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

Abstract

An insulating film forming material including: a first component that is at least one of a polyimide precursor and a polyimide resin, said polyimide precursor being at least one type of resin selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, and polyamic acid amides, and has a post-curing linear expansion coefficient of 1 ppm / K to 25 ppm / K; and a second component that is at least one of a polyimide precursor and a polyimide resin, said polyimide precursor being at least one type of resin selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, and polyamic acid amides, and has a post-curing linear expansion coefficient of 40 ppm / K to 120 ppm / K.

Description

Insulating film forming material, insulating film forming material kit, semiconductor device manufacturing method, and semiconductor device

[0001] The present disclosure relates to an insulating film forming material, an insulating film forming material kit, a method for manufacturing a semiconductor device, and a semiconductor device.

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

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

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

[0005] Japanese Patent Application Laid-Open No. 2019-204818

[0006] FC Chen et al., “System on Integrated Chips(SoIC TM) for 3D Heterogeneous Integration”, 2019 IEEE 69th Electronic Components and Technology Conference (ECTC), p.594-599(2019)

[0007] When three-dimensionally mounting semiconductor chips using C2W bonding, unlike W2W bonding, foreign matter (cutting debris) may be generated during the process of dividing into semiconductor chips, and there is a risk that this foreign matter may adhere to the bonding interface of the semiconductor chips, etc. (surface of the insulating film in hybrid bonding). This insulating film contains silicon dioxide (SiO ２The use of inorganic materials such as SiO2, SiO2, and SiO2 has been considered. However, because inorganic materials are hard, any foreign particles adhering to the insulating film can create large voids at the bonding interface, with widths approaching 1,000 times the height of the foreign particles. Therefore, simply applying the hybrid bonding technology used in W2W bonding to C2W bonding can result in bonding defects due to the creation of such voids, which can reduce the yield of semiconductor device manufacturing. Meanwhile, using high-purity clean rooms and equipment to prevent these bonding defects requires significant capital investment in the clean rooms and other facilities.

[0008] Furthermore, when an organic material such as a cyclic olefin resin is used as the insulating film material, the heat resistance of the organic material is insufficient, and the insulating film is exposed to high temperatures during C2W bonding, which may cause the organic material to deteriorate and lead to poor bonding at the interface between the substrate and the insulating film, for example.

[0009] The present inventors have investigated the use of insulating materials containing organic materials with excellent heat resistance, such as polyimide precursors and polyimide resins, in order to prevent bonding defects and deterioration of organic materials due to the generation of voids. However, when polyimides with a high coefficient of linear expansion (CTE) are used in hybrid bonding techniques, the CTE differs between the electrode material, such as copper, and the polyimide. For example, the CTE of the polyimide is higher than the CTE of the electrode material, which can cause gaps at the bonding interface of the electrode material and lead to bonding defects. On the other hand, when polyimides with a low CTE are used in hybrid bonding techniques, bonding defects of the electrode material can be prevented, but the bonding strength between the polyimides tends to be low. In hybrid bonding techniques, resins that can be bonded at lower temperatures, such as room temperature, are desirable, but when polyimides with a low CTE are used, high temperatures are required for bonding by heating.

[0010] The present disclosure has been made in view of the above, and aims to provide an insulating film-forming material and an insulating film-forming material kit that can manufacture a semiconductor device in which the occurrence of poor bonding of electrode materials and poor bonding of insulating films during hybrid bonding is suppressed, a method for manufacturing a semiconductor device using the insulating film-forming material or the insulating film-forming material kit, and a semiconductor device.

[0011] Specific means for achieving the above object are as follows. <1> An insulating film-forming material comprising: a first component which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K; and a second component which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K. <2> The insulating film-forming material according to <1>, further comprising a polymerizable monomer. <3> The insulating film-forming material according to <1> or <2>, wherein the polyimide precursor in the first component and the polyimide precursor in the second component each independently contain a compound having a structural unit represented by the following general formula (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. <4> The insulating film-forming material according to <3>, wherein in the general formula (1), the tetravalent organic group represented by X is a group represented by the following formula (E): In the polyimide precursor in the first component, C in Formula (E) represents a single bond or a group containing an alicyclic structure, and in the polyimide precursor in the second component, C in Formula (E) represents a group containing an ether bond. <5> The insulating film-forming material according to <3> or <4>, wherein in the polyimide precursor in the first component, the divalent organic group represented by Y is a group represented by the following formula (G), and in the polyimide precursor in the second component, the divalent organic group represented by Y is a group represented by the following formula (H): In formula (G) and formula (H), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom; n each independently represents an integer of 0 to 4; and in formula (H), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ６ and the R ７ The insulating film-forming material according to any one of <3> to <5>, wherein the monovalent organic group is any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, and a t-butyl group: In general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘrepresents a divalent linking group. <7> The insulating film-forming material according to any one of <1> to <6>, for forming an insulating film by hybrid bonding. <8> An insulating film-forming material kit comprising: a first agent including a first component, which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K; and a second agent including a second component, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K. <9> The insulating film-forming material kit according to <8>, wherein at least one of the first agent and the second agent includes a polymerizable monomer. <10> The insulating film-forming material kit according to <8> or <9>, for forming an insulating film by hybrid bonding. <11> A method for manufacturing a semiconductor device, comprising: preparing at least one of a first organic insulating film and a second organic insulating film using the insulating film-forming material according to any one of <1> to <7>, and bonding the first organic insulating film and the second organic insulating film. <12> A semiconductor device comprising: a first semiconductor substrate having a first substrate body, and the first organic insulating film and a first electrode provided on one surface of the first substrate body; a semiconductor chip substrate body, and a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate 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, and at least one of the first organic insulating film and the second organic insulating film is an organic insulating film formed by curing the insulating film-forming material according to any one of <1> to <7>.<13> A method for manufacturing a semiconductor device, comprising: using the first agent in the insulating film-forming material kit according to any one of <8> to <10> to prepare one of a first organic insulating film and a second organic insulating film; using the second agent in the insulating film-forming material kit according to any one of <8> to <10> to prepare the other of the first organic insulating film and the second organic insulating film; and bonding the first organic insulating film and the second organic insulating film together. <14> A semiconductor device comprising: a first semiconductor substrate having a first substrate body and the first organic insulating film and a first electrode provided on one surface 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 provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate and the second organic insulating film of the semiconductor chip are bonded together, and the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are bonded together, one of the first organic insulating film and the second organic insulating film is an organic insulating film formed by curing the first agent in the insulating film forming material kit according to any one of <8> to <10>, and the other of the first organic insulating film and the second organic insulating film is an organic insulating film formed by curing the second agent in the insulating film forming material kit according to any one of <8> to <10>.

[0012] According to the present disclosure, it is possible to provide an insulating film forming material and an insulating film forming material kit capable of manufacturing a semiconductor device in which the occurrence of poor bonding of electrode materials and poor bonding of insulating films during hybrid bonding is suppressed, as well as a method for manufacturing a semiconductor device using the insulating film forming material or insulating film forming material kit, and the semiconductor device.

[0013] Fig. 1 is a cross-sectional view schematically showing an example of a semiconductor device manufactured by a semiconductor device manufacturing method according to one embodiment of the present invention. Fig. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in Fig. 1. Fig. 3 is a diagram more specifically showing a bonding method in the semiconductor device manufacturing method shown in Fig. 2. Fig. 4 is a diagram sequentially showing steps subsequent to the step shown in Fig. 2 in a method for manufacturing the semiconductor device shown in Fig. 1. Fig. 5 is a diagram illustrating an example in which the semiconductor device manufacturing method according to one embodiment of the present invention is applied to Chip-to-Wafer (C2W).

