JP2023151490A - Polyimide precursor, hybrid bonding insulation film-forming material, method for producing semiconductor device, and semiconductor device - Google Patents

Abstract

To provide a polyimide precursor with excellent adhesion to a substrate, a hybrid bonding insulation film-forming material, a method for producing a semiconductor device, and a semiconductor device.SOLUTION: A polyimide precursor has a structure derived from an amine compound including a siloxane bond.SELECTED DRAWING: None

Description

The present disclosure relates to a polyimide precursor, a hybrid bonding 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)

As a method of C2W bonding using hybrid bonding technology, practical use of a method using an inorganic material such as silicon dioxide (SiO ₂ ) for an insulating film is being considered. However, since inorganic materials are hard materials, there is a risk that, for example, foreign matter derived from inorganic materials generated when cutting semiconductor chips into individual pieces may adhere to the surface of the insulating film and create large voids at the bonding interface. There is. As a result, the yield of semiconductor device manufacturing decreases, or manufacturing costs increase because equipment such as a clean room with high cleanliness is required to remove foreign substances.

On the other hand, a method of C2W bonding using hybrid bonding technology using an organic insulating film is still in the study stage and has not yet been put to practical use. When the cyclic olefin resin described in Patent Document 1 is used, the heat resistance of the resulting organic insulating film is insufficient, and bonding occurs at the interface between the substrate and the organic insulating film due to exposure to high temperatures during C2W bonding. There is a risk that defects may occur. It has become clear that when a silane coupling agent is added from the viewpoint of suppressing adhesion defects, self-condensation of the silane coupling agent occurs and may precipitate as foreign matter.

The present disclosure has been made in view of the above, and aims to provide a polyimide precursor that has excellent adhesiveness to a substrate, a hybrid bonding insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device.

Specific means for achieving the above object are as follows.
<1> A polyimide precursor having a structure derived from an amine compound containing a siloxane bond.
<2> The polyimide precursor according to <1>, wherein the main chain is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide.
<3> The polyimide precursor according to <1> or <2>, which has a structural unit represented by the following general formula (1).

In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group. .
<4> The polyimide precursor according to <3>, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by 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.
<5> The polyimide precursor according to <3> or <4>, 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
<6> 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 polyimide precursor according to any one of <3> to <5>.


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.
<7> The polyimide precursor according to any one of <1> to <6>, further having a structure derived from a monoamine compound containing a siloxane bond.
<8> A hybrid bonding insulating film forming material containing the polyimide precursor according to any one of <1> to <7> and a solvent.
<9> The hybrid bonding insulating film forming material according to <7>, further containing a polymerizable monomer.
<10> Prepare a first semiconductor substrate having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body,
preparing a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body;
bonding the first electrode and the second electrode and bonding the first organic insulating film and the second organic insulating film;
A method for manufacturing a semiconductor device using the hybrid bonding insulating film forming material according to <8> or <9> for producing at least one of the first organic insulating film and the second organic insulating film.
<11> The method for manufacturing a semiconductor device according to <10>, wherein the first electrode and the second electrode are bonded after the first organic insulating film and the second organic insulating film are bonded together.
<12> The semiconductor chip is prepared by dividing into pieces a second semiconductor substrate having a second substrate body and a plurality of second electrodes and a second organic insulating region provided on one surface of the semiconductor chip substrate body. The method for manufacturing a semiconductor device according to <10> or <11>.
<13> The first organic insulating film and the second organic insulating film are bonded together at a temperature such that a temperature difference between the semiconductor chip and the first semiconductor substrate is within 10° C. <10> to <12>.The method for manufacturing a semiconductor device according to any one of 12>.
<14> In the manufactured semiconductor device, the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film is 0.1 μm or more <10> to <13>, the method for manufacturing a semiconductor device according to any one of the above.
<15> Before both the first electrode and the second electrode are bonded and the first organic insulating film and the first organic insulating film are bonded, the first semiconductor substrate is The method for manufacturing a semiconductor device according to any one of <10> to <14>, wherein at least one of the one surface and a side of the one surface of the semiconductor chip is polished.
<16> The method for manufacturing a semiconductor device according to <15>, wherein the polishing includes chemical mechanical polishing.
<17> The method for manufacturing a semiconductor device according to <16>, wherein the polishing further includes mechanical polishing.
<18> The first organic insulating film is thicker than the first electrode, and the second organic insulating film is thicker than the second electrode. The method for manufacturing a semiconductor device according to any one of 10> to 17>.
<19> A first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body,
A semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body,
The first organic insulating film and the second organic insulating film are bonded, the first electrode and the second electrode are bonded,
A semiconductor device, wherein at least one of the first organic insulating film and the second organic insulating film is a cured product of the hybrid bonding insulating film forming material according to <8> or <9>.

According to the present disclosure, it is possible to provide a polyimide precursor that has excellent adhesiveness to a substrate, a hybrid bonding insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device.

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. 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 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 present disclosure, 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 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 this disclosure, "(meth)acrylic group" means "acrylic group" and "methacrylic group", "(meth)acrylate" means "acrylate" and "methacrylate", "(meth)acrylate" means "(meth)acrylate", "Acryloyl" means "acryloyl" and "methacryloyl".
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.

<Polyimide precursor>
The polyimide precursor of the present disclosure has a structure derived from an amine compound containing a siloxane bond. Hereinafter, the amine compound containing a siloxane bond will also be referred to as a "specific amine compound." Although it is not clear why the polyimide precursor having the above structure has excellent adhesion to the substrate, it is thought that the inclusion of siloxane bonds is effective. The polyimide precursor of the present disclosure has excellent adhesion to a substrate even when cured.
In addition, since the polyimide precursor of the present disclosure has excellent adhesion to the substrate, it is possible to omit the addition of a silane coupling agent, and as a result, it is possible to suppress the self-condensation product of the silane coupling agent from precipitating as foreign matter. is also possible.

The group bonded to the silicon atom of the siloxane bond is not particularly limited, and includes an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and the like. The number of groups bonded to the silicon atom of the siloxane bond may be one type alone, or two or more types may be used.

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

The aryl group bonded to the silicon atom of the siloxane bond preferably has 6 to 18 carbon atoms, and may be unsubstituted or substituted with a substituent. Specific examples of the substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of such aryl groups include phenyl groups, naphthyl groups, etc., with phenyl groups being preferred.

