Resin composition, method for manufacturing semiconductor device, cured product, semiconductor device, and method for synthesizing polyimide precursor.

Abstract

To provide a resin composition that enables the manufacture of semiconductor devices having an insulating film with excellent heat resistance, while suppressing the generation of voids at the bonding interface. [Solution] The resin composition comprises (A) at least one polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and (B) a solvent, and is intended for use in the production of at least one of the first organic insulating film and the second organic insulating film in a semiconductor device manufacturing method comprising steps (1) to (5).

Description

[Technical Field]

[0001] This disclosure relates to a resin composition, a method for manufacturing a semiconductor device, a cured product, a semiconductor device, and a method for synthesizing a polyimide precursor. [Background technology]

[0002] In recent years, three-dimensional packaging of semiconductor chips has been considered to improve the integration density of LSIs (Large Scale Integrated Circuits). Non-patent document 1 discloses an example of three-dimensional packaging of semiconductor chips.

[0003] When performing three-dimensional mounting of semiconductor chips using C2W (Chip-to-Wafer) bonding, the use of hybrid bonding technology, which is used in W2W (Wafer-to-Wafer) bonding, is being considered in order to achieve fine bonding of the wiring between devices.

[0004] In C2W hybrid bonding, there is a risk of misalignment due to thermal expansion of the substrate, chips, etc., caused by heating during bonding. To address this issue, Patent Document 1 discloses an example of a technology that can lower the bonding temperature by using a cyclic olefin resin. [Prior art documents] [Patent Documents]

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

[0006] [Non-Patent Document 1] FC Chen et al., “System on Integrated Chips(SoIC TM) for 3D Heterogeneous Integration”, 2019 IEEE 69th Electronic Components and Technology Conference (ECTC), p.594-599(2019) [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] When performing three-dimensional mounting of semiconductor chips using C2W bonding, unlike W2W bonding, foreign matter (cutting fragments) may be generated during the process of separating the semiconductor chip into individual components. This foreign matter may adhere to the bonding interface of the semiconductor chip (the surface of the insulating film in hybrid bonding). While the use of inorganic materials such as silicon dioxide (SiO2) for this insulating film is being considered, inorganic materials are hard, and the attached foreign matter can create large voids in the insulating film, for example, voids with a width nearly 1000 times the height of the foreign matter, at the bonding interface. Therefore, simply applying the hybrid bonding technology used in W2W bonding to C2W bonding may cause bonding failures due to the generation of such voids, resulting in a decrease in the yield of semiconductor equipment manufacturing. On the other hand, if a cleanroom and equipment with a high degree of cleanliness are used to prevent these bonding failures, significant costs are required for the investment in cleanrooms and other equipment.

[0008] Furthermore, if organic materials such as cyclic olefin resins are used as the insulating film material, the heat resistance of the organic material may not be sufficient, and the insulating film may be exposed to high temperatures during C2W bonding, causing the organic material to deteriorate and potentially leading to bonding defects at the interface between the substrate and the insulating film.

[0009] This disclosure has been made in view of the above, and aims to provide a resin composition capable of manufacturing a semiconductor device having an insulating film with excellent heat resistance and suppressed void generation at the bonding interface, a method for manufacturing a semiconductor device using the aforementioned resin composition, a cured product obtained by curing the aforementioned resin composition, and a semiconductor device having an insulating film with excellent heat resistance and suppressed void generation at the bonding interface. Furthermore, this disclosure aims to provide a method for synthesizing polyimide precursors that can be used in the preparation of the aforementioned resin compositions. [Means for solving the problem]

[0010] The specific means for achieving the aforementioned objectives are as follows: <1> (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and at least one polyimide resin, and (B) a solvent, A resin composition for use in producing 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) Prepare a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body. Step (2) A second semiconductor substrate is prepared, which has a second substrate body, a second organic insulating film provided on one surface of the second substrate body, and a plurality of second electrodes. Step (3) The second semiconductor substrate is divided into individual pieces to obtain a plurality of semiconductor chips, each of which comprises an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4) The first organic insulating film of the first semiconductor substrate and the portion of the organic insulating film of the semiconductor chip are bonded together. Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together. <2> (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and at least one polyimide resin, and (B) a solvent, A resin composition for use in the production of cured products that are polished by chemical mechanical polishing together with electrodes. <3> The (A) polyimide precursor includes a compound having a structural unit represented by the following general formula (1). <1> or <2> The resin composition described above.

[0011] [ka]

[0012] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R 6 and R 7 Each of these independently represents either a hydrogen atom or a monovalent organic group. <4> In the general formula (1) above, the tetravalent organic group represented by X is the group represented by the following formula (E). <3> The resin composition described above.

[0013] [ka]

[0014] In formula (E), C is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC(=O)-), silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these 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. <5> In the general formula (1), the divalent organic group represented by Y is the group represented by the following formula (H), and the resin composition according to <3> or <4>.

[0015]

Chemical formula

[0016] In formula (H), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and each n independently represents an integer of 0 to 4. D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R A )2-; two Rs A each independently represents a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (-O-(Si(R B )2-O-) n ; two Rs B each 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. <6> In the general formula (1), the monovalent organic groups in the R 6 and the R 7 are any one of the group represented by the following general formula (2), an ethyl group, an isobutyl group or a t-butyl group, and the resin composition according to any one of <3> to <5>.

[0017]

Chemical formula

[0018] In general formula (2), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group. <7> The content of the solvent (B) is 1 to 10,000 parts by mass per 100 parts by mass of the total of the polyimide precursor and polyimide resin (A). <1> ~ <6> A resin composition as described in any one of the following. <8> The solvent (B) includes at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (6). <1> ~ <7> A resin composition as described in any one of the following.

[0019] [ka]

[0020] In formulas (3) to (7), R 1 , R 2 , R 8 and R 10 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 3 ~R 7 and R 9 Each of these is independently either 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 5% thermoweight loss temperature of the cured product obtained by curing the resin composition is 200°C or higher. <1> ~ <8> A resin composition as described in any one of the following. <10> The glass transition temperature of the cured product obtained by curing the resin composition is 100°C to 400°C. <1> ~ <9> A resin composition as described in any one of the following. <11> For a cured product obtained by curing the resin composition, the ratio G2 / G1, which is the ratio of the storage modulus G2 at a temperature 100°C higher than the glass transition temperature (Tg) of the cured product obtained by dynamic viscoelastic measurement to the storage modulus G1 at a temperature 100°C lower than the glass transition temperature (Tg) of the cured product obtained by dynamic viscoelastic measurement, is between 0.001 and 0.02. <1> ~ <10> A resin composition as described in any one of the following. <12> (C) a photopolymerization initiator and (D) a polymerizable monomer are further included. <1> ~ <11> A resin composition as described in any one of the following. <13> A negative-type or positive-type photosensitive resin composition, used for creating multiple through-holes for arranging multiple terminal electrodes in an organic insulating film provided on one surface of a substrate body by photolithography. <1> ~ <12> A resin composition as described in any one of the following. <14> The tensile modulus of the hardened product at 25°C is 7.0 GPa or less. <1> ~ <13> A resin composition as described in any one of the following. <15> The thermal expansion coefficient of the hardened product is 150 ppm / K or less. <1> ~ <14> A resin composition as described in any one of the following. <16> <1> ~ <15> A method for manufacturing a semiconductor device, comprising using a resin composition described in any one of the above to produce at least one of the first organic insulating film and the second organic insulating film, and manufacturing a semiconductor device through the following steps (1) to (5). Step (1) Prepare a first semiconductor substrate having a first substrate body and a first organic insulating film and a first electrode provided on one surface of the first substrate body. Step (2) A second semiconductor substrate is prepared, which has a second substrate body, a second organic insulating film provided on one surface of the second substrate body, and a plurality of second electrodes. Step (3) The second semiconductor substrate is divided into individual pieces to obtain a plurality of semiconductor chips, each of which comprises an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4) The first organic insulating film of the first semiconductor substrate and the portion of the organic insulating film of the semiconductor chip are bonded together. Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together. <17> In step (4) above, the first organic insulating film and the portion of the organic insulating film are bonded together at a temperature such that the temperature difference between the semiconductor chip and the first semiconductor substrate is 10°C or less. <16> A method for manufacturing a semiconductor device as described above. <18> In the manufactured semiconductor device, the thickness of the organic insulating film formed by the bonding of the first organic insulating film and the organic insulating film portion is 0.1 μm or more. <16> or <17> A method for manufacturing a semiconductor device as described above. <19> The following conditions must be met: at least one of the above steps (1) includes polishing one side of the first semiconductor substrate, and at least one of the above steps (2) includes polishing one side of the second semiconductor substrate; 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. <16> ~ <18> A method for manufacturing a semiconductor device as described in any one of the following. <20> The thickness of the second insulating film is greater than the thickness of the first insulating film. <16> ~ <19> A method for manufacturing a semiconductor device as described in any one of the following. <21> The thickness of the second insulating film is smaller than the thickness of the first insulating film. <16> ~ <19> A method for manufacturing a semiconductor device as described in any one of the following. <22> <1> ~ <15> A cured product obtained by curing the resin composition described in any one of the above. <23> A first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body, A semiconductor chip comprising a semiconductor chip substrate body, an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body, The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are joined together, and the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together. At least one of the first organic insulating film and the portion of the organic insulating film is <1> ~ <15> A semiconductor device which is an organic insulating film obtained by curing the resin composition described in any one of the above. <24> A step of reacting a tetracarboxylic dianhydride with a diamine compound represented by H2N-Y-NH2 (wherein Y is a divalent organic group) in 3-methoxy-N,N-dimethylpropanamide to obtain a polyamic acid solution, The process involves reacting the polyamic acid solution with a dehydrating condensation agent and a compound represented by R-OH (wherein R is a monovalent organic group), A method for synthesizing a polyimide precursor, including [the specified substance]. <25> The dehydration condensing agent comprises at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC). <24> A method for synthesizing the polyimide precursor described above. [Effects of the Invention]

[0021] According to this disclosure, it is possible to provide a resin composition capable of manufacturing a semiconductor device having an insulating film with excellent heat resistance and suppressed void generation at the bonding interface, a method for manufacturing a semiconductor device using the aforementioned resin composition, a cured product obtained by curing the aforementioned resin composition, and a semiconductor device having an insulating film with excellent heat resistance and suppressed void generation at the bonding interface. Furthermore, this disclosure can provide a method for synthesizing polyimide precursors that can be used in the preparation of the aforementioned resin compositions. [Brief explanation of the drawing]

[0022] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of a semiconductor device manufactured by a semiconductor device manufacturing method according to one embodiment of the present invention. [Figure 2] Figure 2 is a diagram illustrating, step by step, the method for manufacturing the semiconductor device shown in Figure 1. [Figure 3] Figure 3 is a diagram that shows in more detail the bonding method in the semiconductor device manufacturing method shown in Figure 2. [Figure 4] Figure 4 shows a method for manufacturing the semiconductor device shown in Figure 1, and sequentially illustrates the steps after the process shown in Figure 2. [Figure 5] Figure 5 shows an example of applying a semiconductor device manufacturing method according to one embodiment of the present invention to a chip-to-wafer (C2W) device. [Modes for carrying out the invention]

[0023] The following describes in detail the forms for implementing this disclosure. However, this disclosure is not limited to the following embodiments. In the following embodiments, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit this disclosure.

[0024] In this disclosure, "A or B" means either A or B, or both. In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the terms “layer” or “film” include cases where, when the region in which the layer or film exists is observed, it is formed not only over the entire region but also over only a portion of the region. In this disclosure, the thickness of a layer or film is given as the arithmetic mean of the thicknesses of five points on the layer or film in question. The thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, if the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing the cross-section of the object to be measured using an electron microscope. In this disclosure, "(meth)acrylic group" means "acrylic group" and "methacrylic group". In this disclosure, if a functional group has substituents, the number of carbon atoms in the functional group means the total number of carbon atoms, including the number of carbon atoms in the substituents. When embodiments are described in this disclosure with reference to the drawings, the configuration of such embodiments is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in each figure are conceptual, and the relative relationships between the sizes of the components are not limited thereto.

