Resin composition, method of manufacturing semiconductor device, cured product, and semiconductor device

Abstract

A resin composition comprising: (A) a polyimide precursor and at least one of a polyimide resin, wherein the polyimide precursor is at least one resin selected from the group consisting of polyamide, polyamide ester, polyamide salt, and polyamide amide; and (B) a solvent. The resin composition is used to form at least one of a first organic insulating film and a second organic insulating film in a method for manufacturing a semiconductor device including steps (1) to (5).

Description

[Technical Field]

[0001] This disclosure relates to a resin composition, a method for manufacturing a semiconductor device, a cured material, a semiconductor device, and a method for synthesizing a polyimide precursor. [Previous Technology]

[0002] In recent years, in order to improve the integration density of large-scale integrated circuits, three-dimensional mounting of semiconductor wafers has been studied, and one example of this has been disclosed in non-patent literature 1.

[0003] In the case of three-dimensional mounting of semiconductor wafers by chip-to-wafer (C2W) bonding, in order to perform fine bonding of wiring between devices, the use of hybrid bonding technology used in wafer-to-wafer (W2W) bonding is being investigated.

[0004] During C2W hybrid bonding, the heating during bonding may cause positional displacement of the substrate, wafer, etc., due to thermal expansion. To address this issue, Patent Document 1 discloses an example of a technique that lowers the bonding temperature by using a cyclic olefin resin. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-204818 [Non-Patent Document]

[0006] [Non-patent document 1] FC Chen et al., "System on Integrated Chips (SoIC TM) for 3D Heterogeneous Integration", 2019 IEEE 69thElectronic Components and Technology Conference (ECTC), p. 594-599 (2019) [Summary of the Invention]

[0007] [The problem the invention aims to solve]

[0008] When performing three-dimensional mounting of semiconductor wafers using C2W bonding, unlike W2W bonding, foreign matter (cut fragments) may sometimes be generated during the monolithization process to obtain the semiconductor wafer. This foreign matter may adhere to the bonding interface (the surface of the insulating film of the hybrid bonding) of the semiconductor wafer, etc. For the insulating film, the use of inorganic materials such as silicon dioxide is being investigated. However, since inorganic materials are hard, the adhered foreign matter can create large voids on the insulating film, for example, voids at the bonding interface with a width close to 1000 times the height of the foreign matter. Therefore, even if the hybrid bonding technology used for W2W bonding is simply applied to C2W bonding, the generation of such voids may cause bonding defects, resulting in a decrease in the yield of semiconductor device manufacturing. On the other hand, if a cleanroom and equipment with high cleanliness are used to prevent these bonding defects, a large amount of investment is required in the equipment such as the cleanroom.

[0009] In addition, when organic materials such as cyclic olefin resins are used as the material of the insulating film, the organic materials may deteriorate due to insufficient heat resistance and exposure of the insulating film to high temperature during C2W bonding, which may result in poor bonding at the interface between the substrate and the insulating film.

[0010] This disclosure is made in view of the above circumstances, and its object is to provide a resin composition capable of manufacturing a semiconductor device including an insulating film with suppressed void formation at the bonding interface and excellent heat resistance, a method for manufacturing a semiconductor device using the resin composition, a cured product formed by curing the resin composition, and a semiconductor device including an insulating film with suppressed void formation at the bonding interface and excellent heat resistance. Furthermore, the object of this disclosure is to provide a method for synthesizing a polyimide precursor, which can synthesize a polyimide precursor for preparing the resin composition. [Means for Solving the Problem]

[0011] Specific means for achieving the aforementioned objective are described below. <1> A resin composition comprising: (A) at least one of a polyimide precursor and a polyimide resin, wherein the polyimide precursor is at least one resin selected from the group consisting of polyamide, polyamide ester, polyamide salt, and polyamide amide; and (B) a solvent, and the resin composition is used to fabricate at least one of a first organic insulating film and a second organic insulating film in a semiconductor device manufacturing method comprising the following steps (1) to (5). Step (1): Preparing a first semiconductor substrate having a first substrate body and a first organic insulating film and a first electrode disposed on one side of the first substrate body. Step (2): Preparing a second semiconductor substrate having a second substrate body and a second organic insulating film and a plurality of second electrodes disposed on one side of the second substrate body. Step (3): Monolithically prepare the second semiconductor substrate to obtain a plurality of semiconductor wafers, each including an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one second electrode. Step (4): Adhere the first organic insulating film of the first semiconductor substrate to the organic insulating film portion of the semiconductor wafer. Step (5): Bond the first electrode of the first semiconductor substrate to the second electrode of the semiconductor wafer. <2> A resin composition comprising: (A) at least one of a polyimide precursor and a polyimide resin, wherein the polyimide precursor is at least one resin selected from the group consisting of polyamide, polyamide ester, polyamide salt and polyamide amide; and (B) a solvent, and the resin composition is used to prepare a hardened material that is polished together with an electrode by chemical mechanical polishing. <3> The resin composition as described in <1> or <2>, wherein the (A) polyimide precursor comprises a compound having a structural unit represented by the following general formula (1).

[0012]

[0013] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R6 and R7 independently represent a hydrogen atom or a monovalent organic group, respectively. <4> The resin composition as described in <3>, wherein in general formula (1), the tetravalent organic group represented by X is the group represented by the following formula (E).

[0014]

[0015] In formula (E), C represents a single bond, an alkyl group, a halogenated alkyl group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), an phenyl group, an ester bond (-OC(=O)-), a silylene bond (-Si(RA)2-; each of the two RAs independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n; each of the two RBs independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more) or a divalent group formed by combining at least two of these. <5> Resin composition as described in <3> or <4>, wherein in general formula (1), the divalent organic group represented by Y is the group represented by the following formula (H).

[0016]

[0017] In formula (H), each R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom, and each n independently represents an integer from 0 to 4. D represents a single bond, an alkyl group, a haloalkyl group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), an phenyl group, an ester bond (-OC(=O)-), a silene bond (-Si(RA)2-; each of the two RAs independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n; each of the two RBs independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more) or a divalent group formed by combining at least two of these. <6> A resin composition as described in any one of <3> to <5>, wherein in general formula (1), the monovalent organic groups of R6 and R7 are any one of the following general formula (2): alkyl, ethyl, isobutyl, and tributyl.

[0018]

[0019] In general formula (2), R8 to R10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and Rx represents a divalent linker. <7> The resin composition as described in any one of <1> to <6>, wherein the content of the solvent (B) is 1 to 10,000 parts by mass relative to a total of 100 parts by mass of the polyimide precursor and the polyimide resin described in (A). <8> The resin composition as described in any one of <1> to <7>, wherein the solvent (B) comprises at least one selected from the group consisting of compounds represented by the following formulas (3) to (6).

[0020]

[0021] In formulas (3) to (7), R1, R2, R8 and R10 are each independently an alkyl group having 1 to 4 carbon atoms, and R3 to R7 and R9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, and u is an integer from 0 to 3. <9> The resin composition as described in any one of <1> to <8> has a 5% heat weight reduction temperature of 200°C or higher when cured. <10> The resin composition as described in any one of <1> to <9> has a glass transition temperature of 100°C to 400°C when cured. <11> The resin composition as described in any one of <1> to <10>, wherein the ratio of the storage elastic coefficient G2 at a temperature 100°C higher than the glass transition temperature (Tg) of the cured material obtained by dynamic viscoelasticity measurement to the storage elastic coefficient G1 at a temperature 100°C lower than the glass transition temperature (Tg) of the cured material obtained by dynamic viscoelasticity measurement, i.e., G2 / G1, is 0.001 to 0.02. <12> The resin composition as described in any one of <1> to <11> further comprises (C) a photopolymerization initiator and (D) a polymerizable monomer. <13> The resin composition as described in any one of <1> to <12> is a negative photosensitive resin composition or a positive photosensitive resin composition, used to form a plurality of through holes for arranging a plurality of terminal electrodes on an organic insulating film disposed on one side of a substrate body by photolithography. <14> The resin composition as described in any one of <1> to <13>, when cured, has a tensile elastic modulus of 7.0 GPa or less at 25°C. <15> The resin composition as described in any one of <1> to <14>, when cured, has a coefficient of thermal expansion of 150 ppm / K or less. <16> A method for manufacturing a semiconductor device, comprising using the resin composition as described in any one of <1> to <15> to form at least one of a first organic insulating film and a second organic insulating film, and manufacturing the semiconductor device by performing the following steps (1) to (5). Step (1): Preparing a first semiconductor substrate having a first substrate body and a first organic insulating film and a first electrode disposed on one side of the first substrate body. Step (2): Preparing a second semiconductor substrate having a second substrate body and a second organic insulating film and a plurality of second electrodes disposed on one side of the second substrate body. Step (3): Monolithically processing the second semiconductor substrate to obtain a plurality of semiconductor wafers, each comprising an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one second electrode. Step (4): The first organic insulating film of the first semiconductor substrate is bonded to the organic insulating film portion of the semiconductor wafer.Step (5): The first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor wafer. <17> The method for manufacturing a semiconductor device as described in <16>, wherein in step (4), the first organic insulating film is bonded to the organic insulating film portion at a temperature where the temperature difference between the semiconductor wafer and the first semiconductor substrate is within 10°C. <18> The method for manufacturing a semiconductor device as described in <16> or <17>, wherein in the manufactured semiconductor device, the thickness of the organic insulating film formed by bonding the first organic insulating film to the organic insulating film portion is 0.1 μm or more. <19> A method for manufacturing a semiconductor device according to any one of <16> to <18>, wherein at least one of step (1) includes a step of grinding one side of the first semiconductor substrate and step (2) includes a step of grinding one side of the second semiconductor substrate, and the grinding rate of the first organic insulating film is at least one of 0.1 to 5 times the grinding rate of the first electrode and the grinding rate of the second organic insulating film is at least one of 0.1 to 5 times the grinding rate of the second electrode. <20> A method for manufacturing a semiconductor device according to any one of <16> to <19>, wherein the thickness of the second insulating film is greater than the thickness of the first insulating film. <21> A method for manufacturing a semiconductor device according to any one of <16> to <19>, wherein the thickness of the second insulating film is less than the thickness of the first insulating film. <22> A cured material formed by curing a resin composition according to any one of <1> to <15>. <23> A semiconductor device includes: a first semiconductor substrate having a first substrate body, and a first organic insulating film and a first electrode disposed on one side of the first substrate body; and a semiconductor wafer having a semiconductor wafer substrate body, and an organic insulating film portion and a second electrode disposed on one side of the semiconductor wafer substrate body, wherein the first organic insulating film of the first semiconductor substrate is bonded to the organic insulating film portion of the semiconductor wafer, and the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor wafer, wherein at least one of the first organic insulating film and the organic insulating film portion is an organic insulating film formed by curing a resin composition as described in any one of <1> to <15>. <24> A method for synthesizing a polyimide precursor, comprising the following steps: reacting a tetracarboxylic acid dianhydride and a diamine compound represented by H2N-Y-NH2 (where Y is a divalent organic group) in 3-methoxy-N,N-dimethylpropane amide to obtain a polyimide solution; and acting a dehydrating condensing agent and a compound represented by R-OH (where R is a monovalent organic group) on the polyimide solution.<25> The method for synthesizing polyimide precursors as described in <24>, wherein the dehydrating condensing agent comprises at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC) and 1,3-diisopropylcarbodiimide (DIC). [Effects of the invention].

[0022] According to this disclosure, a resin composition capable of manufacturing a semiconductor device including an insulating film with suppressed void formation at the bonding interface and excellent heat resistance can be provided; a method for manufacturing a semiconductor device using the resin composition; a cured product formed by curing the resin composition; and a semiconductor device including an insulating film with suppressed void formation at the bonding interface and excellent heat resistance can be provided. Furthermore, this disclosure provides a method for synthesizing a polyimide precursor capable of synthesizing a polyimide precursor used to prepare the resin composition.

Implementation Method

[0024] Hereinafter, the forms used to implement this disclosure will be described in detail. However, this disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless specifically stated otherwise. The same applies to numerical values ​​and their ranges, which do not limit this disclosure.

[0025] In this disclosure, the term "A or B" may include either A or B, or both. In this disclosure, the term "process" includes not only processes independent of other processes, but also processes that cannot be clearly distinguished from other processes, as long as the purpose of the process is achieved. In this disclosure, in numerical ranges represented by "~", the values ​​recorded before and after "~" are respectively the minimum and maximum values. In the numerical ranges recorded in stages in this disclosure, the upper or lower limit of one numerical range can also be replaced by the upper or lower limit of other numerical ranges recorded in stages. In addition, in the numerical ranges recorded in this disclosure, the upper or lower limit of the numerical range can also be replaced by the values ​​shown in the embodiments. In this disclosure, each component may also contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, unless otherwise specified, the content or percentage of each component refers to the total content or percentage of the multiple substances present in the composition. In this disclosure, the terms "layer" or "film" are used to refer to both the entirety of the area in which the layer or film exists and the portion of the area in which it is formed. In this disclosure, the thickness of a layer or film is a value provided as an arithmetic mean of the thicknesses measured at five points on the layer or film. The thickness of a layer or film can be measured using a micrometer or similar device. In this disclosure, when the thickness of a layer or film can be measured directly, a micrometer is used. Alternatively, when measuring the thickness of a single layer or the total thickness of multiple layers, the measurement can be performed by observing a cross-section of the object under test using an electron microscope. In this disclosure, "(meth)acrylate" refers to both "acrylate" and "methacrylate". In this disclosure, when a functional group has substituents, the number of carbons in the functional group refers to the total number of carbons, including the number of carbons in the substituents. In this disclosure, when embodiments are described with reference to drawings, the structure of the embodiment is not limited to the structure shown in the drawings. In addition, the size of the components in each figure is conceptual, and the relative size relationship between components is not limited to this.

[0026] <Resin Composition> The resin composition disclosed herein comprises: (A) at least one of a polyimide precursor and a polyimide resin, wherein the polyimide precursor is at least one resin selected from the group consisting of polyamide, polyamide ester, polyamide salt, and polyamide amide; and (B) a solvent, and the resin composition is used to fabricate at least one of a first organic insulating film and a second organic insulating film in a semiconductor device manufacturing method comprising the following steps (1) to (5). Step (1): Preparing a first semiconductor substrate having a first substrate body and a first organic insulating film and a first electrode disposed on one side of the first substrate body. Step (2): Preparing a second semiconductor substrate having a second substrate body and a second organic insulating film and a plurality of second electrodes disposed on one side of the second substrate body. Step (3): Monolithically processing the second semiconductor substrate to obtain a plurality of semiconductor wafers, each comprising an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one second electrode. Step (4): The first organic insulating film of the first semiconductor substrate is bonded to a portion of the organic insulating film of the semiconductor wafer. Step (5): The first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor wafer. Specific examples of each of steps (1) to (5) will be described in the section on the method for manufacturing a semiconductor device described later.

