Method for manufacturing a stack comprising two silicon substrates and the stack

Abstract

The present application relates to a manufacturing method of a laminate including two silicon substrates, comprising: (a) a process of preparing a first silicon substrate having a first bonding portion and a second silicon substrate having a second bonding portion, wherein the first bonding portion and the second bonding portion are portions including silicon oxide; (b) a process of preparing a first composition, wherein the first composition 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, and the particle amount is 3000 pieces / mL or less; and (c) a process of providing a bonding layer using at least one of the organic material and the inorganic material, wherein the bonding layer bonds the first bonding portion and the second bonding portion by the organic material and / or a reaction product from the organic material, or bonds the first bonding portion and the second bonding portion by the inorganic material and / or a reaction product from the inorganic material, and the bonding layer includes a first bonding portion provided on the first bonding portion; the number of clusters of particles contained in a surface of the first bonding portion on a side opposite to the first bonding portion is 5 pieces / cm 2 The following.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a stack comprising two silicon substrates and the stack thereof. Background Technology

[0002] In the field of semiconductor technology, for example, in Patent Document 1, a method of providing an adhesive layer between two silicon substrates was studied as a method of bonding two silicon substrates.

[0003] Existing technical documents Patent documents Patent Document 1: International Publication No. 2023 / 276638 Summary of the Invention

[0004] The problem that the invention aims to solve In the bonding of silicon substrates as described above, it is necessary to improve the bonding strength between the silicon substrates. Therefore, the objective of this invention is to provide a manufacturing method for further increasing the bonding strength between silicon substrates, and a laminate formed by this method.

[0005] Technical solutions for solving the problem To address the aforementioned issues, the present invention provides the following [1] to

[17] .

[0006] [1] A method for manufacturing a laminate comprising two silicon substrates, comprising: (a) A process of preparing a first silicon substrate having a first bonding portion and a second silicon substrate having a second bonding portion, wherein the first bonding portion and the second bonding portion are portions comprising silicon oxide; (b) The step of preparing a first composition, wherein the first composition comprises at least one of an organic material capable of reacting with silyl groups and / or silanol groups, and an inorganic material capable of bonding with silicon oxides, and the particle size is less than 3000 particles / mL; and (c) A step of providing an adhesive layer using at least one of the above-mentioned organic material and the above-mentioned inorganic material, wherein the adhesive layer bonds the first joint portion to the second joint portion by the organic material and / or by a reaction product derived from the organic material, or bonds the first joint portion to the second joint portion by the inorganic material and / or by a reaction product derived from the inorganic material. The adhesive layer includes a first adhesive portion disposed on the first joint portion; The number of particle clusters on the surface of the first adhesive portion opposite to the first joint portion is 5 per cm. 2 the following.

[0007] [2] The manufacturing method described in [1] wherein the organic material has at least one selected from alkenyl, hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, anhydride and siloxane bonds.

[0008] [3] The method for manufacturing a laminate as described in [1] or [2], wherein the organic material comprises at least one selected from (i) to (iv) below: (i) Hydrocarbon compounds having alkenyl groups at both ends; (ii) A hydrocarbon compound having an alkenyl group at one end and a substituted or unsubstituted group selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino and anhydride groups at the other end; (iii) A hydrocarbon compound having multiple terminal portions, and at least two terminal portions having independently substituted or unsubstituted groups selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, phosphate, and anhydride groups; and (iv) Sesquioxanes and their derivatives.

[0009] [4] The manufacturing method as described in any one of [1] to [3], wherein the reaction product is derived from the inorganic material described above.

[0010] [5] The manufacturing method described in [4] includes, wherein the reaction product comprises at least one selected from SiO2, SiOC, SiOF, SiN, SiCN, HfO2 and La2O3.

[0011] [6] The manufacturing method as described in any one of [1] to [5] includes the step of filtering the second composition to refine it into the first composition described above.

[0012] [7] The manufacturing method described in [6] involves using a filter membrane with an effective diameter of 50 nm or less for the above-mentioned filtration.

[0013] [8] The manufacturing method as described in [6] or [7], wherein the particle count in the second composition is higher than 3000 particles / mL.

[0014] [9] The manufacturing method as described in any one of [1] to [8], wherein the bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m. 2 above.

[0015]

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

[0016]

[11] The manufacturing method as described in any one of [1] to

[10] , wherein the adhesive layer further comprises a second adhesive portion that is joined to the first adhesive portion. The second adhesive portion is provided on the second joint portion. The number of particle clusters on the surface of the second adhesive portion opposite to the second joint portion is 5 per cm. 2 the following.

[0017]

[12] The manufacturing method described in

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

[0018]

[13] The manufacturing method as described in

[11] or

[12] , wherein the organic material comprises at least one selected from (i) to (vi) below: (i) A substituted or unsubstituted hydrocarbon compound having multiple terminal portions, and having an alkenyl group at at least two terminal portions; (ii) A hydrocarbon compound having a plurality of terminal portions, each having an alkenyl group at at least one terminal portion, and having a substituted or unsubstituted group selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino and anhydride groups at at least one terminal portion; (iii) A hydrocarbon compound having multiple terminal portions, and having at least two terminal portions independently having substituted or unsubstituted groups selected independently from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, phosphate and anhydride groups; (iv) Silsesquioxanes and their derivatives; (v) A combination of a hydrolyzable hydrogen silane or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrogen silyl 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 hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end, either substituted or unsubstituted.

[0019]

[14] A laminated body having: A first silicon substrate having a first bonding portion; A second silicon substrate located on one side of the first junction and having a second junction; and An adhesive layer located between the first joint and the second joint, which bonds the first joint and the second joint together. The first and second joints described above have silyl groups and / or silanol groups derived from silicon oxide, or have regions that can be bonded to inorganic materials. The aforementioned adhesive layer includes reaction products obtained by reacting with the aforementioned hydrogenated silyl groups and / or the aforementioned silanol groups, or regions bonded to the aforementioned inorganic materials. The number of particle clusters on the surface of the above adhesive layer is 5 per cm. 2 the following, The bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m. 2 above.

[0020]

[15] As described in

[14] , the laminated body wherein the adhesive layer is formed of two or more layers.

[0021]

[16] A composition comprising at least one of an organic material and an inorganic material. The particle count is less than 3000 particles / mL.

[0022]

[17] The composition as described in

[16] is used in the manufacturing method described in [1].

[0023] Invention Effects According to the present invention, a manufacturing method for further increasing the bonding strength between silicon substrates and a stack formed by the method can be provided. Attached Figure Description

[0024] Figure 1 A schematic cross-sectional view of the laminated body according to the first embodiment.

[0025] Figure 2 A schematic cross-sectional view showing the laminated body of the second embodiment.

[0026] Figure 3 A schematic cross-sectional view of a modified example of a laminated body. Detailed Implementation

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited to these embodiments.

[0028] <First Implementation> Figure 1 This is a cross-sectional view illustrating the laminate 40 of the first embodiment. Figure 1As shown, the laminate 40 has a first silicon substrate 10 and a second silicon substrate 20, and an adhesive layer 30 is 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.

[0029] The aforementioned laminate 40 can be obtained by a manufacturing method including the following steps: (a) Prepare a first silicon substrate 10 having a first bonding portion 13 and a second silicon substrate 20 having a second bonding portion 23, wherein the first bonding portion 13 and the second bonding portion 23 are portions containing silicon oxide. (b) The step of preparing a first composition, wherein the first composition comprises at least one of an organic material capable of reacting with silyl groups and / or silanol groups, and an inorganic material capable of bonding with silicon oxides, and the particle size is less than 3000 particles / mL; and (c) A step of providing an adhesive layer 30 using at least one of the above-mentioned organic material and the above-mentioned inorganic material, wherein the adhesive layer 30 bonds the first joint 13 to the second joint 23 by the above-mentioned organic material and / or reaction products from the organic material, or bonds the first joint 13 to the second joint 23 by the inorganic material. The adhesive layer 30 includes a first adhesive portion 31 disposed on the first joint portion 13; The number of particle clusters in the surface of the first adhesive portion 31 opposite to the first joint portion 13 is 5 per cm. 2 the following.

[0030] By employing the above manufacturing method, the bonding strength between the first silicon substrate 10 and the second silicon substrate 20 can be increased. It should be noted that in this specification, "organic materials and / or reaction products from the organic materials" are sometimes referred to as "reaction products from organic materials".

[0031] The following describes each process. It should be noted that in the following text, "on the first silicon substrate 10" is not specifically limited; it can refer to a state where it is in direct contact with the first silicon substrate 10, or a state where other layers are also included on the first silicon substrate 10. The same applies to other substrates, layers, regions, etc.

[0032] [Process 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.

[0033] (First silicon substrate 10 and second silicon substrate 20) The first silicon substrate 10 and the second silicon substrate 20 (hereinafter collectively referred to as "silicon substrates") can be any substrate (or base material) with silicon as the substrate. They can be formed of silicon or contain any other suitable material in addition to silicon. Examples of such other materials include dopants, unavoidably mixed impurities, metals (e.g., electrodes, wiring, vias, etc.), oxides, nitrides, and / or carbides of silicon (e.g., dielectric layers, insulating layers, protective layers, etc.).

[0034] 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.

[0035] 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 constitute the entire surface of the first silicon substrate 10 (typically, one of the two opposing surfaces of the first silicon substrate 10), or it may constitute a portion of its area.

[0036] 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 constitute the entire surface of the second silicon substrate 20 (typically, one of the two opposing surfaces of the second silicon substrate 20), or it may constitute a portion of its area.

[0037] (First joint 13 and second joint 23) In this embodiment, the first junction 13 and the second junction 23 (hereinafter also referred to as "junction") are simply portions containing silicon oxide (hereinafter also referred to as "silicon oxide portions"). The silicon oxide portions may be formed of silicon oxide, or may contain any suitable other substances in addition to silicon oxide. Examples of such other substances include dopants, unavoidably mixed impurities, etc.

[0038] The bonding portion can be formed, for example, by oxidizing the entire surface or a portion 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 can constitute the entire surface or a portion of the surface of the first silicon substrate 10 (typically, one of the two opposing surfaces of the first silicon substrate 10). The second bonding portion 23 can constitute the entire surface or a portion of the surface of the second silicon substrate 20 (typically, one of the two opposing surfaces of the second silicon substrate 20).

[0039] Silicon oxidation can be achieved by heating in an oxygen-containing atmosphere (so-called thermal oxidation) and / or natural oxidation. Alternatively, for example, the bonding portion of this embodiment can be formed by depositing silicon oxide on the entire surface or a portion of the surface of a silicon substrate (typically, one of the two opposing surfaces of the silicon substrate). The deposition of silicon oxide can be carried out by any one or a combination of sputtering, chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), evaporation, etc. Silicon oxidation and silicon oxide deposition can be combined. However, it is not limited to these methods; the bonding portion as the silicon oxide portion can be formed by any suitable method.

[0040] Silanol groups (-Si-OH) are present on the surface of the junction, which is a silicon oxide portion.

[0041] The thickness of the joint is not particularly limited, as long as the final manufactured laminate achieves the desired and acceptable performance. For example, the thickness of the joint as the silicon oxide portion can be 1 nm or more and 1 μm or less, particularly 10 nm or less. The thickness of the joint can be measured, for example, by transmission electron microscopy. Furthermore, if before bonding, the thickness of the joint can be measured, for example, by elliptic polarization. Preferably, the thickness of the joint (both before and after bonding) is measured by elliptic polarization.

[0042] In this embodiment, it is not mandatory, but it is preferable to apply a surface treatment to at least one of the first joint 13 and the second joint 23 to generate hydrazine and / or silanol groups after step (a) and before step (c). This allows hydrazine (-Si-H) and / or silanol (-Si-OH) groups to exist at a higher density on the surface of the joint. The surface treatment can be performed only on the surface of the joint (joint surface), or it can be performed on a wider surface including the surface of the joint. The proportion of hydrazine and / or silanol groups present on the surface of the joint can be determined, for example, using time-of-flight secondary ion mass spectrometry (TOF-SIMS). For example, the proportion of silanol groups (-Si-OH) can be determined by calculating the ratio of -Si-OH to -C4H7. It should be noted that here, the ratio of -Si-OH to -C4H7 refers to the ratio of fragment ions.