The linking group that connects the silicon atom of the siloxane bond and the nitrogen atom of the amine is not particularly limited, and examples thereof include alkylene groups, arylene groups, and the like. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The arylene group preferably has 6 to 18 carbon atoms, and 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. Among these, the arylene group is preferably a phenylene group.
Among these, the linking group is preferably an alkylene group having 1 to 6 carbon atoms, and preferably a methylene group, ethylene group or propylene group.

From the viewpoint of improving heat resistance, the siloxane bond preferably has 2 to 8 silicon atoms, more preferably 2 or 3 silicon atoms, and even more preferably a disiloxane bond. The disiloxane bond is a bond represented by Si--O--Si. Among the remaining three bonds other than the bond to the oxygen atom (O) of the silicon atom (Si), one bond is bonded to the amine directly or via a linking group.

The number of amine sites in the specific amine compound is not particularly limited, and monoamine compounds and diamine compounds are preferred. A monoamine compound and a diamine compound may be used together. When the specific amine compound is a diamine compound, a structure derived from the diamine compound containing a siloxane bond is placed in the main chain of the polyimide precursor. When the specific amine compound is a monoamine compound, a structure derived from the monoamine compound containing a siloxane bond is placed at the terminal site of the polyimide precursor.

Specific examples of the specific amine compound include 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 3-aminopropyltriethoxysilane, and the like. In the polyimide precursor of the present disclosure, one type of structure derived from the specific amine compound may be contained alone, or two or more types may be contained.

The polyimide precursor of the present disclosure may further have a structure derived from an amine compound that does not contain a siloxane bond. Examples of the amine compound not containing a siloxane bond (hereinafter also referred to as "other amine compound") include an amine compound represented by H ₂ N-Y-NH ₂ described below. Y here has the same meaning as Y in general formula (1) (excluding the case of a divalent group having a polysiloxane structure).

In the polyimide precursor of the present disclosure, the ratio of the structure derived from the specific amine compound to the total amount of the structure derived from the specific amine compound and the structures derived from other amine compounds is 50% from the viewpoint of improving adhesiveness to the substrate. It is preferably at least 80% by mass, even more preferably at least 90% by mass, and particularly preferably at least 95% by mass.

The main chain of the polyimide precursor of the present disclosure is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. Since these are the main chains, the polyimide skeleton becomes the main chain in the cured product, and the excellent effects of polyimide tend to be exhibited.
Polyamic acid ester and polyamic acid amide are compounds in which at least some of the carboxy groups in polyamic acid have hydrogen atoms substituted with monovalent organic groups, and polyamic acid salts are compounds in which at least some of the carboxy groups in polyamic acid have been replaced with monovalent organic groups. It is a compound that forms a salt structure with a basic compound having a pH of 7 or more.

The polyimide precursor of the present disclosure preferably has a polymerizable unsaturated bond, and it is more preferable that the polyamic acid, polyamic acid ester, polyamic acid salt, or polyamic acid amide has a polymerizable unsaturated bond.

It is preferable that the polyimide precursor has 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, 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.
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, both may be hydrogen atoms, one may be a hydrogen atom and the other may be a monovalent organic group described below, or both may be the same or different monovalent organic groups. 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 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. .
The tetravalent organic group represented by X may include an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon groups (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), aromatic heterocyclic groups (for example, the number of atoms constituting the heterocycle is 5 to 20), etc. It will be done. The tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring.
When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, and amino groups.
When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains one to four benzene rings, and preferably contains one to three benzene rings. More preferably, it contains one or two benzene rings.
When the tetravalent organic group represented by , ether bond (-O-), sulfide bond (-S-), 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 is an integer of 1 or 2 or more ), or a composite linking group combining at least two of these linking groups. Furthermore, two benzene rings may be bonded at two locations by at least one of a single bond and a linking group, to form a five-membered ring or a six-membered ring containing a linking group 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.

Specific examples of the tetravalent organic group represented by X include groups represented by the following formulas (A) to (G). Among these, a group represented by the following formula (E) 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, and even more preferably an ether bond. The following formula (F) has a structure in which C in the following formula (E) is a single bond.
Note that the present disclosure is not limited to the specific examples below.

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

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. C preferably contains an ether bond, and is preferably an ether bond.
Further, C may have a structure represented by the following formula (C1).

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.

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

In general formula (1), the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms. .
The skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferable skeleton of the divalent organic group represented by Y is It may be the same as the preferred skeleton of the tetravalent organic group represented by. The skeleton of the divalent organic group represented by Y is a tetravalent organic group represented by X, in which two bonding positions are substituted with atoms (e.g. hydrogen atoms) or functional groups (e.g. alkyl groups). It may be a structure.
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 formulas (G) to (I). 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 a single bond or an ether bond, and even more preferably a single bond or an ether bond.

In formulas (G) to (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 from 0 to 4. represent.
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 preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, etc., each independently.

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

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

The halogenated alkyl group represented by R in formulas (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, and preferably a halogenated alkyl group having 1 to 3 carbon atoms. More preferably, it is a halogenated alkyl group having 1 or 2 carbon atoms.
Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (H). Examples include alkyl groups in which 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 formulas (G) to (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 the like.

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.

The divalent organic group represented by Y may be a divalent group having a polysiloxane structure, and may be a divalent group having a disiloxane structure or a divalent group having a trisiloxane structure. Preferably, a divalent group having a disiloxane structure (-Si-O-Si-) is more preferred.
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 the formula (G) is preferably a group represented by the following formula (G'), and the group represented by the formula (H) is preferably a group represented by the following formula (H') or the formula (H'). ') or a group represented by the formula (H''') is preferable, and a group represented by the following formula (H') or the formula (H'') is preferable.

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 (H). Examples include combinations of groups.

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), and the following general It is particularly preferable to include a group represented by formula (2).
Since the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), it has high i-line transmittance and is good even when cured at low temperatures of 400°C or less. It tends to form a cured product. In addition, when the monovalent organic group includes an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond moiety is removed by the compound (C). is detached.

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

When the polyimide precursor contains a compound having a structural unit represented by the above-mentioned general formula (1), the compound represented by general formula (2) with respect to the sum of R ⁶ and R ⁷ of all structural units contained in the compound is The proportion of R ⁶ and R ⁷ , which are the groups represented by R, 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%.

The polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in general formula (1), X corresponds to a residue derived from a tetracarboxylic dianhydride, and Y corresponds to a residue derived from a diamine compound. Note that the polyimide precursor 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'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetra Carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1, 1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2 -Bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane Dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1, 3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'- Examples include sulfonyl diphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and the like.
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 2,2'-dimethylbiphenyl-4,4'-diamine, 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, 2,2'-dimethylbiphenyl-4,4'-diamine, 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 (8)) 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 (8), 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-dimethylpropanamide, and among others, 3-methoxy-N,N- Dimethylpropanamide 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 the polyimide precursor is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then converting it into a diester derivative such as thionyl chloride. It can be obtained by converting it into an acid chloride through the action of a chlorinating agent, and then reacting the acid chloride with a diamine compound represented by H ₂ N--Y--NH ₂ .
The above-mentioned compound contained in the polyimide precursor is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then converting it into a diester derivative in the presence of a carbodiimide compound. It can be obtained by reacting a diamine compound represented by H ₂ N-Y-NH ₂ below with a diester derivative.
The above-mentioned compound contained in the polyimide precursor is produced by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H ₂ N-Y-NH ₂ to form a polyamic 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 (8), X is the same as X in general formula (1), and specific examples and preferred examples are also the same.

The compound represented by R-OH used in the synthesis of the above-mentioned compound contained in the polyimide precursor includes a compound in which a hydroxy group is bonded to R ^x of a group represented by the general formula (2), a compound represented by the general formula (2) It may also be a compound in which a hydroxy group is bonded to the terminal methylene group of the group represented by '). 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.

The molecular weight of the polyimide precursor of the present disclosure is not particularly limited, 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.

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

The insulating film forming material of the present disclosure may further contain a dicarboxylic acid, and the polyimide precursor contained in the insulating film forming material is such that (A) some of the amino groups in the polyimide precursor are the carboxy groups in the dicarboxylic acid. It may have a structure formed by a reaction. For example, when synthesizing the polyimide precursor (A), some 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, (A) when synthesizing the polyimide precursor, a part of the amino group of the diamine compound and the carboxy group of the dicarboxylic acid are reacted to introduce a methacrylic group derived from the dicarboxylic acid into the polyimide precursor. Can be done.

The insulating film forming material of the present disclosure may contain a polyimide resin in addition to the polyimide precursor (A). By combining a polyimide precursor and a polyimide resin, it is possible to suppress the production of volatiles due to dehydration cyclization during imide ring formation, and therefore it tends to be possible 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.

The polyimide resin is not particularly limited as long as it is a polymeric compound having a plurality of structural units containing imide bonds, and preferably includes, for example, a compound having a structural unit represented by the following general formula (X). Thereby, a semiconductor device including an insulating film exhibiting high reliability tends to be obtained.

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

When the insulating film forming material of the present disclosure includes a polyimide resin, the proportion of the polyimide resin to the total of the polyimide precursor and the polyimide resin may be 15% to 50% by mass, or 10% to 20% by mass. There may be.

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

In the insulating film forming material of the present disclosure, the content of the polyimide precursor (A) based on the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass. , more preferably 90% by mass to 100% by mass.

The insulating film forming material of the present disclosure includes (A) a polyimide precursor and (B) a solvent, and optionally (C) a photopolymerization initiator, (D) a polymerizable monomer, and (E) a thermal polymerization initiator. , (F) Contains polymerization inhibitors, antioxidants, coupling agents, surfactants, leveling agents, rust preventives, nitrogen-containing compounds, etc., and contains other components and unavoidable impurities to the extent that the effects of the present disclosure are not impaired. May include. It is preferable that the insulating film forming material of the present disclosure further contains component (D).
Hereinafter, (C) photopolymerization initiator as component (C), (D) polymerizable monomer as component (D), (E) thermal polymerization initiator as component (E), and (F) polymerization inhibitor as component (F). Also called component.

For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the insulating film forming material of the present disclosure,
(A) polyimide precursor and (B) component,
(A) component, (B) component and (D) component,
(A) component, (B) component, (D) component and (E) component,
(A) component, (B) component and (D) component to (F) component,
Consists of component (A), component (B), component (D) to component (F), and component (C), antioxidant, coupling agent, surfactant, leveling agent, rust preventive, and nitrogen-containing compound. At least one selected from the group,
It may consist of.

((B) Solvent)
The insulating film forming material of the present disclosure includes component (B). Component (B) includes at least one selected from the group consisting of compounds represented by the following formulas (3) to (7), for example, from the viewpoint of reducing reproductive toxicity and environmental load of the insulating film forming material. It is preferable.

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

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.

Component (B) may be, for example, at least one of the compounds represented by formulas (4), (5), (6), and (7), and may be a compound represented by formula (5) or It may also be a compound represented by formula (7).

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

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

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, and N-methyl-2-pyrrolidone (NMP).
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.

Preferable examples of the solvent for component (B) include 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, and (A) the polyimide precursor The amount may be 3% by mass or less based on the total amount of the body.

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

Component (B) is at least one solvent (1) selected from the group consisting of compounds represented by formulas (3) to (6), 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, and 10 parts by mass based on 100 parts by mass of the polyimide precursor (A). Parts to 50 parts by mass may be used.

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

Specific examples of component (C) 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, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-benzoyl- Benzophenone derivatives such as 4'-methyldiphenylketone, dibenzylketone, fluorenone; acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- Acetophenone derivatives such as methylpropiophenone and 1-hydroxycyclohexylphenyl ketone; Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and diethylthioxanthone; benzyl, benzyl dimethyl ketal, benzyl-β- Benzyl derivatives such as methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin 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- Oxime derivatives such as benzoyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime); N-arylglycines such as N-phenylglycine; benzoylper Peroxides such as chloride; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o- or aromatic biimidazole such as p-methoxyphenyl)-4,5-diphenylimidazole dimer; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine Examples include acylphosphine oxide derivatives such as oxide, Irgacure OXE03 (manufactured by BASF), Irgacure OXE04 (manufactured by BASF), and the like.
Component (C) 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 and having high reactivity and high sensitivity.

When the insulating film forming material of the present disclosure contains component (C), the content of component (C) is determined based on 100 parts by mass of the polyimide precursor (A) from the viewpoint that photocrosslinking tends to be uniform in the film thickness direction. , is preferably 0.1 parts by weight to 20 parts by weight, more preferably 1 part to 15 parts by weight, and even more preferably 5 parts to 15 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.

((D) Polymerizable monomer)
The insulating film forming material of the present disclosure preferably contains (D) a polymerizable monomer. Component (D) 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 (D) 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 diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol diacrylate. Methacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, Trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate , ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, tricyclodecane dimethanol diacrylate, 2-hydroxyethyl (meth)acrylate, 1,3-bis( (Meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO) modified bisphenol A diacrylate, and ethylene oxide (EO) modified bisphenol A dimethacrylate.