[0027] The cured product, i.e., the insulating film, obtained by curing a resin composition containing at least one of (A) a polyimide precursor and a polyimide resin, has a lower elastic modulus and is more flexible than a molded product containing inorganic materials. Therefore, when a first organic insulating film and a second organic insulating film, both of which are the insulating film, are laminated, even if foreign matter or the like is present on the surface of the first organic insulating film or the surface of the second organic insulating film, the insulating film at the bonding interface is easily deformed, allowing the foreign matter to be contained within the insulating film without creating large voids. Furthermore, compared to a cured product obtained by curing a resin composition containing acrylic resin, epoxy resin, etc., the cured product obtained by curing a resin composition containing at least one of a polyimide precursor and a polyimide resin has higher heat resistance, thus suppressing the tendency for poor bonding at the interface between the substrate and the insulating film due to resin deterioration during the semiconductor device manufacturing process. In the above respects, the resin composition disclosed herein exhibits excellent reliability in the semiconductor device manufacturing process and can achieve high yield.

[0028] A modified example of the resin composition disclosed herein may be as follows: a resin composition comprising (A) at least one of a polyimide precursor and a polyimide resin (the polyimide precursor being at least one resin selected from the group consisting of polyamide, polyamide ester, polyamide salt, and polyamide amide) and (B) a solvent, and used to prepare a hardened material that is ground together with an electrode by chemical mechanical polishing (CMP). In the modified resin composition, when an electrode containing a metal such as copper and an insulating film that is the hardened material obtained by CMP are ground, the thickness of the electrode and the thickness of the insulating film can be easily and appropriately adjusted. For example, the surface of the insulating film can be easily adjusted to a position slightly lower than the surface of the electrode, preferably the height difference between the surface of the insulating film and the surface of the electrode can be easily adjusted to 1 nm to 300 nm. Therefore, the modified resin composition has excellent CMP adaptability.

[0029] From the viewpoint of the heat resistance of the cured material, the 5% heat weight reduction temperature of the cured material obtained by curing the resin composition disclosed herein is preferably 200°C or higher, and more preferably 250°C or higher. Furthermore, there is no particular limitation on the upper limit of the 5% heat weight reduction temperature of the cured material; for example, it may be 450°C or lower.

[0030] The 5% thermogravimetric reduction temperature of the cured material is determined as follows. First, the resin composition is heated in a nitrogen atmosphere at a predetermined curing temperature (e.g., 150°C to 375°C) for at least 1 hour to obtain a cured material. 10 mg of the obtained cured material is placed in a thermogravimetric measuring device (e.g., Shimadzu TGA-50) and heated in a nitrogen atmosphere from 25°C to 500°C at a rate of 10°C / min. The temperature at which the weight decreases by 5% from the point before heating is taken as the 5% thermogravimetric reduction temperature.

[0031] From the viewpoint of bonding at low temperatures, the glass transition temperature of the cured product formed by curing the resin composition disclosed herein is preferably 100 to 400°C, more preferably 150 to 350°C.

[0032] The Tg of the cured material was determined as follows. First, the resin composition was heated for 2 hours in a nitrogen atmosphere at a predetermined curing temperature (e.g., 150°C to 375°C) that allows the curing reaction to occur, to obtain a cured material. The obtained cured material was cut into a 5 mm × 50 mm × 3 mm cuboid, and the dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device (e.g., the RSA-G2 manufactured by TA Instruments) and a tensile clamp, at a frequency of 1 Hz and a heating rate of 5°C / min, within a temperature range of 50°C to 350°C. Regarding Tg, the temperature of the peak portion was defined in tanδ, which was obtained by the ratio of the storage elastic coefficient to the loss elastic coefficient obtained by the above method.

[0033] Regarding the cured product obtained by curing the resin composition disclosed herein, the ratio G2 / G1 of the storage elastic coefficient G2 at a temperature 100°C higher than the Tg of the cured product, determined by dynamic viscoelasticity measurement, to the storage elastic coefficient G1 at a temperature 100°C lower than the Tg of the cured product, determined by dynamic viscoelasticity measurement, is preferably 0.001 to 0.02. In this disclosure, the storage elastic coefficient can be determined by the method described in the description of the method for determining the glass transition temperature.

[0034] The resin composition disclosed herein may be a negative photosensitive resin composition or a positive photosensitive resin composition. Furthermore, the negative photosensitive resin composition or the positive photosensitive resin composition may be used in at least one of the following situations: in step (1), a plurality of through holes for configuring a plurality of terminal electrodes are provided on a first organic insulating film disposed on one side of the first substrate body; and in step (2), a plurality of through holes for configuring a plurality of terminal electrodes are provided on a second organic insulating film disposed on one side of the second substrate body.

[0035] From the viewpoint of containing foreign matter within the insulating film when it adheres to the bonding interface without creating further large voids, thereby appropriately reducing bonding defects, the tensile elastic modulus of the cured product formed by curing the resin composition disclosed herein is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, even more preferably 3.0 GPa or less, particularly preferably 2.0 GPa or less, and even more preferably 1.5 GPa or less. The cured product formed by curing the resin composition disclosed herein has a lower tensile elastic modulus compared to inorganic materials such as silicon dioxide. In this disclosure, the tensile elastic modulus is a value measured at 25°C based on Japanese Industrial Standard (JIS) K 7161 (1994).

[0036] Regarding the hardened material obtained by hardening the resin composition disclosed herein, the storage elastic modulus at 300°C can be 0.5~0.001 GPa or 0.1~0.01 GPa.

[0037] The coefficient of thermal expansion of the cured material formed by curing the resin composition disclosed herein is preferably 150 ppm / K or less, more preferably 100 ppm / K or less, and even more preferably 70 ppm / K or less. Therefore, the coefficient of thermal expansion of the insulating film of the cured material is equal to or close to the coefficient of thermal expansion of the electrode. Thus, even when heat is generated during the use of a semiconductor device, damage to the semiconductor device caused by the difference in the coefficients of thermal expansion between the insulating layer and the electrode can be suppressed. The coefficient of thermal expansion is a measure of the expansion of the length of the cured material per unit temperature due to an increase in temperature, and can be calculated by measuring the change in length of the cured material at 100°C to 150°C using a thermomechanical analysis device or similar apparatus.

[0038] Hereinafter, the components contained in the resin composition disclosed herein and the components that may be contained therein will be described.

[0039] ((A) Polyimide Precursor and Polyimide Resin) The resin composition disclosed herein comprises (A) a polyimide precursor and at least one of a polyimide resin (hereinafter also referred to as "(A) component"), wherein the polyimide precursor is at least one resin selected from the group consisting of polyacrylic acid, polyacrylic ester, polyacrylic acid salt, and polyacrylamide. Component (A) is preferably at least one of a polyimide precursor and a polyimide resin capable of producing a cured material exhibiting high properties (e.g., heat resistance), and more preferably a polyimide precursor containing polymerizable unsaturated bonds as the polyimide precursor. Component (A) contained in the resin composition is preferably a component that does not cause adverse conditions in grinding processes, bonding processes, etc. In this disclosure, a polyimide precursor refers to a compound that conforms to any of the following: polyamide, a compound in which at least a portion of the carboxyl group of polyamide is replaced by a monovalent organic group, or a polyamide salt of a compound in which at least a portion of the carboxyl group of polyamide forms a salt structure with a basic compound at pH 7 or higher. Examples of compounds in which at least a portion of the carboxyl group of polyamide is replaced by a monovalent organic group include polyamide esters and polyamide amides. Polyamide esters and polyamide amides preferably have polymerizable unsaturated bonds.

[0040] When component (A) contains a polyimide precursor, component (A) is preferably a compound containing a structural unit having the structure represented by the following general formula (1). This leads to a tendency to obtain a semiconductor device including an insulating film exhibiting high reliability.

[0041]

[0042] In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. R6 and R7 independently represent a hydrogen atom or a monovalent organic group, respectively. The polyimide precursor may have multiple structural units represented by the general formula (1), and X, Y, R6 and R7 in the multiple structural units may be the same or different. In addition, as long as R6 and R7 are independently hydrogen atoms or monovalent organic groups, their combination is not particularly limited. For example, R6 and R7 may both be hydrogen atoms, or one may be a hydrogen atom and the other may be a monovalent organic group described later, or they may both be the same or different monovalent organic groups. As described above, when the polyimide precursor has multiple structural units represented by the general formula (1), the combination of R6 and R7 in each structural unit may be the same or different.

[0043] In general formula (1), the number of carbon atoms in the tetravalent organic group represented by X is preferably 4 to 25, more preferably 5 to 13, and even more preferably 6 to 12. The tetravalent organic group represented by X may include an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (e.g., the number of carbon atoms constituting the aromatic ring is 6 to 20), aromatic heterocyclic groups (e.g., the number of atoms constituting the heterocycle is 5 to 20), etc. The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, phenanthrene rings, etc. When the tetravalent organic group represented by X includes an aromatic ring, each aromatic ring may have substituents or may be unsubstituted. Examples of substituents for aromatic rings include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, amino groups, etc. When the tetravalent organogroup represented by X contains a benzene ring, the tetravalent organogroup represented by X preferably contains one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organogroup represented by X contains two or more benzene rings, each benzene ring can be linked by a single bond, or by a linking group such as an alkyl group, a halogenated alkyl group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), a silene bond (-Si(RA)2-; where each of the two RAs independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n; where each of the two RBs independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more), or a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings can be bonded at two sites by a single bond and a linker group to form a 5-membered or 6-membered ring containing a linker group between the two benzene rings.

[0044] In general formula (1), the -COOR6 group and the -CONH- group are preferably in adjacent positions, and the -COOR7 group and the -CO- group are preferably in adjacent positions.

[0045] Specific examples of the tetravalent organic group represented by X include the groups represented by formulas (A) to (F) below. From the viewpoint of obtaining an insulating film with excellent flexibility and further suppression of void formation at the interface, the group represented by formula (E) below is preferred, more preferably a group represented by formula (E) below where C contains an ether bond, and even more preferably an ether bond. Formula (F) below is a structure where C in formula (E) below is a single bond. Furthermore, this disclosure is not limited to the specific examples described below.

[0046]

[0047] In formula (D), A and B are each independently a single bond or a divalent group not conjugated with the benzene ring. However, neither A nor B is a single bond. Examples of divalent groups not conjugated with the benzene ring include: methylene, halomethyl, halomethylmethylene, carbonyl, sulfonyl, ether (-O-), thioether (-S-), and silene (-Si(RA)2-; the two RAs independently represent hydrogen atoms, alkyl or phenyl atoms, etc. Preferably, A and B are each independently methylene, bis(trifluoromethyl)methylene, difluoromethylene, ether, thioether, etc., and more preferably ether.

[0048] In formula (E), C represents a single bond, an alkyl group, a halogenated alkyl group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), an phenyl group, an ester bond (-OC(=O)-), a silene bond (-Si(RA)2-; each of the two RAs independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n; each of the two RBs independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more), or a divalent group formed by combining at least two of these. C preferably contains an ether bond, and more preferably is an ether bond. Alternatively, C may also be the structure represented by the following formula (C1).

[0049]

[0050] The alkyl group represented by C in formula (E) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by C in formula (E) include linear alkyl groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene, methyl ethylene, ethyl methylene, dimethylmethylene, 1,1-dimethyl ethylene, 1-methyl trimethylene, 2-methyl trimethylene, ethyl ethylene, 1-methyl tetramethylene, 2-methyl tetramethylene, 1-ethyl trimethylene, 2-ethyl trimethylene, 1,1 -Dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, 1,4-dimethyltetramethylene, and other branched alkyl groups. Among these, methylene is preferred.

[0051] The alkyl halide represented by C in formula (E) is preferably an alkyl halide having 1 to 10 carbon atoms, more preferably one to 5 carbon atoms, and even more preferably one to 3 carbon atoms. Specific examples of the alkyl halide represented by C in formula (E) include alkyl assemblies in which at least one hydrogen atom is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene, difluoromethylene, and hexafluorodimethylmethylene are preferred.

[0052] The alkyl group represented by RA or RB in the silene bond or siloxane bond is preferably an alkyl group with 1 to 5 carbon atoms, more preferably an alkyl group with 1 to 3 carbon atoms, and even more preferably an alkyl group with 1 or 2 carbon atoms. Specific examples of alkyl groups represented by RA or RB include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tert-butyl, etc.

[0053] Specific examples of the tetravalent organic group represented by X can be represented by the following formulas (J)~(O).

[0054]

[0055] In general formula (1), the number of carbon atoms in the divalent organic group represented by Y is preferably 4 to 25, more preferably 6 to 20, and even more preferably 12 to 18. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and a preferred skeleton of the divalent organic group represented by Y may be the same as a preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bond positions in the tetravalent organic group represented by X are replaced by atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (e.g., those with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (e.g., those with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

[0056] Specific examples of the divalent aromatic group represented by Y can be exemplified by the groups represented by formulas (G) to (I) below. Among them, from the viewpoint of obtaining an insulating film with excellent flexibility and further suppression of void formation at the bonding interface, the group represented by formula (H) below is preferred, more preferably the group represented by formula (H) below where D contains an ether bond, and even more preferably an ether bond.

[0057]

[0058] In formulas (G) to (I), each R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom, and each n independently represents an integer from 0 to 4. In formula (H), D represents a single bond, an alkyl group, a haloalkyl group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), an phenyl group, an ester bond (-OC(=O)-), a silene bond (-Si(RA)2-; each of the two RAs independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n; each of the two RBs independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more), or a divalent group formed by combining at least two of these. Additionally, D can also be the structure represented by formula (C1). Specific examples of D in formula (H) are the same as specific examples of C in formula (E). D in formula (H) is preferably an ether bond, a group containing an ether bond and an extended phenyl group, or a group containing an ether bond, an extended phenyl group, and an extended alkyl group.

[0059] The alkyl group represented by R in formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in formulas (G) to (I) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tert-butyl, etc.

[0060] The alkoxy group represented by R in formulas (G) to (I) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (I) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, dibutoxy, and terbutoxy.

[0061] The alkyl halide represented by R in formulas (G) to (I) is preferably an alkyl halide having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples of the alkyl halide represented by R in formulas (G) to (I) include groups formed by substituting at least one hydrogen atom of the alkyl group represented by R in formulas (G) to (I) with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl, difluoromethyl, trifluoromethyl, etc., are preferred.

[0062] Each n in equations (G) to (I) is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0063] Specific examples of the divalent aliphatic group represented by Y include linear or branched alkyl groups, cycloalkyl groups, divalent groups with polyoxyalkylene structures, and divalent groups with polysiloxane structures.

[0064] The linear or branched alkyl group represented by Y is preferably an alkyl group having 1 to 20 carbon atoms, more preferably one having 1 to 15 carbon atoms, and even more preferably one having 1 to 10 carbon atoms. Specific examples of the alkyl group represented by Y include: tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonamethylene, 2-methyldecamethylene, etc.