[0043] Surface treatments that produce hydride silyl groups and / or silanol groups can be at least one selected from hydrogen atom treatment, heat treatment in a hydrogen-containing atmosphere, sputtering treatment, chemical vapor deposition (CVD) treatment, plasma treatment, and terminal treatment using a chemical solution. Hydrogen atoms can be introduced into the surface of the joint through hydrogen atom treatment, heat treatment in a hydrogen-containing atmosphere, sputtering treatment, CVD treatment, plasma treatment, or terminal treatment using a chemical solution, producing hydride silyl groups. Hydroxyl groups can be introduced into the surface of the joint through terminal treatment using a chemical solution, producing silanol groups (-Si-OH).

[0044] Hydrogen atom manipulation, for example, can be achieved by introducing hydrogen atoms into ultra-high vacuum (1×10⁻⁶). ﹣6 A vacuum chamber (below Pa) is supplied with 1×10⁻⁶ Pa. ﹣4 Hydrogen gas at approximately Pa is used, and hydrogen molecules are dissociated into hydrogen atoms through thermionic electrons or plasma, causing the hydrogen atoms to be adsorbed onto the surface of the junction, thereby implementing the process.

[0045] Heating in a hydrogen atmosphere can be performed, for example, by circulating hydrogen as a carrier gas during vacuuming to replace the atmosphere in the chamber with hydrogen, creating a hydrogen atmosphere vacuum (specifically, a hydrogen atmosphere of less than 10 Pa), and heating the substrate to about 100 to 400°C in this atmosphere to allow hydrogen to be adsorbed onto the surface of the joint.

[0046] Sputtering can be performed, for example, by using silicon as a sputtering source and supplying hydrogen, causing the hydrogen to be adsorbed onto the surface of the joint.

[0047] CVD processing can be carried out, for example, by using silane as the CVD gas and adjusting the hydrogen gas pressure to allow hydrogen atoms to be adsorbed onto the surface of the junction.

[0048] Plasma treatment can be carried out, for example, by subjecting a silicon substrate to plasma treatment and then using moisture in the atmosphere or a water bath to cause the substrate surface to react with water molecules.

[0049] Terminal treatment using chemical solutions can be carried out, for example, by immersing a silicon substrate in a solution of hydrofluoric acid (hydrofluoric acid), ammonium fluoride, formic acid, etc., with at least the junction exposed, thereby allowing hydrogen ions and / or hydroxide ions to bind to the surface of the junction, depending on the chemical solution used.

[0050] In this embodiment, it is not necessary, but at least one of the first joint 13 and the second joint 23 may be subjected to a surface treatment that produces fluorosilyl groups after step (a) and before step (c).

[0051] The surface treatment for producing fluorosilyl groups can be at least one selected from CVD, electrical discharge processing, ion implantation, plasma treatment, and terminal treatment using a chemical solution. The surface treatment for introducing fluorosilyl groups and the surface treatment for introducing hydrogenated silyl / silanol groups can be performed separately or simultaneously. When performed separately, any one of these surface treatments can be performed first.

[0052] CVD treatment can be carried out, for example, by using CF4 and / or SF6 as CVD gases to adsorb fluorine atoms onto the surface of the joint.

[0053] Discharge treatment can be carried out, for example, by plasma discharge or corona discharge in an atmosphere containing CF4 and / or SF6, thereby causing fluorine radicals to adsorb onto the surface of the joint.

[0054] Ion implantation can inject fluorine ions into the junction using any suitable method.

[0055] The final treatment using a chemical solution can be carried out, for example, by immersing a silicon substrate, with at least the junction exposed, in a chemical solution such as an aqueous solution of hydrofluoric acid (hydrofluoric acid) or ammonium fluoride. Depending on the chemical solution used, fluoride ions are bonded to the surface of the junction. The final treatment using an aqueous solution of hydrofluoric acid can produce silyl groups (-Si-H), silanol groups (-Si-OH), and fluorosilyl groups (-Si-F).

[0056] While not strictly necessary in this embodiment, chemical mechanical polishing (CMP) can also be performed on the surface of the silicon substrate before the bonding portion is formed. This allows the surface to be planarized or smoothed.

[0057] Furthermore, although not strictly necessary in this embodiment, the surface of the silicon substrate before the bonding portion is formed can be cleaned after CMP or without CMP. This allows for the removal of unwanted substances such as organic matter, particles, metals, and / or metal ions.

[0058] Cleaning is not particularly limited and can be carried out using methods known in the field of semiconductor technology. Cleaning may include rinsing and drying. For example, rinsing can be carried out using any one or a combination of two or more cleaning solutions such as SPM (H2SO4 + H2O2 + H2O: piranha solution), APM (NH4OH + H2O2 + H2O: SC-1, RCA-1), HPM (HCl + H2O2 + H2O: SC-2, RCA-2), DHF (HF + H2O), and BHF (NH4F + HF + H2O), which can be standard compositions and modified compositions. Depending on the circumstances, rinsing may also be carried out by adding any one or two or more of trichloroethylene, alcohol, acetone, deionized water, ultrasound, etc. Furthermore, drying can be performed using rotary drying, isopropanol (IPA) vapor drying, IPA direct displacement drying, etc.

[0059] Depending on the cleaning solution and conditions used, OH-, for example, can be introduced onto the surface of the silicon substrate before the bonding joint is installed. ﹣ H ﹢ Ions and / or molecules such as H2O, H2 and O2 can be generated on the surface, resulting in the formation of hydride silyl and / or silanol groups.

[0060] The first silicon substrate 10 and the second silicon substrate 20 are prepared by operating as described above.

[0061] [Process b] Next, a first composition is prepared, comprising at least one of an organic material capable of reacting with silyl groups and / or silanol groups, and an inorganic material capable of bonding with silicon oxides, wherein the particle quantity is 3000 particles / mL or less. The lower limit of the particle quantity in this first composition is not particularly limited, but may be, for example, 1 particle / mL or more, specifically 0 particles / mL or more.

[0062] (A first composition comprising organic or inorganic materials) At least one of the organic and inorganic materials can be used as a first composition containing a solvent, for example. In addition to the organic and / or inorganic materials, the first composition may also contain a reaction promoter such as a solvent, an acid catalyst, or a base catalyst. Commonly used solvents can be used, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, toluene, tetrahydrofuran, or isopropanol. The water content in the first composition is substantially zero. By reducing the water content in the first composition in this way, the formation of voids can be reduced. It should be noted that the first composition may contain only organic materials, only inorganic materials, or only both organic and inorganic materials.

[0063] In the first composition described above, organic and / or inorganic materials can be dissolved, dispersed, or suspended in a solvent. For example, the first composition described above dissolves organic and / or inorganic materials.

[0064] The particle count in the first composition described above is, for example, 3000 particles / mL or less, preferably 2000 particles / mL or less, more preferably 1000 particles / mL or less, and for example, 500 particles / mL or less. The lower limit of the particle count in the first composition described above is not particularly limited; for example, it can be 0 particles / mL or more.

[0065] Particles can be individual particles or aggregates of particles. That is, particles contain primary and secondary particles. Furthermore, particles can be inorganic or organic. Examples of particles include particles present in the environment, particles supplied along with organic materials, and substances that exist in particle form after the organic material has solidified.

[0066] Particle quantity can be determined, for example, using the SLS-1040 syringe sampling system.

[0067] In the first composition, the organic and / or inorganic materials preferably comprise 50% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. The lower limit of the content of the organic and / or inorganic materials is not particularly limited; for example, it can be 1% by mass or more, 3% by mass or more, or 5% by mass or more. For example, in the first composition, the organic and / or inorganic materials can comprise a range of 1 to 50% by mass, a range of 3 to 35% by mass, or a range of 5 to 30% by mass. Furthermore, in the first composition, the organic and / or inorganic materials can comprise a range of 1 to 30% by mass, or a range of 3 to 30% by mass. It should be noted that when both organic and inorganic materials are included, the total amount of the two materials can be within the above-mentioned ranges.

[0068] Preferably, the first composition described above contains only a solvent and organic and / or inorganic materials.

[0069] (Organic materials in the first composition) The particle count in the organic material is, for example, 3000 particles / mL or less, preferably 2000 particles / mL or less, more preferably 1000 particles / mL or less, and for example, 500 particles / mL or less. There is no particular limitation on the lower limit of the particle count in the organic material; for example, it can be 0 particles / mL or more. The particle count in the organic material can be determined, for example, by the same method as for the particle count of the first composition.

[0070] Organic materials preferably have at least two functional groups. These two functional groups are preferably located at the two ends of the organic material.

[0071] Organic materials can react with hydride silyl groups and / or silanol groups at a terminal functional group to form reaction products. That is, the composition of the reaction products depends on the structure of the organic material.

[0072] The organic material can react with the functional group at another end of the second activated region 23a. The first junction 13 and the second junction 23 are joined using the reaction product from the organic material.

[0073] As the aforementioned functional group, at least one can be selected from alkenyl, hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, acid anhydride, and siloxane bonds.

[0074] Alkenyl groups can react with hydrogenated silyl groups (-Si-H), while hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, anhydride, and siloxane bonds can react with silanol groups (-Si-OH).

[0075] More specifically, the organic material may contain at least one selected from (i) to (iv) below. It should be noted that the organic material may use one compound or a combination of two or more compounds.

[0076] (i) A substituted or unsubstituted hydrocarbon compound having multiple terminal portions, and having an alkenyl group at at least two terminal portions; (ii) A hydrocarbon compound having a plurality of terminal portions, and having an alkenyl group at at least one terminal portion and a substituted or unsubstituted group selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino and anhydride groups at at least another terminal portion; (iii) A hydrocarbon compound having multiple terminal portions, and at least two terminal portions having independently substituted or unsubstituted groups selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, phosphate, and anhydride groups; and (iv) Sesquioxanes and their derivatives.

[0077] The details of (i) to (iv) will be explained later.

[0078] (Inorganic materials in the first composition) The particle count in the inorganic material is, for example, 3000 particles / mL or less, preferably 2000 particles / mL or less, more preferably 1000 particles / mL or less, and for example, 500 particles / mL or less. There is no particular limitation on the lower limit of the particle count in the inorganic material; for example, it can be 0 particles / mL or more. The particle count in the inorganic material can be determined, for example, by the same method as for the particle count of the first composition.

[0079] Inorganic materials can react with hydrazine / silanol groups to form reaction products. These reaction products may, for example, contain at least one selected from SiO2, SiOC, SiOF, SiN, SiCN, HfO2, and La2O3. It should be noted that the inorganic material may also not react with the first silicon substrate 10 or the second silicon substrate 20, but instead, a layer of the inorganic material may be formed on the first silicon substrate 10 or the second silicon substrate 20. In this case, the layer of the inorganic material may contain, for example, at least one selected from SiO2, SiOC, SiOF, SiN, SiCN, HfO2, and La2O3.

[0080] The aforementioned inorganic materials can be used to form at least one thin film. The thickness of the thin film is not particularly limited, for example, it can be less than 10 nm.

[0081] Preferably, the process includes a step of refining the first composition by filtering the second composition. This removes particles from the second composition and reduces the amount of particles in the first adhesive portion 31. Except for the particle size, the organic materials, etc., contained in the second composition have the same composition as those contained in the first composition. For example, the particle size of the second composition exceeds 3000 particles / mL.

[0082] Preferably, the above filtration is performed using a filter membrane with an effective diameter of 50 nm or less. More preferably, the effective diameter of the filter membrane is 10 nm or less. There is no particular limitation on the lower limit of the effective diameter of the filter membrane; for example, it can be 1 nm or more. Here, the effective diameter refers to the value of the average effective diameter of the filter membrane.

[0083] [Process c] Next, at least one of an organic material or an inorganic material is supplied between the first joint 13 and the second joint 23, and an adhesive layer 30 is provided. The adhesive layer 30 joins the first joint 13 and the second joint 23 by a reaction product from the organic material, or joins the first joint 13 and the second joint 23 by the inorganic material.

[0084] (Adhesive layer 30) The adhesive layer 30 includes a first adhesive portion 31 disposed on the first bonding portion 13. In this embodiment, the first silicon substrate 10 and the second silicon substrate 20 are bonded by the first adhesive portion 31. The surface of the first adhesive portion 31 opposite to the first bonding portion 13 contains a particle cluster number of 5 particles / cm. 2 The following is a lower limit for the number of particle clusters on the surface of adhesive layer 30; for example, it may be 1 cluster / cm. 2 The above is specifically 0 per cm. 2 The above should be noted. The number of particle clusters can be determined by disposing of 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 (e.g., the surface of the first bonding portion 13 side of the first silicon substrate 10), and then drying the organic material (or the composition containing an organic material) and the inorganic material (or the composition containing an inorganic material) on the dried surface.