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 (D) is not limited to a compound having a group containing a polymerizable unsaturated double bond, but may be a compound having a polymerizable group other than an unsaturated double bond group (for example, an oxirane ring). .

When the insulating film forming material of the present disclosure contains component (D), the content of component (D) is not particularly limited, and is 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the polyimide precursor (A). The amount is preferably from 1 part by weight to 75 parts by weight, and even more preferably from 1 part by weight to 50 parts by weight.

((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 a 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 1 part by mass to 10 parts by mass.

((F) Polymerization inhibitor)
The insulating film forming material of the present disclosure may contain 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- Examples include 2-naphthylamine, cuperone, 2,5-torquinone, tannic acid, parabenzylaminophenol, nitrosamines, and hindered phenol compounds. 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 the (F) component, the content of the (F) component is determined from the viewpoint of the storage stability of the insulating film forming material and the heat resistance of the obtained cured product. The amount 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 0.05 parts by mass to 5 parts by mass, based on 100 parts by mass of the body. It is even more preferable.

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

(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 with respect to 100 parts by mass of (A) polyimide precursor. , more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 0.1 parts by mass to 5 parts by mass.

(coupling agent)
The insulating film forming material of the present disclosure may contain a coupling agent, but from the viewpoint of suppressing self-condensation of the coupling agent, it is preferable to suppress the amount of the coupling agent added. For example, the amount of the coupling agent added is more preferably less than 0.1 parts by mass, and even more preferably 0 parts by mass, based on 100 parts by mass of the polyimide precursor (A).
In the heat treatment, the coupling agent reacts with the polyimide precursor (A) to crosslink, 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 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of the polyimide precursor (A). It is more preferably from 3 parts by weight to 10 parts by weight, even more preferably from 0.5 parts by weight to 5 parts by weight, and particularly preferably from 1 part by weight to 2 parts by weight.

(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 the leveling agent is 0.01 mass parts with respect to 100 mass parts of (A) polyimide precursor. The amount is preferably from 10 parts to 10 parts by weight, more preferably from 0.05 parts to 5 parts by weight, even more preferably from 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 includes a rust preventive agent, the content of the rust preventive agent is preferably 0.01 parts by mass to 10 parts by mass based on 100 parts by mass of (A) polyimide precursor. , more preferably 0.1 parts by mass to 5 parts by mass, and even more preferably 0.5 parts by mass to 3 parts by mass. 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 resin composition of the present disclosure may contain a nitrogen-containing compound from the viewpoint of accelerating the imidization reaction of (A) the polyimide precursor 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 . The group is preferably a group with 1 to 3 hydroxy groups bonded thereto, and more preferably a group with one to three hydroxy groups bonded thereto. 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 of formula (17), and monovalent aliphatic hydrocarbon groups having a hydroxy group represented by R _31A to R _33A of formula (17) above. Groups similar to the group are mentioned.

When the resin composition 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 (A) polyimide precursor, From the viewpoint of storage stability, the amount is 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.

<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, and a semiconductor chip substrate body. , a semiconductor chip having the second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film and the second organic insulating film are bonded. However, the first electrode and the second electrode are bonded to each other, and at least one of the first organic insulating film and the second organic insulating film is a cured product of the insulating film forming material of the present disclosure.
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 a cured product of the insulating film forming material of the present disclosure, the insulating film has excellent heat resistance.

<Method for manufacturing semiconductor devices>
In the method for manufacturing a semiconductor device of the present disclosure, a semiconductor device is manufactured using the insulating film forming material of the present disclosure. Specifically, the method for manufacturing a semiconductor device of the present disclosure includes a first semiconductor device having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body. A substrate is prepared, a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body is prepared, and the first electrode and the second electrode are provided on one surface of the semiconductor chip substrate body. bonding with two electrodes and bonding the first organic insulating film and the second organic insulating film,
The insulating film forming material of the present disclosure is used to fabricate at least one of the first organic insulating film and the second organic insulating film.

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 have their respective terminal electrodes and their surrounding insulating films firmly and finely bonded to each other by hybrid bonding, which will be described in detail later.

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, the 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 for 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.

The semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n).
(a) A step of preparing a first semiconductor substrate 100 corresponding to the first semiconductor chip 10.
(b) A step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20.
(c) A step of polishing the first semiconductor substrate 100.
(d) A step of polishing the second semiconductor substrate 200.
(e) A step of dividing the second semiconductor substrate 200 into pieces to obtain a plurality of semiconductor chips 205.
(f) A step of aligning the terminal electrodes 203 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 (b) of FIG. 3).
(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.
(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.
(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.
(l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k).
(m) A step of cutting the semi-finished product M3 on which the wiring layer 400 has been formed in step (l) along the cutting line A to form each semiconductor device 1.
(n) A step of inverting the semiconductor device 1a that has been individualized in step (m) and placing it on the substrate 50 and the circuit board 60 (see FIG. 1).

The insulating film forming material of the present disclosure provides a first organic insulating film and a second organic insulating film in a method for manufacturing a semiconductor device including at least one step corresponding to step (f) and steps (i) to (n). It may be an insulating film forming material for use in producing at least one of the insulating films.

[Step (a) and step (b)]
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 or the like. are provided at predetermined intervals, and an insulating film 102 (first insulating film), which is a cured product of the insulating film forming material of the present disclosure, is provided in the spaced portion. A plurality of terminal electrodes 103 may be provided after the insulating film 102 is provided on one surface 101a of the first substrate main body 101, or a plurality of terminal electrodes 103 may be provided on one surface 101a of the first substrate main body 101. The insulating film 102 may be provided after that. Note that a predetermined interval is provided between the plurality of terminal electrodes 103 in order to form the pillar 300 in a process described later, and another terminal electrode (not shown) connected to the pillar 300 is provided between the plurality of terminal electrodes 103. It is formed.

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 An insulating film 202 (second insulating film, organic insulating region) which is a cured product of the insulating film forming material of the present disclosure is provided. The 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 the plurality of terminal electrodes 203 may be provided on the one surface 201a of the second substrate main body 201. Alternatively, the insulating film 202 may be provided.