[0065] The cycloalkyl group represented by Y is preferably a cycloalkyl group having 3 to 10 carbon atoms, and more preferably a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the cycloalkyl group represented by Y include cyclopropyl, cyclohexyl, etc.

[0066] The unit structure contained in the divalent group representing the polyepoxide structure (represented by Y) is preferably an epoxy alkane structure with 1 to 10 carbon atoms, more preferably an epoxy alkane structure with 1 to 8 carbon atoms, and even more preferably an epoxy alkane structure with 1 to 4 carbon atoms. Among these, the polyepoxide structure is preferably a polyepoxide ethylene structure or a polyepoxide propylene structure. The alkyl group in the epoxy alkane structure can be linear or branched. The unit structure in the polyepoxide structure can be one type or two or more types.

[0067] Examples of divalent groups with a polysiloxane structure represented by Y include: divalent groups with a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of alkyl groups having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, tributyl, n-octyl, 2-ethylhexyl, n-dodecyl, etc. Among these, methyl is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents when the aryl group has a substituent include halogen atoms, alkoxy groups, hydroxyl groups, etc. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl, naphthyl, benzyl, etc. Among these, phenyl is preferred. The alkyl group with 1 to 20 carbon atoms or the aryl group with 6 to 18 carbon atoms in the polysiloxane structure can be one or more. The silicon atom constituting the divalent group with the polysiloxane structure represented by Y can be bonded to the NH group in general formula (1) via methylene, ethylene, or other elongated alkyl groups, elongated phenyl, or other elongated aryl groups.

[0068] The basis represented by formula (G) is preferably the basis represented by formula (G') below, the basis represented by formula (H) is preferably the basis represented by formula (H') or formula (H'') below, and the basis represented by formula (I) is preferably the basis represented by formula (I') below.

[0069]

[0070] In formula (I'), each R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom. R is preferably alkyl, and more preferably methyl.

[0071] There is no particular limitation on the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1). The combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y can be listed as follows: the combination of X being a group represented by formula (E) and Y being a group represented by formula (H), the combination of X being a group represented by formula (E) and Y being a group represented by formula (I), etc.

[0072] R6 and R7 each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group with 1 to 4 carbon atoms or an organic group containing an unsaturated double bond, more preferably any one of the groups represented by the following general formula (2), ethyl, isobutyl, and tert-butyl, even more preferably an aliphatic hydrocarbon group containing 1 or 2 carbon atoms or a group represented by the general formula (2), and especially preferably a group represented by the general formula (2). In particular, by including an organic group with an unsaturated double bond in the monovalent organic group, preferably a group represented by the following general formula (2), it can have a high i-ray transmittance and a tendency to form a good cured product even when hardened at low temperatures below 400°C. Specific examples of aliphatic hydrocarbon groups with 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, etc., among which ethyl, isobutyl, and tert-butyl are preferred.

[0073]

[0074] In general formula (2), R8 to R10 each represent a hydrogen atom or an aliphatic hydrocarbon group with 1 to 3 carbon atoms, and Rx represents a divalent linker.

[0075] The aliphatic hydrocarbon groups represented by R8 to R10 in general formula (2) have 1 to 3 carbons, preferably 1 or 2. Specific examples of aliphatic hydrocarbon groups represented by R8 to R10 include methyl, ethyl, n-propyl, isopropyl, etc., with methyl being the most preferred.

[0076] As a combination of R8 to R10 in general formula (2), it is preferred that R8 and R9 are hydrogen atoms and R10 is a combination of hydrogen atoms or methyl groups.

[0077] Rx in general formula (2) is a divalent linker, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include straight-chain or branched alkyl groups. Rx preferably has 1 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2 or 3 carbon atoms.

[0078] In general formula (1), it is preferred that at least one of R6 and R7 is the basis represented by general formula (2), and more preferably that both R6 and R7 are the basis represented by general formula (2).

[0079] When component (A) comprises a compound having a structural unit represented by the general formula (1), the proportion of R6 and R7 as a base represented by the general formula (2) relative to the total of R6 and R7 of all structural units contained in the compound is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. There is no particular upper limit, and it can be 100 mol%. Furthermore, the proportion can be 0 mol% or more but less than 60 mol.

[0080] The basis represented by general formula (2) is preferably the basis represented by the following general formula (2').

[0081]

[0082] In general formula (2'), R8 to R10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group with 1 to 3 carbon atoms, and q represents an integer from 1 to 10.

[0083] In general formula (2'), q is an integer from 1 to 10, preferably an integer from 2 to 5, and more preferably 2 or 3.

[0084] The content of the structural unit represented by general formula (1) in the compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, relative to all structural units. There is no particular upper limit to the content, and it may also be 100 mol%.

[0085] Component (A) can also be synthesized using tetracarboxylic dianhydride and a diamine compound. In the case described, in general formula (1), X corresponds to a residue derived from tetracarboxylic dianhydride, and Y corresponds to a residue derived from a diamine compound. Furthermore, component (A) can also be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[0086] Specific examples of tetracarboxylic dianhydrides include: pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, meta-triphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-triphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride. Examples of dianhydrides include 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonylurea diphthalic acid dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0087] Specific examples of diamine compounds include: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-phenylenedimethyldiamine, m-phenylenedimethyldiamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diamine 3,3'-Diaminodiphenyl sulfide, 2,4'-Diaminodiphenyl sulfide, 2,2'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl sulfide, 3,4'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl sulfide, 2,4'-Diaminodiphenyl sulfide, 2,2'-Diaminodiphenyl sulfide, o-Toluidine, o-Toluidine sulfide, 4,4'-Methylenebis(2,6-diethylaniline), 4,4'-Methylenebis(2,6-diisopropylaniline), 2,4-Diaminotrimethylbenzene, 4,4' Benzyl ketone diamine, bis-{4-(4'-aminophenoxy)phenyl} arsenide, 2,2-bis{4-(4'-aminophenoxy)phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl} arsenide, 2,2-bis(4-aminophenyl) propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexyl Alkane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane, etc. Preferred diamine compounds are m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. A single diamine compound may be used, or two or more may be used in combination.

[0088] A compound having the structural unit represented by general formula (1) and at least one of R6 and R7 in general formula (1) being a monovalent organic group can be obtained, for example, by the methods described in (a) or (b) below. (a) A diester derivative is prepared by reacting a tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by general formula (8) below) with a compound represented by R-OH in an organic solvent, followed by a condensation reaction of the diester derivative with a diamine compound represented by H2N-Y-NH2. (b) A polyamide solution is obtained by reacting a tetracarboxylic dianhydride with a diamine compound represented by H2N-Y-NH2 in an organic solvent, and the compound represented by R-OH is added to the polyamide solution, reacted in an organic solvent, and an ester group is introduced. Here, the Y in the diamine compound represented by H2N-Y-NH2 is the same as the Y in general formula (1), and the specific examples and preferred examples are also the same. Furthermore, in the compound represented by R-OH, R represents a monovalent organic group, and the specific and preferred examples are the same as those for R6 and R7 in general formula (1). The tetracarboxylic acid dianhydride represented by general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH can each be used alone or in combination of two or more. As the organic solvent, examples include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropionic acid, etc., among which 3-methoxy-N,N-dimethylpropionic acid is preferred. The dehydrating condensing agent can also be reacted together with the compound represented by R-OH in a polyamide solution to synthesize a polyimide precursor. The dehydrating condensing agent is preferably at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC) and 1,3-diisopropylcarbodiimide (DIC).

[0089] (A) The compound contained in the ingredient can be obtained by reacting the compound represented by R-OH with the tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, then reacting a chlorinating agent such as thionyl chloride to convert it into a acetyl chloride, and then reacting the diamine compound represented by H2N-Y-NH2 with the acetyl chloride. The compound contained in the ingredient (A) can be obtained by reacting the compound represented by R-OH with the tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, then reacting the diamine compound represented by H2N-Y-NH2 with the diester derivative in the presence of the carbodiimide compound. (A) The compound contained in the component can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H2N-Y-NH2 to prepare polyacrylic acid, followed by isoimidinizing the polyacrylic acid in the presence of a dehydrating condensing agent such as trifluoroacetic anhydride, thereby enabling the compound represented by R-OH to function. Alternatively, the compound represented by R-OH can be pre-treated on a portion of the tetracarboxylic dianhydride, causing the partially esterified tetracarboxylic dianhydride to react with the diamine compound represented by H2N-Y-NH2.

[0090]

[0091] In general formula (8), X is the same as X in general formula (1), and the specific example and the preferred example are also the same.

[0092] The compound represented by R-OH used in the synthesis of the compound contained in component (A) may be a compound in which a hydroxyl group is bonded to the Rx of the group represented by general formula (2), or a compound in which a hydroxyl group is bonded to the terminal methylene group of the group represented by general formula (2'). Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, etc., wherein 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0093] (A) There is no particular limitation on the molecular weight of the component, but it is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, based on the weight average molecular weight. The weight average molecular weight can be determined, for example, by gel permeation chromatography, and can be calculated by using a standard polystyrene calibration curve.

[0094] The resin composition disclosed herein may also contain more dicarboxylic acids, and the (A) polyimide precursor contained in the resin composition may also have a structure formed by the reaction of a portion of the amino group in the (A) polyimide precursor with the carboxyl group in the dicarboxylic acid. For example, during the synthesis of the polyimide precursor, a portion of the amino group of the diamine compound may be reacted with the carboxyl group of the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylate group, for example, it may be a dicarboxylic acid represented by the following formula. In this case, during the synthesis of the (A) polyimide precursor, a methacrylate group derived from the dicarboxylic acid may be introduced into the (A) polyimide precursor by reacting a portion of the amino group of the diamine compound with the carboxyl group of the dicarboxylic acid.

[0095]

[0096] The resin composition disclosed herein may also include polyimide resin as component (A), and may also include the polyimide precursor and polyimide resin.

[0097] As a polyimide resin, any polymeric compound comprising multiple structural units containing amide bonds is acceptable and is not particularly limited. For example, a compound comprising structural units having the structure represented by the following general formula (X) is preferred. This leads to a tendency to obtain semiconductor devices including insulating films exhibiting high reliability.

[0098]

[0099] In general formula (X), X represents a tetravalent organogroup and Y represents a divalent organogroup. Preferred examples of substituents X and Y in general formula (X) are the same as preferred examples of substituents X and Y in general formula (1).

[0100] As component (A), by combining the polyimide precursor and the polyimide resin, the generation of volatiles caused by dehydration cyclization during the formation of the amide ring can be suppressed, thus exhibiting a tendency to suppress void formation. The polyimide resin referred to herein is a resin in which all or part of the resin backbone has an amide backbone. Preferably, the polyimide resin is soluble in a solvent used in a resin composition containing the polyimide precursor.

[0101] When component (A) is a polyimide precursor and a polyimide resin, the proportion of the polyimide resin to the total of the polyimide precursor and the polyimide resin may be 15% to 50% by mass, or 10% to 20% by mass.

[0102] The resin composition disclosed herein may also contain resin components other than component (A). For example, from the viewpoint of heat resistance, the resin composition disclosed herein may also contain other resins such as phenolic varnish resin, acrylic resin, polyether nitrile resin, polyether pyrrolidone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. Other resins may be used alone or in combination of two or more.

[0103] In the resin composition disclosed herein, the content of component (A) relative to the total amount of resin components is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass.

[0104] ((B) Solvent) The resin composition disclosed herein includes a (B) solvent (hereinafter also referred to as "(B) component"). For example, from the viewpoint of reducing the reproductive toxicity and environmental impact of the resin composition, the (B) component is preferably composed of at least one of the group consisting of compounds selected from those represented by formulas (3) to (7) below.

[0105]

[0106] In formulas (3) to (7), R1, R2, R8 and R10 are each an alkyl group with 1 to 4 carbon atoms, and R3 to R7 and R9 are each a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, and u is an integer from 0 to 3.

[0107] In formula (3), s is preferably 0. In formula (4), the alkyl group having 1 to 4 carbons in R2 is preferably methyl or ethyl. t is preferably 0, 1, or 2, more preferably 1. In formula (5), the alkyl group having 1 to 4 carbons in R3 is preferably methyl, ethyl, propyl, or butyl. The alkyl groups having 1 to 4 carbons in R4 and R5 are preferably methyl or ethyl. In formula (6), the alkyl groups having 1 to 4 carbons in R6 to R8 are preferably methyl or ethyl. r is preferably 0 or 1, more preferably 0. In formula (7), the alkyl groups having 1 to 4 carbons in R9 and R10 are preferably methyl or ethyl. u is preferably 0 or 1, more preferably 0.

[0108] (B) The component may be at least one of the compounds represented by formulas (4), (5), (6) and (7), or may be a compound represented by formula (5) or a compound represented by formula (7).

[0109] The following compounds can be listed as specific examples of component (B).

[0110]

[0111] The (B) component contained in the resin composition disclosed herein is not limited to the above-mentioned compounds, but may also be other solvents. The (B) component may also be ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, argon solvents, etc.

[0112] Examples of solvents for esters include: ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate, and other alkyl alkoxyacetic acid esters (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate), methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, and alkyl 3-alkoxypropionate, and alkyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, etc.). Alkyl 2-alkoxypropionate esters such as methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc.

[0113] Examples of solvents that can be used as ethers include: diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of solvents that can be used as ketones include: methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone (NMP), etc. Examples of solvents that can be used as hydrocarbons include limonene, etc. Examples of solvents that can be used as aromatic hydrocarbons include toluene, xylene, anisole, etc. Examples of solvents that can be used as sulfides include dimethyl sulfide, etc.

[0114] Preferably, γ-butyrolactone, cyclopentanone, ethyl lactate, etc. can be used as solvents for component (B).

[0115] In the resin composition disclosed herein, from the viewpoint of reducing reproductive toxicity and other toxicities, the content of NMP may be less than 1% by mass relative to the total amount of the resin composition and less than 3% by mass relative to the total amount of component (A).

[0116] In the resin composition disclosed herein, the content of component (B) is preferably 1 to 10,000 parts by mass relative to 100 parts by mass of component (A), and more preferably 50 to 10,000 parts by mass.

[0117] (B) The component preferably includes at least one of solvent (1) and solvent (2), wherein solvent (1) is at least one of the group consisting of compounds represented by formulas (3) to (6), and solvent (2) is at least one of the group consisting of ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, and argon solvents. In addition, the content of solvent (1) relative to the total of solvent (1) and solvent (2) may be 5% to 100% by mass, or 5% to 50% by mass. The content of solvent (1) relative to 100 parts by mass of component (A) may be 10 to 1000 parts by mass, or 10 to 100 parts by mass, or 10 to 50 parts by mass.

[0118] The resin composition disclosed herein preferably further includes (C) a photopolymerization initiator and (D) a polymerizable monomer (hereinafter also referred to as component (C) and component (D) respectively). Additionally, the resin composition disclosed herein may also further include (E) a thermal polymerization initiator (hereinafter also referred to as component (E)). Preferred forms of components (C) to (E) will be described below.

