Polyimide precursor, hybrid bonding insulating film forming material, method for manufacturing a semiconductor device, and semiconductor device.

Abstract

The present invention provides a polyimide precursor with excellent adhesion to a substrate, a hybrid bonding insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device. [Solution] A polyimide precursor having a structure derived from an amine compound containing a siloxane bond.

Description

[Technical Field]

[0001] This disclosure relates to a polyimide precursor, 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, To achieve fine bonding of wiring between devices, the use of hybrid bonding technology, which is used in W2W (Wafer-to-Wafer) bonding, is being considered.

[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 failure occurring at the interface between the substrate and the organic insulating film when exposed to high temperatures during C2W bonding. It has become clear that when a silane coupling agent is added from the viewpoint of suppressing adhesion failure, self-condensation of the silane coupling agent may occur, and it may precipitate as a foreign substance.

[0009] This disclosure is made in view of the above, and includes a polyimide precursor with excellent adhesion to a substrate, a hybrid bonding insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device The purpose is to provide a place. [Means for solving the problem]

[0010] The specific means for achieving the aforementioned objectives are as follows: <1> A polyimide precursor having a structure derived from an amine compound containing a siloxane bond. <2> The main chain consists of at least one selected from the group comprising polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. <1> The polyimide precursor described above. <3> Having a structural unit represented by the following general formula (1) <1> or <2> The polyimide precursor 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> The polyimide precursor 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) above, the divalent organic group represented by Y is the group represented by the following formula (H). <3> or <4> The polyimide precursor described above.

Chem.

Chem.

[0011] According to this disclosure, it is possible to provide a polyimide precursor with excellent adhesion to a substrate, a hybrid bonding insulating film forming material, 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 measuring the thickness 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] <Polyimide precursor> The polyimide precursor of this disclosure has a structure derived from an amine compound containing a siloxane bond. Hereinafter, the amine compound containing a siloxane bond will also be referred to as the "specific amine compound." The reason why the polyimide precursor exhibits excellent adhesion to the substrate with the above structure is not clear, but it is thought that the inclusion of the siloxane bond contributes to this effect. The polyimide precursor of this disclosure also exhibits excellent adhesion to the substrate when cured. Furthermore, since the polyimide precursor of this disclosure exhibits excellent adhesion to the substrate, it is possible to omit the addition of a silane coupling agent, and as a result, it is possible to suppress the precipitation of self-condensed products of the silane coupling agent as foreign matter.

[0016] The group that bonds to the silicon atom of the siloxane bond is not particularly limited, and includes alkyl groups, aldehydes, etc. Examples include coxy groups, aryl groups, and aralkyl groups. The group bonded to the silicon atom of the siloxane bond may be a single group or two or more groups.

[0017] The number of carbon atoms in the alkyl group bonded to the silicon atom of the siloxane bond is preferably 1 to 20, preferably 1 to 12, and more preferably 1 to 8. Specific examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl groups, among which the methyl group is preferred.

[0018] The aryl group bonded to the silicon atom of the siloxane bond preferably has 6 to 18 carbon atoms and 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 such aryl groups include phenyl groups and naphthyl groups, with phenyl groups being preferred.

[0019] The linking group that connects the silicon atom of the siloxane bond to the nitrogen atom of the amine is not particularly limited, and examples include alkylene groups and arylene groups. The alkylene group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10. The arylene group preferably has 6 to 18 carbon atoms and may be unsubstituted or substituted with substituents. Specific examples of substituents when the aryl group has substituents include halogen atoms, alkoxy groups, and hydroxyl groups. Among these, the arylene group is preferably a phenylene group. Among these, the linking group is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably a methylene group, an ethylene group, or a propylene group.

[0020] From the viewpoint of increasing heat resistance, the number of silicon atoms in the siloxane bond is preferably 2 to 8, more preferably 2 or 3, and even more preferably a disiloxane bond. The disiloxane bond is a bond represented as Si-O-Si. Of the three bonds other than the bond between the silicon atom (Si) and the oxygen atom (O), one bond is bonded to the amine either directly or via a linking group.

[0021] The number of amine moieties in the specific amine compound is not particularly limited, and monoamine compounds and diamine compounds are preferred. Monoamine compounds and diamine compounds may be used in combination. When the specific amine compound is a diamine compound, the structure derived from the diamine compound containing a siloxane bond is positioned in the main chain of the polyimide precursor. When the specific amine compound is a monoamine compound, the structure derived from the monoamine compound containing a siloxane bond is positioned in the terminal portion of the polyimide precursor.

[0022] Examples of specific amine compounds include 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 3-aminopropyltriethoxysilane. In the polyimide precursor of this disclosure, the structure derived from the specific amine compound may be present as a single entity or as two or more entities.

[0023] The polyimide precursors of this disclosure may further have structures derived from amine compounds that do not contain siloxane bonds. Examples of amine compounds that do not contain siloxane bonds (hereinafter also referred to as "other amine compounds") include amine compounds represented by H2N-Y-NH2, which will be described later. Here, Y is synonymous with Y in general formula (1) (except in the case of a divalent group having a polysiloxane structure).

