Laminate, composition, and method for producing laminate

Abstract

To provide a laminate provided with a resin layer having a low coefficient of thermal expansion and excellent bonding strength with a substrate.SOLUTION: A laminate includes a substrate and a resin layer, and the resin layer has a coefficient of thermal expansion (CTE) of 120 ppm / K or less between 50°C and 150°C, a silicon atom content of 0.1 atm% or more and 20 atm% or less, and a ratio (O / Si) of oxygen atoms to silicon atoms is 1 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, a laminate, and a method for making a laminate. [Background technology]

[0002] As electronic devices become smaller, lighter, and more powerful, there is a demand for higher integration of semiconductor chips and the like. However, it is difficult to fully meet this demand through circuit miniaturization alone. Therefore, in recent years, a method has been proposed for achieving higher integration by vertically stacking multiple substrates (wafers), semiconductor chips, etc. to form a multilayer, three-dimensional structure. Proposed methods for stacking substrates (wafers), chips, etc. (hereinafter sometimes referred to as "substrates, etc.") include a method of directly bonding substrates together (fusion bonding) and a method of bonding substrates together via a resin layer (see, for example, Patent Documents 1 to 3 and Non-Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 4-132258 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-226060 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-47895 [Non-patent literature]

[0004] [Non-Patent Document 1] A. Bayrashev, B. Ziaie, Sensors and Actuators A 103 (2003) 16-22. [Non-patent document 2] QY Tong, UM Gosele, Advanced Material 11, No. 17 (1999) 1409-1425. Summary of the Invention [Problem to be solved by the invention]

[0005] While the method of bonding substrates via a resin layer has the advantage of being able to bond substrates at a lower temperature than fusion bonding, it also has the risk of warping or peeling due to strain at the bonding surface caused by the difference in thermal expansion coefficient between the resin layer and the substrate. While adding an inorganic filler is considered a way to reduce the thermal expansion coefficient of the resin layer, the addition of an inorganic filler may reduce the bonding strength with the substrate. Therefore, there is a need for a laminate with a resin layer that can achieve both a low thermal expansion coefficient and high bonding strength.

[0006] One aspect of the present invention has been made in consideration of the above-mentioned problems, and aims to provide a laminate including a resin layer having a low thermal expansion coefficient and excellent bonding strength to a substrate, a composition capable of forming a resin layer having a low thermal expansion coefficient and excellent bonding strength to a substrate, and a method for manufacturing a laminate having excellent bonding strength between a resin layer and a substrate. [Means for solving the problem]

[0007] Specific means for solving the above problems are as follows. <1> A laminate comprising a substrate and a resin layer, wherein the resin layer has a coefficient of thermal expansion (CTE) of 120 ppm / K or less between 50°C and 150°C, a silicon atom content of 0.1 atm% or more and 20 atm% or less, and a ratio of oxygen atoms to silicon atoms (O / Si) of 1 or more. <2> The resin layer has a nitrogen atom content of 0.1 atm % or more and 20 atm % or less. <1> The laminate according to claim 1. <3> 10 -7 The outgassing pressure measured in an environment of 10 Pa is -5 The temperature at which the pressure is above 400°C is <1> or <2> The laminate according to claim 1. <4> the substrate includes a first substrate and a second substrate, and the resin layer is disposed between the first substrate and the second substrate; <1> ~ <3> The laminate according to any one of the preceding claims. <5> The surface energy, which represents the bonding strength between the first substrate and the second substrate, is 0.5 J / m 2 That's all. <4> The laminate according to claim 1. <6> The thickness of the resin layer is 0.001 μm or more and 20 μm or less. <1> ~ <5> The laminate according to any one of the preceding claims. <7> the substrate is a semiconductor substrate; <1> ~ <6> The laminate according to any one of the preceding claims. <8> A composition comprising at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000: [ka] In general formula (1), R1 and R3 each independently represent an organic group having 6 or less carbon atoms, R2 represents a methylene group, an ethylene group, a propylene group, or a phenylene group, a represents 2 or 3, b represents the number 3-a, and X1 represents a structure derived from a carboxylic acid dianhydride. [ka] In general formula (2), R1 and R3 each independently represent an organic group having 6 or less carbon atoms, R2 represents a methylene group, an ethylene group, a propylene group, or a phenylene group, a represents 2 or 3, b represents the number 3-a, X1 represents a structure derived from a carboxylic acid dianhydride, X2 represents a structure derived from an amine compound, and n represents a positive number. <9> The compound (X1) has a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure. <8> The composition described in <10> The compound (X2) has a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure, and a structure obtained by reacting an amine compound (C) having a molecular weight of 90 to 600, no Si—O bond, and a ring structure with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure, <8> The composition described in <11> In general formula (1) or general formula (2), a is 2. <8> ~ <10> The composition according to any one of the preceding claims. <12> Further containing a precursor of resin (D) having a CTE of 90 ppm / K or less between 50 ° C and 150 ° C, <8> ~ <11> The composition according to any one of the preceding claims. <13> The resin (D) contains at least one selected from the group consisting of polyimide and polybenzoxazole. <12> The composition described in <14> For use in manufacturing semiconductor devices, <8> ~ <13> The composition according to any one of the preceding claims. <15> For forming a resin layer on or between substrates, <8> ~ <14> The composition according to any one of the preceding claims. <16> further comprising an organic solvent, <8> ~ <15> The composition according to any one of the preceding claims. <17> A substrate; <8> ~ <16> and a resin layer comprising a cured product of the composition according to any one of the above items. <18> <8> ~ <16> 1. A method for producing a laminate, comprising the steps of: forming a layer containing the composition according to any one of claims 1 to 9 on or between substrates; and curing the layer. [Effects of the Invention]

[0008] According to one aspect of the present invention, there are provided a laminate including a resin layer having a low thermal expansion coefficient and excellent bonding strength with a substrate, a composition capable of forming a resin layer having a low thermal expansion coefficient and excellent bonding strength with a substrate, and a method for manufacturing a laminate having excellent bonding strength between a resin layer and a substrate. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples.

[0010] In the present disclosure, the molecular weight of a compound may be a value calculated from a known molecular structure or may be a value measured by a known method, such as a weight-average molecular weight in terms of polyethylene glycol measured by Gel Permeation Chromatography (GPC). Specifically, when measuring the weight-average molecular weight by GPC, an aqueous solution of sodium nitrate with a concentration of 0.1 mol / L is used as the developing solvent, a Shodex DET RI-101 is used as the analytical device, and two analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP, manufactured by Tosoh Corporation) are used to detect the refractive index at a flow rate of 1.0 mL / min, and the weight-average molecular weight is calculated using analytical software (Empower3, manufactured by Waters Corporation) with polyethylene glycol / polyethylene oxide as standards.

[0011] <Laminate> The laminate of this embodiment comprises a substrate and a resin layer, wherein the resin layer has a coefficient of thermal expansion (CTE) of 120 ppm / K or less between 50°C and 150°C, a silicon atom content of 0.1 atm% or more and 20 atm% or less, and a ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) of 1 or more.

[0012] As a result of the inventors' research, it was found that a laminate having a resin layer that satisfies the above conditions is less likely to warp or peel due to the difference in thermal expansion coefficient between the resin layer and the substrate, and has excellent bonding strength with the substrate.

[0013] The resin layer contained in the laminate has a CTE of 120 ppm / K or less between 50° C. and 150° C. By having a CTE of 120 ppm / K or less between 50° C. and 150° C., the difference in thermal expansion coefficient between the resin layer and the substrate can be reduced, and warping and peeling at the bonding surface can be suppressed. The CTE between 50°C and 150°C is preferably 90 ppm / K or less, more preferably 80 ppm / K or less, and even more preferably 50 ppm / K or less.

[0014] The CTE of the resin layer can be measured by the method described in the examples below.

[0015] The resin layer has a silicon atom content of 0.1 atm% or more and 20 atm% or less. When the silicon atom content is within this range, sufficient bonding strength to the substrate is ensured. The silicon atom content is preferably 0.5 atm% or more and 15 atm% or less, and more preferably 0.5 atm% or more and 10 atm% or less.

[0016] The resin layer has a ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) of 1 or more. When the ratio of the number of oxygen atoms to the number of silicon atoms is 1 or more, adhesion to the substrate tends to be high. The ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) is preferably 1.5 or more, and more preferably 2 or more. From the viewpoint of reducing water absorption, the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) is preferably 20 or less, and more preferably 15 or less.

[0017] The resin layer preferably has a nitrogen atom content of 0.1 atm% or more and 20 atm% or less. If the nitrogen atom content is within this range, adhesion to the substrate tends to be improved when the substrate contains a metal. The nitrogen atom content is preferably 2 atm% or more and 15 atm% or less, and more preferably 5 atm% or more and 10 atm% or less. The silicon atom content, nitrogen atom content, and ratio of the number of oxygen atoms to the number of silicon atoms in the resin layer can be measured by elemental analysis methods such as X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX).