[0119] ((C) Photopolymerization initiator) The resin composition disclosed herein preferably includes (C) photopolymerization initiator. This reduces the number of electrode fabrication steps in the semiconductor device manufacturing process, thereby lowering the overall cost of the semiconductor device manufacturing process. Specific examples of the components

[0120] (C) include: benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's Ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, methyl benzoyl benzoate, 4-benzoyl-4'-methylbenzophenone, dibenzyl ketone, fluorenone and other benzophenone derivatives; acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylacetophenone Acetone, 1-hydroxycyclohexylphenyl ketone and other acetophenone derivatives; thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone and other thioxanthone derivatives; benzoin, benzoin dimethyl ketal, benzoin-β-methoxyethyl acetal and other benzoin derivatives; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, propyl benzoin and other benzoin derivatives; 1-phenyl-1,2-butadiene-2-(O-methoxycarbonyl)oxime, 1-phenyl-1, Oxidime derivatives such as 2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2-octanedione, and 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime); N-aryl glycine and other N-phenylglycine derivatives. Acids; peroxides such as benzoyl perchlorate; aromatic biimidazolium compounds such as 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazolium dimer; phosphine oxide derivatives such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; Irgacure OXE03 (manufactured by BASF); Irgacure OXE04 (manufactured by BASF); etc. (C) Components may be used alone or in combination of two or more. Among these, oxime compound derivatives are preferred from the viewpoint of being free of metal elements, having high reactivity, and high sensitivity.

[0121] When the resin composition disclosed herein contains component (C), from the viewpoint that photocrosslinking is easily made uniform in the film thickness direction, the content of component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 6 parts by mass, relative to 100 parts by mass of component (A).

[0122] From the viewpoint of improving photosensitivity, the resin composition disclosed herein may also contain an antireflective agent that suppresses reflected light from the substrate direction.

[0123] ((D) Polymerizable Monomer) The resin composition disclosed herein preferably includes a (D) polymerizable monomer. The (D) component preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylate group, from the viewpoint that polymerization can be suitably carried out by use with a photopolymerization initiator. From the viewpoint of increasing crosslinking density and photosensitivity, it is preferable to have 2 to 6 groups containing polymerizable unsaturated double bonds, more preferably 2 to 4. The polymerizable monomer may be used alone or in combination of two or more.

[0124] There are no particular limitations on polymerizable monomers containing (meth)acrylate groups, but examples include: diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate. Pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanurate triacrylate, ethoxylated isocyanurate trimethacrylate, isocyanurate acryloxyethyl ester, isocyanurate methacryloyloxyethyl ester, (meth)acrylate-2-hydroxyethyl ester, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO) modified bisphenol A diacrylate and ethylene oxide (EO) modified bisphenol A dimethacrylate.

[0125] The polymerizable monomer is not particularly limited to polymerizable monomers other than those having a (meth)acrylic acid group, and examples include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide and N-hydroxymethylacrylamide.

[0126] (D) The component is not limited to a compound having a group containing a polymeric unsaturated double bond, but may also be a compound having a polymeric group other than an unsaturated double bond group (e.g., an oxirane ring).

[0127] When the resin composition disclosed herein contains component (D), the content of component (D) is not particularly limited, but is preferably 1 to 100 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 75 parts by mass, and even more preferably 1 to 50 parts by mass.

[0128] ((E) thermal polymerization initiator) From the viewpoint of improving the physical properties of the cured material, the resin composition disclosed herein preferably contains (E) thermal polymerization initiator.

[0129] Specific examples of component (E) include: ketone peroxides such as methyl ethyl ketone peroxide; ketal peroxides such as 1,1-di(tert-hexylperoxide)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxide)cyclohexane, and 1,1-di(tert-butylperoxide)cyclohexane; hydrogen peroxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide; dicumyl peroxide and di-tert-butyl peroxide. Dialkyl peroxides; dilauryl peroxide, dibenzoyl peroxide, and other dialkyl peroxides; di(4-tert-butylcyclohexyl) peroxide, di(2-ethylhexyl) peroxide, and other peroxide esters; tert-butyl peroxide-2-ethylhexanoate, trihexyl peroxide isopropyl monocarbonate, tert-butyl peroxide benzoate, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, and other peroxide esters; bis(1-phenyl-1-methylethyl) peroxide, etc. Thermal polymerization initiators can be used alone or in combination of two or more.

[0130] When the resin composition disclosed herein contains component (E), the content of component (E) may be 0.1 to 20 parts by mass, 1 to 15 parts by mass, or 5 to 10 parts by mass relative to 100 parts by mass of the polyimide precursor.

[0131] ((F) Polymerization Inhibitor) From the viewpoint of ensuring good storage stability, the resin composition disclosed herein may also contain a (F) polymerization inhibitor (hereinafter also referred to as "(F) component"). Examples of polymerization inhibitors include free radical polymerization inhibitors, free radical polymerization suppressants, etc.

[0132] Specific examples of component (F) include: p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, cupferron, 2,5-methylbenzoquinone, tannic acid, p-benzylaminophenol, nitrosamines, hindered phenolic compounds, etc. A polymerization inhibitor can be used alone or in combination of two or more. By combining two or more polymerization inhibitors, due to their different reactivity, there is a tendency to easily adjust the photosensitivity properties. Hindered phenolic compounds can have the function of a polymerization inhibitor and the function of an antioxidant (described later), or either one of these functions.

[0133] As a hindered phenolic compound, there are no particular limitations, for example: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3, [5-Di-tri-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylbis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tri-butyl-4-hydroxy-hydrogenated cinnamylamine), 2,2'-methylenebis(4-methyl-6-tri-butylphenol), 2,2'-methylenebis(4-ethyl-6-tri-butylphenol), pentaerythritol-tetra[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tri-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tri-butyl-4-hydroxybenzyl)benzene, 1,3,5-Tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-dibutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-Tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tripropylbutyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tripropylbutyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-3- ... 1,3,5-Triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tributyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tributyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and N,N'-hexane-1,6-diylbis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionylamine]. Of these, N,N'-hexane-1,6-diylbis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionylamine] is preferred. ,

[0134] When the resin composition disclosed herein contains component (F), from the viewpoint of the storage stability of the resin composition and the heat resistance of the obtained cured product, the content of component (F) is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of component (A).

[0135] The resin composition disclosed herein may further include antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors, or nitrogen-containing compounds.

[0136] (Antioxidant) From the viewpoint that the decrease in adhesion can be suppressed by capturing oxygen free radicals and peroxide free radicals generated during high-temperature storage, reflow processing, etc., the resin composition disclosed herein may also contain an antioxidant. By including an antioxidant in the resin composition disclosed herein, the oxidation of the electrode during insulation reliability testing can be suppressed.

[0137] Specific examples of antioxidants include compounds such as N,N'-bis[2-[2-(3,5-di-tri-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxadiamine, N,N'-bis-3-(3,5-di-tri-butyl-4'-hydroxyphenyl)propionic hexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tri-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-tri-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Antioxidants can be used alone or in combination of two or more.

[0138] When the resin composition disclosed herein contains an antioxidant, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of component (A).

[0139] (Coupling Agent) The resin composition disclosed herein may also include a coupling agent. The coupling agent reacts with component (A) during heat treatment to crosslink, or the coupling agent itself polymerizes. This tends to further improve the adhesion between the obtained cured material and the substrate.

[0140] Specific examples of coupling agents are not particularly limited. Examples of coupling agents include: 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)butadieneimine, N-[3-(triethoxysilyl)propyl]phthalene Silane coupling agents such as dimethicone, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, phenyl-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureopropyltriethoxysilane; aluminum-based adhesives such as tri(ethyl acetate)aluminum, tri(acetone)aluminum, and ethyl acetate diisopropionate. Coupling agents can be used alone or in combination of two or more.

[0141] In the case where the resin composition disclosed herein contains a coupling agent, the content of the coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of component (A).

[0142] (Surfactant and leveling agent) The resin composition disclosed herein may also include at least one of a surfactant and a leveling agent. By including at least one of a surfactant and a leveling agent in the resin composition, coating properties (e.g., suppression of striations), adhesion, and compatibility of compounds in the resin composition can be improved.

[0143] As surfactants or leveling agents, examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, and polyoxyethylene octylphenol ether.

[0144] Surfactants and leveling agents can be used alone or in combination of two or more.

[0145] In the case where the resin composition disclosed herein includes at least one of a surfactant and a leveling agent, the total content of the surfactant and the leveling agent relative to 100 parts by weight of component (A) is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight to 5 parts by weight, and even more preferably 0.05 parts by weight to 3 parts by weight.

[0146] (Rust Inhibitor) From the viewpoint of inhibiting corrosion of metals such as copper and copper alloys, and from the viewpoint of inhibiting discoloration of such metals, the resin composition disclosed herein may also contain a rust inhibitor. Examples of rust inhibitors include azole compounds and purine derivatives.

[0147] Specific examples of azole compounds include: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-tributyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)] [3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc.

[0148] Specific examples of purine derivatives include: purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, etc. Derivatives of these, including (-hydroxyethyl) adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, and 8-azahypoxanthine.

[0149] A single rust inhibitor can be used alone, or two or more can be combined.

[0150] When the resin composition disclosed herein contains a rust inhibitor, the content of the rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of component (A). In particular, by having a rust inhibitor content of 0.1 parts by mass or more, when the resin composition disclosed herein is applied to the surface of copper or copper alloy, discoloration of the copper or copper alloy surface can be suppressed.

[0151] From the viewpoint of obtaining a highly reliable cured product by promoting the amide reaction of component (A), the resin composition disclosed herein may also contain nitrogen-containing compounds.

[0152] Specific examples of nitrogen-containing compounds include: 2-(methylphenylamino)ethanol, 2-(ethylaniline)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzoylamine, 2-aminobenzoylamine, nicotinamide, 4-amino-N-methylbenzoylamine, 4-aminoacetoaniline, 4-aminoacetophenone, etc., among which N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, etc. A single nitrogen-containing compound may be used, or two or more may be combined.

[0153] The nitrogen-containing compound is preferably a compound represented by the following formula (17).

[0154]

[0155] In formula (17), R31A to R33A are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups, monovalent aliphatic hydrocarbon groups with hydroxyl groups, or monovalent aromatic groups, respectively, and at least one (preferably one) of R31A to R33A is a monovalent aromatic group. R31A to R33A can form a ring structure with each other through adjacent groups. Examples of the formed ring structures include five-membered rings and six-membered rings that may have substituents such as methyl and phenyl groups. The hydrogen atoms of the monovalent aliphatic hydrocarbon groups may be substituted with functional groups other than hydroxyl groups.

[0156] In formula (17), at least one (preferably one) of R31A to R33A is preferably a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group.

[0157] In formula (17), the monovalent aliphatic hydrocarbon group of R31A~R33A is preferably 1~10 carbons, more preferably 1~6 carbons. The monovalent aliphatic hydrocarbon group is preferably methyl, ethyl, etc.

[0158] In formula (17), the monovalent aliphatic hydrocarbon group with hydroxyl group R31A~R33A is preferably a group with one or more hydroxyl groups bonded to the monovalent aliphatic hydrocarbon group of R31A~R33A, and more preferably a group with one to three hydroxyl groups bonded to it. Specific examples of monovalent aliphatic hydrocarbon groups with hydroxyl groups include hydroxymethyl, hydroxyethyl, etc., among which hydroxyethyl is preferred.

[0159] The monovalent aromatic group R31A to R33A in formula (17) can be a monovalent aromatic hydrocarbon group, a monovalent aromatic heterocyclic group, etc., preferably a monovalent aromatic hydrocarbon group. The monovalent aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of monovalent aromatic hydrocarbon groups include phenyl and naphthyl groups.

[0160] The monovalent aromatic groups of R31A to R33A in formula (17) may also have substituents. As substituents, the same groups as the monovalent aliphatic hydrocarbon groups of R31A to R33A in formula (17) and the monovalent aliphatic hydrocarbon groups of R31A to R33A in formula (17) having hydroxyl groups can be listed.

[0161] In the case where the resin composition disclosed herein contains a nitrogen-containing compound, the content of the nitrogen-containing compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), and more preferably 0.3 to 15 parts by mass from the point of view of preservation stability, and even more preferably 0.5 to 10 parts by mass.

[0162] The resin composition disclosed herein includes components (A) and (B), and may include components (C) to (F), antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors, nitrogen-containing compounds, etc., as needed. Other components and unavoidable impurities may also be included to the extent that the effects of the disclosure are not impaired. For example, the resin composition disclosed herein may contain 80% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, or 100% by mass of components (A) and (B), components (A) to (C), components (A) to (E), components (A) to (F), components (A) to (F), and at least one selected from the group consisting of antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors, and nitrogen-containing compounds.

[0163] <Semiconductor Device> The semiconductor device disclosed herein includes: a first semiconductor substrate having a first substrate body, and a first organic insulating film and a first electrode disposed on one side of the first substrate body; and a semiconductor wafer having a semiconductor wafer substrate body, and an organic insulating film portion and a second electrode disposed on one side of the semiconductor wafer substrate body. The first organic insulating film of the first semiconductor substrate is bonded to the organic insulating film portion of the semiconductor wafer, and the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor wafer. At least one of the first organic insulating film and the organic insulating film portion is an insulating film formed by curing the resin composition disclosed herein. In the semiconductor device disclosed herein, since at least one of the first organic insulating film and the organic insulating film portion is an insulating film formed by curing the resin composition disclosed herein, the generation of voids at the bonding interface of the insulating film is suppressed and the heat resistance of the insulating film is excellent. In addition, the semiconductor device disclosed herein is manufactured through processes (1) to (5).

[0164] <Method for Manufacturing a Semiconductor Device> In the method for manufacturing a semiconductor device disclosed herein, the resin composition disclosed herein is used to manufacture the semiconductor device. Specifically, the semiconductor device can be manufactured by using the resin composition disclosed herein and proceeding through steps (1) to (5).

[0165] <Curing Material> The curing material disclosed herein is formed by curing the resin composition disclosed herein. The curing material is used, for example, as an insulating film for semiconductor devices.

[0166] Hereinafter, an embodiment of the semiconductor device disclosed herein and an embodiment of the manufacturing method of the semiconductor device disclosed herein will be described in detail with reference to the drawings. In the following description, the same or equivalent parts are marked with the same symbols, and repeated descriptions are omitted. In addition, unless otherwise specified, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. Furthermore, the scale of the drawings is not limited to the scale shown in the drawings.

[0167] (An example of a semiconductor device) FIG1 is a schematic cross-sectional view showing an example of a semiconductor device disclosed herein. As shown in FIG1, the semiconductor device 1 is, for example, an example of a semiconductor package, including a first semiconductor wafer 10 (first semiconductor substrate), a second semiconductor wafer 20 (semiconductor wafer), a pillar 30, a redistribution layer 40, a substrate 50, and a circuit board 60.

