Insulating film forming material, method for manufacturing semiconductor device, and semiconductor device

Abstract

A photosensitive insulating film-forming material which contains (A) a polyimide precursor, (B) a solvent, and (C) a filler, and which is characterized in that the i-ray transmittance of an insulating film formed by molding the insulating film-forming material is 5-40%.

Description

Technical Field

[0001] This disclosure relates to an insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device. Background Technology

[0002] In recent years, three-dimensional mounting of semiconductor chips has been studied to improve the integration level of LSI (Large Scale Integrated Circuit). Non-Patent Document 1 discloses an example of three-dimensional mounting of a semiconductor chip.

[0003] In the case of three-dimensional mounting of semiconductor chips via C2W (Chip-to-Wafer) bonding, a hybrid bonding technique for W2W (Wafer-to-Wafer) bonding was investigated to enable fine bonding of the wiring between the devices.

[0004] In C2W hybrid bonding, thermal expansion of the substrate, chip, etc., due to heating during bonding can cause positional displacement as a primary cause. To address this issue, Patent Document 1 discloses an example of a technique that uses a cyclic olefin resin to lower the bonding temperature.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-204818

[0008] Non-patent literature

[0009] Non-patent literature 1: FCC Chen et al., "System on Integrated Chips (SoIC TM) for 3DHeterogeneous Integration", 2019 IEEE 69th Electronic Components and Technology Conference (ECTC), p.594-599 (2019) Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] However, when organic materials such as epoxy resin and benzocyclobutene are used in the insulating film, the heat resistance of the organic materials is not sufficient. During the mixing and bonding process, the organic materials deteriorate due to the insulating film being exposed to high temperatures, which may lead to poor bonding at the interface between the substrate and the insulating film.

[0012] From the viewpoint of excellent heat resistance, the inventors investigated the use of polyimide precursors in hybrid bonding materials. However, when bonding metal-to-metal (e.g., copper) and insulating film-to-insulating film in the same process via hybrid bonding, there is a problem that metal-to-metal bonding defects (e.g., gaps at the bonding interface) are easily generated.

[0013] The inventors, focusing on the difference in the coefficient of linear expansion (CTE) between the insulating film formed using a polyimide precursor and the metal, identified this as a cause of poor metal-to-metal bonding. To suppress this poor bonding, they investigated a method of mixing fillers with the polyimide precursor. However, when using fillers, the photosensitivity of the insulating film forming material tends to decrease. Therefore, an insulating film forming material that possesses photosensitivity and can reduce the coefficient of linear expansion of the insulating film is preferred.

[0014] This disclosure was made in view of the above circumstances, and its object is to provide an insulating film forming material having photosensitive properties and capable of reducing the coefficient of linear expansion of the insulating film, a method for manufacturing a semiconductor device using the insulating film forming material, and a semiconductor device having an insulating film formed from an insulating film forming material having photosensitive properties and having a reduced coefficient of linear expansion.

[0015] Methods for solving problems

[0016] The specific means to achieve the above-mentioned goals are as follows.

[0017] <1> A photosensitive insulating film forming material, comprising (A) a polyimide precursor, (B) a solvent and (C) a filler,

[0018] The i-ray transmittance of the insulating film formed by molding the insulating film forming material is 5%~40%.

[0019] <2> According to the insulating film forming material described in <1>, the polyimide precursor comprises a compound having a structural unit represented by the following general formula (1).

[0020] [Chemistry 1]

[0021]

[0022] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R... 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has polymerizable unsaturated bonds.

[0023] <3> The insulating film forming material according to <1> or <2> further comprises (D) a polymerizable monomer and (E) a photopolymerization initiator.

[0024] <4> The insulating film forming material according to any one of <1> to <3> has an average particle size of 10nm to 100nm.

[0025] <5> The insulating film forming material according to any one of <1> to <4>, wherein the filler has undergone surface treatment.

[0026] <6> The insulating film forming material according to any one of <1> to <5>, wherein the solvent comprises a non-amide solvent.

[0027] <7> According to the insulating film forming material described in <6>, the non-amide solvent comprises a cyclic ester compound.

[0028] <8> An insulating film forming material according to any one of <1> to <7>, used for forming an insulating film used in hybrid bonding.

[0029] <9> A method for manufacturing a semiconductor device, comprising using the insulating film forming material described in <8> to form an organic insulating film of at least one of a first organic insulating film and a second organic insulating film, and bonding the first organic insulating film and the second organic insulating film together.

[0030] <10> A method for manufacturing a semiconductor device, comprising:

[0031] A process of applying an insulating film forming material to a first substrate body and removing a portion of the insulating film forming material applied to the first substrate body to form a through hole;

[0032] A process for preparing a first semiconductor substrate, wherein the first semiconductor substrate has a first organic insulating film and a first electrode disposed on one side of the first substrate body, the process includes curing the insulating film forming material in the first substrate body in which the through holes are formed to form the first organic insulating film, and filling the through holes with electrode material to form the first electrode;

[0033] A process of applying an insulating film forming material to a second substrate body and removing a portion of the insulating film forming material applied to the first substrate body to form a through hole;

[0034] A process for preparing a second semiconductor substrate, the second semiconductor substrate having a second organic insulating film and a second electrode disposed on one side of the second substrate body, the process including curing the insulating film forming material in the second substrate body in which the through holes are formed to form a second organic insulating film, and filling the through holes with electrode material to form a second electrode;

[0035] The process of monolithizing the second semiconductor substrate to obtain multiple semiconductor chips; and

[0036] The process of bonding the first organic insulating film of the first semiconductor substrate to the second organic insulating film of the semiconductor chip, and bonding the first electrode of the first semiconductor substrate to the second electrode of the semiconductor chip.

[0037] At least one of the insulating film forming material applied to the first substrate body and the insulating film forming material applied to the second substrate body is the insulating film forming material described in <8>.

[0038] <11> A semiconductor device comprising:

[0039] A first semiconductor substrate has a first substrate body, a first organic insulating film disposed on one side of the first substrate body, and a first electrode; and

[0040] A semiconductor chip has a semiconductor chip substrate body, a second organic insulating film disposed on one side of the semiconductor chip substrate body, and a second electrode.

[0041] The first organic insulating film of the first semiconductor substrate is bonded to the second organic insulating film of the semiconductor chip, and the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor chip.

[0042] At least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing a photosensitive insulating film forming material comprising (A) a polyimide precursor and (C) a filler, wherein the i-line transmittance of the insulating film is 5% to 40%.

[0043] Invention Effects

[0044] According to this disclosure, it is possible to provide an insulating film forming material having photosensitive properties and capable of reducing the coefficient of linear expansion of the insulating film, a method for manufacturing a semiconductor device using the insulating film forming material, and a semiconductor device having an insulating film formed from an insulating film forming material having photosensitive properties and having a reduced coefficient of linear expansion. Attached Figure Description

[0045] [ Figure 1 ] Figure 1 This is a cross-sectional view schematically illustrating an example of a semiconductor device manufactured by a semiconductor device manufacturing method according to an embodiment of the present invention.

[0046] [ Figure 2 ] Figure 2 It shows the products used in manufacturing in sequence. Figure 1 A diagram illustrating a method using a semiconductor device.

[0047] [ Figure 3 ] Figure 3 To show in more detail Figure 2 A diagram illustrating the bonding method in the manufacturing process of the semiconductor device.

[0048] [ Figure 4 ] Figure 4 It is used for manufacturing Figure 1 The method of showing the semiconductor device is to sequentially show Figure 2 A diagram showing the process following the indicated process.

[0049] [ Figure 5 ] Figure 5 This diagram illustrates an example of applying a semiconductor device manufacturing method according to one embodiment of the present invention to a Chip-to-Wafer (C2W). Detailed Implementation

[0050] The following describes in detail the methods for implementing this disclosure. However, this disclosure is not limited to the following embodiments.

[0051] In this disclosure, except where specifically stated otherwise, its constituent elements (including element steps, etc.) are not essential. Similarly, numerical values ​​and their ranges do not limit this disclosure.

[0052] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that can achieve their purpose, even if they cannot be clearly distinguished from other processes.

[0053] In this disclosure, the numerical range indicated by “~” includes the values ​​recorded before and after “~” as the minimum and maximum values, respectively.

[0054] In the numerical ranges described in this disclosure in stages, the upper or lower limit of a numerical range can be replaced by the upper or lower limit of other numerical ranges described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit of the numerical range can be replaced by the values ​​shown in the embodiments.

[0055] In this disclosure, each component may contain multiple substances equivalent to each component. When multiple substances equivalent to each component are present in the composition, unless otherwise specified, the content or percentage of each component refers to the total content or percentage of the multiple substances present in the composition.

[0056] In this disclosure, the terms "layer" or "film" include not only the case where the layer or film is formed entirely in the region where it is observed, but also the case where it is formed only in a part of the region.

[0057] In this disclosure, the thickness of a layer or film is a value given by measuring the thickness of five points of the layer or film being studied and presenting it as their arithmetic mean.

[0058] The thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, when the thickness of a layer or film can be measured directly, a micrometer is used. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it can be measured by observing a cross-section of the object being measured using an electron microscope.

[0059] In this disclosure, "(meth)acrylate" refers to "acrylate" and "methacrylate", "(meth)acrylate" refers to "acrylate" and "methacrylate", and "(meth)acryloyl" refers to "acryloyl" and "methacryloyl".

[0060] In this disclosure, "insulating film" also includes the concept of insulating layer.

[0061] In this disclosure, when the functional group has substituents, the number of carbon atoms in the functional group refers to the total number of carbon atoms, including the number of carbon atoms of the substituents.

[0062] In this disclosure, while embodiments are described with reference to the accompanying drawings, the configuration of these embodiments is not limited to the configuration shown in the drawings. Furthermore, the sizes of the components in the figures are conceptual, and the relative sizes of the components are not limited thereto.

[0063] <Insulating Film Forming Materials>

[0064] The insulating film forming material disclosed herein comprises (A) a polyimide precursor, (B) a solvent and (C) a filler. The insulating film formed by molding the above insulating film forming material has an i-ray transmittance of 5% to 40% and is a photosensitive material.

