Insulation film forming material, semiconductor device manufacturing method, and semiconductor device

Abstract

To provide an insulation film forming material capable of forming an insulation film having superior insulation reliability during hybrid bonding.SOLUTION: Provided is an insulation film forming material for forming an insulation film through hybrid bonding, the insulation film forming material comprising: (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid esters, polyamic acid salts, and polyamic acid amides; and (B) a polymerizable monomer, wherein the content of a compound classified as the (B) polymerizable monomer and including an alkylene oxide chain and a (meth)acrylic group is less than 20 pts.mass relative to 100 pts.mass of the (A) polyimide precursor.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

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

[0003] When performing three-dimensional mounting of semiconductor chips by C2W (Chip-to-Wafer) bonding, in order to perform fine bonding of wirings between devices, it has been studied to use a hybrid bonding technology used for W2W (Wafer-to-Wafer) bonding.

[0004] In C2W hybrid bonding, there is a possibility that positional deviation may occur due to thermal expansion of a base material, a chip, etc. due to heating during bonding. In response to such a problem, Patent Document 1 discloses an example of a technology capable of lowering the bonding temperature by using a cyclic olefin-based resin.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Non-Patent Documents

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] When performing three-dimensional mounting of semiconductor chips by C2W bonding, different from W2W bonding, foreign substances (cutting fragments) may be generated in the process of singulating the semiconductor chips, and there is a risk that these foreign substances will adhere to the bonding interface (the surface of the insulating film of hybrid bonding) of semiconductor chips and the like. Although it has been considered to use an inorganic material such as silicon dioxide (SiO2) for this insulating film, since the inorganic material is a hard material, the adhered foreign substance will cause a large void in the insulating film, for example, a void with a width nearly 1000 times the height of the foreign substance, at the bonding interface. Therefore, even if the hybrid bonding technology used for W2W bonding is simply applied to C2W bonding, there is a risk of causing bonding failure due to the generation of such voids, resulting in a problem of reduced yield in semiconductor device manufacturing. On the other hand, when using a clean room and equipment with high cleanliness to prevent these bonding failures, a large amount of cost is required for facility investment in the clean room and the like.

[0008] Also, when an organic material such as a cyclic olefin-based resin is used as the material of the insulating film, the heat resistance of the organic material is not sufficient, and when exposed to high temperature during C2W bonding, the organic material may be deteriorated, resulting in bonding failure at the interface between the substrate and the insulating film or the like.

[0009] The inventors considered using an insulating material containing a polyimide precursor, which is an organic material with excellent heat resistance, from the viewpoint of suppressing joint failures due to the generation of voids as described above, deterioration of organic materials, and the like. However, when an insulating material containing a polyimide precursor is applied to C2W bonding, there is a problem that a metal (for example, copper) contained in an electrode or the like to be joined diffuses into an insulating film formed of the insulating material, and the insulation resistance tends to decrease.

[0010] This disclosure has been made in view of the above, and an object thereof is to provide an insulating film forming material capable of forming an insulating film having excellent insulation reliability when performing hybrid bonding, a method for manufacturing a semiconductor device using the insulating film forming material, and a semiconductor device including an insulating film formed from the insulating film forming material.

Means for Solving the Problems

[0011] Specific means for achieving the above problems are as follows. <1> An insulating film forming material for forming an insulating film by hybrid bonding, comprising: (A) a polyimide precursor, which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide; and (B) a polymerizable monomer, wherein the content of a compound containing an alkylene oxide chain and a (meth)acrylic group classified as the (B) polymerizable monomer is less than 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor. <2> The insulating film forming material according to <1>, wherein the (B) polymerizable monomer includes at least one selected from the group consisting of a compound containing an alkylene oxide chain and a (meth)acrylic group, a compound containing an alicyclic structure and a (meth)acrylic group, and a compound containing an aromatic ring structure and a (meth)acrylic group. <3> The insulating film forming material according to <1>, wherein the (B) polymerizable monomer includes a compound containing an alkylene oxide chain and a (meth)acrylic group and a compound containing an alicyclic structure and a (meth)acrylic group. <4> The content of the (B) polymerizable monomer is 30 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor, and it is the insulating film forming material according to any one of <1> to <3>. <5> Further comprising a (C) solvent, and the (C) solvent contains at least one selected from the group consisting of compounds represented by the following formulas (3) to (7), and it is the insulating film forming material according to any one of <1> to <4>.

[0012]

Chemical formula

[0013] In formulas (3) to (7), R 1 , R 2 , R 8 and R 10 are each independently an alkyl group having 1 to 4 carbon atoms, and R 3 ~R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, and u is an integer from 0 to 3. <6> The (C) solvent contains at least the compound represented by the formula (5), and it is the insulating film forming material according to <5>. <7> Further comprising a (D) photoinitiator, and it is the insulating film forming material according to any one of <1> to <6>. <8> The (A) polyimide precursor contains a compound having a structural unit represented by the following general formula (1), and it is the insulating film forming material according to any one of <1> to <7>.

[0014]

Chemical formula

[0015] In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group. <9> In the general formula (1), the tetravalent organic group represented by X is the insulating film forming material according to <8>, which is a group represented by the following formula (E).

[0016]

Chemical formula

[0017] In formula (E), C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R A )2-; two Rs A each independently represent a hydrogen atom, an alkyl group or a phenyl group.) A siloxane bond (-O-(Si(R B )2-O-) n ; two Rs B each independently represent a hydrogen atom, 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. <10> In the general formula (1), the divalent organic group represented by Y is the insulating film forming material according to <8> or <9>, which is a group represented by the following formula (H).

[0018]

Chemical formula

[0019] In formula (H), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and each n independently represents an integer from 0 to 4. D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R A )2-; two Rs A each independently represent a hydrogen atom, an alkyl group or a phenyl group.) A siloxane bond (-O-(Si(R B)2-O-) n ; two Rs B each independently 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 is represented. <11> In the general formula (1), the R 6 and the R 7 The monovalent organic group in is any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group or a t-butyl group. The insulating film forming material according to any one of <8> to <10>.

[0020]

Chemical formula

[0021] In the general formula (2), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group. <12> The insulating film forming material according to any one of <1> to <11> is used for manufacturing at least one of the first organic insulating film and the second organic insulating film, and a semiconductor device is manufactured through the following steps (1) to (5). A method for manufacturing a semiconductor device. Step (1) Prepare a first semiconductor substrate having a first substrate body, the first organic insulating film provided on one surface of the first substrate body, and a first electrode. Step (2) Prepare a second semiconductor substrate having a second substrate body, the second organic insulating film provided on one surface of the second substrate body, and a plurality of second electrodes. Step (3) Fragment the second semiconductor substrate to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4) Bond the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other. Step (5) Bond the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip. <13>A first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body, A semiconductor chip having a semiconductor chip substrate body, an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body, Comprising: the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are joined; the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined, A semiconductor device, wherein at least one of the first organic insulating film and the organic insulating film portion is an organic insulating film formed by curing an insulating film forming material according to any one of <1> to <11>.

Advantages of the Invention

[0022] According to the present disclosure, it is possible to provide an insulating film forming material capable of forming an insulating film excellent in insulation reliability when performing hybrid bonding, a method for manufacturing a semiconductor device using the insulating film forming material, and a semiconductor device including an insulating film formed from the insulating film forming material.

Brief Description of the Drawings

[0023]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Modes for Carrying Out the Invention

[0024] 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, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.

[0025] In the present disclosure, "A or B" means that either A or B may be included, or both may be included. In the present disclosure, the term "step" includes not only a step independent of other steps but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the numerical range indicated by "~" in the present disclosure, the numerical values described before and after "~" are included as the minimum value and the maximum value, respectively. In the numerical ranges described step by step in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other step-by-step descriptions. Also, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, each component may contain a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" or "film" include not only the case where the layer or film is formed over the entire region when observing the region where the layer or film exists but also the case where it is formed only in a part of the region. In the present disclosure, the thickness of a layer or film is the value obtained by measuring the thickness at five points of the target layer or film and taking the arithmetic mean value. The thickness of a layer or film can be measured using a micrometer or the like. In the present disclosure, when the thickness of a layer or film can be directly measured, it is measured using a micrometer. On the other hand, when measuring the thickness of one layer or the total thickness of a plurality of layers, it may be measured by observing a cross-section of the measurement target using an electron microscope. In the present disclosure, the "insulating film" is a concept that also includes an insulating layer. In the present disclosure, the "(meth)acrylic group" means an "acrylic group" and a "methacrylic group". In the present disclosure, when a functional group has a substituent, the number of carbon atoms in the functional group means the total number of carbon atoms including the carbon atoms of the substituent. In the present disclosure, when an embodiment is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Also, the sizes of the members in each figure are conceptual, and the relative relationships of the sizes between the members are not limited thereto.

