JP2023136962A - Insulation film formation material, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Abstract

To provide an insulation film formation material which is excellent in heat resistance and mechanical characteristics, and enables formation of an insulation film that can suppress a joint failure between an insulation film and an electrode or a joint failure between the insulation films in hybrid bonding.SOLUTION: An insulation film formation material contains two or more kinds of (A) polyimide precursors which are at least one selected from the group consisting of a polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide, where the two or more kinds of (A) the polyimide precursors have skeletons represented by the following formula (E), and in the two or more kinds of (A) the polyimide precursors, the numbers of elements constituting main chains in the formula (E) are different.SELECTED DRAWING: None

Description

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

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

When performing three-dimensional mounting of semiconductor chips using C2W (Chip-to-Wafer) bonding, hybrid bonding technology used in W2W (Wafer-to-Wafer) bonding is used to perform fine bonding of wiring between devices. is being considered.

In C2W hybrid bonding, there is a risk that misalignment may occur due to thermal expansion of the base material, chip, etc. due to heating during bonding. In response to such problems, Patent Document 1 discloses an example of a technique that can lower the bonding temperature by using a cyclic olefin resin.

JP2019-204818A

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

When performing three-dimensional mounting of semiconductor chips by C2W bonding, unlike W2W bonding, foreign matter (cutting fragments) may be generated during the process of singulating semiconductor chips, and this foreign matter may interfere with the bonding of semiconductor chips, etc. There is a risk that it may adhere to the interface (the surface of the insulating film of hybrid bonding). The use of inorganic materials such as silicon dioxide (SiO ₂ ) for this insulating film is being considered, but since inorganic materials are hard materials, attached foreign matter can cause large voids in the insulating film, such as the height of the foreign matter. A gap nearly 1000 times wider is created at the bonding interface. For this reason, even if the hybrid bonding technology used in W2W bonding is simply applied to C2W bonding, there is a risk of bonding failure due to the generation of such voids, which reduces the yield of semiconductor device manufacturing. There is a problem. On the other hand, when using a clean room and equipment with high cleanliness to prevent these bonding defects, a large amount of capital is required due to equipment investment for the clean room and the like.

Furthermore, when an organic material such as an epoxy resin or a cyclic olefin resin such as benzocyclobutene is used for the insulating film, the heat resistance of the organic material is insufficient, and the insulating film is exposed to high temperatures during C2W bonding. This may cause deterioration of the organic material and lead to poor bonding at the interface between the substrate and the insulating film.

The present inventors have considered the use of an insulating material containing a polyimide precursor, which is an organic material with excellent heat resistance, from the viewpoint of suppressing bonding defects and deterioration of organic materials due to the generation of voids as described above. did. However, when an insulating material containing a polyimide precursor is applied to C2W bonding, there is room for improvement in adhesive strength between insulating films, adhesive strength between an electrode and an insulating film, and the like.

The present disclosure has been made in view of the above, and provides an insulating film forming material capable of forming an insulating film with excellent adhesiveness, a method for manufacturing a semiconductor device using the insulating film forming material, and a semiconductor device formed from the insulating film forming material. An object of the present invention is to provide a semiconductor device including an insulating film with a high temperature.

Specific means for achieving the above object are as follows.
<1> (A) Contains two or more polyimide precursors that are at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide,
The two or more types of polyimide precursors (A) have a skeleton represented by the following formula (E),
An insulating film-forming material in which two or more of the polyimide precursors (A) have different numbers of elements constituting the main chain of C in the following formula (E).

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)-), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's 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 ^B 's 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 at least these Represents a combination of two divalent groups.
<2> (A) Contains two or more types of polyimide precursors that are at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide,
The two or more polyimide precursors (A) are a first polyimide precursor whose glass transition temperature is 200°C to 400°C when cured, and a polyimide precursor which has a glass transition temperature of 200°C to 400°C when cured than the first polyimide precursor. a second polyimide precursor whose glass transition temperature is 10°C to 250°C lower.
<3> The two or more types of polyimide precursors (A) have a skeleton represented by the following formula (E),
The insulating film forming material according to <2>, wherein the two or more polyimide precursors (A) have different numbers of elements constituting the main chain of C in the following formula (E).

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)-), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's 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 ^B 's 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 at least these Represents a combination of two divalent groups.
<4> The insulating film forming material according to <1> or <3>, wherein the two or more polyimide precursors (A) satisfy any of the following (1) to (3).
(1) A combination of a polyimide precursor in which C in the formula (E) is a single bond and a polyimide precursor in which C in the formula (E) includes an ether bond (-O-);
(2) A polyimide precursor in which C in the formula (E) contains an ether bond (-O-) and a phenylene group; and C in the formula (E) is an ether bond (-O-) or an ether bond. and a combination with a polyimide precursor which is an alkylene group,
(3) A polyimide precursor in which C in the formula (E) is a divalent linking group that does not contain an ether bond (-O-), and a polyimide precursor in which C in the formula (E) is a divalent linking group that does not contain an ether bond (-O-). combination with a polyimide precursor containing.
<5> The two or more polyimide precursors (A) are the insulators according to any one of <1>, <3>, and <4>, which have a structural unit represented by the following general formula (1). Film-forming material.

In general formula (1), X represents a tetravalent organic group represented by the above formula (E), Y represents a divalent organic group, and R ⁶ and R ⁷ each independently represent a hydrogen atom, Or represents a monovalent organic group.
<6> The insulating film forming material according to <5>, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H).

In formula (H), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents an integer of 0 to 4. D is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-O-C(=O) -), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's each independently represent a hydrogen atom, an alkyl group, or a phenyl group), siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; Two R ^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 combination of at least two of these. represents the group of
<7> In the general formula (1), the monovalent organic group in R ⁶ and R ⁷ is 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 <5> and <6>.

In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group.
<8> (B) The insulating film forming material according to any one of <1> to <7>, further comprising a polymerizable monomer.
<9> (C) further comprising a solvent, the (C) solvent comprising at least one type selected from the group consisting of compounds represented by the following formulas (3) to (8) <1> to <8> The insulating film forming material according to any one of the above.

In formulas (3) to (8), R ¹ , R ² , R ⁸ , R ¹⁰ and R ¹¹ 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, u is an integer from 0 to 3, and v is an integer from 0 to 3.
<10> (D) The insulating film forming material according to any one of <1> to <9>, further comprising a photopolymerization initiator.
<11> The insulating film forming material according to any one of <1> to <10> for forming an insulating film by hybrid bonding.
<12> The insulating film forming material according to any one of <1> to <11> is used for producing at least one of the first organic insulating film and the second organic insulating film, and the following steps ( A method for manufacturing a semiconductor device, which manufactures a semiconductor device through steps 1) to (5).
Step (1) A first semiconductor substrate having a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body is prepared.
Step (2) A second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body is prepared.
Step (3) Cutting the second semiconductor substrate into 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 second electrode. do.
Step (4) Bonding 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) Joining 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, the 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;
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, and the first electrode of the first semiconductor substrate and the first organic insulating film portion of the semiconductor chip are bonded to each other. 2 electrodes 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 the insulating film forming material according to any one of <1> to <11>.

According to the present disclosure, an insulating film forming material capable of forming an insulating film with excellent adhesiveness, 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 can be provided.

FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device manufactured by a method for manufacturing a semiconductor device according to an embodiment of the present invention. FIG. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in FIG. FIG. 3 is a diagram showing in more detail the bonding method in the method of manufacturing the semiconductor device shown in FIG. FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing the steps after the step shown in FIG. 2 in order. FIG. 5 is a diagram showing an example in which the method for manufacturing a semiconductor device according to an embodiment of the present invention is applied to Chip-to-Wafer (C2W).

Hereinafter, embodiments for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including elemental steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and they do not limit the present disclosure.

In the present disclosure, "A or B" may include either A or B, or may include both.
In this disclosure, the term "step" includes not only a step that is independent from 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 present disclosure, numerical ranges indicated using "~" include the numerical values written before and after "~" as minimum and maximum values, respectively.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In the present disclosure, each component may contain multiple types of applicable substances. If there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition, unless otherwise specified. means quantity.
In this disclosure, the term "layer" or "film" refers to the case where the layer or film is formed only in a part of the region, in addition to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present. This also includes cases where it is formed.
In the present disclosure, the thickness of a layer or film is a value given as the arithmetic average value of the thicknesses measured at five points of the target layer or film.
The thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, when the thickness of a layer or film can be measured directly, 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 term "insulating film" is a concept that also includes an insulating layer.
In the present disclosure, "(meth)acrylic group" means "acrylic group" and "methacrylic group."
In the present disclosure, when a functional group has a substituent, the number of carbon atoms in the functional group means the total number of carbon atoms including the number of carbon atoms of the substituent.
In the present disclosure, when embodiments are described with reference to drawings, the configuration of the embodiments is not limited to the configuration shown in the drawings. Furthermore, the sizes of the members in each figure are conceptual, and the relative size relationships between the members are not limited thereto.

<Insulating film forming material>
The insulating film forming material of the present disclosure includes (A) two or more types of polyimide precursors that are at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, and polyamic acid amides; The (A) polyimide precursor has a skeleton represented by the following formula (E), and in two or more of the (A) polyimide precursors, the main chain of C in the following formula (E) is The number of elements used is different. In the insulating film forming material, two types of (A) polyimide precursors may be used, or three or more types of (A) polyimide precursors may be used.