[0085] A cluster is a collection of particles (also called "surface particles") existing on a surface. For example, a cluster can consist of a single particle or two or more particles aggregated together. There is no particular limit to the number of particles contained in a cluster; for example, it can contain up to 30 particles.

[0086] The number of clusters can be determined using a surface foreign matter inspection device. This device can be a general-purpose instrument used in previous process inspections, and the measurement can be performed on, for example, a 300mm wafer. For instance, when the thickness of the adhesive layer 30 is small, the particle size may be larger than the thickness of the adhesive layer 30; in this case, the measurement using a surface foreign matter inspection device is particularly useful.

[0087] By ensuring that the number of particle clusters on the surface of the adhesive layer 30 is within the aforementioned range, the bonding strength between the first silicon substrate 10 and the second silicon substrate 20 becomes good. Furthermore, the laminate 40 can be manufactured at a lower temperature, thereby effectively suppressing or preventing the formation of voids in the adhesive layer 30. The bonding strength can be determined, for example, by a blade test. This test, which involves inserting razor blades between wafers and observing the peel distance using an infrared microscope, can be used to determine the bonding strength (adhesion strength) γ. γ=(3Ed 3 y2 ) / (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.

[0088] There is no specific limit to the lower limit of the number of particles in the adhesive layer 30; for example, it can be 0 particles / cm. 3 above.

[0089] The number of particle clusters on the surface of the adhesive layer 30 can be, for example, less than 3000 per wafer, less than 2000 per wafer, or less than 1000 per wafer. There is no particular limitation on the lower limit of the number of clusters on the surface of the adhesive layer 30; it can be more than 0 per wafer or more than 1 per wafer. The wafer mentioned above is a 300mm wafer, i.e., a wafer with a diameter of 300mm, and the wafer area is 706.8 cm². 2 .

[0090] The particle size in the adhesive layer can be, for example, above 60 nm or above 200 nm. There is no particular upper limit to the particle size, for example, it can be below 6 μm.

[0091] Particle size refers to the equivalent diameter of light scattering that can be quantified by a measuring device. Particle size can be measured, for example, using a surface foreign matter inspection device or a liquid particle counter. For example, a surface foreign matter inspection device can measure particle sizes larger than 60 nm.

[0092] The particle count on the surface of adhesive layer 30 can be, for example, 3000 particles / cm². 2 The following can be 2000 pieces / cm 2 The following can also be 1000 pieces / cm 2 The following applies. There is no specific limit to the lower limit of the particle count on the surface of adhesive layer 30; it can be 0 particles / cm². 2 The above can also be 1 per cm. 2 above.

[0093] It should be noted that in the first embodiment, the first adhesive portion 31 is provided on the first joint portion 13, but the first adhesive portion 31 may also be provided on the second joint portion 23. In this case, "first joint portion 13" can be read as "second joint portion 23" and "first joint portion 13" can be read as "second joint portion 23".

[0094] The adhesive layer 30 (first adhesive portion 31) can be formed of two or more layers. That is, the first adhesive portion can be provided on the first silicon substrate 10, and then dried and / or heated as needed, and then the second adhesive portion can be provided. The number of adhesive portions is not particularly limited, for example, it can be three layers or less.

[0095] The thickness of the adhesive layer 30 can be extremely thin. For example, the thickness of the adhesive layer 30 can be less than 10 nm, especially less than 8 nm, and there is no particular limit to the lower limit; for example, it can be greater than 1 nm.

[0096] Using the adhesive layer 30 described above, the first silicon substrate and the second silicon substrate can be bonded together. The preferred bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m. 2 That's all. This can improve the bonding strength.

[0097] The specific manner of supplying and bonding the organic material (or a composition containing an organic material) can be appropriately selected based on the organic material used. Generally speaking, after supplying the organic material to the first bonding portion 13, the first silicon substrate 10 and the second silicon substrate 20 can be held in a state where the organic material is sandwiched between the first bonding portion 13 and the second bonding portion 23, under specified reaction conditions (particularly a specified temperature), thereby bonding the first bonding portion 13 and the second bonding portion 23 by the reaction products. It should be noted that the organic material can also be supplied to the second bonding portion 23 instead of the first bonding portion 13.

[0098] For example, an organic material (or a composition containing an organic material) can be applied to the surface of the first bonding portion 13 side of the first silicon substrate 10 by coating, spraying, printing, etc. The organic material can be applied in its own form or as a composition mixed with any suitable component (e.g., a solvent). Afterward, cleaning and / or drying can be performed as needed. Cleaning and drying can be performed using the same methods as described above; in the case of using a fluorinated organic material, pre-cleaning with a fluorinated solvent can be performed.

[0099] Then, the first silicon substrate 10 and the second silicon substrate 20 are aligned with the first bonding portion 13 and the second bonding portion 23 facing each other, and the first silicon substrate 10 and the second silicon substrate 20 are bonded together with an organic material sandwiched between the first bonding portion 13 and the second bonding portion 23. The first silicon substrate 10 and the second silicon substrate 20 are held together under specified reaction conditions (especially specified temperature) and a reaction is carried out during this period. Then, annealing treatment can be performed as needed.

[0100] For example, when an organic material is applied to the surface of the first joint 13, the second joint 23 can be disposed on the layer formed by the organic material after the surface of the layer formed by the organic material is cleaned with water or an aqueous organic solvent. It should be noted that the organic material can also be applied to the surface of the second joint 23 instead of the surface of the first joint 13.

[0101] ((i) to (iv) organic materials) The following describes exemplary ways of using the organic materials described in (i) to (iv).

[0102] • Examples of organic materials using (i) In this example, the first silicon substrate 10 and the second silicon substrate 20 can be silicon substrates with hydride silane (-Si-H) present on the surfaces of the first bonding portion 13 and the second bonding portion 23 (silicon oxide portions in this embodiment). The first silicon substrate 10 and the second silicon substrate 20 with hydride silane on the surfaces of the first bonding portion 13 and the second bonding portion 23, which are silicon oxide portions, can be obtained, for example, through the surface treatment described above for generating hydride silane.

[0103] As the aforementioned organic material, a substituted or unsubstituted hydrocarbon compound having multiple terminal portions, with an alkenyl group at at least two terminal portions, is used. The alkenyl group is a reactive group to hydride silyl groups. The compound may have an alkenyl group at any two or more terminal portions. For example, it may have an alkenyl group at all terminal portions. The compound may also be fluorinated; in other words, it may be a fluorinated alkyl compound or a fluorinated polyether compound having an alkenyl group at two or more terminal portions.

[0104] As an example, the following describes fluoroalkyl compounds having alkenyl groups at two, three, and four ends. Rf represents fluoroalkyl (as in the following). It should be noted that in the compounds described below, the alkenyl group can be bonded to, for example, different carbon atoms contained in Rf. The number of carbon atoms in the portion other than the terminal reactive group (alkenyl group) is not particularly limited, and can be, for example, 1 to 200, particularly 100 or less. It should be noted that the aforementioned number of carbon atoms can also be, for example, 5 or more. The portion other than the reactive group can be linear, branched, or cyclic. When the portion other than the terminal reactive group is a fluoroalkyl group, the fluorine substitution ratio is not particularly limited, and can be, for example, perfluoroalkyl.

[0105] The fluorinated polyether compounds having alkenyl groups at two or more ends can be, for example, the compound shown in formula (A) (1) or the compound shown in formula (B) (2). (A) Equation (1): [In the formula, R] F2 -Rf 2 p -R F -O q -; Rf 2 C atoms that can be substituted by one or more fluorine atoms1-20 Alkylene; R F Each time it appears, it is independently represented by the group shown in the following formula: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - (where R) Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each an independent integer from 0 to 200, the sum of a, b, c, d, e, and f is greater than 1, and the order of the repeating units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula, where all R Fa If the atoms are hydrogen or chlorine, at least one of a, b, c, e, and f is 1 or more. p is 0 or 1; q is 0 or 1; R D For CH2=CH-; X A Each time it appears, it is independently a single bond or an organic group with a valence of 2 to 10. γ are independent integers from 1 to 9. (B) Equation (2): [In the formula, R] N for or ; R F2 -Rf 2 p -R F -O q -; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1-6 Alkylene; R F Each time it appears, it is independently represented by the group shown in the following formula: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8)c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - (where R) Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f are each an independent integer from 0 to 200, the sum of a, b, c, d, e, and f is greater than 1, and the order of the repeating units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula, where all R Fa If the atoms are hydrogen or chlorine, at least one of a, b, c, e, and f is 1 or more. p is 0 or 1; q is 0 or 1; X a Each time it appears, it is an organic group that is either a single bond or divalent; R A1 Each occurrence is independently assigned to a character containing OR. Ac The radical group; R Ac It is (meth)acryloyl; R B Each occurrence is independently assigned the value R. F1 -X a - or R A1 -X b -, RF 1 -Rf 1 -R F -O q -; Rf 1 C atoms that can be substituted by one or more fluorine atoms 1-16 alkyl, X b It is a divalent organic group.

[0106] It should be noted that in R N In the left-hand formula, as long as any bonding group is with X a Simply bond them together; in the right-hand expression, the left side is connected to X. a Bonding, right side with X b Or R B Bonding. Additionally, in R... F In the example, the sum of a, b, c, d, e, and f can be greater than 5.

[0107] The aforementioned organic material is supplied between the first junction 13 and the second junction 23, causing the alkenyl groups of the organic material to react with the hydrosilylated groups of the first junction 13 and the second junction 23 (hydrosilylation). As a result, the reaction product from the organic material chemically bonds to the Si atoms of the first junction 13 and the second junction 23, thus joining the first junction 13 and the second junction 23 together. Using this reaction, no byproducts are generated, thus fundamentally eliminating the problem of voids formed due to byproducts.

[0108] It should be noted that the reaction can be carried out in one step with the organic material sandwiched between the first joint 13 and the second joint 23, or it can be carried out in two steps by applying the organic material to either the first joint 13 or the second joint 23 and partially reacting, and then placing the other organic material on top of the organic material and allowing the reaction to proceed further.

[0109] As an example, the reaction is shown below in the case of a fluoroalkyl compound having alkenyl groups at both ends. (The same applies to the case of a fluoropolyether compound having alkenyl groups at both ends.) The reaction products derived from the organic material are preferably chemically bonded to both the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23. However, it is not necessary for all the reaction products to be chemically bonded to both the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23. It is also possible for some of the reaction products to be chemically bonded to only one of the Si atoms of the first bonding portion 13 or the Si atoms of the second bonding portion 23, or to two or more Si atoms within the same silicon substrate. To obtain higher bonding strength, it is preferable for more reaction products to be chemically bonded to both the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23. From this viewpoint, the organic material is preferably a linear compound with alkenyl groups at both ends, but is not limited to this.

[0110] • Examples of organic materials using (ii) In this example, the first silicon substrate 10 is a silicon substrate with silanol groups (-Si-OH) on the surface of the first bonding portion 13 (which is a silicon oxide portion in this embodiment). The first silicon substrate 10 with silanol groups on the surface of the first bonding portion 13, which is a silicon oxide portion, does not require special surface treatment, but it can be obtained by the surface treatment described above to generate silanol groups as needed.

[0111] Preferably, the second silicon substrate 20 is a silicon substrate with hydrazine (-Si-H) present on the surface of the second bonding portion 23 (in this embodiment, the silicon oxide portion). The second silicon substrate 20 with hydrazine on the surface of the second bonding portion 23, which is the silicon oxide portion, can be obtained, for example, by the surface treatment described above for generating hydrazine.

[0112] As the aforementioned organic material, a substituted or unsubstituted hydrocarbon compound having multiple terminal groups, having an alkenyl group at at least one terminal end, and having a hydroxyl group at at least one terminal end is used. Specifically, a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one terminal end and a hydroxyl group at another terminal end is used. The alkenyl group is a reactive group to silanyl groups, and the hydroxyl group is a reactive group to silanol groups. The compound may have two or more terminal ends, and may have an alkenyl group at any one or more terminal ends and a hydroxyl group at any one or more terminal ends. The compound may also be fluorinated; in other words, it may be a fluorinated alkyl compound having an alkenyl group at one terminal end and a hydroxyl group at another terminal end, or a compound containing a fluorinated polyether group.

[0113] Furthermore, unless otherwise specified, the foregoing description applies. (The same applies to the fluoroalkyl compounds or fluoropolyether compounds detailed in (i) above, except that they have at least one hydroxyl group at the end.)

