Hybrid bonding insulating film forming material, method for manufacturing a semiconductor device, and semiconductor device.

Abstract

To provide a hybrid bonding insulating film forming material, a semiconductor device manufacturing method, and a semiconductor device that can reduce bonding temperature while maintaining the heat resistance of an insulating film.SOLUTION: A hybrid bonding insulating film forming material includes (A) a polyimide precursor having an ester moiety, (B) a solvent, and (C) a compound that promotes elimination of the ester moiety.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a hybrid bonding insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device. Regarding. [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 project] [Problems that the invention aims to solve]

[0007] In hybrid bonding technology, the practical application of using inorganic materials such as silicon dioxide (SiO2) as the insulating film in C2W bonding methods is being considered. However, because inorganic materials are hard, there is a risk that foreign matter originating from the inorganic material, generated when semiconductor chips are cut for individualization, may adhere to the surface of the insulating film, creating large voids at the bonding interface. As a result, the yield of semiconductor device manufacturing decreases, or manufacturing costs increase because facilities such as cleanrooms with high cleanliness are required to remove foreign matter.

[0008] On the other hand, the method of C2W bonding using hybrid bonding technology with an organic insulating film is still in the investigation stage and has not yet been put into practical use. When using the cyclic olefin resin described in Patent Document 1, the heat resistance of the resulting organic insulating film is insufficient, and there is a risk of bonding defects occurring at the interface between the substrate and the organic insulating film when exposed to high temperatures during C2W bonding. On the other hand, as mentioned above, the method of C2W bonding using hybrid bonding technology with an insulating film requires a low bonding temperature.

[0009] This disclosure has been made in view of the above, and aims to provide a hybrid bonding insulating film forming material that can reduce the bonding temperature while maintaining the heat resistance of the insulating film, a method for manufacturing a semiconductor device, and a semiconductor device. [Means for solving the problem]

[0010] The specific means for achieving the aforementioned objectives are as follows: <1> A hybrid bonding insulating film forming material comprising (A) a polyimide precursor having an ester moiety, (B) a solvent, and (C) an ester moiety desorbing agent that promotes the desorption of the ester moiety. <2> The content of the (C) ester moiety detacher is 1 to 7 parts by mass per 100 parts by mass of the (A) polyimide precursor. <1> Hybrid bonding insulating film forming material as described above. <3> The (A) polyimide precursor includes a compound having a structural unit represented by the following general formula (1). <1> or <2> Hybrid bonding insulating film forming material as described above. [ka] 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> Hybrid bonding insulating film forming material as described above. [ka] 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 hybrid bonding insulating film forming material according to <3> or <4>, which is a group represented by the following formula (H).

Chemical formula

Chemical formula

[0011] According to this disclosure, it is possible to provide a hybrid bonding insulating film forming material that can reduce the bonding temperature while maintaining the heat resistance of the insulating film, a method for manufacturing a semiconductor device, and a semiconductor device. [Brief explanation of the drawing]

[0012] [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. [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 to a chip-to-wafer (C2W). [Modes for carrying out the invention]

[0013] The following describes in detail the forms for implementing this disclosure. However, this disclosure is not limited to the following embodiments. In this disclosure, the components (including elemental steps, etc.) are not required unless otherwise explicitly stated. The same applies to numerical values ​​and their ranges, and they do not limit this disclosure. 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.

[0014] In this disclosure, "(meth)acrylic group" means "acrylic group" and "methacrylic group," "(meth)acrylate" means "acrylate" and "methacrylate," and "(meth)acryloyl" means "acryloyl" and "methacryloyl." 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.

[0015] <Hybrid bonding insulating film forming material> The hybrid bonding insulating film forming material of the present disclosure comprises (A) a polyimide precursor having ester moieties, (B) a solvent, and (C) an ester moiety desorbing agent that promotes the desorption of the ester moieties. Hereinafter, the hybrid bonding insulating film forming material of this disclosure will also be referred to as the "insulating film forming material," (A) the polyimide precursor having an ester moiety will also be referred to as the "(A) polyimide precursor," and (C) the ester moiety desorbing agent that promotes the desorption of the ester moiety will also be referred to as the "(C) ester moiety desorbing agent."

[0016] The reason why the configuration of the hybrid bonding insulating film forming material disclosed herein allows for a reduction in the bonding temperature while maintaining the heat resistance of the insulating film is not immediately clear, but it can be considered as follows. The decrease in heat resistance is presumed to be due to the generation and volatilization of compounds with relatively small molecular weights from the insulating film. These compounds with relatively small molecular weights do not generate and volatilize at the curing temperature during the production of the cured film, but are generated and volatilized by heating during subsequent bonding and annealing processes, which is thought to lead to a decrease in heat resistance. Therefore, it is thought that heat resistance can be improved by actively generating (eliminating) relatively small molecular weight compounds that cause volatilization during the curing (imide cyclization reaction) beforehand, and by suppressing the generation of low molecular weight compounds from the cured film after curing. The following describes the components included in and potentially included in the insulating film forming material of this disclosure.

[0017] ((A) Polyimide precursor) The insulating film forming material of this disclosure comprises (A) a polyimide precursor having an ester moiety. (A) The polyimide precursor is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Polyamic acid esters and polyamic acid amides are compounds in which at least some of the hydrogen atoms of the carboxyl groups in the polyamic acid are replaced with monovalent organic groups, and polyamic acid salts are compounds in which at least some of the carboxyl groups in the polyamic acid form a salt structure with a basic compound with a pH greater than 7.

[0018] (A) The polyimide precursor preferably 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.

[0019] [ka]

[0020] 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 a hydrogen atom or a monovalent organic group. (C) Due to the ester moiety detachment agent, COOR 6 Base and -COOR 7 The elimination of the ester moiety from the group is promoted.