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)-), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's 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 ^B 's 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 at least these Represents a combination of two divalent groups.

By using the insulating film forming material of the present disclosure, it is possible to form an insulating film with excellent adhesiveness. The reason for this is assumed to be as follows. However, the following speculations are not intended to limit the insulating film forming material of the present disclosure, but are explained as an example.
In the insulating film forming material of the present disclosure, two or more compounds represented by the formula (E) and having different numbers of elements constituting the main chain are combined as a polyimide precursor, so that the polyimide precursor is more rigid than the polyimide precursor. A flexible polyimide precursor is mixed in the insulating film forming material. As a result, when thermocompression bonding the insulating film, the portion derived from the more flexible polyimide precursor melts, making it possible to bond at a lower temperature than when using the more rigid polyimide precursor alone. . Therefore, the thermocompression bondability of the insulating film, the adhesion strength at low temperatures between the insulating films, the adhesion strength at low temperature between the insulating film and the electrode, etc. are improved, and an insulating film with excellent adhesion can be obtained.
Further, since the insulating film forming material of the present disclosure contains a more rigid polyimide precursor, the glass transition temperature of the insulating film produced is superior to that when a more flexible polyimide precursor is used alone. Therefore, with the insulating film forming material of the present disclosure, an insulating film with good heat resistance and reliability tends to be obtained.
Furthermore, by using a more flexible polyimide precursor, the insulating film forming material of the present disclosure lowers the temperature when bonding insulating films together compared to the case where only a more rigid polyimide precursor is used. tend to be able to do so.

In the present disclosure, "the number of elements constituting the main chain of C in formula (E)" refers to the number of elements constituting the main chain located between the two benzene rings specified in formula (E). It means a number, and does not include the number of atoms, substituents, etc. bonded to the elements constituting the main chain. Furthermore, when a ring structure such as an aromatic ring is included in the main chain, the number of elements included in the shortest path in the ring structure is included in the number of elements constituting the main chain. For example, when a 1,3-phenylene group is included in the main chain, the number of elements included in the shortest path is 3, and when a 1,4-phenylene group is included in the main chain, the number of elements included in the shortest path is 3. The number of elements included in the route is four.

The insulating film forming material of the present disclosure is a material used for forming an insulating film, and the use of the produced insulating film is not particularly limited, and can be applied to uses that require insulation. For example, the insulating film forming material of the present disclosure may be a material for forming an insulating film by hybrid bonding.

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

Furthermore, the insulating film obtained by curing the insulating film forming material of the present disclosure has a lower elastic modulus and is softer than a molded product made of an inorganic material. Therefore, when bonding insulating films together, the surface of one insulating film (hereinafter also referred to as "first insulating film") or the surface of the other insulating film (hereinafter also referred to as "second insulating film") Even if foreign matter is present in the insulating film, the insulating film at the bonding interface is easily deformed, and the foreign matter tends to be contained within the insulating film without creating large voids in the insulating film.

The insulating film forming material of the present disclosure may be a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material.

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, more preferably 150°C to 350°C, from the viewpoint of bonding at low temperatures. .

The glass transition temperature of the insulating film is measured as follows. First, an insulating film forming material is heated in a nitrogen atmosphere for 2 hours at a predetermined curing temperature (for example, 150° C. to 375° C.) that allows a curing reaction to occur, to obtain an insulating film. The obtained insulating film was cut to create a rectangular parallelepiped of 5 mm x 50 mm x 3 mm, and a dynamic viscoelasticity measurement device (for example, RSA-G2 manufactured by TA Instruments) was used with a tension jig at a frequency of 1 Hz. Dynamic viscoelasticity is measured in a temperature range of 50°C to 350°C under the conditions of heating rate: 5°C/min. The glass transition temperature (Tg) is defined as the temperature at the peak top of tan δ, which is determined from the ratio of the storage modulus and loss modulus obtained by the above method.

In the insulating film forming material of the present disclosure, the thermal expansion coefficient of the insulating film formed by curing is preferably 150 ppm/K or less, more preferably 100 ppm/K or less, and further preferably 70 ppm/K or less. preferable. As a result, the coefficient of thermal expansion of the insulating film, which is a cured product, and the coefficient of thermal expansion of the electrode are the same or close to each other, so even if heat generation occurs during use of the semiconductor device, the insulating film and the electrode Damage to the semiconductor device due to the difference in coefficient of thermal expansion between the two can be suppressed. Thermal expansion coefficient indicates the rate at which the length of the insulating film expands due to temperature rise, and the amount of change in the length of the insulating film at 100°C to 150°C is measured using a thermomechanical analyzer etc. It can be calculated by

Hereinafter, the components contained in the insulating film forming material of the present disclosure and the components that can be contained will be explained.

((A) Polyimide precursor)
The insulating film forming material of the present disclosure is a polyimide precursor (hereinafter referred to as "(A) component ). It is more preferable that component (A) contains a polyimide precursor having a polymerizable unsaturated bond. The component (A) contained in the insulating film forming material is preferably a component that does not cause problems in polishing steps, bonding steps, and the like.
In the present disclosure, the polyimide precursor is a polyamic acid, a compound in which the hydrogen atoms of at least some of the carboxy groups in the polyamic acid are substituted with monovalent organic groups, or a polyamic acid in which at least some of the carboxy groups have a pH of 7 or more. It means a compound that falls under any of the polyamide acid salts, which are compounds that form a salt structure with a basic compound.
Examples of compounds in which at least some of the hydrogen atoms of carboxy groups in polyamic acids are substituted with monovalent organic groups include polyamic acid esters, polyamic acid amides, and the like.
It is preferable that the polyamic acid ester, polyamic acid amide, etc. have a polymerizable unsaturated bond.

It is preferable that two or more types of (A) components have a structural unit represented by the following general formula (1). Thereby, a semiconductor device including an insulating film exhibiting high reliability tends to be obtained.

In the general formula (1), X represents a tetravalent organic group represented by the above formula (E), 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 above general formula (1), and X, Y, R ⁶ and R ⁷ in the plurality of structural units may be the same or different. You can leave it there. Moreover, two or more types of (A) components may or may not each independently contain a structural unit in which X is a tetravalent organic group having a structure other than formula (E). .
Note that the combination of R ⁶ and R ⁷ is not particularly limited as long as they are each independently a hydrogen atom or a monovalent organic group. For example, R ⁶ and R ⁷ may both be hydrogen atoms, one may be a hydrogen atom and the other may be a monovalent organic group described below, and both may be the same or different monovalent organic groups. It may be. As mentioned above, when the polyimide precursor has a plurality of structural units represented by the above general formula (1), the combination of R ⁶ and R ⁷ of each structural unit may be the same or different. .

In general formula (1), the tetravalent organic group represented by X preferably has 12 to 40 carbon atoms, more preferably 12 to 35 carbon atoms, and even more preferably 12 to 30 carbon atoms. .
In X, each benzene ring in formula (E) may have a substituent or may be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, and amino groups.
In formula (E), two benzene rings adjacent to each other in the biphenyl structure, two benzene rings adjacent to each other via a divalent linking group are bonded at two places by at least one of a single bond and a linking group, and 2 A 5-membered ring or 6-membered ring containing a linking group may be formed between the two benzene rings.

In general formula (1), -COOR ⁶ groups and -CONH- groups are preferably located at ortho positions, and -COOR ⁷ groups and -CO- groups are preferably located at ortho positions.

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)-), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's 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 ^B 's 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 at least these Represents a combination of two divalent groups.

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 an alkylene group having 1 to 5 carbon atoms. or 2 alkylene group is more preferable.
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, and hexamethylene group; methylmethylene group; Methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group 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- Branched alkylene groups such as dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, and 1,4-dimethyltetramethylene group; and the like. Among these, methylene group is preferred.

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. Preferably, a halogenated alkylene group having 1 to 3 carbon atoms is more preferable.
As a specific example of the halogenated alkylene group represented by C in formula (E), at least one hydrogen atom contained in the alkylene group represented by C in formula (E) above is a fluorine atom, a chlorine atom, etc. Examples include alkylene groups substituted with halogen atoms. Among these, fluoromethylene group, difluoromethylene group, hexafluorodimethylmethylene group, etc. are preferred.

The alkyl group represented by R ^A or R ^B included in the silylene bond or siloxane bond is preferably an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms. is more preferable, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R ^A or R ^B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, etc. Can be mentioned.

The two or more types of (A) polyimide precursors may be two types of (A) polyimide precursors, and may, for example, satisfy any of the following (1) to (3).
(1) A polyimide precursor (polyimide precursor X) in which C in the formula (E) is a single bond, and a polyimide precursor (polyimide precursor Combination with precursor Y).
(2) A polyimide precursor (polyimide precursor X) in which C in the formula (E) contains an ether bond (-O-) and a phenylene group; ), or a combination with a polyimide precursor (polyimide precursor Y) having an ether bond and an alkylene group.
(3) A polyimide precursor (polyimide precursor Combination with a polyimide precursor (polyimide precursor Y) containing a bond (-O-).

Regarding the mass ratio of the above-mentioned polyimide precursor X and the above-mentioned polyimide precursor Y, polyimide precursor The time may be from 30:70 to 70:30.
The mass ratio of the aforementioned polyimide precursor X to the aforementioned polyimide precursor Y may be adjusted as appropriate depending on the adhesion, reliability, heat resistance, etc. required of the insulating film.