[0065] Regarding the insulating film forming material of this disclosure, it has photosensitive properties and can reduce the coefficient of linear expansion of the insulating film. The reason for this is not yet clear, but it can be assumed to be as follows.

[0066] The insulating film formed by molding the insulating film forming material of this disclosure has an i-line transmittance of greater than or equal to 5%, which can suppress the reduction of photosensitivity, and for example, can obtain an insulating film forming material with high resolution.

[0067] Furthermore, by including filler (C) along with the polyimide precursor (A) in the insulating film forming material, there is a tendency to reduce the coefficient of linear expansion when manufacturing the insulating film compared to the case where filler (C) is not used. As a result, the difference in the coefficients of linear expansion between the insulating film and metals such as copper can be reduced. Thus, poor bonding between metals caused by the difference in the coefficients of linear expansion between the insulating film and metals such as copper can be suppressed.

[0068] The coefficient of linear expansion of the cured insulating film formed by the insulating film forming material disclosed herein is preferably less than or equal to 60 ppm / K, more preferably less than or equal to 50 ppm / K, and even more preferably less than or equal to 45 ppm / K. This effectively suppresses poor bonding between metals. The lower limit of the insulating film coefficient is not particularly limited; for example, it can be greater than or equal to 20 ppm / K or greater than or equal to 25 ppm / K.

[0069] The coefficient of linear expansion is the proportion of the length of the insulating film that expands per unit temperature due to an increase in temperature. It can be calculated by measuring the change in the length of the insulating film at 50℃ to 100℃ using thermomechanical analysis equipment.

[0070] The i-ray transmittance of the insulating film formed by molding the insulating film forming material disclosed herein is 5% to 40%, for example, it can be 10% to 40%, or it can be 12% to 30%.

[0071] The i-line transmittance of the insulating film can be adjusted, for example, according to (A) the type of polyimide precursor, (B) the type of solvent, (C) the type of filler, etc.

[0072] The method for determining the i-line transmittance is as follows. Specifically, an insulating film forming material is coated onto a glass substrate by spin coating or similar methods. The coating is dried at 100°C for 2 minutes, followed by drying at 110°C for 2 minutes to form a resin film. The i-line transmittance of the resin film is measured using a spectrophotometer (e.g., a Hitachi High-Tech U-3900H spectrophotometer). The obtained value is taken as the i-line transmittance of the insulating film.

[0073] The insulating film forming material disclosed herein can also be a material used to form insulating films used in hybrid bonding. For example, the insulating film forming material disclosed herein can also be a material applied to technologies such as W2W (Wafer-to-Wafer) bonding and C2W (Chip-to-Wafer) bonding. When hybrid bonding is performed by laminating insulating films together, it is sufficient that at least one insulating film is formed from the insulating film forming material disclosed herein, and preferably both insulating films are formed from the insulating film forming material disclosed herein.

[0074] (A) Polyimide precursor)

[0075] The insulating film forming material disclosed herein comprises (A) a polyimide precursor (hereinafter also referred to as "(A) component").

[0076] (A) The component is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Polyamic acid ester and polyamic acid amide are compounds in which at least a portion of the hydrogen atoms of the carboxyl groups in polyamic acid are replaced by monovalent organic groups, and polyamic acid salt is a compound in which at least a portion of the carboxyl groups in polyamic acid form a salt structure with a basic compound with a pH greater than 7.

[0077] (A) Components can have polymerizable unsaturated bonds.

[0078] (A) The composition preferably comprises a compound having the structural unit shown in the following general formula (1). Thus, there is a tendency to obtain a semiconductor device having an insulating film exhibiting high reliability.

[0079] [Chemistry 2]

[0080]

[0081] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R... 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has polymerizable unsaturated bonds.

[0082] The polyimide precursor may have multiple structural units as shown in the general formula (1) above, wherein X, Y, R in the multiple structural units 6 and R 7 They can be the same or different.

[0083] It should be noted that R 6 and R 7 When each atom is independently a hydrogen atom or a monovalent organic group, their combination is not particularly limited. For example, R 6 and R 7 It can have at least one hydrogen atom and the rest can be monovalent organic groups as described later, or it can all be the same or different monovalent organic groups. As mentioned above, when the polyimide precursor has multiple structural units shown in the above general formula (1), the R of each structural unit 6 and R 7 The combinations can be the same or different.

[0084] In general formula (1), the number of carbon atoms in the tetravalent organic group represented by X is preferably 4 to 25, more preferably 5 to 13, and even more preferably 6 to 12.

[0085] The tetravalent organic group shown as X may contain an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (e.g., those constituting the aromatic ring with 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., those constituting the heterocycle with 5 to 20 atoms). The tetravalent organic group shown as X is preferably an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include benzene rings, naphthalene rings, and phenanthrene rings.

[0086] When the tetravalent organic group shown by X contains an aromatic ring, each aromatic ring may have substituents or be unsubstituents. Examples of substituents for aromatic rings include alkyl groups, fluorine atoms, haloalkyl groups, hydroxyl groups, and amino groups.

[0087] When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, more preferably contains 1 to 3 benzene rings, and even more preferably contains 1 or 2 benzene rings.

[0088] When the tetravalent organic group shown by X contains more than two benzene rings, the benzene rings can be connected by single bonds, or by alkylene groups, haloalkylene groups, carbonyl groups, sulfonyl groups, ether bonds (-O-), thioether bonds (-S-), or methylene silane bonds (-Si(R)). A )2-:2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group. ), siloxane bond (-O-(Si(R) B )2-O-) n 2 Rs B Each of these elements independently represents a hydrogen atom, an alkyl group, or a phenyl group, where n represents an integer of 1 or 2 or more. Connecting groups, such as single bonds and at least two of these connecting groups, can be combined. Alternatively, two benzene rings can be bonded at two points via single bonds and at least one of the connecting groups, forming a 5- or 6-membered ring containing a connecting group between the two benzene rings.

[0089] In general formula (1), -COOR is preferred. 6 The -COOR group and the -CONH- group are adjacent to each other, preferably -COOR. 7 The -CO- group and the -CO- group are adjacent to each other.

[0090] Specific examples of the tetravalent organic group represented by X include groups shown in formulas (A) to (F) below. From the viewpoint of obtaining an insulating film with excellent flexibility and further suppression of voids generated at the interface, groups shown in formula (E) below are preferred, groups shown in formula (E) below where C contains an ether bond are more preferred, and groups with an ether bond are even more preferred. Formula (F) below is a structure where C in formula (E) is a single bond.

[0091] It should be noted that this disclosure is not limited to the specific examples described below.

[0092] [Chemistry 3]

[0093]

[0094] In formula (D), A and B are each independently a single bond or a divalent group not conjugated with the benzene ring. Not both A and B are single bonds. Examples of divalent groups not conjugated with the benzene ring include methylene, halomethylene, halomethylmethylene, carbonyl, sulfonyl, ether (-O-), thioether (-S-), and methylene silyl (-Si(R)). A )2-:2 R A Each of A and B independently represents a hydrogen atom, alkyl group, or phenyl group. Preferably, A and B are methylene, bis(trifluoromethyl)methylene, difluoromethylene, ether bond, thioether bond, etc., and more preferably ether bond.

[0095] In formula (E), C represents a single bond, alkylene group, haloalkylene group, carbonyl group, sulfonyl group, ether bond (-O-), thioether bond (-S-), phenylene group, ester bond (-OC(=O)-), methylene silyl bond (-Si(R)-). A )2-:2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group. ), siloxane bond (-O-(Si(R) B )2-O-) n 2 Rs B Each of the following can independently represent a hydrogen atom, an alkyl group, or a phenyl group, where n represents an integer of 1 or 2 or more. Alternatively, it can be a divalent group composed of at least two of these. C preferably contains an ether bond, and more particularly an ether bond.

[0096] In addition, C may contain the structure shown in the following formula (C1).

[0097] [Chemistry 4]

[0098]

[0099] As for the alkylene group represented by C in formula (E), it 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.

[0100] Specific examples of the alkylene group represented by C in formula (E) include straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene; methylmethylene, methyl ethylene, ethyl methylene, dimethylmethylene, 1,1-dimethyl ethylene, 1-methyl trimethylene, 2-methyl trimethylene, ethyl ethylene, 1-methyl tetramethylene, 2-methyl tetramethylene, 1-ethyl trimethylene, 2-ethyl trimethylene, 1,1 Branched alkylene groups, such as dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene, are preferred.

[0101] The alkyl halide represented by C in formula (E) is preferably an alkyl halide with 1 to 10 carbon atoms, more preferably an alkyl halide with 1 to 5 carbon atoms, and even more preferably an alkyl halide with 1 to 3 carbon atoms.

[0102] As a specific example of the alkyl halide represented by C in formula (E), an alkyl halide obtained by replacing at least one hydrogen atom in the alkyl halide represented by C in formula (E) with a halogen atom such as a fluorine atom or a chlorine atom is given. Among these, fluoromethylene, difluoromethylene, hexafluorodimethylmethylene, etc. are preferred.

[0103] R contained in the above-mentioned methylene silane bond or siloxane bond A or R B The alkyl group shown 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. As R A or R B Specific examples of alkyl groups shown include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0104] Specific examples of the tetravalent organic groups shown in X can be the groups represented by the following formulas (J) to (O).

[0105] [Chemistry 5]

[0106]

[0107] In general formula (1), the number of carbon atoms in the divalent organic group represented by Y is preferably 4 to 25, more preferably 6 to 20, and even more preferably 12 to 18.

[0108] The skeleton of the divalent organic group shown in Y can be the same as the skeleton of the tetravalent organic group shown in X, and the preferred skeleton of the divalent organic group shown in Y can be the same as the preferred skeleton of the tetravalent organic group shown in X. The skeleton of the divalent organic group shown in Y can be a structure in the tetravalent organic group shown in X, where two bonding positions are replaced by atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups).

[0109] The divalent organic group represented by Y can be either a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups (e.g., those with 6 to 20 carbon atoms constituting the aromatic ring) and divalent aromatic heterocyclic groups (e.g., those with 5 to 20 atoms constituting the heterocycle), with divalent aromatic hydrocarbon groups being preferred.