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

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

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

The polishing rate of the insulating film 102 is 0.1 to 5 times the polishing rate of the terminal electrode 103 in order to facilitate the work in steps (c) and (d) and to simplify these steps. It is preferable that the polishing rate of the insulating film 202 is 0.1 to 5 times the polishing rate of the terminal electrode 203 (preferably both).
stomach. As an example, if the terminal electrode 103 or 203 is made of copper and the polishing rate of copper is 50 nm/min, the polishing rate of the insulating film 102 or 202 is 200 nm/min or less (4 times the polishing rate of copper or less). It is preferably 100 nm/min or less (twice the polishing rate of copper or less), and even more preferably 50 nm/min or less (equal to or less than the polishing rate of copper).

Next, a method for manufacturing an insulating film will be explained. The insulating film is obtained by curing an insulating film forming material. The method for producing the above-mentioned insulating film includes, for example, (α) a step of applying an insulating film forming material onto a substrate and drying it to form a resin film, and a step of heat-treating the resin film; (β) After forming a film with a constant thickness using an insulating film forming material on a film that has been subjected to mold release treatment, the process of transferring the resin film to the substrate by lamination method, and the process of forming the resin film on the substrate after transfer. Examples include a method including a step of heat-treating the resin film. From the viewpoint of flatness, the method (α) above is preferred.

Examples of methods for applying the insulating film forming material include a spin coating method, an inkjet method, and a slit coating method.

In the spin coating method, for example, the rotation speed is 300 rpm (rotations per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, the acceleration is 500 rpm/second to 15,000 rpm/second, and the rotation time is 30 seconds to 300 seconds. The insulating film forming material may be spin coated under certain conditions.

A drying step may be included after applying the insulating film forming material to the support, film, etc. Drying may be performed using a hot plate, oven, or the like. The drying temperature is preferably 75° C. to 130° C., and more preferably 90° C. to 120° C. from the viewpoint of improving the flatness of the insulating film. The drying time is preferably 30 seconds to 5 minutes.
Drying may be performed two or more times. Thereby, it is possible to obtain a resin film in which the above-mentioned insulating film forming material is formed into a film shape.

In the slit coating method, for example, the chemical liquid discharge speed is 10 μL/sec to 400 μL/sec, the chemical liquid discharge part height is 0.1 μm to 1.0 μm, and the stage speed (or chemical liquid discharge part speed) is 1.0 mm/sec to 50.0 mm. /second, stage acceleration 10mm/second to 1000mm/second, ultimate vacuum during vacuum drying 10Pa to 100Pa, vacuum drying time 30 seconds to 600 seconds, drying temperature 60°C to 150°C, and drying time 30 to 300 seconds. The insulating film forming material may be slit coated.

The formed resin film may be heat-treated. The heating temperature is preferably 150°C to 450°C, more preferably 150°C to 350°C. When the heating temperature is within the above range, the insulating film can be suitably produced while suppressing damage to the substrate, devices, etc. and realizing energy saving in the process.

The heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the heat treatment time is within the above range, the crosslinking reaction or dehydration ring closure reaction can proceed sufficiently.
The atmosphere for the heat treatment may be air or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the resin film.

Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, and the like.

When using the insulating film forming material of the present disclosure, which is a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material, the insulating film 202 is provided on one surface 201a of the second substrate main body 201, and then a plurality of When providing the terminal electrode 203, for example, there are a step of applying an insulating film forming material onto the substrate, a step of drying to form a resin film, and a step of exposing the resin film to pattern light and developing it using a developer. A method including a step of obtaining a patterned resin film and a step of heat-treating the patterned resin film may be used. Thereby, a cured patterned insulating film can be obtained.

Alternatively, when providing the plurality of terminal electrodes 203 after providing the insulating film 202 on the one surface 201a of the second substrate main body 201, for example, an insulating film forming material other than the insulating film forming material of the present disclosure may be used on the substrate. a step of coating, a step of drying to form a resin film, and a step of applying and drying the insulating film forming material of the present disclosure, which is a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material, on the resin film. A method may be used that includes a step of later exposing the pattern to light and developing it using a developer to obtain a patterned resin film, and a step of heat-treating the patterned resin film. Thereby, a cured patterned insulating film can be obtained.

In the pattern exposure, for example, a predetermined pattern is exposed through a photomask.
The active light to be irradiated includes i-line, broadband ultraviolet rays, visible light, radiation, etc., and i-line is preferable. As the exposure device, a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, etc. can be used.

By developing after exposure, a patterned resin film, which is a patterned resin film, can be obtained. When the insulating film forming material of the present disclosure is a negative photosensitive insulating film forming material, the unexposed portions are removed with a developer.
The organic solvent used as a negative developing solution may be a good solvent for the photosensitive resin film alone, or a suitable mixture of a good solvent and a poor solvent.
Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, Examples include 3-methoxy-N,N-dimethylpropanamide, cyclopentanone, cyclohexanone, and cycloheptanone.
Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water, and the like.

When the insulating film forming material of the present disclosure is a positive photosensitive insulating film forming material, the exposed portion is removed with a developer.
Examples of the solution used as a positive developer include a tetramethylammonium hydroxide (TMAH) solution and a sodium carbonate solution.

At least one of the negative developer and the positive developer may contain a surfactant. The content of the surfactant is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, based on 100 parts by mass of the developer.

The development time can be, for example, twice the time required for the photosensitive resin film to be completely dissolved after being immersed in the developer.
The development time may be adjusted depending on the polyimide precursor (A) contained in the insulating film forming material of the present disclosure, for example, it is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and productivity From this point of view, a period of 20 seconds to 5 minutes is more preferable.

The patterned resin film after development may be washed with a rinsing liquid.
As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in an appropriate mixture, or they may be used in a stepwise combination. You can.

Note that organic materials constituting the insulating films 102 and 202 other than the cured product of the insulating film forming material of the present disclosure include photosensitive resin, thermosetting non-conductive film (NCF), or thermosetting A synthetic resin may also be used. This organic material may be an underfill material. Further, the organic material forming the insulating films 102 and 202 may be a heat-resistant resin.

[Step (c) and step (d)]
Step (c) is a step of polishing the first semiconductor substrate 100. In step (c), as shown in FIG. 3(a), chemical treatment is applied so that each surface 103a of the terminal electrode 103 is at the same position or slightly higher (protrudes) from the surface 102a of the insulating film 102. One surface 101a, which is the surface of the first semiconductor substrate 100, is polished using a mechanical polishing method (CMP method). In step (c), for example, the first semiconductor substrate 100 may be polished by CMP under the condition that the terminal electrode 103 made of copper or the like is selectively etched deeply. In step (c), each surface 103a of the terminal electrode 103 may be polished by a CMP method so as to match the surface 102a of the insulating film 102. The polishing method is not limited to the CMP method, and back grinding or the like may be used. Prior to polishing by CMP, mechanical polishing may be performed using a polishing device such as a surface planer.
When each surface 103a of the terminal electrode 103 is located at a slightly higher position than the surface 102a of the insulating film 102, the difference in height between each surface 103a and the surface 102a may be 1 nm to 150 nm, or 1 nm to 15 nm. It may be.