[0168] The first semiconductor chip 10 is a semiconductor chip such as an LSI (Large-Scale Integrated Circuit) chip or a Complementary Metal-Oxide-Semiconductor (CMOS) sensor, and is a three-dimensional mounting structure in which a second semiconductor chip 20 is mounted in the downward direction. The second semiconductor chip 20 is a semiconductor chip such as an LSI or memory chip, and is a chip component with a smaller area than the first semiconductor chip 10 when viewed from above. The second semiconductor chip 20 and the back side of the first semiconductor chip 10 are chip-to-chip (C2C) bonded. The first semiconductor chip 10 and the second semiconductor chip 20 are micro-bonded together by a hybrid bonding process described in detail later, in which their respective terminal electrodes and the insulating films around them are firmly and finely bonded to each other without positional displacement.

[0169] The pillar portion 30 is a connection portion formed of a plurality of pillars 31 made of metal such as copper (Cu) and sealed by resin 32. The plurality of pillars 31 are conductive members extending from the upper surface of the pillar portion 30 toward the lower surface. The plurality of pillars 31 may, for example, have a cylindrical shape with a diameter of 3 μm to 20 μm (in one example, a diameter of 5 μm), or may be arranged such that the center distance between each pillar 31 is 15 μm or less. The plurality of pillars 31 connect the terminal electrode on the lower side of the first semiconductor wafer 10 to the terminal electrode on the upper side of the redistribution layer 40 for flip-chip bonding. By using the pillar portion 30, in the semiconductor device 1, the connection electrode can be formed without using a technique called through mold via (TMV) for soldering. The pillar portion 30, for example, has the same thickness as the second semiconductor wafer 20 and is arranged in the horizontal direction on the lateral side of the second semiconductor wafer 20. Furthermore, multiple solder balls can be arranged instead of the pillar portion 30, and the terminal electrodes on the lower side of the first semiconductor wafer 10 can be electrically connected to the terminal electrodes on the upper side of the redistribution layer 40 through the solder balls.

[0170] The rewiring layer 40 is a wiring layer that has the function of packaging substrate, namely terminal pitch transformation function. It is a layer on the insulating film under the second semiconductor wafer 20 and on the lower surface of the pillar portion 30, in which a rewiring pattern is formed by polyimide and copper wiring. The rewiring layer 40 is formed in a state in which the first semiconductor wafer 10 and the second semiconductor wafer 20 are flipped upside down (see Figure 4(d)).

[0171] The rewiring layer 40 electrically connects the terminal electrodes on the lower surface of the second semiconductor wafer 20 and the terminal electrodes of the first semiconductor wafer 10 via the pillar 30 to the terminal electrodes of the substrate 50. The terminal spacing of the substrate 50 is wider than the terminal spacing of the pillar 31 and the terminal spacing of the second semiconductor wafer 20. Furthermore, various electronic components 51 can be mounted on the substrate 50. In addition, when there is a large difference between the terminal spacing of the rewiring layer 40 and the substrate 50, an inorganic interlayer or the like can be used to electrically connect the rewiring layer 40 and the substrate 50.

[0172] The circuit board 60 is a substrate on which a first semiconductor chip 10 and a second semiconductor chip 20 are mounted and which has a plurality of through electrodes inside. The plurality of through electrodes are electrically connected to a substrate 50 that is connected to the first semiconductor chip 10, the second semiconductor chip 20, and electronic components 51. In the circuit board 60, each terminal electrode of the first semiconductor chip 10 and the second semiconductor chip 20 is electrically connected to a terminal electrode 61 disposed on the back side of the circuit board 60 through the plurality of through electrodes.

[0173] (An Example of a Method for Manufacturing a Semiconductor Device) Next, an example of a method for manufacturing the semiconductor device 1 will be described with reference to FIGS. 2(a) to 4(d). FIGS. 2(a) to 2(d) are diagrams showing the method for manufacturing the semiconductor device shown in FIG. 1. FIGS. 3(a) to 3(c) are diagrams showing in more detail the bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in FIGS. 2(a) to 2(d). FIGS. 4(a) to 4(d) are diagrams showing the method for manufacturing the semiconductor device shown in FIG. 1, and are diagrams showing the steps after the steps shown in FIGS. 2(a) to 2(d).

[0174] The semiconductor device 1 may be manufactured, for example, through the following steps (a) to (n). (a) A step of preparing a first semiconductor substrate 100 corresponding to the first semiconductor wafer 10. (b) A step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor wafer 20. (c) A step of polishing the first semiconductor substrate 100. (d) A step of polishing the second semiconductor substrate 200. (e) A step of monolithizing the second semiconductor substrate 200 to obtain a plurality of semiconductor wafers 205. (f) A step of aligning the terminal electrodes 203 of each of the plurality of semiconductor wafers 205 relative to the terminal electrodes 103 of the first semiconductor substrate 100. (g) A step of bonding the insulating film 102 of the first semiconductor substrate 100 to each insulating film portion 202b of the plurality of semiconductor wafers 205 (see FIG3(b)). (h) A step of bonding the terminal electrodes 103 of the first semiconductor substrate 100 to the terminal electrodes 203 of each of the plurality of semiconductor wafers 205 (see FIG3(c)). (i) A process of forming multiple pillars 300 (corresponding to pillars 31) on the connection surface of the first semiconductor substrate 100 and between multiple semiconductor wafers 205. (j) A process of molding resin 301 on the connection surface of the first semiconductor substrate 100 to obtain a semi-finished product M1, covering the semiconductor wafers 205 and the pillars 300. (k) A process of thinning the resin 301 side of the semi-finished product M1 formed in step (j) to obtain a semi-finished product M2. (l) A process of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k). (m) A process of cutting the semi-finished product M3 with the wiring layer 400 formed in step (l) along the cutting line A to become individual semiconductor devices 1. (n) A process of inverting the individualized semiconductor device 1a formed in step (m) and placing it on the substrate 50 and the circuit board 60 (see Figure 1).

[0175] For example, in the resin composition disclosed herein, step (1) corresponds to steps (a) and (c), step (2) corresponds to steps (b) and (d), step (3) corresponds to step (e), step (4) corresponds to step (g), and step (5) corresponds to step (h). Furthermore, the resin composition disclosed herein may be a resin composition used to fabricate at least one of a first organic insulating film and a second organic insulating film in a semiconductor device manufacturing method including at least one step corresponding to step (f) and steps (i) to (n).

[0176] [Process (a) and Process (b)] Process (a) is the process of preparing a first semiconductor substrate 100, which is a silicon substrate corresponding to a plurality of first semiconductor wafers 10 and having an integrated circuit including semiconductor elements and wiring connecting them. In process (a), as shown in FIG2(a), a plurality of terminal electrodes 103 (first electrodes) including copper, aluminum, etc. are provided at predetermined intervals on one side 101a of the first substrate body 101 containing silicon, etc., and an insulating film 102 (first insulating film) is provided as a cured material formed by curing the resin composition disclosed herein. The plurality of terminal electrodes 103 may be provided after the insulating film 102 is provided on one side 101a of the first substrate body 101, or the insulating film 102 may be provided after the plurality of terminal electrodes 103 are provided on one side 101a of the first substrate body 101. Furthermore, a predetermined interval is provided between the plurality of terminal electrodes 103 in order to form the post 300 in the following process, and other terminal electrodes (not shown) connected to the post 300 are formed therebetween.

[0177] Step (b) is the process of preparing a second semiconductor substrate 200, which is a silicon substrate corresponding to a plurality of second semiconductor wafers 20 and having an integrated circuit including semiconductor elements and wiring connecting them. In step (b), as shown in FIG2(a), a plurality of terminal electrodes 203 (a plurality of second electrodes) including copper, aluminum, etc. are continuously disposed on one side 201a of the second substrate body 201 containing silicon, etc., and an insulating film 202 (second insulating film) is disposed as a cured material formed by curing the resin composition disclosed herein. The plurality of terminal electrodes 203 may be disposed after the insulating film 202 is disposed on one side 201a of the second substrate body 201, or the insulating film 202 may be disposed after the plurality of terminal electrodes 203 are disposed on one side 201a of the second substrate body 201.

[0178] The insulating film 102 and insulating film 202 used in steps (a) and (b) are not limited to structures formed by curing the resin composition disclosed herein, but may also be structures in which at least one of the insulating film 102 and insulating film 202 is formed by curing the resin composition disclosed herein. Examples of insulating films other than these curables include those formed by curing a resin composition containing organic materials such as polyimide, polyamide-imide, benzocyclobutene (BCB), polybenzoxazole (PBO), and PBO precursors, without a polyimide precursor. The tensile elastic modulus of insulating film 102 and insulating film 202 at 25°C is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, even more preferably 3.0 GPa or less, particularly preferably 2.0 GPa or less, and even more preferably 1.5 GPa or less.

[0179] The coefficient of thermal expansion of insulating film 102 and insulating film 202 is preferably 150 ppm / K or less, more preferably 100 ppm / K or less, and even more preferably 90 ppm / K or less.

[0180] The thickness of insulating film 102 and insulating film 202 is preferably 0.1 μm to 50 μm, more preferably 1 μm to 15 μm. This ensures the uniformity of the film thickness and shortens the processing time in subsequent polishing processes.

[0181] From the viewpoint that the operations in steps (c) and (d) become easier to perform and that these steps can be simplified, it is preferable to satisfy at least one of the following conditions (preferably both): the polishing rate of the insulating film 102 is 0.1 to 5 times the polishing rate of the terminal electrode 103, and the polishing rate of the insulating film 202 is 0.1 to 5 times the polishing rate of the terminal electrode 203. As an example, when the terminal electrode 103 or the terminal electrode 203 contains copper and the polishing rate of copper is 50 nm / min, the polishing rate of the insulating film 102 or the insulating film 202 is preferably 200 nm / min or less (4 times or less of the polishing rate of copper), more preferably 100 nm / min or less (2 times or less of the polishing rate of copper), and even more preferably 50 nm / min or less (equivalent to or less of the polishing rate of copper).

[0182] Next, the method for manufacturing the insulating film will be described. The insulating film is obtained by curing a resin composition. Examples of methods for manufacturing the insulating film include: (α) a step of coating a resin composition onto a substrate and drying it to form a resin film, and a step of heat-treating the resin film; (β) a step of forming a film of a certain thickness using a resin composition on a film that has undergone a release treatment, and then transferring the resin film onto a substrate by lamination, and a step of heat-treating the resin film formed on the substrate after transfer. Regarding flatness, the method described in (α) is preferred.

[0183] Coating methods for resin components include, for example, spin coating, inkjet coating and slot coating.

[0184] In spin coating, for example, the resin composition can be spin coated at a rotation speed of 300 to 3,500 rpm (rotation per minute), preferably 500 to 1,500 rpm, an acceleration of 500 to 15,000 rpm / second, and a rotation time of 30 to 300 seconds.

[0185] A drying step may also be included after the resin composition is coated onto a support, film, etc. Drying may also be performed using a heating plate, oven, etc. The drying temperature is preferably 75°C to 130°C, and more preferably 90°C to 120°C from the viewpoint of improving the flatness of the insulating film. The drying time is preferably 30 seconds to 5 minutes. Drying may also be performed more than twice. This allows the obtaining of a resin film in which the resin composition is formed into a film-like structure.

[0186] In the slit coating method, for example, the resin composition can be slit coated under the following conditions: liquid spraying speed of 10~400 μL / s, liquid spraying height of 0.1~1.0 μm, platform speed (or liquid spraying speed) of 1.0~50.0 mm / s, platform acceleration of 10~1000 mm / s, ultimate vacuum degree during reduced pressure drying of 10~100 Pa, reduced pressure drying time of 30~600 seconds, drying temperature of 60~150℃, and drying time of 30~300 seconds.

[0187] The formed resin film can be heat-treated. The heating temperature is preferably 150°C to 450°C, and more preferably 150°C to 350°C. By keeping the heating temperature within the range described above, damage to the substrate, devices, etc., can be suppressed, energy saving in the process can be achieved, and an insulating film can be properly produced.

[0188] The heating time is preferably less than 5 hours, and more preferably 30 minutes to 3 hours. Keeping the heating time within this range allows for sufficient cross-linking or dehydration ring-closing reactions. The heating environment can be atmospheric or an inert environment such as nitrogen, but from the viewpoint of preventing resin film oxidation, a nitrogen environment is preferred.

[0189] Among the devices used in heat treatment are: quartz tube furnace, heating plate, rapid annealing furnace, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace, etc.

[0190] When using the resin composition disclosed herein as either a negative or positive photosensitive resin composition, after the insulating film 202 is disposed on one side 201a of the second substrate body 201 and then a plurality of terminal electrodes 203 are disposed, a method including the following steps can be used: coating the resin composition onto the substrate, drying to form a resin film, patterning the resin film and developing it with a developer to obtain a patterned resin film, and heat-treating the patterned resin film. This allows for the acquisition of a cured patterned insulating film.

[0191] Alternatively, when the insulating film 202 is disposed on one side 201a of the second substrate body 201 and then a plurality of terminal electrodes 203 are disposed, a method including the following steps can be used: coating a resin composition other than the resin composition disclosed herein onto the substrate; drying to form a resin film; coating the resin composition disclosed herein, which is either a negative photosensitive resin composition or a positive photosensitive resin composition, onto the resin film, drying it, exposing the pattern, and developing it with a developer to obtain a patterned resin film; and heating the patterned resin film. In this way, a hardened patterned insulating film can be obtained.

[0192] Regarding pattern exposure, for example, exposure is performed with a predetermined pattern using a photomask. Examples of photochemical rays irradiated include i-rays, broadband ultraviolet light, visible light, and radiation, with i-rays being preferred. As the exposure apparatus, parallel exposure machines, projection exposure machines, stepper machines, scanning exposure machines, etc., can be used.

[0193] By exposure followed by development, a patterned resin film, i.e., a patterned resin film, can be obtained. When the resin composition disclosed herein uses a negative photosensitive resin composition, the unexposed areas are removed using a developing solution. The organic solvent used as the negative developing solution can be a good solvent for the photosensitive resin film alone, or a mixture of a good solvent and a poor solvent. Examples of good solvents include: N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, 3-methoxy-N,N-dimethylpropanediamine, cyclopentanone, cyclohexanone, cycloheptanone, etc. Examples of poor solvents include: toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water, etc.

[0194] When the resin composition disclosed herein is a positive photosensitive resin composition, the exposed portion is removed using a developing solution. Examples of solutions used as positive developing solutions include tetramethylammonium hydroxide (TMAH) solution and sodium carbonate solution.

[0195] At least one of the negative developer and the positive developer may contain a surfactant. The surfactant content is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the developer.

[0196] The development time may be set, for example, twice the time required to immerse the photosensitive resin film in the developer and allow the resin film to completely dissolve. The development time may also be adjusted according to component (A) contained in the resin composition disclosed herein, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and from a production point of view, even more preferably 20 seconds to 5 minutes.

[0197] The developed patterned resin film can also be cleaned with a rinsing solution. As a rinsing solution, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in combination. In addition, these can be used in combination in stages.