[0110] Specific examples of the divalent aromatic group represented by Y include the groups shown in formulas (G) and (H) below. From the viewpoint of obtaining an insulating film with excellent flexibility and further suppression of voids at the bonding interface, the group shown in formula (H) below is preferred, wherein in formula (H), D is more preferably a single bond or a group containing an ether bond, even more preferably a single bond or a group containing an ether bond, particularly preferably a group containing an ether bond, and extremely preferably an ether bond.

[0111] [Chemistry 6]

[0112]

[0113] In formulas (G) to (H), R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom, and n independently represents an integer from 0 to 4.

[0114] In formula (H), D represents a single bond, alkylene group, haloalkylene group, carbonyl group, sulfonyl group, ether bond (-O-), thioether bond (-S-), phenylene group, ester bond (-OC(=O)-), methylene silyl bond (-Si(R)-). A )2-:2 R A Each independently represents a hydrogen atom, alkyl group, or phenyl group. ), siloxane bond (-O-(Si(R) B )2-O-) n 2 Rs B Each of these can independently represent a hydrogen atom, an alkyl group, or a phenyl group, where n represents an integer of 1 or more. Alternatively, D can be a divalent group formed by combining at least two of these. Furthermore, D can be the structure shown in formula (C1) above. Specific examples of D in formula (H) are the same as specific examples of C in formula (E).

[0115] As for D in formula (H), it is preferred that each of them is independently 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.

[0116] As for the alkyl group represented by R in formulas (G) to (H), it is preferred to be an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 5 carbon atoms, and even more preferably an alkyl group with 1 or 2 carbon atoms.

[0117] Specific examples of alkyl groups represented by R in formulas (G) to (H) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0118] As for the alkoxy group represented by R in formulas (G) to (H), it is preferred to be an alkoxy group with 1 to 10 carbon atoms, more preferably an alkoxy group with 1 to 5 carbon atoms, and even more preferably an alkoxy group with 1 or 2 carbon atoms.

[0119] Specific examples of alkoxy groups represented by R in formulas (G) to (H) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc.

[0120] As for the alkyl halogroup represented by R in formulas (G) to (H), it is preferred to be an alkyl halogroup with 1 to 5 carbon atoms, more preferably an alkyl halogroup with 1 to 3 carbon atoms, and even more preferably an alkyl halogroup with 1 or 2 carbon atoms.

[0121] As a specific example of a haloalkyl group represented by R in formulas (G) to (H), an alkyl group is obtained by replacing at least one hydrogen atom in the alkyl group represented by R in formulas (G) to (H) with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl, difluoromethyl, trifluoromethyl, etc. are preferred.

[0122] In equations (G) to (H), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0123] Specific examples of the divalent aliphatic group represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups with polyoxyalkylene structures.

[0124] As the linear or branched alkylene group represented by Y, it is preferred to be an alkylene group with 1 to 20 carbon atoms, more preferably an alkylene group with 1 to 15 carbon atoms, and even more preferably an alkylene group with 1 to 10 carbon atoms.

[0125] 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.

[0126] As the cycloalkyl group represented by Y, a cycloalkyl group with 3 to 10 carbon atoms is preferred, and a cycloalkyl group with 3 to 6 carbon atoms is more preferred.

[0127] Specific examples of the cycloalkyl group represented by Y include cyclopropyl and cyclohexyl.

[0128] The unit structure contained in the divalent group of the polyepoxide structure shown in Y is preferably an epoxide structure with 1 to 10 carbon atoms, more preferably an epoxide structure with 1 to 8 carbon atoms, and even more preferably an epoxide structure with 1 to 4 carbon atoms. Among these, a polyepoxide structure or a polyepoxide-propylene structure is preferred as the polyepoxide structure. The alkylene group in the epoxide structure can be linear or branched. The unit structure in the polyepoxide structure can be one type or two or more types.

[0129] The divalent organic group represented by Y can be a divalent group with a polysiloxane structure. Examples of divalent groups with a polysiloxane structure represented by Y include those in which a silicon atom in a polysiloxane structure is bonded to a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 18 carbon atoms.

[0130] Specific examples of alkyl groups with 1 to 20 carbon atoms bonded to silicon atoms in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl. Among these, methyl is preferred.

[0131] The aryl group with 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure can be unsubstituted or substituted. Specific examples of substituents when the aryl group has substituents include halogen atoms, alkoxy groups, hydroxyl groups, etc. Specific examples of aryl groups with 6 to 18 carbon atoms include phenyl, naphthyl, benzyl, etc. Among these, phenyl is preferred.

[0132] The polysiloxane structure may contain one or more alkyl groups with 1 to 20 carbon atoms or aryl groups with 6 to 18 carbon atoms.

[0133] The silicon atoms of the divalent groups that constitute the polysiloxane structure shown in Y can be bonded to the NH group in general formula (1) via alkylene groups such as methylene and ethylene, arylene groups such as phenylene, etc.

[0134] The group represented by formula (G) is preferably the group represented by formula (G') below, and the group represented by formula (H) is preferably the group represented by formula (H'), formula (H”) or formula (H”') below. From the viewpoint of having a soft skeleton and excellent bonding properties, the group represented by formula (H') or formula (H”) below is more preferred.

[0135] [Chemistry 7]

[0136]

[0137] In formula (H”'), each R independently represents an alkyl, alkoxy, haloalkyl, phenyl, or halogen atom. R is preferably an alkyl group, and more preferably a methyl group.

[0138] There is no particular limitation on the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1). Examples of combinations of the tetravalent organic group represented by X and the divalent organic group represented by Y include combinations where X is a group represented by formula (E) and Y is a group represented by formula (H).

[0139] R 6 and R 7 Each group independently represents a hydrogen atom or a monovalent organic group, at least one of which has a polymerizable unsaturated bond. 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 a group represented by the following general formula (2), any one of ethyl, isobutyl, or tert-butyl, and even more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). In this case, R 6 and R 7 At least one of them is a group represented by general formula (2).

[0140] By including an organic group with unsaturated double bonds in a monovalent organic group, preferably a group represented by the following general formula (2), there is a tendency for high i-line transmittance and good curing properties even when cured at low temperatures of less than or equal to 400°C. In addition, when the monovalent organic group includes an organic group with unsaturated double bonds, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond portion is detached due to alkali or the like.

[0141] Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, etc., among which ethyl, isobutyl, and tert-butyl are preferred.

[0142] [Chemistry 8]

[0143]

[0144] In general formula (2), R 8 ~R10 Each can independently represent a hydrogen atom or an aliphatic hydrocarbon group with 1 to 3 carbon atoms, R x This indicates a divalent linker.

[0145] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group shown has 1 to 3 carbon atoms, preferably 1 or 2. As R 8 ~R 10 Specific examples of aliphatic hydrocarbon groups shown include methyl, ethyl, n-propyl, isopropyl, etc., with methyl being preferred.

[0146] R in general formula (2) 8 ~R 10 The combination of R is preferred. 8 and R 9 For hydrogen atoms, R 10 It is a combination of hydrogen atoms or methyl groups.

[0147] R in general formula (2) x It is a divalent linker, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of hydrocarbon groups having 1 to 10 carbon atoms include linear or branched alkylene groups.

[0148] R x The number of carbon atoms in the sample is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0149] In general formula (1), R is preferred. 6 and R 7 At least one of them is a group represented by the general formula (2) above, more preferably R 6 and R 7 Both are groups represented by the general formula (2) above.

[0150] (A) When the polyimide precursor comprises a compound having the structural unit shown in the aforementioned general formula (1), R relative to all the structural units contained in the compound 6 and R 7 The sum of the groups represented by general formula (2) is R. 6 and R 7 The preferred proportion is greater than or equal to 60 mol%, more preferably greater than or equal to 70 mol%, and even more preferably greater than or equal to 80 mol%. There is no particular upper limit, and it can be 100 mol%.

[0151] It should be noted that the aforementioned ratio can be greater than or equal to 0 mol% and less than 60 mol%.

[0152] The group represented by general formula (2) is preferably the group represented by the following general formula (2').

[0153] [Chemistry 9]

[0154]

[0155] In general formula (2'), R 8 ~R 10 Each group independently represents an aliphatic hydrocarbon group with 1 to 3 hydrogen or carbon atoms, and q represents an integer from 1 to 10.

[0156] In general formula (2'), q is an integer from 1 to 10, preferably an integer from 2 to 5, and more preferably 2 or 3.

[0157] The content of the structural unit of general formula (1) in the compound having the structural unit of general formula (1) is preferably greater than or equal to 60 mol% of the total structural units, more preferably greater than or equal to 70 mol%, and even more preferably greater than or equal to 80 mol%. The upper limit of the above content is not particularly limited and can be 100 mol.

[0158] (A) The polyimide precursor can be a polyimide precursor synthesized using tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to residues from tetracarboxylic dianhydride, and Y corresponds to residues from the diamine compound. It should be noted that (A) the polyimide precursor can also be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.

[0159] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4... 9,10-Perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,4,4'-(4,4'-isopropylidenediphenoxy)phthalic anhydride, 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-dicarboxy) 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl} Examples of suitable dianhydrides include 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxobisphthalic dianhydride, 4,4'-sulfonylbisphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, cyclopentanone dispironnorbornene tetracarboxylic dianhydride, and 2,2-bis{4-(4'-phenoxy)phenyl}propane tetracarboxylic dianhydride. Among these, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride and 3,3',4,4'-biphenyl tetracarboxylic dianhydride are preferred, and from the viewpoint of bonding at lower temperatures, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride is more preferred.

[0160] Tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0161] 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-xylenediamine, m-xylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, etc. 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-toluidine, o-toluidine sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminotrimethylbenzene, 1, 5-Diaminonaphthalene, 4,4'-benzophenone diamine, bis{4-(4'-aminophenoxy)phenyl} sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl} sulfone, 2,2-bis(4-aminophenyl)propane, 9,9-bis(4-aminophenyl)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-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane, etc. As diamine compounds, 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene are preferred. From the viewpoint of having a soft skeleton and excellent adhesion, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene and 2,2-bis{4-(4'-aminophenoxy)phenyl}propane are more preferred.