[0021] 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 At least one of them is a hydrogen atom, and the rest may be monovalent organic groups as described later, and they may all 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] [ka]

[0026] 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.

[0027] 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 BEach 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).

[0028] [ka]

[0029] 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.

[0030] 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.

[0031] 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.

[0032] Specific examples of the tetravalent organic group represented by X may be the groups represented by the following formulas (J) to (O).

[0033] [ka]

[0034] 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.

[0035] Specific examples of divalent aromatic groups represented by Y include the groups represented by the following formulas (G) and (H). Among these, the group represented by the following formula (H) 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 the following formula (H) in which D is a single bond or an ether bond, even more preferably a single bond or an ether bond, and even more preferably an ether bond.

[0036] [ka]

[0037] In formulas (G) to (H), 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 AEach 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 a single bond, 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, each independently.

[0038] The alkyl group represented by R in formulas (G) to (H) 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 (H) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups.

[0039] The alkoxy group represented by R in formulas (G) to (H) 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 (H) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, etc.

[0040] The halogenated alkyl group represented by R in formulas (G) to (H) 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 (H) include alkyl groups in which at least one hydrogen atom in the alkyl group represented by R in formulas (G) to (H) 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.

[0041] In equations (G) to (H), n is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0042] Specific examples of divalent aliphatic groups represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups having a polyalkylene oxide structure.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure. Examples of a divalent group having a polysiloxane structure represented by Y include a divalent group having a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of 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.

[0047] The group represented by formula (G) is preferably the group represented by the following formula (G'), and the group represented by formula (H) is preferably the group represented by the following formula (H'), formula (H''), or formula (H'''), and more preferably the group represented by the following formula (H') or formula (H'').

[0048] [ka]

[0049] In formula (H'''), 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.

[0050] 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 such combinations include a combination where X is the group represented by formula (E) and Y is the group represented by formula (H).

[0051] 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, and even more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). The presence of a monovalent organic group containing an unsaturated double bond, preferably a group represented by the following general formula (2), results in high i-ray transmittance and a tendency to form good cured products even at low temperatures below 400°C.

[0052] 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.

[0053] [ka]

[0054] 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 x This represents a divalent linking group.

[0055] 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.

[0056] 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.

[0057] 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. Rx 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.

[0058] 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).

[0059] (A) If the polyimide precursor 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 7 The 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%.

[0060] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0061] [ka]

[0062] 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.

[0063] In general formula (2'), q is an integer between 1 and 10, preferably between 2 and 5, and more preferably 2 or 3.

[0064] 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%.

[0065] (A) The polyimide precursor 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. Note that (A) the polyimide precursor may also be synthesized using a tetracarboxylic acid instead of a tetracarboxylic dianhydride.

[0066] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 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-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1, Examples include 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, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone bisspironorbornanetetracarboxylic acid dianhydride, and 2,2-bis{4-(4'-phenoxy)phenyl}propanetetracarboxylic acid dianhydride. Among these, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride and 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride are preferred, and 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride is more preferred from the viewpoint of bonding at lower temperatures. Tetracarboxylic acid dianhydrides may be used individually or in combination of two or more types.

[0067] Specific examples of diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, 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, and 2 ,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl 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-diisopropylaniline), 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-A Minophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 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,Examples include 9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. Preferred diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene. Among these, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane are preferred from the viewpoint of having a flexible skeleton. Having a flexible skeleton tends to reduce damage to the device, improve throughput in the bonding process, and ensure alignment accuracy. Diamine compounds may be used individually or in combination of two or more.

[0068] 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).

[0069] (A) The aforementioned compounds contained in the polyimide precursor 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. (A) The aforementioned compounds contained in the polyimide precursor 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. (A) The aforementioned compounds contained in the polyimide precursor 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 a compound represented by R-OH. Alternatively, a portion of the tetracarboxylic dianhydride may be reacted with a compound represented by R-OH beforehand, and the partially esterified tetracarboxylic dianhydride may be reacted with a diamine compound represented by H2N-Y-NH2.

[0070] [ka]

[0071] 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.

[0072] (A) The compound represented by R-OH used in the synthesis of the aforementioned compound contained in the polyimide precursor 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.

[0073] (A) There are no particular restrictions on the molecular weight of the polyimide precursor, 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.

[0074] The insulating film forming material of this disclosure may further contain a dicarboxylic acid, and the (A) polyimide precursor contained in the insulating film forming material 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.

[0075] [ka]

[0076] The insulating film forming material of this disclosure may contain a polyimide resin in addition to (A) a polyimide precursor. By combining the polyimide precursor and the polyimide resin, 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 herein is a resin having an imide skeleton in all or part of its resin skeleton. It is preferable that the polyimide resin is soluble in the solvent in the insulating film forming material using the polyimide precursor.

[0077] 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.

[0078] [ka]

[0079] 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.

[0080] When the insulating film forming material of this disclosure includes a polyimide resin, the ratio of the polyimide resin to the total of the polyimide precursor and the polyimide resin may be 15% to 50% by mass, or 10% to 20% by mass.

[0081] The insulating film forming material of this disclosure may contain (A) a polyimide precursor and other resins besides the polyimide resin. Examples of other resins, from the viewpoint of heat resistance, include novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. The other resins may be used individually or in combination of two or more.

[0082] In the insulating film forming material of this disclosure, the content of (A) polyimide precursor relative to the total amount of resin components is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass.

[0083] ((B) Solvent) The insulating film forming material of this disclosure comprises (B) a solvent (hereinafter also referred to as "component (B)"). Component (B) preferably comprises at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (7), for example, from the viewpoint of reducing the reproductive toxicity and environmental burden of the insulating film forming material.

