necessary, and then a second adhesive portion layer may be provided. The number of layers in the adhesive portion is not particularly limited, but may be, for example, three or less layers.

[0072] The thickness of the adhesive layer 30 can be extremely thin, for example, 10 nm or less, particularly 8 nm or less, and although there is no particular lower limit, the thickness of the adhesive layer 30 can be, for example, 1 nm or more.

[0073] The first silicon substrate and the second silicon substrate can be bonded together by the adhesive layer 30. The bonding strength between the first silicon substrate and the second silicon substrate is preferably 1.00 J / m 2 This makes it possible to improve the bonding strength.

[0074] Specific aspects of the method for supplying and bonding the organic material (or a composition containing an organic material) may be selected appropriately depending on the organic material used. Generally, after supplying the organic material to the first bonding portion 13, the first silicon substrate 10 and the second silicon substrate 20 may be maintained under predetermined reaction conditions (particularly, a predetermined temperature) with the organic material interposed between the first bonding portion 13 and the second bonding portion 23, thereby bonding the first bonding portion 13 and the second bonding portion 23 with a reaction product. The organic material may also be supplied to the second bonding portion 23 instead of the first bonding portion 13.

[0075] For example, an organic material (or a composition containing an organic material) is applied to the surface of the first silicon substrate 10 on the first bonding portion 13 side by coating, spraying, printing, or the like. 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.). Thereafter, washing and / or drying may be carried out as necessary. The washing and drying may be the same as those described above, and when a fluorine-containing organic material is used, pre-washing using a fluorine-based solvent may be carried out.

[0076] Thereafter, the first silicon substrate 10 and the second silicon substrate 20 are aligned so that the first bonding portion 13 and the second bonding portion 23 face each other, and the first silicon substrate 10 and the second silicon substrate 20 are brought into close contact with each other with an organic material interposed between the first bonding portion 13 and the second bonding portion 23. The first silicon substrate 10 and the second silicon substrate 20 that have been brought into close contact with each other are maintained under predetermined reaction conditions (particularly, a predetermined temperature) to allow the reaction to proceed. Thereafter, an annealing treatment may be performed as necessary.

[0077] For example, when an organic material is applied to the surface of the first bonding portion 13, the surface of a layer formed from the organic material may be washed with water or a water-containing organic solvent, and then the second bonding portion 23 may be disposed on the layer. Note that the organic material may be applied to the surface of the second bonding portion 23 instead of the surface of the first bonding portion 13.

[0078] (Organic materials (i) to (iv)) Exemplary embodiments using the organic materials (i) to (iv) are described in detail below.

[0079] (i) Example of using organic materials In this example, the first silicon substrate 10 and the second silicon substrate 20 may have hydrosilyl groups (-Si-H) on the surfaces of the first bonding portion 13 and the second bonding portion 23 (which are silicon oxide portions in this embodiment). The first silicon substrate 10 and the second silicon substrate 20 having hydrosilyl groups on the surfaces of the first bonding portion 13 and the second bonding portion 23, which are silicon oxide portions, may be obtained, for example, by the surface treatment that generates hydrosilyl groups described above.

[0080] The organic material is a substituted or unsubstituted hydrocarbon compound having multiple terminals, at least two of which have alkenyl groups. The alkenyl group is a group reactive to a hydrosilyl group. Such a compound may have alkenyl groups at any two or more terminals. For example, all of the terminals may be alkenyl groups. Such a compound may be fluorine-substituted, i.e., a fluoroalkyl compound or a fluoropolyether group-containing compound having alkenyl groups at two or more terminals.

[0081] As an example, fluoroalkyl compounds having alkenyl groups at two, three, or four terminal positions are shown below. Rf represents a fluoroalkyl group (the same applies below). In the following compounds, for example, the alkenyl groups may be bonded to different carbon atoms contained in Rf.

[0082] [ka]

[0083] The number of carbon atoms in the portion excluding the terminal reactive group (alkenyl group) is not particularly limited, but may be, for example, 1 to 200, inclusive, and particularly 100 or less. The number of carbon atoms may be, for example, 5 or more. The portion excluding the reactive group may be linear, branched, or cyclic. When the portion excluding the terminal reactive group is a fluoroalkyl group, the fluorine substitution ratio is not particularly limited, but may be, for example, a perfluoroalkyl group.

[0084] 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 a is, 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. It is to be noted that R N In the left formula, any of the bonding groups is X a In the right equation, the left side is X a , and the right side is X b or R B Also, R FIn the above formula, the sum of a, b, c, d, e, and f may be, for example, 5 or more.

[0085] The organic material is supplied between the first bonding portion 13 and the second bonding portion 23, and the alkenyl groups of the organic material are reacted (hydrosilylated) with the hydrosilyl groups of the first bonding portion 13 and the second bonding portion 23. As a result, a reaction product derived from the organic material chemically bonds to the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23, and the first bonding portion 13 and the second bonding portion 23 are bonded by the reaction product derived from the organic material. This reaction does not produce by-products, fundamentally solving the problem of void formation due to by-products.

[0086] The reaction may be carried out in one step with an organic material sandwiched between the first bonding portion 13 and the second bonding portion 23, or may be carried out in two steps by applying an organic material to one of the first bonding portion 13 or the second bonding portion 23 to partially promote the reaction, and then placing the other bonding portion on top of the organic material to further promote the reaction.

[0087] 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.)

[0088] [ka]

[0089] The reaction products derived from the organic material preferably chemically bond to both the Si atoms in the first bonding portion 13 and the Si atoms in the second bonding portion 23. However, it is not necessary for all reaction products to chemically bond to both the Si atoms in the first bonding portion 13 and the Si atoms in the second bonding portion 23. Some reaction products may be chemically bonded to only one of the Si atoms in the first bonding portion 13 and the Si atoms in the second bonding portion 23, or may be chemically bonded to two or more Si atoms in the same silicon substrate. To obtain higher bonding strength, it is preferable that more reaction products chemically bond to both the Si atoms in the first bonding portion 13 and the Si atoms in the second bonding portion 23. From this perspective, the organic material is preferably, but is not limited to, a linear compound having alkenyl groups at both ends.

[0090] (ii) Example of using organic materials In this example, a substrate having silanol groups (-Si-OH) on the surface of the first bonding portion 13 (which is a silicon oxide portion in this embodiment) is used as the first silicon substrate 10. The first silicon substrate 10 having silanol groups on the surface of the first bonding portion 13, 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.

[0091] Preferably, the second silicon substrate 20 has hydrosilyl groups (-Si-H) on the surface of the second bonding portion 23 (which is a silicon oxide portion in this embodiment). The second silicon substrate 20 having hydrosilyl groups on the surface of the second bonding portion 23, which is a silicon oxide portion, may be obtained by, for example, the above-mentioned surface treatment that generates hydrosilyl groups.