[0014] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0015] In the present disclosure, "A or B" may include either A or B, or may include both. In the present disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the present disclosure, in numerical ranges described in stages, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the present disclosure, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in a composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" or "film" include cases where the layer or film is formed over the entire region when the region where the layer or film is present is observed, as well as cases where the layer or film is formed only over a portion of the region. In the present disclosure, the thickness of a layer or film is a value obtained by measuring the thickness at five points on the target layer or film and calculating the arithmetic average of the measured thicknesses. The thickness of a layer or film can be measured using a micrometer or the like. In the present disclosure, if the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of a single layer or the total thickness of multiple layers, it may be measured by observing the cross section of the target using an electron microscope. In the present disclosure, the term "(meth)acrylic group" refers to "acrylic group" and "methacrylic group." In the present disclosure, when a functional group has a substituent, the number of carbon atoms in the functional group refers to the total number of carbon atoms, including the number of carbon atoms in the substituent. When embodiments are described with reference to drawings in the present disclosure, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of components in each drawing are conceptual, and the relative size relationships between components are not limited thereto.

[0016] <Insulating Film-Forming Material> The insulating film-forming material of the present disclosure includes a first component which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a coefficient of linear expansion (CTE) of 1 ppm / K to 25 ppm / K after curing; and a second component which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a coefficient of linear expansion of 40 ppm / K to 120 ppm / K after curing.

[0017] The insulating film-forming material of the present disclosure, by including a first component and a second component, enables the manufacture of a semiconductor device in which poor bonding of electrode materials and poor bonding of insulating films during hybrid bonding is suppressed. The reason for this is presumed to be as follows: By using a component as the first component that has a relatively small CTE and therefore a small difference in CTE from that of an electrode material such as copper, gaps are less likely to occur at the bonding interface between the electrode materials when the electrode materials are annealed, and poor bonding of the electrode materials is suppressed. Furthermore, by using a component with a relatively high CTE as the second component, poor bonding between insulating films can also be suppressed, and hybrid bonding at low temperatures is also possible.

[0018] The insulating film-forming material of the present disclosure is a material used to form an insulating film, and the use of the insulating film produced is not particularly limited, and the insulating film can be applied to uses requiring insulating properties. For example, the insulating film-forming material of the present disclosure may be a material for forming an insulating film by hybrid bonding.

[0019] The insulating film forming material of the present disclosure may be applied to hybrid bonding techniques such as W2W (Wafer-to-Wafer) bonding, C2W (Chip-to-Wafer) bonding, etc. When insulating films are bonded together for hybrid bonding, it is sufficient that at least one of the insulating films is formed from the insulating film forming material of the present disclosure, and it is preferable that both insulating films are formed from the insulating film forming material of the present disclosure.

[0020] The insulating film-forming material of the present disclosure may be a negative-type photosensitive insulating film-forming material or a positive-type photosensitive insulating film-forming material.

[0021] The components contained in the insulating film-forming material of the present disclosure and the components that can be contained therein will be described below.

[0022] ((A) Polyimide Precursor and Polyimide Resin) The insulating film-forming material of the present disclosure comprises at least one of (A) a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin (hereinafter also referred to as "component (A)"), and includes a first component having a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K, and a second component (A) having a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K. In other words, the insulating film-forming material of the present disclosure includes two types of component (A) having different linear expansion coefficients after curing. At least one of the component (A) in the first component and the component (A) in the second component may include a polyimide precursor having a polymerizable unsaturated bond as a polyimide precursor.

[0023] In the present disclosure, the polyimide precursor refers to a compound corresponding to either a polyamic acid, a compound in which the hydrogen atoms of at least some of the carboxy groups in a polyamic acid are substituted with monovalent organic groups, or a polyamic acid salt, which is a compound in which at least some of the carboxy groups in a polyamic acid form a salt structure with a basic compound having a pH of 7 or higher. Examples of compounds in which the hydrogen atoms of at least some of the carboxy groups in a polyamic acid are substituted with monovalent organic groups include polyamic acid esters and polyamic acid amides. The polyamic acid esters and polyamic acid amides preferably have a polymerizable unsaturated bond.

[0024] The first component has a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K, and from the viewpoint of suitably suppressing poor bonding of the electrode material, the linear expansion coefficient is preferably 1 ppm / K to 20 ppm / K, and more preferably 1 ppm / K to 15 ppm / K.

[0025] The second component has a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K, and from the viewpoint of suitably suppressing bonding defects of the insulating film, it is preferably 50 ppm / K to 100 ppm / K, and more preferably 70 ppm / K to 100 ppm / K.

[0026] The linear expansion coefficient indicates the rate of expansion of the length of a cured product due to an increase in temperature per unit temperature, and can be calculated by measuring the change in length of a cured product at temperatures between 30°C and 100°C using a thermomechanical analyzer or the like according to the method described in the examples.

[0027] When the component (A) contains a polyimide precursor, the component (A) preferably contains a compound having a structural unit represented by the following general formula (1), which tends to provide a semiconductor device having an insulating film that exhibits high reliability.

[0028]

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

[0030] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may contain an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon groups (e.g., aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., heterocyclic rings having 5 to 20 atoms). The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent on the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group. When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably one to three benzene rings, and even more preferably one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be connected by a single bond, or may be connected by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂ each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or greater.) or a composite linking group comprising at least two of these linking groups. Furthermore, two benzene rings may be linked at two positions by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

[0031] In the general formula (1), -COOR ６The —COOR group and the —CONH— group are preferably in the ortho position relative to each other. ７ The group and the —CO— group are preferably in the ortho position relative to each other.

[0032] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulae (A) to (F).

[0033]

[0034] In formula (D), A and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, both A and B cannot be single bonds. Examples of divalent groups that are not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represent a hydrogen atom, an alkyl group, or a phenyl group. Among these, A and B each independently preferably represent a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.

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

[0036]

[0037] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethylethylene group, a branched-chain alkylene groups such as 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; and the like. Among these, a methylene group is preferred.

[0038] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in formula (E) above has been substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.

[0039] R contained in the silylene bond or siloxane bond Ａ or R Ｂ The alkyl group represented by R is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Ａ or R Ｂ Specific examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

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

[0041]

[0042] The tetravalent organic group represented by X may contain an alicyclic ring from the viewpoint of adjusting the thermal expansion coefficient when formed into a cured product. When the tetravalent organic group represented by X contains an alicyclic ring, examples thereof include ring structures not containing unsaturated bonds such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a decahydronaphthalene ring, a norbornane ring, an adamantane ring, and a bicyclo[2.2.2]octane ring, and ring structures containing unsaturated bonds such as a cyclohexene ring. Spirocyclic structures containing these ring structures are also included. The alicyclic ring may have a substituent such as an oxo group (=O), an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, or an amino group, or may be unsubstituted. A specific example of a tetravalent organic group represented by X having a spirocyclic structure is shown below in formula (P):

[0043]

[0044] The polyimide precursor in the first component and the polyimide precursor in the second component may each independently contain a compound having a structural unit represented by general formula (1). In this case, the tetravalent organic group represented by X in general formula (1) is preferably a group represented by formula (E). Furthermore, in the polyimide precursor in the first component, C in formula (E) preferably represents a single bond or a group containing an alicyclic structure, and in the polyimide precursor in the second component, C in formula (E) preferably represents a group containing an ether bond.

[0045] In the polyimide precursor in the first component, C in formula (E) is more preferably a single bond or a group represented by formula (P). In the polyimide precursor in the second component, C in formula (E) is more preferably an ether bond, or the group represented by formula (E) is more preferably a group represented by formula (O).

[0046] In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms. The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X. The skeleton of the divalent organic group represented by Y may be a structure in which two bonding positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups). The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group. Examples of the divalent aromatic group include a divalent aromatic hydrocarbon group (for example, an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (for example, a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.