[0026] <Insulating film forming material> The insulating film forming material of the present disclosure includes (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 (B) a polymerizable monomer. The content of a compound containing an alkylene oxide chain and a (meth)acrylic group classified as the (B) polymerizable monomer is less than 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and is a material for forming an insulating film by hybrid bonding.

[0027] The insulating film forming material of the present disclosure is a material for forming an insulating film when performing three-dimensional mounting of semiconductor chips by applying hybrid bonding technology to W2W (Wafer-to-Wafer) bonding, C2W (Chip-to-Wafer) bonding, etc. When hybrid bonding by bonding insulating films together, it is sufficient that at least one of the insulating films is formed of the insulating film forming material of the present disclosure, and it is preferable that both insulating films are formed of the insulating film forming material of the present disclosure.

[0028] By using the insulating film forming material of the present disclosure, an insulating film excellent in insulating reliability can be formed. The reason is presumed as follows. However, the following presumption does not limitatively interpret the insulating film forming material of the present disclosure and is described as an example. The insulating film forming material of the present disclosure contains (A) a polyimide precursor and (B) a polymerizable monomer, and by reacting these components by heating or the like to form a crosslinked structure, an insulating film that is a cured product is formed. At this time, since the content of the compound containing an alkylene oxide chain and a (meth)acrylic group classified as (B) the polymerizable monomer is less than 20 parts by mass with respect to 100 parts by mass of (A) the polyimide precursor, metals (for example, copper) contained in electrodes or the like to be joined are less likely to diffuse into the insulating film, and it is presumed that the insulating reliability is excellent because the decrease in insulation resistance is suppressed.

[0029] The insulating film obtained by curing the insulating film forming material has a lower elastic modulus and is softer than a molded article made of an inorganic material. Therefore, when bonding insulating films together, even if foreign matter or the like is present on the surface of one insulating film (hereinafter also referred to as the "first insulating film") or the surface of the other insulating film (hereinafter also referred to as the "second insulating film"), the insulating film at the bonding interface is easily deformed, and the foreign matter can be included in the insulating film without causing large voids in the insulating film. Furthermore, the insulating film forming material containing (A) the polyimide precursor tends to have higher heat resistance compared to an insulating film obtained by curing an insulating film forming material containing an acrylic resin, an epoxy resin, or the like.

[0030] 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.

[0031] From the viewpoint of bonding at low temperature, the glass transition temperature of the insulating film formed by curing the insulating film forming material of the present disclosure is preferably 100°C to 400°C, and more preferably 150°C to 350°C.

[0032] The glass transition temperature of the insulating film is measured as follows. First, the insulating film forming material is heated at a predetermined curing temperature (for example, 150°C to 375°C) at which a curing reaction is possible for 2 hours in a nitrogen atmosphere to obtain an insulating film. The obtained insulating film is cut to produce a rectangular parallelepiped of 5 mm × 50 mm × 3 mm, and using a tensile jig with a dynamic viscoelasticity measuring device (for example, RSA-G2 manufactured by TA Instruments), the dynamic viscoelasticity is measured in the temperature range of 50°C to 350°C under the conditions of a frequency of 1 Hz and a heating rate of 5°C / min. The glass transition temperature (Tg) is the temperature at the peak top in tanδ obtained from the ratio of the storage elastic modulus and the loss elastic modulus obtained by the above method.

[0033] The insulating film forming material of the present disclosure preferably has a thermal expansion coefficient of 150 ppm / K or less, more preferably 100 ppm / K or less, and even more preferably 70 ppm / K or less for the cured insulating film. Thereby, since the thermal expansion coefficient of the cured insulating film and the thermal expansion coefficient of the electrode become equal or close values, even when heat generation or the like occurs during the use of the semiconductor device, damage to the semiconductor device due to the difference in thermal expansion coefficient between the insulating film and the electrode can be suppressed. The thermal expansion coefficient indicates the ratio at which the length of the insulating film expands due to a temperature rise per degree Celsius, and can be calculated by measuring the change amount of the length of the insulating film at 100°C to 150°C using a thermomechanical analyzer or the like.

[0034] Hereinafter, the components included in the insulating film forming material of the present disclosure and the components that may be included will be described.

[0035] ((A) Polyimide precursor) The insulating film forming material of the present disclosure contains a polyimide precursor (hereinafter, also referred to as “(A) component”), which is at least one resin selected from the group consisting of (A) polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. The (A) component preferably contains a polyimide precursor having a polymerizable unsaturated bond. The (A) component contained in the insulating film forming material is preferably a component that does not cause problems in the polishing process, bonding process, etc. In the present disclosure, the polyimide precursor means a compound corresponding to any of a polyamic acid, a compound in which at least some of the hydrogen atoms of the carboxy groups in the polyamic acid are substituted with monovalent organic groups, or a polyamic acid salt in which at least some of the carboxy groups in the polyamic acid form a salt structure with a basic compound having a pH of 7 or higher. Examples of the compound in which at least some of the hydrogen atoms of the carboxy groups in the polyamic acid are substituted with monovalent organic groups include polyamic acid esters and polyamic acid amides. Polyamic acid esters, polyamic acid amides, etc. preferably have a polymerizable unsaturated bond.

[0036] Component (A) preferably contains a compound having a structural unit represented by the following general formula (1). Thereby, a semiconductor device including an insulating film showing high reliability tends to be obtained.

[0037] [Chemical formula]

[0038] In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. R 6 and R 7 each independently represent 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, R 6 in the plurality of structural units 7 and R may be the same or different from each other. 6 Incidentally, R 7 and R 6 and R 7may each be a hydrogen atom, one may be a hydrogen atom and the other may be a monovalent organic group described below, or they may both be the same or different monovalent organic groups. When the polyimide precursor has a plurality of structural units represented by the above general formula (1) as described above, R of each structural unit 6 and R 7 may be the same or different combinations respectively.

[0039] In the 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 an aromatic hydrocarbon group (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), an aromatic heterocyclic group (for example, the number of atoms constituting the heterocyclic ring is 5 to 20), etc. 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, a phenanthrene ring, etc. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may or may not have a substituent. Examples of the substituent of the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, an amino group, etc. When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, more preferably 1 to 3 benzene rings, and even more preferably 1 or 2 benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, each benzene ring may be linked by a single bond, or 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 A each independently represent a hydrogen atom, an alkyl group or a phenyl group.), a siloxane bond (-O-(Si(R B )2-O-) n ; two R BEach independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) It may be bonded by a linking group such as, a composite linking group formed by combining at least two of these linking groups, etc. Further, two benzene rings may be bonded at two positions by at least one of a single bond and a linking group, and a 5-membered or 6-membered ring containing a linking group may be formed between the two benzene rings.

[0040] In general formula (1), -COOR 6 The -COOR group and the -CONH- group are preferably in the ortho position to each other, and the -COOR 7 group and the -CO- group are preferably in the ortho position to each other.

[0041] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulas (A) to (F). Among them, from the viewpoint of obtaining an insulating film with excellent flexibility and more suppressed generation of voids at the bonding interface, the group represented by the following formula (E) is preferable, and it is more preferable that C in the following formula (E) is a group containing an ether bond, and it is even more preferable that it is an ether bond. The following formula (F) is a structure in which C in the following formula (E) is a single bond. Note that the present disclosure is not limited to the following specific examples.

[0042]

Chemical formula

[0043] In formula (D), A and B each independently represent a single bond or a divalent group that does not conjugate with a benzene ring. However, both A and B cannot be a single bond. Examples of the divalent group that does not conjugate 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 Rs AEach independently represents a hydrogen atom, an alkyl group, or a phenyl group. Examples thereof include... 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, etc., and an ether bond is more preferable.

[0044] In formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a phenylene group, an ester bond (-O-C(=O)-), a silylene bond (-Si(R A )2-; two Rs A each independently represent a hydrogen atom, an alkyl group, or a phenyl group.) a siloxane bond (-O-(Si(R B )2-O-) n ; two Rs B each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or a divalent group formed by combining at least two of these. C preferably contains an ether bond, and more preferably is an ether bond. Further, C may have a structure represented by the following formula (C1).

[0045]

Chemical formula

[0046] 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 methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group; branched-chain alkylene groups such as methylmethylene group, methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group; and the like. Among these, the methylene group is preferred.

[0047] 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 the above formula (E) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethylene group, difluoromethylene group, hexafluorodimethylmethylene group, etc. are preferred.

[0048] R contained in the above silylene bond or siloxane bond A or R BThe alkyl group represented by 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. R A or R B Specific examples of the alkyl group represented by 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, a t-butyl group, and the like.

[0049] Specific examples of the tetravalent organic group represented by X may be groups represented by the following formulas (J) to (O).