[0162] Diamine compounds can be used alone or in combination with two or more.

[0163] Having the structural unit shown in general formula (1) and R in general formula (1) 6 and R 7 Compounds in which at least one of the organic groups is a monovalent organic group can be obtained, for example, by the following methods (a) or (b).

[0164] (a) After reacting a tetracarboxylic dianhydride (preferably the tetracarboxylic dianhydride shown in general formula (8) below) with the compound shown in R-OH in an organic solvent to prepare a diester derivative, the diester derivative is subjected to a condensation reaction with the diamine compound shown in H2N-Y-NH2.

[0165] (b) A polyamic acid solution is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound shown in H2N-Y-NH2 in an organic solvent, and then adding a compound shown in R-OH to the polyamic acid solution and reacting it in an organic solvent to introduce ester groups.

[0166] Here, the Y in the diamine compound represented by H2N-Y-NH2 is the same as the Y in general formula (1), and the specific examples and preferred examples are also the same. Furthermore, the R in the compound represented by R-OH represents a monovalent organic group, and the specific examples and preferred examples are the same as the R in general formula (1). 6 and R 7 The situation is the same.

[0167] The tetracarboxylic acid dianhydride represented by general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH can each be used individually or in combination of two or more.

[0168] Examples of organic solvents mentioned above include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolinone, and 3-methoxy-N,N-dimethylpropionamide, among which 3-methoxy-N,N-dimethylpropionamide is preferred.

[0169] Alternatively, a dehydrating condensing agent can be reacted with the compound shown in R-OH in a polyamic acid solution to synthesize a polyimide precursor. The dehydrating condensing agent preferably comprises at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0170] (A) The above-mentioned compound contained in the polyimide precursor can be obtained as follows: after reacting the compound shown in R-OH with the tetracarboxylic acid dianhydride shown in the following general formula (8) to form a diester derivative, a chlorinating agent such as thionyl chloride is used to convert it into acyl chloride, and then the diamine compound shown in H2N-Y-NH2 is reacted with the acyl chloride.

[0171] (A) The above-mentioned compound contained in the polyimide precursor can be obtained by reacting the compound shown in R-OH with the tetracarboxylic acid dianhydride shown in the following general formula (8) to form a diester derivative, and then reacting the diamine compound shown in H2N-Y-NH2 with the diester derivative in the presence of the carbodiimide compound.

[0172] (A) The above-mentioned compound contained in the polyimide precursor can be obtained by reacting the tetracarboxylic dianhydride shown in the following general formula (8) with the diamine compound shown in H2N-Y-NH2 to prepare polyamic acid, followed by isoimidization of the polyamic acid in the presence of a dehydrating condensing agent such as trifluoroacetic anhydride, and then reacting the compound shown in R-OH. Alternatively, the compound shown in R-OH can be reacted on a portion of the tetracarboxylic dianhydride beforehand, and the partially esterified tetracarboxylic dianhydride can be reacted with the diamine compound shown in H2N-Y-NH2.

[0173] [Chemistry 10]

[0174]

[0175] 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.

[0176] The compound represented by R-OH used in the synthesis of the above-mentioned compound contained in (A) polyimide precursor can be R-OH of the group represented by general formula (2). x Compounds with a hydroxyl group bonded to the top, and compounds with a hydroxyl group bonded to the terminal methylene group of the group shown in 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, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, etc., among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0177] There is no particular limitation on the molecular weight of (A) polyimide precursor, but it is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, based on weight-average molecular weight.

[0178] Weight-average molecular weight can be determined, for example, by gel permeation chromatography, or by conversion using a standard polystyrene standard curve.

[0179] The insulating film forming material disclosed herein may further comprise a dicarboxylic acid, wherein the (A) polyimide precursor contained in the insulating film forming material may have a structure formed by the reaction of a portion of the amino group in the (A) polyimide precursor with a carboxyl group in the dicarboxylic acid. For example, in the synthesis of the polyimide precursor, a portion of the amino group of the diamine compound may be reacted with a carboxyl group of the dicarboxylic acid.

[0180] The dicarboxylic acid can be a dicarboxylic acid having a (meth)acrylate group, for example, it can be a dicarboxylic acid represented by the following formula. In this case, during the synthesis of the (A) polyimide precursor, a methacrylate group from the dicarboxylic acid can be introduced into the (A) polyimide precursor by reacting a portion of the amino group of the diamine compound with the carboxyl group of the dicarboxylic acid.

[0181] [Chemistry 11]

[0182]

[0183] The insulating film forming material disclosed herein may also include a polyimide resin in addition to (A) the polyimide precursor. By combining the polyimide precursor and the polyimide resin, the generation of volatiles caused by dehydration cyclization during the formation of the imide ring can be suppressed, thus exhibiting a tendency to suppress the formation of voids. The polyimide resin referred to herein is a resin whose entire or partial resin backbone has an imide backbone. The polyimide resin is preferably soluble in a solvent used in the insulating film forming material employing the polyimide precursor.

[0184] As a polyimide resin, there is no particular limitation as long as it is a polymeric compound having multiple structural units containing imide bonds; for example, compounds having structural units having the following general formula (X) are preferred. Therefore, there is a tendency to obtain semiconductor devices with insulating films exhibiting high reliability.

[0185] [Chemistry 12]

[0186]

[0187] 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 those of substituents X and Y in general formula (1) above.

[0188] When the insulating film forming material disclosed herein includes polyimide resin, the proportion of polyimide resin to the total of polyimide precursor and polyimide resin can be 15% to 50% by mass or 10% to 20% by mass.

[0189] The insulating film forming material disclosed herein may also include resins other than (A) the polyimide precursor and the polyimide resin. Examples of other resins, from the viewpoint of heat resistance, include phenolic varnish resins, acrylic resins, polyether nitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, and polyvinyl chloride resins. Other resins may be used alone or in combination of two or more.

[0190] In the insulating film forming material disclosed herein, the content of (A) polyimide precursor relative to the total amount of resin component is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 90% to 100% by mass.

[0191] The insulating film forming material disclosed herein may contain cyclic olefin resins such as benzocyclobutene, resin components such as epoxy resin, or may not contain them. From the viewpoint of superior heat resistance and mechanical properties of the insulating film, and from the viewpoint of appropriately suppressing poor bonding between the insulating film and the electrode and poor bonding between the insulating films themselves during mixed bonding, the content of the cyclic olefin resin and the content of the epoxy resin, independently relative to the total amount of the insulating film forming material disclosed herein, are preferably less than or equal to 30% by mass, more preferably 0% to 10% by mass, and even more preferably 0% to 5% by mass.

[0192] (B) Solvent)

[0193] The insulating film forming material disclosed herein includes (B) solvent (hereinafter also referred to as "(B) component").

[0194] As for component (B), there are no particular limitations, and examples include ester solvents, ketone solvents, carbonate solvents, heterocyclic compound solvents, amide solvents, etc.

[0195] Ester solvents, ketone solvents, carbonate solvents, and amide solvents can each have a cyclic structure or not.

[0196] (B) Components can be used alone or in combination of two or more.

[0197] From the viewpoint of the photosensitivity of the insulating film forming material, component (B) preferably contains a non-amide solvent other than an amide solvent, and more preferably does not contain an amide solvent but is composed of a non-amide solvent.

[0198] Non-amide solvents are not particularly limited as long as they are compounds that do not contain amide groups. Examples include the aforementioned ester solvents, ketone solvents, carbonate solvents, and heterocyclic compound solvents. Among these, ester solvents, such as cyclic ester compounds, are preferred.

[0199] (B) The component may include, for example, at least one of the groups of compounds selected from those shown in formulas (3) to (10) below.

[0200] (B) Components can be used alone or in combination of two or more.

[0201] [Chemistry 13]

[0202]

[0203] [Chemistry 14]

[0204]

[0205] In equations (3) to (10), R 1 R 2 R 8 R 10 R 11 R 13 and R 14 Each is an alkyl group having 1 to 4 carbon atoms, R 3 ~R 7 R 9 and R 12 Each is independently an alkyl group with 1 to 4 hydrogen atoms or 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, u is an integer from 0 to 3, v is an integer from 0 to 3, w is an integer from 0 to 4, and x is an integer from 0 to 5.

[0206] In equation (3), s is preferably 0.

[0207] In equation (4), R is used as 2 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. t is preferably 0, 1 or 2, more preferably 1.

[0208] In equation (5), R is used as 3 An alkyl group having 1 to 4 carbon atoms, preferably methyl, ethyl, propyl, or butyl. As R 4 and R 5 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl.

[0209] In equation (6), R is used as 6 ~R 8 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. r is preferably 0 or 1, more preferably 0.

[0210] In equation (7), R is used as 9 and R 10 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. u is preferably 0 or 1, more preferably 0.

[0211] In equation (8), R is used as 11 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. u is preferably 0 or 1, more preferably 0.

[0212] In equation (9), R is used as 12 An alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. As R 13 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. w is preferably 0 or 1, more preferably 0.

[0213] In equation (10), R is used as 14 It is an alkyl group having 1 to 4 carbon atoms, preferably methyl or ethyl. x is preferably 0 or 1, more preferably 0.

[0214] Specific examples of component (B) include the following compounds. From the viewpoint of improving i-ray transmittance, component (B) may, for example, contain γ-butyrolactone or cyclohexanone, or it may contain γ-butyrolactone.

[0215] [Chemistry 15]

[0216]

[0217] [Chemistry 16]

[0218]

[0219] In the insulating film forming material disclosed herein, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of N-methyl-2-pyrrolidone (NMP) may be less than or equal to 1% by mass relative to the total amount of the insulating film forming material, or less than or equal to 3% by mass relative to the total amount of component (A).

[0220] In the insulating film forming material disclosed herein, the content of component (B) is preferably 1 part to 10,000 parts by mass relative to 100 parts by mass of component (A), and more preferably 50 parts to 10,000 parts by mass.

[0221] (C) Packing

[0222] The hybrid insulating film forming material disclosed herein includes a (C) filler (hereinafter also referred to as the "(C) component"). The (C) component may be an organic filler, an inorganic filler, or an inorganic-organic composite filler.