[0018] The laminate is 10 -7 The outgassing pressure measured in an environment of 10 Pa is -5 It is preferable that the temperature at which the pressure of outgassing is 10 Pa or more is 400° C. or more. When the temperature is 400° C. or more, the decrease in bonding strength due to outgassing tends to be suppressed. -5 The temperature at which the outgas pressure is 10 Pa or more is preferably 420° C. or more, and more preferably 450° C. or more. -5 The upper limit of the temperature at which the thermal expansion coefficient becomes equal to or greater than Pa is not particularly limited, but may be, for example, 600°C or lower, or 550°C or lower.

[0019] 10 of the laminate -7 The outgas pressure measured in an environment of 1 Pa can be measured by the method described in the examples below.

[0020] The thickness of the resin layer is not particularly limited and may be, for example, 0.001 μm to 20 μm, 0.05 μm to 10 μm, or 0.1 μm to 6 μm.

[0021] The resin layer preferably contains inorganic or resin fillers with a maximum diameter of 0.3 μm or more in an amount of 30% by mass or less, more preferably 10% by mass or less, and even more preferably 0% by mass, based on the total mass of the resin layer. When the content of the filler contained in the resin layer is within the above range, bonding defects of the laminate can be suppressed even when the thickness of the resin layer is thin. Furthermore, when a first substrate on which a resin layer is formed is laminated on a second substrate, alignment marks formed on each substrate are sometimes recognized by a machine for alignment. When the content of the filler is within the above range, the transparency of the resin film is improved, enabling more accurate alignment.

[0022] The glass transition temperature (Tg) of the resin layer is preferably 100°C or higher and 350°C or lower. When Tg is within this temperature range, the elastic modulus of the film decreases when subjected to a high-temperature process, thereby reducing warping and internal stress of the laminate and preventing a decrease in bonding strength due to peeling or the like. Tg is more preferably 100°C or higher and 300°C or lower, even more preferably 120°C or higher and 250°C or lower, and even more preferably 120°C or higher and 200°C or lower. The Tg of the resin layer can be measured by the method described in the Examples below.

[0023] The water absorption rate of the resin layer is preferably 3% by mass or less. When the water absorption rate is within the above range, outgassing from the resin can be effectively suppressed, and the occurrence of defects such as voids and peeling in the laminate can be effectively suppressed. The water absorption rate is more preferably 2% by mass or less. The water absorption rate of the resin layer can be measured by the method described in the examples below.

[0024] The elastic modulus of the resin layer at 250°C is preferably 0.01 GPa or more and 20 GPa or less. When the elastic modulus at 250°C is within the above range, the internal stress when the laminate is heated can be reduced, and warping, peeling, malfunction of the device layer, etc. can be suppressed. The elastic modulus at 250°C is more preferably 0.01 GPa or more and 10 GPa or less, and even more preferably 0.1 GPa or more and 5 GPa or less. The elastic modulus of the resin layer at 250° C. can be measured using an atomic force microscope (AFM) by the method described in the Examples.

[0025] The hardness of the resin layer at room temperature (23°C) is preferably 0.05 GPa or more and 1.8 GPa or less. If the hardness is within the above range, cracking of the film can be suppressed when an external force such as wire bonding is applied to the laminate. The hardness is more preferably 0.2 GPa or more and 1.5 GPa or less, and even more preferably 0.3 GPa or more and 1.0 GPa or less. The hardness of the resin layer is measured by a method (nanoindentation) conforming to ISO14577. Specifically, with a resin layer formed on a silicon substrate, a nanoindenter (Berkovich type indenter) is used to measure the unloading-displacement curve at 23°C under the condition of an indentation depth of 20 nm. According to the calculation method in the reference (Handbook of Micro / nano Tribology (Second Edition), edited by Bharat Bhushan, CRC Press), the hardness at 23°C is calculated from the maximum load. The hardness (H) is defined by the following formula: where P max represents the maximum load at an indentation depth of 20 nm, and A c represents the projected area of ​​the indenter onto the sample during indentation.

[0026]

number

[0027] The elastic modulus of the resin layer at room temperature (23°C) is preferably 0.1 GPa or more and 20 GPa or less. If the elastic modulus at room temperature is within the above range, warping and peeling can be suppressed when an external force such as compression or shear is applied to the laminate. The elastic modulus at room temperature is more preferably 0.5 GPa or more and 10 GPa or less, and even more preferably 1 GPa or more and 7 GPa or less. The elastic modulus of the resin layer at room temperature is measured by forming the resin layer on a silicon substrate and measuring the unloading-displacement curve at 23°C using a nanoindentator (Berkovich-type indenter) at an indentation depth of 20 nm. The elastic modulus at 23°C is calculated from the maximum load and maximum displacement according to the calculation method in the reference book (Handbook of Micro / nano Tribology (Second Edition), edited by Bharat Bhushan, CRC Press). The elastic modulus is defined by the following formula: r represents the elastic modulus, and E i represents the Young's modulus of the indenter, which is 1140 GPa, and νi represents the Poisson's ratio of the indenter, which is 0.07, and E s and ν s represent the Young's modulus and Poisson's ratio of the sample, respectively.

[0028]

number

[0029] When the thickness of the resin layer is 400 nm or more, the amount of plastic deformation of the resin layer is preferably 2 nm or more at an indentation depth of 20 nm when measured with a nanoindenter (Berkovich indenter). If the amount of plastic deformation is within the above range, when the resin layer is used in a substrate laminate, the resin layer undergoes plastic deformation when the substrate laminate is further laminated on another substrate, thereby preventing cracking of the substrate laminate. The amount of plastic deformation of the resin layer is determined by measuring the unloading-displacement curve at 23°C using a nanoindentator (Berkovich type indenter) at an indentation depth of 20 nm with the resin layer formed on a silicon substrate, and then determining the amount of plastic deformation from the unloading curve.

[0030] When the thickness of the resin layer is 400 nm or more, the load required to deform the resin layer is preferably 20 μN or less when a nanoindenter (Berkovich indenter) is used to indent the resin layer to a depth of 20 nm. If the load required for deformation is within the above range, when the resin layer is used in a substrate laminate, the resin layer is easily deformed when the substrate laminate is further laminated on another substrate, and cracking of the substrate laminate can be effectively suppressed. The load required to deform the resin layer is determined by measuring the unloading-displacement curve at 23°C using a nanoindentator (Berkovich-type indenter) at an indentation depth of 20 nm with the resin layer formed on the silicon substrate, and calculating the load at an indentation depth of 20 nm.

[0031] The type of resin contained in the resin layer is not particularly limited as long as it satisfies the above conditions. From the viewpoint of insulating properties, the resin layer preferably contains a silicone resin. Furthermore, from the viewpoint of heat resistance, it is preferable to contain a silicone resin containing a ring structure such as an aromatic ring, and it is more preferable to contain a silicone resin containing a ring structure and an imide bond. Examples of silicone resins include cured products of the compound (X1) or compound (X2) contained in the composition described below.

[0032] When the resin layer contains a silicone resin, the organic crosslink density is measured by measuring the peaks derived from Si-O bonds in the Fourier transform infrared spectrum (peak position 1000 to 1100 cm -1 The peak due to the Si-Me bond (peak position 1260 cm) -1 ) intensity ratio (peak intensity ratio) is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.6 or less. When the organic crosslink density of the silicone resin is within the above numerical range, the adhesive strength to a substrate containing Si, such as Si, SiC, SiO2, SiN, or SiCN, tends to be high.

[0033] When the resin layer contains a silicone resin, the basic unit of the silicone resin is: 29 In a Si NMR spectrum, it is preferable that the unit that accounts for 50% or more of the area of ​​all base units (M units, D units, T units, and Q units) is a D unit or a T unit. The area ratio of T units or D units is more preferably 70% or more, and even more preferably 90% or more, of all base units. When the basic unit of the silicone resin satisfies the above conditions, the resin layer can maintain high crack resistance while maintaining good bonding strength. In particular, it is more preferable that the unit that accounts for 50% or more of the total area of ​​all basic units is the D unit.

[0034] When the resin layer contains a silicone resin, the degree of condensation of the silicone resin is: 29In the Si NMR spectrum, it is preferable that the unit that accounts for 70% or more of the area of ​​each of the base units (M unit, D unit, T unit, Q unit) is a D2 unit or a T3 unit. When the base unit satisfies the above conditions, it is possible to suppress outgassing due to water adsorption to SiOH, etc., which are dangling bonds contained in the silicone resin.

[0035] Examples of methods for forming the resin layer include vapor phase film formation methods such as vapor deposition polymerization, CVD (chemical vapor deposition), and ALD (atomic layer deposition), and coating methods such as dipping, spraying, spin coating, and bar coating.

[0036] The resin layer may be formed using a composition described below.

[0037] The number of substrates included in the laminate is not particularly limited and may be one or more. When there are two or more substrates, the materials thereof may be the same or different. From the viewpoint of fully achieving the effects of the present invention, it is preferable for the substrate to have a thermal expansion coefficient equal to or smaller than that of the resin layer.

