Method for manufacturing a laminate and laminate

Abstract

To provide a new laminate and a method for manufacturing the same.SOLUTION: A method for manufacturing a conductive laminate containing two silicon substrates includes: (a) preparing a first silicon substrate having a first conductive region on at least a portion of its surface and a second silicon substrate; (b) bonding a surface of the first silicon substrate containing the first conductive region to the second silicon substrate using an adhesive layer, and the adhesive layer comprises a first reaction product derived from a first organic material capable of reacting with a first activated region, formed on the first activated region provided by activating at least a portion of the surface of the first silicon substrate containing the first conductive region.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a laminate and to a laminate. [Background technology]

[0002] In the field of semiconductor technology, for example, in Patent Document 1, a method of joining two silicon substrates has been considered, which involves providing an adhesive layer between the silicon substrates. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2023 / 276638 [Overview of the project] [Problems that the invention aims to solve]

[0004] The object of this disclosure is to provide a new laminate and a method for manufacturing the same. [Means for solving the problem]

[0005] To solve the aforementioned problems, this disclosure provides the following [1] to

[23] . [1] A method for manufacturing a laminate containing two silicon substrates, (a) Prepare a first silicon substrate having a first conductive region on at least a portion of its surface, and a second silicon substrate, and (b) The surface of the first silicon substrate including the first conductive region and the second silicon substrate are joined together with an adhesive layer. Includes, The adhesive layer includes a first reaction product derived from a first organic material that can react with the first activated region, on a first activated region provided by activating at least a portion of the surface of the first silicon substrate including the first conductive region. A method for manufacturing a conductive laminate. [2] The manufacturing method according to [1], wherein the first conductive region comprises a metal. [3] The manufacturing method according to [2], wherein the metal in the first conductive region is at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf. [4] The manufacturing method according to any one of [1] to [3], wherein the surface of the first conductive region is exposed. [5] The manufacturing method according to any one of [1] to [3], wherein at least a portion of the surface of the first conductive region is in contact with the adhesive layer. [6] The adhesive layer is formed from two or more layers, according to the manufacturing method described in any one of [1] to [5]. [7] The first activation region is provided in at least a portion of the first conductive region and at least a portion of the first silicon substrate. The first conductive region includes at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf. The adhesive layer is in contact with the first activated region, The thickness of the adhesive layer is 5 nm or less. A manufacturing method described in any one of [1] to [6]. [8] moreover, The second silicon substrate has a second conductive region on at least a portion of its surface, The adhesive layer is provided on a second activated region, which is formed by activating at least a portion of the surface of the second silicon substrate facing the second conductive region, and contains a second reaction product derived from a second organic material. A method for manufacturing a laminate according to any one of [1] to [7]. [9] The manufacturing method according to [8], wherein the second conductive region includes a metal.

[10] The manufacturing method according to [8] or [9], wherein the metal in the second conductive region is at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf.

[11] The manufacturing method according to any one of [8] to

[10] , wherein the surface of the second conductive region is exposed.

[12] The manufacturing method according to any one of [8] to

[11] , wherein at least a portion of the surface of the second conductive region is in contact with the adhesive layer.

[13] The manufacturing method according to any one of [8] to

[12] , wherein the distance between the first conductive region and the second conductive region is 5 nm or less.

[14] The manufacturing method according to any one of [1] to

[13] , wherein the thickness of the adhesive layer is 5 nm or less.

[15] The first activation region is provided in at least a portion of the first conductive region and at least a portion of the first silicon substrate. The second activation region is provided in at least a portion of the second conductive region and at least a portion of the second silicon substrate. The first conductive region and the second conductive region each include at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf. The adhesive layer is in contact with the first activated region and the second activated region. The distance between the first conductive region and the second conductive region is 5 nm or less. The manufacturing method described in any one of [8] to

[14] .

[16] A first silicon substrate having a first conductive region on at least a portion of its surface, A second silicon substrate located on the side having the first conductive region, An adhesive layer located between the first silicon substrate and the second silicon substrate, which bonds the surface of the first silicon substrate having a first conductive region to the second silicon substrate, It has, A laminate having conductivity between the first silicon substrate and the second silicon substrate.

[17] The second silicon substrate has a second conductive region on at least a portion of its surface, The laminate according to

[16] , wherein the adhesive layer adheres the surface having the first conductive region to the surface having the second conductive region.

[18] The laminate according to

[17] , wherein the distance between the first conductive region and the second conductive region is 5 nm or less.

[19] The laminate according to any one of

[16] to

[18] , wherein the thickness of the adhesive layer is 5 nm or less.

[20] The adhesive layer is a laminate according to any one of

[16] to

[19] , comprising two or more layers. [twenty one] Having the first conductive region and the second conductive region, The distance between the first conductive region and the second conductive region is 5 nm or less. The adhesive layer adheres the surface having the first conductive region to the surface having the second conductive region. A laminate described in any one of

[17] to

[20] . [twenty two] The conductivity measured in the adhesive layer placed on the first silicon substrate was 1.0 × 10⁻⁶. -2 ~5.0×10 2 A laminate described in any one of

[16] to

[21] within the range of pA. [twenty three] Resistivity is 1.5 × 10⁻⁶ -8 ~2.0×10 5 A laminate described in any one of

[16] to

[22] within the range of Ω·m. [Effects of the Invention]

[0006] This disclosure provides a novel laminate and a method for manufacturing the same. [Brief explanation of the drawing]

[0007] [Figure 1A] A schematic cross-sectional view showing a portion of the laminate in the first embodiment is shown. [Figure 1B] A schematic cross-sectional view showing a portion of the laminate in the first embodiment is shown. [Figure 1C] A schematic cross-sectional view showing a portion of the laminate in the first embodiment is shown. [Figure 2] A schematic cross-sectional view showing a portion of the laminate in the second embodiment is shown. [Figure 3] A schematic cross-sectional view showing a portion of the laminate in a modified example is shown. [Modes for carrying out the invention]

[0008] Embodiments of this disclosure will be described in detail below with reference to the drawings, but this disclosure is not limited to these embodiments.

[0009] <First Embodiment> Figures 1A, 1B, and 1C are schematic cross-sectional views showing a portion of the cross-section of the laminate 40 in the first embodiment. As shown in Figures 1A, 1B, and 1C, the laminate 40 has a first silicon substrate 10 and a second silicon substrate 20. As shown in Figures 1A and 1C, an adhesive layer 30 is located between the first silicon substrate 10 and the second silicon substrate 20. As shown in Figures 1A and 1C, the first conductive region 15 and the second conductive region 25 are joined via the adhesive layer 30.

[0010] As shown in Figures 1A to 1C, the laminate 40 can be obtained by a manufacturing method that includes the following steps. (a) Prepare a first silicon substrate 10 having a first conductive region 15 on at least a portion of its surface, and a second silicon substrate 20, and (b) The surface of the first silicon substrate 10 on the side of the first conductive region 15 and the second silicon substrate 20 are joined together with an adhesive layer 30. Includes, The adhesive layer 30 contains a first reaction product derived from a first organic material that can react with the first activated region 15a, which is provided by activating at least a portion of the surface of the first silicon substrate 10 that includes the first conductive region 15.

[0011] By having the above configuration, a new substrate can be provided.

[0012] The following describes each step. In the following, "on the first silicon substrate 10" may refer to a state of direct contact with the first silicon substrate 10, or a state in which other layers are included on top of the first silicon substrate 10, unless otherwise specified. The same applies to other substrates, layers, and regions.

[0013] [Step a] A first silicon substrate 10 having a first conductive region 15 on at least a portion of its surface, and a second silicon substrate 20 are prepared.

[0014] (First and second silicon substrates 10, 20) The first and second silicon substrates 10 and 20 (hereinafter collectively referred to simply as "silicon substrates") may be any silicon-based substrate (or base material), and may consist solely of silicon, or may contain any other suitable substance in addition to silicon. Examples of such other substances include dopants and impurities that may inevitably be present, metals (e.g., electrodes, wiring, vias, etc.), and oxides, nitrides and / or carbides of silicon, etc. (e.g., dielectric layers, insulating layers, protective layers, etc.).

[0015] 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 one embodiment, the first silicon substrate 10 and the second silicon substrate have different configurations.

[0016] The first silicon substrate 10 may have a first bonding portion on its surface. The second silicon substrate 20 may have a second bonding portion on its surface. The first bonding portion and the second bonding portion are collectively referred to simply as the "bonding portion".

[0017] (1st, 2nd joint) In this embodiment, the joint portion may be any portion containing silicon oxide (hereinafter also referred to as the "silicon oxide portion"). The silicon oxide portion may consist of silicon oxide, or it may contain any other suitable substance in addition to silicon oxide. Examples of such other substances include dopants and impurities that may inevitably be present.

[0018] The joint can be formed, for example, by oxidizing (i.e., surface treating) the entire surface or a portion of the surface of the silicon substrate (typically, one of two opposing surfaces of the silicon substrate). That is, the first joint may make up the entire surface of the first silicon substrate 10 (typically, one of two opposing surfaces of the first silicon substrate 10) or a portion of it. The second joint may make up the entire surface of the second silicon substrate 20 (typically, one of two opposing surfaces of the second silicon substrate 20) or a portion of it.

[0019] Oxidation of silicon can be brought about by heating in an oxygen-containing atmosphere (so-called thermal oxidation) and / or spontaneous oxidation. For example, the joint in this embodiment can be formed by depositing silicon oxide on all or part of the surface of the silicon substrate (typically, one of two opposing surfaces of the silicon substrate). The deposition of silicon oxide may be carried out by sputtering, chemical vapor deposition (CVD), plasma-excited chemical vapor deposition (PECVD), vapor deposition, or any combination of two or more of these methods. Oxidation of silicon and deposition of silicon oxide may also be carried out in combination. However, the joint, which is the silicon oxide portion, may be formed by any suitable method, but is not limited to these.

[0020] The surface of the junction, which is the silicon oxide portion, always contains a small amount of silanol groups (-Si-OH).

[0021] The thickness of the junction is not particularly limited as long as the desired or acceptable properties are achieved in the final manufactured laminate. For example, the thickness of the silicon oxide portion of the junction may be between 1 nm and 1 μm, and particularly between 10 nm. The thickness of the junction can be measured, for example, using a cross-sectional scanning electron microscope (cross-sectional SEM) or SEM, specifically using an SEM.

[0022] (1st and 2nd conductive regions 15, 25) As shown in Figures 1A and 1B, the first and second conductive regions 15 and 25 are regions that conduct electricity easily, preferably regions containing metal, and are provided on at least a portion of the first and second silicon substrates 10 and 20. The first and second conductive regions 15 and 25 are, for example, regions containing a conductive metal. The metal preferably includes at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf, and more preferably includes Cu. The first conductive region 15 may have the same metal as the second conductive region 25, or it may have a different metal.

[0023] The first and second conductive regions 15 and 25 are formed, for example, by chemical vapor deposition (CVD) (e.g., thermal CVD, plasma CVD, etc.), physical vapor deposition (PVD) (e.g., vacuum deposition, sputtering, etc.), atomic layer deposition (ALD), or plating (e.g., electroplating, electroless plating, hot-dip plating, etc.).

[0024] Conductivity can be measured, for example, using scanning spreading resistance microscopy (SSRM). For instance, the conductivity value may be the average current value obtained by SSRM.

[0025] The first conductive region 15 may be provided in a range of 1 to 50% of the surface of the first silicon substrate 10, for example. The second conductive region 25 may be provided in a range of 1 to 50% of the surface of the second silicon substrate 20, for example.

[0026] The first conductive region 15 is provided on the same plane as the first bonding portion if the first silicon substrate 10 has a first bonding portion. In this case, the first bonding portion may be provided first and then the first conductive region 15 may be provided, or the first conductive region 15 may be provided first and then the first bonding portion may be provided, or the first conductive region 15 and the first bonding portion may be provided simultaneously. The first conductive region 15 and the first bonding portion may partially overlap. That is, the first bonding portion may be provided on the first silicon substrate 10, and then the first conductive region 15 may be provided on at least a part of the first bonding portion.

[0027] The second conductive region 25 is provided on the same plane as the second joint if the second silicon substrate 20 has a second joint. In this case, the second joint may be provided first and then the second conductive region 25 may be provided, or the second conductive region 25 may be provided first and then the second joint may be provided, or the second conductive region 25 and the second joint may be provided simultaneously. The second conductive region 25 and the second joint may partially overlap. That is, the second joint may be provided on the second silicon substrate 20, and then the second conductive region 25 may be provided on at least a part of the second joint.

[0028] (First and second activation regions 15a, 25a) Although not essential to this embodiment, a first activation region 15a may be provided on the first silicon substrate 10, and a second activation region 25a may be provided on the second silicon substrate 20.

[0029] The first activated region 15a is an activated region of at least a portion of the surface of the first silicon substrate 10 and / or at least a portion of the surface of the first conductive region 15. The first activated region 15a is formed, for example, by performing at least one treatment selected from the group consisting of hydrogen atom treatment, heat treatment in a hydrogen-containing atmosphere, sputtering, chemical vapor deposition (CVD), and termination treatment using chemicals on the surface including the first conductive region 15. This results in the bonding of H or OH to the first conductive region 15. In one embodiment, the first activated region 15a is formed on a portion of the first conductive region 15. In one embodiment, the first activated region 15a is formed on the entire surface of the first conductive region 15. When there are multiple first conductive regions 15 on the first silicon substrate 10, the first conductive region 15 may not be formed on some of the first activated regions 15a. That is, there may be first conductive regions 15 that do not have the first activated region 15a.