[0092] The organic material is a substituted or unsubstituted hydrocarbon compound having multiple terminal groups, at least one of which has an alkenyl group and at least one of which has a hydroxyl group. Specifically, a substituted or unsubstituted hydrocarbon compound is used that has an alkenyl group at one terminal and a hydroxyl group at the other terminal. 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 terminals, and may have an alkenyl group at any one or more terminals and a hydroxyl group at any one or more terminals. Such a compound may be fluorine-substituted, i.e., a fluoroalkyl compound or a fluoropolyether group-containing compound having an alkenyl group at one terminal and a hydroxyl group at the other terminal.

[0093] 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.)

[0094] The organic material is supplied between the first bonding portion 13 and the second bonding portion 23, causing a reaction (etherification by dehydration) between the hydroxyl groups of the organic material and the silanol groups of the first bonding portion 13, and also causing a reaction (hydrosilylation) between the alkenyl groups of the organic material and the hydrosilyl groups of the second bonding portion 23. As a result, a reaction product derived from the organic material chemically bonds to the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23, and the first bonding portion 13 and the second bonding portion 23 are bonded by the reaction product derived from the organic material.

[0095] More specifically, it is preferable to supply an organic material to the first bonding portion 13, react the hydroxyl groups of the organic material with the silanol groups of the first bonding portion 13 (first stage), and then arrange the first bonding portion 13 and the second bonding portion 23 opposite each other to react the alkenyl groups of the organic material with the hydrosilyl groups of the second bonding portion 23 (second stage). According to this procedure, water is generated as a by-product in the first-stage reaction, but this by-product can be removed without being trapped between the first bonding portion 13 and the second bonding portion 23. Furthermore, since no by-products are generated in the second-stage reaction, the formation of voids due to the by-products can be avoided.

[0096] 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. (The same applies to the case of a fluoropolyether group-containing compound having an alkenyl group at one end and a hydroxyl group at the other end.)

[0097] [ka]

[0098] 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.

[0099] Furthermore, in this example, the first silicon substrate 10 has silanol groups on the surface of the first bonding portion 13, and the second silicon substrate 20 has hydrosilyl groups on the surface of the second bonding portion 23. Therefore, when using an organic material (preferably linear) having an alkenyl group and a hydroxyl group at both ends, 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.

[0100] 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.)

[0101] (iii) First example using organic materials In this example, silanol groups (—Si—OH) are present on the surfaces of the first bonding portion 13 and the second bonding portion 23 (which are silicon oxide portions in this embodiment) as the first silicon substrate 10 and the second silicon substrate 20. The first silicon substrate 10 and the second silicon substrate 20 having silanol groups on the surfaces of the first bonding portion 13 and the second bonding portion 23, which are silicon oxide portions, do not particularly require surface treatment, but may be obtained, if necessary, by the above-mentioned surface treatment that generates silanol groups.

[0102] The organic material is a substituted or unsubstituted hydrocarbon compound having multiple terminals, at least two of which have hydrolyzable silyl groups. Specifically, a substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two terminals is used. 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 or a fluoropolyether group-containing compound having hydrolyzable silyl groups at two terminals.

[0103] 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 14 is 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 c1is 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 35 3-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 Rf1 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:

[0104] 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.

[0105] 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.

[0106] The unsubstituted silane compound may be, for example, R k 3Si-(CH2) n35 -SiR k R k each independently represents a group capable of undergoing a hydrolysis reaction, and preferably each independently represents -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. n35 is an integer of 1 to 18.

[0107] Unless otherwise specified, the above explanations may apply.

[0108] The organic material is supplied between the first bonding portion 13 and the second bonding portion 23, and the hydrolyzable silyl groups of the organic material are reacted with the silanol groups of the first bonding portion 13 and the second bonding portion 23 (for example, when the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). As a result, a reaction product derived from the organic material chemically bonds to the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23, and the first bonding portion 13 and the second bonding portion 23 are bonded by the reaction product derived from the organic material. This reaction produces a by-product, for example, an alcohol, but the number of carbon atoms thereof can be small as described above, and the alcohol can be effectively removed from between the first bonding portion 13 and the second bonding portion 23 to the outside through the gaps in the reaction product, thereby reducing the formation of voids due to the by-product.

[0109] It is preferable to apply the organic material to either the first bonding portion 13 or the second bonding portion 23, react it with the first bonding portion 13 or the second bonding portion 23, and then wash the surface of the layer formed from the organic material with water or a water-containing organic solvent before placing the other on the layer. This converts the hydrolyzable silyl groups present on the surface to silanols, further suppressing the formation of voids derived from by-products such as alcohols that accompany hydrolysis.

[0110] The reaction may be carried out in one step with an organic material sandwiched between the first bonding portion 13 and the second bonding portion 23, or may be carried out in two steps by applying an organic material to one of the first bonding portion 13 or the second bonding portion 23 to partially promote the reaction, and then placing the other bonding portion on top of the organic material to further promote the reaction.

[0111] 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.)

[0112] [ka]

[0113] [ka]

[0114] 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.

[0115] (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.

[0116] 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.

[0117] 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.

[0118] The unsubstituted silane compound is, for example, OCN—(CH) n35 It may be a compound represented by —NCO, where n35 is an integer of 1 to 18.

[0119] As an example, the reaction when an alkyl compound having isocyanate groups at two terminals is used is shown below.

[0120] [ka]

[0121] (iii) Third 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.

[0122] The organic material used is a substituted or unsubstituted hydrocarbon compound having a phosphate group. Such a compound may have two or more terminals, and may have a phosphate group at any two or more terminals.

[0123] In the following, an example is shown in which CH3PO(OH)2 is used as a compound having a phosphate group, but in this embodiment, any compound having a phosphate group may be used as long as it has a different structure. For example, a compound having two or more phosphate groups, such as 1,6-hexanediphosphonic acid, may be used. In the case of a compound having two or more phosphate groups, one phosphate group may react with the first bonding portion 13, and another phosphate group may react with the second bonding portion 23.

[0124] [ka]

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

[0126] 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.

[0127] The organic material is supplied between the first bonding portion 13 and the second bonding portion 23, and the acid anhydride groups of the organic material are reacted with the silanol groups of the first bonding portion 13 and the second bonding portion 23. As a result, a reaction product derived from the organic material chemically bonds to the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23, and the first bonding portion 13 and the second bonding portion 23 are bonded by the reaction product derived from the organic material. This reaction does not produce by-products, fundamentally solving the problem of void formation due to by-products.

[0128] As an example, the reaction when an alkyl compound having acid anhydride groups at two terminals is used is shown below.

[0129] [ka] R represents an alkyl group, for example, -(CH2) n36 n36 is an integer from 1 to 18.

[0130] 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.

[0131] (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.

[0132] 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.

[0133] The organic material is supplied onto the first bonding portion 13, and the siloxane bond sites of the organic material react with the silanol groups of the first bonding portion 13 (cleavage and addition of siloxane bonds). Then, a second bonding portion 23 is provided on the side of the organic material opposite the first bonding portion 13, and the siloxane bond sites of the organic material react with the silanol groups of the second bonding portion 23 (cleavage and addition of siloxane bonds). As a result, a reaction product derived from the organic material chemically bonds to the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23, bonding the first bonding portion 13 and the second bonding portion 23 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. In addition, the organic material may be supplied between the first bonding portion 13 and the second bonding portion 23 to cause the siloxane bond sites of the organic material to react with the silanol groups of the first bonding portion 13 and the second bonding portion 23 (cleavage and addition of the siloxane bond).