[0198] Furthermore, as organic materials constituting the insulating film 102 and insulating film 202 other than the cured product formed by curing the resin composition disclosed herein, photosensitive resin, thermosetting non-conductive film (NCF), or thermosetting resin may also be used. The organic material may also be an underfill material. Additionally, the organic material constituting the insulating film 102 and insulating film 202 may also be a heat-resistant resin.

[0199] [Process (c) and Process (d)] Process (c) is a process of polishing the first semiconductor substrate 100. In process (c), as shown in FIG3(a), the CMP method is used to polish one side 101a of the first semiconductor substrate 100 so that each surface 103a of the terminal electrodes 103 is at the same position or slightly higher (protruding) relative to the surface 102a of the insulating film 102. In process (c), for example, the first semiconductor substrate 100 may also be polished by CMP method under the condition of selectively making deeper cuts of the terminal electrodes 103, etc. In process (c), the CMP method may also be used so that each surface 103a of the terminal electrodes 103 is aligned with the surface 102a of the insulating film 102. The polishing method is not limited to CMP method, and back grinding or the like may also be used. When each surface 103a of the terminal electrode 103 is positioned slightly higher than the surface 102a of the insulating film 102, the height difference between each surface 103a and the surface 102a can be 1 nm to 150 nm, or 1 nm to 15 nm.

[0200] Step (d) is a process of polishing the second semiconductor substrate 200. In step (d), as shown in FIG3(a), the CMP method is used to polish one side 201a of the second semiconductor substrate 200 so that each surface 203a of the terminal electrodes 203 is at the same position or slightly higher (protruding) relative to the surface 202a of the insulating film 202. In step (d), for example, the second semiconductor substrate 200 may also be polished by CMP method under the condition of selectively cutting deeper into the terminal electrodes 203 including copper, etc. In step (d), the CMP method may also be used so that each surface 203a of the terminal electrodes 203 is aligned with the surface 202a of the insulating film 202. The polishing method is not limited to CMP method, and back-side polishing, etc., may also be used. When each surface 203a of the terminal electrode 203 is positioned slightly higher than the surface 202a of the insulating film 202, the height difference between each surface 203a and the surface 202a can be 1 nm to 50 nm, or 1 nm to 15 nm.

[0201] In steps (c) and (d), grinding can be performed with the same thickness as the insulating film 102. However, grinding can also be performed with the insulating film 202 having a greater thickness than the insulating film 102. On the other hand, grinding can also be performed with the insulating film 202 having a smaller thickness than the insulating film 102. When the insulating film 202 has a greater thickness than the insulating film 102, the insulating film 202 can contain most of the foreign matter attached to the bonding interface during the monolithization of the second semiconductor substrate 200 or during wafer mounting, which can further reduce bonding defects. On the other hand, when the insulating film 202 has a smaller thickness than the insulating film 102, the mounted semiconductor wafer 205, i.e., the semiconductor device 1, can achieve a lower backlight.

[0202] [Process (e)] Process (e) is a process of monolithizing the second semiconductor substrate 200 to obtain multiple semiconductor wafers 205. In process (e), as shown in FIG2(b), the second semiconductor substrate 200 is monolithized into multiple semiconductor wafers 205 by cutting means such as dicing. Alternatively, a protective material or the like can be coated on the insulating film 202 when cutting the second semiconductor substrate 200, and then monolithization can be performed. By process (e), the insulating film 202 of the second semiconductor substrate 200 is divided into insulating film portions 202b corresponding to each semiconductor wafer 205. As a cutting method for monolithizing the second semiconductor substrate 200, plasma cutting, stealth cutting, laser cutting, etc. can be listed. As a surface protective material for the second semiconductor substrate 200 during cutting, for example, an organic film that can be removed by water, TMAH, etc., or a thin film such as a carbon film that can be removed by plasma, etc., can be provided.

[0203] [Process (f)] Process (f) is a process of aligning the terminal electrodes 203 of each of the plurality of semiconductor wafers 205 relative to the terminal electrodes 103 of the first semiconductor substrate 100. In process (f), as shown in FIG2(c), the semiconductor wafers 205 are aligned such that the terminal electrodes 203 of each semiconductor wafer 205 face the plurality of terminal electrodes 103 corresponding to the first semiconductor substrate 100. Alignment marks or the like may also be provided on the first semiconductor substrate 100 for the purpose of this alignment.

[0204] [Process (g)] Process (g) involves bonding the insulating film 102 of the first semiconductor substrate 100 to the insulating film portions 202b of each of the plurality of semiconductor wafers 205. In process (g), after removing organic matter, metal oxides, etc., attached to the surface of each semiconductor wafer 205, the semiconductor wafers 205 are aligned relative to the first semiconductor substrate 100 as shown in FIG2(c). Subsequently, the insulating film portions 202b of each of the plurality of semiconductor wafers 205 are bonded to the insulating film 102 of the first semiconductor substrate 100 as a hybrid bonding process (see FIG3(b)). At this time, the insulating film portions of the plurality of semiconductor wafers 205 and the insulating film 102 of the first semiconductor substrate 100 can also be uniformly heated before bonding. By bonding while heating, due to the difference in the coefficient of thermal expansion, the insulating film 102 and the insulating film portions 202b expand more than the terminal electrode 103 and the terminal electrode 203. Alternatively, the height of the insulating film 102 can be made equal to or greater than the height of the terminal electrode 103 through thermal expansion caused by heating during the first semiconductor substrate 100 grinding process (c). Similarly, the height of the insulating film portion 202b can be made equal to or greater than the height of the terminal electrode 203 during the second semiconductor substrate 200 grinding process (d). During bonding, the temperature difference between the semiconductor wafer 205 and the first semiconductor substrate 100 is preferably, for example, below 10°C. Through this heat bonding at a highly uniform temperature, an insulating bonding portion S1 is formed by bonding the insulating film 102 and the insulating film portion 202b, and multiple semiconductor wafers 205 are mechanically and securely mounted on the first semiconductor substrate 100. Furthermore, because the heat bonding is performed at a highly uniform temperature, positional misalignment is less likely to occur at the bonding site, allowing for high-precision bonding. During the mounting stage, the terminal electrodes 103 of the first semiconductor substrate 100 and the terminal electrodes 203 of the semiconductor wafer 205 are separated from each other and not connected (but are aligned). The bonding of the semiconductor wafer 205 to the first semiconductor substrate 100 can be performed by other bonding methods, such as bonding at room temperature.

[0205] The thickness of the organic insulating film in the insulating joint portion formed by bonding the insulating film 102 and the insulating film portion 202b is not particularly limited. For example, it can be 0.1 μm or more. From the point of view of suppressing the influence of foreign matter or device design, it can be 1 to 20 μm, and preferably 1 to 5 μm.

[0206] [Process (h)] Process (h) is a process of bonding the terminal electrode 103 of the first semiconductor substrate 100 to the terminal electrodes 203 of each of the plurality of semiconductor wafers 205. In process (h), when the bonding of process (g) is completed as shown in FIG2(d), heat H, pressure or both are applied to bond the terminal electrode 103 of the first semiconductor substrate 100 to the terminal electrodes 203 of each of the plurality of semiconductor wafers 205 as a mixed bonding (see FIG3(c)). When the terminal electrode 103 and the terminal electrode 203 contain copper, the annealing temperature in process (g) is preferably 150°C or higher and 400°C or lower, more preferably 200°C or higher and 300°C or lower. By this bonding process, an electrode bonding portion S2 is formed by bonding the terminal electrode 103 to its corresponding terminal electrode 203, and the terminal electrode 103 and the terminal electrode 203 are mechanically and firmly electrically bonded. Furthermore, the electrode bonding in step (h) can be performed after the bonding in step (g), or it can be performed simultaneously with the bonding in step (g).

[0207] As described above, a plurality of semiconductor wafers 205 are electrically and mechanically disposed at predetermined positions on the first semiconductor substrate 100 with high precision. Reliability tests (connection tests, etc.) can also be performed at the semi-finished product stage shown in FIG. 2(d), and only the good products can be used in subsequent processes. Next, a manufacturing method for an example of a semiconductor device using this semi-finished product will be described with reference to FIG. 4(a) to 4(d).

[0208] [Process (i)] Process (i) is a process of forming a plurality of pillars 300 on the connection surface 100a of the first semiconductor substrate 100 and between a plurality of semiconductor wafers 205. In process (i), as shown in FIG4(a), a plurality of pillars 300, for example made of copper, are formed between the plurality of semiconductor wafers 205. The pillars 300 may be formed by copper plating, conductive paste, copper pins, etc. The pillars 300 are formed such that one end is connected to a terminal electrode of the first semiconductor substrate 100 that is not connected to the terminal electrode 203 of the semiconductor wafer 205, and the other end extends upward. The pillars 300 have, for example, a diameter of 10 μm or more and 100 μm or less, and a height of 10 μm or more and 1000 μm or less. Furthermore, one or more but less than 10,000 pillars 300 may be provided between a pair of semiconductor wafers 205.

[0209] [Process (j)] Process (j) is a process of molding resin 301 onto the connection surface 100a of the first semiconductor substrate 100 in a manner that covers multiple semiconductor wafers 205 and multiple pillars 300. In process (j), as shown in FIG4(b), epoxy resin or the like is molded to cover multiple semiconductor wafers 205 and multiple pillars 300 integrally. Examples of molding methods include compression molding, transfer molding, and lamination of a film-like epoxy film. By the resin molding, the spaces between the multiple pillars 300 and between the pillars 300 and the semiconductor wafers 205 are filled with resin 301. Thereby, a resin-filled semi-finished product M1 is formed. Furthermore, a curing process may be performed after molding the epoxy resin or the like. In addition, when the column 300 is formed at approximately the same time as the resin molding process (i) and process (j), the column can be formed by using embossing and conductive paste or electroplating as micro-transfer.

[0210] [Process (k)] Process (k) is a process in which the semi-finished product M1, which is molded in process (j) and includes resin 301, multiple pillars 300 and multiple semiconductor wafers 205, is thinned by grinding from the resin 301 side to obtain semi-finished product M2. In process (k), as shown in FIG4(c), the top of the semi-finished product M1 is ground by using a grinding machine or the like, so that the first semiconductor substrate 100 and the like, which are molded by resin, are thinned to form semi-finished product M2. By grinding in process (k), the thickness of semiconductor wafers 205, pillars 300 and resin 301 is reduced to, for example, about several tens of μm, and semiconductor wafers 205 are shaped to correspond to the shape of the second semiconductor wafer 20, and pillars 300 and resin 301 are shaped to correspond to the pillar portion 30.

[0211] [Process (l)] Process (l) is a process in which a wiring layer 400 corresponding to the rewiring layer 40 is formed on the thinned semi-finished product M2 in process (k). In process (l), as shown in FIG4(d), a rewiring pattern is formed on the second semiconductor wafer 20 and pillar 30 of the ground semi-finished product M2 by means of polyimide, copper wiring, etc., thereby forming a semi-finished product M3, which has a wiring structure that expands the terminal spacing of the second semiconductor wafer 20 and pillar 30.

[0212] [Process (m) and Process (n)] Process (m) is a process in which the semi-finished product M3, on which the wiring layer 400 is formed in process (l), is cut along the cutting line A in such a way that it becomes each semiconductor device 1. In process (m), as shown in FIG4(d), the semiconductor device substrate is cut along the cutting line A by cutting or the like in such a way that it becomes each semiconductor device 1. Subsequently, in process (n), the individualized semiconductor devices 1a in process (m) are reversed and placed on the substrate 50 and the circuit board 60 to obtain a plurality of semiconductor devices 1 as shown in FIG1.

[0213] As described above, in the semiconductor device manufacturing method of this embodiment, the insulating film 102 of the first semiconductor substrate 100 and the insulating film 202 of the second semiconductor substrate 200 are hardened products formed by hardening the resin composition disclosed herein. The elastic modulus of this hardened product is lower than that of inorganic materials such as silicon dioxide. Therefore, by using this resin composition in the fabrication of the insulating film for hybrid bonding, even if foreign matter generated during the cutting process of monolithizing the second semiconductor substrate 200 into a semiconductor wafer 205 adheres to the insulating film, the insulating film around the foreign matter is easily deformed, allowing the foreign matter to be contained within the insulating film without creating large gaps. That is, the influence of foreign matter can be suppressed by the insulating film. Therefore, using the manufacturing method of this embodiment, fine bonding between the first semiconductor substrate 100 and the semiconductor wafer 205 can be performed, and bonding defects can be reduced. Furthermore, when the resin composition disclosed herein contains a material with a low elastic modulus or has a resin composition with high toughness, damage to the semiconductor device 1 manufactured by the manufacturing method can be suppressed more reliably.

[0214] Although one embodiment of the method for manufacturing a semiconductor device disclosed herein has been described in detail above, the present invention is not limited thereto. For example, in the above embodiment, in the steps shown in FIG4(a) to (d), after step (i) of forming the pillar 300, step (j) of molding the resin 301 and step (k) of grinding the resin 301 to thin it are performed sequentially. However, it is also possible to first perform step (j) of molding the resin 301 on the bonding surface of the first semiconductor substrate 100, then perform step (k) of grinding the resin 301 to a predetermined thickness to thin it, and then perform step (i) of forming the pillar 300. This can reduce the work of cutting the pillar 300, and since the part of the pillar 300 that needs to be cut is not needed, the material cost can be reduced.

[0215] Furthermore, although the above embodiments illustrate a C2C bonding example, the present invention can also be applied to the wafer-to-wafer (C2W) bonding shown in Figures 5(a) to 5(d). In C2W, a semiconductor wafer 410 (first semiconductor substrate) having a substrate body 411 (first substrate body) and an insulating film 412 (first insulating film) and a plurality of terminal electrodes 413 (first electrodes) disposed on one side of the substrate body 411 is prepared, and a semiconductor substrate (second semiconductor substrate) having a substrate body 421 (second substrate body) and an insulating film portion 422 (second insulating film) and a plurality of terminal electrodes 423 (second electrodes) disposed on one side of the substrate body 421 is prepared before monolithization. Then, similar to the steps (c) and (d) described above, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before monolithization are polished by CMP or the like. Subsequently, the second semiconductor substrate is subjected to the same monolithization process as in process (e) to obtain multiple semiconductor wafers 420.

[0216] Next, as shown in FIG5(a), the terminal electrodes 423 of the semiconductor wafer 420 are aligned relative to the terminal electrodes 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor wafer 420 are bonded together (step (g)), and the terminal electrodes 413 of the semiconductor wafer 410 and the terminal electrodes 423 of the semiconductor wafer 420 are joined (step (h)), obtaining a semi-finished product as shown in FIG5(b). In this way, an insulating bonding portion S3 formed by bonding the insulating film 412 and the insulating film portion 422 is formed, and the semiconductor wafer 420 is mechanically and firmly mounted on the semiconductor wafer 410 with high precision. In addition, an electrode bonding portion S4 formed by bonding the terminal electrode 413 and its corresponding terminal electrode 423 is formed, and the terminal electrode 413 and the terminal electrode 423 are mechanically and firmly electrically bonded.