[0025] <Resin composition> The resin composition of this disclosure comprises (A) at least one polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide, and a polyimide resin, and (B) a solvent, and is a resin composition for use in producing 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) Prepare a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body. Step (2) A second semiconductor substrate is prepared, which has a second substrate body, a second organic insulating film provided on one surface of the second substrate body, and a plurality of second electrodes. Step (3) Step of separating the second semiconductor substrate into individual pieces to obtain a plurality of semiconductor chips, each of which is provided with an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes, Step (4) The first organic insulating film of the first semiconductor substrate and the portion of the organic insulating film of the semiconductor chip are bonded together. Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together. Specific examples of each of the aforementioned steps (1) to (5) will be explained later in the section on semiconductor device manufacturing methods.

[0026] (A) The insulating film, which is a cured product obtained by curing a resin composition containing at least one of a polyimide precursor and a polyimide resin, has a lower elastic modulus and is softer than a molded product made of inorganic material. Therefore, when bonding a first organic insulating film and a second organic insulating film, at least one of which is the insulating film, even if foreign matter is present on the surface of the first organic insulating film or the second organic insulating film, the insulating film at the bonding interface deforms easily, and the foreign matter can be contained within the insulating film without creating large voids in the insulating film. Furthermore, 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 compared to a cured product obtained by curing a resin composition containing acrylic resin, epoxy resin, etc. Therefore, in the semiconductor device manufacturing process, bonding defects caused by deterioration of the resin at the interface between the substrate and the insulating film tend to be suppressed. From the above points, the resin composition of this disclosure can achieve excellent reliability and high yield in the semiconductor device manufacturing process.

[0027] A variation of the resin composition of this disclosure may be a resin composition for use in producing a cured product which is polished together with an electrode by a chemical mechanical polishing (CMP) method, comprising (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and at least one polyimide resin, and (B) a solvent. In the modified resin composition, when polishing an electrode made of a metal such as copper and an insulating film, which is a cured product obtained by curing the resin composition, by the CMP method, the thickness of the electrode and the thickness of the insulating film can be easily adjusted. For example, the surface of the insulating film can be easily adjusted to be slightly lower than the surface of the electrode, and 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.

[0028] The 5% thermoweight loss temperature of the cured product obtained by curing the resin composition of this disclosure is preferably 200°C or higher, and more preferably 250°C or higher, from the viewpoint of the heat resistance of the cured product. Furthermore, there is no particular upper limit to the 5% thermoweight loss temperature of the cured product, and it may be, for example, 450°C or lower.

[0029] The 5% thermogravimetric temperature of the cured product is measured 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 one hour to obtain a cured product. 10 mg of the obtained cured product is placed in a thermogravimetric analyzer (e.g., Shimadzu Corporation, TGA-50) and heated from 25°C to 500°C at a rate of 10°C / min in a nitrogen atmosphere. The temperature at which the weight decreases by 5% from before heating is defined as the 5% thermogravimetric temperature.

[0030] The glass transition temperature of the cured product obtained by curing the resin composition of this disclosure is preferably 100°C to 400°C, and more preferably 150°C to 350°C, from the viewpoint of bonding at low temperatures.

[0031] The glass transition temperature of the cured product is measured as follows. First, the resin composition is heated in a nitrogen atmosphere for 2 hours at a predetermined curing temperature (e.g., 150°C to 375°C) at which the curing reaction can occur to obtain a cured product. The obtained cured product is cut to create a rectangular parallelepiped measuring 5 mm × 50 mm × 3 mm, and the dynamic viscoelasticity is measured using a dynamic viscoelasticity measuring device (e.g., RSA-G2, manufactured by TA Instruments) with a tensile jig, under the conditions of frequency: 1 Hz and heating rate: 5°C / min, in the temperature range of 50°C to 350°C. The glass transition temperature (Tg) is defined as the temperature of the peak top portion of tanδ, which is obtained from the ratio of storage modulus to loss modulus obtained by the above method.

[0032] For a cured product obtained by curing the resin composition of this disclosure, the ratio G2 / G1, which is the ratio of the storage modulus G2 at a temperature 100°C higher than the glass transition temperature (Tg) of the cured product obtained by dynamic viscoelastic measurement to the storage modulus G1 at a temperature 100°C lower than the glass transition temperature (Tg) of the cured product obtained by dynamic viscoelastic measurement, is preferably 0.001 to 0.02. In this disclosure, the storage modulus can be measured using the method described in the explanation of the glass transition temperature measurement method.

[0033] The resin composition of this disclosure may be a negative-type photosensitive resin composition or a positive-type photosensitive resin composition. Furthermore, the negative-type photosensitive resin composition or the positive-type photosensitive resin composition may be used in at least one of the following steps: providing a plurality of through holes for arranging a plurality of terminal electrodes in a first organic insulating film provided on one surface of the first substrate body in step (1), and providing a plurality of through holes for arranging a plurality of terminal electrodes in a second organic insulating film provided on one surface of the second substrate body in step (2).

[0034] The resin composition of this disclosure preferably has a tensile modulus of 7.0 GPa or less at 25°C, 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, from the viewpoint of more favorably reducing bonding defects by containing foreign matter within the insulating film without creating large voids when foreign matter adheres to the bonding interface. The cured product obtained by curing the resin composition of this disclosure has a lower tensile modulus of 1.5 GPa or less compared to inorganic materials such as silicon dioxide (SiO2). In this disclosure, the tensile modulus is a value measured at 25°C in accordance with JIS K 7161 (1994).

[0035] The storage modulus at 300°C for a cured product obtained by curing the resin composition of this disclosure may be 0.5 GPa to 0.001 GPa, or 0.1 GPa to 0.01 GPa.

[0036] The resin composition of this disclosure preferably has a thermal expansion coefficient of 150 ppm / K or less, more preferably 100 ppm / K or less, and even more preferably 70 ppm / K or less. As a result, the thermal expansion coefficient of the insulating film, which is the cured product, and the thermal expansion coefficient of the electrode are equal to or close to each other, so that even if heat generation occurs during use of the semiconductor device, damage to the semiconductor device due to the difference in thermal expansion coefficients between the insulating layer and the electrode can be suppressed. The thermal expansion coefficient is the rate at which the length of the cured product expands per unit temperature due to the rise in temperature, and can be calculated by measuring the change in the length of the cured product between 100°C and 150°C using a thermomechanical analyzer or the like.

[0037] The following describes the components included in and potentially included in the resin composition of this disclosure.

[0038] ((A) Polyimide precursors and polyimide resins) The resin composition of this disclosure comprises (A) at least one polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin (hereinafter also referred to as "component (A)"). Component (A) is preferably at least one of a polyimide precursor and a polyimide resin that enables the production of a cured product exhibiting high properties (e.g., heat resistance), and it is more preferable that the polyimide precursor includes a polyimide precursor having polymerizable unsaturated bonds. Component (A) included in the resin composition is preferably a component that does not cause problems in polishing processes, bonding processes, etc. In this disclosure, polyimide precursor means a compound that is any of the following: a polyamic acid, a compound in which at least some of the hydrogen atoms of the carboxyl groups in a polyamic acid are substituted with a monovalent organic group, or a polyamic acid salt in which at least some of the carboxyl groups in a polyamic acid form a salt structure with a basic compound with a pH of 7 or higher. Examples of compounds in which at least some of the hydrogen atoms of the carboxyl groups in polyamic acids are substituted with monovalent organic groups include polyamic acid esters and polyamic acid amides. Polyamic acid esters, polyamic acid amides, etc., preferably have polymerizable unsaturated bonds.

[0039] If component (A) contains a polyimide precursor, it is preferable that component (A) contains a compound having a structural unit represented by the following general formula (1). This tends to result in a semiconductor device with an insulating film that exhibits high reliability.

[0040] [ka]

[0041] In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. 6 and R 7 Each of these independently represents either a hydrogen atom or a monovalent organic group. The polyimide precursor may have multiple structural units represented by the above general formula (1), and X, Y, R in the multiple structural units 6 and R 7 These may be the same or different. Note, R 6 and R 7 The combination of each is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups. For example, R 6 and R 7 Both may be hydrogen atoms, one may be a hydrogen atom and the other a monovalent organic group described later, and both may be the same or different monovalent organic groups. As mentioned above, when the polyimide precursor has multiple structural units represented by the above general formula (1), the R of each structural unit 6 and R 7 The combinations may be the same or different.

[0042] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may include an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (for example, groups with 6 to 20 carbon atoms) and aromatic heterocyclic groups (for example, groups with 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, alkyl halides, hydroxyl groups, amino groups, and the like. When the tetravalent organic group represented by X contains a benzene ring, it is preferable that the tetravalent organic group represented by X 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 organic group represented by X contains two or more benzene rings, each benzene ring may be linked by a single bond, or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), or a silylene bond (-Si(R)). A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. The rings may be linked by linking groups such as , or by a composite linking group formed by combining at least two of these linking groups. Alternatively, two benzene rings may be linked at two locations by a single bond and at least one of a linking group, forming a five-membered or six-membered ring containing a linking group between the two benzene rings.

[0043] In general formula (1), -COOR 6 The group and the -CONH- group are preferably in the ortho position relative to each other, and -COOR 7 It is preferable that the group and the -CO- group are in the ortho position relative to each other.

[0044] Specific examples of tetravalent organic groups represented by X include the groups represented by formulas (A) to (F) below. Among these, the group represented by formula (E) below is preferred from the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, and more preferably the group represented by formula (E) below, in which C is a group containing an ether bond, and even more preferably an ether bond. Formula (F) below is a structure in which C in formula (E) below is a single bond. This disclosure is not limited to the specific examples listed below.

[0045] [ka]

[0046] In formula (D), A and B are independently single bonds or divalent groups not conjugated to a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups not conjugated to a benzene ring include methylene groups, halide methylene groups, halide methylmethylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), sulfide bonds (-S-), and silylene bonds (-Si(R)). A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group.) are some examples. Among these, A and B are preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, etc., and an ether bond is more preferred.

[0047] In formula (E), C is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC(=O)-), silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these 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. Furthermore, C may have a structure represented by the following formula (C1).

[0048] [ka]

[0049] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of alkylene groups represented by C in formula (E) include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group; methylmethylene group, methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, and 1,1-dimethyl Examples include branched alkylene groups such as methylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, and 1,4-dimethyltetramethylene group. Among these, methylene groups are preferred.

[0050] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom in the alkylene group represented by C in formula (E) above is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene groups, difluoromethylene groups, and hexafluorodimethylmethylene groups are preferred.

[0051] R included in the above silylene bond or siloxane bond A or R B The alkyl group represented is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. A or R B Specific examples of alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and the like.

[0052] Specific examples of the tetravalent organic group represented by X may be the groups represented by the following formulas (J) to (O).

[0053] [ka]

[0054] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20, and even more preferably 12 to 18 carbon atoms. 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 the preferred skeleton of the divalent organic group represented by Y may be the same as the 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 of the tetravalent organic group represented by X are substituted with 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, it is preferable that the divalent organic group represented by Y is a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (for example, groups with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (for example, groups with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

[0055] Specific examples of divalent aromatic groups represented by Y include the groups represented by formulas (G) to (I) below. Among these, the group represented by formula (H) below is preferred from the viewpoint of obtaining an insulating film with excellent flexibility and suppression of void generation at the bonding interface, and more preferably the group represented by formula (H) below, where D is a group containing an ether bond, and even more preferably an ether bond.

[0056] [ka]

[0057] In formulas (G) to (I), R independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. In formula (H), D is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-OC(=O)-), silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these 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. Furthermore, D may be the structure represented by formula (C1) above. Specific examples of D in formula (H) are the same as specific examples of C in formula (E). In formula (H), D is preferably an ether bond, a group containing an ether bond and a phenylene group, or a group containing an ether bond, a phenylene group, and an alkylene group.

[0058] 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 alkyl groups represented by R in formulas (G) to (I) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group.

[0059] 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 group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, etc.

[0060] The halogenated alkyl group represented by R in formulas (G) to (I) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in formulas (G) to (I) include alkyl groups in which at least one hydrogen atom in the alkyl group represented by R in formulas (G) to (I) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl groups, difluoromethyl groups, and trifluoromethyl groups are preferred.

[0061] In equations (G) to (I), n is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0062] Specific examples of divalent aliphatic groups represented by Y include linear or branched alkylene groups, cycloalkylene groups, divalent groups having a polyalkylene oxide structure, and divalent groups having a polysiloxane structure.