[0038] The substrate may be made of an inorganic material, an organic material, or a composite of these. Specific examples of inorganic materials include semiconductors such as Si, InP, GaN, GaAs, InGaAs, InGaAlAs, SiGe, and SiC; oxides, carbides, and nitrides such as boron silicate glass (Pyrex (registered trademark)), quartz glass (SiO2), sapphire (Al2O3), ZrO2, Si3N4, AlN, and MgAl2O4; piezoelectrics or dielectrics such as BaTiO3, LiNbO3, SrTiO3, and LiTaO3; diamond; metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, and Nb; and carbon. Specific examples of organic materials include polydimethylsiloxane (PDMS), epoxy resin, phenolic resin, polyimide, benzocyclobutene resin, and polybenzoxazole.

[0039] The substrate may have a multilayer structure. Examples include a structure in which an inorganic layer such as silicon oxide, silicon nitride, or SiCN (silicon carbonitride) is formed on the surface of a silicon substrate, a structure in which an organic layer such as polyimide resin, polybenzoxazole resin, epoxy resin, or Cyclotene (trade name, Dow Chem) is formed on the surface of a silicon substrate, or a structure in which a composite of an inorganic material and an organic material is formed on a silicon substrate. Furthermore, a device layer, a wiring layer, or the like may be embedded in these multilayer structures.

[0040] The main uses of each material are as follows: Si is used in semiconductor memory, LSI, CMOS image sensors, MEMS, optical devices, LEDs, etc. SiO2 is used in MEMS sealing, microchannels, interposers for 2.5D mounting, displays, etc. BaTiO3, LiNbO3, SrTiO3, and LiTaO3 are used in surface acoustic wave devices, etc. PDMS is used for microfluidics and other applications. InGaAlAs, InGaAs, and InP are used in optical devices, etc. InGaAlAs, GaAs, and GaN are used in LEDs and other applications.

[0041] The surface of the substrate (at least the surface in contact with the resin layer) preferably has at least one group selected from the group consisting of hydroxyl groups, epoxy groups, carboxy groups, amino groups, and mercapto groups, which can further increase the bonding strength with the resin layer.

[0042] A surface having hydroxyl groups can be obtained by subjecting the surface of the substrate to surface treatment such as plasma treatment, chemical treatment, or ozone treatment.

[0043] A surface having an epoxy group, a carboxy group, an amino group, or a mercapto group can be obtained by subjecting the surface of the substrate to a surface treatment using a silane coupling agent having an epoxy group, a carboxy group, an amino group, or a mercapto group.

[0044] At least one selected from the group consisting of a hydroxyl group, an epoxy group, a carboxyl group, an amino group, and a mercapto group is preferably in a state of being bonded to an element contained in the substrate, more preferably in a state of being bonded to at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb, and even more preferably in the form of a silanol group containing a hydroxyl group (Si-OH group).

[0045] The thickness of the substrate is preferably 1 μm to 1 mm, more preferably 10 μm to 900 μm, and even more preferably 20 μm to 300 μm. When there are multiple substrates, the above thickness is the thickness of each substrate, and they may be the same or different.

[0046] The shape of the substrate is not particularly limited. For example, when the substrate is a silicon substrate, it may be a silicon substrate on which an interlayer insulating layer (low-k film) is formed. The substrate may have fine grooves (recesses), fine through-holes, etc. formed therein.

[0047] The laminate of this embodiment may further include a substrate that is not in contact with the resin layer. The preferred materials and other aspects of the substrate that is not in contact with the resin layer are the same as those of the substrate described above.

[0048] The laminate may include an electrode. The electrode may penetrate the resin layer to electrically connect the substrates provided on both sides of the resin layer. The electrode may be provided on the surface of the substrate (substrate surface electrode) or may penetrate the substrate (substrate through-substrate electrode).

[0049] The electrodes are not particularly limited as long as they are electrically conductive, and may be made of, for example, conductive silicon, conductive polymers, commonly used conductive metals, etc. Examples of conductive metals include metallic elements such as Cu, Al, Ni, Fe, Sn, Cr, Pt, Zn, Mg, Ta, Ti, Mn, Co, W, Ru, In, and Au, and may contain non-metallic elements such as N and O in addition to the conductive metals.

[0050] The conductor containing a conductive metal preferably contains Cu, Sn, In or Au as a main component, and more preferably contains Cu or Sn as a main component. Here, the main component refers to the component with the highest content ratio (atomic %). The content is preferably 50 atomic % or more, more preferably 80 atomic % or more, and even more preferably 90 atomic % or more.

[0051] (Example of laminate structure) The laminate can be used in a variety of applications including components for semiconductor devices. Examples of the laminate structure of the substrate laminate for each application are shown below. Examples of MEMS packaging include Si / resin layer / Si, SiO2 / resin layer / Si, SiO2 / resin layer / SiO2, and Cu / resin layer / Cu. Examples of structures for microchannels include PDMS / resin layer / PDMS, PDMS / resin layer / SiO2, and SiO2 / resin layer / SiO2. Examples of substrates for CMOS image sensors include Si / resin layer / Si and SiO2 / resin layer / Si. Examples of structures for through-silicon vias (TSVs) include SiO2 (with Cu electrode) / resin layer / SiO2 (with Cu electrode) and Si (with Cu electrode) / resin layer / Si (with Cu electrode). For memory and LSI, Si / resin layer / Si may be used. For optical devices, examples include (InGaAlAs, InGaAs, InP, GaAs) / resin layer / Si. For LEDs, examples include (InGaAlAs, GaAs, GaN) / resin layer / Si, (InGaAlAs, GaAs, GaN) / resin layer / SiO2, (InGaAlAs, GaAs, GaN) / resin layer / (Au, Ag, Al), and (InGaAlAs, GaAs, GaN) / resin layer / sapphire. For surface acoustic wave devices, examples include (BaTiO3, LiNbO3, SrTiO3, LiTaO3) / resin layer / (MgAl2O4, SiO2, Si, Al2O3), etc.

[0052] The higher the bonding strength of the laminate, the better from the viewpoint of preventing unintentional peeling and reliability. Specifically, when the bonding strength is expressed in terms of surface energy, it is 0.5 J / m 2 Preferably, it is 1.0 J / m or more. 2 More preferably, it is 2.5 J / m or more. 2 More preferably, it is equal to or greater than this. When the laminate includes a first substrate and a second substrate, the surface energy, which represents the bonding strength between the first substrate and the second substrate, is preferably within the above range. The surface energy of the laminate can be determined by the blade insertion test described below.

[0053] The laminate preferably has a ratio of the total area of ​​voids (void area ratio) of 30% or less, more preferably 20% or less, and even more preferably 10% or less. The void area ratio is calculated by dividing the total area of ​​voids by the total area where transmitted light was observable in infrared light transmission observation, and multiplying the result by 100. If infrared light transmission observation is difficult, the void area ratio can be determined by a similar method using reflected waves from an ultrasonic microscope, transmitted waves from an ultrasonic microscope, or reflected infrared light, preferably using reflected waves from an ultrasonic microscope.

[0054] <Composition> The composition of the present embodiment contains at least one of a compound (X1) having a structure represented by the following general formula (1) and a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and a molecular weight of 400 to 5000.

[0055] [ka]

[0056] In general formula (1), R1 and R3 each independently represent an organic group having 6 or less carbon atoms, R2 represents a methylene group, an ethylene group, a propylene group, or a phenylene group, a represents 2 or 3, b represents the number 3-a, and X1 represents a structure derived from a carboxylic acid dianhydride.

[0057] [ka]

[0058] In general formula (2), R1 and R3 each independently represent an organic group having 6 or less carbon atoms, R2 represents a methylene group, an ethylene group, a propylene group, or a phenylene group, a represents 2 or 3, b represents the number 3-a, X1 represents a structure derived from a carboxylic acid dianhydride, X2 represents a structure derived from an amine compound, and n represents a positive number.

[0059] The composition allows the formation of a resin layer with less residual stress than a composition containing unreacted precursors of compound (X1) or compound (X2), such as a silane coupling agent, a carboxylic acid dianhydride, or an amine compound. The reason for this is not entirely clear, but it is thought that, for example, by having the precursors of compound (X1) or compound (X2) in a reacted state before applying the composition to the substrate, the cure shrinkage of the resin layer associated with the reaction is suppressed, and the residual stress of the resin layer is reduced, compared to when a resin layer is formed by reacting these precursors on a substrate.

[0060] In general formula (1), X1 is a structure derived from a carboxylic dianhydride, preferably containing a ring structure. Furthermore, the amide group and carboxyl group bonded to X1 react on the substrate to form an imide bond. Therefore, the resulting resin layer exhibits excellent heat resistance.

[0061] In general formula (1), a is preferably 2. In general formula (1), the organic group having 6 or less carbon atoms represented by R1 and R3 includes an alkyl group having 6 or less carbon atoms, preferably 3 or less carbon atoms, more preferably 2 or less carbon atoms.

[0062] In general formula (2), X1 and X2 are structures derived from a carboxylic acid dianhydride and an amine compound, respectively, and preferably contain a ring structure. Furthermore, the amide group and carboxyl group bonded to X1 react on the substrate to form an imide bond. Therefore, the resulting resin layer exhibits excellent heat resistance.