[0114] The aforementioned organic material is supplied between the first junction 13 and the second junction 23, causing the hydroxyl groups of the organic material to react with the silanol groups of the first junction 13 (through dehydration etherification), and causing the alkenyl groups of the organic material to react with the hydrogenated silyl groups of the second junction 23 (hydrosilylation). As a result, the reaction product from the organic material chemically bonds to the Si atoms of the first junction 13 and the Si atoms of the second junction 23, thus joining the first junction 13 and the second junction 23 together.

[0115] More specifically, it is preferable to supply an organic material to the first junction 13, causing the hydroxyl groups of the organic material to react with the silanol groups of the first junction 13 (first stage). Then, the first junction 13 and the second junction 23 are positioned opposite each other, causing the alkenyl groups of the organic material to react with the hydride silane groups of the second junction 23 (second stage). Using this operation, although water is generated as a byproduct in the first stage reaction, this byproduct can be removed and will not be trapped between the first junction 13 and the second junction 23. Furthermore, since no byproduct is generated in the second stage, voids due to byproducts can be avoided.

[0116] As an example, the following describes the reaction using a fluoroalkyl compound having an alkenyl group at one end and a hydroxyl group at the other end. (The same applies to the case using a fluoropolyether compound having an alkenyl group at one end and a hydroxyl group at the other end.) To achieve higher bonding strength, the aforementioned organic material is preferably a linear compound having an alkenyl group and a hydroxyl group at each of its two end portions, but is not limited thereto.

[0117] Furthermore, according to this example, as the first silicon substrate 10, a silicon substrate with silanol groups on the surface of the first bonding portion 13 is used, and as the second silicon substrate 20, a silicon substrate with hydrogenated silane groups on the surface of the second bonding portion 23 is used. Therefore, when using an organic material (preferably linear) having alkenyl and hydroxyl groups at both ends, chemical bonding of the reaction products with more than two Si atoms in the same silicon substrate can be avoided, thereby obtaining a higher bonding strength.

[0118] The above describes examples of substituted or unsubstituted hydrocarbon compounds having an alkenyl group at one end and a hydroxyl group at the other end as organic materials. However, substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group, isocyanate group, epoxy group, amino group, or anhydride group instead of a hydroxyl group can also be used, or substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group, isocyanate group, epoxy group, amino group, or anhydride group in addition to a hydroxyl group. The hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, and anhydride groups all function as reactive groups to the silanol group. (It should be noted that when using substituted or unsubstituted hydrocarbon compounds having an alkenyl group at one end and a hydroxyl group at the other end, they can be used in the same way as substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group at both ends, except that they have an alkenyl group at at least one end.)

[0119] • First example of using organic materials of (iii) In this example, the first silicon substrate 10 and the second silicon substrate 20 are silicon substrates with silanol groups (-Si-OH) present 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 silanol groups on the surfaces of the first bonding portion 13 and the second bonding portion 23, which are silicon oxide portions, do not require special surface treatment, but can be obtained as needed through the surface treatment described above to generate silanol groups.

[0120] As the aforementioned organic material, a substituted or unsubstituted hydrocarbon compound having multiple terminal portions, with at least two terminal portions containing hydrolyzable silyl groups, is used. Specifically, a substituted or unsubstituted hydrocarbon compound having two terminal portions containing hydrolyzable silyl groups is used. This compound may have two or more terminal portions, with hydrolyzable silyl groups at any two or more terminal portions. This compound may also be fluorinated; in other words, it may be a fluorinated alkyl compound having two terminal portions, or a fluorinated polyether compound, or a fluorinated silane compound.

[0121] The aforementioned fluorinated silane compounds can be, for example, compounds represented by the following formula (11): [In the formula:] R F2 -Rf 2 p -R F r -O q -; Rf 2 C atoms that can be substituted by one or more fluorine atoms 1-20 Alkylene; R F Each time it appears, it is independently represented by the group shown in the following formula: -(OC6F 12 ) a -(OC5F) 10 ) b -(OC4F8) c -(OC3R) Fa 6) d -(OC2F4) e -(OCF2) f - (where R) Fa Each time it appears, it is independently represented by a hydrogen atom, a fluorine atom, or a chlorine atom. a, b, c, d, e, and f are each an independent integer from 0 to 200, the sum of a, b, c, d, e, and f is greater than 1, and the order of the repeating units marked a, b, c, d, e, or f and enclosed in parentheses is arbitrary in the formula, where all R Fa If the atoms are hydrogen or chlorine, at least one of a, b, c, e, and f is 1 or more. p is 0 or 1; q is 0 or 1; r is 0 or 1; Where either p or r is 1; R SiEach time it appears, it is independently represented by the group shown in formula (S1), (S2), (S3), (S4), or (S5): (In the formula: R 11 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group; R 12 Each time it appears, it is either a hydrogen atom or a monovalent organic group; n1 in each (SiR) 11 n1 R 12 3－n1 Each unit contains an independent integer from 0 to 3; X 11 Each time it appears, it is an organic group that is either a single bond or divalent; R 13 Each time it appears, it is either a hydrogen atom or a monovalent organic group; Each occurrence of t is an integer greater than 2. R 14 Each time it appears, it is independently a hydrogen atom, a halogen atom, or -X. 11 -SiR 11 n1 R 12 3－n1 ; R a1 Each occurrence is independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 ; Z 1 Each time it appears, it is independently an oxygen atom or a divalent organic group; R 21 Each occurrence is independently -Z 1' -SiR 21' p1' R 22' q1' R 23' r1' ; R 22 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group; R 23 Each time it appears, it is either a hydrogen atom or a monovalent organic group; p1 is an integer from 0 to 3 each time it appears; q1 is an integer from 0 to 3 each time it appears; r1 is an integer from 0 to 3 each time it appears; Z 1' Each time it appears, it is independently an oxygen atom or a divalent organic group; R 21' Each occurrence is independently -Z 1'' -SiR 22'' q1'' R 23'' r1'' ; R 22'' Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group; R 23'' Each time it appears, it is either a hydrogen atom or a monovalent organic group; p1' is an integer from 0 to 3 each time it appears; Each occurrence of q1' is an independent integer from 0 to 3; r1' is an integer from 0 to 3 each time it appears; Z 1'' Each time it appears, it is independently an oxygen atom or a divalent organic group; R 22'' Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group; R 23'' Each time it appears, it is either a hydrogen atom or a monovalent organic group; q 1'' Each occurrence is an independent integer from 0 to 3; r 1'' Each occurrence is an independent integer from 0 to 3; R b1 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group; R c1 Each time it appears, it is either a hydrogen atom or a monovalent organic group; k1 is an integer from 1 to 3 each time it appears; l1 is an integer from 0 to 3 each time it appears; m1 is an integer from 0 to 3 each time it appears; R d1 Each occurrence is independently -Z 2 -CR 31 p2 R 32 q2 R 33r2 ; Z 2 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group; R 31 Each occurrence is independently -Z 2' -CR 32' q2' R 33' r2' ; R 32 Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 ; R 33 Each time it appears, it is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 is an integer from 0 to 3 each time it appears; q2 is an integer from 0 to 3 each time it appears; r2 is an integer from 0 to 3 each time it appears; Z 2' Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group; R 32' Each occurrence is independently -Z 3 -SiR 34 n2 R 35 3－n2 ; R 33' Each time it appears, it is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is an integer from 0 to 3 each time it appears; r2' is an integer from 0 to 3 each time it appears; Z 3 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group; R 34 Each time it appears, it is independently either a hydroxyl group or a hydrolyzable group; R 35 Each time it appears, it is either a hydrogen atom or a monovalent organic group; n2 is an integer from 0 to 3 each time it appears; R e1 Each occurrence is independently -Z 3 -SiR 34n2 R 35 3－n2 ; R f1 Each time it appears, it is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 is an integer from 0 to 3 each time it appears; l2 is an integer from 0 to 3 each time it appears; m2 is an integer from 0 to 3 each time it appears; R g1 and R h1 Each occurrence is independently -Z 4 -SiR 11 n1 R 12 3－n1 -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 -Z 4 -CR d1 k2 R e1 l2 R f1 m2 ; Z 4 Each time it appears, it is independently a single bond, an oxygen atom, or a divalent organic group; In formulas (S1), (S2), (S3), (S4), and (S5), at least one Si atom is bonded with a hydroxyl group or a hydrolyzable group. X A Each is an independent single bond or an organic group with a valence of 2 to 10. r are independent integers from 1 to 9.

[0122] Hydrolyzable groups are groups that can undergo hydrolysis reactions, preferably -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j Or halogen. R j For substituted or unsubstituted C 1-4 Alkyl groups, preferably unsubstituted C4 groups 1-4 Alkyl group. The C 1-4 The alkyl group is preferably ethyl or methyl, more preferably methyl.

[0123] The simplest hydrolyzable group can be alkoxysilyl. The number of alkoxy groups in the alkoxysilyl group is 1 or more and 3 or less, for example, 3. The number of carbon atoms in the alkoxy group can be, for example, 1 or more and 4 or less, especially 2 or less, and preferably 1.

[0124] The aforementioned unsubstituted silane compounds can be, for example, R k 3Si-(CH2) n35 -SiR k Compound 3 is shown. R k Each group independently represents a functional group capable of undergoing hydrolysis, preferably -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j Or halogen. R j For substituted or unsubstituted C 1-4 Alkyl groups, preferably unsubstituted C4 groups 1-4 Alkyl group. The C 1-4 The alkyl group is preferably ethyl or methyl, more preferably methyl. n35 is an integer from 1 to 18.

[0125] Unless otherwise specified, the above instructions shall apply.

[0126] The aforementioned organic material is supplied between the first junction 13 and the second junction 23, causing the hydrolyzable silane groups of the organic material to react with the silanol groups of the first junction 13 and the second junction 23 (for example, in the case of an alkoxy group, a siloxane bond is formed by de-alcoholization). As a result, the reaction product from the aforementioned organic material chemically bonds with the Si atoms of the first junction 13 and the Si atoms of the second junction 23, thus joining the first junction 13 and the second junction 23 together. In this reaction, alcohols are generated as byproducts, but since their carbon number is relatively small as described above, they can be effectively removed from the first junction 13 and the second junction 23 through the gaps in the reaction products, thereby reducing voids formed by byproducts.

[0127] Preferably, the aforementioned organic material is applied to either the first joint 13 or the second joint 23, reacting with either the first joint 13 or the second joint 23. Then, the surface of the layer formed by the organic material is cleaned with water or an aqueous organic solvent, and the other material is then deposited on that layer. This allows the hydrolyzable silanes present on the surface to be converted into silanols, thereby further suppressing the formation of voids due to byproducts such as alcohols generated during hydrolysis.

[0128] It should be noted that the reaction can be carried out in one step with the organic material sandwiched between the first joint 13 and the second joint 23, or it can be carried out in two steps by applying the organic material to either the first joint 13 or the second joint 23 and partially reacting, and then placing the other organic material on top of the organic material and allowing the reaction to proceed further.

[0129] As an example, the following describes a reaction using an alkyl compound having a trimethoxysilyl group at both ends. (The following also shows an example of a two-step reaction as described above). To achieve higher bonding strength, the aforementioned organic material is preferably a linear compound having hydrolyzable silanes at both ends, but is not limited thereto.

[0130] • Example 2 using organic materials of (iii) In this example, the description focuses on aspects that differ from the first example of the use of organic materials in (iii) described above, and unless otherwise specified, the same description applies as in the first example described above.

[0131] As the aforementioned organic material, a substituted or unsubstituted hydrocarbon compound having isocyanate groups at both ends is used. The compound may have more than two ends, and any two or more ends may have isocyanate groups.

[0132] The aforementioned organic material is supplied between the first and second joints, causing the isocyanate groups of the organic material to react with the silanol groups of the first and second joints (forming urethane bonds). Consequently, the reaction product from the organic material chemically bonds with the Si atoms of the first and second joints, thus joining the first and second joints together. Using this reaction, no byproducts are generated, thus fundamentally eliminating the problem of voids formed due to byproducts.

[0133] The aforementioned unsubstituted silane compounds can be, for example, OCN-(CH2). n35 - The compound represented by NCO. n35 is an integer from 1 to 18.

[0134] As an example, the following describes the reaction using an alkyl compound having isocyanate groups at both ends. • The third example using organic materials of (iii) In this example, the description focuses on aspects that differ from the first example of the use of organic materials in (iii) described above, and unless otherwise specified, the same description applies as in the first example described above.

[0135] As the aforementioned organic material, a substituted or unsubstituted hydrocarbon compound having a phosphate group is used. This compound may have two or more terminal portions, and any two or more terminal portions may have a phosphate group.