[0084] [ka]

[0085] 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.

[0086] In formula (3), s is preferably 0. In formula (4), the alkyl group having 1 to 4 carbon atoms of R 2 is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, and more preferably 1. In formula (5), the alkyl group having 1 to 4 carbon atoms of R 3 is preferably a methyl group, an ethyl group, a propyl group or a butyl group. The alkyl groups having 1 to 4 carbon atoms of R 4 and R 5 are preferably a methyl group or an ethyl group. In formula (6), the alkyl groups having 1 to 4 carbon atoms of R 6 to R 8 are preferably a methyl group or an ethyl group. r is preferably 0 or 1, and more preferably 0. In formula (7), the alkyl groups having 1 to 4 carbon atoms of R 9 and R 10 are preferably a methyl group or an ethyl group. u is preferably 0 or 1, and more preferably 0.

[0087] Component (B) may be, for example, at least one of the compounds represented by formulas (4), (5), (6) and (7), or may be the compound represented by formula (5) or the compound represented by formula (7).

[0088] (B) Specific examples of component include the following compounds.

[0089] [ka]

[0090] The insulating film forming material of this disclosure includes component (B), which is not limited to the aforementioned compounds, but may also include other solvents. Component (B) may be an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, and the like.

[0091] 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.

[0092] 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.

[0093] (B) Preferred solvents for component (B) include γ-butyrolactone, cyclopentanone, and ethyl lactate.

[0094] In the insulating film forming material 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 insulating film forming material, or 3% by mass or less with respect to the total amount of the (A) polyimide precursor.

[0095] In the insulating film forming material 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 polyimide precursor (A).

[0096] 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 polyimide precursor (A).

[0097] ((C) Ester moiety desorbing agent) The insulating film forming material of this disclosure contains (C) an ester moiety desorbing agent. The (C) ester moiety desorbing agent acts on the ester moiety of the (A) polyimide precursor and promotes the desorption of the ester moiety. (C) Examples of ester moiety detachment agents include nitrogen-containing compounds. Nitrogen-containing compounds may also be thermal base generators. Thermal base generators generate a base upon heating, and this base promotes the detachment of the ester moiety of the (A) polyimide precursor.

[0098] Specific examples of nitrogen-containing compounds include anilinediacetic acid, 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, diazabicycloundecene, and salts thereof. Among these, anilinediacetic acid, 4-aminobenzamide, nicotinamide, diazabicycloundecene, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, and salts thereof are preferred. Nitrogen-containing compounds may be used individually or in combination of two or more.

[0099] The nitrogen-containing compound preferably includes a compound represented by the following formula (17) or a compound represented by the following formula (18).

[0100] [ka]

[0101] In equations (17) and (18), R 31A ~R 34A 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 34A At least one (preferably one) of these is a monovalent aromatic group. 31A ~R 34A 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.

[0102] In equations (17) and (18), R 31A ~R 34A It 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.

[0103] In equations (17) and (18), R 31A ~R 34A 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.

[0104] In equations (17) and (18), R 31A ~R 34A A monovalent aliphatic hydrocarbon group having a hydroxyl group is R 31A ~R 34A 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.

[0105] R in equations (17) and (18) 31A ~R 34A 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.

[0106] R in equations (17) and (18) 31A ~R 34A The monovalent aromatic group may have substituents. Substituents include R of formulas (17) and (18). 31A ~R 34AThe monovalent aliphatic hydrocarbon group, and the R of formulas (17) and (18) described above. 31A ~R 34A Examples include monovalent aliphatic hydrocarbon groups having a hydroxyl group.

[0107] (C) The content of the ester moiety detacher is preferably 1 to 7 parts by mass per 100 parts by mass of (A) polyimide precursor, more preferably 1 to 6 parts by mass, and even more preferably 2 to 5 parts by mass from the viewpoint of storage stability.

[0108] The insulating film forming material of this disclosure comprises (A) a polyimide precursor, (B) a solvent, and (C) an ester moiety detacher, and optionally comprises (D) a photopolymerization initiator, (E) a polymerizable monomer, (F) a thermal polymerization initiator, (G) a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, etc., and may also contain other components and unavoidable impurities to the extent that they do not impair the effects of this disclosure. The insulating film forming material of this disclosure preferably further comprises components (D) and (E). Hereinafter, (D) photopolymerization initiator will also be referred to as component (D), (E) polymerizable monomer as component (E), (F) thermal polymerization initiator as component (F), and (G) polymerization inhibitor as component (G).

[0109] 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 insulating film forming material of this disclosure (A) Polyimide precursor ~ (C) Ester moiety desorbing agent, (A) Polyimide precursor ~ (E) Component, (A) Polyimide precursor ~ (F) Component, (A) Polyimide precursor ~ (G) Component, (A) Polyimide precursors ~ (G) Components and at least one selected from the group consisting of antioxidants, coupling agents, surfactants, leveling agents, and rust inhibitors. It may consist of [something]. The preferred forms of each component are described below.

[0110] ((D) Photopolymerization initiator) The insulating film forming material of this disclosure preferably contains (D) a photopolymerization initiator. This makes it possible to reduce the number of steps required to fabricate electrodes in the semiconductor device manufacturing process, thereby reducing the overall cost of the semiconductor device manufacturing process.

[0111] (D)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, 4,4'-bis(diethylamino)benzophenone, o-methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibe Benzophenone derivatives such as benzoyl ketone and fluorenone; acetophenone derivatives such as acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzyl, benzyl Benzyl derivatives such as zyldimethyl ketal and benzyl-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- Oxime derivatives such as toxycarbonyl 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-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 (BASF) and Irgacure OXE04 (BASF). Component (D) 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.