[0063] In general formula (2), a is preferably 2. In general formula (2), the organic group having 6 or less carbon atoms represented by R1 and R3 includes an alkyl group having 6 or less carbon atoms, preferably 3 or less carbon atoms, more preferably 2 or less carbon atoms. In general formula (2), n is not particularly limited as long as it is a positive number, but may be, for example, within the range of 1 or more and 6 or less. The compound (X2) represented by the general formula (2) may be in a state where a structure derived from a carboxylic acid dianhydride and a structure derived from an amine compound are alternately arranged (polyamic acid).

[0064] The compound (X1) contained in the composition may be a compound having a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure. The compound (X2) contained in the composition may be a compound having a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure, and a structure obtained by reacting an amine compound (C) having a molecular weight of 90 to 600, no Si—O bond, and a ring structure, with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure.

[0065] In the present disclosure, the carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure and the amine compound (C) having a molecular weight of 90 to 600 and a ring structure without an Si—O bond may be simply referred to as the carboxylic acid dianhydride (B) and the amine compound (C), respectively.

[0066] (Silane coupling agent (A)) The silane coupling agent (A) is a compound having one or more Si-O bonds in the molecule, which reacts with a carboxylic acid dianhydride to produce the compound (X1) or the compound (X2). The Si-O bonds in the silane coupling agent (A) contribute to improving the bonding strength between the resin layer formed using the composition and the substrate.

[0067] The silane coupling agent (A) is not particularly limited as long as it has a functional group capable of reacting with the anhydride group of the carboxylic acid dianhydride (B). Specific examples of the functional group include an amino group, an epoxy group, and an isocyanate group. From the viewpoint of the thermal expansion coefficient and bonding strength of the resin layer, the silane coupling agent (A) preferably has an amino group, and from the viewpoint of forming an imide structure in the resin layer to improve heat resistance, a compound having a primary amino group (-NH2) is more preferred.

[0068] The silane coupling agent (A) may be used alone or in combination of two or more.

[0069] The molecular weight of the silane coupling agent (A) is not particularly limited and may be, for example, 130 or more and 10,000 or less, 130 or more and 5,000 or less, or 130 or more and 2,000 or less.

[0070] An example of the silane coupling agent (A) having an amino group is a compound represented by the following formula (A-3).

[0071] [ka]

[0072] In formula (A-3), R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted. 2 and R 3 R each independently represents an alkylene group having 1 to 12 carbon atoms, an ether group, or a carbonyl group which may be substituted (the skeleton may contain a carbonyl group, an ether group, etc.). 4 and R 5 each independently represents an optionally substituted alkylene group having 1 to 4 carbon atoms or a single bond. Ar represents a divalent or trivalent aromatic ring. X 1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms which may be substituted. X 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an alkyl group having 1 to 5 carbon atoms which may be substituted (which may contain a carbonyl group, an ether group, etc. in the skeleton). 1 , R 2 , R 3 , R 4 , R 5 , X 1 may be the same or different. R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 In the above, the substituents on the alkyl group and alkylene group each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, and halogens. The divalent or trivalent aromatic ring in Ar includes, for example, a divalent or trivalent benzene ring. 2 Examples of the aryl group in the formula (I) include a phenyl group, a methylbenzyl group, and a vinylbenzyl group.

[0073] Specific examples of the silane coupling agent represented by formula (A-3) include N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, Examples of suitable silane include (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, trimethoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, and acetamidopropyltrimethoxysilane.

[0074] Examples of silane coupling agents containing an amino group other than those represented by formula (A-3) include N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, piperazinylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-(4-(methoxydimethylsilyl)phenyl)benzamide, 3,5-diamino-N-(4-(triethoxysilyl)phenyl)benzamide, and 5-(ethoxydimethylsilyl)benzene-1,3-diamine.

[0075] The silane coupling agent (A) having an amino group may be used alone or in combination of two or more kinds.

[0076] (Carboxylic acid dianhydride (B)) The carboxylic acid dianhydride (B) is a compound having one or more ring structures and two anhydride groups in the molecule and having a molecular weight of 200 or more and 600 or less. The molecular weight of the carboxylic acid dianhydride (B) may be 200 or more and 400 or less. The carboxylic acid dianhydride (B) may be used alone or in combination of two or more.

[0077] Examples of the ring structure that the carboxylic acid dianhydride (B) has in its molecule include an alicyclic structure, an aromatic ring (including a heterocyclic ring), etc. The carboxylic acid dianhydride (B) may have one ring structure or multiple ring structures in its molecule.

[0078] Examples of the alicyclic structure include an alicyclic structure having from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specific examples of the alicyclic structure include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.

[0079] The aromatic ring structure is not particularly limited as long as it is a ring structure exhibiting aromaticity, and examples thereof include benzene-based aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring; aromatic heterocycles such as a pyridine ring and a thiophene ring; and non-benzene-based aromatic rings such as an indene ring and an azulene ring.

[0080] The ring structure contained in the molecule of the carboxylic acid dianhydride (B) is preferably at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a naphthalene ring, and more preferably at least one of a benzene ring and a naphthalene ring from the viewpoint of further improving the heat resistance of the resin layer. Furthermore, from the viewpoint of suppressing the generation of voids in the resin layer when the composition is used to form the resin layer between multiple substrates, it is preferable that the composition contains two or more benzene rings.

[0081] When the carboxylic acid dianhydride (B) has multiple ring structures in the molecule, the multiple ring structures may be the same or different, may form a condensed ring, or may be bonded by a single bond or via a linking group such as an ether group, a carbonyl group, a sulfonyl group, or a methylene group.

[0082] The carboxylic acid dianhydride (B) may have a fluorine atom in the molecule. For example, it may have 1 to 6 fluorine atoms in the molecule, or may have 3 to 6 fluorine atoms in the molecule. For example, the carboxylic acid dianhydride (B) may have a fluoroalkyl group in the molecule, specifically, it may have a trifluoroalkyl group or a hexafluoroisopropyl group.

[0083] Examples of the carboxylic acid dianhydride (B) include dianhydrides of compounds having a ring structure in the molecule and four carboxy groups capable of forming an anhydride group. For example, anhydrides of alicyclic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; benzenetetracarboxylic acid dianhydrides such as pyromellitic acid; naphthalenetetracarboxylic acid dianhydrides such as 1,4,5,8-naphthalenetetracarboxylic acid and 2,3,6,7-naphthalenetetracarboxylic acid; dianhydrides of biphenyltetracarboxylic acids such as 3,3',4,4'-biphenyltetracarboxylic acid; Benzophenonetetracarboxylic acid dianhydrides such as benzophenone-3,3',4,4'-tetracarboxylic acid diphthalic dianhydrides such as 4,4'-oxydiphthalic acid (ODPA), 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid)tetramethyldisiloxane, 4,4'-(ethyne-1,2-diyl)diphthalic acid, 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, and 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid; perylenecarboxylic acid dianhydrides such as perylene-3,4,9,10-tetracarboxylic acid; Anthracenecarboxylic acid dianhydrides such as anthracene-2,3,6,7-tetracarboxylic acid; Fluorinated aromatic carboxylic acid dianhydrides such as 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, and 1,4-ditrifluoromethylpyromellitic acid; Bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene dianhydride; 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic acid (IPBDA) dianhydride; Examples include dianhydride of bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene (TAHQ).

[0084] The content of the carboxylic acid dianhydride (B) in the composition is, for example, an amount such that the ratio (A / B) of the functional group equivalent number A of the silane coupling agent (A) capable of reacting with the anhydride group of the carboxylic acid dianhydride (B) to the anhydride group equivalent number B of the carboxylic acid dianhydride (B) is preferably 0.9 or more and 1.1 or less, more preferably 0.95 or more and 1.05 or less, and even more preferably 0.98 or more and 1.02 or less.

[0085] When the composition further contains a compound capable of reacting with an anhydride group of the carboxylic dianhydride (B), such as the compound (C) described below, the amount is such that the ratio (A' / B') of the functional group equivalent number A' of all the compounds capable of reacting with an anhydride group of the carboxylic dianhydride (B) to the anhydride group equivalent number B' of the carboxylic dianhydride (B) is preferably 0.9 or more and 1.1 or less, more preferably 0.95 or more and 1.05 or less, and even more preferably 0.98 or more and 1.02 or less.

[0086] (Amine compound (C)) The amine compound (C) is a compound having one or more ring structures and one or more amino groups in the molecule, a molecular weight of 90 to 600, and no Si—O bond. The amine compound (C) may be used alone or in combination of two or more.

[0087] The amine compound (C) may have one or more amino groups in its molecule, but from the viewpoint of reducing the thermal expansion coefficient of the resin layer, it preferably has more than one amino group, and more preferably has two (diamine) or three (triamine) amino groups. From the viewpoint of forming an imide structure in the resin layer to improve heat resistance, it is more preferable that the amine compound (C) has a primary amino group (-NH).