[0136] The following example illustrates the use of CH3PO(OH)2 as a compound containing a phosphate group. However, in this embodiment, any compound containing a phosphate group is acceptable, and other compounds with different structures are also possible. For example, compounds containing two or more phosphate groups, such as 1,6-hexamethylenediamine, can be used. In the case of compounds containing two or more phosphate groups, one phosphate group can react with the first junction 13, while the other phosphate groups react with the second junction 23. • Fourth example using organic materials of (iii) In this example, the description focuses on aspects that differ from the first example of the use of organic materials in (iii) described above, and unless otherwise specified, the same description applies as in the first example described above.

[0137] As the aforementioned organic material, a substituted or unsubstituted hydrocarbon compound having anhydride groups at both ends is used. The compound may have more than two ends, and may have anhydride groups at any two or more ends.

[0138] The aforementioned organic material is supplied between the first junction 13 and the second junction 23, causing the anhydride groups of the organic material to react with the silanol groups of the first junction 13 and the second junction 23. As a result, the reaction product from the organic material chemically bonds to the Si atoms of the first junction 13 and the second junction 23, thus joining the first junction 13 and the second junction 23 together. Using this reaction, no byproducts are generated, thus fundamentally eliminating the problem of voids formed due to byproducts.

[0139] As an example, the following describes a reaction using an alkyl compound having anhydride groups at both ends. R represents an alkyl group, for example, -(CH2). n36 - indicates that n36 is an integer from 1 to 18.

[0140] The above have described examples 1 to 3 of substituted or unsubstituted hydrocarbon compounds having hydrolyzable silyl, isocyanate, or anhydride groups at both ends as the aforementioned organic materials. However, substituted or unsubstituted hydrocarbon compounds having hydroxyl, epoxy, and / or amino groups instead of hydrolyzable silyl, isocyanate, or anhydride groups, or substituted or unsubstituted hydrocarbon compounds having hydroxyl, epoxy, and / or amino groups in addition to hydrolyzable silyl, isocyanate, or anhydride groups, may also be used. The hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, and anhydride groups all function as reactive groups to the silanol group. These reactive groups at at least the two ends may be the same or different.

[0141] • Examples of organic materials using (iv) In this example, the description focuses on aspects that differ from the first example of the use of organic materials in (iii) described above, and unless otherwise specified, the same description applies as in the first example described above.

[0142] Silsesquioxanes are used as organic materials. Silsesquioxanes refer to substances in silicon-containing polymers (polysiloxanes) whose basic structural unit is the T unit, where the main chain is composed of siloxane bonds. Silsesquioxanes can be represented by the structural formula (R'SiO). 1.5 ) n (R' can be any organic group, n is 6 or more) This indicates that it can have random, ladder, or cage-like structures (complete or incomplete cage structures). Examples of R' being a hydrocarbon group include: methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, tert-butyl, sec-butyl), pentyl (n-pentyl, isopentyl, neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, isohexyl, cyclohexyl, etc.), heptyl (n-heptyl, isoheptyl, etc.), octyl (n-octyl, isooctyl, tert-octyl, etc.), nonyl (n-nonyl, isononyl, etc.), decyl (n-decyl, isodecyl, etc.), and undecylalkyl (n-undecyl...). Acyclic or cyclic aliphatic hydrocarbon groups such as alkyl, isoundecyl, etc., and dodecyl (n-dodecyl, isododecyl, etc.); acyclic or cyclic alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norbornenyl ethyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and styryl; aralkyl groups such as phenyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl; aryl groups such as arylyl (e.g., PhCH=CH-), phenyl, tolyl or xylyl, substituted aryl groups such as 4-aminophenyl, 4-hydroxyphenyl, 4-methoxyphenyl, and 4-vinylphenyl.

[0143] The aforementioned organic material is supplied to the first bonding portion 13, causing the siloxane bonding sites of the organic material to react with the silanol groups of the first bonding portion 13 (siloxane bond breaking and addition). Then, a second bonding portion 23 is provided on the side of the organic material opposite to the first bonding portion 13, causing the siloxane bonding sites of the organic material to react with the silanol groups of the second bonding portion 23 (siloxane bond breaking and addition). Thus, the reaction product from the aforementioned organic material chemically bonds with the Si atoms of the first bonding portion 13 and the Si atoms of the second bonding portion 23, thereby bonding the first bonding portion 13 and the second bonding portion 23 together. Using this reaction, no byproducts are generated, thus fundamentally eliminating the problem of voids formed due to byproducts. It should be noted that the aforementioned organic material can also be supplied between the first bonding portion 13 and the second bonding portion 23, causing the siloxane bonding sites of the organic material to react with the silanol groups of the first bonding portion 13 and the second bonding portion 23 (siloxane bond breaking and addition).

[0144] As an example, the following indicates the use of T8 silsesquioxane ((R'SiO) with a fully cage-like structure. 1.5 The reaction at )8). To achieve higher bonding strength, the aforementioned organic materials are preferably cage-like silsesquioxanes with well-defined molecular structures, but are not limited to this.

[0145] The above examples illustrate the use of silsesquioxanes as organic materials, but derivatives of silsesquioxanes can also be used. Derivatives of silsesquioxanes are any compounds derived from silsesquioxanes and can have any substituents, modifiers, functional groups, etc.

[0146] (Reaction conditions) Organic materials The reaction conditions vary depending on the organic material used. The reaction temperature is, for example, below 200°C, preferably below 120°C, particularly preferably below 80°C, and simply, room temperature (typically, above 10°C and below 40°C). Using this embodiment, bonding can be performed at a lower temperature as described above, thus reducing bonding misalignment caused by thermal expansion of the silicon substrate, and enabling high-precision bonding of the first bonding portion 13 and the second bonding portion 23. The pressure (absolute pressure, and other pressure values ​​in this specification) is, for example, 10... ﹣8 Pa and above, especially 10 Pa ﹣5 Pa or above, especially 10 ﹣1 Pa or higher, preferably 10 Pa 2Above Pa, or simply put, atmospheric pressure (typically, about 1.01 × 10⁻⁶ Pa). 5 When using reduced pressure, for example, it can be 10 Pa. 5 Below Pa, especially 10 4 Below Pa, especially 10 3 Below Pa.

[0147] Inorganic materials The specific method of supplying and bonding the inorganic material (or a composition containing an inorganic material) can be appropriately selected based on the inorganic material used. Generally speaking, after supplying the inorganic material to the first bonding portion 13, with the inorganic material sandwiched between the first bonding portion 13 and the second bonding portion 23, the first silicon substrate 10 and the second silicon substrate 20 can be held under predetermined reaction conditions (particularly a predetermined temperature), thereby bonding the first bonding portion 13 and the second bonding portion 23 by the reaction products. It should be noted that the inorganic material can also be supplied to the second bonding portion 23 instead of the first bonding portion.

[0148] For example, an inorganic material (or a composition containing an inorganic material) can be applied to the surface of the first bonding portion 13 side of the first silicon substrate 10 by spin coating, vapor deposition, or the like. The inorganic material can be applied in its own form or in the form of a composition mixed with any suitable component (e.g., a solvent). Afterward, cleaning and / or drying can be performed as needed. Pre-cleaning can also be performed as needed.

[0149] Then, the first silicon substrate 10 and the second silicon substrate 20 are aligned with the first bonding portion 13 and the second bonding portion 23 facing each other, and the first silicon substrate 10 and the second silicon substrate 20 are sealed together with an inorganic material sandwiched between the first bonding portion 13 and the second bonding portion 23. The first silicon substrate 10 and the second silicon substrate 20 are then bonded together under specified reaction conditions (especially specified temperature) as needed. It should be noted that the inorganic material can be bonded to the first silicon substrate 10 and the second silicon substrate 20 without reaction, or at least partially reacted.

[0150] Through the above manufacturing method, a stacked body 40 is formed having a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30 located between the first silicon substrate 10 and the second silicon substrate 20. In other words, the stacked body 40 has: A first silicon substrate 10 having a first bonding portion 13; The second silicon substrate 20, located on the side of the first bonding portion 13 and having the second bonding portion 23; and An adhesive layer 30 located between the first joint 13 and the second joint 23, which bonds the first joint 13 and the second joint 23 together. The first joint 13 and the second joint 23 described above have regions of hydride silyl and / or silanol groups derived from silicon oxide, or regions that are bonded to inorganic materials. The adhesive layer 30 includes reaction products that react with the aforementioned hydrogenated silyl group and / or the aforementioned silanol group, or regions that are bonded to the aforementioned inorganic material. The number of particle clusters on the surface of the adhesive layer 30 is 5 per cm. 2 the following, The bonding strength between the first silicon substrate 10 and the second silicon substrate 20 is 1.00 J / m. 2 above.

[0151] It should be noted that, in this embodiment, the surface of the adhesive layer 30 refers to the cured material on the surface when the adhesive layer 30 is provided on the first silicon substrate 10.

[0152] It should be noted that in the laminate 40, the adhesive layer 30 may contain organic substances generated during the formation of the adhesive layer 30. These organic substances can be understood as residues of organic materials capable of reacting with silyl groups and / or silanol groups.

[0153] The organic material can be a material that has chemically bonded to the Si atoms of the first junction 13 and the Si atoms of the second junction 23.

[0154] The inorganic material can be the material bonded to the first bonding portion 13 and the second bonding portion 23. In this case, the inorganic material can be bonded to the first bonding portion 13 and the second bonding portion 23 without reaction, or at least partially reacted. In this case, the adhesive layer 30 in the laminate 40 can contain the inorganic material generated during the formation of the adhesive layer 30. This inorganic material can be understood as the residue of the inorganic material after reacting with the first silicon substrate and the second silicon substrate.

[0155] There is no specific upper limit to the bonding strength; for example, it can be 2.5 J / m. 2 the following.

[0156] <Second Implementation> Figure 2This is a schematic cross-sectional view showing a portion of the laminate 40A according to the second embodiment. In the first embodiment, an adhesive layer 30 is provided between the first joint 13 and the second joint 23. In the second embodiment, the difference is that a first adhesive portion 31A is provided on the first joint 13, and a second adhesive portion 32A is provided on the second joint 23, including both the first adhesive portion 31A and the second adhesive portion 32A. The description will focus on this difference; unless otherwise specified, the configuration is the same as that of the first embodiment.

[0157] (Adhesive layer 30A) like Figure 2 As shown, adhesive layer 30A has a first adhesive portion 31A and a second adhesive portion 32A disposed 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 reaction. In the chemical bonding reaction, heating and / or pressurization or depressurization are performed as needed. The conditions for heating, pressurization, and depressurization are the same as in the first embodiment. The physical properties and constituent materials of adhesive layer 30A are the same as those of adhesive layer 30 in the first embodiment.

[0158] In one embodiment, the first adhesive portion 31A can be obtained by coating the first bonding portion 13 with a first organic material that can react with the first bonding portion 13, and then drying it. The second adhesive portion 32A can be obtained by coating the second bonding portion 23 with a second organic material that can react with the second bonding portion 23, and then drying it. The drying can be performed in the same manner as in the first embodiment.

[0159] In another embodiment, the first adhesive portion 31A can be obtained by supplying a first inorganic material to the first joint portion 13 and then drying it as needed. The second adhesive portion 32A can be obtained by supplying a second inorganic material to the second joint portion 23 and then drying it. The drying can be performed in the same manner as in the first embodiment.

[0160] It should be noted that, for convenience, they are referred to as the first adhesive portion 31A and the second adhesive portion 32A, but they may not form an interface and may be mixed together. Even when an interface is formed, the interface may not be uniform and may have unevenness.

[0161] The number of particle clusters in the surface of the first adhesive portion 31A opposite to the first joint portion 13 is 5 per cm. 2 The following is an explanation of the meaning of particle and cluster number in this embodiment, which is the same as that in the first embodiment.

[0162] Preferably, the number of particle clusters in the surface of the second adhesive portion 32A opposite to the second joint portion 23 is 5 per cm. 2The following is a lower limit for the number of clusters. There is no specific limitation on this lower limit, for example, 1 cluster / cm. 2 The above is specifically 0 per cm. 2 above.

[0163] The second adhesive portion 32A can also be formed of two or more layers. That is, a first layer of the second adhesive portion 32A can be provided on the second joint portion 23, and then dried and / or heated as needed, and then a second layer of the second adhesive portion 32A can be provided. The number of layers of the second adhesive portion 32A is not particularly limited, for example, it can be three layers or less.