[0112] If the insulating film forming material of this disclosure contains component (D), the content of component (D) is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 5 to 15 parts by mass, per 100 parts by mass of polyimide precursor (A), from the viewpoint of ensuring that photocrosslinking is uniform in the film thickness direction.

[0113] The insulating film forming material of this disclosure may include an anti-reflective agent that suppresses reflected light from the substrate direction, from the viewpoint of improving photosensitive properties.

[0114] ((E) Polymerizable monomers) The insulating film forming material of this disclosure preferably contains (E) a polymerizable monomer. Component (E) 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.

[0115] 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, pentaerythritol tetra Examples include acrylates, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanurate triacrylate, ethoxylated isocyanurate trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, tricyclodecanedimethanol diacrylate, 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.

[0116] 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.

[0117] Component (E) 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 (for example, an oxirane ring).

[0118] If the insulating film forming material of this disclosure contains component (E), the content of component (E) 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 polyimide precursor (A).

[0119] ((F) Thermal polymerization initiator) From the viewpoint of improving the physical properties of the cured product, the insulating film forming material of this disclosure preferably contains (F) a thermal polymerization initiator.

[0120] (F)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.

[0121] If the insulating film forming material of this disclosure contains component (F), the content of component (F) may be 0.1 to 20 parts by mass, 1 to 15 parts by mass, or 1 to 10 parts by mass per 100 parts by mass of the polyimide precursor.

[0122] ((G) Polymerization inhibitors) The insulating film forming material of this disclosure may contain component (G) from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization suppressants.

[0123] Specific examples of component (G) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthaquinone, 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.

[0124] 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.

[0125] If the insulating film forming material of this disclosure contains component (G), the content of component (G) 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 polyimide precursor (A), from the viewpoint of storage stability of the insulating film forming material and heat resistance of the resulting cured product.

[0126] The insulating film forming material of this disclosure may further include an antioxidant, a coupling agent, a surfactant, a leveling agent, or a rust inhibitor.

[0127] (Antioxidant) The insulating film forming material 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. By including an antioxidant in the insulating film forming material of this disclosure, oxidation of electrodes during insulation reliability testing can be suppressed.

[0128] 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.

[0129] If the insulating film forming material of this disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the polyimide precursor (A).

[0130] (Coupling agent) The insulating film forming material of this disclosure may contain a coupling agent. The coupling agent reacts with (A) the polyimide precursor 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.

[0131] 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.

[0132] If the insulating film forming material 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 the polyimide precursor (A).

[0133] (Surfactants and leveling agents) The insulating film forming material 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 insulating film forming material, it is possible to improve the coatability (e.g., suppression of striations (unevenness of film thickness)), adhesion, and compatibility of compounds in the insulating film forming material.

[0134] Examples of surfactants or leveling agents include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.

[0135] Surfactants and leveling agents may be used individually or in combination of two or more types.

[0136] If the insulating film forming material 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 (A) polyimide precursor.

[0137] (Rust inhibitor) The insulating film forming material 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.

[0138] 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.

[0139] 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.

[0140] Rust inhibitors may be used individually or in combination of two or more types.

[0141] If the insulating film forming material of this disclosure contains a rust inhibitor, the content of the rust inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of (A) polyimide precursor. In particular, when the content of the rust inhibitor is 0.1 parts by mass or more, discoloration of the surface of copper or copper alloy is suppressed when the insulating film forming material of this disclosure is applied to the surface of copper or copper alloy.

[0142] (Properties of insulating film forming materials) From the viewpoint of bonding at low temperatures, the insulating film forming material of this disclosure preferably has a glass transition temperature of 50°C to 250°C when cured, and more preferably 50°C to 220°C. The glass transition temperature when cured may be 200°C or lower.

[0143] The glass transition temperature of the cured material is measured as follows. First, the insulating film forming material is heated in a nitrogen atmosphere for 2 hours at a predetermined curing temperature (e.g., 150°C to 375°C) where the curing reaction is possible to obtain a cured material. The obtained cured material is cut to create a rectangular parallelepiped measuring 10 mm × 50 mm × 10 μm. A thermomechanical analyzer (e.g., Hitachi High-Tech Science Corporation, TMA7100) is used to measure the elongation (expansion) of the sample in the temperature range of 50°C to 350°C using a tensile jig, under the conditions of an initial sample length of 10 mm, a heating rate of 5°C / min, and a load of 10 g. The glass transition temperature (Tg) is defined as the temperature at the start of the change, determined by the tangent method, at the point in the curve obtained by the above method where there is a sudden change in the expansion rate.

[0144] The insulating film forming material of this disclosure may be a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material. Furthermore, the negative-type photosensitive insulating film forming material or the positive-type photosensitive insulating film forming material may be used for at least one of the following: providing a plurality of through holes for arranging a plurality of terminal electrodes in a first organic insulating film provided on one surface of a first substrate body, as described later, 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 a second substrate body.

[0145] The insulating film forming material of this disclosure preferably has a thermal expansion coefficient of 150 ppm / K or less when cured, 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 cured insulating film 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. Thermal expansion coefficient is the rate at which the length of the cured material expands per unit temperature due to the rise in temperature. The thermal expansion coefficient can be calculated by measuring the change in the length of the cured material at 100°C to 150°C using a thermomechanical analyzer or the like.

[0146] <Semiconductor device> The semiconductor device of the present disclosure comprises a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one side of the first substrate body, and a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one side of the semiconductor chip substrate body, wherein the first organic insulating film and the second organic insulating film are bonded together, the first electrode and the second electrode are bonded together, and at least one of the first organic insulating film and the second organic insulating film is a cured product of the insulating film forming material of the present disclosure. The semiconductor device of this disclosure has excellent heat resistance of the insulating film because at least one of the first organic insulating film and the organic insulating film portion is a cured product of the insulating film forming material of this disclosure.