[0030] The second activated region 25a is an activated region of at least a portion of the surface of the second silicon substrate 20 and / or at least a portion of the surface of the second conductive region 25. The second activated region 25a is formed in the same manner as the first activated region 15a. In one embodiment, the second activated region 25a is formed on a portion of the second conductive region 25. In one embodiment, the second activated region 25a is formed on the entire surface of the second conductive region 25. When there are multiple second conductive regions 25 on the second silicon substrate 20, the second conductive region 25 may not be formed on some of the second activated regions 25a. That is, there may be second conductive regions 25 that do not have a second activated region 25a.

[0031] In one embodiment, after step (a) and before step (b), at least one of the first and second joints may be subjected to a surface treatment that generates hydrosilyl groups and / or silanol groups, thereby providing a first activated region 15a and / or a second activated region 25a. This allows hydrosilyl groups (-Si-H) and / or silanol groups (-Si-OH) to be present on the surface of the joint at a higher density. The surface treatment may be performed on the surface of the joint (joint surface), and may be performed only on the surface of the joint, or on a wider surface including the surface of the joint. The concentrations of hydrosilyl groups and silanol groups on the surface of the joint can be measured, for example, from the peak intensity by time-of-flight secondary ion mass spectrometry (TOF-SIMS), or by X-ray photoelectron spectroscopy (XPS). Note that this surface treatment may be performed before providing the first and second conductive regions 15 and 25.

[0032] The surface treatment for generating hydrosilyl and / or silanol groups may be at least one selected from the group consisting of hydrogen atom treatment, heat treatment in a hydrogen-containing atmosphere, sputtering, chemical vapor deposition (CVD), and chemical termination. Hydrogen atoms can be introduced to the surface of the joint by hydrogen atom treatment, heat treatment in a hydrogen-containing atmosphere, sputtering, CVD, or chemical termination to generate hydrosilyl groups (-Si-H). Hydroxyl groups can be introduced to the surface of the joint by chemical termination to generate silanol groups (-Si-OH).

[0033] Hydrogen atom processing is performed, for example, in an ultra-high vacuum (1 × 10⁻¹⁰ -6 Hydrogen gas is introduced into a vacuum chamber (below Pa) at a rate of 1 × 10⁻¹⁰ -4 This can be carried out by supplying approximately Pa, dissociating hydrogen molecules into hydrogen atoms using thermionic electrons or plasma, and then adsorbing the hydrogen atoms onto the surface of the junction.

[0034] Heat treatment in a hydrogen-containing atmosphere may be carried out, for example, by replacing the air in the chamber with hydrogen gas by flowing hydrogen as a carrier gas during vacuum evacuation to create a hydrogen atmosphere vacuum state (specifically, a hydrogen atmosphere of 10 Pa or less), and then heating the substrate to about 100 to 400°C in this atmosphere to adsorb hydrogen onto the surface of the bonding area.

[0035] The sputtering process may be carried out, for example, by using silicon as a sputtering source, supplying hydrogen, and adsorbing the hydrogen onto the surface of the joint.

[0036] The CVD treatment may be carried out, for example, by using silane as the CVD gas and adjusting the hydrogen gas pressure to adsorb hydrogen atoms onto the surface of the junction.

[0037] Terminal treatment using chemicals may be carried out by immersing a silicon substrate in a chemical solution such as hydrofluoric acid aqueous solution (hydrofluoric acid) or ammonium fluoride, with at least the junctions exposed, and bonding hydrogen ions and / or hydroxide ions to the surface of the junctions depending on the chemical solution used.

[0038] In one embodiment, after step (a) and before step (b), at least one of the first joint and the second joint may be subjected to a surface treatment that generates fluorosilyl groups to provide a first activated region 15a and / or a second activated region 25a. This surface treatment may be performed before providing the first and second conductive regions 15 and 25.

[0039] The surface treatment for generating fluorosilyl groups may be at least one selected from the group consisting of CVD, electrical discharge treatment, ion implantation, and chemical termination treatment. The surface treatment for generating fluorosilyl groups may be performed separately or simultaneously with the surface treatment for generating hydrosilyl groups and / or silanol groups. If performed separately, either of these surface treatments may be performed first.

[0040] The CVD treatment may be carried out by adsorbing fluorine atoms onto the surface of the junction, for example, by using CF4 and / or SF6 as the CVD gas.

[0041] The discharge treatment may be carried out by performing plasma discharge or corona discharge in an atmosphere containing, for example, CF4 and / or SF6, to adsorb fluorine radicals onto the surface of the junction.

[0042] Ion implantation may involve implanting fluoride ions into the junction using any appropriate method.

[0043] Terminal termination using chemicals may be carried out by immersing a silicon substrate in a chemical solution such as hydrofluoric acid aqueous solution (hydrofluoric acid) or ammonium fluoride, with at least the junctions exposed, and bonding fluoride ions to the surface of the junctions depending on the chemical solution used. In particular, terminal termination using hydrofluoric acid aqueous solution can generate hydrosilyl groups (-Si-H), silanol groups (-Si-OH), and fluorosilyl groups (-Si-F).

[0044] The first silicon substrate 10 and the second silicon substrate 20 are prepared in the manner described above.

[0045] [Step b] Next, the surface of the first silicon substrate 10 including the first conductive region 15 and the second silicon substrate 20 are joined together with an adhesive layer 30.

[0046] When the second silicon substrate 20 includes a second conductive region 25, the distance between the first conductive region 15 and the second conductive region 25, that is, the distance between the surface of the first conductive region 15 facing the second conductive region 25 and the surface of the second conductive region 25 facing the first conductive region 15, is preferably 5 nm or less, more preferably 3 nm or less, and may be, for example, 2 nm or less or 1 nm or less. The lower limit of the distance between the first conductive region 15 and the second conductive region 25 is not particularly limited, but for example, it is 0.2 nm or more. The small distance between the first conductive region 15 and the second conductive region 25 ensures conductivity between the conductive regions. If the distance increases, the adhesive layer 30 generally becomes non-conductive, and the first conductive region 15 and the second conductive region 25 become insulated. The above distance can be measured, for example, using an ellipsometer.

[0047] The adhesive layer 30 contains a reaction product derived from a first organic material that can react with the first activated region 15a, which is provided by activating at least a portion of the surface of the first silicon substrate 10 that includes the first conductive region 15.

[0048] As shown in Figure 1A, at least a portion of the surface of the first activated region 15a opposite the first silicon substrate 10 is in contact with the adhesive layer 30. At least a portion of the surface of the second activated region 25a opposite the second silicon substrate 20 is in contact with the adhesive layer 30.

[0049] As shown in Figure 1B, the surface of the first activated region 15a may not have an adhesive layer 30 and may have a void 60, and the surface of the second activated region 25a may not have an adhesive layer 30 and may have a void 60. In other words, the surfaces of the first and second activated regions 15a and 25a may be exposed.

[0050] In Figures 1A and 1B, the first activation region 15a and the second activation region 25a are facing each other, but different regions may be provided facing each other. For example, the first activation region 15a and the second silicon substrate 20 may be provided facing each other, the first activation region 15a and the second junction may be provided facing each other, the second activation region 25a and the second silicon substrate 20 may be provided facing each other, and the second activation region 25a and the first junction may be provided facing each other.

[0051] (Adhesive layer 30) The adhesive layer 30 has a first adhesive portion 31. The adhesive layer 30 (first adhesive portion 31) contains a first reaction product derived from an organic material.

[0052] As shown in Figures 1A and 1B, the adhesive layer 30 is provided on at least a portion of the first and second activation regions 15a and 25a. In this case, the adhesive layer 30 and the first and second activation regions 15a and 25a may be chemically reacting or simply in contact.

[0053] Preferably, the adhesive layer 30 bonds to at least a portion of the first and second activated regions 15a and 25a, i.e., undergoes a chemical reaction. The organic material may bond to the first activated region 15a without reacting with the second activated region 25a, or it may bond to the second activated region 25a without reacting with the first activated region 15a.

[0054] As shown in Figure 1C, the adhesive layer 30 may be in direct contact with the first and second silicon substrates 10 and 20. In Figure 1C, the first silicon substrate 10 and the second silicon substrate 20 are facing each other, but different substrates, regions, etc., may be provided facing each other. For example, the first silicon substrate 10 and the second activation region 25a may be provided facing each other, the first silicon substrate 10 and the second bonding portion may be provided facing each other, the second silicon substrate 20 and the first activation region 15a may be provided facing each other, and the second silicon substrate 20 and the first bonding portion may be provided facing each other.

[0055] The adhesive layer 30 may be provided on at least a portion of the first conductive region 15. When viewed from a direction perpendicular to the first conductive region 15 (first silicon substrate 10), the adhesive layer 30 may cover the entire first activated region 15a, or it may cover at least a portion of the first conductive region 15, or it may not be provided on the first conductive region 15 at all (i.e., the entire surface of the first conductive region 15 is exposed). That is, the surface of the first conductive region 15 may be exposed, or at least a portion of it may be in contact with the adhesive layer 30.

[0056] The adhesive layer 30 may be provided on at least a portion of the second conductive region 25. When viewed from a direction perpendicular to the first conductive region 15 (second silicon substrate 20), the adhesive layer 30 may cover the entire second activated region 25a, or it may cover at least a portion of the second conductive region 25, or it may cover a portion of the second activated region 25a, and may not be provided on the second conductive region 25 at all (i.e., the entire surface of the second conductive region 25 is exposed). That is, the surface of the second conductive region 25 may be exposed, or at least a portion of it may be in contact with the adhesive layer 30.

[0057] The adhesive layer 30 is provided on the first joint and may react with the first joint. The adhesive layer 30 is further provided on the second joint and may react with the second joint. As a result, the adhesive layer 30 joins the first joint and the second joint. Note that a portion of the first joint may be exposed, or the entire first joint may be covered with the adhesive layer 30. Similarly, a portion of the second joint may be exposed, or the entire second joint may be covered with the adhesive layer 30.

[0058] The adhesive layer 30 (first adhesive portion 31) may be formed from, for example, two or more layers. That is, the first adhesive portion may be provided on the first silicon substrate 10, dried and / or heated as necessary, and then the second adhesive portion may be provided. The number of adhesive layers is not particularly limited, but may be five or fewer, for example.

[0059] The thickness of the adhesive layer 30 (for example, the distance between the first activated region 15a and the second activated region 25a) can be extremely thin. The thickness of the adhesive layer 30 is, for example, 10 nm or less, and may be particularly 8 nm or less, 5 nm or less, 3 nm or less, or 1.5 nm or less. The lower limit of the thickness of the adhesive layer 30 is not particularly limited, but may be, for example, 1 nm or more. By having the thickness of the adhesive layer 30 within the above range, the distance between the first conductive region 15 and the second conductive region 25 becomes small, and conductivity between the conductive regions can be ensured. Since the adhesive layer 30 is generally non-conductive, if the thickness increases, it insulates the first conductive region 15 and the second conductive region 25. The thickness of the adhesive layer 30 can be measured, for example, using a cross-sectional SEM, SEM, or ellipsometer, and specifically, it can be measured using a high-speed mapping spectroscopic ellipsometer (theta-SE).

[0060] The amount of particles contained on the side of the first adhesive portion 31 opposite to the first silicon substrate 10 is preferably 0 particles / mm 2 The following applies. The particle quantity may also be measured on the surface after the composition has been placed on a separately prepared substrate, dried, and the composition has been allowed to dry.

[0061] The amount of particles can be measured, for example, using a surface foreign matter inspection device. The measurement can be performed, for example, within an inspection area of ​​300 mm x 300 mm.

[0062] The particle content being within the above range results in good adhesive strength between the first silicon substrate 10 and the second silicon substrate 20. Furthermore, the laminate 40 can be manufactured at a relatively low temperature, thereby effectively suppressing or preventing the occurrence of voids in the adhesive layer 30. The adhesive strength can be measured, for example, using an ultrasonic microscope.

[0063] Here, a particle may be a single particle or an aggregate of particles. That is, a particle includes primary particles and secondary particles. Furthermore, a particle may be inorganic or organic. Examples of particles include particles present in the environment or particles supplied together with organic materials, which exist in particulate form after the hardening of organic materials.

[0064] Particle size refers to the equivalent light scattering diameter 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, particle size can be measured using a surface foreign matter inspection device under conditions of 60 nm or larger.

[0065] There is no particular lower limit to the particle count, but for example, 0 particles / mm 2 That concludes the explanation. The particle size is, for example, 200 nm or larger. There is no particular upper limit to the particle size, but it may be, for example, 6 μm or less.

[0066] In the first embodiment, the first adhesive portion 31 is provided on the first joint, but the first adhesive portion 31 may also be provided on the second joint. In this case, "first joint" should be read as "second joint".

[0067] (Organic materials) The organic material is a material that can react with hydrosilyl groups and / or silanol groups. The organic material has at least two functional groups. Preferably, these two functional groups are located at both ends of the organic material.

[0068] Organic materials react with the first activated region 15a at one of their terminal functional groups to form a reaction product. In other words, the composition of the reaction product depends on the structure of the organic material.

[0069] The organic material can react with the second activated region 25a at the other terminal functional group. The reaction product derived from the organic material bonds the first silicon substrate 10 and the second silicon substrate 20.

[0070] The organic material can react with the first bonding portion if the first silicon substrate 10 has a first bonding portion. The organic material can react with the second bonding portion if the second silicon substrate 20 has a second bonding portion. By having the above configuration, the adhesive strength between the first silicon substrate 10 and the second silicon substrate 20 is improved.

[0071] Preferably, the particle count in the organic material is 500 particles / mL or less. The lower limit of the particle count in the organic material is not particularly limited, but for example, it may be 0 particles / mL or more. The particle count in the organic material can be measured, for example, using a syringe sampling system SLS-1040.

[0072] Preferably, the process includes purifying the organic material by filtering. This removes particles contained in the organic material and reduces the amount of particles contained in the first adhesive portion 31.