[0047] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formulae (G) to (I).

[0048]

[0049] In formulas (G) to (I), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents an integer of 0 to 4. In formula (H), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;Two R's Ｂeach independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group combining at least two of them. D may also be a structure represented by the above formula (C1). Specific examples of D in formula (H) are the same as the specific examples of C in formula (E). D in formula (H) is preferably an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, or the like.

[0050] The alkyl group represented by R in formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in formulas (G) to (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0051] The alkoxy group represented by R in formulas (G) to (I) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in formulas (G) to (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0052] The halogenated alkyl group represented by R in formulas (G) to (I) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in formulas (G) to (I) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (I) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0053] In formulae (G) to (I), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0054] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a divalent group having a polysiloxane structure.

[0055] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.

[0056] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.

[0057] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Of these, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be of one type or two or more types.

[0058] Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl. Among these, methyl is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted. Specific examples of the substituent in the aryl group when it has a substituent include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Among these, phenyl is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or of two or more types. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0059] The group represented by formula (G) is preferably a group represented by the following formula (G'), the group represented by formula (H) is preferably a group represented by the following formula (H') or formula (H"), and the group represented by formula (I) is preferably a group represented by the following formula (I').

[0060]

[0061] In formula (I'), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and is preferably an alkyl group, more preferably a methyl group.

[0062] The polyimide precursor in the first component and the polyimide precursor in the second component may each independently contain a compound having a structural unit represented by general formula (1). In this case, from the viewpoint of obtaining an insulating film that is excellent in flexibility and in which the generation of voids at the bonding interface is further suppressed, in the polyimide precursor in the first component, the divalent organic group represented by Y is preferably a group represented by formula (G), and in the polyimide precursor in the second component, the divalent organic group represented by Y is preferably a group represented by formula (H).

[0063] In the polyimide precursor in the first component, the divalent organic group represented by Y is more preferably a group represented by formula (G'). In the polyimide precursor in the second component, the divalent organic group represented by Y is more preferably a group represented by formula (H') or formula (H"). The polyimide precursor in the second component may contain a structural unit in which the divalent organic group represented by Y is a group represented by formula (G'), and a structural unit in which the divalent organic group represented by Y is a group represented by formula (H') or formula (H").

[0064] R ６ and R ７each independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably any of a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and further preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and particularly preferably contains a group represented by the following general formula (2). In particular, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-line transmittance is high and a good cured product tends to be formed even when cured at a low temperature of 400°C or less. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group, among which an ethyl group, an isobutyl group, and a t-butyl group are preferred.

[0065]

[0066] In general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘ represents a divalent linking group.

[0067] R in general formula (2) ８ ~R １０ The aliphatic hydrocarbon group represented by R has 1 to 3 carbon atoms, preferably 1 or 2. ８ ~R １０ Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0068] R in general formula (2) ８ ~R １０ As a combination of ８ and R ９ is a hydrogen atom, and R １０ is preferably a hydrogen atom or a methyl group.

[0069] R in general formula (2) ｘis a divalent linking group, and is preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups. ｘ The number of carbon atoms in is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0070] In general formula (1), R ６ and R ７ At least one of R is preferably a group represented by the general formula (2), ６ and R ７ It is more preferable that both of the above are groups represented by the general formula (2).

[0071] When the component (A) contains a compound having a structural unit represented by the general formula (1), the R ６ and R ７ The group R represented by general formula (2) ６ and R ７ The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. The upper limit is not particularly limited and may be 100 mol%. The proportion may be 0 mol% or more and less than 60 mol%.

[0072] The group represented by formula (2) is preferably a group represented by the following formula (2').

[0073]

[0074] In general formula (2'), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0075] In formula (2'), q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0076] The content of the structural unit represented by general formula (1) contained in the compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, based on the total structural units. The upper limit of the content is not particularly limited, and may be 100 mol%.

[0077] The component (A) may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. Note that the component (A) may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0078] Having a structural unit represented by general formula (1), and R in general formula (1) ６ and R ７ The compound in which at least one of the above is a monovalent organic group can be obtained, for example, by the following method (a) or (b): (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) is reacted with a compound represented by R—OH in an organic solvent to form a diester derivative, and then the diester derivative and H ２ N-Y-NH ２ (b) A condensation reaction is carried out between a tetracarboxylic acid dianhydride and a diamine compound represented by the formula: ２ N-Y-NH ２ In an organic solvent, a polyamic acid solution is obtained by reacting a diamine compound represented by R—OH with the polyamic acid solution, and the compound represented by R—OH is added to the polyamic acid solution and reacted in an organic solvent to introduce an ester group. ２ N-Y-NH ２ In the diamine compound represented by the formula (1), Y is the same as Y in the general formula (1), and specific examples and preferred examples are also the same. In addition, in the compound represented by R—OH, R represents a monovalent organic group, and specific examples and preferred examples are the same as R in the general formula (1). ６ and R ７ The same applies to the case of the tetracarboxylic acid dianhydride represented by the general formula (8), H ２ N-Y-NH ２The diamine compound represented by the formula (I) and the compound represented by R—OH may each be used alone or in combination of two or more. Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropionamide, with 3-methoxy-N,N-dimethylpropionamide being preferred. A polyimide precursor may be synthesized by reacting a dehydration condensation agent with a polyamic acid solution together with the compound represented by R—OH. The dehydration condensation agent preferably includes at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0079] The compound contained in component (A) can be prepared by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, which is then converted into an acid chloride by reacting with a chlorinating agent such as thionyl chloride, and then reacting with H ２ N-Y-NH ２ The compound contained in component (A) can be obtained by reacting a diamine compound represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, and then reacting the diamine compound with an acid chloride in the presence of a carbodiimide compound. ２ N-Y-NH ２ The compound contained in component (A) can be obtained by reacting a diamine compound represented by the following general formula (8) with a diester derivative. ２ N-Y-NH ２ The polyamic acid is then isoimidized in the presence of a dehydration condensation agent such as trifluoroacetic anhydride, and then reacted with a compound represented by R—OH to obtain a polyamic acid. Alternatively, a compound represented by R—OH may be reacted in advance with a part of a tetracarboxylic dianhydride to obtain a partially esterified tetracarboxylic dianhydride and H ２ N-Y-NH ２ Alternatively, the compound may be reacted with a diamine compound represented by the following formula:

[0080]

[0081] In the general formula (8), X is the same as X in the general formula (1), and specific examples and preferred examples are also the same.

[0082] The compound represented by R—OH used in the synthesis of the compound contained in the component (A) is R in the group represented by general formula (2). ｘ The compound represented by R-OH may be a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'), or a compound having a hydroxy group bonded to the terminal methylene group of a group represented by general formula (2'). Specific examples of the compound represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, and among these, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.

[0083] There are no particular restrictions on the molecular weight of component (A), and for example, the weight-average molecular weight is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000. The weight-average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.

[0084] The insulating film-forming material of the present disclosure may further contain a dicarboxylic acid, and the (A) polyimide precursor contained in the insulating film-forming material may have a structure formed by reaction of some of the amino groups in the (A) polyimide precursor with carboxy groups in the dicarboxylic acid. For example, when synthesizing the polyimide precursor, some of the amino groups of a diamine compound may be reacted with carboxy groups in the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula: In this case, when synthesizing the (A) polyimide precursor, by reacting some of the amino groups of the diamine compound with carboxy groups in the dicarboxylic acid, methacrylic groups derived from the dicarboxylic acid can be introduced into the (A) polyimide precursor.

[0085]

[0086] The insulating film-forming material of the present disclosure may include a first component that is a polyimide resin and has a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K, or may include a second component that is a polyimide resin and has a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K. For example, at least one of the first component and the second component may be a polyimide resin.