[0050] [Chemical formula]

[0051] In the 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 are substituted with an atom (for example, a hydrogen atom) or a functional group (for example, an alkyl group) in the tetravalent organic group represented by X. 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, the number of carbon atoms constituting the aromatic ring is 6 to 20), a divalent aromatic heterocyclic group (for example, the number of atoms constituting the heterocyclic ring is 5 to 20), etc., and a divalent aromatic hydrocarbon group is preferred.

[0052] Specific examples of the divalent aromatic group represented by Y include groups represented by the following formula (G) to the following formula (I). Among them, from the viewpoint of excellent flexibility and more suppression of the generation of voids at the bonding interface, a group represented by the following formula (H) is preferable, and it is more preferable that D in the group represented by the following formula (H) is a group containing an ether bond, and it is even more preferable that D is an ether bond.

[0053]

Chemical formula

[0054] In formula (G) to formula (I), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group or a halogen atom, and each n independently represents an integer of 0 to 4. 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 Rs A each independently represents a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (-O-(Si(R B )2-O-) n ; two Rs B each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these. Further, D may have a structure represented by the above formula (C1). Specific examples of D in formula (H) are the same as specific examples of C in formula (E). As D in formula (H), 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, etc. are preferable.

[0055] The alkyl group represented by R in Formula (G) to Formula (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 Formula (G) to 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, a t-butyl group, and the like.

[0056] The alkoxy group represented by R in Formula (G) to Formula (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 Formula (G) to Formula (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, a t-butoxy group, and the like.

[0057] The halogenated alkyl group represented by R in Formula (G) to Formula (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 Formula (G) to Formula (I) include an alkyl group in which at least one hydrogen atom contained in the alkyl group represented by R in Formula (G) to Formula (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, and the like are preferable.

[0058] n in Formula (G) to Formula (I) is each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0059] 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, a divalent group having a polysiloxane structure, and the like.

[0060] 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, a 2-methyldecamethylene group, and the like.

[0061] 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, a cyclohexylene group, and the like.

[0062] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among them, 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 one type or two or more types.

[0063] Examples of the divalent group having a polysiloxane structure represented by Y include a divalent group having a polysiloxane structure in which a 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a 2-ethylhexyl group, an n-dodecyl group, and the like. Among these, a methyl group is preferable. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of the substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, a hydroxy group, and the like. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, a benzyl group, and the like. Among these, a phenyl group is preferable. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be one kind or two or more kinds. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in the general formula (1) via an alkylene group such as a methylene group or an ethylene group, an arylene group such as a phenylene group, or the like.

[0064] The group represented by the formula (G) is preferably a group represented by the following formula (G'), the group represented by the formula (H) is preferably a group represented by the following formula (H') or formula (H"), and the group represented by the formula (I) is preferably a group represented by the following formula (I').

[0065]

Chemical formula

[0066] In formula (I’), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom. R is preferably an alkyl group, more preferably a methyl group.

[0067] In general formula (1), the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited. Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include a combination where X is a group represented by formula (E) and Y is a group represented by formula (G); a combination where X is a group represented by formula (E) and Y is a group represented by formula (H); a combination where X is a group represented by formula (E) and Y is a group represented by formula (I), and the like.

[0068] R 6 and R 7 each 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 one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, still more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and particularly preferably a group represented by the following general formula (2). In particular, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the transmittance of i-line is high, and a good insulating film tends to be formed even during low-temperature curing at 400°C or lower. 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, a t-butyl group, etc. Among them, an ethyl group, an isobutyl group, and a t-butyl group are preferable.

[0069]

Chemical formula

[0070] In general formula (2), R 8 ~R 10each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group.

[0071] In the general formula (2), R 8 ~R 10 The aliphatic hydrocarbon group represented by has 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms. R 8 ~R 10 Specific examples of the aliphatic hydrocarbon group represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., and a methyl group is preferred.

[0072] In the general formula (2), the combination of R 8 ~R 10 is preferably a combination in which R 8 and R 9 are hydrogen atoms, and R 10 is a hydrogen atom or a methyl group.

[0073] In the general formula (2), R x is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include a linear or branched alkylene group. R x Preferably has 1 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2 or 3 carbon atoms.

[0074] In the general formula (1), at least one of R 6 and R 7 is preferably a group represented by the general formula (2), and more preferably both R 6 and R 7 are groups represented by the general formula (2).

[0075] When the component (A) contains a compound having a structural unit represented by the above general formula (1), R of all the structural units contained in the compound 6 and R 7 For the total of, R which is a group represented by the general formula (2) 6 and R7 The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more. The upper limit is not particularly limited and may be 100 mol%. In addition, the aforementioned proportion may be 0 mol% or more and less than 60 mol%.

[0076] The group represented by the general formula (2) is preferably a group represented by the following general formula (2’).

[0077] [Chemical formula]

[0078] In the 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.

[0079] In the general formula (2’), q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.

[0080] The content of the structural unit represented by the general formula (1) in the compound having the structural unit represented by the general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more with respect to all the structural units. The upper limit of the aforementioned content is not particularly limited and may be 100 mol%.

[0081] The component (A) may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in the general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. In addition, the component (A) may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0082] Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3’,4,4’-biphenyltetracarboxylic dianhydride, 3,3’,4,4’-benzophenonetetracarboxylic dianhydride, 3,3’,4,4’-biphenylethertetracarboxylic dianhydride, 3,3’,4,4’-diphenylsulfonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3’,4,4’-tetracarboxylic dianhydride, p-terphenyl-3,3’,4,4’-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4’-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4’-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4’-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4’-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4’-oxydiphthalic dianhydride, 4,4’-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and the like. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0083] Specific examples of the diamine compound include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,3-bis(3-aminophenoxy)benzene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,Examples include 4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane, etc. Preferred diamine compounds include m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene., The diamine compound may be used alone or in combination of two or more.,

[0084] A compound having a structural unit represented by the general formula (1) and at least one of R and R in the general formula (1) being a monovalent organic group can be obtained, for example, by the following method (a) or (b). 6 and R 7 For example, it can be obtained by the following method (a) or (b). (a) A tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) and a compound represented by R-OH are reacted in an organic solvent to form a diester derivative, and then the diester derivative and a diamine compound represented by H2N-Y-NH2 are subjected to a condensation reaction. (b) A tetracarboxylic dianhydride and a diamine compound represented by H2N-Y-NH2 are reacted in an organic solvent to obtain a polyamic acid solution, a compound represented by R-OH is added to the polyamic acid solution, and the reaction is carried out in an organic solvent to introduce an ester group. Here, Y in the diamine compound represented by H2N-Y-NH2 is the same as Y in the general formula (1), and the specific examples and preferred examples are also the same. Further, R in the compound represented by R-OH represents a monovalent organic group, and the specific examples and preferred examples are the same as those of R and R in the general formula (1). 6 and R 7 The case is the same. The tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH may each be used alone or in combination of two or more. Examples of the aforementioned organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropionamide, etc. Among them, 3-methoxy-N,N-dimethylpropionamide is preferred. A polyimide precursor may be synthesized by allowing a dehydrating condensing agent to act on a polyamic acid solution together with a compound represented by R-OH. The dehydrating condensing agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

[0085] (A) The aforementioned compound contained in the component can be obtained by allowing a compound represented by R-OH to act on a tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, then allowing a chlorinating agent such as thionyl chloride to act thereon to convert it into an acid chloride, and then reacting the acid chloride with a diamine compound represented by H2N-Y-NH2. (A) The aforementioned compound contained in the component can be obtained by allowing a compound represented by R-OH to act on a tetracarboxylic dianhydride represented by the following general formula (8) to form a diester derivative, and then reacting the diester derivative with a diamine compound represented by H2N-Y-NH2 in the presence of a carbodiimide compound. (A) The aforementioned compound contained in the component can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H2N-Y-NH2 to form a polyamic acid, then isimidizing the polyamic acid in the presence of a dehydrating condensing agent such as trifluoroacetic anhydride, and then allowing a compound represented by R-OH to act thereon. Alternatively, a compound represented by R-OH may be allowed to act on a part of the tetracarboxylic dianhydride in advance, and the partially esterified tetracarboxylic dianhydride may be reacted with a diamine compound represented by H2N-Y-NH2.

[0086]

Chemical formula

[0087] In the general formula (8), X is the same as X in the general formula (1), and the specific examples and preferred examples are also the same.

[0088] As the compound represented by R-OH used for the synthesis of the aforementioned compound contained in the component (A), a compound in which a hydroxy group is bonded to R of the group represented by the general formula (2), a compound in which a hydroxy group is bonded to the terminal methylene group of the group represented by the general formula (2’), etc. may be used. 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, 4-hydroxybutyl methacrylate, etc. Among them, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferable. x There is no particular limitation on the molecular weight of the component (A). For example, the weight average molecular weight is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000.

[0089] 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.