[0063] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of alkylene groups represented by Y include tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 2-methylpentamethylene, 2-methylhexamethylene, 2-methylheptamethylene, 2-methyloctamethylene, 2-methylnonamethylene, and 2-methyldecamethylene.

[0064] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of cycloalkylene groups represented by Y include cyclopropylene and cyclohexylene.

[0065] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among these, polyethylene oxide structure or polypropylene oxide structure is preferred as the polyalkylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

[0066] Examples of divalent groups having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atoms in the polysiloxane structure are bonded to hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or aryl groups having 6 to 18 carbon atoms. Specific examples of C1-C20 alkyl groups that bond to silicon atoms in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl groups. Among these, the methyl group 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 on the aryl group include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl groups, naphthyl groups, and benzyl groups. Among these, the phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types. The silicon atoms constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group, etc.

[0067] The group represented by formula (G) is preferably the group represented by the following formula (G'), the group represented by formula (H) is preferably the group represented by the following formula (H') or formula (H"), and the group represented by formula (I) is preferably the group represented by the following formula (I').

[0068] [ka]

[0069] In formula (I'), R independently represents an alkyl group, an alkoxy group, an alkyl halide, a phenyl group, or a halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0070] The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1) is not particularly limited. Examples of combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y include the combination where X is the group represented by formula (E) and Y is the group represented by formula (H); and the combination where X is the group represented by formula (E) and Y is the group represented by formula (I).

[0071] R 6 and R 7 Each of these independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably one of the groups represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, even more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and particularly preferably a group represented by the following general formula (2). In particular, when the monovalent organic group is an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the transmittance of i-rays is high, and good cured products tend to be formed even when curing at low temperatures of 400°C or below. Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups, with ethyl, isobutyl, and t-butyl groups being preferred.

[0072] [ka]

[0073] In general formula (2), R 8 ~R 10 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R xThis represents a divalent linking group.

[0074] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2. 8 ~R 10 Specific examples of the aliphatic hydrocarbon group represented by include the methyl group, ethyl group, n-propyl group, isopropyl group, etc., with the methyl group being preferred.

[0075] R in general formula (2) 8 ~R 10 As for combinations, R 8 and R 9 is a hydrogen atom, and R 10 A combination of hydrogen atoms or methyl groups is preferred.

[0076] R in general formula (2) x The linking group is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups. R x The number of carbon atoms in the compound is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0077] In general formula (1), R 6 and R 7 Preferably, at least one of them is a group represented by the general formula (2), R 6 and R 7 It is more preferable that both are groups represented by the general formula (2).

[0078] (A) If component contains a compound having a structural unit represented by the general formula (1) above, the R of all structural units contained in the compound 6 and R 7 The group R, represented by the general formula (2) for the sum of 6 and R 7The proportion 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 may be 100 mol%. Furthermore, the aforementioned percentage may be between 0 mol% and less than 60 mol%.

[0079] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0080] [ka]

[0081] In general formula (2'), R 8 ~R 10 Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer from 1 to 10.

[0082] In general formula (2'), q is an integer between 1 and 10, preferably between 2 and 5, and more preferably 2 or 3.

[0083] The content of the structural unit represented by general formula (1) in a 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 the total structural units. The upper limit of the aforementioned content is not particularly limited and may be 100 mol%.

[0084] Component (A) may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. Furthermore, component (A) may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0085] 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, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-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, 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-Hexaf Examples include ruolo-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'-sulfonyldiphthalic acid dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. Tetracarboxylic acid dianhydrides may be used individually or in combination of two or more types.

[0086] Specific examples of diamine compounds include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, and 4,4'-diamino Diphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2,6-diethylaniline) Sopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 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}sulfone, 2,2-bis(4-aminophenyl)propane, 9,9-bis(4-aminophenyl) Luoren, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 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,Examples include 4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. Preferred diamine compounds include m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. Diamine compounds may be used individually or in combination of two or more.

[0087] It has a structural unit represented by general formula (1), and R in general formula (1) 6 and R 7 A compound in which at least one of the groups is a monovalent organic group can be obtained, for example, by the following method (a) or (b). (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) is reacted with a compound represented by R-OH in an organic solvent to form a diester derivative, and then the diester derivative is subjected to a condensation reaction with a diamine compound represented by H2N-Y-NH2. (b) A tetracarboxylic dianhydride is reacted with a diamine compound represented by H2N-Y-NH2 in an organic solvent to obtain a polyamic acid solution, and a compound represented by R-OH is added to the polyamic acid solution and reacted in an organic solvent to introduce an ester group. Here, Y in the diamine compound represented by H2N-Y-NH2 is the same as Y in general formula (1), and the specific examples and preferred examples are also the same. Furthermore, R in the compound represented by R-OH represents a monovalent organic group, and the specific examples and preferred examples are the same as R in general formula (1). 6 and R 7 This is the same as in the previous case. The tetracarboxylic dianhydride represented by general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH may each be used individually or in combination of two or more. Examples of the aforementioned organic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropionamide, with 3-methoxy-N,N-dimethylpropionamide being preferred. A polyimide precursor may be synthesized by reacting a dehydrating condensation agent with a compound represented by R-OH in a polyamic acid solution. The dehydrating condensation agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0088] The aforementioned compound contained in component (A) can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, then reacting it with a chlorinating agent such as thionyl chloride to convert it to an acid chloride, and then reacting the acid chloride with a diamine compound represented by H2N-Y-NH2. The aforementioned compound contained in component (A) can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then reacting the diester derivative with a diamine compound represented by H2N-Y-NH2 in the presence of a carbodiimide compound. The aforementioned compound contained in component (A) 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 form a polyamic acid, then isoimidizing the polyamic acid in the presence of a dehydrating condensation agent such as trifluoroacetic anhydride, and then reacting it with the compound represented by R-OH. Alternatively, a portion of the tetracarboxylic dianhydride may be reacted with the compound represented by R-OH beforehand, and the partially esterified tetracarboxylic dianhydride may be reacted with the diamine compound represented by H2N-Y-NH2.

[0089] [ka]

[0090] In general formula (8), X is the same as X in general formula (1), and the specific examples and preferred examples are also the same.

[0091] (A) The compound represented by R-OH used in the synthesis of the aforementioned compound contained in component (A) is the R group represented by general formula (2). x The compound may be one in which a hydroxyl group is bonded to the group, or one 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-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0092] (A) There are no particular restrictions on the molecular weight of component (A), but for example, it is preferably 10,000 to 200,000 in weight-average molecular weight, and more preferably 10,000 to 100,000. The weight-average molecular weight can be measured, for example, by gel permeation chromatography and then converted using a standard polystyrene calibration curve.

[0093] The resin composition of this disclosure may further contain a dicarboxylic acid, and the (A) polyimide precursor contained in the resin composition may have a structure in which some of the amino groups in the (A) polyimide precursor react with the carboxyl groups of the dicarboxylic acid. For example, when synthesizing the polyimide precursor, some of the amino groups of the diamine compound may be reacted with the carboxyl groups of the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula. In this case, when synthesizing the (A) polyimide precursor, a methacrylic group derived from the dicarboxylic acid can 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.

[0094] [ka]

[0095] The resin composition of this disclosure may contain a polyimide resin as component (A), and may also contain the aforementioned polyimide precursor and polyimide resin.

[0096] The polyimide resin is not particularly limited as long as it is a polymer compound having multiple structural units containing imide bonds. For example, it is preferable to include a compound having a structural unit represented by the following general formula (X). This tends to result in a semiconductor device with an insulating film that exhibits high reliability.

[0097] [ka]

[0098] In general formula (X), X represents a tetravalent organic group and Y represents a divalent organic group. 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) described above.

[0099] (A) By combining a polyimide precursor and a polyimide resin as component (A), it is possible to suppress the generation of volatile substances due to dehydration cyclization during imide ring formation, and thus tend to suppress the generation of voids. The polyimide resin referred to here is a resin in which all or part of the resin skeleton has an imide skeleton. It is preferable that the polyimide resin is soluble in the solvent in the resin composition using the polyimide precursor.

[0100] (A) When component is a polyimide precursor and a polyimide resin, the proportion of the polyimide resin to the total of the polyimide precursor and polyimide resin may be 15% to 50% by mass, or 10% to 20% by mass.

[0101] The resin composition of the present disclosure may contain resin components other than the component (A). For example, from the perspective of heat resistance, the resin composition of the present disclosure may contain other resins such as novolak resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polyvinyl chloride resins, etc. The other resins may be used alone or in combination of two or more.

[0102] In the resin composition of the present disclosure, the content of the component (A) relative to the total amount of the resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

[0103] ((B) solvent) The resin composition of the present disclosure contains a (B) solvent (hereinafter also referred to as the “(B) component”). From the perspective of reducing the reproductive toxicity and environmental load of the resin composition, the (B) component preferably contains at least one selected from the group consisting of compounds represented by the following formulas (3) to (7).

[0104] [Chemical formula]

[0105] In formulas (3) to (7), R 1 , R 2 , R 8 and R 10 are each independently an alkyl group having 1 to 4 carbon atoms, and R 3 to R 7 and R 9 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.

[0106] In formula (3), s is preferably 0. In formula (4), R 2The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, more preferably 1. In formula (5), R 3 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a propyl group or a butyl group. R 4 and R 5 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. In formula (6), R 6 ~R 8 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. r is preferably 0 or 1, more preferably 0. In formula (7), R 9 and R 10 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. u is preferably 0 or 1, more preferably 0.

[0107] (Component B) may be, for example, 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).

[0108] Specific examples of (Component B) include the following compounds.

[0109] [[ID=三十一]] [[ID=三十二]] [[ID=三十三]]

Chemical formula

[0110] [[ID=三十九]] [[ID=四十]](Component B) contained in the resin composition of the present disclosure is not limited to the aforementioned compounds, and may be other solvents. (Component B) may be a solvent of esters, a solvent of ethers, a solvent of ketones, a solvent of hydrocarbons, a solvent of aromatic hydrocarbons, a solvent of sulfoxides, etc. [[ID=四十一]] [[ID=四十二]]

[0111] [[ID=四十三]] 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 alkoxyacetates such as methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate and ethyl ethoxyacetate), alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate). Examples include alkyl 2-alkoxypropionates such as ethyl toxypropionate, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, and propyl 2-alkoxypropionate (for example, 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-alkoxy-2-methylpropionate such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate.

[0112] Examples of ether solvents 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, and propylene glycol monopropyl ether acetate. Examples of solvents for ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP). Examples of hydrocarbon solvents include limonene. Examples of solvents for aromatic hydrocarbons include toluene, xylene, and anisole. Examples of solvents for sulfoxides include dimethyl sulfoxide.

[0113] (B) Preferred solvents for component (B) include γ-butyrolactone, cyclopentanone, and ethyl lactate.

[0114] In the resin composition of this disclosure, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of NMP may be 1% by mass or less with respect to the total amount of the resin composition, or 3% by mass or less with respect to the total amount of component (A).

[0115] In the resin composition of this disclosure, the content of component (B) is preferably 1 to 10,000 parts by mass, and more preferably 50 to 10,000 parts by mass, per 100 parts by mass of component (A).

[0116] Component (B) preferably contains at least one of the following: solvent (1), which is selected from the group consisting of compounds represented by formulas (3) to (6); and solvent (2), which is selected from the group consisting of ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, and sulfoxide solvents. Furthermore, the content of solvent (1) may be 5% to 100% by mass, or 5% to 50% by mass, relative to the total of solvent (1) and solvent (2). The content of solvent (1) may be 10 to 1000 parts by mass, 10 to 100 parts by mass, or 10 to 50 parts by mass per 100 parts by mass of component (A).

[0117] The resin composition of this disclosure preferably further comprises (C) a photopolymerization initiator and (D) a polymerizable monomer (hereinafter also referred to as component (C) and component (D), respectively). The resin composition of this disclosure may also further comprise (E) a thermal polymerization initiator (hereinafter also referred to as component (E)). Preferred forms of components (C) to (E) will be described below.

[0118] ((C) Photopolymerization initiator) The resin composition of this disclosure preferably contains (C) a photopolymerization initiator. This reduces the number of steps required to manufacture electrodes in the semiconductor device manufacturing process, thereby reducing the overall cost of the semiconductor device manufacturing process.