[0134] For example, T8 silsesquioxane ((R'SiO)) having a complete cage structure is 1.5 The reaction when 8) is used is shown below.

[0135] [ka]

[0136] 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.

[0137] 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.

[0138] (Reaction conditions) ·Organic materials The reaction conditions may vary depending on the organic material used. The reaction 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 13 and the second bonding portion 23 can be bonded with high precision. The pressure (absolute pressure, the same applies to other pressure values ​​in this specification) 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.

[0139] ·Inorganic materials Specific aspects of the method for supplying the inorganic material (or a composition containing the inorganic material) and the bonding method may be selected appropriately depending on the inorganic material used. Generally, after supplying the inorganic material to the first bonding portion 13, the first silicon substrate 10 and the second silicon substrate 20 may be maintained under predetermined reaction conditions (particularly, a predetermined temperature) with the inorganic material interposed between the first bonding portion 13 and the second bonding portion 23, thereby bonding the first bonding portion 13 and the second bonding portion 23 with a reaction product. The inorganic material may also be supplied to the second bonding portion 23 instead of the first bonding portion.

[0140] For example, an inorganic material (or a composition containing an inorganic material) is applied to the surface of the first silicon substrate 10 on the side of the first bonding portion 13 by spin coating, vapor deposition, or the like. The inorganic 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.). Thereafter, washing and / or drying may be carried out as necessary. Pre-washing may also be carried out as necessary.

[0141] Thereafter, the first silicon substrate 10 and the second silicon substrate 20 are aligned so that the first bonding portion 13 and the second bonding portion 23 face each other, and the first silicon substrate 10 and the second silicon substrate 20 are brought into close contact with each other with an inorganic material interposed between the first bonding portion 13 and the second bonding portion 23. The first silicon substrate 10 and the second silicon substrate 20 that have been brought into close contact are maintained under predetermined reaction conditions (particularly, a predetermined temperature) as necessary to be bonded. Note that the inorganic material and the first silicon substrate 10 and the second silicon substrate 20 may be bonded without reacting, or may at least partially react.

[0142] By undergoing the above manufacturing method, a stacked body 40 is formed, which includes a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30 between the first silicon substrate 10 and the second silicon substrate 20. In other words, the stacked body 40 includes: a first silicon substrate 10 having a first bonding portion 13; a second silicon substrate 20 having a second bonding portion 23 located on the first bonding portion 13 side; an adhesive layer 30 located between the first bonding portion 13 and the second bonding portion 23 and adhering the first bonding portion 13 and the second bonding portion 23; and the first bonding portion 13 and the second bonding portion 23 have a hydrosilyl group and / or a silanol group derived from silicon oxide, or a region that bonds with an inorganic material, the adhesive layer 30 includes a reaction product reacted with the hydrosilyl group and / or the silanol group, or a region that bonds with the inorganic material; The number of particle clusters on the surface of the adhesive layer 30 is 5 / cm 2 is as follows: The bonding strength between the first silicon substrate 10 and the second silicon substrate 20 is 1.00 J / m 2 That's all. Here, the surface of the adhesive layer 30 refers to the hardened surface of the adhesive layer 30 when it is provided on the first silicon substrate 10.

[0143] In the laminate 40, the adhesive layer 30 may contain organic substances generated during the formation of the adhesive layer 30. Such organic substances may be understood as residues of organic materials capable of reacting with hydrosilyl groups and / or silanol groups.

[0144] 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 .

[0145] The inorganic substance may be bonded to the first bonding portion 13 and the second bonding portion 23. In this case, the inorganic substance may be bonded to the first bonding portion 13 and the second bonding portion 23 without reacting with them, or may react with them at least in part. In this case, in the laminate 40, the adhesive layer 30 may contain an inorganic substance that was generated during the formation of the adhesive layer 30. Such an inorganic substance may be understood as a residue of the inorganic material that reacted with the first silicon substrate and the second silicon substrate.

[0146] The upper limit of the bonding strength is not particularly limited, but is, for example, 2.5 J / m 2 It may be the following:

[0147] Second Embodiment 2 is a cross-sectional view schematically illustrating a cross section of a portion of a laminate 40A of the second embodiment. In the first embodiment, an adhesive layer 30 is provided between the first bonding portion 13 and the second bonding portion 23, but in the second embodiment, a first adhesive portion 31A is provided on the first bonding portion 13, and a second adhesive portion 32A is provided on the second bonding portion 23, and the laminate 40A is thus composed of the first adhesive portion 31A and the second adhesive portion 32A. This difference will be mainly described, and unless otherwise noted, the laminate 40A has the same configuration as the first embodiment in other respects.

[0148] (Adhesive layer 30A) As shown in FIG. 2, the adhesive layer 30A has a first adhesive portion 31A and a second adhesive portion 32A provided on the second bonding portion 23 and bonded to the first adhesive portion 31A. The first adhesive portion 31A and the second adhesive portion 32A are bonded by a chemical reaction. Heat and / or pressure or decompression is applied as necessary during the chemical bonding reaction. The conditions for heating, pressurization, and decompression are the same as those in the first embodiment. The physical properties and constituent materials of the adhesive layer 30A are the same as those of the adhesive layer 30 in the first embodiment.

[0149] In one aspect, the first adhesive portion 31A can be obtained by applying a first organic material capable of reacting with the first adhesive portion 13 onto the first adhesive portion 13, followed by drying. The second adhesive portion 32A can be obtained by applying a second organic material capable of reacting with the second adhesive portion 23 onto the second adhesive portion 23, followed by drying. The drying can be performed in the same manner as in the first embodiment.

[0150] In another aspect, the first adhesive portion 31A can be obtained by supplying a first inorganic material onto the first bonding portion 13 and then drying it as necessary. The second adhesive portion 32A can be obtained by supplying a second inorganic material onto the second bonding portion 23 and then drying it. The drying can be performed in the same manner as in the first embodiment.

[0151] For convenience, the adhesive portions are referred to as first adhesive portion 31A and second adhesive portion 32A, but they may not form an interface or may be mixed. Even if an interface is formed, the interface may not be uniform and may have irregularities.

[0152] The number of particle clusters contained on the surface of the first adhesive portion 31A opposite to the first bonding portion 13 is 5 / cm 2 The numbers of particles and clusters in this embodiment have the same meaning as the numbers of particles and clusters in the first embodiment.

[0153] Preferably, the number of particle clusters contained on the surface of the second adhesive portion 32A opposite to the second bonding portion 23 is 5 particles / cm. 2The lower limit of the number of clusters is not particularly limited, but for example, it is 1 cluster / cm 2 Specifically, 0 pieces / cm 2 That's all.

[0154] The second adhesive portion 32A may be formed of two or more layers. That is, a first layer of the second adhesive portion 32A may be provided on the second joining portion 23, and then dried and / or heated as necessary, and then a second layer of the second adhesive portion 32A may be provided. The number of layers of the second adhesive portion 32A is not particularly limited, but may be, for example, three or less.