[0090] 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 in which a part of the amino groups in the (A) polyimide precursor reacts with the carboxy groups in the dicarboxylic acid. For example, when synthesizing the polyimide precursor, a part of the amino groups of the diamine compound may be reacted with the carboxy groups of the dicarboxylic acid. The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, and may be, for example, a dicarboxylic acid represented by the following formula. At this time, by reacting a part of the amino groups of the diamine compound with the carboxy groups of the dicarboxylic acid when synthesizing the (A) polyimide precursor, a methacrylic group derived from the dicarboxylic acid can be introduced into the (A) polyimide precursor.​

[0091] [Chem.]

[0092] The insulating film forming material of the present disclosure may contain a resin component other than the component (A). Examples of the resin component other than the component (A) include polyimide resin, novolak resin, acrylic resin, polyether nitrile resin, polyether sulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, etc. from the viewpoint of heat resistance. Among them, the resin component other than the component (A) preferably contains a polyimide resin. The resin component other than the component (A) may be used alone or in combination of two or more.

[0093] The polyimide resin is not particularly limited as long as it is a high molecular compound having a plurality of structural units containing an imide bond. For example, it preferably contains a compound having a structural unit represented by the following general formula (X). Thereby, a semiconductor device including an insulating film showing high reliability tends to be obtained.

[0094] [Chem.]

[0095] In the 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 the general formula (X) are the same as the preferred examples of the substituents X and Y in the aforementioned general formula (1).

[0096] By combining the polyimide precursor which is the component (A) and the polyimide resin, it is possible to suppress the generation of volatiles due to dehydration cyclization during imide ring formation. Thereby, the generation of voids tends to be suppressed. The polyimide resin referred to here means a resin having an imide skeleton in all or part of the resin skeleton. The polyimide resin is preferably soluble in the solvent in the insulating film forming material using the polyimide precursor.

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

[0098] When the insulating film forming material of the present disclosure contains a resin component other than the component (A) (preferably a polyimide resin), the ratio of the resin component other than the component (A) (preferably a polyimide resin) to the total of the component (A) and the resin component other than the component (A) may be 15% by mass to 50% by mass, or may be 10% by mass to 20% by mass.

[0099] ((B) Polymerizable monomer) The insulating film forming material of the present disclosure contains a (B) polymerizable monomer (hereinafter also referred to as the “(B) component”). The (B) component preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of being suitably polymerizable by combination with a photoinitiator. From the viewpoints of improving the crosslinking density and the photosensitivity, it is preferable to have 2 to 6 groups containing a polymerizable unsaturated double bond, and more preferably 2 to 4 groups. The polymerizable monomer may be used alone or in combination of two or more.

[0100] (Meta) acrylic group-containing polymerizable monomers are not particularly limited. For example, diethylene glycol di (meta) acrylate, triethylene glycol di (meta) acrylate, tetraethylene glycol di (meta) acrylate, 1,4-butanediol di (meta) acrylate, 1,6-hexanediol di (meta) acrylate, trimethylolpropane di (meta) acrylate, trimethylolpropane tri (meta) acrylate, pentaerythritol tri (meta) acrylate, pentaerythritol tetra (meta) acrylate, dipentaerythritol hexa (meta) acrylate, ethoxylated pentaerythritol tetra (meta) acrylate, ethoxylated isocyanuric acid tri (meta) acrylate, (meta) acryloyloxyethyl isocyanurate, 2-hydroxyethyl (meta) acrylate, 1,3-bis ((meta) acryloyloxy) -2-hydroxypropane, ethylene oxide (EO) modified bisphenol A di (meta) acrylate, benzyl (meta) acrylate and phenoxyethyl (meta) acrylate can be mentioned.

[0101] Component (B) may contain at least one selected from the group consisting of a compound containing an alkylene oxide chain and a (meta) acrylic group (hereinafter also referred to as "compound (1)"), a compound containing an alicyclic structure and a (meta) acrylic group (hereinafter also referred to as "compound (2)"), and a compound containing an aromatic ring structure and a (meta) acrylic group (hereinafter also referred to as "compound (3)"). Note that compound (1) may not contain both an alicyclic structure and an aromatic ring structure, and compound (2) may not contain both an alkylene oxide chain and an aromatic ring structure. Compound (3) may contain an alkylene oxide chain. The alkylene oxide chain in component (B) means a group consisting of an alkylene group and an oxygen atom bonded to the alkylene group (excluding the oxygen atom contained in the (meta) acryloyloxy group).

[0102] Component (B) preferably contains compound (1) and compound (2). When the insulating film forming material contains the compound (1), the thermocompression bonding property between the substrate and the insulating film tends to be improved. When the insulating film forming material contains the compound (2), the insulating reliability of the insulating film tends to be more excellent.

[0103] Examples of the compound (1) include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

[0104] Examples of the compound (2) include tricyclodecane dimethanol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, and 1,3 - adamantane dimethanol di(meth)acrylate.

[0105] Examples of the compound (3) include EO - modified bisphenol A di(meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxy methacrylate.

[0106] The component (B) may contain a polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group. 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, methylene bisacrylamide, N,N - dimethylacrylamide, and N - methylolacrylamide.

[0107] The component (B) is not limited to a compound having a group containing a polymerizable unsaturated double bond, and may be a compound having a polymerizable group other than the unsaturated double bond group (for example, an oxirane ring).

[0108] In the insulating film forming material of the present disclosure, from the viewpoint of the insulation reliability of the insulating film, the content of component (B) may be 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 18 parts by mass or less, or 15 parts by mass or less with respect to 100 parts by mass of component (A). When the content of component (B) is 30 parts by mass or less with respect to 100 parts by mass of component (A), unreacted (B) polymerizable monomer is less likely to be generated after curing. As a result, it is presumed that the metal (for example, copper) contained in the electrode or the like to be joined is less likely to diffuse into the insulating film, and the decrease in insulation resistance is suppressed, resulting in excellent insulation reliability. The lower limit of the content of component (B) may be 1 part by mass or more, or 3 parts by mass or more with respect to 100 parts by mass of component (A).

[0109] In the insulating film forming material of the present disclosure, the content of compound (1) is less than 20 parts by mass. When the insulating film forming material of the present disclosure contains compound (1), the content of compound (1) may be 0.5 part by mass to 15 parts by mass, 1 part by mass to 12 parts by mass, or 2 parts by mass to 8 parts by mass with respect to 100 parts by mass of component (A). When the insulating film forming material of the present disclosure contains compound (2), the content of compound (2) may be 2 parts by mass to 20 parts by mass, 5 parts by mass to 15 parts by mass, or 8 parts by mass to 12 parts by mass with respect to 100 parts by mass of component (A).

[0110] ((C) solvent) The insulating film forming material of the present disclosure may contain a (C) solvent (hereinafter, also referred to as “component (C)”). Component (C) preferably contains at least one selected from the group consisting of compounds represented by the following formulas (3) to (7). Component (C) may be used alone or in combination of two or more.

[0111] [Chemical formula]

[0112] In Formulas (3) to (7), R 1 , R 2 , R 8 and R 10 are each independently an alkyl group having 1 to 4 carbon atoms, and R 3 to R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer from 0 to 8, t is an integer from 0 to 4, r is an integer from 0 to 4, and u is an integer from 0 to 3.

[0113] In Formula (3), s is preferably 0. In Formula (4), as the alkyl group having 1 to 4 carbon atoms of R 2 , preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, more preferably 1. In Formula (5), as the alkyl group having 1 to 4 carbon atoms of R 3 , preferably a methyl group, an ethyl group, a propyl group or a butyl group. As the alkyl group having 1 to 4 carbon atoms of R 4 and R 5 , preferably a methyl group or an ethyl group. In Formula (6), as the alkyl group having 1 to 4 carbon atoms of R 6 to R 8 , preferably a methyl group or an ethyl group. r is preferably 0 or 1, more preferably 0. In Formula (7), as the alkyl group having 1 to 4 carbon atoms of R 9 and R 10 , preferably a methyl group or an ethyl group. u is preferably 0 or 1, more preferably 0.

[0114] The component (C) may be, for example, at least one of the compounds represented by Formulas (4), (5), (6) and (7), may be a compound represented by Formula (5) or a compound represented by Formula (7), and from the viewpoint of reducing the reproductive toxicity and environmental load of the insulating film forming material, it may be a compound represented by Formula (5).

[0115] Specific examples of the component (C) include the following compounds.

[0116] [Chemical formula]

[0117] The component (C) that can be included in the insulating film forming material of the present disclosure is not limited to the aforementioned compounds, and other solvents may also be used. The component (C) may be a solvent such as esters, ethers, ketones, hydrocarbons, aromatic hydrocarbons, sulfoxides, etc.