[0024] The polyimide precursors disclosed herein are structures derived from specific amine compounds and other amine compounds. From the viewpoint of improving adhesion to the substrate, the proportion of the structure derived from the specific amine compound to the total amount of the structure derived from the substrate is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0025] The polyimide precursor of this disclosure preferably has a main chain of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. When these are the main chains, the polyimide skeleton becomes the main chain in the cured product, and the excellent effects of polyimide tend to be easily achieved. Polyamic acid esters and polyamic acid amides are compounds in which at least some of the hydrogen atoms of the carboxyl groups in polyamic acid are replaced with monovalent organic groups, and polyamic acid salts are compounds in which at least some of the carboxyl groups in polyamic acid form a salt structure with a basic compound with a pH of 7 or higher.

[0026] The polyimide precursors of this disclosure preferably have polymerizable unsaturated bonds, and more preferably the polyamic acid, polyamic acid ester, polyamic acid salt, or polyamic acid amide has polymerizable unsaturated bonds.

[0027] The polyimide precursor preferably has a structural unit represented by the following general formula (1). This tends to result in a semiconductor device with a highly reliable insulating film.

[0028] [ka]

[0029] In general formula (1), X represents a tetravalent organic group and Y represents a divalent organic group. 6 and R 7 Each of these independently represents either a hydrogen atom or a monovalent organic group. The polyimide precursor may have multiple structural units represented by the above general formula (1), and X, Y, R in the multiple structural units 6 and R 7 These may be the same or different. Note, R 6 and R 7 The combination of each is not particularly limited, as long as they are independently hydrogen atoms or monovalent organic groups. For example, both may be hydrogen atoms, one may be a hydrogen atom and the other a monovalent organic group as described later, or both may be the same or different monovalent organic groups. As mentioned above, when the polyimide precursor has multiple structural units represented by the above general formula (1), the R of each structural unit 6 and R 7 The combinations may be the same or different.

[0030] 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.

[0031] 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.

[0032] Specific examples of tetravalent organic groups represented by X include the groups represented by formulas (A) to (G) 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.

[0033] [ka]

[0034] 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.

[0035] In formula (E), C is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), or phenylene. Group, ester bond (-OC(=O)-), silylene bond (-Si(R) A )2-; Two R A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. C preferably contains an ether bond, and more preferably is an ether bond. Furthermore, C may have a structure represented by the following formula (C1).

[0036] [ka]

[0037] 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.

[0038] 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.

[0039] 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 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. These are some examples.

[0040] Specific examples of the tetravalent organic group represented by X may be the groups represented by the following formulas (J) to (O).

[0041] [ka]

[0042] 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.

[0043] Specific examples of divalent aromatic groups represented by Y are shown in the following formulas (G) to (I): Examples of such groups can be listed. Among them, from the viewpoint of obtaining an insulating film that is highly flexible and in which the generation of voids at the bonding interface is further suppressed, the group represented by the following formula (H) is preferred, and more preferably D is a group represented by the following formula (H), in which case D is a single bond or an ether bond.

[0044] [ka]

[0045] 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 A Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), Siloxane bond (-O-(Si(R B )2-O-) n ; Two R's B Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more. ) or a divalent group formed by combining at least two of these. Furthermore, D may be the structure represented by formula (C1) above. Specific examples of D in formula (H) are the same as specific examples of C in formula (E). In formula (H), D is preferably 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In equations (G) to (H), n is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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 structure may be of one type or of two or more types.

[0054] The divalent organic group represented by Y may be a divalent group having a polysiloxane structure, preferably a divalent group having a disiloxane structure or a divalent group having a trisiloxane structure, and more preferably a divalent group having a disiloxane structure (-Si-O-Si-). Examples of divalent groups having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atoms in the polysiloxane structure are bonded to hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or aryl groups having 6 to 18 carbon atoms. Specific examples of C1-C20 alkyl groups that bond to silicon atoms in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl groups. Among these, the methyl group is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of substituents on the aryl group include halogen atoms, alkoxy groups, and hydroxyl groups. Specific examples of aryl groups having 6 to 18 carbon atoms include phenyl groups, naphthyl groups, and benzyl groups. Among these, the phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types. The silicon atoms constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group, etc.

[0055] 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'''). Preferably, the group is represented by the following formula (H') or formula (H'').

[0056] [ka]

[0057] 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.

[0058] 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).

[0059] R 6 and R 7 Each of these independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably one of the groups represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, even more preferably containing an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and particularly preferably containing a group represented by the following general formula (2). When the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the transmittance of i-rays is high, and good cured products tend to be formed even when curing at low temperatures of 400°C or below. Furthermore, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond portion is removed by the (C) compound.

[0060] Specific examples of aliphatic hydrocarbon groups with 1 to 4 carbon atoms include the methyl group, ethyl group, and n-propyl group. Examples include ethyl groups, isopropyl groups, n-butyl groups, and t-butyl groups, with ethyl groups, isobutyl groups, and t-butyl groups being preferred.

[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 R x This represents a divalent linking group.

[0063] 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.

[0064] R in general formula (2) 8 ~R 10 As for combinations, R 8 and R 9 R is a hydrogen atom, 10 A combination of hydrogen atoms or methyl groups is preferred.