Step (d) is a step of polishing the second semiconductor substrate 200. In step (d), as shown in FIG. 3(a), each surface 203a of the terminal electrode 203 is placed at the same position or slightly higher (protrudes) from the surface 202a of the insulating film 202. One surface 201a side, which is the surface of the second semiconductor substrate 200, is polished using the CMP method. In step (d), the second semiconductor substrate 200 is polished by CMP under conditions that selectively and deeply shave the terminal electrode 203 made of copper or the like, for example. In step (d), each surface 203a of the terminal electrode 203 may be polished using a CMP method so as to match the surface 202a of the insulating film 202. The polishing method is not limited to the CMP method, and back grinding or the like may be employed.
When each surface 203a of the terminal electrode 203 is located at a slightly higher position than the surface 202a of the insulating film 202, the difference in height between each surface 203a and the surface 202a may be 1 nm to 50 nm, or 1 nm to 15 nm. It may be.

In steps (c) and (d), polishing may be performed so that the thickness of the insulating film 102 and the thickness of the insulating film 202 are the same, but for example, the thickness of the insulating film 202 may be the same as the thickness of the insulating film 102. It may be polished to be larger than the diameter. On the other hand, polishing may be performed so that the thickness of the insulating film 202 is smaller than the thickness of the insulating film 102. When the thickness of the insulating film 202 is larger than the thickness of the insulating film 102, the insulating film 202 covers most of the foreign matter that adheres to the bonding interface when the second semiconductor substrate 200 is diced or when chips are mounted. This makes it possible to further reduce bonding defects. On the other hand, when the thickness of the insulating film 202 is smaller than the thickness of the insulating film 102, it is possible to reduce the height of the semiconductor chip 205 to be mounted, that is, the semiconductor device 1.
At least one of step (c) and step (d) may be performed, and it is preferable to perform both step (c) and step (d).

[Step (e)]
Step (e) is a step of dividing the second semiconductor substrate 200 into pieces to obtain a plurality of semiconductor chips 205. In step (e), as shown in FIG. 2B, the second semiconductor substrate 200 is diced into a plurality of semiconductor chips 205 by cutting means such as dicing. When dicing the second semiconductor substrate 200, the insulating film 202 may be coated with a protective material or the like, and then it may be diced. In step (e), the insulating film 202 of the second semiconductor substrate 200 is divided into insulating film portions 202b corresponding to each semiconductor chip 205. Examples of the dicing method for dividing the second semiconductor substrate 200 into pieces include plasma dicing, stealth dicing, laser dicing, and the like. As a surface protection material for the second semiconductor substrate 200 during dicing, for example, an organic film that can be removed with water, TMAH, etc., or a thin film such as a carbon film that can be removed with plasma or the like may be provided.
Note that in this embodiment, a large-area second semiconductor substrate 200 is prepared and then separated into pieces to obtain a plurality of semiconductor chips 205; however, the method for preparing the semiconductor chips 205 is not limited to this.

[Step (f)]
Step (f) is 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. In step (f), as shown in FIG. 2C, each semiconductor chip 205 is placed so that the terminal electrode 203 of each semiconductor chip 205 faces the corresponding plurality of terminal electrodes 103 of the first semiconductor substrate 100. Perform alignment. For this alignment, an alignment mark or the like may be provided on the first semiconductor substrate 100.

[Step (g)]
Step (g) is 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. In step (g), after removing organic substances, metal oxides, etc. attached to the surface of each semiconductor chip 205, the semiconductor chips 205 are aligned with respect to the first semiconductor substrate 100, as shown in FIG. 2(c). After that, the insulating film portions 202b of each of the plurality of semiconductor chips 205 are bonded to the insulating film 102 of the first semiconductor substrate 100 as hybrid bonding (see FIG. 3(b)). At this time, the insulating film portions of the plurality of semiconductor chips 205 and the insulating film 102 of the first semiconductor substrate 100 may be uniformly heated before bonding. By performing the bonding while heating, the insulating film 102 and the insulating film portion 202b are more easily bonded than the terminal electrodes 103 and 203 due to the difference between the coefficient of thermal expansion of the insulating film 102 and the insulating film portion 202b and that of the terminal electrodes 103 and 203. It also expands. The first semiconductor substrate 100 may be polished in step (c) so that the height of the insulating film 102 becomes equal to or higher than the height of the terminal electrode 103 due to thermal expansion due to heating, and the insulating film portion 202b is polished. The second semiconductor substrate 200 may be polished in step (d) so that the height is approximately equal to or higher than the height of the terminal electrode 203. The temperature difference between the semiconductor chip 205 and the first semiconductor substrate 100 during bonding is preferably within 10° C., for example. By heating and bonding at such a highly uniform temperature, the insulating film 102 and the insulating film portion 202b are bonded to form an insulating bonding portion S1, and the plurality of semiconductor chips 205 are mechanically firmly attached to the first semiconductor substrate 100. can be attached to. In addition, since the bonding is performed by heating at a highly uniform temperature, it is difficult for positional deviations to occur at the bonding location, and highly accurate bonding can be performed. At this stage of attachment, the terminal electrodes 103 of the first semiconductor substrate 100 and the terminal electrodes 203 of the semiconductor chip 205 are separated from each other and are not connected (however, they are aligned). The semiconductor chip 205 may be bonded to the first semiconductor substrate 100 by other bonding methods, for example, by room temperature bonding or the like.

The thickness of the organic insulating film, which is the insulating bonding portion where the insulating film 102 and the insulating film portion 202b are bonded, is not particularly limited, and may be, for example, 0.1 μm or more. From this point of view, the thickness may be 1 μm to 20 μm, preferably 1 μm to 5 μm.

[Process (h)]
Step (h) is 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. 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. 3(c)). 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. 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).

As described above, the plurality of semiconductor chips 205 are electrically and mechanically installed at predetermined positions on the first semiconductor substrate 100 with high precision. For example, a product reliability test (connection test, etc.) may be performed at the semi-finished product stage shown in FIG. 2(d), and only non-defective products may be used in subsequent steps. Next, a method for manufacturing an example of a semiconductor device using such a semi-finished product will be described with reference to FIG.