Regarding the above (1), examples of the structure represented by the formula (E) in which C is a single bond include a group represented by the following formula (H).

Regarding (1) above, structures represented by the formula (E) in which C contains an ether bond (-O-) include, for example, groups represented by the following formulas (I) to (O). Can be mentioned.

Regarding (2) above, the structure represented by the formula (E) in which C contains an ether bond (-O-) and a phenylene group includes, for example, the groups represented by the above-mentioned formulas (J) to (O). can be mentioned.

Regarding (2) above, examples of the structure represented by formula (E) in which C is an ether bond (-O-) include the group represented by formula (I) above.
Regarding (2) above, examples of the structure represented by formula (E) in which C is an ether bond and an alkylene group include groups represented by the following formulas (P) to (R).

Regarding (3) above, structures represented by formula (E) in which C is a divalent linking group that does not contain an ether bond (-O-) include the following formulas (S) and (T). Examples include groups represented by:
Regarding (3) above, structures represented by formula (E) in which C contains an ether bond (-O-) include, for example, groups represented by formulas (I) to (O) as described above. Can be mentioned.

In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms. .
The 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 divalent aromatic groups include divalent aromatic hydrocarbon groups (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), divalent aromatic heterocyclic groups (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), The number of atoms is 5 to 20), and divalent aromatic hydrocarbon groups are preferred.

Specific examples of the divalent aromatic group represented by Y include groups represented by the following formula (G), formula (H), and formula (H)'. Among these, a group represented by the following formula (H) is preferable from the viewpoint of obtaining an insulating film that has excellent flexibility and further suppresses the generation of voids at the bonding interface. is more preferably a group containing an ether bond.

In formula (G), formula (H), and formula (H)', R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents Represents an integer from 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)-), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's 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 ^B 's 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 at least these Represents a combination of two divalent groups. Further, D may have a structure represented by the above formula (C1). A specific example of D in formula (H) is the same as a specific example of C in formula (E).
D in formula (H) is an ether bond, a group containing an ether bond and an alkylene group, a group containing an ether bond and a phenylene group, a group containing a phenylene group and an alkylene group, an ether bond, a phenylene group, and an alkylene group. It is preferable that it is a group containing.

The alkyl group represented by R in formula (G), formula (H) and formula (H)' is preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. More preferably, it is an alkyl group having 1 or 2 carbon atoms.
Specific examples of the alkyl group represented by R in formula (G), formula (H), and formula (H)' include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. , s-butyl group, t-butyl group, etc.

The alkoxy group represented by R in formula (G), formula (H) and formula (H)' is preferably an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. More preferably, it is an alkoxy group having 1 or 2 carbon atoms.
Specific examples of the alkoxy group represented by R in formula (G), formula (H), and formula (H)' include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, and isobutoxy group. group, s-butoxy group, t-butoxy group, etc.

The halogenated alkyl group represented by R in formula (G), formula (H), and formula (H)' is preferably a halogenated alkyl group having 1 to 5 carbon atoms; It is more preferably a halogenated alkyl group having 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), formula (H) and formula (H)' include those represented by R in formula (G), formula (H) and formula (H)'. Examples include alkyl groups in which at least one hydrogen atom contained in the alkyl group is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl group, difluoromethyl group, trifluoromethyl group, etc. are preferred.

In formula (G), formula (H), and formula (H)', n is each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

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

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. More preferably, the number is 1 to 10 alkylene groups.
Specific examples of the alkylene group represented by Y include tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 2-methylpentamethylene group. , 2-methylhexamethylene group, 2-methylheptamethylene group, 2-methyloctamethylene group, 2-methylnonamethylene group, 2-methyldecamethylene group, and the like.

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

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 An alkylene oxide structure of 1 to 4 is more preferred. Among these, as the polyalkylene oxide structure, a polyethylene oxide structure or a polypropylene oxide structure is preferable. The alkylene group in the alkylene oxide structure may be linear or branched. The number of unit structures in the polyalkylene oxide structure may be one, or two or more.

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

The group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H1) to formula (H8). The group represented by formula (H') is preferably a group represented by the following formula (H''). The group is more preferably any of the groups represented by formulas (H1) to (H5) below, and even more preferably is a group represented by formula (H3) or formula (H4).

In formula (H"), R each 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. .

The combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1) is not particularly limited. As a combination of a tetravalent organic group represented by X and a divalent organic group represented by Y, X is a group represented by formula (E), and Y is a group represented by formula (G). A combination of groups in which X is a group represented by formula (E) and Y is a group represented by formula (H); X is a group represented by formula (E), and Y is a group represented by formula Examples include combinations of groups represented by (H').

R ⁶ and R ⁷ each independently represent 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, such as a group represented by the following general formula (2), an ethyl group, It is more preferable that it is either an isobutyl group or a t-butyl group, and it is even more preferable that it contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). It is particularly preferable to include a group represented by (2). In particular, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-line transmittance is high, and even when curing at a low temperature of 400°C or less. It tends to form a good insulating film.
Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, etc. Among them, ethyl group, Isobutyl and t-butyl groups are preferred.
In addition, in two or more types of polyimide precursors (A), R ⁶ and R ⁷ may be the same or different.

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

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

The combination of R ⁸ to R ¹⁰ in general formula (2) 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.

R ^x in general formula (2) 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 linear or branched alkylene groups.
The number of carbon atoms in R ^x is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

In general formula (1), at least one of R ⁶ and R ⁷ is preferably a group represented by the above general formula (2), and both R ⁶ and R ⁷ are preferably a group represented by the above general formula (2). It is more preferable to be a group represented by:

When the component (A) contains a compound having a structural unit represented by the above-mentioned general formula (1), it is expressed by the general formula (2) based on the sum of R ⁶ and R ⁷ of all structural units contained in the compound. The proportion of R ⁶ and R ⁷ , which are the groups to be used, is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more. The upper limit is not particularly limited, and may be 100 mol%.
In addition, the above-mentioned ratio may be 0 mol% or more and less than 60 mol%.

The group represented by general formula (2) is preferably a group represented by general formula (2') below.

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

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

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

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

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride. Anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic 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 Anhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, bisphenol A type acid Examples include dianhydrides.
One type of tetracarboxylic dianhydride may be used alone or two or more types may be used in combination.

Specific examples of diamine compounds include 4,4'-diamino-2,2'-dimethylbiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and 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 '-Diaminodiphenylsulfone, 2,4'-diaminodiphenylsulfone, 2,2'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide , 2,4'-diaminodiphenylsulfide, 2,2'-diaminodiphenylsulfide, 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, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane and the like. As the diamine compound, m-phenylenediamine, 4,4'-diaminodiphenyl ether and 1,3-bis(3-aminophenoxy)benzene are preferred.
The diamine compounds may be used alone or in combination of two or more.

A compound having a structural unit represented by general formula (1) and in which at least one of R ⁶ and R ⁷ in general formula (1) is a monovalent organic group is, for example, the following (a) or It can be obtained by the method (b).
(a) A diester is produced by reacting a tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (9)) and a compound represented by R-OH in an organic solvent. After making the derivative, the diester derivative and a diamine compound represented by H ₂ N--Y--NH ₂ are subjected to a condensation reaction.
(b) Tetracarboxylic dianhydride and a diamine compound represented by H ₂ N-Y-NH ₂ are reacted in an organic solvent to obtain a polyamic acid solution, and the compound represented by R-OH is mixed into polyamide. In addition to an acid solution, the reaction is carried out in an organic solvent to introduce an ester group.
Here, Y in the diamine compound represented by H ₂ N-Y-NH ₂ is the same as Y in general formula (1), and specific examples and preferred examples are also the same. Further, R in the compound represented by R-OH represents a monovalent organic group, and specific examples and preferred examples are the same as those for R ⁶ and R ⁷ in general formula (1).
The tetracarboxylic dianhydride represented by the general formula (9), the diamine compound represented by H ₂ N-Y-NH ₂ and the compound represented by R-OH may each be used alone. Often, two or more types may be combined.
Examples of the organic solvents mentioned above include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and among others, 3-methoxy-N,N- Dimethylpropionamide is preferred.
A polyimide precursor may be synthesized by allowing a dehydration condensation agent to act on a polyamic acid solution together with a compound represented by R-OH. The dehydration condensation agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).

The above-mentioned compound contained in component (A) is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (9) with a compound represented by R-OH to form a diester derivative, and then forming a diester derivative such as thionyl chloride. It can be obtained by reacting a diamine compound represented by H ₂ N-Y-NH ₂ with the acid chloride.
The above-mentioned compound contained in component (A) is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (9) with a compound represented by R-OH to form a diester derivative, and then converting it into a carbodiimide compound. It can be obtained by reacting a diamine compound represented by H ₂ N—Y—NH ₂ with a diester derivative in the presence of H 2 N—Y—NH 2 .
The above-mentioned compound contained in component (A) is produced by reacting a tetracarboxylic dianhydride represented by the following general formula (9) with a diamine compound represented by H ₂ N-Y-NH ₂ to form a polyamide acid. After that, the polyamic acid is isoimidized in the presence of a dehydration condensation agent such as trifluoroacetic anhydride, and then a compound represented by R-OH is allowed to act thereon. Alternatively, a compound represented by R-OH may be reacted on a portion of the tetracarboxylic dianhydride in advance to form a partially esterified tetracarboxylic dianhydride and a compound represented by H ₂ N-Y-NH ₂ . may be reacted with a diamine compound.