[0155] (1st and 2nd organic materials) The first organic material has a functional group at one end that reacts with the first bonding portion 13 and a functional group at the other end that reacts with the second organic material. The second organic material has a functional group at one end that reacts with the second bonding portion 23 and a functional group at the other end that reacts with the first organic material. This bonds the first silicon substrate 10 and the second silicon substrate 20. Note that only some of these functional groups may react. Note that, although the above describes a case where one organic material has two functional groups, the organic material may also have three or more functional groups.

[0156] The first organic material and the second organic material may be contained in a composition, which has the same structure as that of the first embodiment.

[0157] Specific aspects of the method for supplying and bonding the first and second organic materials (or a composition containing the first and second organic materials) may be selected appropriately depending on the organic materials used. Generally, after the first and second organic materials are supplied, the first silicon substrate 10 and the second silicon substrate 20 may be maintained under predetermined reaction conditions (particularly, a predetermined temperature) with the first and second organic materials interposed between them, thereby allowing the reaction to proceed.

[0158] More specifically, for example, a first organic material (which may be a composition) is applied to the first bonding portion 13 of the first silicon substrate 10 by coating, spraying, printing, or the like. Similarly, a second organic material (which may be a composition) is applied to the second bonding portion 23 of the second silicon substrate 20. Thereafter, cleaning and / or drying may be performed as necessary. The cleaning and drying may be the same as those described above, and when a fluorine-containing organic material is used, pre-cleaning using a fluorine-based solvent may be performed.

[0159] Thereafter, the first silicon substrate 10 and the second silicon substrate 20 are aligned so that the first bonding portion 13 and the second bonding portion 23 face each other, and the first silicon substrate 10 and the second silicon substrate 20 are brought into close contact with each other with the first and second organic materials interposed between the first bonding portion 13 and the second bonding portion 23. The first silicon substrate 10 and the second silicon substrate 20 that have been brought into close contact with each other are maintained under predetermined reaction conditions (particularly, a predetermined temperature) to allow the reaction to proceed. Thereafter, an annealing treatment may be performed as necessary.

[0160] The properties of the first and second organic materials can be the same as those of the organic materials in the first embodiment.

[0161] The first and second organic materials may contain at least one selected from the group consisting of the following (v) to (vi): Note that the organic materials may be one type of compound or a combination of two or more types of compounds. (v) A hydrolyzable hydrosilane or a combination of 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) Substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group at one end and an alkyl group at the other end.

[0162] The details are described below.

[0163] (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.

[0164] As the organic material, a first organic material and a second organic material are used in combination.

[0165] 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 H and one or more hydrolyzable groups on one Si. 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 having a hydrosilyl group at the other end.

[0166] 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.

[0167] First, a first organic material is supplied to the first bonding portion 13, and the hydrolyzable silyl groups of the first organic material are reacted with the silanol groups of the first bonding portion 13 (for example, if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). Furthermore, the second organic material is supplied to the second bonding portion 23, and the hydrolyzable silyl groups of the second organic material are reacted with the silanol groups of the second bonding portion 23 (for example, if the hydrolyzable groups are alkoxy groups, a siloxane bond is formed by dealcoholization). Then, the first bonding portion 13 and the second bonding portion 23 are arranged so that they face each other, with an intermediate derived from the first organic material and an intermediate derived from the second organic material positioned between them, and these intermediates are reacted (hydrosilylated). As a result, the reaction products derived from the first organic material and the second organic material chemically bond to the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23, and the first bonding portion 13 and the second bonding portion 23 are bonded by the reaction products derived from the first organic material and the second organic material. This reaction produces alcohol as a by-product, but as described above, the number of carbon atoms of the alcohol can be small and can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are arranged to face each other, thereby reducing the formation of voids due to the by-product.

[0168] For example, R k 3Si-(CH2) n37 -CH=CH2 as the second organic material, and SiHR k 3 can be used. R k each independently represents a group capable of undergoing a hydrolysis reaction, and specifically has the same meaning as above. n37 represents an integer of 0 to 18, for example, 0.

[0169] Specifically, the reaction when vinyltrimethoxysilane is used as the first organic material and trimethoxyhydrosilane is used as the second organic material is shown below.

[0170] [ka]

[0171] (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.

[0172] The first and second organic materials each comprise a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end. Such compounds may have two or more end groups, and may have a hydrolyzable silyl group at any one or more end groups and an alkyl group at any one or more end groups. The substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end group may be similar to the substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two end groups detailed in (iii) above, except for the alkyl group at the other end group. The second organic material may have the same or different structure as the first organic material.

[0173] The first organic material is supplied to the first bonding portion 13, and the hydrolyzable silyl groups of the first organic material react with the silanol groups of the first bonding portion 13 (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by dealcoholization). The second organic material is supplied to the second bonding portion 23, and the hydrolyzable silyl groups of the second organic material react with the silanol groups of the second bonding portion 23 (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by dealcoholization). The first bonding portion 13 and the second bonding portion 23 are then arranged facing each other, with an intermediate derived from the organic material positioned between them, and a reaction (radical reaction) is caused between the intermediates. The reaction (radical reaction) between the intermediates may be performed using, for example, ultraviolet irradiation, an ion beam, or weak plasma. As a result, reaction products derived from the first and second organic materials chemically bond to the Si atoms of 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 the reaction products derived from the first and second organic materials. Although alcohol is produced as a by-product in this reaction, the number of carbon atoms thereof can be small as described above and can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, thereby reducing the formation of voids due to the by-products.

[0174] For example, the first organic material and the second organic material may be R k 3Si(CH2) n38 H can be used. k each independently represents a group capable of undergoing a hydrolysis reaction, and specifically has the same meaning as above. n38 represents an integer of 2 to 18, for example, 0.

[0175] Specifically, the reaction when ethyltrimethoxysilane is used as the first and second organic materials is shown below.

[0176] [ka]

[0177] By undergoing the above manufacturing method, a laminate 40A is formed having a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30A between the first silicon substrate 10 and the second silicon substrate 20, and the adhesive layer 30A has a first adhesive portion 31A and a second adhesive portion 32A.

[0178] The first and second organic materials can be obtained by filtering. The particle amounts of the first and second organic materials before filtering and the first and second organic materials after filtering are the same as the particle amounts of the organic materials in the first embodiment.

[0179] (1st and 2nd inorganic materials) As the first and second inorganic materials, the inorganic materials in the first embodiment can be used.

[0180] The first and second inorganic materials can be obtained by filtering. The first and second inorganic materials before filtering and the first and second inorganic materials after filtering each have the same particle amount as the inorganic material of the first embodiment.