[0164] (First organic material and second organic material) The first organic material has a functional group at one end that reacts with the first bonding portion 13, and at the other end that has a functional group 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 at the other end that has a functional group that reacts with the first organic material. Thus, the first silicon substrate 10 and the second silicon substrate 20 are bonded together. It should be noted that only a portion of these functional groups may react. It should also be noted that while the above description illustrates an organic material having two functional groups, an organic material may also have three or more functional groups.

[0165] The first organic material and the second organic material may be included in the composition for use. The composition has the same structure as in the first embodiment.

[0166] The specific manner of supplying and bonding the first organic material and the second organic material (or a composition comprising the first organic material and the second organic material) can be appropriately selected according to the organic material used. Generally speaking, after supplying the first organic material and the second organic material, with the first organic material and the second organic material sandwiched between the first silicon substrate 10 and the second silicon substrate 20, the first silicon substrate 10 and the second silicon substrate 20 can be held under specified reaction conditions (especially a specified temperature) to carry out the reaction.

[0167] More specifically, for example, a first organic material (or a composition) can be applied to the first bonding portion 13 side of the first silicon substrate 10 by coating, spraying, printing, etc. Similarly, a second organic material (or a composition) can be applied to the second bonding portion 23 of the second silicon substrate 20. Afterwards, cleaning and / or drying can be performed as needed. Cleaning and drying can be performed using the same methods as described above; in the case of using a fluorinated organic material, pre-cleaning with a fluorinated solvent can be performed.

[0168] Then, the first silicon substrate 10 and the second silicon substrate 20 are aligned with the first bonding portion 13 and the second bonding portion 23 facing each other, and the first organic material and the second organic material are sandwiched between the first bonding portion 13 and the second bonding portion 23, and then the first silicon substrate 10 and the second silicon substrate 20 are sealed together. The sealed first silicon substrate 10 and the second silicon substrate 20 are kept sealed under specified reaction conditions (especially specified temperature) and a reaction is carried out during this period. Then, annealing treatment can be performed as needed.

[0169] The physical properties of the first organic material and the second organic material are applicable to the organic material of the first embodiment.

[0170] The first organic material and the second organic material may contain at least one selected from (v) to (vi) below. It should be noted that the organic material may use one compound or a combination of two or more compounds.

[0171] (v) A combination of a hydrolyzable hydrogen silane or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrogen silyl 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.

[0172] (vi) A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end.

[0173] The following is a detailed explanation.

[0174] • Examples of organic materials using (v) In this example, the description focuses on aspects that differ from the first example of the use of organic materials in (iii) described above, and unless otherwise specified, the same description applies as in the first example described above.

[0175] As the aforementioned organic material, a first organic material and a second organic material are used in combination.

[0176] The first organic material can 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, depending on the circumstances, a mixture thereof. A hydrolyzable hydrosilane is simply a compound having one or more hydrolyzable groups on one Si atom. A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end can have two or more ends, and can have a hydrolyzable silyl group at any one or more ends and a hydrosilyl group at any one or more ends. A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a hydrosilyl group at the other end is the same as the substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at both ends as detailed in (iii) above.

[0177] 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. This 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. A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkenyl group at the other end is the same as the substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at both end portions as detailed in (iii) above.

[0178] First, a first organic material is supplied to the first junction 13, and the hydrolyzable silane group of the first organic material reacts with the silanol group of the first junction 13 (for example, when the hydrolyzable group is alkoxy, a siloxane bond is formed by de-alcoholization).

[0179] Furthermore, a second organic material is supplied to the second junction 23, causing the hydrolyzable silanyl group of the second organic material to react with the silanol group of the second junction 23 (for example, when the hydrolyzable group is alkoxy, a siloxane bond is formed by de-alcoholization).

[0180] Then, the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, with intermediates from the first organic material and intermediates from the second organic material located between them, and these intermediates are reacted (hydrogenated silylation). As a result, the reaction products 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, thus bonding the first bonding portion 13 and the second bonding portion 23 together. In this reaction, an alcohol is generated as a byproduct, but since its carbon number is small as described above, it can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, thus reducing the formation of voids due to byproducts.

[0181] For example, you can use R k 3Si-(CH2) n37 -CH=CH2 was used as the first organic material, employing SiHR k 3 is used as a second organic material. R k "Separate and independent" refers to groups capable of undergoing hydrolysis, specifically the same meaning as described above. n37 is an integer from 0 to 18, for example, it can be 0.

[0182] Specifically, the following describes the reaction when vinyltrimethoxysilane is used as the first organic material and trimethoxyhydrosilane is used as the second organic material. • Examples of organic materials using (vi) In this example, the description focuses on aspects that differ from the first example of the use of organic materials in (iii) described above, and unless otherwise specified, the same description applies as in the first example described above.

[0183] As the first and second organic materials described above, substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group at one end and an alkyl group at the other end are used. The compound may have two or more end portions, and may have a hydrolyzable silyl group at any one or more end portions and an alkyl group at any one or more end portions. The substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end may be the same as the substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at both end portions as detailed in (iii) above. The second organic material may have the same structure as the first organic material or a different structure.

[0184] The first organic material is supplied to the first junction 13, causing the hydrolyzable silanyl group of the first organic material to react with the silanol group of the first junction 13 (for example, when the hydrolyzable group is alkoxy, a siloxane bond is formed by de-alcoholization). Then, the second organic material is supplied to the second junction 23, causing the hydrolyzable silanyl group of the second organic material to react with the silanol group of the second junction 23 (for example, when the hydrolyzable group is alkoxy, a siloxane bond is formed by de-alcoholization). The first junction 13 and the second junction 23 are then arranged opposite each other with an intermediate from the organic material between them, causing a reaction (free radical reaction) to occur between the intermediates. This reaction (free radical reaction) between the intermediates can be carried out, for example, by ultraviolet irradiation, an ion beam, or a weak plasma. Thus, the reaction products from the first and second organic materials chemically bond with the Si atoms of the first bonding portion 13 and the second bonding portion 23, thereby bonding the first bonding portion 13 and the second bonding portion 23 together. In this reaction, an alcohol is generated as a byproduct, but since its carbon number is relatively small as described above, it can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, thus reducing the formation of voids due to byproducts.

[0185] For example, R can be used as both a first organic material and a second organic material. k 3Si(CH2) n38 H. R k Each group is independent and represents a functional group capable of undergoing hydrolysis, with the same meaning as described above. n38 is an integer from 2 to 18, for example, 0.

[0186] Specifically, the following describes the reaction when ethyltrimethoxysilane is used as the first organic material and the second organic material. Through the above manufacturing method, a stacked body 40A is formed having a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30A located between the first silicon substrate 10 and the second silicon substrate 20. The adhesive layer 30A has a first adhesive portion 31A and a second adhesive portion 32A.

[0187] The first organic material and the second organic material can be obtained by filtration. The particle size of the first organic material and the second organic material before filtration, as well as the particle size of the first organic material and the second organic material after filtration, have the same meaning as the particle size of the organic material in the first embodiment.

[0188] (First inorganic materials and second inorganic materials) The inorganic material in the first embodiment can be used as both the first and second inorganic material.

[0189] The first inorganic material and the second inorganic material can be obtained by filtration. The first inorganic material and the second inorganic material before filtration, as well as the first inorganic material and the second inorganic material after filtration, each have the same particle size as the inorganic material of the first embodiment.

[0190] By means of the above-described manufacturing method, a stacked body 40 is formed having a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30A located between the first silicon substrate 10 and the second silicon substrate 20. That is, the manufacturing method of the stacked body 40A in the second embodiment includes: (a) The step of preparing a first silicon substrate 10 having a first bonding portion 13 and a second silicon substrate 20 having a second bonding portion 23, wherein the first bonding portion 13 and the second bonding portion 23 are portions comprising silicon oxide. (b) A step of providing an adhesive layer 30A using a first organic material and a second organic material capable of reacting with hydrogenated silyl groups and / or silanol groups, wherein the adhesive layer 30A bonds the first joint 13 to the second joint 23 using the first organic material, the second organic material, and / or reaction products derived from the first organic material and the second organic material; or, a step of providing an adhesive layer 30A using a first inorganic material and a second inorganic material capable of bonding with silicon oxides, wherein the adhesive layer 30A bonds the first joint 13 to the second joint 23 using the first inorganic material, the second inorganic material, and / or the first organic material and the second organic material. The adhesive layer 30A includes a first adhesive portion 31A disposed on the first joint portion 13 and a second adhesive portion 32A disposed on the second joint portion 23. The number of particle clusters in the surface of the first adhesive portion 31A opposite to the first joint portion 13 is 5 per cm. 2 The following uses the same meanings for particle and cluster number as in the first embodiment. It should be noted that in this specification, "first organic material, second organic material and / or reaction products from the first organic material and second organic material" are sometimes also written as "reaction products from the first organic material and second organic material".

[0191] Furthermore, the laminate 40A has: A first silicon substrate 10 having at least a first bonding portion 13 on its surface; The second silicon substrate 20, having at least a second bonding portion 23 on at least a portion of its surface on the side of the aforementioned bonding portion 13; and An adhesive layer 30A is located between the first bonding portion 13 and the second bonding portion 23, which bonds the first bonding portion 13 and the second bonding portion 23 of the first silicon substrate 10. The adhesive layer 30A has a reaction product of a first adhesive portion 31A located on the first joint portion 13 and a second adhesive portion 32A located on the second joint portion 23, or a joint of a first adhesive portion 31A located on the first joint portion 13 and a second adhesive portion 32A located on the second joint portion 23. The first silicon substrate 10 and the second silicon substrate 20 are electrically conductive.

[0192] (Modified example) Figure 3 This is a cross-sectional view schematically showing a portion of the cross-section of the laminate 40B in a modified example. Unlike the second embodiment, this modified example has a first adhesive portion 31B on the first joint 13, a second adhesive portion 32B on the second joint 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, as well as the second adhesive portion 32B and the third adhesive portion 33B, are joined together. That is, the adhesive layer 30B comprises three layers: the first adhesive portion 31B, the third adhesive portion 33B, and the second adhesive portion 32B. This different configuration will be described below. Other configurations are the same as in the first embodiment and their descriptions are omitted. It should be noted that in this embodiment, the "first adhesive portion" mentioned 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.

[0193] (Adhesive layer 30B) The adhesive layer 30B sequentially comprises a first adhesive portion 31B, a third adhesive portion 33B, and a second adhesive portion 32B. The first adhesive portion 31B is disposed on the first silicon substrate 10, and the second adhesive portion 32B is disposed on the second silicon substrate 20. The third adhesive portion 33B 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 33B can react as a connecting portion connecting the first adhesive portion 31B and the second adhesive portion 32B. The above reaction can be carried out under heating and / or pressure or decompression as needed. The conditions for heating, pressure, and decompression are the same as in the first embodiment.

[0194] The thickness of adhesive layer 30B can be extremely thin. For example, the thickness of adhesive layer 30B can be less than 10 nm, especially less than 8 nm, and there is no particular limit to the lower limit; for example, it can be greater than 1 nm.

[0195] The first adhesive portion 31B can be obtained by coating the first bonding portion 13 with a first organic material that can react with the first bonding portion 13, and then drying it. The drying process described above can be performed in the same manner as in the first embodiment.

[0196] The second adhesive portion 32B can be obtained by coating the second bonding portion 23 with a second organic material that can react with the second bonding portion 23, and then drying it. The drying process described above can be performed in the same manner as in the first embodiment.

[0197] The third adhesive portion 33B can be formed by coating a third organic material that can react with the first and second organic materials, and then drying it as needed, thereby forming the third organic material and / or reaction products derived from the third organic material. The drying process described above can be performed in the same manner as in the first embodiment. It should be noted that sometimes "the third organic material and / or reaction products derived from the third organic material" is also referred to as "reaction products derived from the third organic material".

[0198] In another embodiment, the first adhesive portion 31B can be obtained by supplying a first inorganic material capable of bonding with the first joint portion 13 onto the first joint portion 13, and then drying it as needed. The drying process described above can be performed in the same manner as in the first embodiment.

[0199] The second adhesive portion 32B can be obtained by supplying a second inorganic material capable of bonding with the second joint portion 23 onto the second joint portion 23, and then drying it as needed. The drying process described above can be performed in the same manner as in the first embodiment.

[0200] The third adhesive portion 33B can be formed by coating a third inorganic material that can bond with the first organic material and the second organic material, and then drying it as needed. The drying process described above can be performed in the same manner as in the first embodiment.