[0118] Examples of the ester solvents include alkyl alkoxyacetates such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, methyl alkoxyacetate, ethyl alkoxyacetate, and butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate), alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate and ethyl 3-alkoxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate), alkyl 2-alkoxypropionates such as methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, and propyl 2-alkoxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionates such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanoate.

[0119] As solvents for ethers, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. can be mentioned. As solvents for ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethylpropionamide, etc. can be mentioned. As solvents for hydrocarbons, limonene, etc. can be mentioned. As solvents for aromatic hydrocarbons, toluene, xylene, anisole, etc. can be mentioned. As solvents for sulfoxides, dimethyl sulfoxide, etc. can be mentioned.

[0120] As the solvent for the component (C), preferably, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone, cyclopentanone, ethyl lactate, etc. can be mentioned.

[0121] In the insulating film forming material of the present disclosure, from the viewpoint of reducing toxicity such as reproductive toxicity, the content rate of NMP may be 1 mass% or less with respect to the total amount of the insulating film forming material, and may be 3 mass% or less with respect to the total amount of the component (A).

[0122] In the insulating film forming material of the present disclosure, the content of the component (C) is preferably 1 part by mass to 10,000 parts by mass, and more preferably 50 parts by mass to 10,000 parts by mass with respect to 100 parts by mass of the component (A).

[0123] The (C) component preferably contains at least one of a solvent (1) selected from the group consisting of compounds represented by Formula (3) to Formula (7) and at least one of a solvent (2) selected from the group consisting of ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, and sulfoxide solvents. Also, the content rate of the solvent (1) may be 5 mass% to 100 mass% or 5 mass% to 50 mass% with respect to the total of the solvent (1) and the solvent (2). The content of the solvent (1) may be 10 parts by mass to 1000 parts by mass, 10 parts by mass to 100 parts by mass, or 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the (A) component.

[0124] The insulating film forming material of the present disclosure preferably further contains a (D) photopolymerization initiator (hereinafter also referred to as the (D) component). Further, the insulating film forming material of the present disclosure may further contain an (E) thermal polymerization initiator (hereinafter also referred to as the (E) component). Hereinafter, preferred forms of the (D) component and the (E) component will be described.

[0125] ((D) Photopolymerization initiator) The insulating film forming material of the present disclosure preferably contains a (D) photopolymerization initiator. Thereby, the number of steps for fabricating electrodes in the process of fabricating a semiconductor device can be reduced, and the cost of the entire process for fabricating a semiconductor device can be reduced.

[0126] Specific examples of the component (D) include benzophenone derivatives such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; acetophenone derivatives such as acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, propyl benzoin; oxime derivatives such as 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxyoxime); N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl peroxide;Aromatic biimidazoles such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, Irgacure OXE03 (manufactured by BASF), Irgacure OXE04 (manufactured by BASF), etc. are included.; Component (D) may be used alone or in combination of two or more kinds. Among these, an oxime compound derivative is preferable from the viewpoints of not containing a metal element and having high reactivity and high sensitivity.

[0127] When the insulating film forming material of the present disclosure contains component (D), the content of component (D) is preferably 0.1 part by mass to 25 parts by mass, more preferably 1 part by mass to 20 parts by mass, and still more preferably 5 parts by mass to 15 parts by mass with respect to 100 parts by mass of component (A) from the viewpoint that photocrosslinking is likely to be uniform in the film thickness direction.

[0128] The insulating film forming material of the present disclosure may contain an antireflection agent that suppresses reflected light from the substrate direction from the viewpoint of improving photosensitivity characteristics.

[0129] ((E) Thermal polymerization initiator) The insulating film forming material of the present disclosure preferably contains an (E) thermal polymerization initiator from the viewpoint of improving the physical properties of the cured product.

[0130] Specific examples of the component (E) include ketone peroxides such as methyl ethyl ketone peroxide, peroxyesters such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, peroxydicarbonates such as di(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, peroxy esters such as t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl) peroxide, dicumyl peroxide, di-t-butyl peroxide, di(2-t-butylperoxyisopropyl) benzene, and the like. The thermal polymerization initiator may be used alone or in combination of two or more kinds.

[0131] When the insulating film forming material of the present disclosure contains the component (E), the content of the component (E) may be 0.1 part by mass to 20 parts by mass, may be 1 part by mass to 15 parts by mass, or may be 5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor.

[0132] ((F) polymerization inhibitor) From the viewpoint of ensuring good storage stability, the insulating film forming material of the present disclosure may contain an (F) polymerization inhibitor (hereinafter, also referred to as "(F) component"). Examples of the polymerization inhibitor include radical polymerization inhibitors and radical polymerization suppressants.

[0133] Specific examples of the (F) component include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-xylenol, tannic acid, para-benzylaminophenol, nitrosoamines, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide, hindered phenol-based compounds, and the like. The polymerization inhibitor may be used alone or in combination of two or more. By combining two or more polymerization inhibitors, it tends to be easy to adjust the photosensitive characteristics due to the difference in reactivity. The hindered phenol-based compound may have both the function of the polymerization inhibitor and the function of the antioxidant described later, or may have either one of the functions.

[0134] The hindered phenolic compound is not particularly limited. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-Dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] are mentioned., Among these, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] is preferred.,

[0135] When the insulating film forming material of the present disclosure contains the (F) component, the content of the (F) component is preferably 0.01 part by mass to 30 parts by mass, more preferably 0.01 part by mass to 10 parts by mass, and even more preferably 0.05 part by mass to 5 parts by mass with respect to 100 parts by mass of the (A) component from the viewpoints of the storage stability of the insulating film forming material and the heat resistance of the resulting cured product.

[0136] The insulating film forming material of the present disclosure may further contain an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor, or a nitrogen-containing compound.

[0137] (Antioxidant) The insulating film forming material of the present disclosure may contain an antioxidant from the viewpoint of suppressing a decrease in adhesiveness by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow treatment, etc. By containing an antioxidant in the insulating film forming material of the present disclosure, oxidation of the electrodes during the insulation reliability test can be suppressed.

[0138] Specific examples of the antioxidant include the compounds exemplified as the above-mentioned hindered phenol-based compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, and the like. The antioxidant may be used alone or in combination of two or more.

[0139] When the insulating film forming material of the present disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 part by mass to 20 parts by mass, more preferably 0.1 part by mass to 10 parts by mass, and even more preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the (A) component.

[0140] (Coupling agent) The insulating film forming material of the present disclosure may contain a coupling agent. The coupling agent reacts with the component (A) and crosslinks during heat treatment, or the coupling agent itself polymerizes. Thereby, the adhesiveness between the obtained cured product and the substrate tends to be further improved.

[0141] Specific examples of the coupling agent are not particularly limited. Examples of the coupling agent include silane coupling agents such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane; aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), aluminum diisopropylate ethylacetoacetate; and the like. The coupling agent may be used alone or in combination of two or more.

[0142] When the insulating film forming material of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 part by mass to 20 parts by mass, more preferably 0.3 part by mass to 10 parts by mass, and still more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the component (A).

[0143] (Surfactant and leveling agent) The insulating film forming material of the present disclosure may contain at least one of a surfactant and a leveling agent. By including at least one of a surfactant and a leveling agent in the insulating film forming material, coating properties (for example, suppression of striations (non-uniformity of film thickness)), improvement of adhesiveness, compatibility of compounds in the insulating film forming material, etc. can be improved.

[0144] Examples of the surfactant or leveling agent include polyoxyethylene urallyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc.

[0145] The surfactant and the leveling agent may be used alone or in combination of two or more.

[0146] When the insulating film forming material of the present disclosure contains at least one of a surfactant and a leveling agent, the total content of the surfactant and the leveling agent is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.05 part by mass to 5 parts by mass, and still more preferably 0.05 part by mass to 3 parts by mass with respect to 100 parts by mass of the component (A).

[0147] (Rust preventive agent) The insulating film forming material of the present disclosure may contain a rust preventive agent from the viewpoints of suppressing corrosion of metals such as copper and copper alloys and suppressing discoloration of the metals. Examples of the rust preventive agent include azole compounds, purine derivatives, etc.

[0148] Specific examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxy-phenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, and the like.

[0149] Specific examples of purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azadenine, 5-azadenine, 8-azadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

[0150] The rust inhibitor may be used alone or in combination of two or more.

[0151] When the insulating film-forming material of the present disclosure contains a rust inhibitor, the content of the rust inhibitor is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.1 part by mass to 5 parts by mass, and even more preferably 0.5 part by mass to 3 parts by mass with respect to 100 parts by mass of the component (A). In particular, when the content of the rust inhibitor is 0.1 part by mass or more, discoloration of the surface of copper or a copper alloy is suppressed when the insulating film-forming material of the present disclosure is applied onto the surface of copper or a copper alloy.

[0152] The insulating film-forming material of the present disclosure may contain a nitrogen-containing compound from the viewpoint of promoting the imidization reaction of the component (A) to obtain a cured product having high reliability.