[0065] R in general formula (2) x The linking group is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups. R x The number of carbon atoms in the compound is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0066] 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).

[0067] 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%.

[0068] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0069] [ka]

[0070] 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.

[0071] In general formula (2'), q is an integer between 1 and 10, preferably between 2 and 5, and more preferably 2 or 3.

[0072] 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%.

[0073] 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. The polyimide precursor may also be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0074] 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, and 2,3,5,6-pyridineteto Dianhydride of tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic acid dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic acid 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 Examples include 3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonyldiphthalic acid dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. ru. Tetracarboxylic acid dianhydrides may be used individually or in combination of two or more types.

[0075] 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. Diamine compounds may be used individually or in combination of two or more.

[0076] 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. Tetracarboxylic dianhydrides represented by general formula (8), dianhydrides represented by H2N-Y-NH2 The amine compounds and the compounds represented by R-OH may 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-dimethylpropanamide, with 3-methoxy-N,N-dimethylpropanamide 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).

[0077] 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. 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. 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 produce 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.

[0078] [ka]

[0079] 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.

[0080] 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 Compounds in which a hydroxyl group is bonded, or compounds in which a hydroxyl group is bonded to the terminal methylene group of the group represented by general formula (2'), etc. 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, and 2-hydroxyethyl acrylate. Examples include roxypropyl, 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.

[0081] There are no particular restrictions on the molecular weight of the polyimide precursor in this disclosure; 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.

[0082] <Hybrid bonding insulating film forming material> The hybrid bonding insulating film forming material of the present disclosure contains the polyimide precursor of the present disclosure and a solvent. Hereinafter, the hybrid bonding insulating film forming material of the present disclosure will also be referred to as the insulating film forming material of the present disclosure, the polyimide precursor of the present disclosure will also be referred to as (A) polyimide precursor, and the solvent will also be referred to as (B) solvent or (B) component.

[0083] The insulating film forming material of this disclosure may further contain a dicarboxylic acid, and the 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 in the dicarboxylic acid. For example, when synthesizing the (A) 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 polyimide precursor (A), a methacrylic group derived from the dicarboxylic acid can be introduced into the polyimide precursor by reacting a portion of the amino group of the diamine compound with the carboxyl group of the dicarboxylic acid.

[0084] [ka]

[0085] 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, thereby suppressing the generation of voids. It tends to be controllable. The polyimide resin referred to here is a resin that has an imide skeleton in all or part of its resin backbone. It is preferable that the polyimide resin is soluble in the solvent in the insulating film forming material using a polyimide precursor.

[0086] 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.

[0087] [ka]

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] The insulating film forming material of this disclosure comprises (A) a polyimide precursor and (B) a solvent, and optionally includes (C) a photopolymerization initiator, (D) a polymerizable monomer, (E) a thermal polymerization initiator, (F) a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, a nitrogen-containing compound, etc., and may also include other components and unavoidable impurities to the extent that they do not impair the effects of this disclosure. Preferably, the insulating film forming material of this disclosure further includes component (D). Below, (C) photopolymerization initiator is component (C), (D) polymerizable monomer is component (D), and (E) The thermal polymerization initiator is also referred to as component (E), and the polymerization inhibitor is also referred to as component (F).

[0093] 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 and (B) Component, (A) component, (B) component and (D) component, (A) component, (B) component, (D) component and (E) component, (A) component, (B) component and (D) to (F) components, (A) component, (B) component and (D) to (F) components, and (C) component, antioxidant, coupling agent, surfactant, leveling agent, rust inhibitor, and nitrogen-containing compound, at least one selected from this group. It may consist of [something].

[0094] ((B) Solvent) The insulating film forming material of this disclosure includes component (B). Component (B) preferably includes 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.

[0095] [ka]

[0096] In formulas (3) to (7), R 1 , R 2 , R 8 and R 10 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 3 ~R 7 and R 9 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, and u is an integer from 0 to 3.

[0097] In equation (3), s is preferably 0. In equation (4), R 2The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, and more preferably 1. In formula (5), R 3 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a propyl group or a butyl group. R 4 and R 5 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. In formula (6), R 6 to R 8 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. r is preferably 0 or 1, and more preferably 0. In formula (7), R 9 and R 10 The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. u is preferably 0 or 1, and more preferably 0.

[0098] Component (B) may, for example, be at least one selected from the compounds represented by formula (4), formula (5), formula (6) and formula (7), and may also be the compound represented by formula (5) or the compound represented by formula (7).

[0099] Specific examples of component (B) include the following compounds.

[0100] Chemical formula

[0101] Component (B) contained in the insulating film forming material of the present disclosure is not limited to the aforementioned compounds, and may be 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, or the like.

[0102] 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.

[0103] Examples of ether-type solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Examples include 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.

[0104] (B) Preferred solvents for component (B) include γ-butyrolactone, cyclopentanone, and ethyl lactate.

[0105] 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.

[0106] 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).

[0107] 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).

[0108] ((C) Photopolymerization initiator) The insulating film forming material of this disclosure preferably contains (C) a photopolymerization initiator. This reduces 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.