[0201] It should be noted that, for convenience, these are referred to as the first adhesive portion 31B, the second adhesive portion 32B, and the third adhesive portion 33B, but they may not form an interface. Even when an interface is formed, the interface may not be uniform and may have unevenness. Furthermore, organic and inorganic materials can be used in appropriate combinations.

[0202] The number of particle clusters in the surface of the first adhesive portion 31B on the side opposite to the first joint portion 13 is 5 per cm. 2 The following is an explanation of the meaning of particle and cluster number in this embodiment, which is the same as that in the first embodiment.

[0203] Preferably, the number of particle clusters in the surface of the second adhesive portion 32B opposite to the second joint portion 23 is 5 per cm.2 The following is a lower limit for the number of clusters. There is no specific limitation on this lower limit; for example, it could be 0 clusters / cm. 2 above.

[0204] Preferably, the number of particle clusters in the surface of the third adhesive portion 33B on the side opposite to the first adhesive portion 31B is 5 per cm. 2 The following is a lower limit for the number of clusters. There is no specific limitation on this lower limit; for example, it could be 0 clusters / cm. 2 above.

[0205] (First to third organic materials) The first organic material has a functional group at one end that reacts with the first bonding portion 13, and 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 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 at the other end that can react with the second organic material. Thus, the first silicon substrate 10 and the second silicon substrate 20 are bonded. It should be noted that only a portion of these functional groups may react. It should also be noted that while the above description illustrates an organic material having two functional groups, an organic material may also have three or more functional groups.

[0206] The first to third organic materials can be used in the form of a composition. The composition has the same structure as in the first embodiment.

[0207] The specific manner of supplying and bonding the first to third organic materials (or compositions containing the first to third organic materials) can be appropriately selected according to the organic materials used. Generally speaking, after supplying the first to third organic materials, with the organic materials sandwiched between the first silicon substrate 10 and the second silicon substrate 20, the first silicon substrate 10 and the second silicon substrate 20 can be held under specified reaction conditions (especially specified temperature) to carry out the reaction.

[0208] More specifically, for example, a first organic material (or a composition) can be applied to the surface of the first silicon substrate 10 having the first bonding portion 13 by coating, spraying, printing, etc. Similarly, a second organic material (or a composition) can be applied to the second bonding portion 23 of the second silicon substrate 20. Afterwards, cleaning and / or drying can be performed as needed. Cleaning and drying can be performed using the same methods as described above; in the case of using a fluorinated organic material, pre-cleaning with a fluorinated solvent can be performed.

[0209] Then, a third organic material (or a combination thereof) is applied (e.g., by coating, spraying, printing, etc.) to the area from the first organic material. Afterward, cleaning and / or drying may be performed as needed. Cleaning and drying can be performed using the same methods as described above; in the case of using fluorinated organic materials, pre-cleaning with fluorinated solvents may be performed.

[0210] Furthermore, a region from the second organic material is then formed on the region from the third organic material. Specifically, the first silicon substrate 10 and the second silicon substrate 20 are aligned with the first bonding portion 13 and the second bonding portion 23 facing each other, and the first organic material to the third organic material are sandwiched between the first bonding portion 13 and the second bonding portion 23, and then the first silicon substrate 10 and the second silicon substrate 20 are sealed together. The sealed first silicon substrate 10 and the second silicon substrate 20 are kept sealed under specified reaction conditions (especially specified temperature), and a reaction is carried out during this period. Then, annealing treatment can be performed as needed.

[0211] The material properties and composition of the first to third organic materials are applicable to the content of the first organic material in the first embodiment.

[0212] The organic materials are shown below. It should be noted that the description here focuses on aspects that differ from the first example of the use of organic materials (iii) described above, and unless otherwise specified, the same description as the first example above applies.

[0213] The following materials can be used as organic materials.

[0214] (vii) A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one end and a reactive functional group at the other end.

[0215] The following details the exemplification method.

[0216] • Examples of organic materials using (vii) In this example, the description focuses on aspects that differ from the first example of the use of organic materials in (iii) described above, and unless otherwise specified, the same description applies as in the first example described above.

[0217] As the first and second organic materials, substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group at one end and a reactive functional group at the other end are used. The compound may have two or more end portions, and may have a hydrolyzable silyl group at any one or more end portions and a reactive functional group at any one or more end portions. The first and second organic materials, except for having a reactive functional group at the other end portion, may be the same as the substituted or unsubstituted hydrocarbon compounds with hydrolyzable silyl groups at both end portions as detailed in (iii) above. It should be noted that the first and second organic materials may have the same or different structures except for the aforementioned end portions.

[0218] Typically, the aforementioned reactive functional group can be at least one selected from isocyanate group, amino group, hydroxyl group and thiol group (also known as mercapto group), but is not limited thereto.

[0219] In this embodiment, a third organic material is also used. The third organic material has two groups capable of bonding with the reactive functional groups of the first and second organic materials. The third organic material may have two (or more) of the aforementioned bondable groups; more specifically, it may have the aforementioned bondable groups at any two (or more) ends. The number of carbon atoms in the portion of the third organic material other than the aforementioned bondable groups is not particularly limited, for example, it may be 1 to 20, particularly 5 or less. The portion other than the aforementioned bondable groups may be linear, branched, or cyclic. Representatively, the third organic material may be a linear organic compound having the aforementioned bondable groups at both ends, but it is not limited to this.

[0220] The bondable groups mentioned above are selected based on the reactive functional groups. Examples of combinations of reactive functional groups and bondable groups are given below, but are not limited to these. There can be one or more reactive functional groups, and the bondable groups only need to be able to bond with the reactive functional groups; there can be one or more such groups.

[0221] [Table 1] The aforementioned reactive functional groups and bondable groups can be groups capable of reacting with hydrazyl and / or silanol groups, or they can be substantially non-reactive groups. When both the aforementioned reactive functional groups and bondable groups are groups capable of reacting with hydrazyl and / or silanol groups, it can be understood that two types of organic materials described in (iii) have been used; however, this need not be considered when using organic materials described in (vii).

[0222] For example, when R is used as a first organic material and a second organic material k 3Si-(CH2) n31 In the case of -NCO, the third organic material can be, for example, H2N-(CH2). n32 -NH2, HS-(CH2) n32 -SH and HO-(CH2) n32 At least one of -OH groups. R is used as both a first and second organic material. k 3Si-(CH2) n33 When -NH2 is present, the third organic material can use OCN-(CH2). n34 -NCO. n31 is an integer from 1 to 18, for example, 1. n32 is an integer from 1 to 18, for example, 2. n33 is an integer from 1 to 18, for example, 1. n34 is an integer from 1 to 18, for example, 2.

[0223] R k This refers to groups that can undergo hydrolysis, preferably each being independently -OR. j -OCOR j -O-N=CR j 2. -NR j 2. -NHR j Or halogen. R j For substituted or unsubstituted C 1-4 Alkyl groups, preferably unsubstituted C4 groups 1-4 Alkyl group. The C 1-4 The alkyl group is preferably ethyl or methyl, more preferably methyl.

[0224] Specifically, the following describes the reaction when methyl isocyanate-based trimethoxysilane is used as the first and second organic materials, and ethylenediamine (1,2-diaminoethane) is used as the third organic material. It should be noted that, for convenience, the upper section of the following diagram only shows the junction of a silicon substrate. The first method described above corresponds to the flow indicated by the arrow from the left side of the upper section to the lower section; the second method described above corresponds to the flow indicated by the arrows from the left side of the upper section to the center of the upper section and from the center of the upper section to the lower section; and the third method described above corresponds to the flow indicated by the arrows from the left side of the upper section to the center of the upper section, from the center of the upper section to the right side of the upper section, and from the right side of the upper section to the lower section (the same applies below). Specifically, the reactions are shown below when methyl isocyanate-based trimethoxysilane is used as the first organic material, methyl isocyanate-based trimethoxysilane is used as the second organic material, and 1,2-ethylenedithiol is used as the third organic material. Specifically, the reactions are shown below when methyl isocyanate-based trimethoxysilane is used as the first organic material, methyl isocyanate-based trimethoxysilane is used as the second organic material, and ethylene glycol (1,2-ethylene glycol) is used as the third organic material. Specifically, the reaction is described below when aminomethyltrimethoxysilane is used as the first organic material, aminomethyltrimethoxysilane as the second organic material, and ethylene diisocyanate (1,2-ethane diisocyanate) as the third organic material. The method of joining the first joint 13 and the second joint 23 using the first organic material to the third organic material B can employ any suitable method (process). Three methods are given below, but are not limited to these.

[0225] (Method 1) In the first method, a first organic material, a second organic material, and a third organic material (e.g., just before use) are mixed, and the resulting mixture is supplied between the first junction 13 and the second junction 23. This causes the hydrolyzable silanyl groups of the first and second organic materials to react with the silanol groups of the first and second junctions 13 and 23 (e.g., forming siloxane bonds through de-alcoholization when the hydrolyzable group is an alkoxy group). As a result, the first organic material chemically bonds to the Si atoms of the first junction 13, and the second organic material chemically bonds to the Si atoms of the second junction 23.

[0226] Furthermore, the reactive functional groups of the first organic material and the second organic material are reacted and bonded to the bondable groups of the third organic material. Thus, the first organic material chemically bonded to the Si atoms of the first junction 13 and the second organic material chemically bonded to the Si atoms of the second junction 23 are combined via the third organic material.

[0227] The reactions between the hydrolyzable silyl group of the first organic material and the silanol group of the first bonding portion 13, and between the hydrolyzable silyl group of the first organic material and the silanol group of the second bonding portion 23, as well as 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, any one reaction can proceed first, or they can proceed simultaneously. As a result, the first bonding portion 13 and the second bonding portion 23 are bonded by the reaction products from the first to the third organic materials. Alcohols may be generated as byproducts, but since their carbon number is small as described above, they can be effectively removed from the first bonding portion 13 and the second bonding portion 23 through the gaps in the reaction products, thus reducing the formation of voids due to byproducts.

[0228] (Method 2) In the second method, a first organic material is supplied to the first bonding portion 13, causing the hydrolyzable silane group of the first organic material 5 to react with the silanol group of the first bonding portion 13 (for example, forming a siloxane bond through de-alcoholization when the hydrolyzable group is alkoxy). A second organic material is supplied to the second bonding portion 23, causing the hydrolyzable silane group of the second organic material to react with the silanol group of the second bonding portion 23 (for example, forming a siloxane bond through de-alcoholization when the hydrolyzable group is alkoxy). (The first organic material supplied to the first bonding portion 13 and the second organic material supplied to the second bonding portion 23 can be the same or different). This results in the first organic material chemically bonding to the Si atoms of the first bonding portion 13, and the second organic material chemically bonding to the Si atoms of the second bonding portion 23.

[0229] Then, the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, with the intermediate from the first organic material, the second organic material, and the third organic material located between them, so that the reactive functional groups of the first organic material and the second organic material react and bond with the bondable groups of the third organic material. Thus, 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 combined via the third organic material.

[0230] As a result, the first joint 13 and the second joint 23 are joined by reaction products from the first to third organic materials. An alcohol is generated as a byproduct, but since its carbon number is small as described above, it can be effectively removed before the first joint 13 and the second joint 23 are arranged opposite each other, thus reducing the formation of voids due to byproducts.

[0231] (The third method) In the third method, a first organic material is supplied to the first junction 13, causing the hydrolyzable silane group of the first organic material to react with the silanol group of the first junction 13 (e.g., forming a siloxane bond through de-alcoholization when the hydrolyzable group is alkoxy). A second organic material is supplied to the second junction 23, causing the hydrolyzable silane group of the second organic material to react with the silanol group of the second junction 23 (e.g., forming a siloxane bond through de-alcoholization when the hydrolyzable group is alkoxy). (The first organic material supplied to the first junction 13 and the second organic material supplied to the second junction 23 can be the same or different). This results in the first organic material chemically bonding to the Si atoms of the first junction 13 (intermediate X1), and the second organic material chemically bonding to the Si atoms of the second junction 23 (intermediate X2). Then, for convenience, intermediate X1 is selected as one of intermediates X1 and X2, and a third organic material is supplied to the first junction 13, so that the reactive functional groups of the first organic material react and bond with the bondable groups of the third organic material (intermediate Y).

[0232] Then, the intermediate Y obtained therefrom is arranged opposite to the intermediate X2 obtained as described above, with the intermediate Y from the third organic material located on the first junction 13 side and the intermediate X2 from the second organic material located on the second junction 23 side, so that the reactive functional groups of the intermediate X2 (second organic material) react and bond with the bondable groups of the intermediate Y (first organic material + third organic material). Thus, the first organic material chemically bonded to the Si atoms of the first junction 13 and the second organic material chemically bonded to the Si atoms of the second junction 23 are combined via the third organic material.