[0087] The polyimide resin is not particularly limited as long as it is a polymer compound having a plurality of structural units containing imide bonds, and preferably contains, for example, a compound having a structural unit represented by the following general formula (X): This tends to provide a semiconductor device having an insulating film that exhibits high reliability.

[0088]

[0089] In general formula (X), X represents a tetravalent organic group, and Y represents a divalent organic group. Preferred examples of the substituents X and Y in general formula (X) are the same as the preferred examples of the substituents X and Y in general formula (1).

[0090] For example, the polyimide resin in the first component and the polyimide resin in the second component may each independently contain a compound having a structural unit represented by general formula (X). In this case, the tetravalent organic group represented by X in general formula (X) is preferably a group represented by formula (E). Furthermore, in the polyimide resin in the first component, C in formula (E) preferably represents a single bond or a group containing an alicyclic structure, and in the polyimide resin in the second component, C in formula (E) preferably represents a group containing an ether bond.

[0091] In the polyimide resin of the first component, C in formula (E) is more preferably a single bond or a group represented by formula (P). In the polyimide resin of the second component, C in formula (E) is more preferably an ether bond, or the group represented by formula (E) is more preferably a group represented by formula (O).

[0092] From the viewpoint of obtaining an insulating film that is excellent in flexibility and in which the generation of voids at the bonding interface is further suppressed, in the polyimide resin of the first component, the divalent organic group represented by Y is preferably a group represented by formula (G), and in the polyimide resin of the second component, the divalent organic group represented by Y is preferably a group represented by formula (H).

[0093] In the polyimide resin in the first component, the divalent organic group represented by Y is more preferably a group represented by formula (G'). In the polyimide resin in the second component, the divalent organic group represented by Y is more preferably a group represented by formula (H') or formula (H"). The polyimide resin in the second component may contain a structural unit in which the divalent organic group represented by Y is a group represented by formula (G'), and a structural unit in which the divalent organic group represented by Y is a group represented by formula (H') or formula (H").

[0094] Combining a polyimide precursor and a polyimide resin as component (A) can suppress the generation of volatiles due to dehydration cyclization during imide ring formation, which tends to suppress the generation of voids. The polyimide resin referred to here refers to a resin having an imide skeleton in all or part of the resin skeleton. The polyimide resin is preferably soluble in a solvent in an insulating film-forming material using the polyimide precursor.

[0095] When the component (A) is a polyimide precursor and a polyimide resin, the proportion of the polyimide resin relative to the total of the polyimide precursor and the polyimide resin may be 15% by mass to 50% by mass, or may be 10% by mass to 20% by mass.

[0096] The insulating film-forming material of the present disclosure may contain a resin component other than component (A). For example, from the viewpoint of heat resistance, the insulating film-forming material of the present disclosure may contain other resins such as novolac resin, acrylic resin, polyethernitrile resin, polyethersulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, and polyvinyl chloride resin. The other resins may be used alone or in combination of two or more.

[0097] In the insulating film-forming material of the present disclosure, the content of component (A) relative to the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

[0098] In the insulating film-forming material of the present disclosure, the content of the first component relative to the total of the first component and the second component is preferably 60% by mass to 95% by mass, more preferably 70% by mass to 90% by mass, and even more preferably 75% by mass to 85% by mass.

[0099] The insulating film-forming material of the present disclosure may contain, as needed, at least one of a solvent, a polymerizable monomer, a photopolymerization initiator, a thermal polymerization initiator, a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, a nitrogen-containing compound, or a dicarboxylic acid.

[0100] The method for preparing the insulating film-forming material of the present disclosure is not particularly limited, and it is sufficient to mix the above-mentioned components.

[0101] (Solvent (B)) The insulating film-forming material of the present disclosure may contain a solvent (B) (hereinafter also referred to as "component (B)"). The component (B) preferably contains, for example, at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (10). The component (B) may be used alone or in combination of two or more compounds.

[0102]

[0103] In formulas (3) to (10), R １ , R ２ , R ８ , R １０ , R １１ , R １３ and R １４ are each independently an alkyl group having 1 to 4 carbon atoms, and R ３ ~R ７ , R ９ and R １２ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer of 0 to 8, t is an integer of 0 to 4, r is an integer of 0 to 4, u is an integer of 0 to 3, v is an integer of 0 to 3, w is an integer of 0 to 4, and x is an integer of 0 to 5.

[0104] In formula (3), s is preferably 0. In formula (4), R ２ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, more preferably 1. In formula (5), R ３ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, or a butyl group. ４ and R ５ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. ６ ~R ８The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. r is preferably 0 or 1, more preferably 0. In formula (7), R ９ and R １０ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. u is preferably 0 or 1, more preferably 0. In formula (8), R １１ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. u is preferably 0 or 1, more preferably 0. In formula (9), R １２ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. １３ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. w is preferably 0 or 1, more preferably 0. In formula (10), R １４ The alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group. x is preferably 0 or 1, and more preferably 0.

[0105] Specific examples of the component (B) include the following compounds:

[0106]

[0107] In the insulating film-forming material of the present disclosure, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of N-methyl-2-pyrrolidone (NMP) may be 1 mass % or less relative to the total amount of the insulating film-forming material, and may be 3 mass % or less relative to the total amount of the component (A).

[0108] In the insulating film-forming material of the present disclosure, the content of the component (B) is preferably 1 to 10,000 parts by mass, and more preferably 50 to 10,000 parts by mass, per 100 parts by mass of the component (A).

[0109] (Polymerizable Monomer (C)) The insulating film-forming material of the present disclosure preferably contains a polymerizable monomer (C). The component (C) preferably has at least one group containing a polymerizable unsaturated double bond, and from the viewpoint of being able to polymerize favorably when used in combination with a photopolymerization initiator, it more preferably has at least one (meth)acrylic group. From the viewpoint of improving crosslink density and improving photosensitivity, it preferably has 2 to 6 groups containing polymerizable unsaturated double bonds, and more preferably has 2 to 4 groups. The polymerizable monomer may be used alone or in combination of two or more types.

[0110] The polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof 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, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol ... Examples of the hydroxypropyl acrylate include triethyl acrylate, propyl ...

[0111] The polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide.

[0112] The component (C) is not limited to a compound having a group containing a polymerizable unsaturated double bond, but may also be a compound having a polymerizable group other than an unsaturated double bond group (for example, an oxirane ring).

[0113] When the insulating film-forming material of the present disclosure contains the component (C), the content of the component (C) is not particularly limited, and is preferably 1 part by mass to 100 parts by mass, more preferably 1 part by mass to 75 parts by mass, and even more preferably 1 part by mass to 50 parts by mass, per 100 parts by mass of the component (A).

[0114] <Insulating Film Forming Material Kit> The insulating film forming material kit of the present disclosure includes a first agent including a first component (component (A)) which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K; and a second agent including a second component (component (A)) which is component (A) and has a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K.

[0115] The insulating film-forming material kit of the present disclosure, by using a first agent and a second agent, enables the manufacture of a semiconductor device in which poor bonding of electrode materials and poor bonding of insulating films during hybrid bonding is suppressed. The reason for this is presumed to be as follows: Using the insulating film-forming material kit of the present disclosure, hybrid bonding can be performed between an insulating film formed by curing a first agent containing a component with a relatively small CTE and therefore a small difference in CTE from an electrode material such as copper, and an insulating film formed by curing a second agent containing a component with a relatively high CTE. In this case, by using a component with a small difference in CTE as the first component, gaps are less likely to occur at the bonding interface between the electrode materials when annealing the electrode materials, thereby suppressing poor bonding of the electrode materials. Furthermore, by using a component with a relatively high CTE as the second component, poor bonding of insulating films can be suppressed and hybrid bonding at low temperatures is also possible.