[0073] The organic material may be used as a composition containing, for example, a solvent. In addition to the organic material, the composition may also contain a solvent, an acid / base catalyst, or other reaction accelerator. As the solvent, commonly used solvents can be used; for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, toluene, tetrahydrofuran, and isopropyl alcohol can be used. The water content in the composition is substantially zero. By reducing the water content in the composition in this way, the generation of voids can be reduced.

[0074] The above composition may contain organic materials dissolved, dispersed, or suspended in a solvent. For example, the above composition dissolves organic materials.

[0075] The amount of particles in the above composition is, for example, 500 particles / mL or less. The lower limit of the amount of particles in the composition is not particularly limited, but for example, 0 particles / mL or more.

[0076] Preferably, the above composition is purified by filtering. This removes particles contained in the composition and reduces the amount of particles contained in the first adhesive portion 31.

[0077] Preferably, the filtering is performed using a membrane with an effective diameter of 100 nm or less. More preferably, the effective diameter of the membrane is 50 nm or less, and even more preferably 10 nm or less. The lower limit of the effective diameter of the membrane is not particularly limited, but may be, for example, 1 nm or more. Here, the effective diameter refers to the average effective diameter value of the membrane.

[0078] The specific methods for supplying the organic material (or a composition containing the organic material) and the joining method may be appropriately selected depending on the organic material used. Generally speaking, after supplying the organic material to the first joining portion, the reaction may proceed by maintaining the first silicon substrate 10 and the second silicon substrate 20 under predetermined reaction conditions (particularly a predetermined temperature) with the organic material interposed between them. Alternatively, the organic material may be supplied to the second joining portion instead of the first.

[0079] For example, an organic material (which may be a composition) is applied (e.g., by coating, spraying, printing, etc.) to either or both of the surfaces of the first silicon substrate 10 having the first conductive region 15 (the surface having at least a portion of the first activated region 15a) and the second silicon substrate having the second conductive region 25 (the surface having at least a portion of the second activated region 25a). The organic material may be applied in its original form or in the form of a composition mixed with any suitable component (e.g., a solvent). Afterwards, cleaning and / or drying may be carried out as necessary. Cleaning and drying may be carried out in the same manner as described above, and if an organic material containing fluorine is used, pre-cleaning with a fluorinated solvent may be performed.

[0080] Subsequently, the first silicon substrate 10 and the second silicon substrate 20 are aligned so that the first conductive region 15 and the second conductive region 25 face each other, and the first silicon substrate 10 and the second silicon substrate 20 are brought into close contact with the organic material interposed between them. The first silicon substrate 10 and the second silicon substrate 20, which are brought into close contact, are maintained under predetermined reaction conditions (particularly a predetermined temperature), and the reaction is allowed to proceed during this time. After that, annealing treatment may be performed as needed.

[0081] As another example, an organic material (or a composition containing an organic material) may be supplied to the surface having the first conductive region 15 (at least part of which has the first activated region 15a), and then the first silicon substrate 10 and the second silicon substrate 20 may be bonded together by the reaction product by maintaining the first silicon substrate 10 and the second silicon substrate 20 under predetermined reaction conditions (particularly a predetermined temperature) with the organic material interposed between the first conductive region 15 and the second conductive region 25.

[0082] In one embodiment, when an organic material is applied to the surface of the first conductive region 15, the surface of the layer formed from the organic material may be washed with water or an aqueous organic solvent before the second conductive region 25 is placed on the layer. The organic material may also be applied to the surface of the second conductive region 25, rather than the surface of the first conductive region 15.

[0083] The functional groups of organic materials include, for example, at least one selected from the group consisting of alkenyl groups, hydroxyl groups, hydrolyzable silyl groups, isocyanate groups, epoxy groups, amino groups, acid anhydride groups, and siloxane bonds. Alkenyl groups are reactive with hydrosilyl groups (-Si-H), and hydroxyl groups, hydrolyzable silyl groups, isocyanate groups, epoxy groups, amino groups, acid anhydride groups, and siloxane bonds are reactive with silanol groups (-Si-OH).

[0084] More specifically, the organic material may include at least one selected from the group consisting of (i) to (iv) below. This organic material may be composed of a single compound or a combination of two or more compounds. Furthermore, while the following describes the reaction between the organic material and the first and second active regions 15a and 25a, or the reaction between the organic material and the first and second junctions, other combinations of compounds may also react. For example, the organic material may react with the first active region 15a and the second junction, or the organic material may react with the second active region 25a and the first junction. (i) A substituted or unsubstituted hydrocarbon compound having alkenyl groups at two terminal ends. (ii) A substituted or unsubstituted hydrocarbon compound having an alkenyl group at one terminal end and any of the groups selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, and an acid anhydride group at the other terminal end. (iii) A substituted or unsubstituted hydrocarbon compound having at two terminal ends any one independently selected from the group consisting of a hydroxyl group, a hydrolyzable silyl group, an isocyanate group, an epoxy group, an amino group, a phosphate group, and an acid anhydride group. (iv) Silsesquioxane and its derivatives

[0085] Exemplary embodiments using the organic materials described in (i) to (iv) are described in detail below.

[0086] • Example using organic materials (i) (Example 1) In this example, first and second conductive regions 15 and 25 are formed on parts of the surfaces of the first silicon substrate 10 and the second silicon substrate 20. The first and second conductive regions have first and second activated regions 15a and 25a, in which at least a portion is activated. The first and second activated regions 15a and 25a may, for example, have hydrogen atoms on their surfaces.

[0087] Furthermore, the first silicon substrate 10 and the second silicon substrate 20 may have a first junction and a second junction (which in this example is a silicon oxide portion). Materials may be used in which hydrosilyl groups (-Si-H) are present on the surfaces of the first and second junctions. The first silicon substrate 10 and the second silicon substrate 20, which have hydrosilyl groups on the surfaces of the first and second junctions (which are silicon oxide portions), may be obtained, for example, by a surface treatment that generates the hydrosilyl groups described above.

[0088] As an organic material, a substituted or unsubstituted hydrocarbon compound having alkenyl groups at two terminal ends is used. The alkenyl group is a reactive group for the hydrogen atom in the active region and / or the hydrosilyl group at the junction. Such a compound may have two or more terminal ends, and may have alkenyl groups at any two or more terminal ends. Such a compound may be fluorine-substituted, in other words, it may be a fluoroalkyl compound or a fluoropolyether group-containing compound having alkenyl groups at two or more terminal ends.

[0089] Exemplary examples of fluoroalkyl compounds having two, three, or four alkenyl groups at their terminal ends are shown below. Rf represents a fluoroalkyl group (the same applies below). In the compounds below, for example, alkenyl groups may be bonded to different carbon atoms in Rf.

[0090] [ka]

[0091] The number of carbon atoms in the portion excluding the terminal reactive group (alkenyl group) is not particularly limited, but may be, for example, 1 to 200, and particularly 100 or less. The number of carbon atoms may also be, for example, 5 or more. The portion excluding the reactive group may be linear, branched, or cyclic. If the portion excluding the terminal reactive group is a fluoroalkyl group, the fluorine substitution ratio is not particularly limited, but may be, for example, a perfluoroalkyl group.

[0092] The fluoropolyether group-containing compound having an alkenyl group at the above two or more terminal portions is, for example, (A) Formula (1):

Chemical formula

[0093] The above organic material is supplied between the first silicon substrate 10 and the second silicon substrate 20 and allowed to react. The organic material may react with the first and second active regions 15a and 25a. Specifically, the alkenyl groups of the organic material may react with the hydrogen atoms of the first and second active regions 15a and 25a, respectively. Furthermore, if the first and second silicon substrates 10 and 20 each have first and second junctions, the alkenyl groups of the organic material may react (hydrosilylate) with the hydrosilyl groups of the first and second junctions. As a result, the reaction products derived from the organic material chemically bond to the metals of the first and second active regions 15a and 25a and / or the Si atoms of the first and second junctions. With this reaction, no by-products are produced, thus fundamentally eliminating the problem of void formation due to by-products.

[0094] The reaction may be carried out in one step with the organic material sandwiched between the first silicon substrate 10 and the second silicon substrate 20, or it may be carried out in two steps, by applying the organic material to either the first silicon substrate 10 or the second silicon substrate 20 to partially allow the reaction to proceed, and then placing the other substrate on top of the organic material to further allow the reaction to proceed.

[0095] The following shows an example of a reaction using a fluoroalkyl compound having alkenyl groups at both ends. In the following, Cu is described as an example of the first and second conductive regions 15 and 25. The same applies to a fluoropolyether group-containing compound having alkenyl groups at both ends.

[0096] [ka]

[0097] As shown in the schematic diagram above, the first reaction product derived from the organic material chemically bonds to both the metal atoms in the first conductive region 15 and the metal atoms in the second conductive region 25. However, it is not necessary for all reaction products to chemically bond to both the Si atoms of the metal atoms in the first conductive region 15 and the metal atoms in the second conductive region 25. Some reaction products may chemically bond to only one of the metal atoms in the first conductive region 15 and the metal atoms in the second conductive region 25, or they may chemically bond to two or more metal atoms. To obtain higher bonding strength, it is preferable that more reaction products chemically bond to both the metal atoms in the first conductive region 15 and the metal atoms in the second conductive region 25. From this viewpoint, the organic material is preferably a linear compound having alkenyl groups at both ends, but is not limited thereto.

[0098] Furthermore, the first reaction product derived from the organic material chemically bonds to both the Si atoms of the first junction and the Si atoms of the second junction. However, it is not necessary for all reaction products to chemically bond to both the Si atoms of the first and second junctions. Some reaction products may chemically bond to only one of the Si atoms of the first or second junction, or to two or more Si atoms within the same silicon substrate. To obtain higher bonding strength, it is preferable that more reaction products chemically bond to both the Si atoms of the first and second junctions.

[0099] Furthermore, although not shown in the schematic diagram, the first reaction product derived from the organic material may bond the Si atoms of the first or second junction to the metal atoms of the first or second conductive regions 15,25. From the above viewpoint, the organic material is preferably a linear compound having alkenyl groups at both ends, but is not limited thereto.

[0100] Furthermore, the first reaction product may bond only to the metal atoms in the first conductive region 15 and the metal atoms in the second conductive region 25, and may not bond to the Si atoms in the first or second junction. Similarly, in the following examples, it may bond only to the metal atoms and not to the Si atoms.

[0101] (Example 2) In the first example described above, the first reaction product chemically reacted between the first and second silicon substrates 10, 20 and between the first and second conductive regions 15, 25, linking them together. However, in this second example, there is a portion A between the first and second conductive regions 15, 25 that remains unreacted with the first and second conductive regions 15, 25, and no chemical reaction occurs between the first and second conductive regions 15, 25 and portion A. In other words, the first and second conductive regions 15, 25 are not chemically linked via portion A. Otherwise, the configuration is the same as in the first example described above. For example, a first reaction product exists between the first and second silicon substrates 10 and 20, and chemically reacts with the surfaces of the first and second silicon substrates 10 and 20 to bond them together. As a result, the bonding strength between the first and second silicon substrates 10 and 20 is good.

[0102] The first and second conductive regions may have first and second activated regions 15a and 25a in which at least a portion is activated, but they may not have the first and second activated regions 15a and 25a.

[0103] For example, as shown in the schematic diagram, when a fluoroalkyl compound having alkenyl groups at both ends is used, the chemical reaction proceeds at the first and second junctions in the same manner as in the first example.

[0104] [ka]

[0105] Part A is located between the metal atoms of the first conductive region 15 and the metal atoms of the second conductive region 25. Part A is located in at least a portion of the first and second conductive regions 15 and 25. It is unreacted with the metal atoms of the first conductive region 15 and the second conductive region 25. The entire surface of the first conductive region 15 and the second conductive region 25 may have part A, or only a portion may have part A, and the other portion may not have part A.

[0106] The above-mentioned portion A may contain metal atoms in the first conductive region 15 and an organic compound that has not reacted with the second conductive region 25 (hereinafter referred to as "unreacted organic compound"). The unreacted organic compound is preferably a conductive compound. The conductivity of portion A is, for example, 1.0 × 10⁻⁶. -2 ~5.0×10 2 It may be within the range of pA.

[0107] Part A may include, for example, oil. Examples of oils include (non-reactive) fluoro(poly)ether compounds, preferably perfluoro(poly)ether compounds (hereinafter referred to as "fluorine-containing oil"), which can be understood as fluorine-containing oils.

[0108] The above-mentioned fluorine-containing oils are not particularly limited, but examples include compounds represented by the following general formula (I) (perfluoro(poly)ether compounds). Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 ...(I)

[0109] In the formula, Rf 5 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms. 1―16 Rf represents a perfluoroalkyl group. 6 C1-16 alkyl group (preferably C) may be substituted with one or more fluorine atoms.1-16 represents a perfluoroalkyl group, a fluorine atom or a hydrogen atom, and Rf 5 and Rf 6 are more preferably, each independently, C 1-3 perfluoroalkyl groups.

[0110] a', b', c' and d' each represent the number of four types of repeating units of the perfluoro(poly)ether constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less, and the sum of a', b', c' and d' is at least 1, preferably 1 to 300, more preferably 20 to 300. The order of existence of each repeating unit enclosed in parentheses with the subscript a', b', c' or d' is arbitrary in the formula. Among these repeating units, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and -(OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)- and -(OCF2CF(CF3))-, and is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0111] Examples of the perfluoro(poly)ether compound represented by the above general formula (I) include compounds (which may be a mixture of one or more) represented by any of the following general formulas (Ia) and (Ib). Rf 5 -(OCF2CF2CF2) b’’ -Rf 6 ···(Ia) Rf 5 -(OCF2CF2CF2CFa’’ -(OCF2CF2CF2) b’’ -(OCF2CF2) c’’ -(OCF2) d’’ -Rf 6 ···(Ib) In these formulas, Rf 5 and Rf 6 are as described above; in formula (Ia), b'' is an integer of 1 or more and 100 or less; in formula (Ib), a'' and b'' are each independently an integer of 1 or more and 30 or less, and c'' and d'' are each independently an integer of 1 or more and 300 or less. The order of existence of each repeating unit enclosed in parentheses with subscripts a'', b'', c'', d'' is arbitrary in the formula.