[0147] <Manufacturing method for semiconductor devices> The semiconductor device manufacturing method of the present disclosure involves manufacturing a semiconductor device using the insulating film forming material of the present disclosure. Specifically, the semiconductor device manufacturing method of the present disclosure involves preparing a first semiconductor substrate having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body, preparing a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, and bonding the first electrode and the second electrode, The insulating film forming material of this disclosure is used to produce at least one of the first organic insulating film and the second organic insulating film.

[0148] 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.

[0149] (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.

[0150] 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 firmly and 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 joined together.

[0151] 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 placed in place of the pillar portion 30, and the solder balls may be used to electrically connect the lower terminal electrode of the first semiconductor chip 10 to the upper terminal electrode of the redistribution layer 40.

[0152] The redistribution layer 40 is a wiring layer that has the function of terminal pitch conversion, which is a function of the package substrate. It is a layer in which a redistribution pattern is formed using polyimide and copper wiring on the insulating film on the underside of the second semiconductor chip 20 and on the underside of the pillar portion 30. The redistribution layer 40 is formed with the first semiconductor chip 10, the second semiconductor chip 20, etc. inverted (see Figure 4(d)).

[0153] The redistribution layer 40 electrically connects the terminal electrodes on the underside of the second semiconductor chip 20 and the terminal electrodes of the first semiconductor chip 10 via 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. Various electronic components 51 may be mounted on the substrate 50. If there is a large difference in terminal pitch between the redistribution layer 40 and the substrate 50, an inorganic interposer or the like may be used to make an electrical connection between the redistribution layer 40 and the substrate 50.

[0154] The circuit board 60 is a substrate on which the first semiconductor chip 10 and the second semiconductor chip 20 are mounted, and which has a plurality of through electrodes inside that are electrically connected to the substrate 50 to which the first semiconductor chip 10, the second semiconductor chip 20 and electronic components 51 are connected. In the circuit board 60, the terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 are electrically connected to terminal electrodes 61 provided on the back surface of the circuit board 60 by the plurality of through electrodes.

[0155] (An example of a semiconductor device manufacturing method) Next, an example of a method for manufacturing the semiconductor device 1 will be described with reference to Figures 2 to 4. Figure 2 is a diagram showing the method for manufacturing the semiconductor device shown in Figure 1 in sequence. Figure 3 is a diagram showing the bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in Figure 2 in more detail. Figure 4 is a diagram showing the method for manufacturing the semiconductor device shown in Figure 1, sequentially following the steps shown in Figure 2.

[0156] The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n). (a) A step of preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10. (b) A step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20. (c) A step of polishing the first semiconductor substrate 100. (d) A step of polishing the second semiconductor substrate 200. (e) A step of separating the second semiconductor substrate 200 into individual pieces and obtaining a plurality of semiconductor chips 205. (f) A step of aligning the terminal electrodes 203 of each of the multiple semiconductor chips 205 with respect to the terminal electrodes 103 of the first semiconductor substrate 100. (g) A step of bonding the insulating film 102 of the first semiconductor substrate 100 and each insulating film portion 202b of the plurality of semiconductor chips 205 to each other (see Figure 3(b)). (h) A step of joining the terminal electrodes 103 of the first semiconductor substrate 100 to the terminal electrodes 203 of each of the multiple semiconductor chips 205 (see Figure 3(c)). (i) A step of forming a plurality of pillars 300 (corresponding to pillars 31) between a plurality of semiconductor chips 205 on the connection surface of the first semiconductor substrate 100. (j) A step of obtaining a semi-finished product M1 by molding resin 301 onto the connection surface of the first semiconductor substrate 100 so as to cover the semiconductor chip 205 and the pillar 300. (k) A process in which the resin 301 side of the semi-finished product M1 molded in process (j) is ground down to thin it and obtain a semi-finished product M2. (l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k). (m) A step of cutting the semi-finished product M3, which has a wiring layer 400 formed in step (l), along the cutting line A so that it becomes each semiconductor device 1. (n) A step in which the semiconductor device 1a, which has been individualized in step (m), is inverted and placed on the substrate 50 and the circuit board 60 (see Figure 1).

[0157] The insulating film forming material of this disclosure may be an insulating film forming material used for 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).

[0158] [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 of the insulating film forming material of this disclosure, is provided in the space between them. 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 in between.

[0159] 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, an organic insulating region) which is a cured product of the insulating film forming material 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.

[0160] Even if both insulating films 102 and 202 used in steps (a) and (b) are cured products of the insulating film forming material of this disclosure, one of the insulating films 102 and 202 may be a cured product of the insulating film forming material of this disclosure and the other may be another cured product. Examples of insulating film forming materials for forming other cured products include (A) those that do not contain a polyimide precursor and (A) those that contain other resins other than the polyimide precursor, and (C) those that do not contain an ester moiety detacher. Examples of other resins include insulating film forming materials containing a polyimide precursor without an ester moiety, polyimide, polyamideimide, benzocyclobutene (BCB), polybenzoxazole (PBO), PBO precursor, etc. The tensile modulus of 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, and particularly preferably 2.5 GPa or less.

[0161] 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.

[0162] 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.

[0163] 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).

[0164] Next, a method for manufacturing an insulating film will be described. The insulating film is obtained by curing an insulating film forming material. Examples of the above-mentioned methods for manufacturing an insulating film include (α) a method comprising the steps of applying and drying an insulating film forming material onto a substrate to form a resin film, and heat-treating the resin film, and (β) a method comprising the steps of forming an insulating film with a constant thickness on a film that has been subjected to a release treatment using an insulating film forming material, then transferring the resin film to a substrate by a lamination method, and heat-treating the resin film formed on the substrate after the transfer. From the viewpoint of flatness, method (α) is preferred.