[0116] The insulating film-forming material kit of the present disclosure is a material used for forming an insulating film, and the use of the insulating film to be produced is not particularly limited, and the insulating film can be applied to uses requiring insulating properties. For example, the insulating film-forming material of the present disclosure may be a material for forming an insulating film by hybrid bonding.

[0117] The insulating film forming material kit of the present disclosure may be applied to hybrid bonding techniques such as W2W (Wafer-to-Wafer) bonding, C2W (Chip-to-Wafer) bonding, etc. When insulating films are bonded together for hybrid bonding, it is preferable that one insulating film is formed from a first agent and the other insulating film is formed from a second agent.

[0118] The preferred (A) component in the first agent is the same as the preferred (A) component in the first component of the insulating film-forming material of the present disclosure. The preferred (A) component in the second agent is the same as the preferred (A) component in the second component of the insulating film-forming material of the present disclosure.

[0119] The first agent and the second agent may each independently contain a component other than component (A). The first agent and the second agent may each independently contain, as necessary, at least one of a resin component other than component (A), a solvent, a polymerizable monomer, a photopolymerization initiator, a thermal polymerization initiator, a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, a nitrogen-containing compound, or a dicarboxylic acid. For example, at least one of the first agent and the second agent may contain a polymerizable monomer.

[0120] <Semiconductor Device> The semiconductor device disclosed herein includes a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body, and a semiconductor chip having a semiconductor chip substrate body and a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate is bonded to the second organic insulating film of the semiconductor chip, the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor chip, and at least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing an insulating film-forming material disclosed herein. In the semiconductor device disclosed herein, at least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing an insulating film-forming material disclosed herein, thereby suppressing bonding defects of the electrode material and the insulating film. Furthermore, the semiconductor device disclosed herein can be manufactured, for example, by the semiconductor device manufacturing method described below.

[0121] (Variation) In a variation of the semiconductor device of the present disclosure, one of the first organic insulating film and the second organic insulating film is an organic insulating film formed by curing the first agent in the insulating film-forming material kit of the present disclosure, and the other of the first organic insulating film and the second organic insulating film is an organic insulating film formed by curing the second agent in the insulating film-forming material kit of the present disclosure. Even in this case, hybrid bonding can be performed between an organic insulating film formed by curing a first agent containing a component whose CTE is relatively small and therefore has a small difference in CTE from that of an electrode material such as copper, and an organic insulating film formed by curing a second agent containing a component whose CTE is relatively high. As a result, poor bonding of the electrode material and poor bonding of the insulating film are suppressed.

[0122] <Method for Manufacturing a Semiconductor Device> The method for manufacturing a semiconductor device according to the present disclosure includes preparing at least one of a first organic insulating film and a second organic insulating film using the insulating film-forming material according to the present disclosure, and then bonding the first organic insulating film and the second organic insulating film together. Alternatively, the method for manufacturing a semiconductor device according to the present disclosure may include preparing one of the first organic insulating film and the second organic insulating film using the first agent in the insulating film-forming material kit according to the present disclosure, preparing the other of the first organic insulating film and the second organic insulating film using the second agent in the insulating film-forming material kit according to the present disclosure, and then bonding the first organic insulating film and the second organic insulating film together. For example, a semiconductor device can be manufactured through the following steps (1) to (5). Step (1): Preparing a first semiconductor substrate having a first substrate body and the first organic insulating film and a first electrode provided on one surface of the first substrate body. Step (2): Preparing a second semiconductor substrate having a second substrate body and the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body. Step (3): Dividing the second semiconductor substrate into individual pieces to obtain a plurality of semiconductor chips, each of which includes the second organic insulating film and at least one of the second electrodes. Step (4): Bonding the first organic insulating film of the first semiconductor substrate and the second organic insulating film of the semiconductor chip together. Step (5): Bonding the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip together.

[0123] In step (1), a first semiconductor substrate may be prepared by forming a first electrode on a first substrate body and then forming a first organic insulating film around the first electrode. In step (2), a second semiconductor substrate may be prepared by forming a second electrode on a second substrate body and then forming a second organic insulating film around the second electrode.

[0124] An embodiment of a semiconductor device according to the present disclosure and an embodiment of a method for manufacturing a semiconductor device according to the present disclosure will be described in detail below with reference to the drawings. In the following description, identical or equivalent parts will be denoted by the same reference numerals, and duplicated explanations will be omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings. Furthermore, the dimensional ratios of the drawings are not limited to those shown.

[0125] 1 is a cross-sectional view schematically illustrating an example of a semiconductor device according to the present disclosure. As shown in FIG. 1, the semiconductor device 1 is an example of a semiconductor package, and includes 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.

[0126] The first semiconductor chip 10 is a semiconductor chip such as an LSI (large-scale integrated circuit) chip or a CMOS (complementary metal oxide semiconductor) sensor, and the second semiconductor chip 20 is mounted downward in a three-dimensional mounting structure. The second semiconductor chip 20 is a semiconductor chip such as an LSI or memory, and is a chip component having a smaller area in a plan view than the first semiconductor chip 10. The second semiconductor chip 20 is bonded to the back surface of the first semiconductor chip 10 by chip-to-chip (C2C) bonding. The first semiconductor chip 10 and the second semiconductor chip 20 are finely bonded to each other by hybrid bonding, the details of which will be described later, with their respective terminal electrodes and surrounding insulating films firmly and without misalignment.

[0127] The pillar portion 30 is a connection portion in which multiple pillars 31 formed of a metal such as copper (Cu) are sealed with resin 32. The multiple pillars 31 are conductive members extending from the upper surface to the lower surface of the pillar portion 30. The multiple pillars 31 may have a cylindrical shape with a diameter of, for example, 3 μm to 20 μm (for example, a diameter of 5 μm) and may be arranged so that the center-to-center distance between each pillar 31 is 15 μm or less. The multiple pillars 31 flip-chip connect the lower terminal electrodes of the first semiconductor chip 10 to the upper terminal electrodes of the redistribution layer 40. By using the pillar portion 30, the semiconductor device 1 can form connection electrodes without using a technique known as TMV (Through Mold Via), which involves drilling holes in a mold and soldering the connection. The pillar portion 30 has, for example, a thickness approximately the same as that of the second semiconductor chip 20 and is arranged on the side of the second semiconductor chip 20 in the horizontal direction. In addition, multiple solder balls may be arranged instead of the pillar portions 30, and the solder balls may electrically connect the lower terminal electrodes of the first semiconductor chip 10 and the upper terminal electrodes of the rewiring layer 40.

[0128] The rewiring layer 40 is a wiring layer having a terminal pitch conversion function, which is a function of the package substrate, and is a layer in which a rewiring pattern is formed using polyimide, copper wiring, etc. on the insulating film below the second semiconductor chip 20 and on the lower surface of the pillar portion 30. The rewiring layer 40 is formed in a state in which the first semiconductor chip 10 (first semiconductor substrate 100), the second semiconductor chip 20, etc. are turned upside down (see (d) of FIG. 4).

[0129] The redistribution layer 40 electrically connects the terminal electrodes on the underside of the second semiconductor chip 20 and the terminal electrodes of the first semiconductor chip 10 via the pillar portions 30 to the terminal electrodes of the substrate 50. The terminal pitch of the substrate 50 is wider than the terminal pitch of the pillars 31 and the terminal pitch of the second semiconductor chip 20. Various electronic components 51 may be mounted on the substrate 50. Furthermore, if there is a large difference in the terminal pitch between the redistribution layer 40 and the substrate 50, an inorganic interposer or the like may be used between the redistribution layer 40 and the substrate 50 to establish electrical connection between the redistribution layer 40 and the substrate 50.