[0088] From the viewpoint of reducing the thermal expansion coefficient of the resin layer, it is preferable that the amine compound (C) has one or more amino groups directly bonded to the ring structure. When the molecular structure of the compound (X2) contains a structure derived from an amino group directly bonded to the ring structure, it is thought that the rigidity of the molecular structure increases, further reducing the thermal expansion coefficient.

[0089] In the present disclosure, an "amino group directly bonded to a ring structure" refers to an amino group bonded to a ring structure via a single bond (i.e., not via a carbon atom, etc.).

[0090] The amine compound (C) may have one ring structure or multiple ring structures in the molecule. When the amine compound (C) has multiple ring structures in the molecule, the multiple ring structures may be the same or different, or may form a condensed ring. Alternatively, the multiple ring structures may be bonded by a single bond or via a linking group such as an ether group, a carbonyl group, a sulfonyl group, or a methylene group.

[0091] Examples of the ring structure contained in the amine compound (C) include an alicyclic structure, an aromatic ring (including a heterocyclic ring) structure, and a condensed ring structure thereof. Examples of the alicyclic structure include alicyclic structures having 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms. The ring structure may be saturated or unsaturated. More specific examples include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.

[0092] Examples of aromatic ring structures include aromatic ring structures having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Specific examples include benzene-based aromatic ring structures such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring, and non-benzene-based aromatic ring structures such as a pyridine ring, a thiophene ring, an indene ring, and an azulene ring.

[0093] The heterocyclic structure may be a 3- to 10-membered ring, preferably a 5- or 6-membered ring. Heteroatoms contained in the heterocyclic ring include sulfur, nitrogen, and oxygen atoms, and may be one or more of these. Specific examples of the heterocyclic structure include an oxazole ring, a thiophene ring, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, an isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a triazine ring, an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, a purine ring, and a quinoxaline ring.

[0094] The ring structure contained in the molecule of the amine compound (C) is more preferably a benzene ring, a cyclohexane ring, or a benzoxazole ring.

[0095] The ring structure contained in the molecule of the amine compound (C) may have a substituent other than an amino group, such as an alkyl group having 1 to 6 carbon atoms or an alkyl group substituted with a halogen atom.

[0096] Specific examples of the amine compound (C) include the following compounds: Examples of the alicyclic amine include cyclohexylamine and dimethylaminocyclohexane. Examples of aromatic ring amines include diaminodiphenyl ether, xylylene diamine (preferably paraxylylene diamine), diaminobenzene, diaminotoluene, methylenedianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl (TFDB), diaminobenzophenone, diaminobenzanilide, bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcinol, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2'-dimethylbenzidine, and tris(4-aminophenyl)amine. For example, heterocyclic amines having a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, and tris(4-aminophenyl)amine. Furthermore, examples of amine compounds having both a heterocycle and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine and 2-(4-aminophenyl)benzoxazol-5-amine (AAPD).

[0097] (Method for obtaining compound (X1)) As a method for obtaining the compound (X1) by reacting the silane coupling agent (A) with the carboxylic acid dianhydride (B), for example, a method can be mentioned in which the silane coupling agent (A) is gradually added dropwise to the carboxylic acid dianhydride (B) while adding the silane coupling agent (A) to a solvent and stirring, to obtain the compound (X1).

[0098] (Method for obtaining compound (X2)) Examples of a method for obtaining the compound (X2) by reacting the silane coupling agent (A), the carboxylic acid dianhydride (B), and the amine compound (C) include a method in which a solvent is added to the amine compound (C) and the mixture is stirred while the carboxylic acid dianhydride (B) is added, the mixture is stirred until the viscosity of the resulting reaction product (polymer) becomes constant, and then the silane coupling agent (A) is gradually added dropwise to obtain the compound (X2).

[0099] (Precursor of Resin (D)) The composition of this embodiment may further contain a compound other than the compound (X1) and the compound (X2). For example, it may further contain a precursor of a resin (D) having a CTE of 90 ppm / K or less between 50° C. and 150° C. When the composition contains a precursor of the resin (D), the thermal expansion coefficient of the resulting resin layer tends to be further reduced.

[0100] Specific examples of the resin (D) having a CTE of 90 ppm / K or less between 50° C. and 150° C. include at least one selected from the group consisting of polyimides and polybenzoxazoles. The CTE of the resin (D) can be measured in the same manner as the CTE of the resin layer.

[0101] When the composition contains resin (D), the proportion of resin (D) contained in the composition is preferably 99% by mass to 30% by mass of the total non-volatile content of the composition, from the viewpoint of the balance between the thermal expansion coefficient and bonding strength of the resulting resin layer. In the present disclosure, "non-volatile content" refers to components other than components (such as solvents) that are removed when the composition becomes a cured product.

[0102] (organic solvent) The composition may contain an organic solvent. The organic solvent is not particularly limited as long as it can dissolve compound (X). Examples of the organic solvent include aprotic solvents, phenolic solvents, ether solvents, and glycolic solvents. The organic solvent may be used alone or in combination of two or more kinds.

[0103] Specific examples of aprotic solvents include amide solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylcaprolactam, 1,3-dimethylimidazolidinone, and tetramethylurea; lactone solvents such as γ-butyrolactone and γ-valerolactone; phosphorus-containing amide solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide; sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide, and sulfolane; ketone solvents such as cyclohexanone and methylcyclohexanone; tertiary amine solvents such as picoline and pyridine; and ester solvents such as 2-methoxy-1-methylethyl acetate. Specific examples of phenol-based solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol. Specific examples of ether-based solvents and glycol-based solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, and 1,4-dioxane.

[0104] The boiling point of the organic solvent at normal pressure is preferably 60°C to 300°C, more preferably 140°C to 280°C, and even more preferably 170°C to 270°C. If the boiling point of the solvent is 300°C or lower, the organic solvent can be easily volatilized and removed in the resin layer formation step. If the boiling point of the solvent is 60°C or higher, a resin layer with a uniform surface condition can be obtained.

[0105] When the composition contains an organic solvent, the content thereof is not particularly limited, and may be, for example, 1.0% by mass or more and 99.99896% by mass or less, or 40% by mass or more and 99.99896% by mass or less, relative to the entire composition.

[0106] (Other ingredients) The composition may contain components other than those described above, if necessary. For example, when the composition is required to have selectivity in plasma etching resistance (for example, when used as a gap fill material or a buried insulating film), it may contain a metal alkoxide represented by the following general formula (I). R1 n M(OR2) m-n (I) (In the formula, R1 is a non-hydrolyzable group, R2 is an alkyl group having 1 to 6 carbon atoms, M is at least one metal atom selected from the group consisting of Ti, Al, Zr, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In, m is the valence of the metal atom M and is 3 or 4, n is an integer of 0 to 2 when m is 4, and is 0 or 1 when m is 3, when there are multiple R1s, each R1 may be the same as or different from another, and when there are multiple OR2s, each OR2 may be the same as or different from another.)

[0107] When insulating properties are required for a film produced from the composition (for example, for use as an insulating film for a through-silicon via or as a buried insulating film), the composition may contain a silane compound (excluding those that fall under the category of silane coupling agent (A)) to improve insulating properties or mechanical strength. Specific examples of silane compounds include tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxylcyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisilethylene, and 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

[0108] The composition may also contain benzotriazole or a derivative thereof, for example to inhibit copper corrosion.

[0109] The pH of the composition is not particularly limited, but is preferably 2.0 or higher and 12.0 or lower. The composition preferably contains sodium and potassium at an elemental content of 10 ppb by mass or less, which can prevent problems with the electrical properties of the semiconductor device, such as transistor malfunctions.

[0110] The content of inorganic or resin fillers having a maximum diameter of 0.3 μm or more in the composition is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 0% by mass, of the total nonvolatile content. When the content of the filler in the composition is within the above range, bonding defects of the laminate can be suppressed even when the thickness of the resin layer formed using the composition is thin. Furthermore, when a first substrate on which a resin layer has been formed is laminated on a second substrate, alignment marks formed on each substrate may be recognized by a machine for alignment. When the content of the filler is within the above range, the transparency of the resin film is improved, enabling more accurate alignment.

[0111] (Use of the composition) The use of the composition of the present embodiment is not particularly limited, and it can be used for various purposes including the manufacture of semiconductor devices. For example, it may be used to form a layer on or between substrates, or it may be used to manufacture the above-mentioned laminate.

[0112] <Method of manufacturing laminate> The method for producing a laminate of this embodiment includes a first step of forming a layer containing the above-described composition on or between substrates, and a second step of curing the layer.

[0113] The details and preferred embodiments of the substrate and composition used in the above method are the same as those described above for the composition and laminate.

[0114] (1st step) The method for carrying out the first step is not particularly limited. From the viewpoint of forming a layer of uniform thickness on or between substrates, the composition is preferably in the form of a solution. The solution can be prepared, for example, using a solvent that may be contained in the composition described above.