[0119] (C)Specific examples of components include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, o-methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzos. Phenone derivatives; acetophenone derivatives such as acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone; benzyl, benzyldimethylketal, benzyl Benzyl derivatives such as benzoin-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, and propyl benzoin; 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime Oxime derivatives such as nyl)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, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime); N-arylglycines such as N-phenylglycine; Peroxides such as benzoyl perchloride;Examples include aromatic biimidazoles such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and Irgacure OXE03 (manufactured by BASF) and Irgacure OXE04 (manufactured by BASF). (C) Component may be used alone or in combination of two or more types. Among these, oxime compound derivatives are preferred because they do not contain metal elements, are highly reactive, and offer high sensitivity.

[0120] If the resin composition of this disclosure contains component (C), 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, per 100 parts by mass of component (A), from the viewpoint of ensuring that photocrosslinking is uniform in the film thickness direction.

[0121] The resin composition disclosed herein may include an anti-reflective agent that suppresses reflected light from the substrate direction, from the viewpoint of improving photosensitive properties.

[0122] ((D) Polymerizable monomer) The resin composition of this disclosure preferably contains a polymerizable monomer (D). Component (D) preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of being suitably polymerizable in combination with a photopolymerization initiator. From the viewpoint of improving crosslinking density and photosensitivity, it is preferable to have 2 to 6 groups containing polymerizable unsaturated double bonds, and more preferably 2 to 4 groups. Polymerizable monomers may be used individually or in combination of two or more.

[0123] Polymerizable monomers having a (meth)acrylic group are not particularly limited, and include, for example, 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, pen Examples include tetraerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanurate triacrylate, ethoxylated isocyanurate trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, 2-hydroxyethyl (meth)acrylate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO)-modified bisphenol A diacrylate, and ethylene oxide (EO)-modified bisphenol A dimethacrylate.

[0124] Polymerizable monomers other than those having a (meth)acrylic group are not particularly limited, and include, for example, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide.

[0125] Component (D) is not limited to compounds having a polymerizable unsaturated double bond group, but may also be a compound having a polymerizable group other than an unsaturated double bond group (e.g., an oxirane ring).

[0126] If the resin composition of the present disclosure contains component (D), the content of component (D) is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 1 to 75 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of component (A).

[0127] ((E) Thermal polymerization initiator) From the viewpoint of improving the physical properties of the cured product, the resin composition of this disclosure preferably contains (E) a thermal polymerization initiator.

[0128] (E)Specific examples of component include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide, and dialdehydes such as dicumyl peroxide and di-t-butyl peroxide. Examples include diacyl peroxides such as quill peroxide, dilauroyl peroxide, and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; and bis(1-phenyl-1-methylethyl)peroxide. The thermal polymerization initiator may be used alone or in combination of two or more.

[0129] If the resin composition of the present disclosure 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 per 100 parts by mass of the polyimide precursor.

[0130] ((F) Polymerization inhibitor) The resin composition of this disclosure may contain (F) a polymerization inhibitor (hereinafter also referred to as "component (F)") from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization suppressants.

[0131] Specific examples of component (F) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenantraquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, nitrosamines, hindered phenol compounds, etc. Polymerization inhibitors may be used alone or in combination of two or more. Combining two or more polymerization inhibitors tends to make it easier to adjust the photosensitive properties due to differences in reactivity. Hindered phenol compounds may have both the function of a polymerization inhibitor and the function of an antioxidant described later, or they may have only one of the functions.

[0132] The hindered phenol compounds are not particularly limited, and include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t- [Butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-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-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-s-butyl-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-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-Tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-Tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1, 3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl- Examples include 3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and N,N'-hexane-1,6-diyrbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]. Among these, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] is preferred.

[0133] If the resin composition of this disclosure contains component (F), 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, per 100 parts by mass of component (A), from the viewpoint of storage stability of the resin composition and heat resistance of the resulting cured product.

[0134] The resin compositions of this disclosure may further contain antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors, or nitrogen-containing compounds.

[0135] (Antioxidant) The resin composition of this disclosure may contain an antioxidant, from the viewpoint of suppressing a decrease in adhesion by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow processing, etc. The inclusion of an antioxidant in the resin composition of this disclosure can suppress oxidation of electrodes during insulation reliability testing.

[0136] Specific examples of antioxidants include the compounds exemplified above as hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Antioxidants may be used individually or in combination of two or more types.

[0137] If the resin composition of this disclosure contains an antioxidant, the amount 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, per 100 parts by mass of component (A).

[0138] (Coupling agent) The resin composition of this disclosure may contain a coupling agent. The coupling agent reacts with component (A) to crosslink during heat treatment, or the coupling agent itself polymerizes. This tends to improve the adhesion between the resulting cured product and the substrate.

[0139] 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-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamidoic acid, and benzophenone-3,3'-bis(N-[3-triethoxy Examples include silane coupling agents such as sisilyl)propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane; and aluminum-based adhesive aids such as aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate. The coupling agent may be used alone or in combination of two or more types.

[0140] If the resin composition of this disclosure 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, per 100 parts by mass of component (A).

[0141] (Surfactants and leveling agents) The resin composition of this disclosure may contain 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, it is possible to improve the applicability (e.g., suppression of striations (unevenness in film thickness)), adhesion, and compatibility of compounds in the resin composition.

[0142] Examples of surfactants or leveling agents include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.

[0143] Surfactants and leveling agents may be used individually or in combination of two or more types.

[0144] If the resin composition of the present disclosure contains at least one of a surfactant and a leveling agent, the total content of the surfactant and the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, per 100 parts by mass of component (A).

[0145] (Rust inhibitor) The resin composition of this disclosure may contain a rust inhibitor from the viewpoint of suppressing the corrosion of metals such as copper and copper alloys, and from the viewpoint of suppressing discoloration of said metals. Examples of rust inhibitors include azole compounds and purine derivatives.

[0146] 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-t-butyl-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, and 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benz Examples include zotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazol, 5-methyl-1H-tetrazol, 5-phenyl-1H-tetrazol, 5-amino-1H-tetrazol, and 1-methyl-1H-tetrazol.

[0147] 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, and 8-amino Examples include adenine, 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, 8-azahypoxanthine, and their derivatives.

[0148] Rust inhibitors may be used individually or in combination of two or more types.

[0149] If the resin composition of this disclosure contains a rust inhibitor, the amount of 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, per 100 parts by mass of component (A). In particular, when the amount of rust inhibitor is 0.1 parts by mass or more, discoloration of the surface of copper or copper alloy is suppressed when the resin composition of this disclosure is applied to the surface of copper or copper alloy.

[0150] The resin composition of this disclosure may contain a nitrogen-containing compound in order to promote the imidization reaction of component (A) and obtain a highly reliable cured product.

[0151] Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, etc. Among these, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. Nitrogen-containing compounds may be used individually or in combination of two or more.

[0152] The nitrogen-containing compound preferably includes a compound represented by the following formula (17).

[0153] [ka]

[0154] In formula (17), R 31A ~R 33A Each of these is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, R 31A ~R 33A At least one (preferably one) of these is a monovalent aromatic group. 31A ~R 33A The groups may form a ring structure with adjacent groups. Examples of the formed ring structure include five-membered rings, six-membered rings, etc., which may have substituents such as methyl groups and phenyl groups. The hydrogen atoms of the monovalent aliphatic hydrocarbon group may be substituted with functional groups other than hydroxyl groups.

[0155] In formula (17), R 31A ~R 33AIt is preferable that at least one (preferably one) of these is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group.

[0156] In formula (17), R 31A ~R 33A The monovalent aliphatic hydrocarbon group has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. The monovalent aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, etc.

[0157] In formula (17), R 31A ~R 33A A monovalent aliphatic hydrocarbon group having a hydroxyl group is R 31A ~R 33A Preferably, the group is a monovalent aliphatic hydrocarbon group to which one or more hydroxyl groups are bonded, and more preferably, a group to which one to three hydroxyl groups are bonded. Specific examples of monovalent aliphatic hydrocarbon groups having hydroxyl groups include methylol group and hydroxyethyl group, with the hydroxyethyl group being preferred.

[0158] R in equation (17) 31A ~R 33A Examples of monovalent aromatic groups include monovalent aromatic hydrocarbon groups and monovalent aromatic heterocyclic groups, with monovalent aromatic hydrocarbon groups being preferred. For monovalent aromatic hydrocarbon groups, those with 6 to 12 carbon atoms are preferred, and those with 6 to 10 carbon atoms are more preferred. Examples of monovalent aromatic hydrocarbon groups include phenyl groups and naphthyl groups.

[0159] R in equation (17) 31A ~R 33A The monovalent aromatic group may have substituents. The substituent may be R of formula (17). 31A ~R 33A The monovalent aliphatic hydrocarbon group and the R of formula (17) described above. 31A ~R 33A Examples include monovalent aliphatic hydrocarbon groups having a hydroxyl group.

[0160] If the resin composition of this disclosure contains a nitrogen-containing compound, the content of the nitrogen-containing compound is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A).

[0161] The resin composition of this disclosure comprises component (A) and component (B), and optionally comprises components (C) to (F), antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors, nitrogen-containing compounds, etc., and may also contain other components and unavoidable impurities to the extent that they do not impair the effects of this disclosure. For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the resin composition of this disclosure (A) component and (B) component, (A) component ~ (C) component, (A) component ~ (E) component, (A) component ~ (F) component, (A) Components to (F) and at least one selected from the group consisting of antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors, and nitrogen-containing compounds, It may consist of [something].

[0162] <Semiconductor device> The semiconductor device of this disclosure comprises a first substrate body, a first semiconductor substrate having a first organic insulating film and a first electrode provided on one surface of the first substrate body, a semiconductor chip substrate body, and a semiconductor chip having an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded, the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are bonded, and 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 of this disclosure. In the semiconductor device of this disclosure, at least one of the first organic insulating film and the organic insulating film portion is an insulating film obtained by curing the resin composition of this disclosure. Therefore, the generation of voids at the bonding interface of the insulating film is suppressed, and the insulating film has excellent heat resistance. Furthermore, the semiconductor device of this disclosure is manufactured through steps (1) to (5).

[0163] <Manufacturing method for semiconductor devices> The method for manufacturing a semiconductor device according to the present disclosure involves manufacturing a semiconductor device using the resin composition of the present disclosure. Specifically, a semiconductor device can be manufactured by going through steps (1) to (5) using the resin composition of the present disclosure.

[0164] <Cured product> The cured product of this disclosure is obtained by curing the resin composition of this disclosure. The cured product is used, for example, as an insulating film in semiconductor devices.

[0165] Hereinafter, an embodiment of the semiconductor device of the present disclosure and an embodiment of the method for manufacturing the semiconductor device of the present disclosure will be described in detail with reference to the drawings. In the following description, the same or corresponding parts will be denoted by the same reference numerals, and redundant descriptions will be omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings. In addition, the dimensional ratios in the drawings are not limited to those shown.

[0166] (An example of a semiconductor device) Figure 1 is a schematic cross-sectional view showing an example of a semiconductor device of the present disclosure. As shown in Figure 1, the semiconductor device 1 is, for example, an example of a semiconductor package, and comprises a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar portion 30, a redistribution layer 40, a substrate 50, and a circuit board 60.

[0167] The first semiconductor chip 10 is a semiconductor chip such as an LSI (Large-Scale Integrated Circuit) chip or a CMOS (Complementary Metal Oxide Semiconductor) sensor, and has a three-dimensional mounting structure with the second semiconductor chip 20 mounted downwards. The second semiconductor chip 20 is a semiconductor chip such as an LSI or memory, and is a chip component with a smaller area in a planar view than the first semiconductor chip 10. The second semiconductor chip 20 is chip-to-chip (C2C) bonded to the back surface of the first semiconductor chip 10. The first semiconductor chip 10 and the second semiconductor chip 20 are finely bonded to each other by hybrid bonding, which will be described in detail later, with their respective terminal electrodes and the insulating films around them being firmly and precisely bonded without misalignment.