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

[Process (j)]
Step (j) is a step of molding resin 301 on the connection surface 100a of the first semiconductor substrate 100 so as to cover the plurality of semiconductor chips 205 and the plurality of pillars 300. In step (j), as shown in FIG. 4B, epoxy resin or the like is molded to completely cover the plurality of semiconductor chips 205 and the plurality of pillars 300. Examples of the molding method include compression molding, transfer molding, and a method of laminating film-like epoxy films. With this resin mold, the spaces between the plurality of pillars 300 and between the pillars 300 and the semiconductor chip 205 are filled with the resin 301.
As a result, a semifinished product M1 filled with resin is formed. Note that a curing treatment may be performed after molding the epoxy resin or the like. In addition, when step (i) and step (j) are performed almost simultaneously, that is, when the pillar 300 is also formed at the same time as resin molding, the pillar is formed using imprint, which is fine transfer, and conductive paste or electrolytic plating. may be formed.

[Step (k)]
In step (k), the semi-finished product M1, which is molded in step (j) and includes the resin 301, a plurality of pillars 300, and a plurality of semiconductor chips 205, is ground from the resin 301 side to obtain a semi-finished product M2. It is a process. In step (k), as shown in FIG. 4(c), the resin-molded first semiconductor substrate 100 and the like are thinned by polishing the upper part of the semi-finished product M1 with a grinder, etc., to form a semi-finished product M2. . By polishing in step (k), the thickness of the semiconductor chip 205, the pillar 300, and the resin 301 is reduced to, for example, about several tens of μm, and the semiconductor chip 205 has a shape corresponding to the second semiconductor chip 20, and the pillar 300 and the resin 301 are thinned. 301 has a shape corresponding to the pillar portion 30.

[Step (l)]
Step (l) is a step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k). In step (l), as shown in FIG. 4(d), a rewiring pattern is formed using polyimide, copper wiring, etc. on the second semiconductor chip 20 and pillar portion 30 of the ground semi-finished product M2. As a result, a semi-finished product M3 having a wiring structure in which the terminal pitch of the second semiconductor chip 20 and the pillar section 30 is widened is formed.

[Step (m) and step (n)]
Step (m) is 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. In step (m), as shown in FIG. 4(d), the semiconductor device substrate is cut along cutting lines A by dicing or the like to form each semiconductor device 1. Thereafter, in step (n), the semiconductor devices 1a that were individualized in step (m) are reversed and placed on the substrate 50 and the circuit board 60 to obtain a plurality of semiconductor devices 1 shown in FIG.

According to the above embodiment, which is an example of a method for manufacturing a semiconductor device, the insulating film 102 of the first semiconductor substrate 100 and the insulating film 202 of the second semiconductor substrate 200 contain the polyimide precursor of the present disclosure. This is a cured product of an insulating film forming material. Since the cured product of the polyimide precursor of the present disclosure has excellent adhesion to the substrate, peeling of the insulating film is suppressed. Moreover, when the polyimide precursor of the present disclosure is used, it is possible to omit the addition of a silane coupling agent, and as a result, it is also possible to suppress the self-condensation product of the silane coupling agent from precipitating as foreign matter.

Although one embodiment of the method for manufacturing a semiconductor device according to the present disclosure has been described above in detail, the present invention is not limited to the above embodiment. For example, in the above embodiment, in the steps shown in FIG. 4, after the step (i) of forming the pillar 300, the step (j) of molding the resin 301 and the step (k) of grinding and thinning the resin 301 etc. were carried out in order, but the step (j) of molding the resin 301 on the connection surface of the first semiconductor substrate 100 was first performed, and then the step (k) of thinning the resin 301 by grinding it to a predetermined thickness. After that, the step (i) of forming the pillar 300 may be performed. In this case, the work of cutting the pillar 300, etc. can be reduced, and since the portion of the pillar 300 to be cut is not necessary, the material cost can be reduced.

Further, in the above embodiment, an example of bonding using C2C was described, but the present invention may also be applied to bonding using Chip-to-Wafer (C2W) shown in FIG. In C2W, a semiconductor wafer 410 has 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). (first semiconductor substrate), 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 (first semiconductor substrate). A semiconductor substrate (second semiconductor substrate) before being diced into pieces of a plurality of semiconductor chips 420 having two electrodes) is prepared. Then, one surface side of the semiconductor wafer 410 and one surface side of the second semiconductor substrate before being singulated into semiconductor chips 420 are subjected to the CMP process in the same manner as in the above steps (c) and (d). Polish by etc. 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.

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 material. Therefore, even if foreign particles generated during dicing during singulation into semiconductor chips 420 adhere to the insulating film, the insulating film around the foreign particles easily deforms, and the foreign particles can be removed without creating large gaps in the insulating film. It can be included within an insulating film. In other words, the influence of foreign matter can be suppressed by the insulating film. Therefore, similarly to C2C, the manufacturing method related to C2W described above can perform fine bonding between semiconductor wafer 410 and semiconductor chip 420 while reducing bonding defects.

Furthermore, in the above-described method for manufacturing a semiconductor device, an inorganic material may be included in a part of the insulating film 102 of the semiconductor substrate 110, the insulating film 202 of the semiconductor chip 205, etc., as long as the effects of the present invention are achieved.

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))
7.07 g of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA), 3.87 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP), and 1. 0.28 g of 3-bis(3-aminopropyl)tetramethyldisiloxane was dissolved in 50 g of 3-methoxy-N,N-dimethylpropanamide. After stirring at 30° C. for 2 hours, the reaction solution was added dropwise to dehydrated ethanol, and the precipitate was filtered off, followed by drying 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 20,000. 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

(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))
Polyimide precursor A2 was obtained by carrying out the same operation except that DMAP in Synthesis Example 1 was changed to 2.9 g of 4,4'-diaminodiphenyl ether (ODA) and 0.39 g of m-phenylenediamine (MPD). The weight average molecular weight of A2 was 25,000.

(Synthesis example 3 (synthesis of A3))
7.07 g of ODPA, 2.7 g of 4,4'-diaminodiphenyl ether (ODA), 0.62 g of m-phenylenediamine (MPD), and 0.20 g of 3-aminopropyltriethoxysilane were mixed with 3-methoxy-N, It was dissolved in 30 g of N-dimethylpropanamide. After stirring the obtained solution at 30° C. for 2 hours, the reaction solution was added dropwise to dehydrated ethanol, and the precipitate was filtered off, followed by drying under reduced pressure to obtain polyimide precursor A3. The weight average molecular weight of A3 was 25,000.