[0112] The fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000. In particular, the number average molecular weight of the compound represented by formula (Ia) is preferably 2,000 to 8,000. In one aspect, the number average molecular weight of the compound represented by formula (Ib) is 3,000 to 8,000. In another aspect, the number average molecular weight of the compound represented by formula (Ib) is 8,000 to 30,000.

[0113] Also, from another perspective, the fluorine-containing oil may be a compound represented by the general formula Rf'-F (wherein Rf' is a C 5-16 perfluoroalkyl group).) It may also be a chlorotrifluoroethylene oligomer. The compound represented by Rf'-F and the chlorotrifluoroethylene oligomer are preferred in that a high affinity can be obtained with the perfluoro(poly)ether group-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group.

[0114] Furthermore, portion A may contain voids or consist solely of voids. That is, voids may exist between the first conductive region 15 and the second conductive region 25. Also, unreacted organic compounds contained in portion A may be present in other portions, specifically between the first and second silicon substrates 10 and 20, for example, between the first and second silicon substrates 10 and 20 bonded together by a fluoroalkyl compound.

[0115] The following example may also have a similar configuration as part A.

[0116] • Example using organic materials (ii) (Example 3) In this example, first and second conductive regions 15 and 25 are formed on parts of the surfaces of the first silicon substrate 10 and the second silicon substrate 20. The first and second conductive regions have first and second activated regions 15a and 25a, at least in part. For example, the first activated region 15a may have hydroxyl groups on its surface, and the second activated region 25a may have hydrogen atoms on its surface.

[0117] Furthermore, the first silicon substrate 10 and the second silicon substrate 20 may have a first junction and a second junction (which in this example is a silicon oxide portion). The first silicon substrate 10 is one in which silanol groups (-Si-OH) are present on the surface of the first junction (which in this example is a silicon oxide portion). The first silicon substrate 10 having silanol groups on the surface of the first junction, which is a silicon oxide portion, does not require any special surface treatment, but may be obtained by the above-mentioned surface treatment to generate silanol groups if necessary.

[0118] As an organic material, a substituted or unsubstituted hydrocarbon compound having an alkenyl group at one terminal and a hydroxyl group at the other terminal is used. The alkenyl group is a reactive group for the hydroxyl group of the first active region 15a and / or the hydrosilyl group of the first junction, and the hydroxyl group is a reactive group for the hydrogen atom of the second active region 25a and / or the silanol group of the second junction. Such a compound may have two or more terminal regions, and may have an alkenyl group at any one or more terminal regions and a hydroxyl group at any one or more terminal regions. Such a compound may be fluorine-substituted, in other words, it may be a fluoroalkyl compound or a fluoropolyether group-containing compound having an alkenyl group at one terminal and a hydroxyl group at the other terminal.

[0119] Unless otherwise specified, the above description may apply. (Except for having a hydroxyl group at at least one terminal, it may be the same as the fluoroalkyl compound or fluoropolyether group-containing compound detailed in (i) above.)

[0120] The above-mentioned organic material is supplied between the first silicon substrate 10 and the second silicon substrate 20. At this time, the organic material is supplied so as to be in contact with the opposing first and second active regions 15a and 25a. As a result, reaction products originating from the first organic material chemically bond to the metal atoms of the first and second active regions 15a and 25a, and the first conductive region 15 and the second conductive region 25 are joined by the reaction products originating from the organic material. Furthermore, the organic material is supplied between the first and second junctions to react the hydroxyl groups of the first organic material with the silanol groups of the first junction (etherification by dehydration), and to react the alkenyl groups of the organic material with the hydrosilyl groups of the second junction (hydrosilylation). As a result, the reaction product derived from the first organic material chemically bonds to the Si atoms of the first junction and the Si atoms of the second junction, and the first junction and the second junction are joined by the reaction product derived from the organic material.

[0121] More specifically, an organic material is supplied and the hydroxyl groups of the organic material react with the hydroxyl groups of the first activated region 15a (first step). At this time, the hydroxyl groups of the organic material may also react with the silanol groups of the first junction. Subsequently, it is preferable to arrange the first conductive region 15 and the second conductive region 25 opposite each other and react the hydrogen atoms of the second activated region 25a with the alkenyl groups of the organic material (second step). At this time, the alkenyl groups of the organic material may also react with the hydrosilyl groups of the second junction. According to this procedure, water is produced as a byproduct in the first step reaction, but this byproduct can be removed without being trapped between the first silicon substrate 10 and the second silicon substrate 20, and since no byproducts are produced in the second step reaction, the formation of voids due to byproducts can be avoided.

[0122] As an example, the reaction of a fluoroalkyl compound having an alkenyl group at one end and a hydroxyl group at the other end is shown below. In the following, Cu is described as an example of the first and second conductive regions 15 and 25. Furthermore, although only the reactions in the first and second active regions 15a and 25a are described below, the same reactions can occur in the first and second junctions as in the first and second active regions 15a and 25a. The same applies to fluoropolyether group-containing compounds having an alkenyl group at one end and a hydroxyl group at the other end. [ka]

[0123] To obtain higher bonding strength, the above organic material is preferably a linear compound having an alkenyl group and a hydroxyl group at both ends, but is not limited thereto.

[0124] Furthermore, in this example, since a material is used in which a hydroxyl group is present on the surface of the first activated region 15a and a silanol group is present on the surface of the first junction, and a hydrogen atom is present on the surface of the second activated region 25a and a hydrosilyl group is present on the surface of the second junction, when an organic material (preferably linear) having a hydroxyl group and an alkenyl group at both ends is used, it is possible to avoid the reaction product chemically bonding to two or more Si atoms within the same silicon substrate, and thus an even higher bonding strength can be obtained.

[0125] (Case 4) In the third example above, the organic material chemically reacted with the first and second conductive regions 15 and 25 to connect them. However, in this fourth example, a portion A exists on at least a part of the surface of the first and second conductive regions 15 and 25, and no chemical reaction occurs between the first and second conductive regions 15 and 25 and portion A. In other words, the first and second conductive regions 15 and 25 are not chemically connected via portion A. Otherwise, it has the same configuration as the third example above, and portion A has the same configuration as the second example above.

[0126] The above describes examples of using substituted or unsubstituted hydrocarbon compounds having an alkenyl group at one terminal end and a hydroxyl group at the other terminal as the organic material. However, substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group, isocyanate group, epoxy group, amino group, or acid anhydride group in place of / in addition to the hydroxyl group may also be used. Hydroxyl groups, hydrolyzable silyl groups, isocyanate groups, epoxy groups, amino groups, and acid anhydride groups can all function as reactive groups for silanol groups. (Note that substituted or unsubstituted hydrocarbon compounds having an alkenyl group at one terminal end and a hydroxyl group at the other terminal may be the same as substituted or unsubstituted hydrocarbon compounds having two hydrolyzable silyl groups at two terminal ends, as detailed in (iii) below, except that they have an alkenyl group at at least one terminal.)

[0127] • The first example (fifth example) using organic materials of (iii) In this example, first and second conductive regions 15 and 25 are formed on parts of the surfaces of the first silicon substrate 10 and the second silicon substrate 20. The first and second conductive regions have first and second activated regions 15a and 25a, in which at least a portion is activated. For example, the first and second activated regions 15a and 25a may have hydroxyl groups on their surfaces.

[0128] Furthermore, the first silicon substrate 10 and the second silicon substrate 20 may be those in which silanol groups (-Si-OH) are present on the surface of the first and second junctions (which in this example are silicon oxide portions). The first silicon substrate 10 and the second silicon substrate 20, which have silanol groups on the surface of the first and second junctions that are silicon oxide portions, do not require any special surface treatment, but may be obtained by surface treatment that generates the silanol groups as described above, if necessary.

[0129] As the above organic material, a substituted or unsubstituted hydrocarbon compound having hydrolyzable silyl groups at two terminal ends is used. Such a compound may have two or more terminal ends, and may have hydrolyzable silyl groups at any two or more terminal ends. Such a compound may be fluorine-substituted, in other words, it may be a fluorine-containing silane compound such as a fluoroalkyl compound or a fluoropolyether group-containing compound having hydrolyzable silyl groups at two terminal ends.

[0130] The above fluorine-containing silane compounds are, for example, those of the following formula (11): [ka] [In formula: R F2 -Rf 2 p -R F r -O q -and; Rf 2 C may be substituted with one or more fluorine atoms. 1-20 It is an alkylene group; R Fis, in each occurrence independently, the following formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - (wherein, R Fa is, in each occurrence independently, a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f attached is arbitrary in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.) is a group represented by; p is 0 or 1; q is 0 or 1; r is 0 or 1; however, either p or r is 1; R Si is, in each occurrence independently, the following formula (S1), (S2), (S3), (S4) or (S5):

Chemical formula

[0131] A hydrolyzable group refers to a group that can undergo hydrolysis, preferably -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , or halogen. R j C is either substituted or non-substituted. 1-4 Alkyl alkyl groups, preferably unsubstituted C 1-4 It is an alkyl group. 1-4 The alkyl group is preferably an ethyl group or a methyl group, more preferably a methyl group.

[0132] The hydrolyzable silyl group may, in its simplest form, be an alkoxysilyl group. The number of alkoxy groups in the alkoxysilyl group is between 1 and 3, for example, 3. The number of carbon atoms in the alkoxy group may be between 1 and 4, particularly 2 or less, preferably 1.

[0133] The above unsubstituted silane compounds include, for example, R k 3Si-(CH2) n35 -SiR k It may be a compound represented by 3. k Each of these independently represents a group that can undergo hydrolysis, and preferably each independently represents -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , or halogen. R j C is either substituted or non-substituted. 1-4 Alkyl alkyl groups, preferably unsubstituted C 1-4 It is an alkyl group. 1-4 The alkyl group is preferably an ethyl group or a methyl group, more preferably a methyl group. n35 is an integer from 1 to 18.

[0134] Unless otherwise specified, the above explanation may apply.

[0135] The above organic material is supplied between the first silicon substrate 10 and the second silicon substrate 20 and allowed to react. The organic material may react with the first and second active regions 15a and 25a. Specifically, the alkenyl group of the organic material may react with the hydrogen atoms of the first and second active regions 15a and 25a, respectively. Alternatively, the organic material may be supplied between the first and second junctions to react the hydrolyzable silyl group of the organic material with the silanol group of the first and second junctions (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation by de-alcoholization). As a result, the first reaction product derived from the organic material chemically bonds with the metal of the first and second conductive regions 15 and 25 and / or the Si atoms of the first and second junctions. In this reaction, for example, an alcohol is produced as a byproduct, but as mentioned above, its carbon number can be small, and it can be effectively removed to the outside through the gaps in the reaction products between the first silicon substrate 10 and the second silicon substrate 20, thus reducing the formation of voids originating from the byproduct.

[0136] The above-mentioned organic material may be placed on the first activated region 15a and reacted with it. After that, the surface of the layer formed from the organic material may be washed with water or an aqueous organic solvent, and then the second activated region 25a may be placed on the layer. This allows hydrolyzable silyl groups present on the surface to be converted to silanols, and the formation of by-products such as hydrolyzable silyl groups or voids derived from by-products can be suppressed. The organic material may be applied to the surface of the second activated region 25a instead of the surface of the first activated region 15a.

[0137] The reaction may be carried out in one step with the organic material sandwiched between the first silicon substrate 10 and the second silicon substrate 20, or it may be carried out in two steps, by applying the organic material to either the first silicon substrate 10 or the second silicon substrate 20 to partially allow the reaction to proceed, and then placing the other substrate on top of the organic material to further allow the reaction to proceed.

[0138] As an example, the reaction using an alkyl compound having trimethoxysilyl groups at both ends is shown below. Below, an example of carrying out the reaction in two stages as described above is also shown. In the following, Cu is listed as an example of the first and second conductive regions 15 and 25. Furthermore, although only the reactions in the first and second active regions 15a and 25a are described below, the first and second junctions can also react in the same way as the first and second active regions 15a and 25a.

[0139] [ka]

[0140] [ka]

[0141] To obtain higher bonding strength, the above organic material is preferably a linear compound having hydrolyzable silyl groups at both ends, but is not limited thereto.

[0142] • A second example (sixth example) using organic materials of (iii) This example will focus on the differences from the first example using the organic material described in (iii) above, and unless otherwise noted, the same explanation as in the first example may apply.

[0143] As the above organic material, a substituted or unsubstituted hydrocarbon compound having isocyanate groups at two terminal ends is used. Such a compound may have two or more terminal ends, and may have isocyanate groups at any two or more terminal ends.

[0144] The above organic material is supplied between the first silicon substrate 10 and the second silicon substrate 20, and the isocyanate groups of the organic material react with the hydroxyl groups of the first and second active regions 15a and 25a. As a result, the first reaction product derived from the organic material chemically bonds to the metal atoms of the first and second conductive regions 15 and 25, and the first conductive region 15 and the second conductive region 25 are joined by the reaction product derived from the organic material. Furthermore, the isocyanate groups of the organic material may be reacted with the silanol groups of the first and second junctions (forming a urethane bond). As a result, the first reaction product derived from the organic material chemically bonds to the Si atoms of the first and second junctions, and the first and second junctions are joined by the first reaction product derived from the first organic material. With this reaction, no by-products are produced, so the problem of void formation due to by-products can be fundamentally resolved.

[0145] The above unsubstituted silane compounds include, for example, OCN-(CH2) n35 It may be a compound represented as -NCO, where n35 is an integer between 1 and 18.