[0109] (C)Specific examples of components include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, o-methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl Benzophenone derivatives such as lucetone, dibenzyl 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, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone. Benzyl derivatives; benzyl derivatives such as benzyl, benzyl dimethyl 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-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxy Examples include oxime derivatives such as cypropanetrione-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; 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, as well as Irgacure OXE03 (manufactured by BASF) and Irgacure OXE04 (manufactured by BASF). (C) Component may be used alone or in combination of two or more types. Among these, oxime compound derivatives are preferred because they do not contain metal elements, are highly reactive, and offer high sensitivity.

[0110] If the insulating film forming material of this disclosure contains component (C), the content of component (C) 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 the polyimide precursor (A), from the viewpoint of ensuring that the photocrosslinking is uniform in the film thickness direction.

[0111] 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.

[0112] ((D) Polymerizable monomer) The insulating film forming material of this disclosure preferably contains a polymerizable monomer (D). Component (D) preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of being suitably polymerizable in combination with a photopolymerization initiator. From the viewpoint of improving crosslinking density and photosensitivity, it is preferable to have 2 to 6 groups containing polymerizable unsaturated double bonds, and more preferably 2 to 4 groups. Polymerizable monomers may be used individually or in combination of two or more.

[0113] 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 tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol Examples include lithritol 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.

[0114] 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.

[0115] Component (D) is not limited to compounds having a polymerizable unsaturated double bond group, but may also be a compound having a polymerizable group other than an unsaturated double bond group (e.g., an oxirane ring).

[0116] If the insulating film forming material of the present disclosure contains component (D), the content of component (D) is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 1 to 75 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of the polyimide precursor (A).

[0117] ((E) 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 (E) a thermal polymerization initiator.

[0118] (E)Specific examples of component include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide, and dialdehydes such as dicumyl peroxide and di-t-butyl peroxide. Examples include diacyl peroxides such as quill peroxide, dilauroyl peroxide, and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; and bis(1-phenyl-1-methylethyl)peroxide. The thermal polymerization initiator may be used alone or in combination of two or more.

[0119] If the insulating film forming material of this disclosure contains component (E), the content of component (E) may be 0.1 to 20 parts by mass, 1 to 15 parts by mass, or 1 to 10 parts by mass per 100 parts by mass of the polyimide precursor.

[0120] ((F) Polymerization inhibitor) The insulating film forming material of this disclosure may contain component (F) from the viewpoint of ensuring good storage stability. Examples of polymerization inhibitors include radical polymerization inhibitors and radical polymerization suppressants.

[0121] Specific examples of component (F) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenantraquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-tholquinone, tannic acid, parabenzylaminophenol, nitrosamines, hindered phenol compounds, etc. Polymerization inhibitors may be used alone or in combination of two or more. Combining two or more polymerization inhibitors tends to make it easier to adjust the photosensitive properties due to differences in reactivity. Hindered phenol compounds may have both the function of a polymerization inhibitor and the function of an antioxidant described later, or they may have only one of the functions.

[0122] 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'-thio-bis(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)-isosia Nurate, 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,3 H,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, Examples include -2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-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.

[0123] If the insulating film forming material of this disclosure contains component (F), the content of component (F) is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, per 100 parts by mass of polyimide precursor (A), from the viewpoint of storage stability of the insulating film forming material and heat resistance of the resulting cured product.

[0124] 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.

[0125] (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.

[0126] 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.

[0127] 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).

[0128] (Coupling agent) The insulating film forming material of this disclosure may contain a coupling agent, but from the viewpoint of suppressing self-condensation of the coupling agent, it is preferable to reduce the amount of coupling agent added. For example, the amount of coupling agent added is more preferably less than 0.1 parts by mass per 100 parts by mass of (A) polyimide precursor, and even more preferably 0 parts by mass. During heat treatment, the coupling agent either crosslinks with (A) the polyimide precursor or polymerizes itself. This tends to improve the adhesion between the resulting cured product and the substrate.

[0129] The specific examples of coupling agents are not particularly limited. As for coupling agents, 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, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl Examples include silane coupling agents such as 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.

[0130] 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, even more preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 2 parts by mass, per 100 parts by mass of the polyimide precursor (A).

[0131] (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.

[0132] Examples of surfactants or leveling agents include polyoxyethylene uraryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.

[0133] Surfactants and leveling agents may be used individually or in combination of two or more types.

[0134] 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.

[0135] (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.

[0136] 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, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl- Examples include 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-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole.

[0137] 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.

[0138] Rust inhibitors may be used individually or in combination of two or more types.

[0139] 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.

[0140] The resin composition of this disclosure may contain a nitrogen-containing compound from the viewpoint of promoting the imidation reaction of the polyimide precursor to obtain a highly reliable cured product.

[0141] Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, etc. Among these, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, and 2,2'-(4-methylphenylimino)diethanol are preferred. Nitrogen-containing compounds may be used individually or in combination of two or more.

[0142] The nitrogen-containing compound preferably includes a compound represented by the following formula (17).

[0143] [ka]

[0144] In formula (17), R 31A to R 33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group, and at least one (preferably one) of R 31A to R 33A is a monovalent aromatic group. R 31A to R 33A may mutually form a ring structure between adjacent groups. Examples of the formed ring structure include 5-membered rings, 6-membered rings and the like which may have a substituent such as a methyl group, a phenyl group, or the like. A hydrogen atom in the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than a hydroxy group.