In general formula (9), X is the same as X in general formula (1), and specific examples and preferred examples are also the same.

Compounds represented by R-OH used in the synthesis of the above-mentioned compounds contained in component (A) include compounds in which a hydroxy group is bonded to R ^x of a group represented by general formula (2), and compounds represented by general formula ( It may also be a compound in which a hydroxy group is bonded to the terminal methylene group of the group represented by 2'). Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and acrylic. Examples include 2-hydroxypropyl acid, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. -hydroxyethyl and 2-hydroxyethyl acrylate are preferred.

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

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 is such that some of the amino groups in the (A) polyimide precursor are in the dicarboxylic acid. It may have a structure formed by reacting with a carboxy group. For example, when synthesizing a polyimide precursor, a portion of the amino groups of the diamine compound and the carboxy groups of the dicarboxylic acid may be reacted.
The dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula. At this time, when synthesizing the (A) polyimide precursor, by reacting a part of the amino group of the diamine compound with the carboxy group of the dicarboxylic acid, the methacrylic group derived from the dicarboxylic acid is added to the (A) polyimide precursor. can be introduced.

The insulating film forming material of the present disclosure may contain a resin component other than the component (A). From the viewpoint of heat resistance, resin components other than component (A) include polyimide resins, novolac resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, and polychlorinated resins. Examples include vinyl resin. Among these, it is preferable that the resin components other than the component (A) include a polyimide resin.
Resin components other than component (A) may be used alone or in combination of two or more.

By combining the polyimide precursor that is the component (A) and the polyimide resin, it is possible to suppress the production of volatiles due to dehydration cyclization during imide ring formation. This tends to suppress the generation of voids. The polyimide resin herein refers to a resin having an imide skeleton in all or part of the resin skeleton. It is preferable that the polyimide resin is soluble in a solvent in an insulating film forming material using a polyimide precursor.

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

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

The insulating film forming material of the present disclosure may or may not contain a resin component such as a cyclic olefin resin such as benzocyclobutene or an epoxy resin. The content of the cyclic olefin resin is determined from the viewpoint of improving the heat resistance and mechanical properties of the insulating film, and from the viewpoint of suitably suppressing bonding defects between the insulating film and the electrode and bonding defects between the insulating films when performing hybrid bonding. The content of epoxy resin and epoxy resin is preferably 30% by mass or less, more preferably 0% by mass to 10% by mass, and 0% by mass, based on the total amount of the insulating film forming material of the present disclosure. % to 5% by mass is more preferable.

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

The polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,4-butane Diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, (meth)acryloyloxyethyl isocyanurate, 2-hydroxyethyl(meth)acrylate, Examples include 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO) modified bisphenol A di(meth)acrylate, benzyl(meth)acrylate and phenoxyethyl(meth)acrylate.

Component (B) is a compound containing an alkylene oxide chain and a (meth)acrylic group (hereinafter also referred to as "compound (1)"), a compound containing an alicyclic structure and a (meth)acrylic group (hereinafter referred to as "compound (1)"), (2)), and a compound containing an aromatic ring structure and a (meth)acrylic group (hereinafter also referred to as "compound (3)"). Good too.
Note that compound (1) does not need to contain both an alicyclic structure and an aromatic ring structure, and compound (2) does not need to 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 (meth)acryloyloxy group).

When the insulating film forming material contains the compound (1), the thermocompression bondability between the substrate and the insulating film tends to improve.
When the insulating film forming material contains the compound (2), the insulation reliability of the insulating film tends to be more excellent.

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

Examples of compound (2) include tricyclodecane dimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and 1,3-adamantanedimethanol di(meth)acrylate.

Examples of the compound (3) include EO-modified bisphenol A di(meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxymethacrylate.

Component (B) may contain a polymerizable monomer other than the (meth)acrylic group-containing polymerizable monomer. The polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N , N-dimethylacrylamide and N-methylolacrylamide.

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 an unsaturated double bond group (for example, an oxirane ring). .

In the insulating film forming material of the present disclosure, the content of component (B) is 30 parts by mass or less with respect to 100 parts by mass of component (A), and from the viewpoint of insulation reliability of the insulating film, the content of component (B) is 25 parts by mass or less. The amount may be 20 parts by mass or less.
The lower limit of the content of component (B) may be 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more based on 100 parts by mass of component (A). The amount may be 10 parts by mass or more.
The content of component (B) is preferably 15 parts by mass to 25 parts by mass based on 100 parts by mass of component (A).

((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 (8), for example.
Component (C) may be used alone or in combination of two or more.

In formulas (3) to (8), R ¹ , R ² , R ⁸ , R ¹⁰ and R ¹¹ 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, u is an integer from 0 to 3, and v is an integer from 0 to 3.

In formula (3), s is preferably 0.
In formula (4), the alkyl group having 1 to 4 carbon atoms in R ² is preferably a methyl group or an ethyl group. t is preferably 0, 1 or 2, more preferably 1.
In formula (5), the alkyl group having 1 to 4 carbon atoms for R ³ is preferably a methyl group, ethyl group, propyl group or butyl group. The alkyl group having 1 to 4 carbon atoms for R ⁴ and R ⁵ is preferably a methyl group or an ethyl group.
In formula (6), the alkyl group having 1 to 4 carbon atoms in R ⁶ to R ⁸ is preferably a methyl group or an ethyl group. r is preferably 0 or 1, more preferably 0.
In formula (7), the alkyl group having 1 to 4 carbon atoms in R ⁹ and R ¹⁰ is preferably a methyl group or an ethyl group. u is preferably 0 or 1, more preferably 0.
In formula (8), the alkyl group having 1 to 4 carbon atoms for R ¹¹ is preferably a methyl group or an ethyl group. u is preferably 0 or 1, more preferably 0.

Component (C) may be, for example, at least one of the compounds represented by formulas (4), (5), (6), (7) and (8), and may be represented by formula (5). It may be a compound represented by the formula (7) or a compound represented by the formula (8), and from the viewpoint of reducing the reproductive toxicity and environmental load of the insulating film forming material, the compound represented by the formula (5) may be It may be a compound represented by

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

The component (C) that may be included in the insulating film forming material of the present disclosure is not limited to the above-mentioned compounds, and may be other solvents. Component (C) may be an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, or the like.

Solvents for esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone. , ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates such as methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g. methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate and ethyl ethoxy acetate), 3-Alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxypropionate) 2-alkoxypropionate alkyl esters (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 - Ethyl 2-alkoxy-2-methylpropionate such as ethyl methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. can be mentioned.

Ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene. Examples include glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.
Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone (NMP), and 3-methoxy-N,N-dimethylpropionamide.
Examples of hydrocarbon solvents include limonene and the like.
Examples of aromatic hydrocarbon solvents include toluene, xylene, anisole, and the like.
Examples of solvents for sulfoxides include dimethyl sulfoxide and the like.

Preferred examples of the solvent for component (C) include 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone, cyclopentanone, and ethyl lactate.

In the insulating film forming material of the present disclosure, from the viewpoint of reducing toxicity such as reproductive toxicity, the content of NMP may be 1% by mass or less based on the total amount of the insulating film forming material; It may be 3% by mass or less based on the total amount.

In the insulating film forming material of the present disclosure, the content of component (C) is preferably 1 part by mass to 10,000 parts by mass, and preferably 50 parts by mass to 10,000 parts by mass, per 100 parts by mass of component (A). It is more preferable.

Component (C) is at least one solvent (1) selected from the group consisting of compounds represented by formulas (3) to (8), as well as ester solvents, ether solvents, and ketone solvents. , a hydrocarbon solvent, an aromatic hydrocarbon solvent, and a sulfoxide solvent.
Further, the content of the solvent (1) may be 5% by mass to 100% by mass, or even 5% by mass to 50% by mass, based on the total of the solvent (1) and the solvent (2). good.
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, 10 parts by mass to 100 parts by mass, based on 100 parts by mass of component (A). It may be 50 parts by mass.

The insulating film forming material of the present disclosure preferably further includes (D) a photopolymerization initiator (hereinafter also referred to as (D) component). Further, the insulating film forming material of the present disclosure may further include (E) a thermal polymerization initiator (hereinafter also referred to as (E) component). Preferred forms of component (D) and component (E) will be described below.

((D) Photopolymerization initiator)
The insulating film forming material of the present disclosure preferably contains (D) a photopolymerization initiator. This makes it possible to reduce the number of steps for manufacturing electrodes in the process of manufacturing a semiconductor device, and to reduce the cost of the entire process when manufacturing a semiconductor device.

Specific examples of component (D) include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy- 4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, Benzophenone derivatives such as fluorenone; acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone Acetophenone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone; benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal; benzoin, benzoin Benzoin derivatives such as methyl ether, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin, propylbenzoin; 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, Oxime derivatives such as 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime); N-arylglycines such as N-phenylglycine; peroxides such as benzoyl peroxide; 2-( o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5- Aromatic biimidazoles such as diphenylimidazole dimer, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis( Examples include acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyl)phenylphosphine oxide, Irgacure OXE03 (manufactured by BASF), Irgacure OXE04 (manufactured by BASF), and the like.
Component (D) may be used alone or in combination of two or more.
Among these, oxime compound derivatives are preferred from the viewpoints of not containing metal elements, having high reactivity, and high sensitivity.