[0165] Examples of coating methods for insulating film-forming materials include spin coating, inkjet coating, and slit coating.

[0166] In the spin coating method, for example, the insulating film forming material 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.

[0167] The process may include a drying step after applying the insulating film forming material to a support, film, etc. 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 insulating film forming material is formed in a film-like manner.

[0168] In the slit coating method, for example, the insulating film forming material 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.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] When using the insulating film forming material of this disclosure, which is a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material, when the insulating film 202 is provided on one surface 201a of the second substrate body 201 and then a plurality of terminal electrodes 203 are provided, for example, a method may be used that includes the steps of: coating the insulating film forming material onto the substrate; drying to form a resin film; pattern exposure of the resin film, developing with a developer to obtain a patterned resin film; and heat treatment of the patterned resin film. This makes it possible to obtain a cured patterned insulating film.

[0173] 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 the steps of: applying an insulating film forming material other than the insulating film forming material of the present disclosure on the substrate; drying to form a resin film; applying and drying the insulating film forming material of the present disclosure, which is a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material, on the resin film, then performing pattern exposure, and developing using a developer to obtain a patterned resin film; and heat-treating the patterned resin film may be used. Thereby, a cured patterned insulating film can be obtained.

[0174] Pattern exposure is performed, for example, by exposing to a predetermined pattern through a photomask. The active light rays to be irradiated include i-line, ultraviolet rays such as broadband, visible light rays, radiation, etc., and it is preferably i-line. As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, etc. can be used.

[0175] By developing after exposure, a patterned resin film, which is a resin film with a pattern formed thereon, can be obtained. When the insulating film forming material of the present disclosure is a negative photosensitive insulating film forming material, the unexposed portion is removed with a developer. As the organic solvent used as the negative developer, as the developer, a good solvent of the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used. Examples of the good solvent 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, cycloheptanone, etc. Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water, etc.

[0176] If the insulating film forming material of this disclosure is a positive-type photosensitive insulating film forming material, the exposed area is removed with a developer. Examples of solutions used as developers for positive film include tetramethylammonium hydroxide (TMAH) solution and sodium carbonate solution.

[0177] 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.

[0178] 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 solution. The development time may be adjusted according to the (A) polyimide precursor contained in the insulating film forming material 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.

[0179] 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.

[0180] In addition, other organic materials constituting the insulating films 102 and 202, besides the cured product of the insulating film forming material of this disclosure, may be photosensitive resins, thermosetting non-conductive films (NCF), or thermosetting resins. 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.

[0181] [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 chemical mechanical polishing (CMP) 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 by CMP under conditions that selectively and deeply grind the terminal electrode 103, which is made of copper or the like. In step (c), the terminal electrode 103 may be polished by CMP so that each surface 103a of the terminal electrode 103 coincides with the surface 102a of the insulating film 102. The polishing method is not limited to CMP, and back grinding or the like may be used. Prior to polishing by CMP, mechanical polishing may be performed using a polishing device such as a surface planer, or these may be combined. 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.

[0182] 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 surface 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 using 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 using 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.

[0183] 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. Steps (c) and (d) may be performed at least one of the two, and it is preferable to perform both steps (c) and (d).

[0184] [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. In this embodiment, a large-area second semiconductor substrate 200 is prepared and then fragmented to obtain multiple semiconductor chips 205, but the method of preparing the semiconductor chips 205 is not limited to this.

[0185] [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.

[0186] [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, within 10°C. 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.

[0187] 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.

[0188] [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).

[0189] 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.

[0190] [Step (i)] Step (i) is a step of forming a plurality of pillars 300 on the connection surface 100a of the first semiconductor substrate 100 and between a plurality of semiconductor chips 205. In step (i), as shown in (a) of FIG. 4, a plurality of pillars 300, for example, made of copper are formed between the plurality of semiconductor chips 205. The pillars 300 can be formed from copper plating, conductive paste, copper pins, or the like. The pillars 300 are formed such that one end is connected to a terminal electrode of the first semiconductor substrate 100 that is not connected to the terminal electrode 203 of the semiconductor chip 205, and the other end extends upward. The pillars 300 are, for example, 10 μm or more and 100 μm or less in diameter and 10 μm or more and 1000 μm or less in height. Note that, between a pair of semiconductor chips 205, for example, 1 or more and 10000 or less pillars 300 may be provided.

[0191] [Step (j)] Step (j) is a step of molding a resin 301 on the connection surface 100a of the first semiconductor substrate 100 so as to cover the plurality of semiconductor chips 205 and the plurality of pillars 300. In step (j), as shown in (b) of FIG. 4, an epoxy resin or the like is molded to entirely cover the plurality of semiconductor chips 205 and the plurality of pillars 300. Examples of the molding method include compression molding, transfer molding, a method of laminating a film-shaped epoxy film, and the like. By this resin molding, the spaces between the plurality of pillars 300 and between the pillars 300 and the semiconductor chips 205 are filled with the resin 301. Thereby, a semi-finished product M1 filled with resin is formed. Note that, after molding an epoxy resin or the like, a curing process may be performed. Also, when steps (i) and (j) are performed substantially simultaneously, that is, when the pillars 300 are also formed at the timing of resin molding, the pillars may be formed using imprint, which is micro-transfer, and a conductive paste or electrolytic plating.

[0192] [Step (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.

[0193] [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.

[0194] [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.