[0145] In formula (17), it is preferable that at least one (preferably one) of R 31A to R 33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group.

[0146] In formula (17), for the monovalent aliphatic hydrocarbon group of R 31A to R 33A , the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6. Preferred examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group and the like.

[0147] In formula (17), the monovalent aliphatic hydrocarbon group having a hydroxy group for R 31A to R 33A is preferably a group obtained by bonding one or more hydroxy groups to the monovalent aliphatic hydrocarbon group of R 31A to R 33A , and more preferably a group obtained by bonding 1 to 3 hydroxy groups. Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a methylol group, a hydroxyethyl group and the like, and among these, a hydroxyethyl group is preferable.

[0148] In formula (17), R 31A to R 33AExamples 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.

[0149] R in equation (17) 31A ~R 33A The monovalent aromatic group may have substituents. Examples of substituents include R of formula (17). 31A ~R 33A The monovalent aliphatic hydrocarbon group and the R of formula (17) described above. 31A ~R 33A Examples include monovalent aliphatic hydrocarbon groups having a hydroxyl group.

[0150] If the resin composition of the present disclosure contains a nitrogen-containing compound, the content of the nitrogen-containing compound is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyimide precursor (A).

[0151] <Semiconductor device> The semiconductor device of this 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 joined 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 this 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.

[0152] <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.

[0153] 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.

[0154] (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.

[0155] 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 the second semiconductor chip 2 The 0 is mounted in a three-dimensional mounting structure. 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.

[0156] 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.

[0157] The redistribution layer 40 is a wiring layer that has the function of terminal pitch conversion, which is a function of the package substrate. Yes, it is a layer in which a redistribution pattern is formed using polyimide and copper wiring, etc., 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)).

[0158] 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.

[0159] 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.

[0160] (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.

[0161] 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).

[0162] 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).

[0163] [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.

[0164] 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.

[0165] Even if both the insulating films 102 and 202 used in step (a) and step (b) are cured products of the insulating film-forming material of the present disclosure, one of the insulating films 102 and 202 may be a cured product of the insulating film-forming material of the present disclosure and the other may be another cured product. Examples of the insulating film-forming material for forming another cured product include those that do not contain the (A) polyimide precursor of the present disclosure. Examples of other resins include insulating film-forming materials containing polyimide precursors, polyimides, polyamideimides, benzocyclobutene (BCB), polybenzoxazole (PBO), PBO precursors and the like that do not have a structure derived from an amine containing a siloxane bond. The tensile elastic modulus at 25°C of the insulating films 102 and 202 is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, still more preferably 3.0 GPa or less, particularly preferably 2.0 GPa or less, and even more preferably 1.5 GPa or less.

[0166] The coefficient of thermal expansion of the insulating films 102 and 202 is preferably 150 ppm / K or less, more preferably 100 ppm / K or less, and still more preferably 90 ppm / K or less.

[0167] The thickness of the insulating films 102 and 202 is preferably 0.1 μm to 50 μm, more preferably 1 μm to 15 μm. This makes it possible to shorten the processing time in the subsequent polishing step while ensuring the uniformity of the film thickness of the insulating film.

[0168] From the viewpoint of facilitating the work in step (c) and step (d) and simplifying these steps, the polishing rate of the insulating film 102 is 0.1 to 5 times the polishing rate of the terminal electrode 103 It is preferable to satisfy at least one of the following conditions (and preferably satisfy both): the polishing rate of the insulating film 202 is 0.1 to 5 times the polishing rate of the terminal electrode 203. As an example, when the terminal electrode 103 or 203 is made of copper and the polishing rate of copper is 50 nm / min, the polishing rate of the insulating film 102 or 202 is preferably 200 nm / min or less (4 times or less the polishing rate of copper), more preferably 100 nm / min or less (2 times or less the polishing rate of copper), and still more preferably 50 nm / min or less (equal to or less than the polishing rate of copper).

[0169] Next, a method for producing an insulating film will be described. The insulating film is obtained by curing an insulating film-forming material. Examples of the method for producing the above-described insulating film include a method comprising: (α) a step of applying an insulating film-forming material onto a substrate and drying the material to form a resin film, and a step of heat-treating the resin film; and (β) a method comprising: forming a film with a constant thickness on a release-treated film using an insulating film-forming material, then transferring the resin film to a substrate by a lamination method, and a step of heat-treating the resin film formed on the substrate after the transfer. From the viewpoint of flatness, the method of (α) above is preferable.

[0170] Examples of application methods for the insulating film-forming material include spin coating, inkjet coating, and slit coating.

[0171] In the spin coating method, the insulating film-forming material may be spin-coated under, for example, the following conditions: 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 / sec to 15,000 rpm / sec, and a rotation time of 30 seconds to 300 seconds.

[0172] A drying step may be included after applying the insulating film-forming material to a support, a film, or the like. Drying may be performed using a hot plate, an oven, or the like. 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] Equipment used for heat treatment includes quartz tube furnaces, hot plates, and rapid surges. Examples include malannealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, and microwave curing furnaces.

[0177] 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.