[0130] The circuit board 60 is a substrate on which the first semiconductor chip 10 and the second semiconductor chip 20 are mounted, and has a plurality of through electrodes therein that are electrically connected to the substrate 50 that is connected to the first semiconductor chip 10, the second semiconductor chip 20, and electronic components 51. In the circuit board 60, the plurality of through electrodes electrically connect the terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 to terminal electrodes 61 provided on the back surface of the circuit board 60.

[0131] (Example of a method for manufacturing a semiconductor device) Next, an example of a method for manufacturing the semiconductor device 1 will be described with reference to Figs. 2 to 4. Fig. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in Fig. 1. Fig. 3 is a diagram showing in more detail a bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in Fig. 2. Fig. 4 is a diagram sequentially showing steps subsequent to the step shown in Fig. 2 in a method for manufacturing the semiconductor device shown in Fig. 1.

[0132] The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n): (a) preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10; (b) preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20; (c) polishing the surface 101a of the first semiconductor substrate 100 using a CMP method so that the surfaces 103a of the terminal electrodes 103 are positioned at the same level as or protrude from the surface 102a of the insulating film 102 (see FIG. 3A); (d) polishing the surface 201a of the second semiconductor substrate 200 using a CMP method so that the surfaces 203a of the terminal electrodes 203 are positioned at the same level as or protrude from the surface 202a of the insulating film 202 (see FIG. 3A); and (e) singulating the second semiconductor substrate 200 to obtain multiple semiconductor chips 205, as shown in FIG. 2B. (f) a step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with the terminal electrodes 103 of the first semiconductor substrate 100, as shown in (c) of Figure 2. (g) a step of bonding the insulating film 102 of the first semiconductor substrate 100 and each insulating film 202b of the plurality of semiconductor chips 205 to each other (see (d) of Figure 2 and (b) of Figure 3). At this time, heat H, pressure, or both may be applied. (h) a step of bonding the terminal electrodes 103 of the first semiconductor substrate 100 to the terminal electrodes 203 of each of the plurality of semiconductor chips 205 (see (c) of Figure 3). (i) a step of forming a plurality of pillars 300 (corresponding to pillars 31) on the connection surface of the first semiconductor substrate 100 and between the plurality of semiconductor chips 205 (see (a) of Figure 4). (j) A process of molding resin 301 onto the connection surface of the first semiconductor substrate 100 so as to cover the semiconductor chip 205 and the pillar 300, thereby obtaining a semi-finished product M1 (see FIG. 4B). (k) A process of grinding the resin 301 side of the semi-finished product M1 molded in process (j) to thin it, thereby obtaining a semi-finished product M2 (see FIG. 4C). (l) A process of forming a wiring layer 400 corresponding to the rewiring layer 40 in the semi-finished product M2 thinned in process (k) (see FIG. 4D). (m) A process of cutting the semi-finished product M3 on which the wiring layer 400 has been formed in process (l) along cutting lines A to obtain each semiconductor device 1 (see FIG. 4D).(n) A step of inverting the semiconductor device 1a made into an individual package in the step (m) and placing it on the substrate 50 and the circuit board 60 (see FIG. 1).

[0133] For example, in the method for manufacturing a semiconductor device according to the present 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 according to the present disclosure may be an insulating film-forming material for use in producing at least one of the first organic insulating film and the second organic insulating film in the method for manufacturing a semiconductor device.

[0134] Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate on which integrated circuits composed of semiconductor elements and wiring connecting them are formed, corresponding to a plurality of first semiconductor chips 10. In step (a), as shown in FIG. 2A, a plurality of terminal electrodes 103 (first electrodes) made of copper, aluminum, or the like are provided at predetermined intervals on one surface 101a of a first substrate body 101 made of silicon or the like, and an insulating film 102 (first insulating film) which is a cured product obtained by curing an insulating film forming material of the present disclosure is provided. When the insulating film forming material is a photosensitive material such as a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material, the insulating film 102 may be provided on the one surface 101a of the first substrate body 101 after the insulating film 102 is provided on the one surface 101a of the first substrate body 101, or the plurality of terminal electrodes 103 may be provided on the one surface 101a of the first substrate body 101 before the insulating film 102 is provided. When the insulating film forming material is a non-photosensitive material, the insulating film 102 may be formed after the terminal electrodes 103 are formed on the one surface 101 a of the first substrate body 101 .

[0135] Step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate on which integrated circuits including semiconductor elements and wiring connecting them are formed, corresponding to the plurality of second semiconductor chips 20. In step (b), as shown in (a) of FIG. 2, a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, or the like are continuously provided on one surface 201a of a second substrate body 201 made of silicon or the like, and an insulating film 202 (a second insulating film) that is a cured product obtained by curing the insulating film forming material of the present disclosure is provided. When the insulating film forming material is a photosensitive material such as a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material, the insulating film 202 may be provided on the one surface 201a of the second substrate body 201 before the plurality of terminal electrodes 203 are provided, or the plurality of terminal electrodes 203 may be provided on the one surface 201a of the second substrate body 201 before the insulating film 202 is provided. When the insulating film forming material is a non-photosensitive material, the insulating film 202 may be formed after the terminal electrodes 203 are formed on the one surface 201 a of the second substrate body 201 .

[0136] The insulating films 102 and 202 used in steps (a) and (b) are not limited to being both cured products obtained by curing the insulating film-forming material of the present disclosure, and at least one of the insulating films 102 and 202 may be a cured product obtained by curing the insulating film-forming material of the present disclosure. Examples of insulating films other than the cured product include cured products obtained by curing an insulating film-forming material containing an organic material such as polyamideimide, benzocyclobutene (BCB), polybenzoxazole (PBO), or a PBO precursor.

[0137] Although FIG. 1 illustrates an example of C2C bonding, the present invention may also be applied to chip-to-wafer (C2W) bonding as shown in FIG. 5 . In C2W, a semiconductor wafer 410 (first semiconductor substrate) is prepared, which includes a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes). Furthermore, a semiconductor substrate (second semiconductor substrate) is prepared, which includes a substrate body 421 (second substrate body), an insulating film 422 (second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes). Then, one surface of the semiconductor wafer 410 and one surface of the second semiconductor substrate before being singulated into the semiconductor chips 420 are polished by CMP or the like, similar to steps (c) and (d) above. Thereafter, the second semiconductor substrate is subjected to a singulation process similar to that in step (e) to obtain a plurality of semiconductor chips 420 .

[0138] Next, as shown in FIG. 5A, the terminal electrodes 423 of the semiconductor chip 420 are aligned with the terminal electrodes 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film 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 bonded together (step (h)), resulting in the semi-finished product shown in FIG. 5B. This results in an insulating bonded portion S3 where the insulating film 412 and the insulating film 422 are bonded together, and the semiconductor chip 420 is mechanically firmly attached to the semiconductor wafer 410 with high precision. Furthermore, the terminal electrodes 413 and the corresponding terminal electrodes 423 are bonded together to form an electrode bonded portion S4, where the terminal electrodes 413 and 423 are mechanically and electrically firmly bonded together.

[0139] In step (h), as shown in FIG. 2(d), after the lamination in step (g) is completed, heat H, pressure, or both are applied to bond the terminal electrodes 103 of the first semiconductor substrate 100 to the respective terminal electrodes 203 of the multiple semiconductor chips 205 by hybrid bonding (see FIG. 3(c)). When the terminal electrodes 103 and 203 are made of copper, the annealing temperature in step (g) is preferably 150°C or higher and 400°C or lower, and more preferably 200°C or higher and 300°C or lower. In particular, the use of the insulating film-forming material of the present disclosure makes it possible to set the annealing temperature low. This bonding process forms an electrode bonding portion S2 where the terminal electrode 103 and the corresponding terminal electrode 203 are bonded, and the terminal electrodes 103 and 203 are firmly bonded mechanically and electrically. The electrode bonding in step (h) may be performed after the lamination in step (g) or simultaneously with the lamination in step (g).