[0195] According to the above embodiment, which is an example of a semiconductor device manufacturing method, the insulating film 102 of the first semiconductor substrate 100 and the insulating film 202 of the second semiconductor substrate 200 are cured products of the insulating film forming material of this disclosure. Since the cured products of the insulating film forming material of this disclosure have high heat resistance, deterioration of the insulating film caused by heating such as bonding is suppressed, and the occurrence of peeling, degradation, etc. of the insulating film is suppressed. Furthermore, since it is possible to lower the bonding temperature by using the insulating film forming material of this disclosure, the occurrence of defects such as deterioration of the insulating film is further reduced.

[0196] 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.

[0197] 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 side of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes). Simultaneously, a semiconductor substrate (second semiconductor substrate) is prepared, having a substrate body 421 (second substrate body), an insulating film portion 422 (second insulating film) provided on one side of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes) before the individualization of a plurality of semiconductor chips 420. Then, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before individualization of the 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.

[0198] 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.

[0199] 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.

[0200] 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 of the insulating film forming material 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.

[0201] 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]

[0202] 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.

[0203] (Synthesis Example 1 (Synthesis of A1)) 7.07 g of 3,3',4,4'-biphenyl 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 to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added at room temperature (25°C), 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.

[0204] (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.

[0205] <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%.

[0206] (Measurement conditions) Measuring instrument: Bruker BioSpin AV400M Magnetic field strength: 400MHz Reference substance: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0207] (Synthesis Example 2 (Synthesis of A2)) Polyimide precursor A2 was obtained by performing the same procedure as in Synthesis Example 1, except that DMAP was replaced with 3.6 g of 4,4'-diaminodiphenyl ether (ODA) and 0.2 g of m-phenylenediamine (MPD). The weight-average molecular weight of A2 was 25,000.

[0208] The esterification rate of A2 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%.

[0209] (Composite Example 3 (Composite of A3)) The same procedure as in Synthesis Example 1 was followed, except that DMAP was replaced with 5.67 g of 1,3-bis(3-aminophenoxy)benzene (APB-1,3,3), to obtain polyimide precursor A3. The weight-average molecular weight of A3 was 25,000.

[0210] The esterification rate of A3 was calculated by performing NMR measurements under the aforementioned conditions. The esterification rate was 80 mol%, and the proportion of unreacted carboxyl groups was 20 mol%.

[0211] (Composite example 4 (Composite of A4)) The same procedure as in Synthesis Example 1 was followed, except that DMAP was replaced with 3.89 g of ODA to obtain polyimide precursor A4. The weight-average molecular weight of A4 was 21,000.

[0212] 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%.

[0213] (Synthesis Example 5 (Synthesis of A5)) Polyimide precursor A5 was obtained by performing the same procedure as in Synthesis Example 1, except that ODPA was replaced with 6.71 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and DMAP was replaced with 3.89 g of ODA. The weight-average molecular weight of A5 was 20,000.

[0214] The esterification rate of A5 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%.

[0215] [Examples 1-11, Comparative Examples 1-2] (Preparation of insulating film forming material) The insulating film forming materials for Examples 1-11 and Comparative Examples 1-2 were prepared as follows, using the components and amounts shown in Table 1. The units for the amount 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 (25°C) in a general solvent-resistant container, and then pressure filtered using a filter with 0.2 μm pores. The following evaluations were performed using the obtained insulating film forming materials.

[0216] The components listed in Table 1 are as follows: • (A) Component: Polyimide precursor A1-A5 as described above (B) Component: Solvent B1: 3-Methoxy-N,N-dimethylpropanamide B2: γ-Butyrolactone B3: Dimethyl sulfoxide • (C) Ingredient: Ester moiety desorbing agent C1: Aniline diacetic acid C2:4-aminobenzamide C3: Phthalates, diazabicycloundecene salts C4: Nicotinamide

[0217] (D) Component; Photopolymerization initiator D1: 1-Phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime (PDO) D2: 4,4'-Bis(diethylamino)benzophenone (EMK) • (E) Component: Polymerizable monomer E1: Triethylene glycol dimethacrylate (TEGDMA) (F) Component; thermal polymerization initiator F1: Bis(1-phenyl-1-methylethyl)peroxide (G) Ingredient: Polymerization inhibitor G1: N,N'-Hexane-1,6-diyrbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] • Rust inhibitor Rust inhibitor 1:1H-benzotriazole Rust inhibitor 2: 5-amino-1H-tetrazol

[0218] (Measurement of the glass transition temperature (Tg) of the cured film) Using the insulating film forming materials of Examples 1 to 11 and Comparative Examples 1 to 2, cured films were formed as follows, and then the storage modulus was measured. First, a photosensitive insulating film forming material was spin-coated onto a Si substrate, heated and dried on a hot plate at 95°C for 120 seconds, and then dried again at 105°C for 120 seconds to form a photosensitive resin film with a thickness of approximately 10 μm after drying.

[0219] The obtained photosensitive resin film was broadband (BB) exposed using a mask aligner MA-8 (manufactured by Suss Microtec) at the exposure levels shown in Table 1. The exposed resin film was developed with cyclopentanone using a coater developer ACT8 (manufactured by Tokyo Electron Limited) for a total development time of 20 seconds 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 230°C for 2 hours to obtain a patterned cured product with a thickness of 10 μm. The obtained patterned cured product was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and a 10 mm wide patterned cured product was peeled off from the Si substrate.

[0220] Using a Hitachi High-Tech Science Corporation TMA7100 model and a tensile jig, the elongation (expansion) of the sample was measured in the temperature range of 50°C to 350°C under the conditions of an initial sample length of 10 mm, a heating rate of 5°C / min, and a load of 10 g. The glass transition temperature (Tg) was defined as the temperature at the start of the change, which was determined by the tangent method at the point where a rapid change in the expansion rate occurred in the curve obtained by the above method.