[0181] By going through the above manufacturing method, a stacked body 40 is formed, which has a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30A between the first silicon substrate 10 and the second silicon substrate 20. That is, the manufacturing method of the stacked body 40A of the second embodiment is as follows: (a) preparing a first silicon substrate 10 having a first bonding portion 13 and a second silicon substrate 20 having a second bonding portion 23, the first bonding portion 13 and the second bonding portion 23 being portions containing silicon oxide; and (b) Using first and second organic materials capable of reacting with hydrosilyl groups and / or silanol groups, an adhesive layer 30A is provided to bond the first bonding portion 13 and the second bonding portion 23 with the first and second organic materials and / or a reaction product derived from the first and second organic materials, or using first and second inorganic materials capable of bonding with silicon oxide, an adhesive layer 30A is provided to bond the first bonding portion 13 and the second bonding portion 23 with the first and second inorganic materials and / or the first and second organic materials, Including, The adhesive layer 30A includes a first adhesive portion 31A provided on the first bonding portion 13 and a second adhesive portion 32A provided on the second bonding portion 23, The number of particle clusters contained on the surface of the first adhesive portion 31A opposite to the first joining portion 13 is 5 / cm 2 The numbers of particles and clusters have the same meanings as those in the first embodiment. In this specification, "the first and second organic materials and / or reaction products derived from the first and second organic materials" may be referred to as "reaction products derived from the first and second organic materials."

[0182] Moreover, the laminate 40A is a first silicon substrate 10 having a first bonding portion 13 on at least a portion of its surface; a second silicon substrate (20) located on the bonding portion (13) side and having a second bonding portion (23) on at least a part of its surface; an adhesive layer (30A) located between the first bonding portion (13) and the second bonding portion (23) and bonding the first bonding portion (13) and the second bonding portion (23) of the first silicon substrate (10); and The adhesive layer 30A has a reaction product between a first adhesive portion 31A located on the first bonding portion 13 and a second adhesive portion 32A located on the second bonding portion 23, or a bonded product between the first adhesive portion 31A located on the first bonding portion 13 and the second adhesive portion 32A located on the second bonding portion 23, The first silicon substrate 10 and the second silicon substrate 20 have electrical conductivity therebetween.

[0183] (Variation) FIG. 3 is a cross-sectional view schematically illustrating a portion of a laminate 40B according to a modified example. Unlike the second embodiment, the modified example includes a first adhesive portion 31B on the first bonding portion 13, a second adhesive portion 32B on the second bonding portion 23, and a third adhesive portion 33B between the first adhesive portion 31B and the second adhesive portion 32B. The first adhesive portion 31B and the third adhesive portion 33B are bonded to each other, and the second adhesive portion 32B and the third adhesive portion 33B are bonded to each other. That is, the adhesive layer 30B is composed of three layers: the first adhesive portion 31B, the third adhesive portion 33B, and the second adhesive portion 32B. This difference in structure is explained below. The remaining structure is the same as that of the first embodiment, and therefore its explanation is omitted. In this embodiment, the "first adhesive portion" described in the claims corresponds to the first adhesive portion 31B and the third adhesive portion 33B, and the "second adhesive portion" corresponds to the second adhesive portion 32B.

[0184] (Adhesive layer 30B) The adhesive layer 30B has a first adhesive portion 31B, a third adhesive portion 33B, and a second adhesive portion 32B, in that order. The first adhesive portion 31B is provided on the first silicon substrate 10, and the second adhesive portion 32B is provided on the second silicon substrate 20. The third adhesive portion 33 can react with the first adhesive portion 31B at one end and with the second adhesive portion 32B at the other end. That is, the third adhesive portion 33 can react as a connecting portion connecting the first adhesive portion 31B and the second adhesive portion 32B. The above reaction is carried out under heating and / or pressure or vacuum, as necessary. The conditions for heating, pressure, and vacuum are the same as those in the first embodiment.

[0185] The thickness of adhesive layer 30B can be extremely thin, for example, 10 nm or less, particularly 8 nm or less, and although there is no particular lower limit, the thickness of adhesive layer 30B can be, for example, 1 nm or more.

[0186] The first adhesive portion 31B can be obtained by applying a first organic material capable of reacting with the first bonding portion 13 onto the first bonding portion 13 and then drying the applied material. The drying can be performed in the same manner as in the first embodiment.

[0187] The second adhesive portion 32B can be obtained by applying a second organic material capable of reacting with the second bonding portion 23 onto the second bonding portion 23 and then drying the applied material. The drying can be performed in the same manner as in the first embodiment.

[0188] The third adhesive portion 33B can be formed by applying a third organic material capable of reacting with the first organic material and the second organic material, followed by drying as necessary, to form the third organic material and / or a reaction product derived from the third organic material. The drying can be performed in the same manner as in the first embodiment. Note that the "third organic material and / or a reaction product derived from the third organic material" may also be referred to as the "reaction product derived from the third organic material."

[0189] In another aspect, the first adhesive portion 31B can be obtained by supplying a first inorganic material capable of bonding to the first bonding portion 13 onto the first bonding portion 13, and then drying it as necessary. The drying can be performed in the same manner as in the first embodiment. The second adhesive portion 32B can be obtained by supplying a second inorganic material capable of bonding to the second bonding portion 23 onto the second bonding portion 23, and then drying it as necessary. The drying can be performed in the same manner as in the first embodiment. The third adhesive portion 33B is formed by applying a third inorganic material that can bond to the first organic material and the second organic material, and then drying it as necessary. The drying can be performed in the same manner as in the first embodiment.

[0190] For convenience, the first adhesive portion 31B, the second adhesive portion 32B, and the third adhesive portion 33B are referred to, but they do not necessarily form an interface. Even if an interface is formed, the interface does not have to be a uniform surface and may have irregularities. Furthermore, an appropriate combination of organic and inorganic materials may be used.

[0191] The number of particle clusters contained on the surface of the first adhesive portion 31B opposite to the first joining portion 13 is 5 / cm 2The numbers of particles and clusters in this embodiment have the same meaning as the numbers of particles and clusters in the first embodiment.

[0192] Preferably, the number of particle clusters contained on the surface of the second adhesive portion 32B opposite to the second bonding portion 23 is 5 particles / cm. 2 The lower limit of the number of clusters is not particularly limited, but for example, it is 0 clusters / cm 2 That's all.

[0193] Preferably, the number of particle clusters contained on the surface of the third adhesive portion 33B opposite to the first adhesive portion 31B is 5 particles / cm. 2 The lower limit of the number of clusters is not particularly limited, but for example, it is 0 clusters / cm 2 That's all.

[0194] (1st to 3rd organic materials) The first organic material has a functional group at one end that reacts with the first bonding portion 13 and a functional group at the other end that reacts with the third organic material. The second organic material has a functional group at one end that reacts with the second bonding portion 23 and a functional group at the other end that reacts with the third organic material. The third organic material has a functional group at one end that can react with the first organic material and a functional group at the other end that can react with the second organic material. This bonds the first silicon substrate 10 and the second silicon substrate 20. Note that only some of these functional groups may react. Note that although the above describes a case where one organic material has two functional groups, the organic material may also have three or more functional groups.

[0195] The first to third organic materials may each be used as a composition, and the composition has the same structure as in the first embodiment.