[0146] One embodiment shows the reaction when an alkyl compound having isocyanate groups at two terminal ends is used. In the following, Cu is described as an example of the first and second conductive regions 15 and 25. Furthermore, although only the reactions in the first and second active regions 15a and 25a are described below, reactions may also occur in the first and second junctions in the same manner as in the first and second active regions 15a and 25a. In this embodiment, similar to the alkyl compound having trimethoxysilyl groups at two terminal ends, one isocyanate group may react first, and then the other isocyanate group may react.

[0147] [ka]

[0148] As another embodiment, the reaction using a compound having a phosphate group is shown below. In the following example, CH3PO(OH)2 is used as the compound having a phosphate group, but any compound having a phosphate group is acceptable, and compounds with other structures may also be used. For example, a compound containing two or more phosphate groups, such as 1,6-hexanediphosphonic acid, may be used. In the case of a compound containing two or more phosphate groups, one phosphate group may react with the first conductive region 15, and the other phosphate group may react with the second conductive region 25. In the following, Cu is described as an example of the first and second conductive regions 15 and 25. In the following, only the reactions in the first and second activated regions 15a and 25a are described, but reactions similar to those in the first and second junctions can also occur in the first and second activated regions 15a and 25a.

[0149] [ka]

[0150] Furthermore, as shown below, the first activated region 15a may first react with the compound having a phosphate group, and then the second conductive region 25 may react with the compound having a phosphate group.

[0151] [ka]

[0152] • A third example (seventh example) using organic materials of (iii) This example will focus on the differences from the first example, which uses the organic material described in (iii) above, and unless otherwise noted, the same explanations as in the first example may apply.

[0153] As the above organic material, a substituted or unsubstituted hydrocarbon compound having acid anhydride groups at two terminal ends is used. Such a compound may have two or more terminal ends, and may have acid anhydride groups at any two or more terminal ends.

[0154] The above organic material is supplied between the first silicon substrate 10 and the second silicon substrate 20, and the acid anhydride groups of the organic material react with the hydroxyl groups of the first and second active regions 15a and 25a. As a result, the reaction products derived from the organic material chemically bond to the metal atoms of the first and second active regions 15a and 25a, and the first active region 15a and the second active region 25a are joined by the reaction products derived from the organic material. Furthermore, the acid anhydride groups of the organic material react with the silanol groups of the first and second junctions. As a result, the first reaction product derived from the organic material chemically bonds to the Si atoms of the first junction and the Si atoms of the second junction, and the first junction and the second junction are joined by the reaction products derived from the organic material. With this reaction, no by-products are produced, so the problem of void formation due to by-products can be fundamentally resolved.

[0155] As an example, the reaction when using an alkyl compound having acid anhydride groups at both terminal ends is shown below. In the following, Cu is described as an example of the first and second conductive regions 15 and 25. Furthermore, although only the reactions in the first and second active regions 15a and 25a are described below, reactions can also occur in the first and second junctions in a similar manner to those in the first and second active regions 15a and 25a.

[0156] [ka]

[0157] R represents an alkyl group, for example, -(CH2) n36 It is represented by -. n36 is an integer from 1 to 18. Alternatively, the first activated region 15a may react with the alkyl compound having an acid anhydride group first, and then the second conductive region 25 may react with the compound having an acid anhydride group. Similarly, in the following steps, the reaction may occur with the first activated region 15a first, followed by a reaction with the second conductive region 25.

[0158] (Case 8) In the above examples 5 to 7, the organic material chemically reacted with the first and second conductive regions 15 and 25 to connect them. However, in this example 8, a portion A exists on at least a part of the surface of the first and second conductive regions 15 and 25, and no chemical reaction occurs between the first and second conductive regions 15 and 25 and portion A. In other words, the first and second conductive regions 15 and 25 are not chemically connected via portion A. Otherwise, it has the same configuration as in example 5, and portion A has the same configuration as in example 2.

[0159] The above describes the first to third examples of using substituted or unsubstituted hydrocarbon compounds having hydrolyzable silyl groups, isocyanate groups, or acid anhydride groups at two terminal ends as the organic material. However, substituted or unsubstituted hydrocarbon compounds having hydroxyl groups, epoxy groups, and / or amino groups may be used instead of / in addition to the hydrolyzable silyl groups, isocyanate groups, or acid anhydride groups. Hydroxyl groups, hydrolyzable silyl groups, isocyanate groups, epoxy groups, amino groups, and acid anhydride groups can all function as reactive groups for silanol groups. These reactive groups at at least two terminal ends may be the same or different.

[0160] • Example using organic materials (iv) (Case 9) This example will focus on the differences from the first example using the organic material described in (iii) above, and unless otherwise noted, the same explanation as in the first example may apply.

[0161] Silsesquioxane is used as the organic material. Silsesquioxane refers to a silicon-containing polymer (polysiloxane) whose main chain is composed of siloxane bonds, and whose basic structural unit is the T unit. Silsesquioxane is (R'SiO 1.5 ) nIt can be represented by the empirical formula (where R' can be any organic group and n is 6 or greater), and may have random structures, ladder structures, cage structures (complete cage structures, incomplete cage structures), etc. Examples of R' being a hydrocarbon group include methyl, ethyl, propyl (n-propyl, i-propyl), butyl (n-butyl, i-butyl, t-butyl, sec-butyl), pentyl (n-pentyl, i-pentyl, neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, i-hexyl, cyclohexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl (n-octyl, i-octyl, t-octyl, etc.), nonyl (n-nonyl, i-nonyl, etc.), decyl (n-decyl, i-decyl, etc.), and Acyclic or cyclic aliphatic hydrocarbon groups such as n-undecyl (n-undecyl, i-undecyl, etc.) and dodecyl (n-dodecyl, i-dodecyl, etc.); acyclic and cyclic alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norborneylethyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, styrenyl; and aralkyl groups such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl. Other examples include ara-alkenyl groups such as PhCH=CH- groups, aryl groups such as phenyl groups, tolyl groups, or xylyl groups, and substituted aryl groups such as 4-aminophenyl groups, 4-hydroxyphenyl groups, 4-methoxyphenyl groups, and 4-vinylphenyl groups.

[0162] The above organic material is supplied between the first silicon substrate 10 and the second silicon substrate 20 to react the siloxane bonding sites of the organic material with the hydroxyl groups of the first and second active regions 15a and 25a. As a result, the first reaction product derived from the organic material chemically bonds to the metal atoms of the first and second conductive regions 15 and 25, and the first conductive region 15 and the second conductive region 25 are joined by the first reaction product derived from the organic material. Furthermore, the organic material is supplied between the first and second junctions to react (cleavage and addition of siloxane bonds) between the siloxane bonding sites of the organic material and the silanol groups of the first and second junctions. As a result, the reaction product derived from the first organic material chemically bonds to the Si atoms of the first and second junctions, and the first and second junctions are joined by the reaction product derived from the organic material. This reaction does not produce byproducts, thus fundamentally eliminating the problem of void formation resulting from byproducts.

[0163] Exemplary example, T8 silsesquioxane ((R'SiO)) having a complete cage structure. 1.5 The reaction when using 8) is shown below. In the following, Cu is described as an example of the first and second conductive regions 15 and 25. In addition, although only the reactions in the first and second activated regions 15a and 25a are described below, the same reactions can occur in the first and second junctions as in the first and second activated regions 15a and 25a.

[0164] [ka]

[0165] To obtain higher bonding strength, the above organic material is preferably a cage-type silsesquioxane with a clearly defined molecular structure, but is not limited to this.

[0166] (Case 10) In the ninth example above, the organic material chemically reacted with the first and second conductive regions 15 and 25 to connect them. However, in this tenth example, a portion A exists on at least a part of the surface of the first and second conductive regions 15 and 25, and no chemical reaction occurs between the first and second conductive regions 15 and 25 and portion A. In other words, the first and second conductive regions 15 and 25 are not chemically connected via portion A. Otherwise, it has the same configuration as the ninth example above, and portion A has the same configuration as the second example above.

[0167] The above describes an example of using silsesquioxane as the organic material, but derivatives of silsesquioxane may also be used. The derivatives of silsesquioxane can be any compound derived from silsesquioxane and may have arbitrary substituents, modifying groups, functional groups, etc.

[0168] (Reaction conditions for organic materials) The reaction conditions may vary depending on the organic material used, but the specified temperature may be, for example, 200°C or lower, particularly 120°C or lower, and more particularly 80°C or lower, and for convenience, room temperature (typically 10°C to 40°C). According to this embodiment, since bonding can be performed at such a relatively low temperature, bonding misalignment caused by thermal expansion of the first and second silicon substrates 10 and 20 can be reduced, and bonding can be performed with high precision. The pressure (absolute pressure, the same applies to other pressure values ​​in this specification) is, for example, 10 -8 Pa or higher, especially 10 -5 Pa or higher, especially 10 -1 Pa or higher, and especially 10 2 It can be above Pa, and for simplicity, normal pressure (typically about 1.01 × 10⁻⁶). 5 It may be Pa). When applying reduced pressure, for example 10 5 It can be less than Pa, especially 10 4 Pa or less, especially 10 3 It may be less than Pa.

[0169] Through the above manufacturing method, a laminate 40 is formed having a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30 between the first silicon substrate 10 and the second silicon substrate 20. In other words, the laminate 40 is A first silicon substrate 10 having a first conductive region 15 on at least a part of its surface, A second silicon substrate 20 located on the side having the first conductive region 15, An adhesive layer 30 is located between the first silicon substrate 10 and the second silicon substrate 20, and bonds the surface of the first silicon substrate 10 having the first conductive region 15 to the second silicon substrate 20. It has, The first silicon substrate 10 and the second silicon substrate 20 are electrically conductive.

[0170] The adhesive layer 30 may consist of two or more layers.

[0171] Preferably, the conductivity measured in the adhesive layer 30 placed on the first silicon substrate 10 is 1.0 × 10⁻¹⁰. -2 ~5.0×10 2 It is in the range of pA, more preferably 1.0 × 10 -1 ~1.9×10 2 It is within the range of pA. Note that the conductivity was measured using SSRM.

[0172] Preferably, the resistivity is 1.5 × 10 -8 ~2.0×10 5 It is in the range of Ω·m, and more preferably 1.6 × 10 -8 ~1.6×10 4 It is within the range of Ω·m. The resistivity was measured as follows: First, two first silicon substrates 10 are prepared. The conductivity (average current value) of the first first silicon substrate 10 is measured, and the resistance value R(b)[Ω] of the first silicon substrate 10 is determined based on voltage V[V] = current I[pA] × resistance R[Ω]. After surface treatment is performed on the second first silicon substrate 10 as necessary, an organic material, which is the raw material for the adhesive layer 30, is deposited to form a sample with a film deposited on the first silicon substrate 10. The conductivity of the sample is measured, and the resistance value R(all)[Ω] of the sample is determined. Since R(all) = resistance value R(a) + R(b) of the film-deposited portion, the value of R(a) is obtained. Then, R(a)[Ω] = resistivity of the sample [Ω·m] × film thickness of the sample [m] / effective probe area [m] 2 The resistivity of the sample is determined based on [the given formula]. Conductivity is measured using SSRM.

[0173] <Second Embodiment> Figure 2 is a schematic cross-sectional view showing a portion of the cross-section of the laminate 40A of the second embodiment. In the first embodiment, there is an adhesive layer 30 between the first conductive region 15 and the second conductive region 25, but in the second embodiment, there is an adhesive layer 30A between the first conductive region 15 and the second conductive region 25, and the adhesive layer 30A has a first adhesive portion 31A located on the first conductive region 15 and a second adhesive portion 32A located on the second conductive region 25, and at least a portion of the second conductive region 25 has a second activated region 25a. The explanation will focus on this difference, and unless otherwise specified, the other aspects are the same as described above.

[0174] (Adhesive layer 30A) As shown in Figure 2, the adhesive layer 30A has a first adhesive portion 31A and a second adhesive portion 32A provided on the second silicon substrate 20 and chemically bonded to the first adhesive portion 31A. The first adhesive portion 31A and the second adhesive portion 32A are joined by a reaction. During the chemical bonding reaction, heating and / or pressurization or depressurization is performed as necessary. The heating, pressurization, and depressurization conditions are the same as in the first embodiment. The physical properties of the adhesive layer 30A are the same as those of the adhesive layer 30 in the first embodiment.

[0175] The thickness of the adhesive layer 30A can be extremely thin. The thickness of the adhesive layer 30A may be, for example, 10 nm or less, and may be particularly 8 nm or less, 5 nm or less, 3 nm or less, or 1.5 nm or less. The lower limit of the thickness of the adhesive layer 30A is not particularly limited, but may be, for example, 1 nm or more. The above thickness can be measured in the same manner as in the first embodiment.

[0176] The first adhesive portion 31A contains a first reaction product derived from a first organic material that can react with the first activated region 15a. That is, the composition of the first reaction product depends on the structure of the first organic material. The first adhesive portion 31A can be obtained by applying the first organic material to the first activated region 15a and, if necessary, to the first joint, and then drying. The drying can be carried out in the same manner as in the first embodiment.

[0177] The second adhesive portion 32A contains a second reaction product derived from a second organic material that can react with the second activated region 25a. That is, the composition of the second reaction product depends on the structure of the second organic material. The second adhesive portion 32A can be obtained by applying the second organic material to the second activated region 25a and, if necessary, to the second joint, and then drying it. The drying can be carried out in the same manner as in the first embodiment.

[0178] That is, the second silicon substrate 20 has a second conductive region 25 on at least a portion of its surface, The adhesive layer 30A is provided on a second activated region 25a, which is formed by activating at least a portion of the surface of the second silicon substrate 20 on the side facing the second conductive region 25, and contains a second reaction product derived from the second organic material.

[0179] For convenience, the first adhesive portion 31A and the second adhesive portion 32A are used, but they do not necessarily have to form an interface, and they may be mixed together. Even if an interface is formed, the interface does not have to be a uniform surface and may have irregularities.