[0153] Specific examples of the nitrogen-containing compound include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, etc. Among them, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, etc. are preferable. The nitrogen-containing compound may be used alone or in combination of two or more.

[0154] The nitrogen-containing compound preferably includes a compound represented by the following formula (17).

[0155]

Chemical formula

[0156] In formula (17), R 31A ~R 33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group, and at least one (preferably one) of R 31A ~R 33A is a monovalent aromatic group. R 31A ~R 33A may form a ring structure with adjacent groups. Examples of the formed ring structure include a 5-membered ring, a 6-membered ring, etc. which may have substituents such as a methyl group and a phenyl group. The hydrogen atom of the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than a hydroxy group.

[0157] In formula (17), R 31A ~R 33AIt is preferable that at least one (preferably one) of them is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group.

[0158] In formula (17), R 31A ~R 33A For the monovalent aliphatic hydrocarbon group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6. The monovalent aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, etc.

[0159] In formula (17), R 31A ~R 33A The monovalent aliphatic hydrocarbon group having a hydroxy group is preferably a group in which one or more hydroxy groups are bonded to the monovalent aliphatic hydrocarbon group of R 31A ~R 33A More preferably, it is a group to which 1 to 3 hydroxy groups are bonded. Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a hydroxymethyl group, a hydroxyethyl group, etc. Among them, a hydroxyethyl group is preferable.

[0160] For the monovalent aromatic group of R 31A ~R 33A in formula (17), examples include a monovalent aromatic hydrocarbon group, a monovalent aromatic heterocyclic group, etc., and a monovalent aromatic hydrocarbon group is preferable. For the monovalent aromatic hydrocarbon group, the number of carbon atoms is preferably 6 to 12, more preferably 6 to 10. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a naphthyl group, etc.

[0161] The monovalent aromatic group of R 31A ~R 33A in formula (17) may have a substituent. Examples of the substituent include the monovalent aliphatic hydrocarbon group of R 31A ~R 33A in formula (17), and the same groups as the monovalent aliphatic hydrocarbon group having a hydroxy group of R 31A ~R 33A in the above formula (17).

[0162] When the insulating film forming material of the present disclosure contains a nitrogen-containing compound, the content of the nitrogen-containing compound is preferably 0.1 part by mass to 20 parts by mass, more preferably 0.3 part by mass to 15 parts by mass, and even more preferably 0.5 part by mass to 10 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of storage stability.

[0163] <Semiconductor device> The semiconductor device of the present disclosure 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, a semiconductor chip substrate body, and a semiconductor chip having an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate is joined to the organic insulating film portion of the semiconductor chip, the first electrode of the first semiconductor substrate is joined to the second electrode of the semiconductor chip, and at least one of the first organic insulating film and the organic insulating film portion is an insulating film formed by curing the insulating film forming material of the present disclosure. Since at least one of the first organic insulating film and the organic insulating film portion of the semiconductor device of the present disclosure is an insulating film formed by curing the insulating film forming material of the present disclosure, metals (for example, copper) contained in electrodes and the like to be joined are less likely to diffuse into the insulating film, and a decrease in insulation resistance is suppressed. Thereby, a semiconductor device having an insulating film excellent in insulation reliability can be obtained. Further, the semiconductor device of the present disclosure is manufactured, for example, through steps (1) to (5) described later.

[0164] <Method for manufacturing a semiconductor device> The semiconductor device of the present disclosure is manufactured using the insulating film forming material of the present disclosure. Specifically, a semiconductor device can be manufactured by passing through steps (1) to (5) using the insulating film forming material of the present disclosure. Step (1): Prepare a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body. Step (2): Prepare a second semiconductor substrate having a second substrate body, a second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body. Step (3): Separate the second semiconductor substrate into individual pieces to obtain a plurality of semiconductor chips, each including an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4): Bond the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other. Step (5): Join the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.

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

[0166] (An example of a semiconductor device) FIG. 1 is a cross-sectional view schematically showing an example of the semiconductor device of the present disclosure. As shown in FIG. 1, the semiconductor device 1 is, for example, 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.

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

[0168] The pillar portion 30 is a connection portion in which a plurality of pillars 31 formed of a metal such as copper (Cu) are sealed by a resin 32. The plurality of pillars 31 are conductive members extending from the upper surface to the lower surface of the pillar portion 30. The plurality of pillars 31 may have, for example, a cylindrical shape with a diameter of 3 μm or more and 20 μm or less (in one example, a diameter of 5 μm), and may be arranged such that the center-to-center distance between the pillars 31 is 15 μm or less. The plurality of pillars 31 make a flip-chip connection between the terminal electrode on the lower side of the first semiconductor chip 10 and the terminal electrode on the upper side of the redistribution layer 40. By using the pillar portion 30, in the semiconductor device 1, a connection electrode can be formed without using a technique of forming a hole in a mold called TMV (Through mold via) and soldering. The pillar portion 30 has, for example, a thickness comparable to that of the second semiconductor chip 20 and is arranged laterally of the second semiconductor chip 20 in the horizontal direction. Note that a plurality of solder balls may be arranged instead of the pillar portion 30, and the terminal electrode on the lower side of the first semiconductor chip 10 and the terminal electrode on the upper side of the redistribution layer 40 may be electrically connected by the solder balls.

[0169] The redistribution layer 40 is a wiring layer having a function of converting a terminal pitch, which is a function of the package substrate, and is a layer in which a redistribution pattern is formed of polyimide, copper wiring, etc. on the insulating film on the lower side of the second semiconductor chip 20 and on the lower surface of the pillar portion 30. The redistribution layer 40 is formed in a state where the first semiconductor chip 10 (the first semiconductor substrate 100), the second semiconductor chip 20, etc. are turned upside down (see (d) in FIG. 4).

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

[0171] The circuit board 60 is a board that mounts the first semiconductor chip 10 and the second semiconductor chip 20 thereon and has a plurality of through electrodes inside that are electrically connected to the substrate 50 connected to the first semiconductor chip 10, the second semiconductor chip 20, the electronic components 51, etc. In the circuit board 60, each terminal electrode of the first semiconductor chip 10 and the second semiconductor chip 20 is electrically connected to a terminal electrode 61 provided on the back surface of the circuit board 60 by the plurality of through electrodes.

[0172] (An example of a method for manufacturing a semiconductor device) Next, an example of a method for manufacturing the semiconductor device 1 will be described with reference to FIGS. 2 to 4. FIG. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in FIG. 1. FIG. 3 is a diagram showing in more detail the bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in FIG. 2. FIG. 4 is a method for manufacturing the semiconductor device shown in FIG. 1 and is a diagram sequentially showing the steps after the steps shown in FIG. 2.

[0173] The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n). (a) A step of preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10. (b) A step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20. (c) A step of polishing the surface on the side of surface 101a, which is the surface of the first semiconductor substrate 100, using the CMP method so that each surface 103a of the terminal electrode 103 is at the same position as or protrudes from the surface 102a of the insulating film 102 (see (a) of FIG. 3). (d) A step of polishing the surface on the side of surface 201a, which is the surface of the second semiconductor substrate 200, using the CMP method so that each surface 203a of the terminal electrode 203 is at the same position as or protrudes from the surface 202a of the insulating film 202 (see (a) of FIG. 3). (e) A step of dicing the second semiconductor substrate 200 as shown in (b) of FIG. 2 to obtain a plurality of semiconductor chips 205. (f) A step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with the terminal electrode 103 of the first semiconductor substrate 100 as shown in (c) of FIG. 2. (g) A step of bonding the insulating film 102 of the first semiconductor substrate 100 and each insulating film portion 202b of the plurality of semiconductor chips 205 to each other (see (d) of FIG. 2 and (b) of FIG. 3). At this time, heat H, pressure, or both may be applied. (h) A step of bonding the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrodes 203 of each of the plurality of semiconductor chips 205 (see (c) of FIG. 3). (i) A step of forming a plurality of pillars 300 (corresponding to pillar 31) between the plurality of semiconductor chips 205 on the connection surface of the first semiconductor substrate 100 (see (a) of FIG. 4). (j) A step of molding resin 301 on the connection surface of the first semiconductor substrate 100 so as to cover the semiconductor chip 205 and the pillar 300 to obtain a semi-finished product M1 (see (b) of FIG. 4). (k) A step of grinding and thinning the resin 301 side of the semi-finished product M1 molded in step (j) to obtain a semi-finished product M2 (see (c) of FIG. 4). (l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k) (see (d) of FIG. 4). (m) A step of cutting the semi-finished product M3 on which the wiring layer 400 is formed in step (l) along the cutting line A so as to become each semiconductor device 1 (see (d) of FIG. 4). (n) Step of inverting the semiconductor device 1a individualized by the engineering (m) and installing it on the substrate 50 and the circuit board 60 (see Fig. 1).