[0178] Alternatively, when providing the insulating film 202 on one surface 201a of the second substrate body 201 and then providing the multiple terminal electrodes 203, a method may be used that includes, for example, the steps of: applying an insulating film forming material other than the insulating film forming material of the present disclosure onto the substrate; drying to form a resin film; applying and drying the insulating film forming material of the present disclosure, which is a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material, onto the resin film, then pattern exposure, developing with a developer to obtain a patterned resin film; and heat-treating the patterned resin film. This makes it possible to obtain a cured patterned insulating film.

[0179] Pattern exposure involves exposing a predetermined pattern to light, for example, through a photomask. The active light to be irradiated can be i-rays, broadband ultraviolet light, visible light, or radiation, with i-rays being preferred. Exposure equipment can include parallel exposure machines, projection exposure machines, steppers, scanner exposure machines, etc.

[0180] A patterned resin film, which is a resin film with a pattern formed on it, can be obtained by developing it after exposure. If the insulating film forming material of this disclosure is a negative-type photosensitive insulating film forming material, the unexposed areas are removed with a developer. For use as a developer for negative film, an organic solvent suitable for photosensitive resin films can be used alone, or a mixture of a good solvent and a poor solvent as appropriate. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, cyclopentanone, cyclohexanone, and cycloheptanone. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

[0181] 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 developer for positive film include tetramethylammonium hydroxide (TMAH) solution and sodium carbonate solution.

[0182] 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.

[0183] The development time can be, for example, twice the time it takes for a photosensitive resin film to completely dissolve when immersed in the developer. The development time may be adjusted according to the (A) polyimide precursor contained in the insulating film forming material of this disclosure, for example, preferably 10 seconds to 15 minutes, and more preferably 10 seconds to 5 minutes. From a productivity standpoint, 20 seconds to 5 minutes is even more preferable.

[0184] The pattern resin film may be washed with a rinsing solution after development. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in an appropriate mixture, or these may be used in combination stepwise.

[0185] Note that as organic materials constituting the insulating films 102 and 202 other than the cured product of the insulating film forming material of the present disclosure, photosensitive resins, thermosetting non-conductive films (NCF: Non Conductive Film ), or a thermosetting resin may be used. The organic material may be an underfill material. Further, the organic material constituting the insulating films 102 and 202 may be a heat-resistant resin.

[0186] [Step (c) and Step (d)] Step (c) is a step of polishing the first semiconductor substrate 100. In step (c), as shown in (a) of FIG. 3, the first semiconductor substrate 100 is subjected to chemical mechanical polishing (CMP) such that each surface 103a of the terminal electrodes 103 is at a position equal to or slightly higher (protruding) than the surface 102a of the insulating film 102. The one surface 101a side, which is the surface of the semiconductor substrate 100, is polished. In step (c), for example, the first semiconductor substrate 100 can also be polished by CMP under conditions that selectively and deeply grind the terminal electrodes 103 made of copper or the like. In step (c), polishing may be performed by CMP so that each surface 103a of the terminal electrodes 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 employed. Prior to polishing by CMP, mechanical polishing may be performed by a polishing apparatus such as a surface planarer. When each surface 103a of the terminal electrodes 103 is at a position slightly higher than the surface 102a of the insulating film 102, the height difference between each surface 103a and the surface 102a may be 1 nm to 150 nm, or 1 nm to 15 nm.

[0187] 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.

[0188] 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, and steps (c) and ( It is preferable to perform both of the above (d).

[0189] [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.

[0190] [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.

[0191] [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.

[0192] The thickness of the organic insulating film, which is the insulating junction where insulating film 102 and insulating film portion 202b are joined. The particle size is not particularly limited and may be, for example, 0.1 μm or larger, 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.

[0193] [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).

[0194] 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.

[0195] [Step (i)] Step (i) is a step of forming a plurality of pillars 300 between a plurality of semiconductor chips 205 on the connection surface 100a of the first semiconductor substrate 100. In step (i), as shown in Figure 4(a), a plurality of pillars 300 made of, for example, copper are formed between the plurality of semiconductor chips 205. The pillars 300 can be formed from copper plating, conductive paste, copper pins, etc. One end of the pillar 300 is formed to be connected to a terminal electrode of the first semiconductor substrate 100 that is not connected to the terminal electrode 203 of the semiconductor chip 205, and the other end extends upward. The pillar 300 has, for example, a diameter of 10 μm or more and 100 μm or less, and a height of 10 μm or more and 1000 μm or less. Note that, for example, one to 10,000 pillars 300 may be provided between a pair of semiconductor chips 205.

[0196] [Process (j)] Step (j) is a step of molding resin 301 onto the connection surface 100a of the first semiconductor substrate 100 so as to cover the multiple semiconductor chips 205 and the multiple pillars 300. In step (j), as shown in Figure 4(b), epoxy resin or the like is molded to completely cover the multiple semiconductor chips 205 and the multiple pillars 300. Examples of molding methods include compression molding, transfer molding, and lamination of a film-like epoxy film. This resin molding fills the spaces between the multiple pillars 300 and the spaces between the pillars 300 and the semiconductor chips 205 with resin 301. This forms a semi-finished product M1 filled with resin. Note that a curing treatment may be performed after molding with epoxy resin or the like. Furthermore, when steps (i) and (j) are performed almost simultaneously, i.e., when the pillar 300 is formed at the same time as the resin molding, the pillar may be formed using a fine transfer method called imprinting and a conductive paste or electroplating.