[0217] Subsequently, as shown in Figures 5(c) and 5(d), a plurality of semiconductor wafers 420 are bonded to a semiconductor wafer 410, which is a semiconductor wafer, in the same manner to obtain a semiconductor device 401. Furthermore, the plurality of semiconductor wafers 420 may be bonded to the semiconductor wafer 410 one by one by mixed bonding, or they may be bonded to the semiconductor wafer 410 together by mixed bonding.

[0218] In the manufacturing method of this semiconductor device 401, similarly to the manufacturing method of the semiconductor device 1, at least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor wafer 420 is an insulating film formed by curing the resin composition disclosed herein. Therefore, even if foreign matter generated during the dicing process of monolithically forming the semiconductor wafer 420 adheres to the insulating film, the insulating film around the foreign matter is easily deformed, allowing the foreign matter to be contained within the insulating film without creating large gaps in the insulating film. That is, the influence of foreign matter can be suppressed by the insulating film. Therefore, in the manufacturing method of C2W, similarly to C2C, fine bonding of the semiconductor wafer 410 and the semiconductor wafer 420 can be performed, and bonding defects are reduced.

[0219] Furthermore, in the method for manufacturing the semiconductor device, to the extent that the effects of the present invention can be achieved, a portion of the insulating film 102 of the semiconductor substrate 110, the insulating film 202 of the semiconductor wafer 205, etc., may contain inorganic materials. [Example]

[0220] Hereinafter, the present disclosure will be described in more detail based on embodiments and comparative examples. Furthermore, the present disclosure is not limited to the following embodiments.

[0221] (Synthesis Example 1 (Synthesis of A1)) 7.07 g of 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 30 g of N-methyl-2-pyrrolidone (NMP). The resulting solution was stirred at 30°C for 4 hours, and then stirred at room temperature overnight to obtain polyamide. 9.45 g of trifluoroacetic anhydride was added to the solution at room temperature, followed by 7.08 g of 2-hydroxyethyl methacrylate (HEMA), and the mixture was stirred at 45°C for 10 hours. The reaction solution was added dropwise to distilled water, the precipitate was filtered and collected, and dried under reduced pressure to obtain polyimide precursor A1. The weight-average molecular weight of A1 was determined to be 20,000 based on standard polystyrene using gel permeation chromatography (GPC). Specifically, the determination was performed using a solution obtained by dissolving 0.5 mg of A1 in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] under the following conditions. (Measurement Conditions) Measurement Apparatus: Shimadzu Corporation SPD-M20A Pump: Shimadzu Corporation LC-20AD Column Oven: Shimadzu Corporation CTO-20A Measurement Conditions: Column Gelpack GL-S300MDT-5×2 eluent: THF / DMF=1 / 1 (volume ratio) LiBr (0.03 mol / L), H3PO4 (0.06 mol / L) Flow Rate: 1.0 mL / min, Detector: UV 270 nm, Column Temperature 40℃ Standard Polystyrene: Standard curves were prepared using TSKgel Standard Polystyrene models F-1, F-4, F-20, F-80, and A-2500 manufactured by Tosoh Corporation.

[0222] <Esterification Rate> NMR measurements were performed under the following conditions to calculate the esterification rate of A1 (the ratio of ester groups formed by the reaction with HEMA to the total of the ester groups and the carboxyl groups that did not react with HEMA). The esterification rate was 80 mol%, and the proportion of unreacted carboxyl groups was 20 mol%. (Measurement Conditions) Measurement Equipment: Bruker BioSpin AV400M Magnetic Field Strength: 400 MHz Reference Material: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0223] (Synthesis Example 2 (Synthesis of A2)) In Synthesis Example 1, NMP was replaced with 3-methoxy-N,N-dimethylpropaneamide. Otherwise, the synthesis of the polyimide precursor was carried out by the same method to obtain polyimide precursor A2. The weight average molecular weight of A2 is 22,000.

[0224] The esterification rate of A2 was calculated by NMR determination under the conditions described. The esterification rate was 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.

[0225] (Synthesis Example 3 (Synthesis of A3)) The 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) in Synthesis Example 1 was replaced with 3.6 g of 4,4'-diaminodiphenyl ether and 0.2 g of m-phenylenediamine. Otherwise, the same operation was performed to obtain polyimide precursor A3. The weight average molecular weight of A3 was 25,000.

[0226] The esterification rate of A3 was calculated by NMR determination under the conditions described. The esterification rate was 72 mol%, and the proportion of unreacted carboxyl groups was 28 mol%.

[0227] (Synthesis Example 4 (Synthesis of A4)) The NMP in Synthesis Example 3 was replaced with 3-methoxy-N,N-dimethylpropaneamide. Otherwise, the synthesis of the polyimide precursor was carried out by the same method to obtain polyimide precursor A4. The weight average molecular weight of A4 is 22,000.

[0228] The esterification rate of A4 was calculated by NMR determination under the conditions described. The esterification rate was 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.

[0229] (Synthesis Example 5 (Synthesis of A5)) 61.0 g of 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride (ODPA) and 52.0 g of 1,3-bis(3-aminophenoxy)benzene were dissolved in 200 g of 3-methoxy-N,N-dimethylpropane amide. The resulting solution was stirred at 30°C for 2 hours, and then stirred overnight at room temperature to obtain polyamide. 80 g of trifluoroacetic anhydride was added to the solution at room temperature and stirred for a specified time, followed by the addition of 7.2 g of 2-hydroxyethyl methacrylate (HEMA), and the mixture was stirred at 45°C for 10 hours. The reaction solution was dropped into distilled water, filtered to separate and collect the precipitate, and then dried under reduced pressure to obtain polyimide precursor A5 with a weight average molecular weight of 25,000.

[0230] (Synthesis Example 6 (Synthesis of A6)) In a reaction vessel, 155 g of ODPA and 131.2 g of HEMA were dissolved in 400 mL of γ-butyrolactone. The mixture was stirred at room temperature, and 81 g of pyridine was added while stirring to obtain the reaction mixture. After the reaction was heated to completion, the reaction mixture was allowed to cool to room temperature and left to stand for 15 hours.

[0231] Next, a solution of 206.3 g of dicyclohexylcarbodiimide dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture under ice bath cooling for 40 minutes with stirring. Then, a suspension of 93 g of 4,4'-diaminodiphenyl ether suspended in 350 mL of γ-butyrolactone was added to the reaction mixture under stirring for 60 minutes. The reaction mixture was then stirred at room temperature for 2 hours, followed by the addition of 30 mL of ethanol and stirring for 1 hour. Finally, 400 mL of γ-butyrolactone was added to the reaction mixture. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0232] The resulting reaction solution was added to 3 liters of ethanol, generating a precipitate containing crude polymer. The crude polymer was separated by filtration and dissolved in 1 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to water to precipitate the polymer. The precipitate was then filtered and dried under vacuum to obtain polyimide precursor A6 as a powdered polymer. The weight average molecular weight of A6 was 24,000.

[0233] The esterification rate of A6 was calculated by NMR determination under the conditions described above. The esterification rate is 100 mol%.

[0234] (Synthesis Example 7 (Synthesis of A7)) In Synthesis Example 6, 155 g of ODPA was replaced with 147 g of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride. Otherwise, the synthesis of the polyimide precursor was carried out by the same method to obtain polyimide precursor A7. The weight average molecular weight of A7 is 28,000.

[0235] The esterification rate of A7 was calculated by NMR determination under the conditions described. The esterification rate was approximately 100 mol%.

[0236] In Comparative Example 1 described below, the following polymeric components A8 and A9 were used as polymers other than the polyimide precursor. A8: Cresol-formaldehyde resin (manufactured by Asahi Organic Materials Co., Ltd.), weight average molecular weight 12000 A9: Acrylic polymer (butyl acrylate / acrylic acid / 4-hydroxybutyl acrylate)

[0237] (Synthesis Example 10 (Synthesis of A10)) 18.7 g of ODPA dried at 160°C for 24 hours and 6.54 g of pyromellitic dianhydride (PMDA) were added to 400 g of 3-methoxy-N,N-dimethylpropanediamine. A suspension obtained by stirring 29.1 g of 1,3-bis(3-aminophenoxy)benzene suspended in 100 g of 3-methoxy-N,N-dimethylpropanediamine was added dropwise to prepare a mixture. The mixture was stirred at 30°C for 4 hours, and then 1.5 g of diazabicycloundecene was added, followed by stirring at 150°C for 2 hours. The mixture was added dropwise to distilled water, and the precipitate was filtered, collected, and dried under reduced pressure to obtain polyimide precursor A10. The weight average molecular weight of A10 was 10,000.

[0238] [Examples 1-8, Comparative Example 1] (Preparation of Resin Compositions) The resin compositions of Examples 1-8 and Comparative Example 1 were prepared according to the components and dosages shown in Table 1 as follows. The dosage of each component in Table 1 is in parts by mass, and blank columns indicate that the corresponding component was not prepared. In each example and comparative example, the mixture of each component was kneaded overnight at room temperature in a general solvent-resistant container, and then pressure filtered using a filter with a pore size of 0.2 μm. The resulting resin compositions were evaluated as follows.

[0239] The components in Table 1 are described below. • Polymer components A1~A10 • (B) Components (solvents) B1: 3-Methoxy-N,N-dimethylpropionic acid B2: N-methyl-2-pyrrolidone B3: Methyl lactate B4: γ-butyrolactone • (D) Components (polymerizable monomers) D1: Triethylene glycol dimethacrylate (TEGDMA) D2: 1,6-hexanediol diglycidyl ether D3: Triglycidyl-p-aminophenol D4: Hexa(methoxymethyl)melamine (Cymel) D5: Urea-alkyl (C1~C5)aldehyde-alkyl (C2~C10) poly(2~4)aldehyde-alkyl (C1~C12) monool condensate (MX270) D6: 4,4'-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)bis[2,6-bis(hydroxymethyl)phenol] • Rust Inhibitors: Rust Inhibitor 1: Benzotriazole; Rust Inhibitor 2: 5-amino-1H-tetrazole; Rust Inhibitor 3: 1-H-tetrazole. • Adhesive Additives: Adhesive Additive 1: 50% methanol solution of 3-ureopropyltriethoxysilane; Adhesive Additive 2: 60% ethanol solution of N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane (SIB1140). • (C) Components (Photopolymerization Initiator): C1: 1-Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime; C2: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetylgoxyoxime); C3: 4,4'-bis(diethylamino)benzophenone; C4: Irgacure OXE01 C5: Compound represented by the following formula (Y) · (E) component (thermal polymerization initiator) E1: Bis(1-phenyl-1-methylethyl) peroxide · (F) component (polymerization inhibitor) F1: N,N'-hexane-1,6-dimethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]

[0240]

[0241] (Determination of storage elasticity coefficient, etc., of the hardened film) Hardened films were formed using the resin compositions of Examples 1-4, 7, 8, and Comparative Example 1 as photosensitive resin compositions, and the storage elasticity coefficient was then measured. The photosensitive resin composition was spin-coated onto a Si substrate and heated and dried on a hot plate at the temperature (°C) and time (seconds, s in Table 1) under the drying conditions during film formation as shown in Table 1, to form a photosensitive resin film with a hardened thickness of approximately 10 μm. The obtained photosensitive resin film was subjected to broadband (BB) exposure using a mask aligner MA-8 (manufactured by SUSS MicroTec) at the exposure amounts shown in Table 1. For Examples 1-4, 7, and 8, cyclopentanone (corresponding to Dev1 in Table 1) was used; for Comparative Example 1, 2.38% TMAH aqueous solution (corresponding to Dev2 in Table 1) was used. The exposed resin films were developed using coating developer ACT8 (manufactured by Tokyo Electron) for the times shown in Table 1 to obtain elongated patterned resin films 10 mm wide. The obtained patterned resin films were cured using a vertical diffusion furnace μ-TF under nitrogen atmosphere at the temperatures and times shown in Table 1 to obtain patterned hardened products with a film thickness of 10 μm. The obtained patterned hardened products were immersed in a 4.9% (w / w) hydrofluoric acid aqueous solution, and the 10 mm wide patterned hardened products were peeled off from the Si substrate. Using an RSA-G2 instrument manufactured by TA Instruments, the storage elastic coefficient and loss elastic coefficient of the patterned hardened material peeled from the Si substrate were measured under the following conditions: test frequency 1 Hz, heating rate 5 °C / min, test mode: tensile, N2 environment, test range -50 °C to 400 °C, clamp distance 10 mm, and sample width 2.0 mm. The loss tangent was calculated from the obtained storage elastic coefficient and loss elastic coefficient, and the peak of the loss tangent was taken as Tg (glass transition temperature). Furthermore, G2 / G1 was calculated from the storage elastic coefficient at a temperature 100 °C lower than Tg (G1 in Table 2) and the storage elastic coefficient at a temperature 100 °C higher than Tg (G2 in Table 2). The results are shown in Table 2. For G2 / G1 in Table 2, it is preferably 0.3 or less, more preferably 0.1 or less, and even more preferably 0.05 or less.

[0242] (Fabrication of a Wafer-Curing Film) The resin compositions of Examples 1-8 and Comparative Example 1 were spin-coated onto an 8-inch silicon wafer using a spin coater, and dried to form a resin film. When the resin composition was a photosensitive resin composition, a mask capable of forming a circular resin film with a diameter of 180 mm was placed on the resulting resin film, and it was irradiated with light of a wavelength of 365 nm at a specified exposure. Subsequently, cyclopentanone or 2.38% TMAH was used for development for a specified time, removing 10 mm from the outer periphery of the resin film on the silicon wafer to create a patterned resin film. When the resin composition was not a photosensitive resin composition, the edges of the spin-coated resin film were edge-washed with cyclopentanone to remove approximately 10 mm from the outer periphery of the wafer, creating a circular resin film with a diameter of approximately 180 mm. The resin film was heated in a clean oven under nitrogen atmosphere at the temperatures shown in Table 3 for a specified time to obtain a cured film with a thickness of 2 μm to 8 μm.

[0243] The obtained hardened film was polished using CMP to obtain a hardened film with a surface roughness Ra of 0.5~3 nm within 10 μm² as measured by atomic force microscopy. After cleaning the polished hardened film with a general cleaning solution, a portion of the cleaned polished hardened film was cut into 5 mm squares using a DISCO DFD-6362 blade cutter to obtain resin-coated wafers. The obtained resin-coated wafers were pressed onto the polished hardened film for 15 seconds using a flip chip bonding machine at a specified pressure and bonding temperature shown in Table 3 to produce a wafer-coated hardened film. For each resin composition, the five wafers pressed onto the polished hardened film were evaluated individually as described later.