[0140] 5(c) and 5(d), a plurality of semiconductor chips 420 are bonded to a semiconductor wafer 410 in a similar manner to obtain a semiconductor device 401. Note that the plurality of semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or may be bonded collectively to the semiconductor wafer 410 by hybrid bonding.

[0141] In the manufacturing method of the semiconductor device 401, as in the manufacturing method of the semiconductor device 1, at least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film 422 of the semiconductor chip 420 is an insulating film that is a cured product obtained by curing the insulating film-forming material of the present disclosure. Therefore, a semiconductor device having an insulating film with excellent insulating reliability can be obtained.

[0142] (Variation 1) In the semiconductor device and semiconductor device manufacturing method of the present disclosure, a configuration in which the first electrode and the second electrode are bonded has been described. However, the present disclosure is not limited to this configuration. For example, in the semiconductor device of the present disclosure, the first electrode and the second electrode may be through-hole electrodes that penetrate the first semiconductor substrate and the second semiconductor substrate. The semiconductor device manufacturing method of the present disclosure may, for example, use the insulating film-forming material of the present disclosure to form at least one of the first organic insulating film and the second organic insulating film, and manufacture a semiconductor device through the following steps (1)' to (5)'. Step (1)': Preparing a first semiconductor substrate having a first substrate body and the first organic insulating film provided on one surface of the first substrate body. Step (2)': Preparing a second semiconductor substrate having a second substrate body and the second organic insulating film provided on one surface of the second substrate body. Step (3)': Slicing the second semiconductor substrate to obtain multiple semiconductor chips each including the second organic insulating film. Step (4)': Bonding the first organic insulating film of the first semiconductor substrate and the second organic insulating film of the semiconductor chip together. In step (5)', through holes are formed in parts of the bonded first and second semiconductor substrates, and through electrodes are formed in the through holes. In step (5)', the method for forming the through holes and the method for forming the through electrodes are not particularly limited. For example, the through holes may be formed by etching or the like, and the through electrodes may be formed by electroplating, electroless plating, sputtering, or the like.

[0143] The present disclosure will be described in more detail below based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0144] Synthesis Example 1 (Synthesis of A1) 6.71 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 2.09 g of p-phenylenediamine (PPD) were dissolved in 30 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 2 hours to obtain polyimide precursor A1 (hereinafter referred to as polymer A1). The obtained polymer A1 was added dropwise to dehydrated ethanol, and the precipitate was collected by filtration and dried under reduced pressure to obtain polymer A1. The weight average molecular weight of polymer A1 was determined using gel permeation chromatography (GPC) in terms of standard polystyrene. The weight average molecular weight of polymer A1 was 20,000.

[0145] Synthesis Example 2 (Synthesis of A2) 7.07 g of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (ODPA), 3.6 g of 4,4'-diaminodiphenyl ether, and 0.2 g of m-phenylenediamine were dissolved in 30 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 4 hours and then at room temperature overnight to obtain polyamic acid. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A2 (hereinafter referred to as polymer A2). The weight-average molecular weight of polymer A2 was determined using gel permeation chromatography (GPC) in terms of standard polystyrene. The weight-average molecular weight of polymer A2 was 22,000.

[0146] Synthesis Example 3 (Synthesis of A3) A polyimide precursor A3 containing the structural unit shown below was prepared. In a reaction vessel, 15.5 g of ODPA was suspended in 50 mL of γ-butyrolactone and stirred at 25°C. Next, a suspension of 9.3 g of 4,4'-diaminodiphenyl ether suspended in 35 mL of γ-butyrolactone was added to the reaction mixture over 60 minutes while stirring. The reaction mixture was further stirred at 25°C for 4 hours, and the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added dropwise to distilled water to precipitate a polymer. The resulting precipitate was filtered and then vacuum-dried to obtain a powdery polymer, polyimide precursor A3 (hereinafter referred to as polymer A3). The weight-average molecular weight of polymer A3, as determined by GPC using standard polystyrene standards, was 35,000.

[0147]

[0148] Synthesis Example 4 (Synthesis of A4) 61.0 g of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (ODPA) and 52.0 g of 1,3-bis(3-aminophenoxy)benzene were dissolved in 200 g of 3-methoxy-N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 4 hours to obtain polyamic acid. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A4 (hereinafter referred to as polymer A4). The weight-average molecular weight of polymer A4 was determined using gel permeation chromatography (GPC) in terms of standard polystyrene. The weight-average molecular weight of polymer A4 was 25,000.

[0149] The weight-average molecular weights of Polymers A1 to A4 were determined by gel permeation chromatography (GPC) using a solution of 0.5 mg of Polymer A1 to A4 dissolved in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] under the following conditions:

[0150] (Measurement conditions) Measuring device: Shimadzu Corporation SPD-M20A Pump: Shimadzu Corporation LC-20AD Column oven: Shimadzu Corporation: CTO-20A Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1 / 1 (volume ratio) LiBr (0.03 mol / L), H3PO4 (0.06 mol / L) Flow rate: 1.0 mL / min, Detector: UV 270 nm, Column temperature: 40°C Standard polystyrene: Tosoh TSKgel standard Polystyrene Type F-1, F-4, F-20, F-80, A-2500 Calibration curve created using

[0151] [Examples 1 to 3, Comparative Example 1] (Preparation of insulating film-forming material) Using the components and blending amounts shown in Table 1, insulating film-forming materials of Examples 1 to 3 and Comparative Example 1 were prepared as follows. The blending amount of each component in Table 1 is expressed in parts by mass. A blank space in Table 1 indicates that the corresponding component was not blended. In each example and comparative example, a mixture of the components was kneaded overnight at room temperature in a general solvent-resistant container, and then pressure filtered using a filter with 0.2 μm pores. The following evaluations were carried out using the obtained insulating film-forming materials.

[0152] The components in Table 1 are as follows: Component (A) (polymer component) A1 to A4 described above Component (B) (solvent) B1: 3-methoxy-N,N-dimethylpropionamide Rust inhibitor C1 Coupling agent D1: 50% methanol solution of 3-ureidopropyltriethoxysilane

[0153] (Bonding Evaluation) The insulating film forming materials of Examples 1 to 3 and Comparative Example 1 were spin-coated onto an 8-inch Si wafer using a spin coater coating device, and then heated and dried at 100°C for 120 seconds, and then heated and dried at 110°C for 120 seconds to form a resin film. The obtained exposed resin film and the resin film of Comparative Example 1 were cured in a nitrogen atmosphere using a vertical diffusion furnace μ-TF at the curing temperature and for the curing time listed in Table 1 to obtain a cured film.

[0154] The cured films of Examples 1 to 3 and Comparative Example 1 were polished by CMP to an arithmetic mean surface roughness (Ra) of 2 nm or less to obtain polished cured films. The polished cured films were then scrubbed using a standard cleaning solution, and the cleaned cured films were then diced into 4 mm square and 8 mm square pieces using a blade dicer (DISCO DFD-6362) to obtain resin-coated top chips and resin-coated bottom chips. Bonded chips were produced by compressing the resulting resin-coated top chip to the resin-coated bottom chip using a flip chip bonder (Toray Engineering Co., Ltd. MD4000) at a predetermined pressure and bonding temperature for 15 seconds. The bonded chips were then heat-treated at 250°C for 30 minutes in an inert gas oven (JTEKT Corporation). Ten bonded chips produced for each insulating film-forming material were evaluated as described below. A shear test was performed on the resulting bonded chip using a bond tester (System 650 manufactured by Hugle Electronics Inc.) under conditions of a shear height of 20 μm and a shear speed of 20 μm per second, and the load applied when the chip peeled off was measured. The load applied when the chip peeled off was used to calculate the shear strength of the adhesive layer using the following formula: Shear strength (MPa) = Load (N) / Chip area (mm ２ The results are shown in Table 1. Evaluation criteria for poor bonding A: The average shear strength of the 10 chips was 3 MPa or more. B: The average shear strength of the 10 chips was 3 MPa or less, or the chip peeled off during measurement.