[0196] Specific aspects of the method for supplying and bonding the first to third organic materials (or compositions containing the first to third organic materials) may be selected appropriately depending on the organic materials used. Generally, after the first to third organic materials are supplied, the reaction may proceed by maintaining the first silicon substrate 10 and the second silicon substrate 20 under predetermined reaction conditions (particularly, a predetermined temperature) with the organic materials interposed between them.

[0197] More specifically, for example, a first organic material (which may be a composition) is applied (for example, by coating, spraying, printing, etc.) to the surface of the first silicon substrate 10 on the side having the first bonding portion 13. Similarly, a second organic material (which may be a composition) is applied to the second bonding portion 23 of the second silicon substrate. Thereafter, cleaning and / or drying may be performed as necessary. The cleaning and drying may be the same as those described above, and when an organic material containing fluorine is used, pre-cleaning using a fluorine-based solvent may be performed.

[0198] Then, a third organic material (which may be a composition) is applied (for example, by coating, spraying, printing, etc.) to the region derived from the first organic material. This may be followed by washing and / or drying, if necessary. The washing and drying may be the same as those described above, and when a fluorine-containing organic material is used, pre-washing with a fluorine-based solvent may be performed.

[0199] Then, a region derived from the second organic material is formed on the region derived from the third organic material. Specifically, the first silicon substrate 10 and the second silicon substrate 20 are aligned so that the first bonding portion 13 and the second bonding portion 23 face each other, and the first silicon substrate 10 and the second silicon substrate 20 are brought into close contact with each other with the first to third organic materials interposed between the first bonding portion 13 and the second bonding portion 23. The first silicon substrate 10 and the second silicon substrate 20 that have been brought into close contact with each other are maintained under predetermined reaction conditions (particularly, a predetermined temperature) to allow the reaction to proceed. Thereafter, an annealing treatment may be performed as necessary.

[0200] The properties and constituent materials of the first to third organic materials can be the same as those of the first organic material in the first embodiment.

[0201] Each organic material is described below. Note that the following mainly describes the differences from the first example using the organic material (iii) described above, and unless otherwise specified, the same description as in the first example above can be applied.

[0202] As the organic material, the following materials can be used. (vii) A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end.

[0203] Exemplary embodiments are described in detail below.

[0204] (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.

[0205] The first and second organic materials are substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group at one end and a reactive functional group at the other end. Such compounds 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 first and second organic materials may be similar to the substituted or unsubstituted hydrocarbon compounds having hydrolyzable silyl groups at two end portions detailed in (iii) above, except for the reactive functional group at the other end portion. The first and second organic materials may have the same or different structures apart from the end portions.

[0206] 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.

[0207] In this embodiment, a third organic material is further used. The third organic material has two groups capable of bonding to the reactive functional groups of the first and second organic materials. The third organic material may have two (or more) of the bondable groups, more specifically, the bondable groups may be present at any two (or more) of its terminal ends. The number of carbon atoms in the portion of the third organic material 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 third organic material may be a linear organic compound having the bondable groups at both terminal ends, but is not limited thereto.

[0208] 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.

[0209] [Table 1]

[0210] 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 as the use of two organic materials (iii) above, but this need not be taken into consideration when using an organic material (vii).

[0211] For example, the first organic material and the second organic material may be R k 3Si-(CH2) n31 When -NCO is used, the third organic material is, for example, H2N-(CH2) n32-NH2, HS-(CH2) n32 -SH and HO-(CH2) n32 As the first organic material and the second organic material, at least one of R k 3Si-(CH2) n33 When -NH2 is used, the third organic material is OCN-(CH2) n34 -NCO can be used. n31 is an integer of 1 to 18, for example, 1. n32 is an integer of 1 to 18, for example, 2. n33 is an integer of 1 to 18, for example, 1. n34 is an integer of 1 to 18, for example, 2.

[0212] R k means a group capable of undergoing a hydrolysis reaction, and preferably each independently represents -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.

[0213] Specifically, the reaction when isocyanatomethyltrimethoxysilane is used as the first and second organic materials, and ethylenediamine (1,2-diaminoethane) is used as the third organic material is shown below. In the following schematic diagram, the upper part conveniently shows only the bonding portion of one of the substrates, and the first method corresponds to the scheme indicated by the arrows pointing from the left side of the upper part to the lower part, the second method corresponds to the scheme indicated by the arrows pointing from the left side of the upper part 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 left side of the upper part to the center, from the center to the right side, and from the right side to the lower part (the same applies below).

[0214] [ka]

[0215] Specifically, the reaction when isocyanatomethyltrimethoxysilane is used as the first and second organic materials and 1,2-ethanedithiol is used as the third organic material is shown below.

[0216] [ka]

[0217] Specifically, the reaction when isocyanatomethyltrimethoxysilane is used as the first and second organic materials and ethylene glycol (1,2-ethanediol) is used as the third organic material is shown below.

[0218] [ka]

[0219] Specifically, the reaction when aminomethyltrimethoxysilane is used as the first and second organic materials and ethylene diisocyanate (1,2-ethane diisocyanate) is used as the third organic material is shown below.

[0220] [ka]

[0221] Any appropriate method (scheme) may be applied as a method for bonding the first bonding portion 13 and the second bonding portion 23 using the first to third organic materials B. Three methods are shown below, but the present invention is not limited to these.

[0222] (First method) In the first method, the first and second organic materials and the third organic material are mixed (for example, immediately before use), and the resulting mixture is supplied between the first bonding portion 13 and the second bonding portion 23. The hydrolyzable silyl groups of the first and second organic materials are reacted with the silanol groups of the first bonding portion 13 and the second bonding portion 23 (for example, siloxane bonds are formed by dealcoholization when the hydrolyzable groups are alkoxy groups). This chemically bonds the first organic material to the Si atoms of the first bonding portion 13, and the second organic material to the Si atoms of the second bonding portion 23.

[0223] Furthermore, the reactive functional groups of the first and second organic materials are reacted with and bonded to the bondable groups of the third organic material, thereby bonding the first organic material chemically bonded to the Si atoms of the first bonding portion 13 and the second organic material chemically bonded to the Si atoms of the second bonding portion 23 via the third organic material.

[0224] The reactions between the hydrolyzable silyl groups of the first organic material and the silanol groups of the first bonding portion 13 and the second bonding portion 23, and the reactions between the reactive functional groups of the first and second organic materials and the bondable groups of the third organic material can occur at any time. For example, either reaction can proceed first, or they can occur simultaneously. As a result, the first bonding portion 13 and the second bonding portion 23 are bonded together by a reaction product derived from the first to third organic materials. While alcohol may be generated as a by-product, its carbon number may be small as described above, and it can be effectively removed from between the first bonding portion 13 and the second bonding portion 23 to the outside through the gaps in the reaction product, thereby reducing the formation of voids due to the by-product.

[0225] (Second method) In the second method, a first organic material is supplied to the first bonding portions 13, causing the hydrolyzable silyl groups of the first organic material 5 to react with the silanol groups of the first bonding portions 13 (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by dealcoholization), and a second organic material is supplied to the second bonding portions 23, causing the hydrolyzable silyl groups of the second organic material to react with the silanol groups of the second bonding portions 23 (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by dealcoholization). (The first organic material supplied to the first bonding portions 13 and the second organic material supplied to the second bonding portions 23 may be the same or different.) As a result, the first organic material chemically bonds to the Si atoms of the first bonding portions 13, and the second organic material chemically bonds to the Si atoms of the second bonding portions 23.