[0197] [Process (k)] In process (k), the semi-finished product M1, which consists of the resin 301 molded in process (j), multiple pillars 300, and multiple semiconductor chips 205, is thinned by grinding from the resin 301 side, and the semi-finished product This is the process for obtaining M2. In process (k), as shown in Figure 4(c), the first semiconductor substrate 100, which is resin-molded, is thinned by polishing the upper part of the semi-finished product M1 with a grinder or the like to obtain the semi-finished product M2. Through polishing in process (k), the thickness of the semiconductor chip 205, pillar 300, and resin 301 is thinned to, for example, several tens of micrometers, and the semiconductor chip 205 takes on a shape corresponding to the second semiconductor chip 20, and the pillar 300 and resin 301 take on a shape corresponding to the pillar portion 30.

[0198] [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.

[0199] [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.

[0200] 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 the present disclosure, which includes the polyimide precursor of the present disclosure. Since the cured product of the polyimide precursor of the present disclosure has excellent adhesion to the substrate, peeling of the insulating film is suppressed. Furthermore, by using the polyimide precursor of the present disclosure, it is possible to omit the addition of a silane coupling agent, and as a result, it is possible to suppress the precipitation of self-condensed products of the silane coupling agent as foreign matter.

[0201] 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.

[0202] Furthermore, although the above embodiment describes an example of bonding using C2C, the present invention may also be applied to bonding using Chip-to-Wafer (C2W) as shown in Figure 5. In C2W, the substrate body 411 (first base A semiconductor wafer 410 (first semiconductor substrate) is prepared, having a board 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. After that, an individualization process similar to step (e) is performed on the second semiconductor substrate to obtain a plurality of semiconductor chips 420.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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]

[0207] 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.

[0208] (Synthesis Example 1 (Synthesis of A1)) 7.07 g of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA), 3.87 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP), and 0.28 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were dissolved in 50 g of 3-methoxy-N,N-dimethylpropanamide. After stirring at 30°C for 2 hours, the reaction solution was added dropwise to dehydrated ethanol, the precipitate was filtered off, and the mixture was 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.

[0209] (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.

[0210] (Measurement conditions) Measuring instrument: Bruker BioSpin AV400M Magnetic field strength: 400MHz Reference substance: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0211] (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 2.9 g of 4,4'-diaminodiphenyl ether (ODA) and 0.39 g of m-phenylenediamine (MPD). The weight-average molecular weight of A2 was 25,000.

[0212] (Composite Example 3 (Composite of A3)) 7.07 g of ODPA, 2.7 g of 4,4'-diaminodiphenyl ether (ODA), 0.62 g of m-phenylenediamine (MPD), and 0.20 g of 3-aminopropyltriethoxysilane were dissolved in 30 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 2 hours, and then the reaction solution was added dropwise to dehydrated ethanol. After filtering off the precipitate, the mixture was dried under reduced pressure to obtain polyimide precursor A3. The weight-average molecular weight of A3 was 25,000.

[0213] (Composite Example 4 (Composite of A4)) The same procedure as in Synthesis Example 2 was followed, except that DMAP was replaced with 5.66 g of 1,3-bis(3-aminophenoxy)benzene (APB-1,3,3), to obtain polyimide precursor A4. The weight-average molecular weight of A4 was 22,000.

[0214] (Synthesis Example 5 (Synthesis of A5)) The same procedure as in Synthesis Example 3 was followed, except that 2.7 g of 4,4'-diaminodiphenyl ether (ODA) and 0.62 g of m-phenylenediamine (MPD) were replaced with 5.66 g of APB-1,3,3 to obtain polyimide precursor A5. The weight-average molecular weight of A5 was 23,000.

[0215] (Synthesis Example 6 (Synthesis of A6)) The same procedure as in Synthesis Example 1 was followed, except that DMAP was replaced with 3.88 g of ODA, to obtain polyimide precursor A6. The weight-average molecular weight of A6 was 20,000.

[0216] (Synthesis Example 7 (Synthesis of A7)) Polyimide precursor A7 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 3.65 g of ODA. The weight-average molecular weight of A7 was 28,000.

[0217] (Synthesis Example 8 (Synthesis of A8)) 7.07 g of ODPA, 2.71 g of 4,4'-diaminodiphenyl ether (ODA), 0.62 g of m-phenylenediamine (MPD), and 0.25 g of 3-aminopropyltriethoxysilane were dissolved in 50 g of 3-methoxy-N,N-dimethylpropanamide. 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 solution was added dropwise to dehydrated ethanol, the precipitate was filtered off and collected, and dried under reduced pressure to obtain polyimide precursor A8. The weight-average molecular weight of A8 was 25000.

[0218] <Esterification rate> The esterification rate of A8 (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 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.

[0219] (Measurement conditions) Measuring instrument: Bruker BioSpin AV400M Magnetic field strength: 400MHz Reference substance: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0220] (Synthesis Example 9 (Synthesis of A9)) In Synthesis Example 8, the same procedure was followed except that 0.25 g of 3-aminopropyltriethoxysilane was not used to obtain polyimide precursor A9. The weight-average molecular weight of A9 was 25,000. The esterification rate of A9 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%.