[0168] The pillar portion 30 is a connection portion in which a plurality of pillars 31 made of a metal such as copper (Cu) are sealed with resin 32. The plurality of pillars 31 are conductive members that extend from the upper surface to the lower surface of the pillar portion 30. The plurality of pillars 31 may have a cylindrical shape with a diameter of 3 μm or more and 20 μm or less (5 μm in one example), and may be arranged so that the distance between the centers of each pillar 31 is 15 μm or less. The plurality of pillars 31 make a flip-chip connection between the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the redistribution layer 40. By using the pillar portion 30, the semiconductor device 1 can form connection electrodes without using a technique called TMV (Through mold via), which involves drilling holes in a mold and soldering the connections. The pillar portion 30 has a thickness of approximately the same as the second semiconductor chip 20, and is arranged horizontally to the side of the second semiconductor chip 20. Alternatively, multiple solder balls may be arranged instead of the pillar portion 30, and the lower terminal electrodes of the first semiconductor chip 10 and the upper terminal electrodes of the redistribution layer 40 may be electrically connected by the solder balls.

[0169] The rewiring layer 40 is a wiring layer having the function of terminal pitch conversion which is a function of the package substrate, and is a layer in which a rewiring pattern is formed of polyimide, copper wiring, etc. on the insulating film below the second semiconductor chip 20 and on the lower surface of the pillar portion 30. The rewiring layer 40 is formed in a state where the first semiconductor chip 10, the second semiconductor chip 20, etc. are turned upside down (see (d) of FIG. 4).

[0170] The rewiring layer 40 electrically connects the terminal electrodes of the first semiconductor chip 10 via the terminal electrodes on the lower surface of the second semiconductor chip 20 and the pillar portion 30 to the terminal electrodes of the substrate 50. The terminal pitch of the substrate 50 is wider than the terminal pitch of the pillar 31 and the terminal pitch of the second semiconductor chip 20. Note that various electronic components 51 may be mounted on the substrate 50. Also, when there is a large gap in the terminal pitch between the rewiring layer 40 and the substrate 50, an inorganic interposer or the like may be used between the rewiring layer 40 and the substrate 50 to make an electrical connection between the rewiring layer 40 and the substrate 50.

[0171] The circuit board 60 is a board having a plurality of through electrodes inside which mounts the first semiconductor chip 10 and the second semiconductor chip 20 thereon and is electrically connected to the substrate 50 connected to the first semiconductor chip 10, the second semiconductor chip 20, the electronic component 51, etc. 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 provided on the back surface of the circuit board 60 by the plurality of through electrodes.

[0172] (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 to 4. FIG. 2 is a diagram showing in order the method for manufacturing the semiconductor device shown in FIG. 1. FIG. 3 is a diagram showing in more detail the bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in FIG. 2. FIG. 4 is a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing in order the steps after the steps shown in FIG. 2.

[0173] The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n). (a) Step of preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10. (b) Step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20. (c) Step of polishing the first semiconductor substrate 100. (d) Step of polishing the second semiconductor substrate 200. (e) Step of singulating the second semiconductor substrate 200 to obtain a plurality of semiconductor chips 205. (f) Step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with the terminal electrodes 103 of the first semiconductor substrate 100. (g) Step of bonding the insulating film 102 of the first semiconductor substrate 100 and the insulating film portions 202b of the plurality of semiconductor chips 205 to each other (see (b) in FIG. 3). (h) Step of joining the terminal electrodes 103 of the first semiconductor substrate 100 and the terminal electrodes 203 of each of the plurality of semiconductor chips 205 (see (c) in FIG. 3). (i) Step of forming a plurality of pillars 300 (corresponding to pillar 31) between the plurality of semiconductor chips 205 on the connection surface of the first semiconductor substrate 100. (j) Step of molding a resin 301 on the connection surface of the first semiconductor substrate 100 to cover the semiconductor chips 205 and the pillars 300 to obtain a semi-finished product M1. (k) Step of grinding and thinning the resin 301 side of the semi-finished product M1 molded in step (j) to obtain a semi-finished product M2. (l) Step of forming a wiring layer 400 corresponding to the redistribution layer 40 on the semi-finished product M2 thinned in step (k). (m) Step of cutting the semi-finished product M3 on which the wiring layer 400 is formed in step (l) along the cutting line A so as to form each semiconductor device 1. (n) Step of inverting the semiconductor device 1a individualized in step (m) and installing it on the substrate 50 and the circuit board 60 (see FIG. 1).

[0174] For example, in the resin composition of this disclosure, step (1) corresponds to steps (a) and (c) above, step (2) corresponds to steps (b) and (d) above, step (3) corresponds to step (e), step (4) corresponds to step (g), and step (5) corresponds to step (h). Furthermore, the resin composition of this disclosure may be a resin composition for use in producing at least one of the first organic insulating film and the second organic insulating film in a semiconductor device manufacturing method comprising at least one step corresponding to step (f) and steps (i) to (n).

[0175] [Process (a) and Process (b)] Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate on which integrated circuits consisting of semiconductor elements and wiring connecting them are formed, corresponding to a plurality of first semiconductor chips 10. In step (a), as shown in Figure 2(a), a plurality of terminal electrodes 103 (first electrodes) made of copper, aluminum, etc. are provided at predetermined intervals on one surface 101a of the first substrate body 101 made of silicon, etc., and an insulating film 102 (first insulating film), which is a cured product made by curing the resin composition of this disclosure, is provided. The insulating film 102 may be provided on one surface 101a of the first substrate body 101 and then the plurality of terminal electrodes 103 may be provided, or the plurality of terminal electrodes 103 may be provided on one surface 101a of the first substrate body 101 and then the insulating film 102 may be provided. A predetermined interval is provided between the plurality of terminal electrodes 103 in order to form pillars 300 in a step described later, and another terminal electrode (not shown) connected to the pillars 300 is formed between them.

[0176] Step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate on which an integrated circuit comprising semiconductor elements and wiring connecting them is formed, corresponding to a plurality of second semiconductor chips 20. In step (b), as shown in Figure 2(a), a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc. are continuously provided on one surface 201a of the second substrate body 201 made of silicon, etc., and an insulating film 202 (a second insulating film) which is a cured product made by curing the resin composition of this disclosure is provided. The insulating film 202 may be provided on one surface 201a of the second substrate body 201 and then the plurality of terminal electrodes 203 may be provided, or the plurality of terminal electrodes 203 may be provided on one surface 201a of the second substrate body 201 and then the insulating film 202 may be provided.

[0177] The insulating films 102 and 202 used in steps (a) and (b) are not limited to a configuration in which both are cured products obtained by curing the resin composition of the present disclosure, but at least one of the insulating films 102 and 202 may be a cured product obtained by curing the resin composition of the present disclosure. Examples of insulating films other than the cured products include cured products obtained by curing a resin composition that does not contain a polyimide precursor and contains organic materials such as polyimide, polyamideimide, benzocyclobutene (BCB), polybenzoxazole (PBO), and PBO precursor. The tensile modulus of the insulating films 102 and 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.

[0178] The thermal expansion coefficients of the insulating films 102 and 202 are preferably 150 ppm / K or less, more preferably 100 ppm / K or less, and even more preferably 90 ppm / K or less.

[0179] The thickness of insulating films 102 and 202 is preferably 0.1 μm to 50 μm, and more preferably 1 μm to 15 μm. This ensures uniformity of the insulating film thickness while shortening the processing time in subsequent polishing steps.

[0180] From the viewpoint of making the work in steps (c) and (d) easier to perform and simplifying these steps, it is preferable that at least one of the following conditions be met (preferably both conditions be met): 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. For example, if the terminal electrode 103 or 203 is made of copper and the polishing rate of the copper is 50 nm / min, the polishing rate of the insulating film 102 or 202 is preferably 200 nm / min or less (four times or less the polishing rate of copper), more preferably 100 nm / min or less (twice the polishing rate of copper) and even more preferably 50 nm / min or less (equivalent to or less the polishing rate of copper).

[0181] Next, a method for producing an insulating film will be described. The insulating film is obtained by curing a resin composition. Examples of the above-mentioned methods for producing an insulating film include (α) a method comprising the steps of applying and drying a resin composition onto a substrate to form a resin film, and heat-treating the resin film, and (β) a method comprising the steps of forming a film of a certain thickness using a resin composition on a film that has been subjected to a release treatment, transferring the resin film to a substrate by lamination, and heat-treating the resin film formed on the substrate after the transfer. From the viewpoint of flatness, method (α) is preferred.

[0182] Examples of methods for applying the resin composition include spin coating, inkjet coating, and slit coating.

[0183] In the spin coating method, for example, the resin composition may be spin-coated under conditions such as a rotation speed of 300 rpm (revolutions per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, an acceleration of 500 rpm / second to 15,000 rpm / second, and a rotation time of 30 seconds to 300 seconds.

[0184] The resin composition may be applied to a support, film, etc., and a drying step may be included. Drying may be performed using a hot 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 be performed two or more times. This makes it possible to obtain a resin film in which the above-mentioned resin composition is formed into a film.

[0185] In the slit coating method, for example, the resin composition may be slit coated under the following conditions: chemical dispensing speed of 10 μL / sec to 400 μL / sec, chemical dispensing section height of 0.1 μm to 1.0 μm, stage speed (or chemical dispensing section speed) of 1.0 mm / sec to 50.0 mm / sec, stage acceleration of 10 mm / sec to 1000 mm / sec, ultimate vacuum level of 10 Pa to 100 Pa during reduced-pressure drying, reduced-pressure drying time of 30 seconds to 600 seconds, drying temperature of 60°C to 150°C, and drying time of 30 to 300 seconds.

[0186] The formed resin film may be heat-treated. The heating temperature is preferably 150°C to 450°C, and more preferably 150°C to 350°C. By heating the temperature within the above range, damage to the substrate, device, etc., is suppressed, energy saving in the process is achieved, and an insulating film can be suitably produced.

[0187] The heating time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the heating time within the above range, the crosslinking reaction or the dehydration ring-closing reaction can be carried out sufficiently. The heat treatment can be performed in the atmosphere of air or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the resin film.

[0188] Examples of equipment used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0189] When using the resin composition of the present disclosure, which is a negative photosensitive resin composition or a positive photosensitive resin composition, when providing the insulating film 202 on one surface 201a of the second substrate body 201 and then providing a plurality of terminal electrodes 203, for example, a method including a step of applying the resin composition on the substrate, a step of drying to form a resin film, a step of pattern-exposing the resin film and developing it using a developer to obtain a patterned resin film, and a step of heat-treating the patterned resin film may be used. Thereby, a cured pattern insulating film can be obtained.

[0190] Alternatively, when providing the insulating film 202 on one surface 201a of the second substrate body 201 and then providing a plurality of terminal electrodes 203, for example, a method including a step of applying a resin composition other than the resin composition of the present disclosure on the substrate, a step of drying to form a resin film, a step of applying and drying the resin composition of the present disclosure, which is a negative photosensitive resin composition or a positive photosensitive resin composition, on the resin film, pattern-exposing it, and developing it using a developer to obtain a patterned resin film, and a step of heat-treating the patterned resin film may be used. Thereby, a cured pattern insulating film can be obtained.

[0191] Pattern exposure is performed, for example, by exposing through a photomask to a predetermined pattern. The active light rays to be irradiated include i-line, ultraviolet rays such as broadband, visible light rays, radiation, etc., and it is preferably the i-line. As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, etc. can be used.

[0192] By developing after exposure, a patterned resin film, which is a resin film with a pattern formed, can be obtained. When the resin composition of the present disclosure is a negative photosensitive resin composition, the unexposed portion is removed with a developer. The organic solvent used as the negative developer can be used alone as a good solvent for the photosensitive resin film, or can be appropriately mixed with a good solvent and a poor solvent as the developer. 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-dimethylpropanamide, cyclopentanone, cyclohexanone, and cycloheptanone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0193] If the resin composition of this disclosure is a positive-type photosensitive resin composition, the exposed area is removed with a developer. Examples of solutions used as developer for positive film include tetramethylammonium hydroxide (TMAH) solution and sodium carbonate solution.

[0194] At least one of the negative-type developer and the positive-type developer may contain a surfactant. The surfactant content is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.

[0195] The development time can be, for example, twice the time it takes for a photosensitive resin film to completely dissolve when immersed in the developer. The development time may be adjusted according to component (A) contained in the resin composition of the present disclosure, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.

[0196] The pattern resin film may be washed with a rinsing solution after development. As the rinsing solution, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used individually or in appropriate mixtures, or these may be used in a stepwise combination.