[0180] (1st and 2nd organic materials) The first organic material has a functional group at one end that reacts with the first conductive region 15 or the first junction, and a functional group at the other end that reacts with the second organic material. The second organic material has a functional group at one end that reacts with the second conductive region 25 or the second junction, and a functional group at the other end that reacts with the first organic material. This bonds the first silicon substrate 10 and the second silicon substrate 20. Note that only some of these functional groups may react. Although the above describes a case where one organic material has two functional groups, the organic material may have three or more functional groups.

[0181] The first organic material and the second organic material may each be used as a composition. The composition has the same configuration as in the first embodiment.

[0182] The specific methods for supplying and joining the first and second organic materials (or compositions containing the first and second organic materials) may be appropriately selected depending on the organic materials used. Generally speaking, after supplying the first and second organic materials, the reaction may proceed by maintaining the first silicon substrate 10 and the second silicon substrate 20 under predetermined reaction conditions (particularly a predetermined temperature) with the first and second organic materials interposed between them.

[0183] More specifically, for example, a first organic material (which may be a composition) is applied (e.g., by coating, spraying, printing, etc.) to the surface of the first silicon substrate 10 having the first conductive region 15 (the surface having at least a portion of the first activated region 15a). Similarly, a second organic material (which may be a composition) is applied to the surface of the second silicon substrate 20 having the second conductive region 25 (the surface having at least a portion of the second activated region 25a). After that, cleaning and / or drying may be performed as necessary. Cleaning and drying may be performed using the same methods as described above, and if an organic material containing fluorine is used, pre-cleaning with a fluorine-based solvent may be performed.

[0184] Subsequently, the first silicon substrate 10 and the second silicon substrate 20 are aligned so that the first conductive region 15 and the second conductive region 25 face each other, and the first silicon substrate 10 and the second silicon substrate 20 are brought into close contact with the first organic material interposed between the first conductive region 15 and the second conductive region 25. The first silicon substrate 10 and the second silicon substrate 20, brought into close contact, are maintained under predetermined reaction conditions (particularly a predetermined temperature), and the reaction is allowed to proceed during this time. After that, annealing treatment may be performed as necessary.

[0185] The physical properties of the first and second organic materials can be those of the first organic material in the first embodiment.

[0186] The first and second organic materials may include at least one selected from the group consisting of (v) to (vi) below. Such organic materials may use one compound or a combination of two or more compounds. Furthermore, while the first activation region 15a and the second activation region 25a are described as being paired, and the first junction and the second junction are described as being paired, the combination is not limited to these. For example, the reaction product formed from the first and second organic materials may have the first activation region 15a and the second junction linked, or the first junction and the second activation region 25a joined. (v) A combination of a hydrolyzable hydrosilane, or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal and a hydrosilyl group at the other terminal, and a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal and an alkenyl group at the other terminal. (vi) A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal and an alkyl group at the other terminal.

[0187] The details are described below.

[0188] • Example using organic materials (v) (Case 11) This example will focus on the differences from the first example using the organic material described in (iii) above, and unless otherwise noted, the same explanation as in the first example may apply.

[0189] The above-mentioned organic material is a combination of the first organic material and the second organic material.

[0190] The first organic material may be a hydrolyzable hydrosilane, or a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal and a hydrosilyl group at the other terminal, and may optionally be a mixture thereof. A hydrolyzable hydrosilane may have one Si atom with H and one or more hydrolyzable groups. A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal and a hydrosilyl group at the other terminal may have two or more terminals, and may have a hydrolyzable silyl group at any one or more terminals and a hydrosilyl group at any one or more terminals. A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal and a hydrosilyl group at the other terminal may be the same as the substituted or unsubstituted hydrocarbon compound having two hydrolyzable silyl groups at two terminals described in detail in (iii) above, except that the other terminal has a hydrosilyl group.

[0191] The second organic material is a substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal end and an alkenyl group at the other terminal end. Such a compound may have two or more terminal ends, and may have a hydrolyzable silyl group at any one or more terminal ends and an alkenyl group at any one or more terminal ends. A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal end and an alkenyl group at the other terminal end may be the same as the substituted or unsubstituted hydrocarbon compound having two hydrolyzable silyl groups at two terminal ends described in detail in (iii) above, except that the other terminal end has an alkenyl group.

[0192] First, the first organic material is supplied to the first silicon substrate 10 and reacted with the hydroxyl group in the first activated region 15a. The first organic material is then supplied to the second silicon substrate 20 and reacted with the hydroxyl group in the second activated region 25a. Alternatively, the hydrolyzable silyl group of the first organic material may be reacted with the silanol group of the first junction (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation may occur by de-alcoholization), or the hydrolyzable silyl group of the second organic material may be reacted with the silanol group of the second junction (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation may occur by de-alcoholization).

[0193] Subsequently, the first conductive region 15 and the second conductive region 25 are positioned facing each other, with intermediates derived from the first organic material and intermediates derived from the second organic material located between them, and these intermediates are reacted (hydrosilylated). As a result, the reaction products derived from the first organic material and the second organic material react with the metal atoms of the first and second conductive regions 15 and 25, and the reaction products derived from the first and second organic materials are bonded to the first and second conductive regions 15 and 25. Furthermore, the first and second organic materials chemically bond to the Si atoms of the first and second junctions, and the first and second junctions can be joined by the reaction products derived from the first and second organic materials. Although alcohol is produced as a byproduct in the above reaction, its carbon number can be small as described above, and it can be effectively removed before the first silicon substrate 10 and the second silicon substrate 20 are positioned facing each other, thus reducing the formation of voids derived from byproducts.

[0194] For example, as the first organic material, R k 3Si-(CH2) n37 -CH=CH2 is used as a second organic material in SiHR k 3 can be used. k Each of these terms independently represents a group that can undergo hydrolysis, and specifically has the same meaning as described above. n37 is an integer from 0 to 18, for example, 0.

[0195] Specifically, the reaction when vinyltrimethoxysilane is used as the first organic material and trimethoxyhydrosilane is used as the second organic material is shown below. In the following, Cu is listed as an example of the first and second conductive regions 15 and 25. Furthermore, although only the reactions in the first and second active regions 15a and 25a are described below, reactions can also occur in the first and second junctions in a similar manner to those in the first and second active regions 15a and 25a.

[0196] [ka]

[0197] (Case 12) In the 11th example above, the first organic material reacted with the first conductive region 15, and the second organic material reacted with the second conductive region 25, and the reaction between the first and second organic materials linked the first conductive region 15 and the second conductive region 25. However, in this 12th example, a portion A exists on at least a part of the surface of the first and second conductive regions 15 and 25, and no chemical reaction occurs between the first and second conductive regions 15 and 25 and portion A. In other words, the first and second conductive regions 15 and 25 are not chemically linked via portion A. Otherwise, it has the same configuration as the 11th example above.

[0198] Specifically, when vinyltrimethoxysilane is used as the first organic material and trimethoxyhydrosilane is used as the second organic material, the first organic material reacts with the Si atoms of the first junction, and the second organic compound bonds to the Si atoms of the second junction. Subsequently, the first junction and the second junction can be joined by reaction products derived from the first and second organic materials.

[0199] Part A is located between the metal atoms of the first conductive region 15 and the metal atoms of the second conductive region 25. Part A is located on at least a portion of the surface between the first and second conductive regions 15 and 25. Part A is unreacted with the metal atoms of the first conductive region 15 and the metal atoms of the second conductive region 25. The entire surface of the first conductive region 15 and the second conductive region 25 may have part A, or only a portion may have part A, and the other portion may not have part A. Part A has the same configuration as described above.

[0200] • Example of using organic materials (vi) (Case 13) This example will focus on the differences from the first example using the organic material described in (iii) above, and unless otherwise noted, the same explanation as in the first example may apply.

[0201] As the first and second organic materials described above, substituted or unsubstituted hydrocarbon compounds are used, each having a hydrolyzable silyl group at one terminal end and an alkyl group at the other terminal end. Such compounds may have two or more terminal ends, and may have a hydrolyzable silyl group at any one or more terminal ends and an alkyl group at any one or more terminal ends. A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal end and an alkyl group at the other terminal end may be the same as the substituted or unsubstituted hydrocarbon compound having two hydrolyzable silyl groups at two terminal ends described in detail in (iii) above, except that the other terminal end has an alkyl group. The second organic material may have the same configuration as the first organic material, or it may have a different configuration.

[0202] The first organic material is supplied to the first silicon substrate 10 and reacted with the hydroxyl groups in the first activated region 15a. The first organic material is also supplied to the second silicon substrate 20 and reacted with the hydroxyl groups in the second activated region 25a. Alternatively, the first organic material may be supplied to the first junction and reacted with the hydrolyzable silyl groups of the first organic material and the silanol groups of the first junction (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation may occur by de-alcoholization), or the second organic material may be supplied to the second junction and reacted with the hydrolyzable silyl groups of the second organic material and the silanol groups of the second junction (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation may occur by de-alcoholization).

[0203] Subsequently, the first conductive region 15 and the second conductive region 25 are positioned facing each other, with intermediates derived from the first organic material and intermediates derived from the second organic material located between them, and these intermediates are reacted (radical reaction). At this time, the intermediates derived from the first organic material and intermediates derived from the second organic material located between the first and second junctions are also reacted in the same manner. The reaction between the intermediates (radical reaction) may be carried out by, for example, ultraviolet irradiation, an ion beam, or a weak plasma. As a result, the reaction products derived from the first and second organic materials react with the metal atoms of the first and second conductive regions 15 and 25 and / or the Si atoms of the first and second junctions, and the reaction products derived from the first and second organic materials bond with the first and second conductive regions 15 and 25 and / or the first and second junctions. Although alcohol is produced as a byproduct in this reaction, its carbon number can be small as described above, and it can be effectively removed before the first silicon substrate 10 and the second silicon substrate 20 are placed facing each other, thus reducing the formation of voids originating from the byproduct.

[0204] For example, as the first organic material and the second organic material, R k 3Si(CH2) n38 H can be used. kEach of these terms independently represents a group that can undergo hydrolysis, and specifically has the same meaning as described above. n38 is an integer between 2 and 18, for example, 0.

[0205] Specifically, the reaction when ethyltrimethoxysilane is used as the first and second organic materials is shown below. In the following, Cu is listed as an example of the first and second conductive regions 15 and 25. Furthermore, although only the reactions in the first and second active regions 15a and 25a are described below, reactions can also occur in the first and second junction in a similar manner to those in the first and second active regions 15a and 25a.

[0206] [ka]

[0207] By following the above manufacturing method, a laminate 40A is formed comprising a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30A between the first silicon substrate 10 and the second silicon substrate 20, wherein the adhesive layer 30A has a first adhesive portion 31A and a second adhesive portion 32A.

[0208] Through the above manufacturing method, a laminate 40 is formed comprising a first silicon substrate 10, a second silicon substrate 20, and an adhesive layer 30A between the first silicon substrate 10 and the second silicon substrate 20. In other words, the laminate 40A is A first silicon substrate 10 having a first conductive region 15 on at least a part of its surface, A second silicon substrate 20 located on the side having the first conductive region 15 and having a second conductive region 25 on at least a portion of its surface, An adhesive layer 30A is located between the first silicon substrate 10 and the second silicon substrate 20, and bonds the surface of the first silicon substrate 10 having the first conductive region 15 to the second conductive region 25 of the second silicon substrate 20, It has, The adhesive layer 30A has a reaction product between a first adhesive portion 31A located on the first conductive region 15 and a second adhesive portion 32A located on the first conductive region 15. The first silicon substrate 10 and the second silicon substrate 20 are electrically conductive.

[0209] The physical properties of the laminate 40A are the same as those of the laminate 40 in the first embodiment.

[0210] (Case 14) In the 13th example above, the first organic material reacts with the first conductive region 15, and the second organic material reacts with the second conductive region 25, thereby chemically linking the first and second conductive regions 15 and 25. However, in this 14th example, a portion A exists on at least a part of the surface of the first and second conductive regions 15 and 25, and no chemical reaction occurs between the first and second conductive regions 15 and 25 and portion A. In other words, the first and second conductive regions 15 and 25 are not chemically linked via portion A. Otherwise, it has the same configuration as the 13th example above, and portion A has the same configuration as the 2nd example above.

[0211] (modified version) Figure 3 is a schematic cross-sectional view showing a portion of the cross-section of the modified laminate 40B. Unlike the second embodiment, the modified form has a first adhesive portion 31B on the first conductive region 15, a second adhesive portion 32B on the second conductive region 25, and a third adhesive portion 33B between the first adhesive portion 31B and the second adhesive portion 32B, with the first adhesive portion 31B and the third adhesive portion 33B and the second adhesive portion 32B being bonded together. That is, the adhesive layer 30B consists of three layers: the first adhesive portion 31B, the third adhesive portion 33B, and the second adhesive portion 32B. This differing configuration will be explained below. Other configurations are the same as in the first embodiment and will not be explained.

[0212] (Adhesive layer 30B) The adhesive layer 30B has, in order, a first adhesive portion 31B, a third adhesive portion 33B, and a second adhesive portion 32B. The first adhesive portion 31B is provided on the first silicon substrate 10, the second adhesive portion 32B is provided on the second silicon substrate 20, and the third adhesive portion 33 can react with the first adhesive portion 31B at one end and with the second adhesive portion 32B at the other end. That is, the third adhesive portion 33 can react as a connecting portion between the first adhesive portion 31B and the second adhesive portion 32B. The above reactions are carried out by heating and / or pressurizing or depressurizing as necessary. The heating, pressurizing, and depressurizing conditions are the same as in the first embodiment.

[0213] The thickness of the adhesive layer 30B can be extremely thin. The thickness of the adhesive layer 30B may be, for example, 10 nm or less, and may be particularly 8 nm or less, 5 nm or less, 3 nm or less, or 1.5 nm or less. The lower limit of the thickness of the adhesive layer 30B is not particularly limited, but may be, for example, 1 nm or more. The above thickness can be measured in the same manner as in the first embodiment.