[0115] The method for forming a layer containing the composition is not particularly limited, and may be a commonly used method. Examples include dipping, spraying, spin coating, and bar coating. Among these, bar coating is preferred when forming a layer having a thickness on the order of microns, and spin coating is preferred when forming a layer having a thickness on the order of nanometers (several nm to several hundred nm).

[0116] The method for forming a layer by spin coating is not particularly limited, and for example, a method can be used in which a solution is dropped onto the surface of a substrate while the substrate is rotating with a spin coater, and then the rotation speed of the substrate is increased to dry the substrate. The conditions such as the rotation speed of the substrate, the amount and time of dropping the solution, and the rotation speed of the substrate during drying are not particularly limited, and may be appropriately adjusted taking into account the thickness of the layer to be formed, etc.

[0117] (2nd process) In the second step, the layer containing the composition is cured. Specifically, the compound (X1) or the compound (X2) contained in the layer is reacted to form a layer containing a cured product (resin layer). The method for reacting the compound (X1) or the compound (X2) includes a method of heating the compound (X1) or the compound (X2) at a temperature at which the compound (X1) or the compound (X2) undergoes a curing reaction (for example, 70°C to 450°C). The temperature is preferably 100°C to 450°C, more preferably 100°C to 400°C, and even more preferably 150°C to 350°C.

[0118] The pressure during heating is not particularly limited. For example, heating may be performed at an absolute pressure exceeding 17 Pa but not exceeding atmospheric pressure. The pressure is preferably 1,000 Pa or more but not exceeding atmospheric pressure, more preferably 5,000 Pa or more but not exceeding atmospheric pressure, and even more preferably 10,000 Pa or more but not exceeding atmospheric pressure.

[0119] The heating method is not particularly limited, and can be a conventional method using a furnace or a hot plate. Examples of furnaces that can be used include SPX-1120 manufactured by Apex Corporation and VF-1000LP manufactured by Koyo Thermo Systems Co., Ltd. The heating step may be carried out in an air atmosphere or in an inert gas atmosphere (nitrogen gas, argon gas, helium gas, etc.).

[0120] The heating time is not particularly limited and may be, for example, 3 hours or less, or 1 hour or less. The lower limit of the heating time is not particularly limited and may be, for example, 30 seconds or more, 3 minutes or more, or 5 minutes or more.

[0121] When heating is performed at 70°C to 250°C, the heating time may be 300 seconds or less, 200 seconds or less, 120 seconds or less, or 80 seconds or less. In this case, the heating time may be 10 seconds, 20 seconds or more, or 30 seconds or more.

[0122] The heating temperature may be constant or may be varied. For example, the method may include a low-temperature heating step (70°C to 250°C) and a higher-temperature heating step (100°C to 450°C).

[0123] To shorten the heating step time, the layer containing the composition formed on the substrate may be irradiated with ultraviolet light. The ultraviolet light preferably has a wavelength of 170 to 230 nm, an excimer light having a wavelength of 222 nm, or an excimer light having a wavelength of 172 nm. Furthermore, it is preferable to irradiate the layer with ultraviolet light under an inert gas atmosphere.

[0124] (Pressure process) In the method for producing the laminate, it is preferable to press the laminate simultaneously with or after the second step (heating). By pressing the laminate, the contact area between the substrate and the resin layer increases, which tends to further improve the bonding strength.

[0125] When the laminate is pressed while being heated, the pressing pressure is preferably 0.1 MPa to 50 MPa, more preferably 0.1 MPa to 10 MPa, and even more preferably 0.1 MPa to 5 MPa. As the pressing device, for example, TEST MINI PRESS manufactured by Toyo Seiki Seisaku-sho, Ltd. may be used. When the laminate is pressed while being heated, the heating temperature is preferably 100° C. to 450° C., more preferably 100° C. to 400° C., and even more preferably 150° C. to 350° C. This tends to suppress damage to semiconductor circuits formed on the substrate.

[0126] When the laminate is heated and then pressed, the pressing pressure is preferably 0.1 MPa to 50 MPa, and more preferably 0.1 MPa to 10 MPa. As a pressing device, for example, TEST MINI PRESS manufactured by Toyo Seiki Seisaku-sho, Ltd. may be used. Furthermore, the pressing time is not particularly limited, but can be, for example, 0.5 seconds to 1 hour.

[0127] The temperature at which the laminate is heated and then pressed is preferably 10° C. or higher and lower than 100° C., more preferably 10° C. to 70° C., even more preferably 15° C. to 50° C., and particularly preferably 20° C. to 30° C. The temperature refers to the temperature of the surface of the substrate to which the composition is applied.

[0128] (Post-heating process) The method for producing the laminate may include a post-heating step of further heating the laminate after the second step. By including the post-heating step, the bonding strength tends to be better.

[0129] The heating temperature in the post-heating step is preferably 100°C to 450°C, more preferably 150°C to 420°C, and even more preferably 150°C to 400°C. The pressure during the post-heating step may be an absolute pressure of more than 17 Pa and equal to or less than atmospheric pressure, preferably equal to or more than 1000 Pa and equal to or less than atmospheric pressure, more preferably equal to or more than 5000 Pa and equal to or less than atmospheric pressure, and even more preferably equal to or more than 10000 Pa and equal to or less than atmospheric pressure. In the post-heating step, it is preferable not to press the laminate. [Example]

[0130] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0131] Example 1 A solution of 5.30 g of 4,4'-diamino-2,2'-dimethylbiphenyl (DMDB) in 77.00 g of N,N-dimethylacetamide (DMAc) was cooled to -5°C, followed by the addition of 6.81 g of pyromellitic dianhydride (PMDA) and stirring for 120 minutes. 2.39 g of 3-aminopropyldiethoxymethylsilane (3APDES) was then added dropwise and mixed to prepare a composition containing an amic acid-crosslinked silane compound (structure shown below, molecular weight calculated from the molecular structure: 1462).

[0132] [ka]

[0133] DMAc was added to the above composition to adjust the concentration to the film thickness shown in Table 1, and the solution was spin-coated onto a silicon substrate. After drying at 150°C for 1 minute, the substrate was heated at 350°C for 1 hour in a nitrogen atmosphere to form a layer containing imide-crosslinked siloxane (structure shown below).

[0134] [ka]

[0135] <Example 2> A composition containing an amic acid cross-linked silane compound (structure shown below, molecular weight calculated from the molecular structure: 1678) was prepared in the same manner as in Example 1, except that DMDB was changed to 8.00 g of TFDB.

[0136] [ka]

[0137] DMAc was added to the above composition to adjust the concentration to the film thickness shown in Table 1, and the solution was spin-coated onto a silicon substrate. After drying at 150°C for 1 minute, the substrate was heated at 350°C for 1 hour in a nitrogen atmosphere to form a layer containing imide-crosslinked siloxane (structure shown below).

[0138] [ka]

[0139] Example 3 A siloxaneimide film was formed on a Si substrate in the same manner as in Example 1, except that the concentration of the solution was changed so as to obtain the film thickness shown in Table 1.

[0140] Example 4 A siloxaneimide film was formed on a Si substrate in the same manner as in Example 2, except that the concentration of the solution was changed so as to obtain the film thickness shown in Table 1.

[0141] <Example 5> A composition containing an amic acid-crosslinked silane compound (structure shown below, molecular weight calculated from the molecular structure: 677) was prepared by dissolving 6.00 g of 3,3',4,4'-biphthalic dianhydride (BPDA) in 96.00 g of DMAc, followed by dropwise addition of 15.60 g of 3APDES.

[0142] [ka]

[0143] The composition was spin-coated onto a silicon substrate, dried at 150°C for 1 minute, and then heated at 200°C for 1 hour in a nitrogen atmosphere to form a layer containing imide-crosslinked siloxane (structure shown below).

[0144] [ka]

[0145] Example 6 A solution of 12.29 g of DMDB in 96.00 g of DMAc was cooled to −5°C, and then 11.36 g of PMDA and 0.85 g of phthalic acid were added to prepare a composition containing polyamic acid (structure shown below, molecular weight calculated from the molecular structure: 1369). Further, 21.52 g of the polyamic acid-containing composition was added to 9.41 g of the polyamic acid-containing composition, followed by mixing with 23.63 g of the composition of Example 3, to prepare a mixed composition containing polyamic acid and an amide-crosslinked silane compound. The mass ratio of the polyamic acid to the amide-crosslinked silane compound (polyamic acid:amide-crosslinked silane compound) was 80:20.

[0146] [ka]

[0147] The mixed composition was spin-coated onto a silicon substrate, dried at 150°C for 1 minute, and then heated at 350°C for 1 hour in a nitrogen atmosphere to form a layer containing polyimide and imide-crosslinked siloxane. The structure of the polyimide is represented by the following formula:

[0148] [ka]

[0149] Example 7 A solution of 5.30 g of DMDB in 90.00 g of DMAc was cooled to -5°C, followed by the addition of 9.69 g of ODPA and stirring for 120 minutes. 2.39 g of 3APDES was then added dropwise and mixed to prepare a composition containing an amic acid-crosslinked silane compound (structure shown below, molecular weight calculated from the molecular structure: 1738).