[0221] (Evaluation of bonding properties) The insulating film forming materials of Examples 1-11 and Comparative Examples 1-2 were spin-coated onto an 8-inch Si wafer using a spin coater and dried to form a resin film. A mask capable of creating a circular resin film with a diameter of 180 mm was placed over the obtained resin film, and it was irradiated with light of a wavelength of 365 nm for a predetermined exposure amount. Subsequently, it was developed with cyclopentanone 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. The obtained patterned resin film was cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at 230°C for 2 hours to obtain a patterned cured film with a thickness of 10 μm.

[0222] A resin-coated tip was obtained by breaking down a portion of the cured film into 5mm square pieces using a blade dicer (DISCO DFD-6362). The obtained resin-coated chips were applied to the cured film using a thermocompression press (manufactured by Showa Denko Materials Co., Ltd.) under a predetermined pressure and pressed for 15 seconds at the bonding temperature shown in Table 1 to produce a cured film with chips attached. For each insulating film forming material, 50 chips pressed onto the cured film were evaluated as described below.

[0223] At room temperature (25°C), a load was applied to the chip using tweezers to the resulting cured film with the attached chip. The adhesion defects between the resin interface or between the resin and the substrate were observed to determine whether the resin-coated chip, once pressed, peeled off the cured film. The evaluation criteria for adhesion were as follows. The results are shown in Table 2. An evaluation of A or B indicates that the product is considered practically acceptable. -Evaluation Criteria for Bonding Properties- A: Out of 50 chips, 5 or fewer chips showed bonding defects. B: Out of 50 chips, more than 5 but less than or equal to 7 chips showed bonding defects. C: Out of 50 chips, more than 7 showed bonding defects.

[0224] [Table 1]

[0225] As shown in Table 1, in Examples 1 to 11, the occurrence of adhesion defects was suppressed even when the bonding temperature was lower compared to Comparative Examples 1 to 2. On the other hand, in Comparative Examples 1 and 2, lowering the bonding temperature resulted in a higher incidence of bonding defects. [Explanation of Symbols]

[0226] 1,1a,401…Semiconductor device, 10…First semiconductor chip, 20…Second semiconductor chip, 30…Pillar portion, 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, 20 5...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 having an ester moiety, (B) a solvent, and (C) an ester moiety desorbing agent that promotes the desorption of the ester moiety, The content of the (C) ester moiety desorbing agent is 1 to 7 parts by mass per 100 parts by mass of the (A) polyimide precursor, in a hybrid bonding insulating film forming material.

2. The hybrid bonding insulating film forming material according to claim 1, 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.

3. The hybrid bonding insulating film forming material according to claim 2, 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 is 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, It represents an alkyl group or a phenyl group, where n is an integer of 1 or 2 or more. ) Or it represents a divalent group formed by combining at least two of these.

4. The hybrid bonding insulating film forming material according to claim 2 or claim 3, 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.

5. In the above general formula (1), the R ６ and R ７ The hybrid bonding insulating film forming material according to any one of claims 2 to 4, wherein the monovalent organic group in is one of a 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.

6. Claims 1 to 5, wherein the glass transition temperature when cured is 50°C to 250°C A hybrid bonding insulating film forming material as described in item 1.

7. A hybrid bonding insulating film forming material according to any one of claims 1 to 6, wherein the coefficient of thermal expansion when cured is 150 ppm / K or less.

8. A hybrid bonding insulating film forming material according to any one of claims 1 to 7, further comprising (D) a photopolymerization initiator and (E) a polymerizable monomer.

9. A first semiconductor substrate is prepared, having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body. A semiconductor chip is prepared, comprising a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, The first electrode and the second electrode are joined together, and the first organic insulating film and the second organic insulating film are bonded together. A method for manufacturing a semiconductor device, using a hybrid bonding insulating film forming material according to any one of claims 1 to 8 to produce at least one of the first organic insulating film and the second organic insulating film.

10. A method for manufacturing a semiconductor device according to claim 9, wherein the first electrode and the second electrode are bonded together after the first organic insulating film and the second organic insulating film are bonded together.

11. The method for manufacturing a semiconductor device according to claim 9 or 10, wherein the semiconductor chip is prepared by framing a second semiconductor substrate having a second substrate body, a plurality of second electrodes and a second organic insulating region provided on one surface of the semiconductor chip substrate body.

12. The method for manufacturing a semiconductor device according to any one of claims 9 to 11, wherein the bonding of the first organic insulating film and the second organic insulating film is performed at a temperature such that the temperature difference between the semiconductor chip and the first semiconductor substrate is 10°C or less.

13. A method for manufacturing a semiconductor device according to any one of claims 9 to 12, wherein the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film in the manufactured semiconductor device is 0.1 μm or more.

14. A method for manufacturing a semiconductor device according to any one of claims 9 to 13, wherein, before either bonding the first electrode and the second electrode, or bonding the first organic insulating film and the first organic insulating film, one surface of the first semiconductor substrate and at least one side of the one surface of the semiconductor chip are polished.

15. The method for manufacturing a semiconductor device according to claim 14, which includes chemical mechanical polishing.

16. The method for manufacturing a semiconductor device according to claim 15, further comprising mechanical polishing.

17. A method for manufacturing a semiconductor device according to any one of claims 9 to 16, wherein the thickness of the first organic insulating film is greater than the thickness of the first electrode, and the thickness of the second organic insulating film is greater than the thickness of the second electrode.

18. 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, The semiconductor chip comprises a semiconductor chip substrate body and a semiconductor chip having a second organic insulating film and a second electrode provided on one side of the semiconductor chip substrate body. The first organic insulating film and the second organic insulating film are joined together, and the first electrode and the second electrode are joined together, A semiconductor device in which at least one of the first organic insulating film and the second organic insulating film is a cured product of the hybrid bonding insulating film forming material according to any one of claims 1 to 8.

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