[0197] In addition, as the organic material constituting the insulating films 102 and 202 other than the cured product obtained by curing the resin composition of this disclosure, a photosensitive resin, a thermosetting non-conductive film (NCF), or a thermosetting resin may be used. This organic material may also be an underfill material. Furthermore, the organic material constituting the insulating films 102 and 202 may be a heat-resistant resin.

[0198] [Step (c) and step (d)] Step (c) is a step of polishing the first semiconductor substrate 100. In step (c), as shown in Figure 3(a), one side 101a of the surface of the first semiconductor substrate 100 is polished using the CMP method so that each surface 103a of the terminal electrode 103 is at the same position as or slightly higher (protruding) than the surface 102a of the insulating film 102. In step (c), the first semiconductor substrate 100 can also be polished using the CMP method under conditions that selectively and deeply grind the terminal electrode 103, which is made of copper or the like. In step (c), the surface 103a of the terminal electrode 103 may be polished using the CMP method so that it coincides with the surface 102a of the insulating film 102. The polishing method is not limited to the CMP method, and back grinding or the like may be employed. If each surface 103a of the terminal electrode 103 is slightly higher than the surface 102a of the insulating film 102, the height difference between each surface 103a and surface 102a may be 1 nm to 150 nm, or 1 nm to 15 nm.

[0199] Step (d) is a step of polishing the second semiconductor substrate 200. In step (d), as shown in Figure 3(a), one side 201a of the second semiconductor substrate 200 is polished using the CMP method so that each surface 203a of the terminal electrode 203 is at the same position as or slightly higher (protruding) than the surface 202a of the insulating film 202. In step (d), the second semiconductor substrate 200 is polished by the CMP method under conditions that selectively and deeply grind the terminal electrode 203, which is made of, for example, copper. In step (d), the terminal electrode 203 may be polished by the CMP method so that each surface 203a of the terminal electrode 203 coincides with the surface 202a of the insulating film 202. The polishing method is not limited to the CMP method, and back grinding or the like may be employed. If each surface 203a of the terminal electrode 203 is slightly higher than the surface 202a of the insulating film 202, the height difference between each surface 203a and surface 202a may be 1 nm to 50 nm, or 1 nm to 15 nm.

[0200] In steps (c) and (d), the insulating film 102 and the insulating film 202 may be polished to the same thickness, or for example, the insulating film 202 may be polished to a thickness greater than that of the insulating film 102. Alternatively, the insulating film 202 may be polished to a thickness less than that of the insulating film 102. When the insulating film 202 is thicker than that of the insulating film 102, much of the foreign matter adhering to the bonding interface when the second semiconductor substrate 200 is pieced or when chip mounting can be contained by the insulating film 202, further reducing bonding defects. On the other hand, when the insulating film 202 is thinner than that of the insulating film 102, the height of the mounted semiconductor chip 205, i.e., the semiconductor device 1, can be reduced.

[0201] [Step (e)] Step (e) is a step in which the second semiconductor substrate 200 is divided into individual pieces to obtain a plurality of semiconductor chips 205. In step (e), as shown in Figure 2(b), the second semiconductor substrate 200 is divided into a plurality of semiconductor chips 205 by a cutting means such as dicing. When dicing the second semiconductor substrate 200, a protective material may be applied to the insulating film 202 before dividing it into individual pieces. In step (e), the insulating film 202 of the second semiconductor substrate 200 is divided into insulating film portions 202b corresponding to each semiconductor chip 205. Examples of dicing methods for dividing the second semiconductor substrate 200 include plasma dicing, stealth dicing, and laser dicing. As a surface protective material for the second semiconductor substrate 200 during dicing, for example, a thin film such as an organic film that can be removed with water, TMAH, etc., or a carbon film that can be removed with plasma, etc. may be provided.

[0202] [Process (f)] Step (f) is a step in which the terminal electrodes 203 of each of the multiple semiconductor chips 205 are aligned with respect to the terminal electrodes 103 of the first semiconductor substrate 100. In step (f), as shown in Figure 2(c), each semiconductor chip 205 is aligned so that the terminal electrodes 203 of each semiconductor chip 205 face the corresponding multiple terminal electrodes 103 of the first semiconductor substrate 100. Alignment marks or the like may be provided on the first semiconductor substrate 100 for this alignment.

[0203] [Process (g)] Step (g) is a step in which the insulating film 102 of the first semiconductor substrate 100 and each insulating film portion 202b of the multiple semiconductor chips 205 are bonded to each other. In step (g), after removing organic matter, metal oxides, etc. adhering to the surface of each semiconductor chip 205, the semiconductor chips 205 are aligned with the first semiconductor substrate 100 as shown in Figure 2(c), and then the insulating film portions 202b of each of the multiple semiconductor chips 205 are bonded to the insulating film 102 of the first semiconductor substrate 100 as a hybrid bonding (see Figure 3(b)). At this time, the insulating film portions of the multiple semiconductor chips 205 and the insulating film 102 of the first semiconductor substrate 100 may be uniformly heated before bonding. By bonding while heating, the insulating film 102 and insulating film portions 202b expand more than the terminal electrodes 103 and 203 due to the difference in thermal expansion coefficients between the insulating film 102 and insulating film portions 202b and the terminal electrodes 103 and 203. In step (c), the first semiconductor substrate 100 may be polished so that the height of the insulating film 102 becomes approximately equal to or greater than the height of the terminal electrode 103 due to thermal expansion caused by heating, and in step (d), the second semiconductor substrate 200 may be polished so that the height of the insulating film portion 202b becomes approximately equal to or greater than the height of the terminal electrode 203. The temperature difference between the semiconductor chip 205 and the first semiconductor substrate 100 during bonding is preferably, for example, 10°C or less. By heating and bonding at such a highly uniform temperature, an insulating bond portion S1 is formed in which the insulating film 102 and the insulating film portion 202b are bonded, and multiple semiconductor chips 205 are mechanically firmly attached to the first semiconductor substrate 100. Furthermore, because the heating and bonding is performed at a highly uniform temperature, misalignment at the bonding location is less likely to occur, and high-precision bonding can be achieved. At this attachment stage, the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of the semiconductor chip 205 are spaced apart from each other and are not connected (however, alignment is performed). The semiconductor chip 205 may be bonded to the first semiconductor substrate 100 by other bonding methods, such as room temperature bonding.

[0204] The thickness of the organic insulating film, which is the insulating junction portion where the insulating film 102 and the insulating film portion 202b are joined, is not particularly limited and may be, for example, 0.1 μm or more, or from the viewpoint of suppressing the influence of foreign matter and device design, it may be 1 μm to 20 μm, and preferably 1 μm to 5 μm.

[0205] [Process (h)] Step (h) is a step in which the terminal electrodes 103 of the first semiconductor substrate 100 are joined to the terminal electrodes 203 of each of the multiple semiconductor chips 205. In step (h), as shown in Figure 2(d), once the bonding in step (g) is completed, heat H, pressure, or both are applied to join the terminal electrodes 103 of the first semiconductor substrate 100 to each of the terminal electrodes 203 of the multiple semiconductor chips 205 as a hybrid bond (see Figure 3(c)). If the terminal electrodes 103 and 203 are made of copper, the annealing temperature in step (g) is preferably 150°C to 400°C, and more preferably 200°C to 300°C. Through this joining process, the terminal electrodes 103 and their corresponding terminal electrodes 203 are joined to form an electrode joint portion S2, and the terminal electrodes 103 and 203 are firmly joined mechanically and electrically. Note that the electrode bonding in step (h) may be performed after the bonding in step (g), or it may be performed simultaneously with the bonding in step (g).

[0206] As described above, multiple semiconductor chips 205 are electrically and mechanically positioned with high precision at predetermined locations on the first semiconductor substrate 100. At the semi-finished product stage shown in Figure 2(d), for example, a product reliability test (such as a connection test) may be performed, and only good products may be used in subsequent processes. Next, an example of a manufacturing method for a semiconductor device using such a semi-finished product will be described with reference to Figure 4.

[0207] [Process (i)] Step (i) is a step of forming a plurality of pillars 300 between a plurality of semiconductor chips 205 on the connection surface 100a of the first semiconductor substrate 100. In step (i), as shown in Figure 4(a), a plurality of pillars 300 made of, for example, copper are formed between the plurality of semiconductor chips 205. The pillars 300 can be formed from copper plating, conductive paste, copper pins, etc. One end of the pillar 300 is formed to be connected to a terminal electrode of the first semiconductor substrate 100 that is not connected to the terminal electrode 203 of the semiconductor chip 205, and the other end extends upward. The pillar 300 has, 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. Note that, for example, one to 10,000 pillars 300 may be provided between a pair of semiconductor chips 205.

[0208] [Process (j)] Step (j) is a step of molding resin 301 onto the connection surface 100a of the first semiconductor substrate 100 so as to cover the multiple semiconductor chips 205 and the multiple pillars 300. In step (j), as shown in Figure 4(b), epoxy resin or the like is molded to completely cover the multiple semiconductor chips 205 and the multiple pillars 300. Examples of molding methods include compression molding, transfer molding, and lamination of a film-like epoxy film. This resin molding fills the spaces between the multiple pillars 300 and the spaces between the pillars 300 and the semiconductor chips 205 with resin 301. This forms a semi-finished product M1 filled with resin. Note that a curing treatment may be performed after molding with epoxy resin or the like. Furthermore, when steps (i) and (j) are performed almost simultaneously, i.e., when the pillar 300 is formed at the same time as the resin molding, the pillar may be formed using a fine transfer method called imprinting and a conductive paste or electroplating.

[0209] [Process (k)] Step (k) is a process in which a semi-finished product M1, which consists of a resin 301 molded in step (j), a plurality of pillars 300, and a plurality of semiconductor chips 205, is thinned by grinding from the resin 301 side to obtain a semi-finished product M2. In step (k), as shown in Figure 4(c), the first semiconductor substrate 100 etc., which is molded in resin, is thinned by polishing the upper part of the semi-finished product M1 with a grinder or the like to obtain a semi-finished product M2. Through polishing in step (k), the thickness of the semiconductor chips 205, pillars 300, and resin 301 is thinned to, for example, several tens of micrometers, the semiconductor chips 205 take on a shape corresponding to the second semiconductor chip 20, and the pillars 300 and resin 301 take on a shape corresponding to the pillar portion 30.

[0210] [Process (l)] Step (l) is a process in which a wiring layer 400 corresponding to the rewiring layer 40 is formed on the semi-finished product M2 that was thinned in step (k). In step (l), as shown in Figure 4(d), a rewiring pattern is formed on the second semiconductor chip 20 and pillar portion 30 of the ground semi-finished product M2 using polyimide, copper wiring, etc. This forms a semi-finished product M3 having a wiring structure with widened terminal pitch of the second semiconductor chip 20 and pillar portion 30.

[0211] [Process (m) and process (n)] Step (m) is a process in which the semi-finished product M3, on which the wiring layer 400 was formed in step (l), is cut along the cutting line A so that it becomes each semiconductor device 1. In step (m), as shown in Figure 4(d), the semiconductor device substrate is cut along the cutting line A so that it becomes each semiconductor device 1 by dicing or the like. Then, in step (n), the semiconductor devices 1a that were individualized in step (m) are inverted and placed on the substrate 50 and the circuit board 60 to obtain multiple semiconductor devices 1 as shown in Figure 1.

[0212] As described above, according to 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 cured products obtained by curing the resin composition of this disclosure. Since the cured product obtained by curing the resin composition of this disclosure has a lower elastic modulus than inorganic materials such as silicon dioxide, by using this resin composition to produce the insulating film for hybrid bonding, even if foreign matter generated by dicing when the second semiconductor substrate 200 is separated into semiconductor chips 205 adheres to the insulating film, the insulating film around the foreign matter deforms easily, and the foreign matter can be contained within the insulating film without creating large voids in the insulating film. In other words, the effect of foreign matter can be suppressed by the insulating film. Therefore, according to the manufacturing method of this embodiment, bonding defects can be reduced while performing fine bonding between the first semiconductor substrate 100 and the semiconductor chip 205. Furthermore, if the resin composition of this disclosure 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 above manufacturing method can be suppressed more reliably.