[0150] [ka]

[0151] The composition was spin-coated onto a silicon substrate, dried at 150°C for 1 minute, and then heated at 350°C for 1 hour in a nitrogen atmosphere to form a layer containing imide-crosslinked siloxane (structure shown below).

[0152] [ka]

[0153] Example 8 A solution of 5.63 g of AAPD in 77.00 g of DMAc was cooled to -5°C, followed by the addition of 6.81 g of PMDA and stirring for 120 minutes. 2.39 g of 3APDES was then added dropwise to prepare a composition containing an amic acid-crosslinked silane compound (structure shown below, molecular weight calculated from the molecular structure: 1488).

[0154] [ka]

[0155] The composition was spin-coated onto a silicon substrate, dried at 150°C for 1 minute, and then heated at 350°C for 1 hour in a nitrogen atmosphere to form a layer containing imide-crosslinked siloxane (structure shown below).

[0156] [ka]

[0157] <Reference example 1> A composition containing an amic acid-crosslinked silane compound (structure shown below, molecular weight calculated from the molecular structure: 841) was prepared by dissolving 14.31 g of TAHQ in 70.00 g of DMAc, and then slowly adding 11.96 g of 3APDES dropwise thereto and reacting.

[0158] [ka]

[0159] The composition was spin-coated onto a silicon substrate, dried at 150°C for 1 minute, and then heated at 200°C for 1 hour in a nitrogen atmosphere to form a layer containing imide-crosslinked siloxane (structure shown below).

[0160] [ka]

[0161] <Reference example 2> A composition containing an amic acid cross-linked silane compound (structure shown below, molecular weight calculated from the molecular structure: 903) was prepared by dissolving 11.27 g of IPBDA in 60.00 g of DMAc, and then adding 11.96 g of 3APDES dropwise to the solution to cause a reaction.

[0162] [ka]

[0163] The composition was spin-coated onto a silicon substrate, dried at 150°C for 1 minute, and then heated at 350°C for 1 hour in a nitrogen atmosphere to form a layer containing imide-crosslinked siloxane (structure shown below).

[0164] [ka]

[0165] <Comparative Example 1> A solution of 10.00 g of TFDB dissolved in 86.67 g of DMAc was cooled to −5° C., and then 6.82 g of PMDA was added and mixed to prepare a composition containing polyamic acid (structure shown below).

[0166] [ka]

[0167] The composition was spin-coated onto a silicon substrate, dried at 150° C. for 1 minute, and then heated at 350° C. for 1 hour in a nitrogen atmosphere to form a layer containing polyimide (structure shown below).

[0168] [ka]

[0169] <Comparative Example 2> According to the A2** method in THE JOURNAL OF PHYSICAL CHEMISTRY C, Vol. 115, pp. 12981-12989, 2011, a mixed solution of ethanol (EtOH), water, and nitric acid (HNO3) containing a hydrolyzate of bistriethoxysilylethane (BTESE) and a siloxane polymer was prepared. Water, ethanol, and 1-propanol were then added to prepare a solution containing 4.2% by weight of BTESE, 6.8% by weight of EtOH, 88.9% by weight of 1PrOH, and 0.075% by weight of HNO3. This composition was spin-coated onto a silicon substrate, dried at 125°C for 1 minute, and then heated at 400°C for 10 minutes in a nitrogen atmosphere to form a layer containing ethylene-bridged silicate.

[0170] <Comparative Example 3> According to the A2** method in THE JOURNAL OF PHYSICAL CHEMISTRY C, Vol. 115, pp. 12981-12989, 2011, a mixed solution of ethanol (EtOH), water, and nitric acid containing a tetraethoxysilane (TEOS) hydrolyzate and a siloxane polymer was prepared. Water, ethanol, and 1-propanol were then added to prepare a solution containing 8.4% by weight of TEOS, 12.9% by weight of EtOH, 75% by weight of 1-propanol (1PrOH), and 0.075% by weight of nitric acid (HNO). This composition was spin-coated onto a silicon substrate, dried at 125°C for 1 minute, and then heated at 400°C for 10 minutes in a nitrogen atmosphere to form a silica-containing layer.

[0171] <Comparative Example 4> A solution of 12.29 g of DMDB dissolved in 96.00 g of DMAc was cooled to −5°C, and then 11.36 g of PMDA and 0.85 g of phthalic acid were added to prepare a composition containing polyamic acid (structure shown below, molecular weight calculated from the molecular structure: 1369).

[0172] [ka]

[0173] The composition was spin-coated onto a silicon substrate, dried at 150° C. for 1 minute, and then heated at 350° C. for 1 hour in a nitrogen atmosphere to form a layer containing polyimide (structure shown below). [ka]

[0174] <Comparative Example 5> A silicon substrate was prepared on which a film (degree of cure: 100%) made of a polymer obtained by polymerizing divinylsiloxane-bis-benzocyclobutene (DVS-BCB) was formed.

[0175] <Evaluation> The physical properties of the layers formed on the silicon substrates in the examples and comparative examples were evaluated by the methods described below. The results are shown in Table 1. Table 1 shows the basic units of silicone resins estimated from raw material monomers.

[0176] (Analysis of cross-linked structure) The crosslinked structure in the resin layer was analyzed by FT-IR (Fourier transform infrared spectroscopy). The analytical equipment used is as follows. The results are shown in Table 1. ~FT-IR analyzer~ Infrared absorption analyzer (DIGILAB Excalibur (DIGILAB)) ~Measurement conditions~ IR light source: air-cooled ceramic Beam splitter: Wide range KBr Detector: Peltier-cooled DTGS Measurement wavenumber range: 7500 cm -1 ~400cm -1 Resolution: 4cm -1 Accumulation count: 256 Background: Si bare wafer Measurement atmosphere: N2 (10 L / min) IR (infrared) incident angle: 72° (=Brewster angle of Si) ~Judgment conditions~ The presence of imide bonds is at 1770 cm -1 , 1720cm -1 This was determined by the presence of a vibration peak. The presence of siloxane bonds is 1000 cm -1 ~1080cm -1 The vibration was judged by the presence of a vibration peak between The presence of an amide bond is indicated by a peak at 1650 cm -1 , 1520cm -1 This was determined by the presence of a vibration peak. The presence of the tetrahydronaphthalene structure is confirmed by the 1500 cm -1 This was determined by the presence of a vibration peak.

[0177] (Measurement of Si-Me / Si-O peak intensity ratio) The compositions used to form layers in the examples and comparative examples were applied to a resin film using an applicator (gap 250 μm) and cured by baking in a nitrogen atmosphere at 350°C for 1 hour. The films were then peeled off from the resin film to obtain freestanding films with thicknesses of 10 μm to 70 μm. The chemical bond state of the freestanding films was measured by a microscopic transmission method using a Fourier transform infrared (FTIR) spectrometer (Nicolet / iN10MX, manufactured by Thermo Scientific). The 1230 cm spectrum derived from Si-Me bonds was -1 ~1270cm -1 and the peak intensity of 1000-1100 cm due to Si-O bonds. -1 The ratio of the peak intensities between the two peaks was calculated, and the results are shown in Table 1.

[0178] (CTE measurement) Using a thermomechanical analyzer (TMA) (Hitachi High-Tech Science Corporation, TMA7100C), the expansion coefficient (tensile mode, load 0.1 N) of the freestanding film obtained in the same manner as in the measurement of the peak intensity ratio was measured in a nitrogen atmosphere at 0°C to 400°C. The CTE was calculated by fitting the equation (expansion coefficient) = (CTE) × (temperature) + (constant) to the data from 50°C to 150°C using the least squares method for the relationship curve between the expansion coefficient and temperature. The results are shown in Table 1.

[0179] (Tg measurement) Using a differential scanning calorimeter (DSC) (TA Instruments, DSC2500), the heat flow (heating rate and cooling rate: 10°C / min) of the freestanding film obtained in the same manner as in the peak intensity ratio measurement was measured in a nitrogen atmosphere from 23°C to 400°C, and Tg was calculated from the temperature of the inflection point. The results are shown in Table 1. Note that the heat flow measurement results from the second heating were used from the viewpoint of measurement reproducibility.

[0180] (Measurement of water absorption rate) According to the standard test method for water absorption (ASTM D570), the free-standing membrane obtained in the same manner as in the measurement of the peak intensity ratio was immersed in pure water (23°C, 24 hours) and the mass change before and after was measured to measure the water absorption. The results are shown in Table 1.

[0181] (Film thickness measurement) The thickness of the resin layer on the Si substrate was measured using an ellipsometer (SEMILAB PS-1100). The measured data was fitted with an optical multilayer model of air / resin layer / native oxide film / silicon substrate (the refractive index of the resin layer was calculated using a Cauchy model + Lorentz oscillator model). The results are shown in Table 1.

[0182] (Measurement of silicon atomic weight) Using an AXIS-NOVA (KRATOS) X-ray photoelectron spectrometer (XPS), the silicon atomic weight of the resin layer on the Si substrate was measured. Specifically, the total amount of each element detected in the wide spectrum was taken as 100%, and the silicon atomic weight on the surface of the resin layer was measured by measuring the atomic ratio from the peak intensity of the narrow spectrum of each element. The results are shown in Table 1.