[0233] As a result, the first bonding portion 13 and the second bonding portion 23 are bonded by reaction products from the first to third organic materials. An alcohol is generated as a byproduct, but since its carbon number is small as described above, it can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, thus reducing voids formed by the byproduct. Furthermore, in this method, unreacted organic binders that may remain on the second bonding portion can be effectively removed before the first bonding portion 13 and the second bonding portion 23 are arranged opposite each other, thus reducing the residue of unnecessary (non-bonding) substances between the first bonding portion 13 and the second bonding portion 23 in the final laminate.

[0234] The embodiments of the present invention have been described above, but the present invention is not limited to such embodiments and various modifications can be made.

[0235] Example The invention will be described in more detail through the following embodiments, but the invention is not limited to these embodiments.

[0236] (Example 1) First, propylene glycol monomethyl ether acetate, used as a cleaning solvent, and a 30wt% solution of 1,6-bis(trimethoxysilyl)hexane / propylene glycol monomethyl ether acetate were passed through filters to remove particles.

[0237] A 4-inch silicon wafer with a thermally oxidized film was assembled into a plasma device and irradiated with plasma at 250W for 3 minutes. The wafer was then assembled into a spin coater, and a 30wt% solution of 1,6-bis(trimethoxysilyl)hexane / propylene glycol monomethyl ether acetate was added, followed by a 5-minute settling period. Then, spin coating was performed at 2000 rpm for 30 seconds. Next, propylene glycol monomethyl ether acetate was added as a cleaning solvent to the wafer, and spin-drying was performed at 2000 rpm for 30 seconds. After treating the wafer on a 100°C hot plate for 5 minutes, it was mounted onto a manual attachment jig, overlapped with a silicon wafer that had also been irradiated with plasma at 250W for 3 minutes, and bonded together. Finally, a 2kg weight was placed on the wafer, and it was heated in an oven at 200°C for 30 minutes.

[0238] [Plasma irradiation conditions] The following apparatus was used for plasma irradiation.

[0239] Device: SAMCO Aqua Plasma (registered trademark) Cleaner AQ-500 Irradiation plasma: H2O Irradiation time: 3 minutes Irradiation temperature: room temperature [Filter Processing] Effective diameter of filter: 50nm [Determination of Bond Strength] The bonding strength γ is determined by a blade test, in which razor blades are inserted between wafers and the peeling distance is observed using an infrared microscope. The bonding strength γ is expressed by the following formula.

[0240] 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.

[0241] [Particle size] The particle content in the composition was determined using an SLS-1040 syringe sampling system to quantify particles larger than 40 nm in the composition.

[0242] [Surface Foreign Object Inspection] For surface foreign matter inspection, a 300mm silicon wafer with a natural oxide film was used. After surface activation treatment (plasma irradiation) using a plasma device (SAMCO Aqua Plasma Cleaner AQ-2000), the 1,6-bis(trimethoxysilyl)hexane / propylene glycol monomethyl ether acetate solution of Example 1 was coated on a 300mm spin coater. 40ml of propylene glycol monomethyl ether acetate was sprayed from the center of the rotating wafer through a nozzle, thereby obtaining a cleaned wafer.

[0243] The number of particle clusters was determined using a surface foreign matter inspection device for this wafer. The wafer is a 300mm wafer with an area of ​​706.8 cm². 2 .

[0244] (Example 2) As the first organic material, bis[3-(trimethoxysilyl)propyl]amine was used instead of 1,6-bis(trimethoxysilyl)hexane in Example 1, and otherwise the same procedure was followed as in Example 1.

[0245] (Example 3) As the first organic material, hexamethylene diisocyanate was used instead of 1,6-bis(trimethoxysilyl)hexane in Example 1, and otherwise the same procedure was followed as in Example 1.

[0246] Except for omitting the filter treatment, the procedure is the same as in Example 3.

[0247] Table 2 shows the amount of particles in the cleaning solvent and the effective pore size of the filter used in particle removal; Table 3 shows the effective pore size 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.

[0248] [Table 2] [Table 3] [Table 4] (Example 4) First, the cleaning solvents ethanol, propylene glycol monomethyl ether acetate, 30 wt% 3-aminopropyl dimethoxymethylsilane / ethanol solution, and 30 wt% hexamethylene diisocyanate / propylene glycol monomethyl ether acetate solution are passed through filters to remove particles.

[0249] Two 4-inch silicon wafers with thermally oxidized films were assembled into a plasma device and irradiated with plasma at 250W for 3 minutes. The wafers were then mounted into a spin coater, and a 30wt% solution of 3-aminopropyldimethoxymethylsilane (first organic material, second organic material) / ethanol was added, followed by standing for 5 minutes. Then, spin coating was performed at 2000 rpm for 30 seconds. Next, propylene glycol monomethyl ether acetate was added as a cleaning solvent to the wafers, and the mixture was spin-dried at 2000 rpm for 30 seconds. Two wafers of this type, after being treated on a 100°C hot plate for 5 minutes, were prepared. On one of these wafers, a further spin coating with a 30wt% hexamethylene diisocyanate (third organic material) / propylene glycol monomethyl ether acetate solution was performed, followed by spin-drying with the cleaning solvent propylene glycol monomethyl ether acetate, and then heat-treated at 100°C for 5 minutes. After joining the two wafers with the adhesive layer on the inside using a manual attachment fixture, a 2kg weight is placed on the wafer and heated to 200℃ for 30 minutes.

[0250] (Example 5) Except for changing the concentrations of the first and second organic materials, the process was the same as in Example 4.

[0251] Table 5 shows the amount of particles in the cleaning solvent and the effective pore size of the filter used to remove the particles. Table 6 shows the concentration of the organic material. Tables 7-9 show the effective pore size, particle amount, and cluster number of the filter. Table 10 shows the bonding temperature and bonding strength.

[0252] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] (Example 6) First, propylene glycol monomethyl ether acetate, used as a cleaning solvent, and a 0.2 wt% solution of bis[3-(trimethoxysilyl)propyl]amine / propylene glycol monomethyl ether acetate were passed through filters to remove particles.

[0253] A 4-inch silicon wafer with a thermally oxidized film was assembled into a plasma device and irradiated with plasma at 250W for 3 minutes. The wafer was then assembled into a spin coater, and a 0.2wt% solution of bis[3-(trimethoxysilyl)propyl]amine / propylene glycol monomethyl ether acetate was added. Spin-coating was performed at 2000 rpm for 30 seconds, followed by a 5-minute resting period. Next, propylene glycol monomethyl ether acetate (5.5wt% water content) was added as a cleaning solvent to the wafer, and after a 10-minute resting period, it was spin-dried at 2000 rpm for 30 seconds. The wafer was then treated on a 100°C hot plate for 5 minutes, loaded onto a manual attachment jig, and overlapped and bonded with a silicon wafer that had also been irradiated with plasma at 250W for 3 minutes. Finally, a 2kg weight was placed on the wafer, and it was heated in an oven at 200°C for 7 hours.

[0254] Table 10 shows the amount of particles in the cleaning solvent and the effective pore size of the filter used to remove the particles, while Table 11 shows the bonding temperature and cluster number.

[0255] [Table 10] [Table 11] Industrial availability By employing the manufacturing method of the stack of the present invention, the bonding strength between the first silicon substrate and the second silicon substrate can be improved.

[0256] Symbol Explanation 10, 20: Silicon substrate 11, 21: Main body 13, 23: Joint 30, 30A, 30B: Adhesive layer 31, 31A, 32A, 31B, 32B, 33B: Adhesive parts 40, 40A, 40B: Laminated structures.

Claims

1. A method for manufacturing a laminate comprising two silicon substrates, characterized in that, include: (a) A process of preparing a first silicon substrate having a first bonding portion and a second silicon substrate having a second bonding portion, wherein the first bonding portion and the second bonding portion are portions comprising silicon oxide; (b) The step of preparing a first composition, wherein the first composition comprises at least one of an organic material capable of reacting with silyl groups and / or silanol groups, and an inorganic material capable of bonding with silicon oxides, and the particle size is less than 3000 particles / mL; and (c) A step of providing an adhesive layer using at least one of the organic material and the inorganic material, wherein the adhesive layer bonds the first joint to the second joint through the organic material and / or a reaction product from the organic material, or bonds the first joint to the second joint through the inorganic material and / or a reaction product from the inorganic material. The adhesive layer includes a first adhesive portion disposed on the first joint portion; The number of particle clusters on the surface of the first adhesive portion opposite to the first joint portion is 5 per cm. 2 the following.

2. The manufacturing method as described in claim 1, characterized in that: The organic material has at least one bond selected from alkenyl, hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, anhydride, and siloxane.

3. The method for manufacturing a laminate as described in claim 1 or 2, characterized in that: The organic material comprises at least one selected from (i) to (iv) below: (i) Hydrocarbon compounds having alkenyl groups at both ends; (ii) A hydrocarbon compound having an alkenyl group at one end and a substituted or unsubstituted group selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino and anhydride groups at the other end; (iii) A hydrocarbon compound having multiple terminal portions, and at least two terminal portions having independently substituted or unsubstituted groups selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, phosphate, and anhydride groups; and (iv) Sesquioxanes and their derivatives.

4. The manufacturing method according to any one of claims 1 to 3, characterized in that: The reaction products are derived from the inorganic material.

5. The manufacturing method as described in claim 4, characterized in that: The reaction products contain at least one selected from SiO2, SiOC, SiOF, SiN, SiCN, HfO2, and La2O3.

6. The manufacturing method according to any one of claims 1 to 5, characterized in that: The process includes the step of filtration of the second composition to refine the first composition.

7. The manufacturing method as described in claim 6, characterized in that: The filtration is performed using a filter membrane with an effective diameter of less than 50 nm.

8. The manufacturing method as described in claim 6 or 7, characterized in that: The particle count in the second composition is higher than 3000 particles / mL.

9. The manufacturing method according to any one of claims 1 to 8, characterized in that: The bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m. 2 above.

10. The manufacturing method according to any one of claims 1 to 9, characterized in that: The first adhesive portion is formed of two or more layers.

11. The manufacturing method according to any one of claims 1 to 10, characterized in that: The adhesive layer also has a second adhesive portion that engages with the first adhesive portion. The second adhesive portion is disposed on the second joint portion. The number of particle clusters on the surface of the second adhesive portion opposite to the second joint portion is 5 per cm. 2 the following.

12. The manufacturing method as described in claim 11, characterized in that: The second adhesive portion is formed by two or more layers.

13. The manufacturing method as described in claim 11 or 12, characterized in that: The organic material comprises at least one selected from (i) to (vi) below: (i) A substituted or unsubstituted hydrocarbon compound having multiple terminal portions, and having an alkenyl group at at least two terminal portions; (ii) A hydrocarbon compound having a plurality of terminal portions, each having an alkenyl group at at least one terminal portion, and having a substituted or unsubstituted group selected from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino and anhydride groups at at least one terminal portion; (iii) A hydrocarbon compound having multiple terminal portions, and having at least two terminal portions independently having substituted or unsubstituted groups selected independently from hydroxyl, hydrolyzable silyl, isocyanate, epoxy, amino, phosphate and anhydride groups; (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 hydrocarbon compound having a hydrolyzable silyl group at one end and an alkyl group at the other end, either substituted or unsubstituted.

14. A laminated body, characterized in that, have: A first silicon substrate having a first bonding portion; A second silicon substrate located on one side of the first bonding portion and having a second bonding portion; and An adhesive layer located between the first joint and the second joint, which bonds the first joint and the second joint together. The first and second joints have regions of hydrogenated silyl and / or silanol groups derived from silicon oxide, or regions that are bonded to inorganic materials. The adhesive layer includes reaction products obtained by reacting with the hydrogenated silyl group and / or the silanol group, or regions bonded to the inorganic material. The number of particle clusters on the surface of the adhesive layer is 5 per cm. 2 the following, The bonding strength between the first silicon substrate and the second silicon substrate is 1.00 J / m. 2 above.

15. The laminate as described in claim 14, characterized in that: The adhesive layer is formed by two or more layers.

16. A composition, characterized in that: It includes at least one of organic and inorganic materials. The particle count is less than 3000 particles / mL.

17. The composition of claim 16, characterized in that: The composition is used in the manufacturing method according to claim 1.

Images