[0213] Although one embodiment of the semiconductor device manufacturing method of the present disclosure has been described in detail above, the present invention is not limited to the above embodiment. For example, in the above embodiment, in the process shown in Figure 4, the steps of forming the pillar 300 (i), molding the resin 301 (j), and grinding the resin 301 to thin it (k) were performed in order. However, the step of molding the resin 301 onto the connection surface of the first semiconductor substrate 100 (j) may be performed first, followed by the step of grinding the resin 301 to a predetermined thickness to thin it (k), and then the step of forming the pillar 300 (i). In this case, the work of grinding the pillar 300 can be reduced, and the portion of the pillar 300 that is to be ground is no longer needed, thus reducing material costs.

[0214] Furthermore, although the above embodiment describes a C2C bonding example, the present invention may also be applied to Chip-to-Wafer (C2W) bonding as shown in Figure 5. In C2W, a semiconductor wafer 410 (first semiconductor substrate) is prepared having a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes). Simultaneously, a semiconductor substrate (second semiconductor substrate) is prepared before the individualization of a plurality of semiconductor chips 420, having a substrate body 421 (second substrate body), an insulating film portion 422 (second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes). Then, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before individualization into semiconductor chips 420 are polished by CMP or the like, in the same manner as in steps (c) and (d) above. Subsequently, the same fragmentation process as in step (e) is performed on the second semiconductor substrate to obtain multiple semiconductor chips 420.

[0215] Next, as shown in Figure 5(a), the terminal electrode 423 of the semiconductor chip 420 is aligned with the terminal electrode 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 chip 420 are bonded together (step (g)), and the terminal electrode 413 of the semiconductor wafer 410 and the terminal electrode 423 of the semiconductor chip 420 are joined together (step (h)), obtaining the semi-finished product shown in Figure 5(b). This creates an insulating joint portion S3 where the insulating film 412 and the insulating film portion 422 are joined, and the semiconductor chip 420 is mechanically firmly and precisely attached to the semiconductor wafer 410. Furthermore, an electrode joint portion S4 is created where the terminal electrode 413 and its corresponding terminal electrode 423 are joined together, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly joined.

[0216] Subsequently, as shown in Figures 5(c) and 5(d), a semiconductor device 401 is obtained by bonding multiple semiconductor chips 420 to a semiconductor wafer 410 in the same manner. Note that the multiple semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or they may be bonded together to the semiconductor wafer 410 by hybrid bonding.

[0217] In this method for manufacturing the semiconductor device 401, similar to the method for manufacturing the semiconductor device 1 described above, at least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 is an insulating film that is a cured product obtained by curing the resin composition of this disclosure. Therefore, even if foreign matter generated by dicing during the individualization of the semiconductor chip 420 adheres to the insulating film, the insulating film around the foreign matter can be easily deformed, and the foreign matter can be contained within the insulating film without creating large voids in the insulating film. In other words, the effect of foreign matter can be suppressed by the insulating film. Thus, in the manufacturing method relating to C2W described above, similar to C2C, it is possible to reduce bonding defects while performing fine bonding of the semiconductor wafer 410 and the semiconductor chip 420.

[0218] Furthermore, in the above-described method for manufacturing a semiconductor device, inorganic materials may be included in a portion of the insulating film 102 of the semiconductor substrate 110, the insulating film 202 of the semiconductor chip 205, etc., to the extent that the effects of the present invention are achieved. [Examples]

[0219] The present disclosure will be described in more detail below based on examples and comparative examples. However, the present disclosure is not limited to the examples described below.

[0220] (Synthesis Example 1 (Synthesis of A1)) 7.07 g of 3,3',4,4'-diphenyl ether tetracarboxylic 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, then at room temperature overnight, to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added at room temperature, followed by 7.08 g of 2-hydroxyethyl methacrylate (HEMA), and the mixture was stirred at 45°C for 10 hours. This reaction mixture was added dropwise to distilled water, the precipitate was filtered off and collected, and dried under reduced pressure to obtain polyimide precursor A1. The weight-average molecular weight of A1 was determined using gel permeation chromatography (GPC) on a standard polystyrene basis. The weight-average molecular weight of A1 was 20,000. Specifically, a solution prepared by dissolving 0.5 mg of A1 in 1 mL of solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] was used for the measurement under the following conditions. (Measurement conditions) Measuring device: Shimadzu Corporation SPD-M20A Pump: Shimadzu Corporation LC-20AD Column Oven: Shimadzu Corporation: CTO-20A Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF=1 / 1 (volume ratio) LiBr(0.03mol / L), H3PO4(0.06mol / L) Flow rate: 1.0 mL / min, Detector: UV270 nm, Column temperature: 40°C Calibration curves were created using standard polystyrene: TSKgel standard Polystyrene Type F-1, F-4, F-20, F-80, and A-2500 manufactured by Tosoh Corporation.

[0221] <Esterification rate> The esterification rate of A1 (the ratio of ester groups formed by reacting with HEMA to the total of ester groups formed by reacting with HEMA and unreacted carboxyl groups) was calculated by performing NMR measurements under the following conditions. The esterification rate was 80 mol%, and the proportion of unreacted carboxyl groups was 20 mol%. (Measurement conditions) Measuring instrument: Bruker BioSpin AV400M Magnetic field strength: 400MHz Reference substance: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0222] (Synthesis Example 2 (Synthesis of A2)) The polyimide precursor was synthesized using the same method as in Synthesis Example 1, except that NMP was replaced with 3-methoxy-N,N-dimethylpropanamide, to obtain polyimide precursor A2. The weight-average molecular weight of A2 was 22,000.

[0223] The esterification rate of A2 was calculated by performing NMR measurements under the aforementioned conditions. The esterification rate was 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.

[0224] (Composite Example 3 (Composite of A3)) Polyimide precursor A3 was obtained by performing the same procedure as in Synthesis Example 1, except that 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was replaced with 3.6 g of 4,4'-diaminodiphenyl ether and 0.2 g of m-phenylenediamine. The weight-average molecular weight of A3 was 25,000.

[0225] The esterification rate of A3 was calculated by performing NMR measurements under the aforementioned conditions. The esterification rate was 72 mol%, and the proportion of unreacted carboxyl groups was 28 mol%.

[0226] (Composite example 4 (Composite of A4)) The polyimide precursor was synthesized using the same method as in Synthesis Example 3, except that NMP was replaced with 3-methoxy-N,N-dimethylpropanamide, to obtain polyimide precursor A4. The weight-average molecular weight of A4 was 22,000.

[0227] The esterification rate of A4 was calculated by performing NMR measurements under the aforementioned conditions. The esterification rate was 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.

[0228] (Synthesis Example 5 (Synthesis of A5)) 61.0 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 52.0 g of 1,3-bis(3-aminophenoxy)benzene were dissolved in 200 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 2 hours, and then at room temperature overnight to obtain polyamic acid. 80 g of trifluoroacetic anhydride was added to this solution at room temperature and stirred for a predetermined time, after which 7.2 g of 2-hydroxyethyl methacrylate (HEMA) was added and stirred at 45°C for 10 hours. This reaction mixture was added dropwise to distilled water, the precipitate was filtered off and collected, and dried under reduced pressure to obtain polyimide precursor A5. The weight-average molecular weight of A5 was 25,000.

[0229] (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 and stirred at room temperature. While stirring, 81 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the reaction mixture was allowed to cool to room temperature and left for 15 hours.

[0230] Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 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 over 60 minutes with stirring. After stirring the reaction mixture at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, and then 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.

[0231] The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered off 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, and the resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor A6, which is a powdered polymer. The weight-average molecular weight of A6 was 24,000.

[0232] The esterification rate of A6 was calculated by performing NMR measurements under the aforementioned conditions. The esterification rate was 100 mol%.

[0233] (Synthesis Example 7 (Synthesis of A7)) In Synthesis Example 6, the polyimide precursor was synthesized using the same method as in Synthesis Example 6, except that 155 g of ODPA was replaced with 147 g of 3,3'-4,4'-biphenyltetracarboxylic dianhydride, yielding polyimide precursor A7. The weight-average molecular weight of A7 was 28,000.

[0234] The esterification rate of A7 was calculated by performing NMR measurements under the aforementioned conditions. The esterification rate was approximately 100 mol%.

[0235] In Comparative Example 1, described later, the following polymer components A8 and A9 were used as polymers other than the polyimide precursor. A8: Cresol-formaldehyde resin (manufactured by Asahi Organic Chemicals Co., Ltd.), weight-average molecular weight 12000 A9: Acrylic acid polymer (butyl acrylate / acrylic acid / 4-hydroxybutyl acrylate)

[0236] (Synthesis Example 10 (Synthesis of A10)) 18.7 g of ODPA and 6.54 g of PMDA, dried in a 160°C oven for 24 hours, were added to 400 g of 3-methoxy-N,N-dimethylpropanamide. To the solution obtained by stirring, a suspension of 29.1 g of 1,3-bis(3-aminophenoxy)benzene suspended in 100 g of 3-methoxy-N,N-dimethylpropanamide was added dropwise to prepare a mixture. After stirring the mixture at 30°C for 4 hours, 1.5 g of diazabicycloundecene was added to the mixture and stirred at 150°C for 2 hours. The mixture was added dropwise to distilled water, the precipitate was filtered off and collected, and polyimide resin A10 was obtained by vacuum drying. The weight-average molecular weight of A10 was 10,000.

[0237] [Examples 1-8, Comparative Example 1] (Preparation of resin composition) The resin compositions for Examples 1-8 and Comparative Example 1 were prepared as follows, using the components and amounts shown in Table 1. The units for the amounts of each component in Table 1 are parts by mass. Blank spaces in Table 1 indicate that the corresponding component was not included. 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 0.2 μm pore filter. The obtained resin compositions were evaluated as follows.

[0238] The components listed in Table 1 are as follows: ·Polymer component A1 to A10 as described above • (B) Component (solvent) B1:3-Methoxy-N,N-dimethylpropionamide B2: N-methyl-2-pyrrolidone B3: Methyl lactate B4: γ-Butyrolactone • (D) Component (polymerizable monomer) D1: Triethylene glycol dimethacrylate (TEGDMA) D2: 1,6-Hexanediol diglycidyl ether D3: Triglycidyl-p-aminophenol D4: Hexakis(methoxymethyl)melamine(Cymel) D5: Urea-alkyl (C1-5) aldehyde-alkyl (C2-10) polyhydric (2-4) aldehyde-alkyl (C1-12) monoalcohol polycondensate (MX270) D6:4,4'-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)bis[2,6-bis(hydroxymethyl)phenol] • Rust inhibitor Rust inhibitor 1: Benzotriazole Rust inhibitor 2: 5-amino-1H-tetrazol Rust inhibitor 3: 1-H-tetrazol • Adhesion aid Adhesion aid 1: 50% methanol solution of 3-ureidopropyltriethoxysilane Adhesion aid 2: 60% ethanol solution of N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane (SIB1140) • (C) Component (Photopolymerization Initiator) C1: 1-Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime C2: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) 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-diyrbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]

[0239] [ka]

[0240] (Measurement of storage modulus of cured film, etc.) Using the photosensitive resin compositions of Examples 1-4, 7, 8 and Comparative Example 1, cured films were formed as follows, and then the storage modulus was 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) specified in the drying conditions for film formation in Table 1, to form a photosensitive resin film with a thickness of approximately 10 μm after curing. The obtained photosensitive resin films were broadband (BB) exposed using a mask aligner MA-8 (manufactured by Suss Microtec) at the exposure levels shown in Table 1. After exposure, the resin films were developed using a coater developer ACT8 (manufactured by Tokyo Electron Limited) for the times shown in Table 1, with cyclopentanone (corresponding to Dev1 in Table 1) for Examples 1-4, 7, and 8, and with a 2.38% TMAH aqueous solution (corresponding to Dev2 in Table 1) for Comparative Example 1, to obtain strip-shaped patterned resin films with a width of 10 mm. The obtained patterned resin film was cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at the temperatures and times shown in Table 1 to obtain a patterned cured product with a film thickness of 10 μm. The resulting patterned cured material was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and a 10 mm wide patterned cured material was peeled off from the Si substrate. Using an RSA-G2 from TA Instruments, the storage modulus and loss modulus of patterned hardened material peeled from a Si substrate were measured under the following conditions: test frequency 1 Hz, heating rate 5 °C / min, measurement mode: tensile, measurement range -50 °C to 400 °C, chuck distance 10 mm, sample width 2.0 mm. The loss tangent was determined from the obtained storage modulus and loss modulus, and the peak of the loss tangent was defined as Tg (glass transition temperature). Furthermore, G2 / G1 was determined from the storage modulus at a temperature 100°C lower than Tg (G1 in Table 2) and the storage modulus 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.