[0223] (C) Components can be used alone or in combination of two or more.

[0224] Examples of organic fillers include polyethylene fibers, polypropylene fibers, polyester fibers, polyamide fibers, fluorofibers, hard rubber powder, thermosetting resin hollow spheres, epoxy resin fillers, silicone fillers, salaene resin hollow spheres, shellac, wood flour, cork powder, polyvinyl alcohol fibers, cellulose powder, and wood pulp. Among these, epoxy resin fillers, silicone fillers, thermosetting resin hollow particles, and fluorofibers are preferred, especially for their excellent heat resistance and mechanical properties.

[0225] Examples of inorganic fillers include silica, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, zirconium silicate, calcium oxide, magnesium oxide, titanium oxide, silicon nitride, aluminum nitride, boron nitride, calcium titanate, barium titanate, beryllium oxide, zircon, zircon, forsterite, talc, spinel, mullite, titanium dioxide, talc, clay, and mica. Among these, silica and alumina are particularly preferred, and silica is more preferred.

[0226] When component (C) is in particulate form, its volume average particle size is not particularly limited. For example, the volume average particle size is preferably 10 nm to 1 μm, more preferably 10 nm to 500 nm, and from the viewpoint of filler dispersibility, it is even more preferably 10 nm to 100 nm, and particularly preferably 15 nm to 50 nm.

[0227] (C) The volume average particle size refers to the value measured using a laser diffraction scattering particle size distribution measuring device as the volume average particle size (D50).

[0228] The volume average particle size of component (C) in the insulating film forming material or the insulating film can be determined by known methods. For example, component (C) (preferably an inorganic filler) is extracted from the insulating film forming material or the insulating film using organic solvents, nitric acid, aqua regia, etc., and a dispersion is prepared by thoroughly dispersing it using an ultrasonic disperser or the like. The volume average particle size of component (C) (preferably an inorganic filler) can be determined using this dispersion based on the particle size distribution measured using a laser diffraction particle size distribution measuring device. Alternatively, the insulating film can be embedded in a transparent epoxy resin or the like, and the volume average particle size of component (C) can be determined based on the particle size distribution obtained by observing the cross-section obtained after grinding using a scanning electron microscope. Furthermore, the volume average particle size can also be determined by continuously observing the two-dimensional cross-section of the insulating film using a FIB device (focused ion beam SEM) or the like, and performing three-dimensional structural analysis.

[0229] Component (C) preferably undergoes surface treatment. As a result, there is a tendency for improved dispersion of component (C) in the insulating film forming material of this disclosure, which in turn tends to result in good photosensitivity.

[0230] The insulating film forming material disclosed herein preferably comprises a surface-treated inorganic filler, and more preferably comprises at least one of surface-treated silica and surface-treated alumina.

[0231] As a surface treatment, hydrophobic treatment can be cited from the viewpoint of improving the dispersibility of component (C). Commercially available fillers can be used as the surface-treated component (C). Alternatively, various surface-treatment agents, such as coupling agents described later, can be used to surface-treat the untreated component (C).

[0232] In the insulating film forming material disclosed herein, the content of component (C) may be 5 to 200 parts by mass, 10 to 150 parts by mass, 10 to 100 parts by mass, 15 to 50 parts by mass, or 25 to 50 parts by mass relative to 100 parts by mass of component (A).

[0233] When using fillers dispersed in a dispersion solvent, the content of component (C) refers to the content of solid components, i.e., fillers, excluding the dispersion solvent.

[0234] From the perspective of suppressing aggregation, component (C) can be a filler dispersed in a dispersion solvent. There are no particular limitations on the dispersion solvent; known solvents such as cyclohexanone and dimethylacetamide can be cited.

[0235] The insulating film forming material disclosed herein may, as needed, include at least one of (D) a polymerizable monomer, (E) a photopolymerization initiator, (F) a sensitizer, (G) a coupling agent, a thermal polymerization initiator, a polymerization inhibitor, an antioxidant, a surfactant, a leveling agent, a rust inhibitor, a nitrogen-containing compound, or a dicarboxylic acid.

[0236] The insulating film forming material disclosed herein may comprise (D) a polymerizable monomer and (E) a photopolymerization initiator.

[0237] ((D) polymerizable monomer)

[0238] The insulating film forming material disclosed herein may contain a (D) polymerizable monomer (hereinafter also referred to as "(D) component"). The (D) component preferably has at least one group comprising a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylate group, from the viewpoint that it can be suitably polymerized in combination with an (E) photopolymerization initiator. From the viewpoint of increasing crosslink density and photosensitivity, it is preferable to have 2 to 6 groups comprising polymerizable unsaturated double bonds, and more preferably 2 to 4.

[0239] Polymerizable monomers can be used alone or in combination of two or more.

[0240] As a polymerizable monomer having a (meth)acrylate group, there are no particular limitations; examples include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate, etc. Acrylates, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanurate triacrylate, ethoxylated isocyanurate trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, 2-hydroxyethyl (meth)acrylate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO) modified bisphenol A diacrylate and ethylene oxide (EO) modified bisphenol A dimethacrylate.

[0241] Polymerizable monomers having (meth)acrylate groups can be tetraethylene glycol dimethacrylate, ethoxylated pentaerythritol tetraacrylate, or mixtures thereof.

[0242] There are no particular limitations on polymerizable monomers other than those having a (meth)acrylic acid group, and examples include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide.

[0243] (D) The component is not limited to a compound having a group containing a polymeric unsaturated double bond, but may also be a compound having a polymeric group other than an unsaturated double bond group (e.g., an ethylene oxide ring).

[0244] When the insulating film forming material disclosed herein contains component (D), the content of component (D) is not particularly limited, but is preferably 1 to 100 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 75 parts by mass, and even more preferably 1 to 50 parts by mass.

[0245] When component (D) is a mixture of tetraethylene glycol dimethacrylate (D1) and ethoxylated pentaerythritol tetraacrylate (D2), the mass ratio of D2 to D1 (D2 / D1) can be 50 / 100 to 100 / 100 or 60 / 100 to 90 / 100.

[0246] (E) Photopolymerization initiator)

[0247] The insulating film forming material disclosed herein may contain (E) photopolymerization initiator (hereinafter also referred to as "(E) component").

[0248] As component (E), there are no particular limitations, but examples include: 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-diphenyltriketone-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxytriketone-2-(O-benzoyl)oxime. Oxime compounds such as 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-(O-benzoyl oxime), O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl] acetophenone oxime, 1-[4-(4-hydroxyethoxy-phenylthio)phenyl]-1,2-propanedione-2-(O-acetyl oxime); acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy- Acetophenone derivatives such as 2-methylphenylacetone, 4'-(methylthio)-α-morpholino-α-methylphenylacetone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzoin derivatives such as benzoin, benzoin dimethyl ketal, and benzoin-β-methoxyethyl acetal; and benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, and propyl benzoin. Derivatives; N-arylglycine derivatives such as N-phenylglycine; peroxide derivatives such as benzoyl peroxide; aromatic biimidazol derivatives such as 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazolium dimer; acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; Irgacure OXE03 (manufactured by BASF); Irgacure OXE04 (manufactured by BASF); etc.

[0249] From the viewpoint of excellent exposure sensitivity and suppression of voids generated during bonding, component (E) preferably contains oxime compounds.

[0250] (E) Components can be used alone or in combination of two or more.

[0251] The content of oxime compounds relative to the total amount of component (E) is preferably greater than or equal to 60% by mass, more preferably greater than or equal to 80% by mass, further preferably greater than or equal to 90% by mass, and particularly preferably greater than or equal to 95% by mass.

[0252] The total amount of component (E) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 20 parts by mass, and even more preferably 2 to 10 parts by mass.

[0253] (F) Sensitizer)

[0254] The insulating film forming material disclosed herein may contain a (F) sensitizer. Examples of (F) sensitizers include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (milchone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzophenone derivatives.

[0255] (F) Components can be used alone or in combination of two or more.

[0256] When the insulating film forming material disclosed herein contains component (F), the content of component (F) is not particularly limited, but is preferably 0.01 to 3 parts by mass relative to 100 parts by mass of component (A), and more preferably 0.1 to 1 part by mass.

[0257] (G) Coupling agent)

[0258] The insulating film forming material disclosed herein may include a (G) coupling agent. No particular limitation is made to the (G) coupling agent, but examples include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-epoxypropoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, and N-[3-(triethoxysilyl)propyl] Phthalic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-ureopropyltriethoxysilane, and other silane coupling agents; aluminum-based adhesives such as tri(ethyl acetoacetate)aluminum, tri(acetylacetone)aluminum, and ethyl acetoacetate diisopropoxide aluminum, etc.

[0259] (G) Components can be used alone or in combination of two or more.

[0260] These coupling agents can be used for surface treatment of the above-mentioned component (C).

[0261] The preparation method of the insulating film forming material disclosed herein is not particularly limited; it is sufficient to mix the above-mentioned components.

[0262] Semiconductor Devices

[0263] The semiconductor device disclosed herein comprises: a first semiconductor substrate having a first substrate body and a first organic insulating film and a first electrode disposed on one side of the first substrate body; and a semiconductor chip having a semiconductor chip substrate body and a second organic insulating film and a second electrode disposed on one side of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate is bonded to the second organic insulating film of the semiconductor chip, and the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor chip, wherein at least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing a photosensitive insulating film forming material comprising (A) a polyimide precursor and (C) a filler, and the i-line transmittance of the insulating film is 5% to 40%.

[0264] In the semiconductor device of this disclosure, at least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing a photosensitive insulating film forming material comprising (A) a polyimide precursor and (C) a filler. Furthermore, the i-line transmittance of the insulating film is 5% to 40%. Thus, the semiconductor device of this disclosure includes an insulating film formed from a photosensitive insulating film forming material, which reduces the coefficient of linear expansion.

[0265] The insulating film forming material used in the semiconductor device disclosed herein only needs to contain (A) a polyimide precursor and (C) a filler, be photosensitive, and have an i-line transmittance of 5% to 40%. For example, the insulating film forming material may be the insulating film forming material of the present disclosure described above.