[0221] [Examples 1-7, Comparative Example 1] (Preparation of insulating film forming material) The insulating film forming materials for Examples 1-7 and Comparative Example 1 were prepared as follows, using the components and amounts shown in Table 1. The units for the amounts of each component in Table 1 are parts by mass. Blank spaces in Table 1 indicate that the corresponding component was not included. In each example and comparative example, the mixture of each component was kneaded overnight at room temperature (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.

[0222] The components listed in Table 1 are as follows: • (A) Component: Polyimide precursor A1-A8 as described above (B) Component: Solvent B1: 3-Methoxy-N,N-dimethylpropanamide B2: γ-Butyrolactone B3: Dimethyl sulfoxide • (D) Component: Polymerizable monomer D1: Tricyclodecane dimethanol diacrylate (A-DCP) D2:TEGDMA (E) Component; thermal polymerization initiator E1: Bis(1-phenyl-1-methylethyl) peroxide (F) Ingredient: Polymerization inhibitor F1:N,N'-Hexane-1,6-Diirubis[3-(3,5-Di-tert-Butyl [4-hydroxyphenyl)propionamide] • Rust inhibitor: 1H-benzotriazole

[0223] (Evaluation of adhesive properties) The above-mentioned insulating film forming material was spin-coated onto a Si wafer using a coating apparatus Act8 (manufactured by Tokyo Electron Limited), dried at 95°C for 2 minutes, and then dried at 105°C for 2 minutes to form a resin film. The obtained resin film was heated in a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere at 250°C for 2 hours to obtain a cured film (cured film thickness approximately 10 μm). The resulting cured film was treated in a saturated pressure cooker (manufactured by Hirayama Seisakusho Co., Ltd.) at a temperature of 130°C and a relative humidity of 85% for 300 hours. The adhesion of the cured film before and after treatment was calculated according to the cross-cut method of JIS K5600-5-6 standard, and the results were evaluated based on the following evaluation criteria.

[0224] -Evaluation Criteria for Adhesion- A: The hardened resin bonded to the substrate has a grid of 90 or more cells. B: Products in which the number of lattice units of the cured resin bonded to the substrate is less than 90.

[0225] Furthermore, a grid count of 90 or more indicates that the adhesive strength between the resin and the substrate is greater than the adhesive strength of the adhesive tape used during cross-cutting.

[0226] [Table 1]

[0227] As shown in Table 1, Examples 1-7 exhibited superior adhesion to the substrate compared to Comparative Example 1. Furthermore, since Examples 1-7 did not use a silane coupling agent, no precipitation of foreign substances, which are self-condensed products of the silane coupling agent, was observed. [Explanation of Symbols]

[0228] 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 polyimide precursor having a structure derived from an amine compound containing a siloxane bond.

2. The polyimide precursor according to claim 1, wherein the main chain is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide.

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

4. The polyimide precursor according to claim 3, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E). 【Chemistry 2】 In formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R Ａ ) ２ -; the two R Ａ each independently represent a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; the two R Ｂ each independently represent a hydrogen atom, an alkyl group or a phenyl group, n represents an integer of 1 or 2 or greater), or a divalent group formed by combining at least two of the foregoing groups.

5. In the general formula (1) above, the divalent organic group represented by Y is a group represented by the following formula (H). A polyimide precursor according to claim 3 or claim 4. 【Transformation 3】 In formula (H), R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n independently represents an integer from 0 to 4. D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), or a silylene bond (-Si(R) Ａ ) ２ -; Two R's Ａ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group. ), siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ Each of these independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more. ) or a divalent group formed by combining at least two of these.

6. In the above general formula (1), the R ６ and R ７ The polyimide precursor according to any one of claims 3 to 5, wherein the monovalent organic group in is any one of the group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group. 【Chemistry 4】 In general formula (2), R ８ ~R １０ Each of these independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, R ｘ This represents a divalent linking group.

7. A polyimide precursor according to any one of claims 1 to 6, further having a structure derived from a monoamine compound containing a siloxane bond.

8. A hybrid bonding insulating film forming material comprising a polyimide precursor according to any one of claims 1 to 7 and a solvent.

9. The hybrid bonding insulating film forming material according to claim 7, further comprising a polymerizable monomer.

10. 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 the hybrid bonding insulating film forming material described in claim 8 or claim 9 to produce at least one of the first organic insulating film and the second organic insulating film.

11. A method for manufacturing a semiconductor device according to claim 10, 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.

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

13. A method for manufacturing a semiconductor device according to any one of claims 10 to 12, 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.

14. A method for manufacturing a semiconductor device according to any one of claims 10 to 13, 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.

15. A method for manufacturing a semiconductor device according to any one of claims 10 to 14, 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.

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

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

18. A method for manufacturing a semiconductor device according to any one of claims 10 to 17, satisfying either that the thickness of the first organic insulating film is greater than the thickness of the first electrode, or that the thickness of the second organic insulating film is greater than the thickness of the second electrode.

19. 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 claim 8 or claim 9.

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