[0241] (Preparation of a hardened film with a tip) The resin compositions of Examples 1-8 and Comparative Example 1 were spin-coated onto an 8-inch Si wafer using a spin coater, and a drying process was performed to form a resin film. If the resin composition was a photosensitive resin composition, a mask capable of creating a circular resin film with a diameter of 180 mm was placed on the obtained resin film, and light with a wavelength of 365 nm was irradiated for a predetermined exposure amount. Subsequently, the film was developed with cyclopentanone or 2.38% TMAH for a predetermined time, and 10 mm from the outer edge of the resin film on the Si wafer was removed to create a patterned resin film. If the resin composition was not a photosensitive resin composition, the edge portion of the spin-coated resin film was edge-rinsed with cyclopentanone to remove approximately 10 mm from the outer edge of the wafer, thereby creating a circular resin film with a diameter of approximately 180 mm. The resin film was heated in a clean oven under a nitrogen atmosphere at the temperatures shown in Table 3 for a predetermined time to obtain a cured film with a post-curing thickness of 2 μm to 8 μm.

[0242] The resulting cured film was polished using a CMP process, and measured using an AFM (atomic force microscope) to determine a thickness of 10 μm. 2 Polished cured films with an internal surface roughness Ra of 0.5 nm to 3 nm were obtained. After scrubbing the polished cured films with a general cleaning solution, a portion of the cleaned polished cured films was cut into 5 mm square pieces using a blade dicer (DISCO DFD-6362) to obtain resin-coated chips. The obtained resin-coated chips were pressed onto the polished cured films using a flip-chip bonder at a predetermined pressure and bonding temperature shown in Table 3 for 15 seconds to produce chip-coated cured films. Five chips pressed onto each polished cured film for each resin composition were evaluated as described below.

[0243] [Comparative Example 2] (Fabrication of SiO2 wafers with chips) A SiO2 wafer was prepared by thermal oxidation and polished using the method described in the above-mentioned method for preparing samples for adhesion evaluation to produce polished SiO2 wafers. A portion of the prepared polished SiO2 wafer was fragmented to produce SiO2 chips. The obtained SiO2 chips were bonded to the polished SiO2 wafer using the same method as when preparing the chipped cured film described above to produce a chipped SiO2 wafer. In the chipped SiO2 wafer, five SiO2 chips were pressed onto the polished SiO2 wafer.

[0244] The obtained chipped cured film and chipped SiO2 wafer were examined for the presence of voids indicating poor adhesion between the resin interface or between the resin and substrate using SAT (Scanning Acoustic Tomography). The evaluation criteria for voids are as follows. The results are shown in Table 3. An evaluation of A indicates that void formation is suppressed and the evaluation is considered good. -Void's Evaluation Criteria- A: Voids were observed in two or fewer of the five chips. B: More than two out of the five chips showed voids. One or more chips were detached when measuring C:SAT.

[0245] The adhesive strength between the SiO2 insulating layer or the cured film itself was measured using a shear tester for the obtained chip-attached cured film and the chip-attached SiO2 wafer. The adhesive strength was evaluated using the following criteria. The results are shown in Table 3. - Criteria for evaluating adhesive strength - A: The average share strength of the five chips is 1 MPa or higher. B: The average share strength of the five chips is 1 MPa or less. C: Adhesion is too low to measure. If the adhesive strength was 1 MPa or higher, the subsequent processes after the creation of the cured film with the tip could be carried out without any problems.

[0246] (Consideration of heat sealing) When hybrid bonding copper terminals with an insulating layer, bonding is generally performed at a temperature of 200°C to 400°C under pressure due to reliability issues with the copper terminals. If the insulating layer is a cured insulating resin film, voids may occur due to volatile components generated by the thermal decomposition of the insulating resin during bonding. Therefore, we evaluated whether voids occur and whether the adhesive strength decreases when the aforementioned cured film with a tip is subjected to even higher temperature thermocompression bonding.

[0247] (Evaluation after heat bonding) A carbon sheet for absorbing steps was placed over the aforementioned chipped cured film, and a pressure bonding device (manufactured by EVG) was used to apply a load of 7200N to an 8-inch pressure area at 300°C for 4 hours under specified vacuum conditions to perform heat bonding. Subsequently, the presence or absence of voids and the adhesive strength between the cured films were evaluated using the same method as described above. The evaluation criteria for the presence or absence of voids and the adhesive strength are as follows. The results are shown in Table 3. - Criteria for evaluating voids after thermocompression bonding - A: Voids were observed in two or fewer of the five chips. B: More than two out of the five chips showed voids. One or more chips were detached when measuring C:SAT. -Evaluation criteria for adhesive strength after heat-press bonding- A+: At least three of the five chips exhibited cohesive fracture of the Si portion as their failure mode. A: The average share strength of the five chips is 5 MPa or higher. B: The average share strength of the five chips is less than 5 MPa. C: Adhesion is too low to measure.

[0248] [Table 1]

[0249] [Table 2]

[0250] [Table 3]

[0251] As shown in Table 3, in Examples 1 to 8, the occurrence of voids in the cured film with the tip was suitably suppressed compared to Comparative Example 1. On the other hand, in Comparative Example 2, chip detachment was observed in the SiO2 wafer with the chip due to the influence of voids.

[0252] The disclosure of PCT / JP2020 / 037322, filed on 30 September 2020, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference. [Explanation of Symbols]

[0253] 1,1a,401…Semiconductor device, 10…First semiconductor chip, 20…Second semiconductor chip, 30…Pillar section, 40…Redistribution layer, 50…Substrate, 60…Circuit board, 61…Terminal electrode, 100…First semiconductor substrate, 101…First substrate body, 101a…One side, 102…Insulating film (First insulating film), 103…Terminal electrode (First electrode), 103a…Surface, 200…Second semiconductor substrate, 201…Second substrate body, 201a…One side, 202…Insulating film (Second insulating film), 203…Terminal electrode (Second electrode), 203a…Surface, 205… Semiconductor chip, 300...pillar, 301...resin, 410...semiconductor wafer (first semiconductor substrate), 411...substrate body (first substrate body), 412...insulating film (first insulating film), 413...terminal electrode (first electrode), 420...semiconductor chip (second semiconductor substrate), 421...substrate body (second substrate body), 422...insulating film portion (second insulating film), 423...terminal electrode (second electrode), A...cutting line, H...heat, M1~M3...semi-finished product, S1...insulating joint portion, S2...electrode joint portion, S3...insulating joint portion, S4...electrode joint portion.

Claims

1. (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and at least one polyimide resin, and (B) a solvent, A resin composition for use in producing 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) Prepare a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body. Step (2) A second semiconductor substrate is prepared, which has a second substrate body, the second organic insulating film provided on one surface of the second substrate body, and a plurality of second electrodes. Step (3) The second semiconductor substrate is divided into individual pieces to obtain a plurality of semiconductor chips, each chip comprising an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4) The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded together. Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together.

2. (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and at least one polyimide resin, and (B) a solvent, A resin composition for use in the production of cured products that are polished by chemical mechanical polishing together with electrodes.

3. The resin composition according to claim 1 or claim 2, wherein the (A) polyimide precursor comprises a compound having a structural unit represented by the following general formula (1). 【Chemistry 1】 In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ６ and R ７ Each of these independently represents either a hydrogen atom or a monovalent organic group.

4. The resin composition according to claim 3, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E). 【Chemistry 2】 In formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (–O–), a sulfide bond (–S–), a phenylene group, an ester bond (–O–C(=O)–), a silylene bond (–Si(R Ａ )) ２ –; two Rs Ａ each independently represent a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (–O–(Si(R Ｂ )) ２ –O–) ｎ ; two Rs Ｂ each independently represent 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. The resin composition according to claim 3 or claim 4, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H). 【Transformation 3】 In formula (H), R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), or a silylene bond (-Si(R) Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of these 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. In the above general formula (1), the R ６ and R ７ The resin composition according to any one of claims 3 to 5, wherein the monovalent organic group in is any one of the group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group. 【Chemistry 4】 In general formula (2), R ８ ~R １０ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, R ｘ This represents a divalent linking group.

7. The resin composition according to any one of claims 1 to 6, wherein the content of the solvent (B) is 1 to 10,000 parts by mass per 100 parts by mass of the total of the polyimide precursor (A) and the polyimide resin.

8. The resin composition according to any one of claims 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 (7). 【Transformation 5】 In formulas (3) to (7), R １ , R ２ , R ８ and R １０ Each of these is an alkyl group having 1 to 4 carbon atoms, and R ３ ~R ７ and R ９ Each of these is independently either 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 according to any one of claims 1 to 8, wherein the 5% thermoweight loss temperature of the cured product obtained by curing the resin composition is 200°C or higher.

10. The resin composition according to any one of claims 1 to 9, wherein the glass transition temperature of the cured product obtained by curing the resin composition is 100°C to 400°C.

11. The resin composition according to any one of claims 1 to 10, wherein the ratio G2 / G1 of the storage modulus G2 at a temperature 100°C higher than the glass transition temperature (Tg) of the cured product obtained by curing the resin composition is 0.001 to 0.02, to the storage modulus G1 at a temperature 100°C lower than the glass transition temperature (Tg) of the cured product obtained by dynamic viscoelastic measurement.

12. The resin composition according to any one of claims 1 to 11, further comprising (C) a photopolymerization initiator and (D) a polymerizable monomer.

13. A negative-type photosensitive resin composition or a positive-type photosensitive resin composition, the resin composition according to any one of claims 1 to 12, for use in providing a plurality of through holes for arranging a plurality of terminal electrodes in an organic insulating film provided on one surface of a substrate body by a photolithography method.

14. The resin composition according to any one of claims 1 to 13, wherein the tensile modulus of the cured product at 25°C is 7.0 GPa or less.

15. The resin composition according to any one of claims 1 to 14, wherein the thermal expansion coefficient of the cured product is 150 ppm / K or less.

16. A method for manufacturing a semiconductor device, comprising using the resin composition described in any one of claims 1 to 15 to produce at least one of the first organic insulating film and the second organic insulating film, and manufacturing the semiconductor device through the following steps (1) to (5). Step (1) Prepare a first semiconductor substrate having a first substrate body and a first organic insulating film and a first electrode provided on one surface of the first substrate body. Step (2) A second semiconductor substrate is prepared, which has a second substrate body, the second organic insulating film provided on one surface of the second substrate body, and a plurality of second electrodes. Step (3) The second semiconductor substrate is divided into individual pieces to obtain a plurality of semiconductor chips, each chip comprising an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4) The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded together. Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together.

17. The method for manufacturing a semiconductor device according to claim 16, wherein in step (4), the first organic insulating film and the organic insulating film portion are bonded at a temperature such that the temperature difference between the semiconductor chip and the first semiconductor substrate is 10°C or less.

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

19. A method for manufacturing a semiconductor device according to any one of claims 16 to 18, wherein 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 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. The method for manufacturing a semiconductor device according to any one of claims 16 to 19, wherein the thickness of the second insulating film is greater than the thickness of the first insulating film.

21. The method for manufacturing a semiconductor device according to any one of claims 16 to 19, wherein the thickness of the second insulating film is smaller than the thickness of the first insulating film.

22. A cured product obtained by curing the resin composition according to any one of claims 1 to 15.

23. A first semiconductor substrate having a first substrate body, and a first organic insulating film and a first electrode provided on one surface of the first substrate body, A semiconductor chip comprising a semiconductor chip substrate body, an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body, The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are joined together, and the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together. A semiconductor device in which at least one of the first organic insulating film and the portion of the organic insulating film is an organic insulating film obtained by curing the resin composition described in any one of claims 1 to 15.

24. Tetracarboxylic acid dianhydride and H ２ N-Y-NH ２ A step of reacting a diamine compound represented by (wherein Y is a divalent organic group) with 3-methoxy-N,N-dimethylpropanamide to obtain a polyamic acid solution, The process involves reacting the polyamic acid solution with a dehydrating condensation agent and a compound represented by R-OH (wherein R is a monovalent organic group), A method for synthesizing a polyimide precursor, including [the specified substance].

25. The method for synthesizing a polyimide precursor according to claim 24, wherein the dehydration condensation agent comprises at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

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