[0214] The first adhesive portion 31B contains a first reaction product derived from a first organic material that can react with the first activated region 15a. That is, the composition of the first reaction product depends on the structure of the first organic material. The first adhesive portion 31B can be obtained by applying the first organic material to the first activated region 15a and, if necessary, to the first joint, and then drying. The drying can be carried out in the same manner as in the first embodiment.

[0215] The second adhesive portion 32B contains a second reaction product derived from a second organic material that can react with the second activated region 25a. That is, the composition of the second reaction product depends on the structure of the second organic material. The second adhesive portion 32B can be obtained by applying the second organic material to the second activated region 52a and, if necessary, to the second joint, and then drying. The drying can be carried out in the same manner as in the first embodiment.

[0216] The third adhesive portion 33B contains a reaction product derived from a third organic material that reacts with the first organic material and the second organic material. The third adhesive portion 33B can be obtained by applying the third organic material to the first reaction product and, if necessary, to the first joint, and then drying. The drying can be carried out in the same manner as in the first embodiment.

[0217] For convenience, these will be referred to as the first adhesive portion 31A, the second adhesive portion 32A, and the third adhesive portion 33B, but they do not necessarily have to form an interface, and they may be mixed together. Even if an interface is formed, the interface does not have to be a uniform surface and may have irregularities.

[0218] (Organic materials from the first to the third stage) The first organic material has a functional group at one end that reacts with the first conductive region 15B or the first junction, and a functional group at the other end that reacts with the third organic material. The second organic material has a functional group at one end that reacts with the second conductive region 25B or the second junction, and a functional group at the other end that reacts with the third organic material. The third organic material has a functional group at one end that can react with the first organic material, and a functional group at the other end that can react with the second organic material. This bonds the first silicon substrate 10 and the second silicon substrate 20. Note that only some of these functional groups may react. Although the above describes a case where one organic material has two functional groups, the organic material may have three or more functional groups.

[0219] The first to third organic materials may each be used as a composition. The composition has the same configuration as in the first embodiment.

[0220] The specific methods for supplying the first to third organic materials (or compositions containing the first to third organic materials) and joining them may be appropriately selected depending on the organic materials used. Generally speaking, after supplying the first to third organic materials, the reaction may proceed by maintaining the first silicon substrate 10 and the second silicon substrate 20 under predetermined reaction conditions (particularly a predetermined temperature) with the organic materials interposed between them.

[0221] More specifically, for example, a first organic material (which may be a composition) is applied (e.g., by coating, spraying, printing, etc.) to the surface of the first silicon substrate 10 having the first conductive region 15 (the surface having at least a portion of the first activated region 15a). Similarly, a second organic material (which may be a composition) is applied to the surface of the second silicon substrate having the second conductive region 25 (the surface having at least a portion of the second activated region 25a). After that, cleaning and / or drying may be performed as necessary. Cleaning and drying may be performed using the same methods as described above, and if an organic material containing fluorine is used, pre-cleaning with a fluorine-based solvent may be performed.

[0222] Subsequently, the third organic material (which may be a composition) is applied (e.g., by coating, spraying, printing, etc.) to the region derived from the first organic material. After that, cleaning and / or drying may be carried out as necessary. Cleaning and drying may be carried out in the same manner as described above, and if an organic material containing fluorine is used, pre-cleaning with a fluorine-based solvent may be performed.

[0223] Furthermore, a region derived from the second organic material is provided on the region derived from the third organic material. Specifically, the first silicon substrate 10 and the second silicon substrate 20 are aligned so that the first conductive region 15 and the second conductive region 25 face each other, and the first silicon substrate 10 and the second silicon substrate 20 are brought into close contact with the first to third organic materials interposed between the first conductive region 15 and the second conductive region 25. The first silicon substrate 10 and the second silicon substrate 20, brought into close contact, are maintained under predetermined reaction conditions (particularly a predetermined temperature), and the reaction is allowed to proceed during this time. After that, annealing treatment may be performed as necessary.

[0224] The physical properties of the first to third organic materials can be applied to those of the first organic material in the first embodiment.

[0225] The physical properties of the first to third organic materials can be applied to those of the first organic material in the first embodiment.

[0226] Each organic material is described below. Note that this explanation will focus on the differences from the first example using the organic material described in (iii) above, and unless otherwise specified, the same explanation as in the first example may apply.

[0227] The following materials can be used as organic materials. (vii) A substituted or unsubstituted hydrocarbon compound having a hydrolyzable silyl group at one terminal end and a reactive functional group at the other terminal end.

[0228] The following describes some exemplary embodiments in detail.

[0229] • Example using organic materials (vii) (Case 15) This example will focus on the differences from the first example using the organic material described in (iii) above, and unless otherwise noted, the same explanation as in the first example may apply.

[0230] As the first and second organic materials described above, substituted or unsubstituted hydrocarbon compounds having a hydrolyzable silyl group at one terminal end and a reactive functional group at the other terminal end are used. Such compounds may have two or more terminal ends, and may have a hydrolyzable silyl group at any one or more terminal ends and a reactive functional group at any one or more terminal ends. The first and second organic materials may be the same as the substituted or unsubstituted hydrocarbon compounds having hydrolyzable silyl groups at two terminal ends described in detail in (iii) above, except that the other terminal end has a reactive functional group. The first and second organic materials may have the same configuration or different configurations in addition to the terminal ends.

[0231] The above-mentioned reactive functional group may be, but is not limited to, at least one selected from the group consisting of isocyanate groups, amino groups, hydroxyl groups, and thiol groups (also called sulfanyl groups).

[0232] In this embodiment, a third organic material is further used. The third organic material has two groups that can bond to the reactive functional groups of the first and second organic materials. The third organic material may have two (or more) of the above-mentioned bondable groups, and more specifically, it may have the above-mentioned bondable groups at any two (or more) terminal ends. The number of carbon atoms in the portion of the third organic material excluding the above-mentioned bondable groups is not particularly limited, but may be, for example, 1 to 20, and particularly 5 or less. The portion excluding the above-mentioned bondable groups may be linear, branched, or cyclic. Typically, the third organic material may be a linear organic compound having the above-mentioned bondable groups at both terminal ends, but is not limited thereto.

[0233] The above-mentioned bondable groups are selected according to the above-mentioned reactive functional groups. Examples of combinations of reactive functional groups and bondable groups are shown below, but are not limited to these. There may be one or more reactive functional groups, and there may be one or more bondable groups, as long as they can bond to the reactive functional groups.

[0234] [Table 1]

[0235] The above-mentioned reactive functional groups and bondable groups may be reactable with hydroxyl groups and / or hydrogen atoms, as well as hydrosilyl groups and / or silanol groups, or they may be substantially non-reactive. If all of the above-mentioned reactive functional groups and bondable groups are reactable with hydroxyl groups and / or hydrogen atoms, as well as hydrosilyl groups and / or silanol groups, it can be understood that two types of the organic materials described in (iii) above are used, but this does not need to be considered when using the organic materials described in (vii).

[0236] For example, as the first organic material and the second organic material, R k 3Si-(CH2) n31 -When using NCO, the third organic material is, for example, H2N-(CH2) n32 -NH2, HS-(CH2) n32 -SH and HO-(CH2) n32 At least one of -OH can be used. As the first organic material and the second organic material, R k 3Si-(CH2) n33 When using -NH2, the third organic material is OCN-(CH2) n34 -NCO can be used. n31 is an integer between 1 and 18, for example, 1. n32 are each independent integers between 1 and 18, for example, 2. n33 is an integer between 1 and 18, for example, 1. n34 is an integer between 1 and 18, for example, 2.

[0237] R k -OR means a group that can undergo hydrolysis, and preferably each is independently -OR j , -OCOR j , -ON=CR j 2. -NR j 2, -NHR j , or halogen. R j C is either substituted or non-substituted.1-4 Alkyl alkyl groups, preferably unsubstituted C 1-4 It is an alkyl group. 1-4 The alkyl group is preferably an ethyl group or a methyl group, more preferably a methyl group.

[0238] Specifically, the reactions when isocyanatomethyltrimethoxysilane is used as the first and second organic materials, and ethylenediamine (1,2-diaminoethane) is used as the third organic material are shown below. In the schematic diagrams below, the upper section shows only the junction of one of the substrates for convenience. The first method corresponds to the scheme indicated by the arrow from the upper left to the lower section, the second method corresponds to the scheme indicated by the arrow from the upper left to the upper center and the arrow from the upper center to the lower section, and the third method corresponds to the scheme indicated by the arrow from the upper left to the upper center, the arrow from the upper center to the upper right, and the arrow from the upper right to the lower section (the same applies below). In the following, Cu is described as an example of the first and second conductive regions 15 and 25. Furthermore, although only the reactions in the first and second activation regions 15a and 25a are described below, reactions can also occur in the first and second junction 23 in a similar manner to those in the first and second activation regions 15a and 25a.

[0239] [ka]

[0240] Specifically, the reaction when isocyanatomethyltrimethoxysilane is used as the first and second organic materials, and ethylene glycol (1,2-ethanediol) is used as the third organic material is shown below.

[0241] [ka]

[0242] Specifically, the reactions when aminomethyltrimethoxysilane is used as the first and second organic materials, and ethylene diisocyanate (1,2-ethane diisocyanate) is used as the third organic material are shown below.

[0243] [ka]

[0244] Any suitable method (scheme) may be applied to join the first silicon substrate 10 and the second silicon substrate 20 using the first to third organic materials. Three methods are shown below, but are not limited to these.

[0245] (Method 1) In the first method, the first and second organic materials and the third organic material are mixed (for example, immediately before use), and the resulting mixture is supplied between the first silicon substrate 10 and the second silicon substrate 20 to react the hydrolyzable silyl groups of the first and second organic materials with the hydroxyl groups of the first and second active regions 15a and 25a. This causes the first organic material to chemically bond to the metal atoms of the first conductive region 15, and the second organic material to the metal atoms of the second conductive region 25. In addition, the reactive functional groups of the first and second organic materials are reacted with the bondable groups of the third organic material to form a bond. As a result, the first organic material chemically bonded to the metal atoms of the first conductive region 15 and the second organic material chemically bonded to the metal atoms of the second conductive region 25 are bonded via the third organic material.

[0246] Furthermore, the hydrolyzable silyl groups of the first and second organic materials are reacted with the silanol groups of the first and second junctions (for example, if the hydrolyzable group is an alkoxy group, siloxane bonds are formed by de-alcoholization). This chemically bonds the first organic material to the Si atoms of the first junction, and the second organic material to the Si atoms of the second junction. Additionally, the reactive functional groups of the first and second organic materials are reacted with the bondable groups of the third organic material to form bonds. As a result, the first organic material chemically bonded to the Si atoms of the first junction and the second organic material chemically bonded to the Si atoms of the second junction are bonded via the third organic material.

[0247] The reactions between the hydrolyzable silyl groups of the first organic material and the first activated region 15a or the first junction, the reactions between the hydrolyzable silyl groups of the first organic material and the silanol groups of the second activated region 25a or the second junction, and the reactions between the reactive functional groups of the first and second organic materials and the bondable groups of the third organic material can occur at any time, for example, either proceeding first or proceeding simultaneously. As a result, the first silicon substrate 10 and the second silicon substrate 20 are joined by reaction products derived from the first to third organic materials. By-products, such as alcohols, may be produced, but their carbon number may be small as described above, and they can be effectively removed from the gap between the first silicon substrate 10 and the second silicon substrate 20 through the reaction product gap, thus reducing the formation of voids due to by-products.

[0248] (Second method) In the second method, the first organic material is supplied to the first activated region 15a, and the hydrolyzable silyl group of the first organic material reacts with the hydroxyl group of the first activated region 15a (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation occurs by de-alcoholization). The second organic material is supplied to the second activated region 25a, and the hydrolyzable silyl group of the second organic material reacts with the hydroxyl group of the second activated region 25a (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation occurs by de-alcoholization). (The first organic material supplied to the first activated region 15a and the second organic material supplied to the second activated region 25a may be the same or different.) As a result, the first organic material chemically bonds to the metal atoms of the first conductive region 15, and the second organic material chemically bonds to the metal atoms of the second conductive region 25.

[0249] Subsequently, the first conductive region 15 and the second conductive region 25 are positioned facing each other, with an intermediate derived from the first and second organic materials located between them together with the third organic material. The reactive functional groups of the first and second organic materials react with the bondable groups of the third organic material to form a bond. As a result, the first organic material chemically bonded to the metal atoms of the first conductive region 15 and the second organic material chemically bonded to the metal atoms of the second conductive region 25 are bonded via the third organic material.

[0250] Furthermore, the first organic material is supplied to the first junction to react with the hydrolyzable silyl group of the first organic material and the silanol group of the first junction (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by de-alcoholization), and the second organic material is supplied to the second junction to react with the hydrolyzable silyl group of the second organic material and the silanol group of the second junction (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by de-alcoholization). (The first organic material supplied to the first junction and the second organic material supplied to the second junction may be the same or different.) As a result, the first organic material chemically bonds to the Si atoms of the first junction, and the second organic material chemically bonds to the Si atoms of the second junction.

[0251] Subsequently, the first and second joints are positioned facing each other, with an intermediate derived from the first and second organic materials located between them together with the third organic material. The reactive functional groups of the first and second organic materials react with the bondable groups of the third organic material to form a bond. As a result, the first organic material chemically bonded to the Si atoms of the first joint and the second organic material chemically bonded to the Si atoms of the second joint are bonded via the third organic material.