[0183] (O / Si element ratio measurement) Using an AXIS-NOVA (KRATOS) for XPS, the O / Si element ratio of the resin layer on the Si substrate was measured. Specifically, the O / Si element ratio on the surface of the resin layer was measured by measuring the element ratio from the peak intensity of the O and Si narrow spectrum. The results are shown in Table 1.

[0184] (Measurement of nitrogen atomic weight) Using an AXIS-NOVA (KRATOS) XPS, the amount of nitrogen atoms in the resin layer of the Si substrate on which the resin layer was formed was measured. Specifically, the amount of nitrogen atoms on the surface of the resin layer was measured by measuring the atomic ratio from the peak intensity of the narrow spectrum of each element when the total amount of each element detected in the wide spectrum was taken as 100%. The results are shown in Table 1.

[0185] (Outgassing is 10 -5 (Measurement of temperature above 100 Pa) The Si substrate on which the resin layer was formed was cut into a 10 mm x 10 mm square to prepare a sample for outgassing measurement. Using the sample for outgassing measurement, the amount of outgassing was measured by heating using an ESCO EMD-WA1000S. The ambient pressure (base pressure) was 10 -7 The temperature was measured at a rate of 30°C / min. The surface temperature of the silicon substrate was measured by calibrating the thermocouple under the stage using the outgas peaks of standard samples (H+-implanted silicon, CaCO4-droplet, and Ar+-implanted silicon wafer). The temperature rises and the outgas pressure reaches 1×10 -5 The temperature at which the viscosity reached 1 Pa was determined. The results are shown in Table 1. The higher the temperature, the less likely the outgassing is to occur.

[0186] (Elastic modulus measured by AFM at 250℃) The elastic modulus of the Si substrate on which the resin layer was formed was calculated by fitting the force curve measured under vacuum at a stage temperature of 250°C using an AFM (product name E-sweep, manufactured by SII NanoTechnology, AFM force mapping mode, Si probe (spring constant equivalent to 2 N / m)) using the DMT theoretical formula. The results are shown in Table 1. The theoretical formula for DMT is shown below. In the formula, E represents the elastic modulus of the resin film, ν represents the Poisson's ratio of the resin film, R represents the tip diameter of the cantilever, δ represents the indentation depth, F represents the force applied to the sample, and F c indicates the maximum adhesive force. Poisson's ratio is assumed to be 0.33.

[0187]

number

[0188] (Measurement of uniformity) The cross section of the resin film on the Si substrate on which the resin layer was formed was observed using a scanning electron microscope (SEM) at an acceleration voltage of 10 kV, 3,000x magnification, and a 40 μm wide field of view to evaluate whether the resin layer had a uniform structure. If no voids or fillers were observed, the resin layer was judged to be uniform and rated as ○. If voids or fillers were observed, the resin layer was judged to have a non-uniform structure and rated as ×. The results are shown in Table 1.

[0189] <Preparation of laminate> A silicon substrate with a native oxide film formed on its surface was stacked on top of the layer prepared on the silicon substrate in the examples and comparative examples, and heated at 200°C for 30 minutes in a nitrogen atmosphere to prepare a laminate with a structure of silicon substrate / resin layer (layer equivalent to a resin layer in the comparative examples) / silicon substrate. The resulting laminate was evaluated for bonding strength (surface energy) and for void generation after heating at 300° C. for 30 minutes. The results are shown in Table 1.

[0190] (surface energy measurement) The surface energy (bonding strength) at the bonded interface of the laminate was measured by a blade insertion test according to the method described in the non-patent document "MP Maszara, G. Goetz, A. Cavigila, and J.B.M. McKitterick, Journal of Applied Physics, 64 (1988) 4943-4950." Specifically, a 0.25 mm thick blade was inserted between the substrates, and the distance from the blade edge to the separation of the substrates was measured using an infrared light source and an infrared camera. The surface energy was then measured according to the following formula:

[0191]

number

[0192] In the formula, γ is the surface energy (J / m 2), tb is the blade thickness (m), E is the Young's modulus (GPa) of the silicon substrates included in the first and second substrates, t is the thickness (m) of the first and second substrates, and L is the peeling distance (m) between the substrates from the blade tip. The results are shown in Table 1.

[0193] (Evaluation of void occurrence) The presence or absence of voids between the substrates of the laminate was observed using an infrared microscope. Specifically, the laminate was observed using infrared transmitted light using a semiconductor internal observation device C9597-42U30 (Hamamatsu Photonics K.K.) and an infrared microscope MX63-IR (Olympus Corporation). The voids on the entire surface of the laminate were compared before and after heating at 300°C for 30 minutes in a nitrogen atmosphere, and the presence or absence of newly generated voids after heating at 300°C for 30 minutes was confirmed. If no voids were observed, the result was recorded as "absent," and if voids were observed, the result was recorded as "present." The results are shown in Table 1.

[0194] [Table 1]

[0195] Blank cells in Table 1 indicate that the relevant item has not been tested. As shown in Table 1, the resin layer satisfying the conditions of this embodiment has a low coefficient of thermal expansion, and the surface energy measurement results show that it has excellent bonding strength with the substrate. Furthermore, no voids were observed after heating at 300°C for 30 minutes, indicating that it has excellent heat resistance.

Claims

1. a substrate and a resin layer, The resin layer has a coefficient of thermal expansion (CTE) of 50 ppm / K or less between 50°C and 150°C, a silicon atom content of 0.5 atm% or more and 10 atm% or less, a ratio of oxygen atoms to silicon atoms (O / Si) of 1 or more and 15 or less, a nitrogen atom content of 5 atm% or more and 10 atm% or less, and contains an imide-crosslinked siloxane.

2. a substrate and a resin layer, The resin layer has a coefficient of thermal expansion (CTE) of 50 ppm / K or less between 50°C and 150°C, a silicon atom content of 0.5 atm% or more and 10 atm% or less, a ratio of oxygen atoms to silicon atoms (O / Si) of 1 or more and 15 or less, and a 10 －７ The outgassing pressure measured in an environment of 10 Pa is －５ The laminate has a temperature of 450°C or higher.

3. a substrate and a resin layer, a resin layer having a coefficient of thermal expansion (CTE) of 50 ppm / K or less between 50°C and 150°C, a silicon atom content of 0.5 atm% or more and 10 atm% or less, and a ratio of oxygen atoms to silicon atoms (O / Si) of 1 or more and 15 or less, the substrate including a first substrate and a second substrate, and the resin layer being disposed between the first substrate and the second substrate.

4. The surface energy, which represents the bonding strength between the first substrate and the second substrate, is 2.5 J / m ２ The laminate according to claim 3 .

5. The laminate according to any one of claims 1 to 4, wherein the resin layer has a thickness of 0.001 µm or more and 20 µm or less.

6. The laminate according to any one of claims 1 to 5, wherein the substrate is a semiconductor substrate.

7. A composition for forming a resin layer of the laminate according to any one of claims 1 to 6, comprising at least one of a compound (X1) having a structure represented by the following general formula (1) and having a molecular weight of 400 to 5000, and a compound (X2) having a structure represented by the following general formula (2) and having a molecular weight of 400 to 5000: 【Chemistry 1】 In general formula (1), R １ and R ３ are each independently an organic group having 6 or less carbon atoms, and R ２ is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number 3-a, and X １ is a structure derived from a carboxylic acid dianhydride. 【Chemistry 2】 In general formula (2), R １ and R ３ are each independently an organic group having 6 or less carbon atoms, and R ２ is a methylene group, an ethylene group, a propylene group, or a phenylene group, a is 2 or 3, b is the number 3-a, and X １ is a structure derived from a carboxylic acid dianhydride, and X ２ is a structure derived from an amine compound, and n is a positive number.

8. The composition according to claim 7, wherein the compound (X1) has a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure.

9. The composition according to claim 7, wherein the compound (X2) has a structure obtained by reacting a silane coupling agent (A) with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure, and a structure obtained by reacting an amine compound (C) having a molecular weight of 90 to 600, having no Si—O bond, and a ring structure with a carboxylic acid dianhydride (B) having a molecular weight of 200 to 600 and a ring structure.

10. The composition according to any one of claims 7 to 9, wherein a in general formula (1) or general formula (2) is 2.

11. The composition according to any one of claims 7 to 10, further comprising a precursor of a resin (D) having a CTE of 90 ppm / K or less between 50°C and 150°C.

12. The composition according to claim 11, wherein the resin (D) comprises at least one selected from the group consisting of polyimides and polybenzoxazoles.

13. The composition according to any one of claims 7 to 12, further comprising an organic solvent.

14. A laminate comprising a substrate and a resin layer containing a cured product of the composition according to any one of claims 7 to 13.

15. A method for producing a laminate, comprising the steps of forming a layer containing the composition according to any one of claims 7 to 13 on or between substrates, and curing the layer.

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