When the insulating film-forming material of the present disclosure contains component (D), the content of component (D) is 0% based on 100 parts by mass of component (A) from the viewpoint that photocrosslinking tends to be uniform in the film thickness direction. .1 part by weight to 20 parts by weight is preferable, 1 part to 15 parts by weight is more preferable, and even more preferably 5 parts to 10 parts by weight.

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.

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

Specific examples of component (E) include ketone peroxide such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy) ) Peroxyketals such as cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide hydroperoxides such as dicumyl peroxide, dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di(4-t-butylcyclohexyl) peroxydicarbonate, di(2- peroxydicarbonates such as ethylhexyl) peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, 1,1,3,3- Examples include peroxy esters such as tetramethylbutyl peroxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl) peroxide, and the like. Thermal polymerization initiators may be used alone or in combination of two or more.

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

((F) Polymerization inhibitor)
The insulating film forming material of the present disclosure may contain (F) a polymerization inhibitor (hereinafter also referred to as "component (F)") from the viewpoint of ensuring good storage stability. Examples of the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.

Specific examples of component (F) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl- 2-naphthylamine, cuperone, 2,5-torquinone, tannic acid, parabenzylaminophenol, nitrosamines, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2 , 3-dioxide, hindered phenol compounds, and the like. The polymerization inhibitors may be used alone or in combination of two or more. By combining two or more polymerization inhibitors, it tends to be easier to adjust the photosensitive characteristics due to the difference in reactivity. The hindered phenol compound may have both the function of a polymerization inhibitor and the function of an antioxidant described below, or it may have either one of the functions.

The hindered phenol compound is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5- di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di- t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl) -4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol) , pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate , 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6- dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy- 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy- 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3 -Hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3- hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6- dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy- 2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5- Ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t- butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- t-Butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5- Tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1, 3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-tris(4-t-butyl-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].
Among these, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] is preferred.

When the insulating film forming material of the present disclosure contains component (F), the content of component (F) is 100% of component (A) from the viewpoint of storage stability of the insulating film forming material and heat resistance of the obtained cured product. It is preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.01 parts by mass to 10 parts by mass, and preferably 0.05 parts by mass to 5 parts by mass. More preferred.

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

(Antioxidant)
The insulating film forming material of the present disclosure may contain an antioxidant from the viewpoint of suppressing deterioration of adhesive properties by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow treatment, etc. . Since the insulating film forming material of the present disclosure contains an antioxidant, oxidation of the electrode during an insulation reliability test can be suppressed.

Specific examples of antioxidants include the compounds listed above as the hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethyl] carbonyloxy]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 antioxidants may be used alone or in combination of two or more.

When the insulating film forming material of the present disclosure contains an antioxidant, the content of the antioxidant is preferably 0.1 parts by mass to 20 parts by mass, and 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of component (A). The amount is more preferably from .1 parts by weight to 10 parts by weight, and even more preferably from 0.1 parts by weight to 5 parts by weight.

(coupling agent)
The insulating film forming material of the present disclosure may contain a coupling agent. In the heat treatment, the coupling agent reacts with component (A) and crosslinks, or the coupling agent itself polymerizes. This tends to further improve the adhesiveness between the obtained cured product and the substrate.

Specific examples of the coupling agent are not particularly limited. Coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, -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 and other silane coupling agents; aluminum tris(ethyl acetoacetate), aluminum tris(acetylacetonate), ethyl acetate Aluminum adhesive aids such as acetate aluminum diisopropylate; and the like.
The coupling agents may be used alone or in combination of two or more.

When the insulating film forming material of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, and 0.3 parts by mass, based on 100 parts by mass of component (A). Parts by weight to 10 parts by weight are more preferable, and 1 part to 10 parts by weight are even more preferable.

(Surfactant and leveling agent)
The insulating film forming material of the present disclosure may include at least one of a surfactant and a leveling agent. When the insulating film forming material contains at least one of a surfactant and a leveling agent, it improves coating properties (for example, suppressing striae (unevenness in film thickness)), improves adhesion, and improves the compatibility of compounds in the insulating film forming material. etc. can be improved.

Examples of the surfactant or leveling agent include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.

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

When the insulating film forming material of the present disclosure includes at least one of a surfactant and a leveling agent, the total content of the surfactant and leveling agent is 0.01 parts by mass to 100 parts by mass of component (A). The amount is preferably 10 parts by weight, more preferably 0.05 parts to 5 parts by weight, and even more preferably 0.05 parts to 3 parts by weight.

(anti-rust)
The insulating film forming material of the present disclosure may contain a rust preventive agent from the viewpoint of suppressing corrosion of metals such as copper and copper alloys, and from the viewpoint of suppressing discoloration of the metals. Examples of rust preventive agents include azole compounds and purine derivatives.

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

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) Examples include guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthin, 8-azahypoxanthine, and derivatives thereof. It will be done.

The rust inhibitors may be used alone or in combination of two or more.

When the insulating film forming material of the present disclosure contains a rust preventive agent, the content of the rust preventive agent is preferably 0.01 parts by mass to 10 parts by mass, and 0.01 parts by mass to 10 parts by mass, based on 100 parts by mass of component (A). The amount is more preferably from .1 part by weight to 5 parts by weight, and even more preferably from 0.5 parts by weight to 3 parts by weight. In particular, when the content of the rust preventive agent is 0.1 parts by mass or more, when the insulating film forming material of the present disclosure is applied on the surface of copper or copper alloy, discoloration of the surface of copper or copper alloy is prevented. suppressed.

The insulating film forming material of the present disclosure may contain a nitrogen-containing compound from the viewpoint of accelerating the imidization reaction of component (A) and obtaining a highly reliable cured product.

Specific examples of nitrogen-containing compounds include 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N- Phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide , 4-aminoacetophenone, among others, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2 '-(4-methylphenylimino)diethanol and the like are preferred. One type of nitrogen-containing compound may be used alone, or two or more types may be used in combination.

It is preferable that the nitrogen-containing compound includes a compound represented by the following formula (17).

In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group. and at least one (preferably one) of R _31A to R _33A is a monovalent aromatic group. Adjacent groups of R _31A to R _33A may form a ring structure. Examples of the ring structure formed include a 5-membered ring and a 6-membered ring which may have a substituent such as a methyl group or a phenyl group. The hydrogen atom of the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than a hydroxy group.

In formula (17), at least one (preferably one) of R _31A to R _33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic A group group is preferred.

In formula (17), the monovalent aliphatic hydrocarbon groups R _31A to R _33A preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. The monovalent aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, or the like.

In formula (17), the monovalent aliphatic hydrocarbon group having a hydroxy group of R _31A to R _33A is one or more hydroxy groups bonded to the monovalent aliphatic hydrocarbon group of R _31A to R _33A . It is preferable that the hydroxyl group is a bonded group, and a group that has one to three hydroxy groups bonded is more preferable. Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a methylol group, a hydroxyethyl group, and the like, with a hydroxyethyl group being preferred.

Examples of the monovalent aromatic group R _31A to R _33A in formula (17) include a monovalent aromatic hydrocarbon group, a monovalent aromatic heterocyclic group, etc. Groups are preferred. The monovalent aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a naphthyl group.

The monovalent aromatic groups R _31A to R _33A in formula (17) may have a substituent. Examples of the substituent include monovalent aliphatic hydrocarbon groups represented by R _31A to R _33A in formula (17), and monovalent aliphatic hydrocarbon groups having a hydroxy group represented by R _31A to R _33A in formula (17) above. Groups similar to the group are mentioned.

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 parts by mass to 20 parts by mass with respect to 100 parts by mass of component (A). From the viewpoint of stability, the amount is more preferably 0.3 parts by mass to 15 parts by mass, and even more preferably 0.5 parts by mass to 10 parts by mass.

The method for preparing the insulating film forming material of the present disclosure is not particularly limited, and the above-mentioned components may be mixed. For example, for two or more types of (A) components, two or more types of (A) components may be mixed in advance and then added to the (C) component, or two or more types of (A) components may be added to the (C) component. may be added respectively.

(Modified example)
Modifications of the insulating film forming material of the present disclosure will be described. In the following modified examples, the forms and preferred forms of the insulating film forming material of the present disclosure may be combined as appropriate.
The insulating film forming material of the modified example includes (A) two or more types of polyimide precursors that are at least one selected from the group consisting of polyamic acids, polyamic acid esters, polyamic acid salts, and polyamic acid amides; The polyimide precursor (A) is a first polyimide precursor that has a glass transition temperature of 200° C. to 400° C. when made into a cured product, and a glass transition temperature when made into a cured product that is higher than that of the first polyimide precursor. a second polyimide precursor whose temperature is 10°C to 250°C lower.

In the modified insulating film forming material, two types of polyimide precursors having different glass transition temperatures are combined to form a first polyimide precursor which is a more rigid polyimide precursor and a second polyimide precursor which is a more flexible polyimide precursor. The insulating film-forming material is mixed with the body. As a result, when thermocompression bonding the insulating film, the portion derived from the more flexible polyimide precursor melts, making it possible to bond at a lower temperature than when using the more rigid polyimide precursor alone. . Therefore, the thermocompression bondability of the insulating film, the adhesion strength at low temperatures between the insulating films, the adhesion strength at low temperature between the insulating film and the electrode, etc. are improved, and an insulating film with excellent adhesion can be obtained.