[0244] [Comparative Example 2] (Fabrication of SiO2 Wafer with Wafer) A SiO2 wafer fabricated by thermal oxidation was prepared and ground according to the method described in the above description of the adhesion evaluation sample preparation method to produce a ground SiO2 wafer. A portion of the ground SiO2 wafer was monolithically processed to produce a SiO2 wafer. The obtained SiO2 wafer was attached to the ground SiO2 wafer using the same method as for fabricating the wafer-based hardening film to produce a wafer-based SiO2 wafer. In the wafer-based SiO2 wafer, five SiO2 wafers were pressed onto the ground SiO2 wafer.

[0245] For the obtained hardened film with wafers and SiO2 wafers with wafers, ultrasonic deep flaw inspection (SAT) was used to observe whether there were pores indicating poor adhesion between resin interfaces or between resin and substrate. The evaluation criteria for pores are as follows. The results are shown in Table 3. If the evaluation is A, the formation of pores is suppressed, and it is judged as a good evaluation. -Evaluation criteria for pores- A: No more than two out of five wafers have pores observed. B: More than two out of five wafers have pores observed. C: More than one wafer peels off during SAT measurement.

[0246] The adhesion between the obtained hardened film with wafers and the SiO2 wafer with wafers was measured using a shear tester. The adhesion was evaluated using the following criteria. The results are shown in Table 3. -Evaluation criteria for adhesion- A: The average shear strength of the five wafers is 1 MPa or more. B: The average shear strength of the five wafers is 1 MPa or less. C: The adhesion is too low to be measured. If an adhesion of 1 MPa or more is present, the subsequent processes after the fabrication of the hardened film with wafers can be carried out without problems.

[0247] (Research on Hot-Pressure Bonding) When copper terminals and insulating layers are bonded together, due to reliability issues with the copper terminals, pressure is generally applied at a temperature of 200°C to 400°C for bonding. When the insulating layer is a hardened film of insulating resin, porosity and other defects may occur during bonding due to volatile components generated by the thermal decomposition of the insulating resin. Therefore, hot-pressing at high temperature is further performed on the hardened film with the wafer to evaluate whether voids are generated and whether the adhesion strength decreases.

[0248] (Evaluation after hot-pressing) A carbon sheet for step absorption was covered on the above-mentioned wafer-coated hardened film. Using a pressing device (manufactured by EVG Corporation), a load of 7200 N was applied to an 8-inch pressing area at 300°C for 4 hours under specified vacuum conditions. Subsequently, the presence or absence of pores and the adhesion between the hardened films were evaluated using the same method as described above. The evaluation criteria for the presence or absence of pores and adhesion are as follows. The results are shown in Table 3. -Evaluation criteria for pores after hot-pressing- A: No more than two out of five wafers showed pores. B: More than two out of five wafers showed pores. C: More than one wafer peeled off during SAT measurement. -Evaluation criteria for adhesion after hot-pressing- A+: At least three out of five wafers exhibited Si agglomeration failure as the failure mode. A: The average shear strength of the five wafers was 5 MPa or more. B: The average shear strength of the five wafers was less than 5 MPa. C: The adhesion was too low to be measured.

[0249] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 (A)Ingredients polymer A1 100 A2 100 A3 100 A4 100 100 100 A5 100 A6 25 A7 100 A8 100 A9 25 A10 30 (B) Ingredients solvent B1 150 150 170 170 250 B2 150 170 B3 80 200 B4 20 (D) Components Polymerizable monomers D1 15 15 15 15 15 10 15 D2 25 D3 20 D4 1 D5 D6 Rust inhibitor 1 3 3 3 3 3 3 3 2 2 2 3 Next, the additives 1 5 5 2 2 2 2 2 2 (C) Components Photopolymerization initiator C1 5 5 C2 2 2 2 C3 1 1 C4 3 C5 10 (E) Components Thermal polymerization initiator E1 2 2 (F)Ingredients Polymerization inhibitors G1 3 3 3 Drying conditions during film making ℃ / s 100 / 240 100 / 240 100 / 240 100 / 240 100 / 240 100 / 240 100 / 240 100 / 240 120 / 180 Development conditions Solvent / Developing Time (seconds) Dev1 / 20 Dev1 / 20 Dev1 / 20 Dev1 / 20 - - Dev1 / 20 Dev1 / 20 Dev2 / 100 Exposure mJ / cm 2 300 300 300 300 - - 300 300 600 Hardening conditions Hardening temperature 375℃ 300℃, 375℃ 375℃ 300℃, 375℃ 375℃ 350℃ 230℃, 300℃, 350℃ 250℃ 250℃ Hardening time (Hour) 2 2 2 2 2 2 2 2 1

[0250] Table 2 Hardening temperature (°C) Storage elasticity coefficient G1 (GPa) Measurement temperature of G1 (°C) Storage elasticity coefficient G2 (GPa) Measurement temperature (°C) for G2 G2 / G1 Example 1 375 1.89 225 0.08 425 0.042 Example 2 375 1.9 230 0.09 430 0.047 Example 3 375 1.96 180 0.0099 380 0.005 Example 4 375 1.85 175 0.0096 370 0.005 Example 5 375 2.0 150 0.012 350 0.006 Example 6 350 1.3 150 0.043 350 0.033 Example 7 230 1.9 50 0.012 250 0.006 Example 8 250 2.1 140 0.0098 340 0.005 Comparative Example 1 250 1.6 100 0.04 300 0.025

[0251] Table 3 Hardening temperature (°C) Evaluation of hardened films with wafers and SiO2 wafers with wafers Evaluation after hot pressing Does CMP exist? Bonding temperature (°C) Porosity evaluation Then force Porosity evaluation Then force Example 1 375 have 350 A A A A+ Example 2 300 have 250 A A A A+ 375 have 250 A A A A+ 375 have 300 A A A A+ 375 have 350 A A A A+ Example 3 375 have 350 A A A A+ Example 4 300 have 250 A A A A+ 375 Yes 250 A A A A+ 375 Yes 300 A A A A+ 375 Yes 350 A A A A+ 375 None 350 A B A A+ Actual example 5 375 Yes 350 A A A A+ Actual example 6 350 Yes 300 A A A A+ Actual example 7 250 Yes 250 A A A A+ 300 Yes 300 A A A A+ 350 None 350 A A A A+ Example 8 250 have 250 A B A A+ Comparative Example 1 250 have 200 B B - - Comparative Example 2 - have 25 C C - - - have 50 C C - - - have 150 C C - - - have 350 C C - - - none 350 C C - -

[0252] As shown in Table 3, compared with Comparative Example 1, the generation of pores in the hardened film with wafers was appropriately suppressed in Examples 1 to 8. On the other hand, in Comparative Example 2, it was confirmed that the wafers in the SiO2 wafers with wafers were peeled off due to the influence of pores.

[0253] The entire contents of PCT / JP2020 / 037322, filed on September 30, 2020, are incorporated herein by reference. All documents, patent applications and technical specifications described in this specification are incorporated herein by reference to the extent that each document, patent application and technical specification is specifically and separately described herein. [Simplified Explanation of the Diagram]

[0023] FIG1 is a schematic cross-sectional view showing an example of a semiconductor device manufactured by a semiconductor device manufacturing method according to an embodiment of the present invention. FIG2(a) to 2(d) are diagrams showing the methods for manufacturing the semiconductor device shown in FIG1. ​​FIG3(a) to 3(c) are diagrams showing in more detail the bonding methods in the manufacturing method of the semiconductor device shown in FIG2(a) to 2(d). FIG4(a) to 4(d) are diagrams showing the methods for manufacturing the semiconductor device shown in FIG1, and are diagrams showing the processes after the process shown in FIG2. FIG5(a) to 5(d) are diagrams showing an example of applying the semiconductor device manufacturing method according to an embodiment of the present invention to a chip-to-wafer (C2W) process.

Claims

1. A resin composition comprising: (A) at least one of a polyimide precursor and a polyimide resin, said polyimide precursor being at least one resin selected from the group consisting of polyamide, polyamide ester, polyamide salt, and polyamide amide; and (B) a solvent, wherein said resin composition is used to fabricate at least one organic insulating film selected from a first organic insulating film and a second organic insulating film in a semiconductor device manufacturing method comprising steps (1) to (5) below, wherein step (1) is: preparing a first semiconductor substrate having a first substrate body and the first organic insulating film and a first electrode disposed on one side of the first substrate body. Step (2): Prepare a second semiconductor substrate having a second substrate body and a second organic insulating film disposed on one side of the second substrate body and a plurality of second electrodes. Step (3): Monolithize the second semiconductor substrate to obtain a plurality of semiconductor wafers, each including an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one second electrode. Step (4): Adhere the first organic insulating film of the first semiconductor substrate to the organic insulating film portion of the semiconductor wafer. Step (5): Join the first electrode of the first semiconductor substrate to the second electrode of the semiconductor wafer.

2. The resin composition of claim 1, comprising: (A) at least one of a polyimide precursor and a polyimide resin, said polyimide precursor being at least one resin selected from the group consisting of polyamide, polyamide ester, polyamide salt and polyamide amide; and (B) a solvent, and said resin composition being used to produce a hardened material that is polished together with an electrode by chemical mechanical polishing.

3. The resin composition as claimed in claim 1 or 2, wherein the (A) polyimide precursor comprises a compound having a structural unit represented by the following general formula (1), 3. In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R6 and R7 each independently represent a hydrogen atom or a monovalent organic group.

4. The resin composition as claimed in claim 3, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E).

4. In formula (E), C represents a single bond, an alkyl group, a halogenated alkyl group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), an phenyl group, an ester bond (-OC(=O)-), a silene bond (-Si(RA)2-; each of the two RAs independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n); each of the two RBs independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or more).

5. The resin composition as claimed in claim 3, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H), 5. In formula (H), each R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom, each n independently represents an integer from 0 to 4, and D represents a single bond, an alkyl group, a haloalkyl group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a thioether bond (-S-), an phenyl group, an ester bond (-OC(=O)-), a silene bond (-Si(RA)2-; each of the two RAs independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(RB)2-O-)n); each of the two RBs independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more).

6. The resin composition as claimed in claim 3, wherein in general formula (1), the monovalent organic groups of R6 and R7 are any one of the following general formula (2): ethyl, isobutyl, and tributyl.

6. In general formula (2), R8~R10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group with 1~3 carbon atoms, and Rx represents a divalent linkage group.

7. The resin composition as claimed in claim 1 or 2, wherein the content of the solvent (B) is 1 to 10,000 parts by mass relative to a total of 100 parts by mass of the polyimide precursor and the polyimide resin (A).

8. The resin composition as claimed in claim 1 or 2, wherein the solvent (B) comprises at least one compound selected from the group consisting of compounds represented by formulas (3) to (7).

8. In formulas (3) to (7), R1, R2, R8 and R10 are each independently an alkyl group with 1 to 4 carbon atoms, R3 to R7 and R9 are each independently a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, and u is an integer from 0 to 3.

9. The resin composition as claimed in claim 1 or 2, wherein the 5% heat weight reduction temperature of the cured product obtained by curing the resin composition is above 200°C.

10. The resin composition as claimed in claim 1 or 2, wherein the glass transition temperature of the cured product formed by curing the resin composition is 100 to 400°C.

11. The resin composition as claimed in claim 1 or 2, wherein the ratio of the storage elastic coefficient G2 at a temperature 100°C higher than the glass transition temperature (Tg) of the cured material obtained by dynamic viscoelasticity measurement to the storage elastic coefficient G1 at a temperature 100°C lower than the glass transition temperature (Tg) of the cured material obtained by the dynamic viscoelasticity measurement, i.e., G2 / G1, is 0.001 to 0.

02.

12. The resin composition as claimed in claim 1 or 2 further comprises (C) a photopolymerization initiator and (D) a polymerizable monomer.

13. The resin composition as claimed in claim 1 or 2, which is a negative photosensitive resin composition or a positive photosensitive resin composition, is used to form a plurality of through holes for arranging a plurality of terminal electrodes on an organic insulating film disposed on one side of a substrate body by photolithography.

14. The resin composition as described in claim 1 or 2, wherein the cured product thereof has a tensile modulus of elasticity of 7.0 GPa or less at 25°C.

15. The coefficient of thermal expansion of the cured product formed from the resin composition as described in claim 1 or 2 is 150 ppm / K or less.

16. A method for manufacturing a semiconductor device, comprising using a resin composition as described in any one of claims 1 to 15 to form at least one of a first organic insulating film and a second organic insulating film, and manufacturing the semiconductor device by means of the following steps (1) to (5): Step (1): preparing a first semiconductor substrate having a first substrate body and a first organic insulating film and a first electrode disposed on one side of the first substrate body; Step (2): preparing a second semiconductor substrate having a second substrate body and a second organic insulating film and a plurality of second electrodes disposed on one side of the second substrate body; Step (3): monolithizing the second semiconductor substrate to obtain a plurality of semiconductor wafers, each including an organic insulating film portion corresponding to a portion of the second organic insulating film and at least one second electrode; Step (4): bonding the first organic insulating film of the first semiconductor substrate to the organic insulating film portion of the semiconductor wafer; Step (5): bonding the first electrode of the first semiconductor substrate to the second electrode of the semiconductor wafer.

17. A method for manufacturing a semiconductor device as claimed in claim 16, wherein in step (4), the first organic insulating film is partially bonded to the organic insulating film at a temperature at which the temperature difference between the semiconductor wafer and the first semiconductor substrate is within 10°C.

18. A method for manufacturing a semiconductor device as claimed in claim 16 or 17, wherein in the manufactured semiconductor device, the thickness of the organic insulating film formed by bonding the first organic insulating film to a portion of the organic insulating film is 0.1 μm or more.

19. A method of manufacturing a semiconductor device as claimed in claim 16 or 17, wherein at least one of step (1) includes a step of polishing one side of the first semiconductor substrate and step (2) includes a step of polishing one side of the second semiconductor substrate, and wherein at least one of the following conditions is met: the polishing rate of the first organic insulating film is 0.1 to 5 times the polishing rate of the first electrode and the polishing rate of the second organic insulating film is 0.1 to 5 times the polishing rate of the second electrode.

20. A method of manufacturing a semiconductor device as claimed in claim 16 or 17, wherein the thickness of the second organic insulating film is greater than the thickness of the first organic insulating film.

21. A method of manufacturing a semiconductor device as claimed in claim 16 or 17, wherein the thickness of the second organic insulating film is smaller than the thickness of the first organic insulating film.

22. A hardened material formed by hardening a resin composition as described in any one of claims 1 to 15.

23. A semiconductor device, comprising: The first semiconductor substrate has a first substrate body, and a first organic insulating film and a first electrode disposed on one side of the first substrate body; And a semiconductor wafer, having a semiconductor wafer substrate body, an organic insulating film portion disposed on one side of the semiconductor wafer substrate body and a second electrode, wherein the first organic insulating film of the first semiconductor substrate is bonded to the organic insulating film portion of the semiconductor wafer, the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor wafer, and at least one of the first organic insulating film and the organic insulating film portion is an organic insulating film formed by curing a resin composition as described in any one of claims 1 to 15.

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