[0252] As a result, the first conductive region 15 and the second conductive region 25, as well as the first and second junctions, are joined by reaction products derived from the first to third organic materials, respectively. Although by-products, such as alcohols, may be produced, their carbon number can be small as described above, and they can be effectively removed before the first silicon substrate 10 and the second silicon substrate 20 are placed facing each other, thus reducing the formation of voids due to by-products.

[0253] (Third method) In the third method, the first organic material is supplied to the first activated region 15a to react with the hydrolyzable silyl group of the first organic material with the hydroxyl group of the first activated region 15a (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation occurs by de-alcoholization), and the second organic material is supplied to the second activated region 25a to react with the hydrolyzable silyl group of the second organic material with the hydroxyl group of the second activated region 25a (for example, if the hydrolyzable group is an alkoxy group, siloxane bond formation occurs by de-alcoholization). (The first organic material supplied to the first activated region 15a and the second organic material supplied to the second activated region 25a may be the same or different.) As a result, the first organic material chemically bonds to the metal atoms of the first conductive region 15 (intermediate X1), and the second organic material chemically bonds to the metal atoms of the second conductive region 25 (intermediate X2). Then, intermediate X1 is conveniently selected as one of the two intermediates X1 and X2, and the third organic material is supplied to intermediate X1 to react and bond the reactive functional groups of the first organic material with the bondable groups of the third organic material (intermediate Y). Subsequently, the intermediate Y obtained in this way and the intermediate X2 obtained above are placed facing each other, and the reactive functional groups of intermediate X2 (second organic material) are reacted and bonded with the bondable groups of intermediate Y (first organic material + third organic material). As a result, the first organic material chemically bonded to the metal atoms in the first conductive region 15 and the second organic material chemically bonded to the metal atoms in the second conductive region 25 are bonded via the third organic material.

[0254] Furthermore, the first organic material is supplied to the first junction to react with the hydrolyzable silyl group of the first organic material and the silanol group of the first junction (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by de-alcoholization), and the second organic material is supplied to the second junction to react with the hydrolyzable silyl group of the second organic material and the silanol group of the second junction (for example, if the hydrolyzable group is an alkoxy group, a siloxane bond is formed by de-alcoholization). (The first organic material supplied to the first junction and the second organic material supplied to the second junction may be the same or different.) As a result, the first organic material chemically bonds to the Si atom of the first junction (intermediate X1), and the second organic material chemically bonds to the Si atom of the second junction (intermediate X2). Then, for convenience, intermediate X1 is selected as one of the two intermediates X1 and X2, and the third organic material is supplied to intermediate X1 to react and bond the reactive functional group of the first organic material with the bondable group of the third organic material (intermediate Y).

[0255] Subsequently, the intermediate Y obtained in this way and the intermediate X2 obtained above are arranged facing each other, and the reactive functional groups of intermediate X2 (second organic material) react with the bondable groups of intermediate Y (first organic material + third organic material) to form a bond. As a result, the first organic material chemically bonded to the Si atoms of the first junction and the second organic material chemically bonded to the Si atoms of the second junction are bonded via the third organic material.

[0256] As a result, the first conductive region 15 and the second conductive region 25, as well as the first and second junctions, are joined by reaction products derived from the first to third organic materials. Although by-products, such as alcohols, may be produced, their carbon number can be small as described above, and they can be effectively removed before the first silicon substrate 10 and the second silicon substrate 20 are placed facing each other, thus reducing the formation of voids due to by-products. Furthermore, in this method, any unreacted third organic material that may remain on the intermediate Y on the first silicon substrate 10 can be effectively removed before the first silicon substrate 10 and the second silicon substrate 20 are placed facing each other, thus reducing the amount of unwanted (non-contributing) material remaining between the first silicon substrate 10 and the second silicon substrate 20 in the final laminate.

[0257] (Case 16) In the 15th example above, the first organic material reacts with the first conductive region 15, and the second organic material reacts with the second conductive region 25, thereby chemically reacting the first organic material and the third organic material, which is reactive with the second organic material, to link the first conductive region 15 and the second conductive region 25. However, in this 16th example, a portion A exists on at least a part of the surface of the first and second conductive regions 15 and 25, and no chemical reaction occurs between the first and second conductive regions 15 and 25 and portion A. In other words, the first and second conductive regions 15 and 25 are not chemically linked via portion A. Otherwise, it has the same configuration as the 15th example above, and portion A has the same configuration as the 2nd example above.

[0258] Part A is located between the metal atoms of the first conductive region 15 and the metal atoms of the second conductive region 25. Part A is located on at least a portion of the surface between the first and second conductive regions 15 and 25. Part A is unreacted with the metal atoms of the first conductive region 15 and the metal atoms of the second conductive region 25. The entire surface of the first conductive region 15 and the second conductive region 25 may have part A, or only a portion may have part A, and the other portion may not have part A. Part A has the same configuration as described above.

[0259] Although embodiments of the present disclosure have been described above, the present disclosure is not limited to such embodiments, and various modifications are possible. [Examples]

[0260] This disclosure will be explained in more detail through the following examples, but is not limited to these examples.

[0261] (Comparative Example 1) A single Cu wafer was irradiated with N2RIE plasma at 250W for 3 minutes.

[0262] (Example 1) • Preparation of samples for conductivity and resistivity measurements A single Cu wafer was irradiated with N2RIE plasma to activate the wafer surface and remove organic contamination. A 5 wt% solution of 1,6-bis(trimethoxysilyl)hexane (in a 2-methoxy-1-methylethyl acetate (PGMEA) solution) was passed through a filter to remove particles. Subsequently, the PGMEA solution was applied to the wafer by spin coating to form a film. After standing for 5 minutes, the wafer surface was washed with PGMEA to wash away any organic material that was not adhering properly. Then, the wafer was heated on a hot stage at 100°C for 5 minutes to react with the organic material and form an organic film on the wafer (i.e., in Example 1, the reactants of the organic material were located on a single wafer). Subsequently, the conductivity and resistivity of the wafer obtained as described above were measured. 1,6-Bis(trimethoxysilyl)hexane: [ka]

[0263] (Example 2) The procedure was carried out in the same manner as in Example 1, except that bis[3-(trimethoxysilyl)propyl]amine was used as the first organic material instead of 1,6-bis(trimethoxysilyl)hexane as in Example 1. Bis[3-(trimethoxysilyl)propyl]amine: [ka]

[0264] (Example 3) The procedure was carried out in the same manner as in Example 1, except that 1,6-Hexylenediphosphonic Acid was used as the first organic material instead of 1,6-bis(trimethoxysilyl)hexane as in Example 1. 1,6-Hexanediphosphonic acid: [ka]

[0265] [Plasma irradiation conditions] • Equipment: Mikasa Corporation AQ-500 • Irradiated plasma: N2 • Irradiation time: 3 minutes • Irradiation output: 250W

[0266] [Measurement conditions for film thickness] The film thickness was measured using an ellipsometer. ·Measurement wavelength range: 400-1000nm ·Incidence angle: 65° The film thickness was determined by measuring the same substrate before (after pretreatment) and after film deposition, and calculating the difference.

[0267] [Measurement of conductivity] • Device name: Bruker AXS NanoscopeV+ Dimension ICON (also measures current simultaneously) • Sample bias voltage: 5V • Measurement range: 20 μm x 20 μm • Measurement environment: Under Ar atmosphere • Probe (cantilever) part number: Bruker DDESP-V2 • Probe effective area: 3.14159 × 10 -14 m 2 The tip diameter of the measurement probe was determined under identical conditions. Furthermore, the contact resistance between the measurement probe and the sample was always constant, or any differences were negligibly small. The measured conductivity value is the average current value obtained.

[0268] [Measurement of resistivity] Let R(all) = the total resistance of the wafer (wafer + organic film) obtained in Example 1 [Ω], R(a) = the resistance of the region with the organic film (the region containing both the wafer and the organic film) [Ω], and R(b) = the resistance of the region without the organic film (the region where only the wafer exists) [Ω]. R(all) = R(a) + R(b) ... (er1) It is represented as follows.

[0269] The average current value of the Cu wafer (without organic film) in Comparative Example 1 was 160 pA. From this value, R(b) [Ω] for Comparative Example 1 was determined. Specifically, Voltage V[V]=Current I[pA]×Resistance[Ω]...(er2) Therefore, the sample bias voltage 5[V] = 160[pA] × R(b)[Ω], and R(b)[Ω] = 1 / 32 of that in Comparative Example 1. This value was used as R(b) in Examples 1 and 2.

[0270] Using the value of R(b) above, the resistance value R(a) for each of Examples 1 and 2 was calculated from equation (er1) above. Furthermore, the resistivity ρ of the organic film was calculated based on the following equation (er3). R(a) = ρ × l ÷ S ···(er3) [In the formula: ρ = resistivity of the organic film [Ω·m], l = thickness of the organic film [nm], S = effective probe area [m]2 ]]

[0271] Tables 2 and 3 show the measurement conditions and results.

[0272] [Table 2]

[0273] As the film thickness increases, insulation occurs (conductivity becomes 0 pA), but it was found that current flows in Examples 1-3. Furthermore, while general organic films do not have conductivity, it was found that the present invention has conductivity, as shown in Examples 1-3.

[0274] In the above Examples 1 to 3, an organic film was formed on a wafer, but by placing another wafer on top of the organic film, the organic film became the adhesive layer of the present invention. That is, the laminate of the present invention was formed. [Industrial applicability]

[0275] The manufacturing method for the laminate according to this disclosure expands the range of applications when the first silicon substrate and the second silicon substrate have conductive regions. [Explanation of Symbols]

[0276] 10,20 silicon substrate 15,25 conductive region 15a,25a activation area 30,30A,30B Adhesive layer 31,32A,33A,32B,33B,33C Adhesive part 40, 40A, 40B laminate 60 vacant section

Claims

1. A method for manufacturing a laminate containing two silicon substrates, (a) Prepare a first silicon substrate having a first conductive region on at least a portion of its surface, and a second silicon substrate having a second conductive region on at least a portion of its surface, and (b) The surface of the first silicon substrate including the first conductive region and the second silicon substrate are joined by an adhesive layer. Includes, The first silicon substrate has a first activated region provided by activating at least a portion of the surface including the first conductive region, The adhesive layer is provided on at least a portion of the first activated region and at least a portion of the second conductive region. The adhesive layer has a first reaction product derived from a first organic material, The first reaction product is present at least on the surface facing the first activation region and is capable of reacting with the first activation region. The thickness of the adhesive layer is 10 nm or less. A method for manufacturing a conductive laminate.

2. The manufacturing method according to claim 1, wherein the first conductive region includes a metal.

3. The manufacturing method according to claim 2, wherein the metal in the first conductive region is at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf.

4. The manufacturing method according to claim 1, wherein the surface of the first conductive region is exposed.

5. The manufacturing method according to claim 1, wherein at least a portion of the surface of the first conductive region is in contact with the adhesive layer.

6. The manufacturing method according to claim 1, wherein the adhesive layer is formed from two or more layers.

7. The first activation region is provided in at least a portion of the first conductive region and at least a portion of the first silicon substrate. The first conductive region includes at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf. The adhesive layer is in contact with the first activated region, The thickness of the adhesive layer is 5 nm or less. The manufacturing method according to claim 1.

8. The adhesive layer is provided on a second activated region, which is formed by activating at least a portion of the surface of the second silicon substrate facing the second conductive region, and contains a second reaction product derived from a second organic material. A method for manufacturing a laminate according to claim 1.

9. The manufacturing method according to claim 8, wherein the second conductive region includes a metal.

10. The manufacturing method according to claim 9, wherein the metal in the second conductive region is at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf.

11. The manufacturing method according to claim 8, wherein the surface of the second conductive region is exposed.

12. The manufacturing method according to claim 8, wherein at least a portion of the surface of the second conductive region is in contact with the adhesive layer.

13. The manufacturing method according to claim 1, wherein there is a gap between the first silicon substrate and the second silicon substrate that is in contact with both the first activated region and the second conductive region.

14. The manufacturing method according to claim 1, wherein the thickness of the adhesive layer is 5 nm or less.

15. The first activation region is provided in at least a portion of the first conductive region and at least a portion of the first silicon substrate. The second activation region is provided in at least a portion of the second conductive region and at least a portion of the second silicon substrate. The first conductive region and the second conductive region each include at least one selected from the group consisting of Cu, Co, Fe, Al, W, Ru, and Hf. The adhesive layer is in contact with the first activated region and the second activated region. The thickness of the adhesive layer is 5 nm or less. The manufacturing method according to claim 8.

16. A first silicon substrate having a first conductive region on at least a portion of its surface, A second silicon substrate located on the side having the first conductive region, An adhesive layer located between the first silicon substrate and the second silicon substrate, which bonds the surface of the first silicon substrate having the first conductive region to the second silicon substrate, It has, A laminate having conductivity between the first silicon substrate and the second silicon substrate, At least a portion of the surface of the first silicon substrate including the first conductive region has an activated first activated region, The second silicon substrate has a second conductive region on at least a portion of its surface, The adhesive layer is provided on at least a portion of the first activated region and at least a portion of the second conductive region, and has a first reaction product derived from the first organic material. The first reaction product is present at least on the surface facing the first activation region and is capable of reacting with the first activation region. A laminate in which the thickness of the adhesive layer is 10 nm or less.

17. The laminate according to claim 16, wherein the thickness of the adhesive layer is 5 nm or less.

18. The laminate according to claim 16, wherein the adhesive layer consists of two or more layers.

19. The thickness of the adhesive layer is 5 nm or less. The adhesive layer adheres the surface having the first conductive region to the surface having the second conductive region. The laminate according to claim 16.

20. The conductivity measured in the adhesive layer disposed on the first silicon substrate was 1.0 × 10 －２ ~5.0 x 10 ２ A laminate according to claim 16, which is in the range of pA.

21. The resistivity is 1.5 × 10 －８ ~2.0 x 10 ５ The laminate according to claim 16, which is in the range of Ω·m.

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