The insulating film forming material of the modified example may contain two types of polyimide precursors, or may contain three or more types of polyimide precursors. A preferred form of the polyimide precursor contained in the insulating film forming material of the modified example is the same as the preferred form of the polyimide precursor (A) contained in the insulating film forming material of the present disclosure described above.

The glass transition temperature of the first polyimide precursor as a cured product is 200°C to 400°C, may be 220°C to 350°C, or may be 240°C to 320°C.
The glass transition temperature when the second polyimide precursor is made into a cured product may be 10°C to 200°C, or 20°C to 150°C, higher than the glass transition temperature when the first polyimide precursor is made into a cured product. It may be ℃.
The glass transition temperature of the cured product of the first polyimide precursor and the cured product of the second polyimide precursor can be measured by the method described above. At this time, it is preferable to unify the conditions (for example, composition ratio and temperature conditions) other than the type of polyimide precursor used for the first polyimide precursor and the second polyimide precursor.

Regarding the mass ratio of the first polyimide precursor to the second polyimide precursor, the ratio of the first polyimide precursor to the second polyimide precursor may be 10:90 to 90:10, or 20:80 to 80:20. The time may be from 30:70 to 70:30.

The following (1) is a preferable combination of the glass transition temperature (Tg1) when the first polyimide precursor is made into a cured product and the glass transition temperature (Tg2) when the second polyimide precursor is made into a cured product. ~(4) can be mentioned.
(1) Tg1 is 250°C to 320°C, Tg2 is 140°C to 190°C
(2) Tg1 is 240°C to 290°C, Tg2 is 140°C to 190°C
(3) Tg1 is 270°C to 320°C, Tg2 is 140°C to 190°C
(2) Tg1 is 270°C to 320°C, Tg2 is 240°C to 290°C

<Semiconductor device>
A semiconductor device of the present disclosure includes a first semiconductor substrate including a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body, a semiconductor chip substrate body, and the first substrate body. a semiconductor chip having an organic insulating film portion and a second electrode provided on one surface of a semiconductor chip substrate body, the first organic insulating film of the first semiconductor substrate and the organic insulating film of the semiconductor chip; the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined, and at least one of the first organic insulating film and the organic insulating film part is in contact with the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip. This is a semiconductor device having an insulating film formed by curing the disclosed insulating film forming material.
In the semiconductor device of the present disclosure, since 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, metal ( For example, copper) becomes difficult to diffuse into the insulating film, and a decrease in insulation resistance is suppressed. Thereby, a semiconductor device including an insulating film with excellent insulation reliability can be obtained. Further, the semiconductor device of the present disclosure is manufactured, for example, through steps (1) to (5) described below.

<Method for manufacturing semiconductor devices>
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 through steps (1) to (5) using the insulating film forming material of the present disclosure.
Step (1) A first semiconductor substrate having a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body is prepared.
Step (2) A second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body is prepared.
Step (3) Cutting the second semiconductor substrate into 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 second electrode. .
Step (4) Bonding 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) Joining the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.

Hereinafter, one embodiment of the semiconductor device of the present disclosure and one embodiment of the method of manufacturing the semiconductor device of the present disclosure will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are given the same reference numerals, and overlapping description will be omitted. In addition, the positional relationships such as top, bottom, 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.

(Example of semiconductor device)
FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present disclosure. As shown in FIG. 1, the semiconductor device 1 is an example of a semiconductor package, and includes a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar part 30, and a rewiring layer 40. , a substrate 50, and a circuit board 60.

The first semiconductor chip 10 is a semiconductor chip such as an LSI (large scale integrated circuit) chip or a CMOS (complementary metal oxide semiconductor) sensor, and has a three-dimensional mounting structure in which the second semiconductor chip 20 is mounted downward. There is. 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, the details of which will be described later, so that the respective terminal electrodes and the insulating films around the terminal electrodes are firmly and without misalignment.

The pillar portion 30 is a connection portion in which a plurality of pillars 31 made of metal such as copper (Cu) are sealed with a resin 32. The plurality of pillars 31 are conductive members extending from the upper surface to the lower surface of the pillar section 30. The plurality of pillars 31 may have a cylindrical shape, for example, 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 distance between the centers of each pillar 31 is 15 μm or less. The plurality of pillars 31 connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40 by flip-chip connection. By using the pillar section 30, the connection electrode can be formed in the semiconductor device 1 without using a technique called TMV (Through Mold Via) in which a hole is made in a mold and a solder connection is made. The pillar section 30 has, for example, the same thickness as the second semiconductor chip 20, and is arranged on the side 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 solder balls electrically connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40. You may.

The rewiring layer 40 is a wiring layer that has a terminal pitch conversion function, which is a function of a package substrate, and is made 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 section 30. This is a layer in which a rewiring pattern is formed. The rewiring layer 40 is formed by turning the first semiconductor chip 10 (first semiconductor substrate 100), second semiconductor chip 20, etc. upside down (see (d) in FIG. 4).

The rewiring layer 40 electrically connects the terminal electrodes of the first semiconductor chip 10 via the terminal electrodes on the lower surface of the second semiconductor chip 20 and 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 board 50. In addition, if 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 ensure electrical connection between the rewiring layer 40 and the substrate 50. You can also make a connection.

The circuit board 60 has the first semiconductor chip 10 and the second semiconductor chip 20 mounted thereon, and is electrically connected to the board 50 which is connected to the first semiconductor chip 10, the second semiconductor chip 20, the electronic component 51, etc. This is a substrate that has a plurality of through electrodes inside. 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 a plurality of through electrodes.

(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. FIG. 3 is a diagram showing in more detail the bonding method (hybrid bonding) in the method of manufacturing the semiconductor device shown in FIG. FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram sequentially showing steps after the step shown in FIG. 2.

The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n).
(a) Step of preparing the 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) One surface 101a side, which is the surface of the first semiconductor substrate 100, is polished using the CMP method so that each surface 103a of the terminal electrode 103 is at the same position or in a protruding position with respect to the surface 102a of the insulating film 102. (see FIG. 3(a)).
(d) One surface 201a, which is the surface of the second semiconductor substrate 200, is polished using a CMP method so that each surface 203a of the terminal electrode 203 is at the same position or in a protruding position with respect to the surface 202a of the insulating film 202. Polishing step (see FIG. 3(a)).
(e) As shown in FIG. 2B, a step of dividing the second semiconductor substrate 200 into pieces to obtain a plurality of semiconductor chips 205.
(f) As shown in FIG. 2C, a step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with respect to the terminal electrodes 103 of the first semiconductor substrate 100.
(g) A step of bonding the insulating film 102 of the first semiconductor substrate 100 and each insulating film portion 202b of the plurality of semiconductor chips 205 to each other (see (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 electrode 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 the pillars 31) on the connection surface of the first semiconductor substrate 100 and between the plurality of semiconductor chips 205 (see (a) of FIG. 4).
(j) A step of molding resin 301 on the connection surface of first semiconductor substrate 100 so as to cover semiconductor chip 205 and pillar 300 to obtain semi-finished product M1 (see (b) of FIG. 4).
(k) A process 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) in 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) in FIG. 4).
(m) A step of cutting the semi-finished product M3 on which the wiring layer 400 was formed in step (l) along the cutting line A to form each semiconductor device 1 (see (d) in FIG. 4).
(n) A step of inverting the semiconductor device 1a individualized in step (m) and placing it on the substrate 50 and the circuit board 60 (see FIG. 1).

For example, in the method for manufacturing a semiconductor device of the present disclosure, step (1) corresponds to the above-mentioned step (a) and step (c), and step (2) corresponds to the above-mentioned step (b) and step (d). However, step (3) corresponds to step (e), step (4) corresponds to step (g), and step (5) corresponds to step (h). Furthermore, the insulating film forming material of the present disclosure may be an insulating film forming material for use in manufacturing at least one of a first organic insulating film and a second organic insulating film in a method for manufacturing a semiconductor device. .

Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate, corresponding to a plurality of first semiconductor chips 10 and on which an integrated circuit including semiconductor elements and wiring 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 placed on one surface 101a of the first substrate body 101 made of silicon etc. in a predetermined manner. An insulating film 102 (first insulating film) is provided at intervals and is a cured product obtained by curing the insulating film forming material of the present disclosure. The plural terminal electrodes 103 may be provided after the insulating film 102 is provided on the one surface 101a of the first substrate main body 101, or the plural terminal electrodes 103 may be provided on the one surface 101a of the first substrate main body 101 and then the insulating film is provided. 102 may be provided.

Step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate, on which an integrated circuit corresponding to a plurality of second semiconductor chips 20 and including semiconductor elements and wiring 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 formed on one surface 201a of the second substrate main body 201 made of silicon or the like. are continuously provided, and an insulating film 202 (second insulating film) which is a cured product obtained by curing the insulating film forming material of the present disclosure is provided. A plurality of terminal electrodes 203 may be provided after the insulating film 202 is provided on the one surface 201a of the second substrate main body 201, or a plurality of terminal electrodes 203 may be provided on the one surface 201a of the second substrate main body 201 and then the insulating film 202 is provided. may be provided.