[0174] For example, in the method for manufacturing a semiconductor device of 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). Further, the insulating film forming material of the present disclosure may be an insulating film forming material for producing at least one of the first organic insulating film and the second organic insulating film in the method for manufacturing a semiconductor device.

[0175] Step (a) corresponds to a plurality of first semiconductor chips 10, and is a step of preparing a first semiconductor substrate 100 which is a silicon substrate on which an integrated circuit including semiconductor elements and wirings connecting them is formed. In step (a), as shown in Fig. 2(a), a plurality of terminal electrodes 103 (first electrodes) made of copper, aluminum, etc. are provided at predetermined intervals on one surface 101a of 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 the insulating film forming material of the present disclosure is provided. After the insulating film 102 is provided on the one surface 101a of the first substrate body 101, the plurality of terminal electrodes 103 may be provided, or after the plurality of terminal electrodes 103 are provided on the one surface 101a of the first substrate body 101, the insulating film 102 may be provided.

[0176] Step (b) corresponds to a plurality of second semiconductor chips 20, and is a step of preparing a second semiconductor substrate 200 which is a silicon substrate on which an integrated circuit including semiconductor elements and wirings connecting them is formed. In step (b), as shown in FIG. 2(a), a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc. are continuously provided on one surface 201a of a second substrate body 201 made of silicon or the like, and an insulating film 202 (a second insulating film), which is a cured product obtained by curing the insulating film forming material of the present disclosure, is provided. The insulating film 202 may be provided on one surface 201a of the second substrate body 201 before providing the plurality of terminal electrodes 203, or the insulating film 202 may be provided after providing the plurality of terminal electrodes 203 on one surface 201a of the second substrate body 201.

[0177] The configuration is not limited to one in which both the insulating films 102 and 202 used in step (a) and step (b) are cured products obtained by curing the insulating film forming material of the present disclosure, and a configuration in which at least one of the insulating films 102 and 202 is a cured product obtained by curing the insulating film forming material of the present disclosure may also be acceptable.

[0178] Also, although a bonding example in C2C is illustrated in FIG. 1, the present invention may be applied to the bonding in Chip-to-Wafer (C2W) shown in FIG. 5. In C2W, a semiconductor wafer 410 (a first semiconductor substrate) having a substrate body 411 (a first substrate body), an insulating film 412 (a first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (a first electrode) is prepared. Further, a semiconductor substrate (a second semiconductor substrate) before singulation of a plurality of semiconductor chips 420, which has a substrate body 421 (a second substrate body), an insulating film portion 422 (a second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (a second electrode), is prepared. Then, one surface side of the semiconductor wafer 410 and one surface side of the second semiconductor substrate before singulation into the semiconductor chips 420 are polished by a CMP method or the like in the same manner as in the above steps (c) and (d). Thereafter, a singulation process similar to step (e) is performed on the second semiconductor substrate to obtain a plurality of semiconductor chips 420.

[0179] Subsequently, as shown in FIG. 5(a), alignment of the terminal electrode 423 of the semiconductor chip 420 with respect to the terminal electrode 413 of the semiconductor wafer 410 is performed (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 are bonded to each other (step (g)), and the terminal electrode 413 of the semiconductor wafer 410 and the terminal electrode 423 of the semiconductor chip 420 are joined (step (h)) to obtain a semi-finished product shown in FIG. 5(b). As a result, an insulating joint portion S3 in which the insulating film 412 and the insulating film portion 422 are joined is formed, and the semiconductor chip 420 is mechanically and firmly and highly accurately attached to the semiconductor wafer 410. In addition, an electrode joint portion S4 in which the terminal electrode 413 and the corresponding terminal electrode 423 are joined is formed, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly joined.

[0180] Thereafter, as shown in FIGS. 5(c) and 5(d), a semiconductor device 401 is obtained by joining a plurality of semiconductor chips 420 to a semiconductor wafer 410, which is a semiconductor wafer, in the same manner. Note that the plurality of semiconductor chips 420 may be joined to the semiconductor wafer 410 one by one by hybrid bonding, or may be joined to the semiconductor wafer 410 together by hybrid bonding.

[0181] Also in such a method for manufacturing a semiconductor device 401, as in the method for manufacturing the semiconductor device 1 described above, at least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 is an insulating film that is a cured product obtained by curing the insulating film forming material of the present disclosure. Therefore, a semiconductor device including an insulating film having excellent insulation reliability can be obtained.

[0182] (Modification example) In the semiconductor device and the method for manufacturing a semiconductor device of the present disclosure, the configuration in which the first electrode and the second electrode are joined has been described, but the present invention is not limited to these configurations. For example, in the semiconductor device of the present disclosure, the first electrode and the second electrode may be through electrodes that penetrate the first semiconductor substrate and the second semiconductor substrate. The method for manufacturing a semiconductor device according to the present disclosure may be, for example, a method for manufacturing a semiconductor device by using the insulating film forming material of the present disclosure in the production of at least one of the first organic insulating film and the second organic insulating film, and through the following steps (1)' to (5)'. Step (1)' Prepare 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)' Prepare 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)' Singulate the second semiconductor substrate to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film. Step (4)' Bond the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other. Step (5)' Provide a through hole in a part of the bonded first semiconductor substrate and second semiconductor substrate, and provide a through electrode in the through hole. In the above (5)', the method for providing the through hole and the method for providing the through electrode are not particularly limited. For example, the through hole may be provided by etching or the like, and the through electrode may be provided by electroplating, electroless plating, sputtering or the like.

Example

[0183] Hereinafter, the present disclosure will be described more specifically based on examples and comparative examples. It should be noted that the present disclosure is not limited to the following examples.

[0184] (Synthesis Example 1 (Synthesis of A1)) 62 g of 3,3’,4,4’-biphenyl ether tetracarboxylic dianhydride (ODPA), 23 g of 4,4’-diaminodiphenyl ether, and 5 g of m-phenylenediamine were dissolved in 915 g of 3-methoxy-N,N-dimethylpropionamide. The resulting solution was stirred at 30 °C for 4 hours and then overnight at room temperature to obtain a polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added thereto at room temperature, and the mixture was stirred at 45 °C for 10 hours. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor A1. Using gel permeation chromatography (GPC), the weight average molecular weight of A1 was determined in terms of standard polystyrene. The weight average molecular weight of A1 was 22,000. Specifically, a solution prepared by dissolving 0.5 mg of A1 in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] was used for measurement under the following conditions. (Measurement conditions) Measuring device: SPD-M20A manufactured by Shimadzu Corporation Pump: LC-20AD manufactured by Shimadzu Corporation Column oven: CTO-20A manufactured by Shimadzu Corporation Measurement conditions: Two Gelpack GL-S300MDT-5 columns 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: Calibration curve was prepared using TSKgel standard Polystyrene Type F-1, F-4, F-20, F-80, A-2500 manufactured by Tosoh Corporation

[0185] <Esterification rate> The esterification rate of A1 (the ratio of the ester groups formed by reacting with HEMA to the total of the ester groups formed by reacting with HEMA and the carboxy groups unreacted with HEMA) was calculated by performing NMR measurement under the following conditions. The esterification rate was 78 mol%, and the ratio of the unreacted carboxy groups was 22 mol%. (Measurement conditions) Measuring instrument: AV400M of Bruker BioSpin Magnetic field strength: 400 MHz Reference substance: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0186] [Examples 1 to 19, Comparative Example 1] (Preparation of insulating film forming material) The insulating film forming materials of Examples 1 to 19 and Comparative Example 1 were prepared as follows with the components and blending amounts shown in Tables 1 and 2. The unit of the blending amount of each component in Tables 1 and 2 is parts by mass. Also, the blanks in Tables 1 and 2 mean that the corresponding components were not blended. In each example and comparative example, the mixture of each component was kneaded overnight at room temperature in a general solvent-resistant container, and then pressure filtration was performed using a 0.2 μm pore filter. The following evaluations were performed using the obtained insulating film forming material.