[0266] In addition, the semiconductor device disclosed herein can be manufactured, for example, by the semiconductor device manufacturing method shown below.

[0267] The i-line transmittance of the insulating film formed from the insulating film forming material used in the semiconductor device of this disclosure is 5% to 40%, for example, it can be 10% to 40%, or it can be 12% to 30%.

[0268] <Methods for Manufacturing Semiconductor Devices>

[0269] The method for manufacturing a semiconductor device disclosed herein uses the insulating film forming material of the present disclosure to form an organic insulating film, which is at least one of a first organic insulating film and a second organic insulating film, and then bonds the first organic insulating film and the second organic insulating film together. More specifically, the semiconductor device can be manufactured by performing the following steps (1) to (5).

[0270] Step (1): Prepare a first semiconductor substrate, which has a first substrate body and the first organic insulating film and the first electrode disposed on one side of the first substrate body.

[0271] Step (2): Prepare a second semiconductor substrate, which has a second substrate body and the second organic insulating film disposed on one side of the second substrate body and a plurality of second electrodes.

[0272] Step (3): The second semiconductor substrate is monolithically processed to obtain a plurality of semiconductor chips, each having the second organic insulating film and at least one second electrode.

[0273] Step (4): The first organic insulating film of the first semiconductor substrate and the second organic insulating film of the semiconductor chip are bonded together.

[0274] Step (5): Connect the first electrode of the first semiconductor substrate to the second electrode of the semiconductor chip.

[0275] Process (1) may also include the following processes:

[0276] The process of applying an insulating film forming material to a first substrate body, and removing a portion of the insulating film forming material applied to the first substrate body to form a through-hole; and

[0277] The process of preparing a first semiconductor substrate, wherein the first semiconductor substrate has a first organic insulating film and a first electrode disposed on one side of the first substrate body, the process includes curing the insulating film forming material in the first substrate body in which the through holes are formed to form the first organic insulating film, and filling the through holes with electrode material to form the first electrode.

[0278] Process (2) may also include the following processes:

[0279] The process of applying an insulating film forming material to a second substrate body, removing a portion of the insulating film forming material applied to the first substrate body to form a through-hole; and

[0280] The process of preparing a second semiconductor substrate, wherein the second semiconductor substrate has a second organic insulating film and a second electrode disposed on one side of the second substrate body, the process includes curing the insulating film forming material in the second substrate body in which the through holes are formed to form the second organic insulating film, and filling the through holes with electrode material to form the second electrode.

[0281] Alternatively, step (1) may include the following steps: after forming a first electrode on a first substrate body, forming a first organic insulating film around the first electrode to prepare a first semiconductor substrate having the first organic insulating film and the first electrode disposed on one side of the first substrate body.

[0282] Step (2) may also include the following steps: after forming the second electrode on the second substrate body, forming a second organic insulating film around the second electrode to prepare a second semiconductor substrate, the second semiconductor substrate having the second organic insulating film and the second electrode disposed on one side of the second substrate body.

[0283] Hereinafter, an embodiment of the semiconductor device of the present disclosure and an embodiment of the manufacturing method of the semiconductor device of the present disclosure will be described in detail with reference to the accompanying drawings. In the following description, the same or equivalent parts will be labeled with the same reference numerals, and repeated descriptions will be omitted. In addition, unless otherwise specified, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. Furthermore, the scale of the drawings is not limited to the scale shown in the drawings.

[0284] (An example of a semiconductor device)

[0285] Figure 1 This is a schematic cross-sectional view illustrating an example of a semiconductor device of this disclosure. Figure 1 As shown, the semiconductor device 1 is, for example, a semiconductor package, comprising 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.

[0286] The first semiconductor chip 10, such as an LSI (Large-Scale Integrated Circuit) chip or a CMOS (Complementary Metal-Oxide Semiconductor) sensor, forms a three-dimensional mounting structure with the second semiconductor chip 20 mounted downwards. The second semiconductor chip 20, such as an LSI or memory chip, is a chip component with a smaller area than the first semiconductor chip 10 when viewed from above. The second semiconductor chip 20 is chip-to-chip (C2C) bonded to the back side of the first semiconductor chip 10. The first semiconductor chip 10 and the second semiconductor chip 20 are finely bonded to each other, without positional displacement, by a hybrid bonding process described later, where their respective terminal electrodes are securely bonded to the surrounding insulating film.

[0287] The support portion 30 is a connection portion formed by sealing multiple supports 31 made of metal such as copper (Cu) with resin 32. The multiple supports 31 are conductive members extending from the upper surface to the lower surface of the support portion 30. The multiple supports 31 can, for example, have a cylindrical shape with a diameter greater than or equal to 3 μm and less than or equal to 20 μm (in one example, a diameter of 5 μm), or they can be arranged such that the center-to-center distance between each support 31 is less than or equal to 15 μm. The multiple supports 31 perform 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 support portion 30, connection electrodes can be formed in the semiconductor device 1 without using a technique called through-mold via (TMV) for opening a mold and soldering. The support portion 30, for example, has the same thickness as the second semiconductor chip 20 and is arranged horizontally on the lateral side of the second semiconductor chip 20. It should be noted that multiple solder balls can be configured instead of the support portion 30, and the terminal electrodes on the lower side of the first semiconductor chip 10 can be electrically connected to the terminal electrodes on the upper side of the redistribution layer 40 through the solder balls.

[0288] The rewiring layer 40 is a wiring layer that functions as a packaging substrate and modifies the terminal spacing. It is a layer on the insulating film below the second semiconductor chip 20 and on the lower surface of the pillar portion 30, where a rewiring pattern is formed using polyimide and copper wiring. The rewiring layer 40 is formed with the first semiconductor chip 10 (first semiconductor substrate 100) and the second semiconductor chip 20 flipped vertically (see reference). Figure 4 (d)

[0289] The redistribution layer 40 electrically connects the terminal electrodes on the lower surface of the second semiconductor chip 20 and the terminal electrodes of the first semiconductor chip 10 via the support portion 30 to the terminal electrodes of the substrate 50. The terminal spacing of the substrate 50 is wider than the terminal spacing of the support portion 31 and the terminal spacing of the second semiconductor chip 20. It should be noted that various electronic components 51 can also be mounted on the substrate 50. In addition, when there is a large distance between the terminal spacing of the redistribution layer 40 and the substrate 50, an inorganic interposer or the like can be used between the redistribution layer 40 and the substrate 50 to achieve electrical connection between the redistribution layer 40 and the substrate 50.

[0290] The circuit board 60 is a substrate having multiple through electrodes electrically connected to the substrate 50. A first semiconductor chip 10 and a second semiconductor chip 20 are mounted on the substrate 50, and the substrate 50 is connected to the first semiconductor chip 10, the second semiconductor chip 20, and electronic components 51, etc. In the circuit board 60, each terminal electrode of the first semiconductor chip 10 and the second semiconductor chip 20 is electrically connected to a terminal electrode 61 disposed on the back side of the circuit board 60 via the multiple through electrodes.

[0291] (An example of a semiconductor device manufacturing method)

[0292] Next, refer to Figures 2-4 An example of a method for manufacturing semiconductor device 1 will be described. Figure 2 It shows the products used in manufacturing in sequence. Figure 1 A diagram illustrating a method using a semiconductor device. Figure 3 To show in more detail Figure 2 A diagram of a bonding method (hybrid bonding) in the manufacturing process of a semiconductor device. Figure 4 It is used for manufacturing Figure 1 The method of showing the semiconductor device is to sequentially show Figure 2 A diagram showing the process following the indicated process.

[0293] Semiconductor device 1 can be manufactured, for example, via the following processes (a) to (n).

[0294] (a) A process of preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10.

[0295] (b) The process of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20.

[0296] (c) A process of polishing one side 101a of the first semiconductor substrate 100 using polishing methods such as CMP or grinding with a planer, so that each surface 103a of the terminal electrode 103 is at the same position or protruding relative to the surface 102a of the insulating film 102 (see reference). Figure 3 (a)

[0297] (d) A process of polishing one side 201a of the surface of the second semiconductor substrate 200 using a polishing method such as CMP or a planer, so that each surface 203a of the terminal electrode 203 is in an equal or protruding position relative to the surface 202a of the insulating film 202 (see reference). Figure 3 (a)

[0298] (e) such as Figure 2 As shown in (b), the process of monolithizing the second semiconductor substrate 200 to obtain multiple semiconductor chips 205.

[0299] (f) such as Figure 2 As shown in (c), a process is performed to align 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.

[0300] (g) The process of bonding the insulating film 102 of the first semiconductor substrate 100 to the insulating films 202b of the plurality of semiconductor chips 205 (see reference). Figure 2 (d) and Figure 3 (b)). At this point, heat H, pressure, or both can also be applied.

[0301] (h) The process of bonding the terminal electrode 103 of the first semiconductor substrate 100 to the terminal electrode 203 of each of the plurality of semiconductor chips 205 (see reference). Figure 3 (c)).

[0302] (i) The process of forming a plurality of pillars 300 (corresponding to pillars 31) on the bonding surface of the first semiconductor substrate 100 and between a plurality of semiconductor chips 205 (see reference). Figure 4 (a)

[0303] (j) The process of molding resin 301 onto the bonding surface of the first semiconductor substrate 100 to obtain a semi-finished product M1 in a manner that covers the semiconductor chip 205 and the pillar 300 (see reference). Figure 4 (b)

[0304] (k) The resin 301 side of the semi-finished product M1, which was molded in step (j), is thinned by grinding to obtain the semi-finished product M2 (see step (j)). Figure 4 (c)).

[0305] (l) The process of forming a wiring layer 400 corresponding to the rewiring layer 40 on the thinned semi-finished product M2 in process (k) (refer to) Figure 4 (d)

[0306] (m) The process of cutting the semi-finished product M3 with wiring layer 400 formed in process (l) along the cutting line A in such a way as to become each semiconductor device 1 (see reference) Figure 4 (d)

[0307] (n) The process in which the monolithically formed semiconductor device 1a is flipped and placed on the substrate 50 and the circuit board 60 in process (m) (refer to) Figure 1 ).