[0226] Then, the first bonding portion 13 and the second bonding portion 23 are arranged so that they face each other, and an intermediate derived from the first and second organic materials is positioned between them together with a third organic material, and the reactive functional groups of the first and second organic materials react with the bondable groups of the third organic material to bond them. As a result, the first organic material chemically bonded to the Si atoms of the first bonding portion 13 and the second organic material chemically bonded to the Si atoms of the second bonding portion 23 are bonded via the third organic material.

[0227] As a result, the first bonding portion 13 and the second bonding portion 23 are bonded together by a reaction product derived from the first to third organic materials. Although alcohol, for example, may be generated as a by-product, the number of carbon atoms thereof may be small as described above, and the alcohol can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are disposed opposite each other, thereby reducing the formation of voids resulting from the by-product.

[0228] (Third Method) In the third method, a first organic material is supplied to the first bonding portion 13, causing the hydrolyzable silyl groups of the first organic material to react with the silanol groups of the first bonding portion 13 (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by dealcoholization), and a second organic material is supplied to the second bonding portion 23, causing the hydrolyzable silyl groups of the second organic material to react with the silanol groups of the second bonding portion 23 (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by dealcoholization). (The first organic material supplied to the first bonding portion 13 and the second organic material supplied to the second bonding portion 23 may be the same or different.) As a result, the first organic material chemically bonds to the Si atoms of the first bonding portion 13 (intermediate X1), and the second organic material chemically bonds to the Si atoms of the second bonding portion 23 (intermediate X2). Then, intermediate X1 is conveniently selected as one of intermediates X1 and X2, and a third organic material is supplied to the first bonding portion 13 to react and bond the reactive functional group of the first organic material with the bondable group of the third organic material (intermediate Y).

[0229] Thereafter, the intermediate Y thus obtained and the intermediate X2 obtained above are arranged facing each other, with the intermediate Y derived from the third organic material positioned on the first bonding portion 13 side and the intermediate X2 derived from the second organic material positioned on the second bonding portion 23 side, and the reactive functional group of the intermediate X2 (second organic material) is reacted with the bondable group of the intermediate Y (first organic material + third organic material) to bond them. As a result, the first organic material chemically bonded to the Si atom of the first bonding portion 13 and the second organic material chemically bonded to the Si atom of the second bonding portion 23 are bonded via the third organic material.

[0230] As a result, the first bonding portion 13 and the second bonding portion 23 are bonded together by a reaction product derived from the first to third organic materials. While alcohol, for example, may be generated as a by-product, its carbon number may be small as described above, and it can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, 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 the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, thereby reducing the amount of unnecessary material (that does not contribute to bonding) remaining between the first bonding portion 13 and the second bonding portion 23 in the final laminate.

[0231] Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to such embodiments and various modifications are possible. [Example]

[0232] The present disclosure will be explained in more detail through the following examples, but is not limited to these examples.

[0233] Example 1 First, the cleaning solvents, propylene glycol monomethyl ether acetate and a 30 wt% 1,6-bis(trimethoxysilyl)hexane / propylene glycol monomethyl ether acetate solution, were passed through a filter to remove particles.

[0234] A 4-inch silicon wafer with a thermal oxide film was placed in a plasma device and irradiated for 3 minutes at 250 W. The wafer was then placed in a spin coater, and a 30 wt% 1,6-bis(trimethoxysilyl)hexane / propylene glycol monomethyl ether acetate solution was dripped onto it and allowed to stand for 5 minutes. It was then spin-coated at 2000 rpm for 30 seconds. Propylene glycol monomethyl ether acetate was then dripped onto the wafer as a cleaning solvent, and the wafer was spin-dried at 2000 rpm for 30 seconds. The wafer was then treated on a hot plate at 100°C for 5 minutes, then placed on a manual bonding jig, and bonded to a silicon wafer that had also been irradiated for 3 minutes at 250 W in a plasma device. A 2 kg weight was then placed on the wafer, and the wafer was heated in an oven at 200°C for 30 minutes.

[0235] [Plasma irradiation conditions] The plasma was irradiated using the following equipment. Equipment: Samco Aqua Plasma (registered trademark) Cleaner AQ-500 Irradiation plasma: H2O Irradiation time: 3 minutes ·Irradiation temperature: normal temperature

[0236] [Filter processing] Effective filter diameter: 50nm

[0237] [Measurement of Bonding Strength] The bond strength γ was measured by a blade test in which a razor blade was inserted between the wafers and the peel distance was observed under an infrared microscope. The bond strength γ is expressed by the following formula: γ = (3Ed 3 y 2 ) / (32L 4 ) where E is the Young's modulus of the wafer, y is the blade thickness, d is the wafer thickness, and L is the peel distance.

[0238] [Particle amount] The amount of particles in the composition was measured using a syringe sampling system SLS-1040, and the number of particles of 40 nm or larger in the composition was quantified.

[0239] [Surface foreign matter inspection] For surface contamination testing, a 300 mm silicon wafer with a native oxide film was used. After similar surface activation (plasma irradiation) using a plasma device (Samco Aqua Plasma® Cleaner AQ-2000), the wafer was coated with the 1,6-bis(trimethoxysilyl)hexane / propylene glycol monomethyl ether acetate solution of Example 1 using a 300 mm spin coater. 40 ml of propylene glycol monomethyl ether acetate was then dispensed from a nozzle onto the center of the rotating wafer, resulting in a cleaned wafer. The number of particle clusters was measured on the wafer using a surface foreign matter inspection device. The wafer was a 300 mm wafer with an area of ​​706.8 cm. 2 It was.

[0240] Example 2 The same procedure as in Example 1 was carried out, except that bis[3-(trimethoxysilyl)propyl]amine was used as the first organic material instead of 1,6-bis(trimethoxysilyl)hexane.

[0241] Example 3 The same procedure as in Example 1 was carried out, except that hexamethylene diisocyanate was used as the first organic material instead of 1,6-bis(trimethoxysilyl)hexane.

[0242] The same procedure as in Example 3 was carried out except that no filtering was performed.

[0243] Table 2 shows the amount of particles in the cleaning solvent and the effective diameter of the filter used to remove the particles, Table 3 shows the effective diameter of the filter and the amount of particles in the composition containing the first organic solvent, and Table 4 shows the bonding temperature, the number of clusters in the adhesive layer, and the bonding strength.

[0244] [Table 2]

[0245] [Table 3]

[0246] [Table 4]

[0247] Example 4 First, the cleaning solvents, ethanol, propylene glycol monomethyl ether acetate, a 30 wt% 3-aminopropyldimethoxymethylsilane / ethanol solution, and a 30 wt% hexamethylene diisocyanate / propylene glycol monomethyl ether acetate solution, were each passed through a filter to remove particles.