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

Further, although FIG. 1 shows an example of C2C bonding, the present invention may also be applied to Chip-to-Wafer (C2W) bonding shown in FIG. In C2W, a semiconductor wafer 410 (first substrate body) having a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes) is used. 1 semiconductor substrate) is prepared. Furthermore, a plurality of semiconductor chips each having a substrate body 421 (second substrate body), an insulating film portion 422 (second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes). 420 semiconductor substrates (second semiconductor substrates) before being separated into individual pieces are prepared. Then, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before being singulated into semiconductor chips 420 are polished by CMP or the like in the same manner as in the above steps (c) and (d). . Thereafter, the second semiconductor substrate is subjected to the same singulation process as in step (e) to obtain a plurality of semiconductor chips 420.

Subsequently, as shown in FIG. 5A, the terminal electrodes 423 of the semiconductor chip 420 are aligned with the terminal electrodes 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 are bonded together (step (g)), and the terminal electrodes 413 of the semiconductor wafer 410 and the terminal electrodes 423 of the semiconductor chip 420 are bonded. (step (h)) to obtain a semi-finished product shown in FIG. 5(b). As a result, the insulating film portion 412 and the insulating film portion 422 become an insulating bonding portion S3, and the semiconductor chip 420 is mechanically firmly attached to the semiconductor wafer 410 with high accuracy. Further, the terminal electrode 413 and the corresponding terminal electrode 423 are joined to form an electrode joint portion S4, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly joined.

In step (h), as shown in FIG. 2(d), after the bonding in step (g) is completed, heat H, pressure, or both are applied to bond the terminals of the first semiconductor substrate 100 as hybrid bonding. The electrode 103 and each terminal electrode 203 of the plurality of semiconductor chips 205 are bonded (see FIG. 3C). When the terminal electrodes 103 and 203 are made of copper, the annealing temperature in step (g) is preferably 150°C or more and 400°C or less, more preferably 200°C or more and 300°C or less. In particular, by using the insulating film forming material of the present disclosure, it is also possible to set the annealing temperature low. Through such a bonding process, the terminal electrode 103 and the corresponding terminal electrode 203 are bonded to form an electrode bonding portion S2, and the terminal electrode 103 and the terminal electrode 203 are mechanically and electrically strongly bonded. Note that the electrode bonding in step (h) may be performed after the bonding in step (g), or may be performed simultaneously with the bonding in step (g).

Thereafter, as shown in FIGS. 5C and 5D, a semiconductor device 401 is obtained by bonding a plurality of semiconductor chips 420 to a semiconductor wafer 410 in the same manner. Note that the plurality of semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or may be bonded to the semiconductor wafer 410 all together by hybrid bonding.

Also in this method of manufacturing the semiconductor device 401, as in the method of 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 made of the insulating film of the present disclosure. This is an insulating film that is a cured product obtained by curing the forming material. Therefore, a semiconductor device including an insulating film with excellent insulation reliability can be obtained.

(Modified example)
In the semiconductor device and semiconductor device manufacturing method of the present disclosure, a configuration in which the first electrode and the second electrode are bonded has been described, 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 of the present disclosure includes, for example, using the insulating film forming material of the present disclosure for producing at least one of a first organic insulating film and a second organic insulating film, and performing the following step (1)' It may be a method of manufacturing a semiconductor device through steps (5)'.
Step (1)' A first semiconductor substrate having a first substrate body and the first organic insulating film provided on one surface of the first substrate body is prepared.
Step (2)' A second semiconductor substrate having a second substrate body and the second organic insulating film provided on one surface of the second substrate body is prepared.
Step (3)' The second semiconductor substrate is cut into pieces 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)' The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded together.
Step (5)' A through hole is provided in a part of the first semiconductor substrate and the second semiconductor substrate that are bonded together, and a through electrode is provided in the through hole.
In the above (5)', the method of providing the through hole and the method of providing the through electrode are not particularly limited. For example, a through hole may be provided by etching or the like, or a through electrode may be provided by electrolytic plating, electroless plating, sputtering, or the like.

Hereinafter, the present disclosure will be described in more detail based on Examples and Comparative Examples. Note that the present disclosure is not limited to the following examples.

(Synthesis Example 1 (Synthesis of A1))
62 g of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA) and 36 g of 4,4'-diamino-2,2'-dimethylbiphenyl (DMAP) were mixed into 3-methoxy-N,N -Dissolved in 915 g of dimethylpropionamide. The resulting solution was stirred at 30°C for 2 hours to obtain polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added thereto at room temperature, and the mixture was stirred at 45° C. for 10 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor 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 25,000. Specifically, measurements were made under the following conditions using a solution in which 0.5 mg of A1 was dissolved in 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF) = 1/1 (volume ratio)].
(Measurement condition)
Measuring device: Shimadzu Corporation SPD-M20A
Pump: Shimadzu Corporation LC-20AD
Column oven: Shimadzu Corporation: CTO-20A
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF/DMF = 1/1 (volume ratio)
LiBr (0.03mol/L), _H3PO4 ( _0.06mol /L)
Flow rate: 1.0 mL/min, detector: UV270 nm, column temperature: 40°C
Standard polystyrene: Create a calibration curve using Tosoh TSKgel standard Polystyrene Type F-1, F-4, F-20, F-80, A-2500

<Esterification rate>
By performing NMR measurements under the following conditions, the esterification rate of A1 (ratio of ester groups reacted with HEMA to the total of ester groups reacted with HEMA and carboxyl groups not reacted with HEMA) was calculated. . The esterification rate was 76 mol%, and the proportion of unreacted carboxyl groups was 24 mol%.
(Measurement condition)
Measuring equipment: Bruker Biospin AV400M
Magnetic field strength: 400MHz
Reference material: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

(Synthesis Example 2 (Synthesis of A2))
62 g of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA) and 34 g of 4,4'-diaminodiphenyl ether were dissolved in 915 g of 3-methoxy-N,N-dimethylpropionamide. The resulting solution was stirred at 30°C for 2 hours to obtain polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added thereto at room temperature, and the mixture was stirred at 45° C. for 10 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A2.
In the same manner as A1 above, the weight average molecular weight of A2 was determined in terms of standard polystyrene using gel permeation chromatography (GPC). The weight average molecular weight of A2 was 23,000.
The esterification rate of A2 was calculated in the same manner as A1. The esterification rate of A2 was 77%.

(Synthesis Example 3 (Synthesis of A3))
59 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and 34 g of 4,4'-diaminodiphenyl ether were dissolved in 915 g of 3-methoxy-N,N-dimethylpropionamide. . The resulting solution was stirred at 30°C for 2 hours to obtain polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added thereto at room temperature, and the mixture was stirred at 45° C. for 10 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A3.
In the same manner as A1 above, the weight average molecular weight of A3 was determined in terms of standard polystyrene using gel permeation chromatography (GPC). The weight average molecular weight of A3 was 24,000.
The esterification rate of A3 was calculated in the same manner as A1. The esterification rate of A3 was 75%.

(Synthesis example 4 (synthesis of A4))
104 g of bisphenol A type acid dianhydride (BPADA) represented by the following chemical formula and 51 g of 1,3-bis(3-aminophenoxy)benzene were dissolved in 915 g of 3-methoxy-N,N-dimethylpropionamide. The resulting solution was stirred at 30°C for 2 hours to obtain polyamic acid. 78 g of trifluoroacetic anhydride and 109 g of 2-hydroxyethyl methacrylate (HEMA) were added thereto at room temperature, and the mixture was stirred at 45° C. for 10 hours. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A4.
In the same manner as A1 above, the weight average molecular weight of A4 was determined in terms of standard polystyrene using gel permeation chromatography (GPC). The weight average molecular weight of A4 was 25,000.
The esterification rate of A4 was calculated in the same manner as A1. The esterification rate of A4 was 78%.

[Examples 1 to 7, Comparative Examples 1 to 3]
(Preparation of insulating film forming material)
Insulating film forming materials of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared as follows using the components and blending amounts shown in Table 1. The unit of the amount of each component in Table 1 is parts by mass. In addition, a blank column in Table 1 means that the corresponding component is 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 filtered under pressure using a 0.2 μm pore filter. The following evaluations were performed using the obtained insulating film forming material.

Each component in Table 1 is as follows.
・Component (A) and other components A1 to A4: Polyimide precursors A1 to A4 synthesized in Synthesis Examples 1 and 2 above
・(B) Component B1: Triethylene glycol dimethacrylate ・(C) Component (solvent)
C1: 3-methoxy-N,N-dimethylpropionamide C2: γ-butyrolactone/adhesion aid Adhesion aid: 50% methanol solution of 3-ureidopropyltriethoxysilane/Component (D) (photopolymerization initiator)
D1: 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime D2: N,N'-tetraethyl-4,4'-diaminobenzophenone/(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: benzotriazole

[Evaluation of thermocompression bondability]
(Preparation of insulating film with chip)
The insulating film forming materials of Examples 1 to 7 and Comparative Examples 1 to 3 were spin coated onto a 6-inch Si wafer using a spin coater coating device, and a drying process was performed to form a resin film. The obtained resin film was subjected to broadband exposure using an exposure machine (SUSS Microtech Mask Aligner MA-8). Thereafter, development was performed with cyclopentanone for a predetermined period of time, and 5 mm from the outer periphery of the resin film on the Si wafer was removed to prepare a patterned resin film. The resin film was heated in a clean oven at 200° C. for a predetermined time in a nitrogen atmosphere to obtain an insulating film having a thickness of 2 μm to 12 μm after curing.

After scrubbing the resulting insulating film using a general cleaning solution, a part of the cleaned insulating film was cut into 4 mm square pieces using a blade dicer (DISCO DFD-6362) to create chips with resin. I got it.