[0187] Each component in Tables 1 and 2 is as follows. · Component (A) The above-mentioned A1 · Component (B) B1: Tetraethylene glycol dimethacrylate B2: Tricyclodecane dimethanol diacrylate B3: EO-modified bisphenol A diacrylate B4: 2-Phenoxyethyl acrylate · Component (C) (solvent) C1: 3-Methoxy-N,N-dimethylpropionamide · Adhesion aid Adhesion aid 1: 50% methanol solution of 3-ureidopropyltriethoxysilane · Component (D) (photoinitiator) D1: 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime D2: 4,4'-Bis(diethylamino)benzophenone · (F) component (polymerization inhibitor) F1: 1,4,4-Trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide · Rust inhibitor Rust inhibitor 1: Benzotriazole Rust inhibitor 2: 5-Amino-1H-tetrazole

[0188] [HAST test] The insulation reliability of the insulating film was evaluated by the HAST (Highly Accelerated Temperature and Humidity Stress Test). After titanium and copper sputtering were performed on one side composed of a silicon wafer (Si substrate having an SiO2 film) and polyimide as shown in Fig. 6, a plurality of copper electrodes were provided at the intervals shown in Fig. 6 by electroplating, and the unnecessary sputtered layer was removed. An insulating film formed by curing the insulating film forming material of each example and comparative example was produced between the electrodes under the following conditions. First, the insulating film forming material was spin-coated on the silicon wafer using a spin coater as a coating device, and a drying process was performed to form a resin film. The obtained resin film was exposed using a proximity exposure machine "Mask Aligner MA8" (manufactured by Zeiss Microtech Co., Ltd.) at an exposure amount such that the remaining film ratio after development was about 80% or more. Then, the resin film was heated at 230 °C for a predetermined time in a nitrogen atmosphere using a clean oven to be cured, thereby producing an insulating film. Further, the insulating film provided between the electrodes was treated for 300 hours under the HAST conditions of 130 °C, 85% RH, 3.3 V, 5 V, or 10 V. Further, under the HAST conditions, the insulation resistance value of the insulating film at 100 h or 300 h was observed, and the evaluation of the insulation reliability in each example and comparative example was performed according to the following criteria. The results are shown in Tables 1 and 2. - Evaluation criteria - A ··· Insulation resistance value 1 e+6 Observation less than 1 time below Ω. B··· The insulation resistance value was less than 1 e+6 Ω and was observed more than twice within a test time of less than 300 h.

[0189] [Evaluation of thermocompression bonding property] (Fabrication of insulated film with chips) The insulation film forming materials of Examples 1 to 19 and Comparative Example 1 were spin-coated on a 6-inch silicon wafer or a glass substrate using a spin coater as a coating device, and a drying process was performed to form a resin film. The obtained resin film was exposed using a proximity aligner "Mask Aligner MA8" (manufactured by Zeiss Microtech Co., Ltd.) at an exposure amount such that the remaining film ratio after development was about 80% or more. Then, the resin film was heated and cured at 230 °C for a predetermined time in a nitrogen atmosphere using a clean oven to obtain an insulation film having a film thickness of about 10 μm after curing. A part of the insulation film formed on the silicon wafer was diced into 4 mm squares by a blade dicing machine (DISCO DAD-3360) to obtain chips with resin. The obtained chips with resin were pressure-bonded to the insulation film formed on the silicon wafer or the glass substrate at a predetermined pressure and 210 °C for 3 minutes using a thermocompression bonding device (Nikka Seibi Engineering Co., Ltd.). Then, the evaluation of the thermocompression bonding property between the insulation films was carried out as described below.

[0190] (Evaluation after thermocompression bonding) For each example and comparative example, the evaluation of the thermocompression bonding property was performed multiple times, and the evaluation was carried out by (the number of times with good thermocompression bonding property / the number of times of evaluation of the thermocompression bonding property). Specifically, after thermocompression bonding, only the chip with resin was picked up using tweezers, and when the silicon wafer or the glass substrate was lifted together with the chip with resin when the chip with resin was lifted, it was judged that the evaluation of the thermocompression bonding property was good. On the other hand, when the silicon wafer or the glass substrate peeled off and only the chip with resin was lifted when the chip with resin was picked up using tweezers, it was judged that the evaluation of the thermocompression bonding property was poor. The results are shown in Tables 1 and 2.

[0191]

Table 1

[0192]

Table 2

[0193] As shown in Table 1 and Table 2, in Examples 1 to 19, an insulating film excellent in insulation reliability could be formed as compared with Comparative Example 1.

Explanation of Reference Numerals

[0194] 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 body, 101a... one surface, 102... insulating film (first insulating film), 103... terminal electrode (first electrode), 103a... surface, 200... second semiconductor substrate, 201... second substrate body, 201a... one surface, 202... insulating film (second insulating film), 203... terminal electrode (second electrode), 203a... surface, 205... semiconductor chip, 300... pillar, 301... resin, 410... semiconductor wafer (first semiconductor substrate), 411... substrate body (first substrate body), 412... insulating film (first insulating film), 413... terminal electrode (first electrode), 420... semiconductor chip (second semiconductor substrate), 421... substrate body (second substrate body), 422... insulating film portion (second insulating film), 423... terminal electrode (second electrode), A... cutting line, H... heat, M1 to M3... semi-finished products, S1... insulating joint portion, S2... electrode joint portion, S3... insulating joint portion, S4... electrode joint portion.

Claims

1. (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide; and (B) a polymerizable monomer, and the content of the compound containing an alkylene oxide chain and a (meth)acrylic group classified as the (B) polymerizable monomer is less than 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, an insulating film forming material for forming an insulating film by hybrid bonding.

2. The insulating film forming material according to claim 1, wherein the (B) polymerizable monomer contains at least one selected from the group consisting of a compound containing an alkylene oxide chain and a (meth)acrylic group, a compound containing an alicyclic structure and a (meth)acrylic group, and a compound containing an aromatic ring structure and a (meth)acrylic group.

3. The insulating film forming material according to claim 1, wherein the (B) polymerizable monomer contains a compound containing an alkylene oxide chain and a (meth)acrylic group and a compound containing an alicyclic structure and a (meth)acrylic group.

4. The insulating film forming material according to any one of claims 1 to 3, wherein the content of the (B) polymerizable monomer is 30 parts by mass or less with respect to 100 parts by mass of the (A) polyimide precursor.

5. Further comprising (C) a solvent, and the (C) solvent contains at least one selected from the group consisting of compounds represented by the following formulas (3) to (7), the insulating film forming material according to any one of claims 1 to 4. 【Chemical 1】 In formulas (3) to (7), R １ , R ２ , R ８ and R １０ are each independently an alkyl group having 1 to 4 carbon atoms; R ３ ~R ７ and R ９ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. s is an integer of 0 to 8, t is an integer of 0 to 4, r is an integer of 0 to 4, and u is an integer of 0 to 3.

6. The insulating film forming material according to claim 5, wherein the (C) solvent contains at least the compound represented by the formula (5).

7. The insulating film forming material according to any one of claims 1 to 6, further comprising (D) a photoinitiator.

8. The insulating film forming material according to any one of claims 1 to 7, wherein the (A) polyimide precursor contains a compound having a structural unit represented by the following general formula (1). [[Chemical 2]] 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.

9. In the general formula (1), the tetravalent organic group represented by X is a group represented by the following formula (E), the insulating film forming material according to claim 8. 【Chemical Formula 3】 In formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ )) ２ —; two Rs Ａ each independently represent a hydrogen atom, an alkyl group or a phenyl group. ), a siloxane bond (—O—(Si(R Ｂ )) ２ —O—) ｎ ; two Rs Ｂ each independently represent a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group formed by combining at least two of these.

10. In the general formula (1), the divalent organic group represented by Y is a group represented by the following formula (H), the insulating film forming material according to claim 8 or claim 9. 【Chemical Formula 4】 In formula (H), each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and each n independently represents an integer from 0 to 4. D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, an ester bond (—O—C(═O)—), a silylene bond (—Si(R Ａ )) ２ —; two Rs Ａ each independently represent a hydrogen atom, an alkyl group, or a phenyl group. ), a siloxane bond (—O—(Si(R Ｂ )) ２ —O—) ｎ ; two Rs Ｂ each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or more. ) or a divalent group formed by combining at least two of these.

11. In the general formula (1), the R ６ and the R ７ The monovalent organic group in is any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group. The insulating film forming material according to any one of claims 8 to 10. [Chemical Formula 5] In the general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ｘ represents a divalent linking group.

12. A method for manufacturing a semiconductor device, which uses the insulating film forming material according to any one of claims 1 to 11 in manufacturing at least one of a first organic insulating film and a second organic insulating film, and manufactures a semiconductor device through the following steps (1) to (5). Step (1): Prepare a first semiconductor substrate having a first substrate body, a first organic insulating film provided on one surface of the first substrate body, and a first electrode. Step (2): Prepare a second semiconductor substrate having a second substrate body, a second organic insulating film provided on one surface of the second substrate body, and a plurality of second electrodes. Step (3): Separate the second semiconductor substrate into individual pieces, and obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4): Bond the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other. Step (5): Bond the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.

13. A first semiconductor substrate having a first substrate body, a first organic insulating film provided on one surface of the first substrate body, and a first electrode, A semiconductor chip having a semiconductor chip substrate body, an organic insulating film portion provided on one surface of the semiconductor chip substrate body, and a second electrode, Comprising: the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded to each other; the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are bonded to each other; A semiconductor device in which at least one of the first organic insulating film and the organic insulating film portion is an organic insulating film formed by curing the insulating film forming material according to any one of claims 1 to 11.

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