[0155] (Evaluation of Linear Expansion Coefficient After Curing) The linear expansion coefficients of Polymers A1 to A4 in Examples 1 to 3 and Comparative Example 1 were evaluated as follows. First, a composition for evaluating the linear expansion coefficient was prepared in which component (A) in Example 1 (A1 + A2, 100 parts by mass) was replaced with any one of Polymers A1 to A4 (100 parts by mass of any one of A1 to A4). A cured film was formed using the composition for evaluating the linear expansion coefficient as follows, and the thermal expansion coefficient was then measured. The composition was spin-coated onto a Si substrate and heated and dried on a hot plate at 95°C for 120 seconds, followed by heating and drying at 105°C for 120 seconds, to form a resin film with a thickness of approximately 10 μm after curing. A resin film obtained using a composition containing A1 was cured in a vertical diffusion furnace μ-TF under a nitrogen atmosphere at 250°C for 2 hours to obtain a cured product with a film thickness of 10 μm. The resulting cured product was immersed in a 4.9% by mass aqueous hydrofluoric acid solution and peeled from the Si substrate. The resulting cured product was shaped to a width of 10 mm using a razor to obtain a patterned cured product having a width of 10 mm.

[0156] Using a TMA tester (TMA2940 manufactured by DuPont), the linear expansion coefficient of the patterned cured product (measurement sample) in the surface direction from 50°C to 100°C was measured under the following conditions: initial sample length 10 mm, sample width 5 mm, load 10 g, and heating rate 5°C / min. The results obtained are as follows: Composition containing A1... 7 ppm / K Composition containing A2... 54 ppm / K Composition containing A3... 65 ppm / K Composition containing A4... 72 ppm / K Furthermore, the thermal properties of the Examples and Comparative Examples were evaluated according to the following criteria. -Evaluation criteria for thermal properties- A: Linear thermal expansion coefficient is 50 ppm / K or less. B: Linear thermal expansion coefficient is greater than 50 ppm / K.

[0157] (Evaluation of Glass Transition Temperature after Curing) The glass transition temperature was evaluated in the same manner as in the evaluation of the linear thermal expansion coefficient, and calculated from the obtained temperature vs. displacement graph using the tangent method. The results obtained are as follows: Composition containing A1: 290°C Composition containing A2: 238°C Composition containing A3: 210°C Composition containing A4: 178°C

[0158]

[0159] As shown in Table 1, Examples 1 to 3 had a good thermal expansion coefficient and were evaluated as having a good bonding property compared to Comparative Example 1.

[0160] The disclosure of Japanese Patent Application No. 2023-185855, filed on October 30, 2023, 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 if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

[0161] DESCRIPTION OF SYMBOLS 1, 1a, 401...semiconductor device, 10...first semiconductor chip, 20...second semiconductor chip, 30...pillar portion, 40...rewiring layer, 50...substrate, 60...circuit board, 61...terminal electrode, 100...first semiconductor substrate, 101...first substrate main body, 101a...one surface, 102...insulating film (first insulating film), 103...terminal electrode (first electrode), 103a...surface, 200...second semiconductor substrate, 201...second substrate main body, 201a...one surface, 202...insulating film (second insulating film), 203...terminal electrode Pole (second electrode), 203a...surface, 205...semiconductor chip, 300...pillar, 301...resin, 410...semiconductor wafer (first semiconductor substrate), 411...substrate main body (first substrate main body), 412...insulating film (first insulating film), 413...terminal electrode (first electrode), 420...semiconductor chip (second semiconductor substrate), 421...substrate main body (second substrate main body), 422...insulating film portion (second insulating film), 423...terminal electrode (second electrode), A...cutting line, H...heat, M1 to M3...semi-finished product, S1...insulating junction portion, S2...electrode junction portion, S3...insulating junction portion, S4...electrode junction portion.

Claims

1. An insulating film forming material comprising: a first component which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K; and a second component which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K.

2. The insulating film forming material according to claim 1, further comprising a polymerizable monomer.

3. The insulating film forming material according to claim 1, wherein the polyimide precursor in the first component and the polyimide precursor in the second component each independently contain a compound having a structural unit represented by the following general formula (1): In the general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, R ６ and R ７ each independently represents a hydrogen atom or a monovalent organic group.

4. The insulating film forming material according to claim 3, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E): In the polyimide precursor in the first component, C in formula (E) represents a single bond or a group containing an alicyclic structure, and in the polyimide precursor in the second component, C in formula (E) represents a group containing an ether bond.

5. The insulating film forming material according to claim 3, wherein in the polyimide precursor in the first component, the divalent organic group represented by Y is a group represented by the following formula (G): and in the polyimide precursor in the second component, the divalent organic group represented by Y is a group represented by the following formula (H): In formula (G) and formula (H), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, n each independently represents an integer of 0 to 4, and in formula (H), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R Ａ ) ２ -; Two R's Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (-O-(Si(R Ｂ ) ２ -O-) ｎ ; Two R's Ｂ each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more; or a divalent group formed by combining at least two of these.

6. In the general formula (1), ６ and the R ７ 4. The insulating film forming material according to claim 3, wherein the monovalent organic group is any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, and a t-butyl group: In general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘ represents a divalent linking group.

7. The insulating film forming material according to any one of claims 1 to 6, for forming an insulating film by hybrid bonding.

8. An insulating film forming material kit comprising: a first agent containing a first component which is at least one of a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 1 ppm / K to 25 ppm / K; and a second agent containing a second component which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and a polyimide resin, and which has a linear expansion coefficient after curing of 40 ppm / K to 120 ppm / K.

9. The insulating film forming material kit according to claim 8, wherein at least one of the first agent and the second agent contains a polymerizable monomer.

10. An insulating film forming material kit according to claim 8 or 9 for forming an insulating film by hybrid bonding.

11. A method for manufacturing a semiconductor device, comprising the steps of: preparing at least one of a first organic insulating film and a second organic insulating film using the insulating film forming material according to claim 7; and bonding the first organic insulating film and the second organic insulating film together.

12. A semiconductor device comprising: a first substrate body, a first semiconductor substrate having the first organic insulating film and a first electrode provided on one surface of the first substrate body; a semiconductor chip substrate body, and a semiconductor chip having a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate 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, and at least one of the first organic insulating film and the second organic insulating film is an organic insulating film formed by hardening the insulating film forming material according to claim 7.

13. A method for manufacturing a semiconductor device, comprising: preparing one of a first organic insulating film and a second organic insulating film using the first agent in the insulating film forming material kit described in claim 10; preparing the other of the first organic insulating film and the second organic insulating film using the second agent in the insulating film forming material kit described in claim 10; and bonding the first organic insulating film and the second organic insulating film.

14. A semiconductor device comprising: a first substrate body, a first semiconductor substrate having the first organic insulating film and a first electrode provided on one surface of the first substrate body; a semiconductor chip substrate body, and a semiconductor chip having a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate 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, one of the first organic insulating film and the second organic insulating film is an organic insulating film formed by hardening the first agent in the insulating film forming material kit described in claim 10, and the other of the first organic insulating film and the second organic insulating film is an organic insulating film formed by hardening the second agent in the insulating film forming material kit described in claim 10.

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