(Evaluation of thermocompression bondability)
The resin-coated chip described above was placed on an insulating film formed on a Si wafer manufactured under the same conditions as described above, and a carbon sheet for absorbing the step difference was covered. Using a crimping device (manufactured by EVG), crimping was carried out under atmospheric conditions at 180° C. for 180 seconds by applying a load of 100 N to a 1 cm sized pressure area. Three chips were crimped, and whether or not the chips would come off even if a small external force was applied to the crimped chips was used as an index of thermocompression bondability. The evaluation criteria for thermocompression bondability for each Example and Comparative Example are as follows.
-Evaluation criteria-
A: Adhesion was observed in all three chips.
B: Adhesion was observed in one or two of the three chips.
C: No adhesion was observed in any of the three chips.

[Evaluation of adhesion between insulating film and copper]
The insulating film forming materials of Examples 1 to 7 and Comparative Examples 1 to 3 were spin-coated onto a 6-inch Cu wafer using a spin coater coating device, and a drying process was performed to form a resin film. The obtained resin film was subjected to broadband exposure using an exposure machine (SUSS Microtech Mask Aligner MA-8). Thereafter, the resulting resin film was developed with cyclopentanone for a predetermined time, and the resulting resin film was heated at 200°C for a predetermined time in a nitrogen atmosphere using a clean oven to obtain an insulating film with a thickness of 2 μm to 11 μm after curing. Ta. The resulting insulating film was subjected to a 100-mass peel test in accordance with the cross-cut method of the JIS K 5600-5-6 standard to evaluate the adhesion properties between the insulating film and the Cu substrate. For each Example and Comparative Example, the evaluation criteria for adhesion between the insulating film and copper are as follows.
-Evaluation criteria-
A: The number of squares of the insulating film bonded to the Cu substrate is 100.
B: The number of squares of the insulating film bonded to the Cu substrate is 50 to 99.
C: The number of squares of the insulating film adhered to the Cu substrate is less than 50.

[Evaluation of adhesion between insulating films]
(Evaluation of Thermocompression Bondability) Regarding the insulating films with chips obtained in (Evaluation of Thermocompression Adhesion), the adhesion between the insulating films was measured using a shear tester. The adhesion between the insulating layers was evaluated using the following criteria.
-Evaluation criteria-
A: The average shear strength of the three chips is 1 MPa or more.
B: The average shear strength of the three chips is less than 1 MPa.
C: Adhesive strength is low and cannot be measured.
As long as the adhesive strength was 1 MPa or more, the steps after the production of the chip-attached insulating film could be carried out without any problem.

[Evaluation of elongation at break]
(Preparation of patterned cured product)
The insulating film forming materials of Examples 1 to 7 and Comparative Examples 1 to 3 were spin coated onto a 6-inch Si wafer using a spin coater coating device, and a drying process was performed to form a resin film. The obtained resin film was subjected to broadband exposure using an exposure machine (SUSS Microtech Mask Aligner MA-8). Thereafter, it was developed with cyclopentanone for a predetermined time to obtain a strip-shaped patterned resin film with a width of 10 mm. The patterned resin film was heated in a clean oven at 200° C. for a predetermined time in a nitrogen atmosphere to obtain a cured film having a thickness of 2 μm to 11 μm after curing.

(Evaluation of elongation at break)
The cured film obtained as described above was immersed in a 4.9% by mass aqueous hydrofluoric acid solution, and a 10 mm wide cured film was peeled off from the wafer. A tensile test was conducted on the peeled cured film with a width of 10 mm using Autograph AGS-X 100N. The distance between the chucks was 20 mm, the pulling speed was 5 mm/min, and the measurement temperature was 18° C. to 25° C., and measurements were taken for each cured product of each Example and Comparative Example. Measurements were performed five times, and the average elongation at break was determined. The evaluation criteria for elongation at break for each Example and Comparative Example are as follows.
-Evaluation criteria-
A+: Average elongation at break is 80% or more.
A: Average elongation at break is 50% or more and less than 80%.
B: Average elongation at break is 20% or more and less than 50%.
C: Average elongation at break is less than 20%.

Table 1 shows the evaluation results of each Example and each Comparative Example.

As shown in Table 1, Examples 1 to 7 had good evaluation results in terms of thermocompression adhesion, adhesion between an insulating film and copper, adhesion between insulating films, and elongation at break.

DESCRIPTION OF SYMBOLS 1, 1a, 401... Semiconductor device, 10... First semiconductor chip, 20... Second semiconductor chip, 30... Pillar part, 40... Rewiring layer, 50... Substrate, 60... Circuit board, 61... Terminal electrode, 100... First semiconductor substrate, 101... First substrate body, 101a... One side, 102... Insulating film (first insulating film), 103... Terminal electrode (first electrode), 103a... Surface, 200... Second semiconductor substrate, 201... Second substrate body, 201a... One side, 202... Insulating film (second insulating film), 203... Terminal electrode (second electrode), 203a... Surface, 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 product, S1...Insulating bonding portion, S2...Electrode bonding portion, S3...Insulating bonding portion, S4...Electrode bonding portion.

Claims (13)

(A) containing two or more types of polyimide precursors that are at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide;
The two or more types of polyimide precursors (A) have a skeleton represented by the following formula (E),
An insulating film forming material in which the number of elements constituting the main chain of C in the following formula (E) is different in two or more types of polyimide precursors (A).

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)-), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's 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 ^B 's 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 at least these Represents a combination of two divalent groups. (A) containing two or more types of polyimide precursors that are at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide;
The two or more types of polyimide precursors (A) include a first polyimide precursor whose glass transition temperature is 200°C to 400°C when cured, and a polyimide precursor which has a glass transition temperature of 200°C to 400°C when cured than the first polyimide precursor. a second polyimide precursor whose glass transition temperature is 10°C to 250°C lower. The two or more types of polyimide precursors (A) have a skeleton represented by the following formula (E),
The insulating film forming material according to claim 2, wherein the two or more types of polyimide precursors (A) have different numbers of elements constituting the main chain of C in the following formula (E).

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)-), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's 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 ^B 's 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 at least these Represents a combination of two divalent groups. The insulating film forming material according to claim 1 or 3, wherein the two or more types of polyimide precursors (A) satisfy any of the following (1) to (3).
(1) A combination of a polyimide precursor in which C in the formula (E) is a single bond and a polyimide precursor in which C in the formula (E) includes an ether bond (-O-);
(2) A polyimide precursor in which C in the formula (E) contains an ether bond (-O-) and a phenylene group; and C in the formula (E) is an ether bond (-O-) or an ether bond. and a combination with a polyimide precursor which is an alkylene group,
(3) A polyimide precursor in which C in the formula (E) is a divalent linking group that does not contain an ether bond (-O-), and a polyimide precursor in which C in the formula (E) is a divalent linking group that does not contain an ether bond (-O-). combination with a polyimide precursor containing. The insulating film forming material according to any one of claims 1, 3, and 4, wherein the two or more types of polyimide precursors (A) have a structural unit represented by the following general formula (1). .

In the general formula (1), X represents a tetravalent organic group represented by the above formula (E), Y represents a divalent organic group, and R ⁶ and R ⁷ each independently represent a hydrogen atom, Or represents a monovalent organic group. The insulating film forming material according to claim 5, wherein the divalent organic group represented by Y in the general formula (1) is a group represented by the following formula (H).

In formula (H), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom, and n each independently represents an integer of 0 to 4. D is a single bond, alkylene group, halogenated alkylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), phenylene group, ester bond (-O-C(=O) -), silylene bond (-Si(R ^A ) ₂ -; two R ^A 's each independently represent a hydrogen atom, an alkyl group, or a phenyl group), siloxane bond (-O-(Si(R ^B ) ₂ -O-) _n ; Two R ^B 's 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 combination of at least two of these. represents the group of In the general formula (1), the monovalent organic group in R ⁶ and R ⁷ is 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 claim 5 or 6.

In general formula (2), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ^x represents a divalent linking group. (B) The insulating film forming material according to any one of claims 1 to 7, further comprising a polymerizable monomer. Any one of claims 1 to 8, further comprising (C) a solvent, wherein the (C) solvent comprises at least one type selected from the group consisting of compounds represented by the following formulas (3) to (8). The insulating film forming material according to item 1.

In formulas (3) to (8), R ¹ , R ² , R ⁸ , R ¹⁰ and R ¹¹ 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, u is an integer from 0 to 3, and v is an integer from 0 to 3. (D) The insulating film forming material according to any one of claims 1 to 9, further comprising a photopolymerization initiator. The insulating film forming material according to any one of claims 1 to 10, for forming an insulating film by hybrid bonding. The insulating film forming material according to any one of claims 1 to 11 is used for producing at least one of the first organic insulating film and the second organic insulating film, and the following steps (1) to A method for manufacturing a semiconductor device, comprising manufacturing a semiconductor device through step (5).
Step (1) A first semiconductor substrate having a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body is prepared.
Step (2) A second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body is prepared.
Step (3) Cutting the second semiconductor substrate into 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 second electrode. do.
Step (4) Bonding 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) Joining the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip. a first semiconductor substrate having a first substrate body, the 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;
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, and the first electrode of the first semiconductor substrate and the first organic insulating film portion of the semiconductor chip are bonded to each other. 2 electrodes 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 the insulating film forming material according to any one of claims 1 to 11.