[0308] For example, in the semiconductor device manufacturing method of this disclosure, step (1) corresponds to the aforementioned steps (a) and (c), step (2) corresponds to the aforementioned steps (b) and (d), step (3) corresponds to step (e), step (4) corresponds to step (g), and step (5) corresponds to step (h). Furthermore, the insulating film forming material of this disclosure can also be an insulating film forming material used in the semiconductor device manufacturing method for forming an insulating film of at least one of a first organic insulating film and a second organic insulating film.

[0309] Step (a) is the process of preparing a first semiconductor substrate 100, which corresponds to a plurality of first semiconductor chips 10 and is a silicon substrate on which an integrated circuit composed of semiconductor elements and wiring connecting them is formed. In step (a), as Figure 2 As shown in (a), a plurality of terminal electrodes 103 (first electrodes) made of copper, aluminum, etc., are disposed at predetermined intervals on one side 101a of the first substrate body 101 made of silicon or the like, and a cured product, namely an insulating film 102 (first insulating film), formed by curing the insulating film forming material of the present disclosure, is disposed thereon. When the insulating film forming material is a photosensitive material such as a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material, the plurality of terminal electrodes 103 can be disposed after the insulating film 102 is disposed on one side 101a of the first substrate body 101, or the insulating film 102 can be disposed after the plurality of terminal electrodes 103 are disposed on one side 101a of the first substrate body 101. When the insulating film forming material is a non-photosensitive material, the insulating film 102 can be disposed after the plurality of terminal electrodes 103 are disposed on one side 101a of the first substrate body 101.

[0310] Step (b) is the process of preparing a second semiconductor substrate 200, which corresponds to a plurality of second semiconductor chips 20 and is a silicon substrate on which integrated circuits with semiconductor elements and wiring connecting them are formed. In step (b), as Figure 2 As shown in (a), a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc., are continuously disposed on one side 201a of the second substrate body 201 made of silicon or the like, and a cured product, namely an insulating film 202 (second insulating film), formed by curing the insulating film forming material of the present disclosure, is disposed thereon. When the insulating film forming material is a photosensitive material such as a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material, the plurality of terminal electrodes 203 can be disposed after the insulating film 202 is disposed on one side 201a of the second substrate body 201, or the insulating film 202 can be disposed after the plurality of terminal electrodes 203 are disposed on one side 201a of the second substrate body 201. When the insulating film forming material is a non-photosensitive material, the insulating film 202 can also be disposed after the plurality of terminal electrodes 203 are disposed on one side 201a of the second substrate body 201.

[0311] The insulating films 102 and 202 used in steps (a) and (b) are not limited to being cured products formed by curing the insulating film forming material of the present disclosure, but may also be at least one of the insulating films 102 and 202 being cured products formed by curing the insulating film forming material of the present disclosure.

[0312] In addition, Figure 1 The diagram illustrates a C2C-based connection example, but the invention can also be applied to other applications. Figure 5 The diagram illustrates a chip-to-wafer (C2W) based bonding process. In C2W, a semiconductor wafer 410 (first semiconductor substrate) is prepared, comprising a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) disposed on one side of the substrate body 411, and multiple terminal electrodes 413 (first electrodes). Next, a semiconductor substrate (second semiconductor substrate) is prepared before monolithization, comprising a substrate body 421 (second substrate body), an insulating film 422 (second insulating film) disposed on one side of the substrate body 421, and multiple terminal electrodes 423 (second electrodes). Then, similarly to steps (c) and (d) above, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before monolithization are polished using polishing methods such as CMP or polishing with a planer. Then, the second semiconductor substrate undergoes the same monolithization process as in step (e) to obtain multiple semiconductor chips 420.

[0313] Next, as Figure 5 As shown in (a), the terminal electrodes 413 of the semiconductor wafer 410 are aligned with the terminal electrodes 423 of the semiconductor chip 420 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film 422 of the semiconductor chip 420 are bonded together (step (g)), and the terminal electrodes 413 of the semiconductor wafer 410 and the terminal electrodes 423 of the semiconductor chip 420 are joined (step (h)) to obtain... Figure 5 The semi-finished product shown in (b). Thus, insulating film 412 and insulating film 422 are bonded to form insulating bonding portion S3, and semiconductor chip 420 is mechanically and securely mounted on semiconductor wafer 410 with high precision. Furthermore, terminal electrode 413 and its corresponding terminal electrode 423 are bonded to form electrode bonding portion S4, and terminal electrode 413 and terminal electrode 423 are mechanically and securely electrically bonded.

[0314] In process (h), such as Figure 2 As shown in (d), when the bonding of process (g) is completed, heat, pressure, or both are applied to bond the terminal electrodes 103 of the first semiconductor substrate 100 to the terminal electrodes 203 of the plurality of semiconductor chips 205 in a mixed bonding manner (see Figure 10). Figure 3(c) When the terminal electrodes 103 and 203 are made of copper, the annealing temperature in step (g) is preferably greater than or equal to 150°C and less than or equal to 400°C, more preferably greater than or equal to 200°C and less than or equal to 300°C. In particular, by using the insulating film forming material of this disclosure, the annealing temperature can also be set to a low level. Through such a bonding process, the terminal electrode 103 and its corresponding terminal electrode 203 are bonded to form an electrode bonding portion S2, and the terminal electrode 103 and the terminal electrode 203 are mechanically and firmly electrically bonded. It should be noted that the electrode bonding in step (h) can be performed after the bonding in step (g) or simultaneously with the bonding in step (g).

[0315] After that, as Figure 5 As shown in (c) and (d), a semiconductor device 401 is obtained by bonding a plurality of semiconductor chips 420 to a semiconductor wafer 410, which is a semiconductor wafer, using the same method. It should be noted that the plurality of semiconductor chips 420 can be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or they can be bonded to the semiconductor wafer 410 in aggregate by hybrid bonding.

[0316] In the manufacturing method of such a semiconductor device 401, similarly to the manufacturing method of semiconductor device 1 described above, at least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film 422 of the semiconductor chip 420 is a cured product, i.e., an insulating film, formed by curing the insulating film forming material of this disclosure. Therefore, the difference in the coefficient of linear expansion between the insulating film and terminal electrodes such as copper electrodes can be reduced, and when the terminal electrodes are bonded together, poor bonding between the terminal electrodes caused by the difference in the coefficient of linear expansion between the insulating film and the terminal electrodes can be suppressed.

[0317] (Modified Example)

[0318] In the semiconductor device and the method of manufacturing the semiconductor device disclosed herein, the configuration of joining the first electrode and the second electrode has been described, but the present invention is not limited to these configurations.

[0319] For example, in the semiconductor device disclosed herein, the first electrode and the second electrode may also be through electrodes that penetrate the first semiconductor substrate and the second semiconductor substrate.

[0320] The method for manufacturing a semiconductor device disclosed herein may, for example, be to use the insulating film forming material disclosed herein to make an organic insulating film of at least one of a first organic insulating film and a second organic insulating film, and to manufacture a semiconductor device by proceeding through the following steps (1)' to (5)'.

[0321] Step (1): Prepare a first semiconductor substrate, which has a first substrate body and the first organic insulating film disposed on one side of the first substrate body.

[0322] Step (2): Prepare a second semiconductor substrate, which has a second substrate body and the second organic insulating film disposed on one side of the second substrate body.

[0323] Step (3): The second semiconductor substrate is monolithically processed to obtain a plurality of semiconductor chips having the second organic insulating film.

[0324] Step (4): The first organic insulating film of the first semiconductor substrate and the second organic insulating film of the semiconductor chip are bonded together.

[0325] Step (5): A through hole is provided in a portion of the first semiconductor substrate and the second semiconductor substrate that are bonded together, and a through electrode is provided in the through hole.

[0326] In the above (5)', there are no particular limitations on the method of setting the through hole and the method of setting the through electrode. For example, the through hole can be set by etching, and the through electrode can be set by electroplating, electroless plating, sputtering, etc.

[0327] Example

[0328] The present disclosure will be further described in detail below based on embodiments and comparative examples. It should be noted that the present disclosure is not limited to the following embodiments.

[0329] (Synthesis Example 1 (Synthesis of A1))

[0330] 62 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 36 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were dissolved in 915 g of 3-methoxy-N,N-dimethylpropionamide. The resulting solution was stirred at 30 °C for 2 hours to obtain polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added to the solution at room temperature (25 °C), and the mixture was stirred at 45 °C for 10 hours. The reaction mixture was added dropwise to distilled water, the precipitate was filtered and collected, and dried under reduced pressure to obtain the polyimide precursor (hereinafter referred to as polymer A1).

[0331] The weight-average molecular weight of polymer A1 was determined using gel permeation chromatography (GPC) and converted to standard polystyrene. The weight-average molecular weight of polymer A1 was 25,000. Specifically, the determination was performed using a solution obtained by dissolving 0.5 mg of polymer A1 in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] under the following conditions.

[0332] (Measurement conditions)

[0333] Measuring device: Shimadzu Corporation SPD-M20A

[0334] Pump: Shimadzu Corporation LC-20AD

[0335] Column oven: Shimadzu Corporation: CTO-20A

[0336] Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 columns

[0337] Eluent: THF / DMF = 1 / 1 (volume ratio)

[0338] LiBr(0.03mol / L), H3PO4(0.06mol / L)

[0339] Flow rate: 1.0 mL / min, detector: UV 270 nm, column temperature: 40℃

[0340] Standard polystyrene: Standard curves were prepared using TSK gel standard polystyrene Type F-1, F-4, F-20, F-80, and A-2500 manufactured by Tosoh.

[0341] (Synthesis Example 2 (Synthesis of A2))

[0342] 62 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 23 g of 4,4'-diaminodiphenyl ether (ODA), and 5 g of m-phenylenediamine (MPD) were dissolved in 915 g of 3-methoxy-N,N-dimethylpropionamide. The resulting solution was stirred at 30 °C for 2 hours to obtain polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added to the solution at room temperature (25 °C), and the mixture was stirred at 45 °C for 10 hours. The reaction mixture was added dropwise to distilled water, the precipitate was filtered and collected, and dried under reduced pressure to obtain polyimide precursor A2 (hereinafter referred to as polymer A2).