[0248] Two 4-inch silicon wafers with thermally oxidized films were placed in a plasma generator and irradiated for 3 minutes at 250 W. The wafers were then placed in a spin coater, and a 30 wt% 3-aminopropyldimethoxymethylsilane (first and second organic materials) / ethanol solution was dripped onto them and allowed to stand for 5 minutes. The wafers were then spin-coated at 2000 rpm for 30 seconds. A cleaning solvent, propylene glycol monomethyl ether acetate, was then dripped onto the wafers, and the wafers were spin-dried at 2000 rpm for 30 seconds. Two wafers were then treated on a hot plate at 100°C for 5 minutes. One of the wafers was then spin-coated with a 30 wt% hexamethylene diisocyanate (third organic material) / propylene glycol monomethyl ether acetate solution, spin-dried with the cleaning solvent, and then heat-treated at 100°C for 5 minutes. The two wafers were bonded together using a manual bonding tool with the adhesive layer facing inward, and then a 2 kg weight was placed on the wafers, followed by heating at 200°C for 30 minutes.

[0249] Example 5 The same procedure as in Example 4 was carried out except that the concentrations of the first organic material and the second organic material were changed.

[0250] Table 5 shows the amount of particles in the cleaning solvent and the effective diameter of the filter used to remove the particles, Table 6 shows the concentration of organic materials, Tables 7 to 9 show the effective diameter of the filter, the amount of particles, and the number of clusters, and Table 10 shows the bonding temperature and bonding strength.

[0251] [Table 5]

[0252] [Table 6]

[0253] [Table 7]

[0254] [Table 8]

[0255] [Table 9]

[0256] Example 6 First, the cleaning solvent propylene glycol monomethyl ether acetate and and a 0.2 wt % bis[3-(trimethoxysilyl)propyl]amine / propylene glycol monomethyl ether acetate solution were passed through a filter to remove particles.

[0257] A 4-inch silicon wafer with a thermal oxide film was placed in a plasma device and irradiated for 3 minutes at 250 W. The wafer was placed in a spin coater, and a 0.2 wt% bis[3-(trimethoxysilyl)propyl]amine / propylene glycol monomethyl ether acetate solution was dripped onto it. The wafer was then spin-coated at 2000 rpm for 30 seconds and then allowed to stand for 5 minutes. Furthermore, propylene glycol monomethyl ether acetate (water content 5.5 wt%) was dripped onto the wafer as a cleaning solvent, allowed to stand for 10 minutes, and then spin-dried at 2000 rpm for 30 seconds. The wafer was then treated on a hot plate at 100 °C for 5 minutes, then loaded onto a manual bonding jig, and bonded to a silicon wafer that had also been irradiated for 3 minutes at 250 W in a plasma device. A 2 kg weight was then placed on the wafer, and the wafer was heated in an oven at 200 °C for 7 hours.

[0258] Table 10 shows the amount of particles in the cleaning solvent and the effective diameter of the filter used to remove the particles, and Table 11 shows the bonding temperature and the number of clusters.

[0259] [Table 10]

[0260] [Table 11] [Industrial Applicability]

[0261] By using the method for manufacturing a stacked body according to the present disclosure, the bonding strength between the first silicon substrate and the second silicon substrate can be improved. [Explanation of symbols]

[0262] 10,20 Silicon substrate 11,21 Main body 13,23 Joint 30,30A,30B Adhesive layer 31,31A,32A,31B,32B,33B Adhesive part 40, 40A, 40B 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 containing silicon oxide; (b) preparing a first composition containing at least one of an organic material capable of reacting with a hydrosilyl group and / or a silanol group and an inorganic material capable of bonding with silicon oxide, the first composition having a particle amount of 3,000 particles / mL or less; and (c) using at least one of the organic material and the inorganic material, a step of providing an adhesive layer that bonds the first bonding portion and the second bonding portion with the organic material and / or a reaction product derived from the organic material, or that bonds the first bonding portion and the second bonding portion with the inorganic material and / or a reaction product derived from the inorganic material; Including, the adhesive layer includes a first adhesive portion provided on the first bonding portion, The number of particle clusters contained on the surface of the first adhesive portion opposite to the first bonding portion is 5 / cm ２ The manufacturing method is as follows.

2. 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; The method of claim 1.

3. The organic material is (i) a 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 a plurality of terminal ends, at least two of which have, independently, one group selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, a phosphoric acid group, and an acid anhydride group; and (iv) silsesquioxanes and their derivatives; The method for producing a laminate according to claim 1 or 2, comprising at least one selected from the group consisting of:

4. The manufacturing method according to claim 1 , wherein the reaction product is derived from the inorganic material.

5. The reaction product is SiO ２ , SiOC, SiOF, SiN, SiCN, HfO ２ , and La ２ O ３ The method according to claim 4, comprising at least one selected from the group consisting of:

6. 3. The method of claim 1 or 2, further comprising filtering the second composition to refine the first composition.

7. The manufacturing method according to claim 6 , wherein the filtering is performed using a membrane having an effective diameter of 50 nm or less.

8. The method of claim 6 , wherein the amount of particles in the second composition is more than 3,000 particles / mL.

9. The bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m ２ The manufacturing method according to claim 1 or 2, wherein the above is performed.

10. The manufacturing method according to claim 1 or 2, wherein the first adhesive portion is formed of two or more layers.

11. The adhesive layer further includes a second adhesive portion bonded to the first adhesive portion, the second adhesive portion is provided on the second joining portion, The number of particle clusters contained on the surface of the second adhesive portion opposite to the second bonding portion is 5 / cm ２ Below is the The method according to claim 1 or 2.

12. The manufacturing method according to claim 11 , wherein the second adhesive portion is formed from two or more layers.

13. The organic material is (i) a substituted or unsubstituted hydrocarbon compound having multiple terminal ends, at least two of which have alkenyl groups; (ii) A substituted or unsubstituted hydrocarbon compound having a plurality of terminal ends, at least one of which has an alkenyl group at one terminal end and at least one of which has any one 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 one terminal end. (iii) a substituted or unsubstituted hydrocarbon compound having a plurality of terminal ends, at least two of which independently have any one group selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, a phosphoric acid 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 according to claim 11 , comprising at least one selected from the group consisting of:

14. a first silicon substrate having a first bonding portion; a second silicon substrate having a second bonding portion located on the first bonding portion side; an adhesive layer located between the first bonding portion and the second bonding portion and adhering the first bonding portion and the second bonding portion; and the first bonding portion and the second bonding portion have a hydrosilyl group and / or a silanol group derived from silicon oxide, or a region bonding to an inorganic material, the adhesive layer includes a reaction product reacted with the hydrosilyl group and / or the silanol group, or a region that bonds with the inorganic material; The number of particle clusters on the surface of the adhesive layer is 5 / cm ２ is as follows: The bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m ２ That's all. Laminate.

15. The laminate according to claim 14 , wherein the adhesive layer comprises two or more layers.

16. The method of claim 1, comprising: The substrate includes at least one of an organic material capable of reacting with a hydrosilyl group and / or a silanol group and an inorganic material capable of bonding with silicon oxide; The composition has a particle amount of 3,000 particles / mL or less.

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