[0343] Calculate the weight-average molecular weight of polymer A2 in the same manner as polymer A1. The weight-average molecular weight of polymer A2 is 22000.

[0344] [Examples 1-7, Comparative Examples 1-3]

[0345] (Preparation of insulating film forming materials)

[0346] The insulating film forming materials of Examples 1-7 and Comparative Examples 1-3 were prepared according to the components and proportions shown in Table 1. The proportions of each component in Table 1 are in parts by mass. Additionally, "-" in Table 1 indicates that the component was not incorporated. In each example and comparative example, the mixture of each component was kneaded overnight at room temperature in a general solvent-resistant container, and then pressure filtered using a filter with 3 μm pores. The resulting insulating film forming materials were evaluated as follows.

[0347] Regarding components C1 and C2 in (C), fillers dispersed in a solvent are used. The values ​​in parentheses for components (C) in Table 1 refer to the amount of solid content of the filler relative to 100 parts by mass of component (A).

[0348] The components in Table 1 are described below.

[0349] ·(A)Ingredients

[0350] A1: Polymer A1 synthesized in Synthesis Example 1 above.

[0351] A2: Polymer A2 synthesized in Synthesis Example 2 above.

[0352] • (B) Component

[0353] B1: γ-Butyrolactone

[0354] B2: 3-Methoxy-N,N-Dimethylpropionamide

[0355] B3: Cyclohexanone

[0356] (C) Components

[0357] C1: Silica particles (volume average particle size: 22nm, surface treatment: hydrophobic treatment, dispersion solvent: cyclohexanone, non-volatile components: 30% by mass)

[0358] C2: Silica particles (volume average particle size: 50 nm, surface treatment: methacrylic acid treatment, dispersion solvent: cyclohexanone, non-volatile components: 40% by mass)

[0359] C3: Silica particles (volume average particle size: 12nm, untreated powder, no dispersing solvent)

[0360] ·(D) component

[0361] D1: Tetraethylene glycol dimethacrylate (TEGDMA)

[0362] D2: Ethoxylated pentaerythritol tetraacrylate (ATM-4E, total number of ethoxy groups: 4)

[0363] ·(E) component

[0364] E: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime

[0365] ·(F)Component

[0366] F: 4,4'-bis(diethylamino)benzophenone

[0367] • (G) Ingredients:

[0368] G: 50% ethanol solution of 3-ureopropyltriethoxysilane

[0369] [i-line transmittance]

[0370] The obtained insulating film forming material was spin-coated onto a glass substrate using a spin coater. After drying at 100°C for 2 minutes, it was dried at 110°C for 2 minutes to form a resin film. The i-line transmittance at 365 nm of the formed resin film was measured using a U-3900H spectrophotometer (manufactured by Hitachi High-Tech Co., Ltd.). The results are shown in Table 1.

[0371] [Resolution Evaluation]

[0372] Using the Act8 coating apparatus (manufactured by Tokyo Electron Co., Ltd.), the obtained insulating film forming material was spin-coated onto a silicon wafer, dried at 100°C for 2 minutes, and then dried at 110°C for 2 minutes to form a photosensitive resin film with a dry film thickness of 10~12μm.

[0373] The development time is set as twice the time it takes for the obtained photosensitive resin film to be immersed in cyclopentanone until it is completely dissolved.

[0374] In addition, a photosensitive resin film was formed in the same manner as described above, using an i-line stepper exposure machine NES2WA06 (manufactured by Nikon) at an exposure dose of 400 mJ / cm. 2 The obtained photosensitive resin film was exposed under the specified conditions.

[0375] For the resin film after exposure and heating, Act8 is used to perform immersion development in cyclopentanone for the above-mentioned development time, followed by rinsing and cleaning with propylene glycol monomethyl ether acetate (PGMEA) to obtain the patterned resin film.

[0376] The resulting patterned cured material was observed using an optical microscope. The minimum diameter of the opening formed with an area relative to the mask size of the through-hole that exposed more than 55% of the substrate surface was used as the resolution. A resolution less than or equal to 30 μm was designated as Evaluation A, a resolution greater than 30 μm and less than or equal to 50 μm as Evaluation B, and a resolution greater than 50 μm as Evaluation C. Evaluation A or Evaluation B indicates a good resolution result.

[0377] The results are shown in Table 1.

[0378] [Determination of thermal expansion coefficient]

[0379] Using the obtained insulating film forming material, a cured film was formed as follows, and then the thermal expansion coefficient was measured. The insulating film forming material was spin-coated onto a Si substrate, heated and dried at 100°C for 120 seconds on a hot plate, and then heated and dried at 110°C for 120 seconds, thereby forming a resin film of approximately 10 μm after curing.

[0380] The obtained resin film was cured using a vertical diffusion furnace μ-TF under a nitrogen atmosphere, at a curing temperature of 200°C and a curing time of 2 hours, resulting in a cured film with a thickness of 10 μm. The cured film was then immersed in a 4.9% (w / w) hydrofluoric acid aqueous solution and peeled off from the Si substrate. The cured film was then shaped into a 10 mm wide pattern using a razor, thus obtaining a 10 mm wide patterned cured film.

[0381] Using a TMA testing apparatus (Rigaku, TMA8310), the linear thermal expansion coefficient in the face direction of the patterned cured material used as the test specimen was measured from 50°C to 100°C under the conditions of an initial sample length of 10 mm, a load of 10 g, and a heating rate of 5°C / min. The results are presented in Table 1 as the coefficient of linear expansion (ppm / K).

[0382] [Table 1]

[0383]

[0384] As shown in Table 1, in Examples 1-7, the resolution evaluation was good, and the coefficient of linear expansion was also reduced. On the other hand, in Comparative Examples 1 and 2, the coefficient of linear expansion was higher than that in Examples 1-7. In Comparative Example 3, the resolution evaluation was poor compared to Examples 1-7.

[0385] The disclosure of Japanese Patent Application No. 2023-068850 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as those specifically described herein.

[0386] Explanation of reference numerals in the attached figures

[0387] 1, 1a, 401… Semiconductor device; 10… First semiconductor chip; 20… Second semiconductor chip; 30… Support section; 40… Redistribution layer; 50… Substrate; 60… Circuit board; 61… Terminal electrode; 100… First semiconductor substrate; 101… First substrate body; 101a… One side; 102… Insulating film (first insulating film); 103… Terminal electrode (first electrode); 103a… Surface; 200… Second semiconductor substrate; 201… Second substrate body; 201a… One side; 202… Insulating film (second insulating film); 203… Terminal electrode (second electrode); 203a… Surface; 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 (second insulating film); 423… Terminal electrode (second electrode); A… Cutting wire; H… Heat; M1~M3… Semi-finished product; S1… Insulating bonding portion; S2… Electrode bonding portion; S3… Insulating bonding portion; S4… Electrode bonding portion.

Claims

1. A photosensitive insulating film forming material, comprising (A) a polyimide precursor, (B) a solvent, and (C) a filler. The i-ray transmittance of the insulating film formed by molding the insulating film forming material is 5%~40%.

2. The insulating film forming material according to claim 1, wherein the polyimide precursor comprises a compound having a structural unit represented by the following general formula (1), [Chemistry 1] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R... 6 and R 7 Each independently represents a hydrogen atom or a monovalent organic group, R 6 and R 7 At least one of them has polymerizable unsaturated bonds.

3. The insulating film forming material according to claim 1, further comprising (D) a polymerizable monomer and (E) a photopolymerization initiator.

4. The insulating film forming material according to claim 1, wherein the average particle size of the filler is 10 nm to 100 nm.

5. The insulating film forming material according to claim 1, wherein the filler has undergone surface treatment.

6. The insulating film forming material according to claim 1, wherein the solvent comprises a non-amide solvent.

7. The insulating film forming material according to claim 6, wherein the non-amide solvent comprises a cyclic ester compound.

8. The insulating film forming material according to any one of claims 1 to 7, used for forming an insulating film used in hybrid bonding.

9. A method for manufacturing a semiconductor device, comprising using the insulating film forming material of claim 8 to form an organic insulating film of at least one of a first organic insulating film and a second organic insulating film, and bonding the first organic insulating film and the second organic insulating film.

10. A method for manufacturing a semiconductor device, comprising: A process of applying an insulating film forming material to a first substrate body and removing a portion of the insulating film forming material applied to the first substrate body to form a through hole; A process for preparing a first semiconductor substrate, wherein the first semiconductor substrate has a first organic insulating film and a first electrode disposed on one side of the first substrate body, the process includes curing the insulating film forming material in the first substrate body in which the through holes are formed to form the first organic insulating film, and filling the through holes with electrode material to form the first electrode; A process of applying an insulating film forming material to a second substrate body and removing a portion of the insulating film forming material applied to the first substrate body to form a through hole; A process for preparing a second semiconductor substrate, the second semiconductor substrate having a second organic insulating film and a second electrode disposed on one side of the second substrate body, the process including curing the insulating film forming material in the second substrate body having the through holes to form the second organic insulating film, and filling the through holes with electrode material to form the second electrode; The process of monolithizing the second semiconductor substrate to obtain multiple semiconductor chips; as well as The process of bonding the first organic insulating film of the first semiconductor substrate to the second organic insulating film of the semiconductor chip, and bonding the first electrode of the first semiconductor substrate to the second electrode of the semiconductor chip. At least one of the insulating film forming material applied to the first substrate body and the insulating film forming material applied to the second substrate body is the insulating film forming material as described in claim 8.

11. A semiconductor device comprising: A first semiconductor substrate has a first substrate body, a first organic insulating film disposed on one side of the first substrate body, and a first electrode; and A semiconductor chip has a semiconductor chip substrate body, a second organic insulating film disposed on one side of the semiconductor chip substrate body, and a second electrode. The first organic insulating film of the first semiconductor substrate is bonded to the second organic insulating film of the semiconductor chip, and the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor chip. At least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing a photosensitive insulating film forming material comprising (A) a polyimide precursor and (C) a filler, wherein the i-line transmittance of the insulating film is 5% to 40%.

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