(Synthesis example 4 (synthesis of A4))
Polyimide precursor A4 was obtained in the same manner as in Synthesis Example 2 except that DMAP was changed to 5.66 g of 1,3-bis(3-aminophenoxy)benzene (APB-1,3,3). The weight average molecular weight of A4 was 22,000.

(Synthesis Example 5 (Synthesis of A5))
The same operation was performed except that 2.7 g of 4,4'-diaminodiphenyl ether (ODA) and 0.62 g of m-phenylenediamine (MPD) in Synthesis Example 3 were changed to 5.66 g of APB-1,3,3. , polyimide precursor A5 was obtained. The weight average molecular weight of A5 was 23,000.

(Synthesis Example 6 (Synthesis of A6))
Polyimide precursor A6 was obtained by performing the same operation as in Synthesis Example 1 except that DMAP was changed to 3.88 g of ODA. The weight average molecular weight of A6 was 20,000.

(Synthesis Example 7 (Synthesis of A7))
Perform the same operation as in Synthesis Example 1 except that ODPA was changed to 6.71 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and DMAP was changed to 3.65 g of ODA. Polyimide precursor A7 was obtained. The weight average molecular weight of A7 was 28,000.

(Synthesis Example 8 (Synthesis of A8))
7.07 g of ODPA, 2.71 g of 4,4'-diaminodiphenyl ether (ODA), 0.62 g of m-phenylenediamine (MPD), and 0.25 g of 3-aminopropyltriethoxysilane were mixed into 3-methoxy- It was dissolved in 50 g of N,N-dimethylpropanamide. The resulting solution was stirred at 30°C for 4 hours to obtain polyamic acid. After 9.45 g of trifluoroacetic anhydride was added thereto at room temperature (25°C), 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added, and the mixture was stirred at 45°C for 10 hours. This reaction solution was added dropwise to dehydrated ethanol, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyimide precursor A8. The weight average molecular weight of A8 was 25,000.

<Esterification rate>
By performing NMR measurements under the following conditions, the esterification rate of A8 (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 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.

(Measurement condition)
Measuring equipment: Bruker Biospin AV400M
Magnetic field strength: 400MHz
Reference material: Tetramethylsilane (TMS)
Solvent: dimethyl sulfoxide (DMSO)

(Synthesis Example 9 (Synthesis of A9))
The same operation as in Synthesis Example 8 was performed except that 0.25 g of 3-aminopropyltriethoxysilane was not used to obtain polyimide precursor A9. The weight average molecular weight of A9 was 25,000.
The esterification rate of A9 was calculated by performing NMR measurement under the conditions described above. The esterification rate was 72 mol%, and the proportion of unreacted carboxyl groups was 28 mol%.

[Examples 1 to 7, Comparative Example 1]
(Preparation of insulating film forming material)
Insulating film forming materials of Examples 1 to 7 and Comparative Example 1 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 (25°C) in a general solvent-resistant container, and then filtered under pressure using a 0.2 μm pore filter. Ta. The following evaluations were performed using the obtained insulating film forming material.

Each component in Table 1 is as follows.
・(A) Component: Polyimide precursor A1 to A8 mentioned above
・(B) component: Solvent B1: 3-methoxy-N,N-dimethylpropanamide B2: γ-butyrolactone B3: Dimethyl sulfoxide ・(D) component: Polymerizable monomer D1: Tricyclodecane dimethanol diacrylate (A- DCP)
D2:TEGDMA
・Component (E): Thermal polymerization initiator E1: Bis(1-phenyl-1-methylethyl) peroxide ・Component (F): Polymerization inhibitor F1: N,N'-hexane-1,6-diylbis[3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]
・Rust inhibitor: 1H-benzotriazole

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

-Adhesiveness evaluation criteria-
A: The number of lattices of the cured resin bonded to the substrate is 90 or more B: The number of lattices of the cured resin bonded to the substrate is less than 90

Note that a grid number of 90 or more indicates that the adhesive strength between the resin and the substrate is greater than the adhesive strength of the adhesive tape used for cross-cutting.

As shown in Table 1, Examples 1 to 7 had superior adhesion to the substrate compared to Comparative Example 1. Further, in Examples 1 to 7, since no silane coupling agent was used, no precipitation of foreign matter, which was a self-condensation product of the silane coupling agent, was observed.

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 surface, 102... Insulating film (first insulating film), 103... Terminal electrode (first electrode), 103a... Surface, 200... Second semiconductor substrate, 201... Second substrate main body, 201a... One surface, 202... Insulating film (second insulating film), 203... Terminal electrode (second electrode), 203... 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 (first substrate body) 2 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 joint part, S2…Electrode joint part, S3…Insulating joint part, S4…Electrode joint part

Claims (19)

A polyimide precursor having a structure derived from an amine compound containing a siloxane bond. The polyimide precursor according to claim 1, wherein the main chain is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide. The polyimide precursor according to claim 1 or 2, which has a structural unit represented by the following general formula (1).

In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent organic group. . The polyimide precursor according to claim 3, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E).

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 polyimide precursor according to claim 3 or 4, 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 polyimide precursor according to any one of claims 3 to 5.


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 polyimide precursor according to any one of claims 1 to 6, further having a structure derived from a monoamine compound containing a siloxane bond. A hybrid bonding insulating film forming material containing the polyimide precursor according to any one of claims 1 to 7 and a solvent. The hybrid bonding insulating film forming material according to claim 7, further comprising a polymerizable monomer. preparing a first semiconductor substrate having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body;
preparing a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body;
bonding the first electrode and the second electrode and bonding the first organic insulating film and the second organic insulating film;
A method of manufacturing a semiconductor device using the hybrid bonding insulating film forming material according to claim 8 or 9 for producing at least one of the first organic insulating film and the second organic insulating film. 11. The method of manufacturing a semiconductor device according to claim 10, wherein the first electrode and the second electrode are bonded after the first organic insulating film and the second organic insulating film are bonded together. The semiconductor chip is prepared by dividing into pieces a second semiconductor substrate having a second substrate body, a plurality of second electrodes, and a second organic insulating region provided on one surface of the semiconductor chip substrate body. The method for manufacturing a semiconductor device according to claim 10 or claim 11. The first organic insulating film and the second organic insulating film are bonded together at a temperature such that a temperature difference between the semiconductor chip and the first semiconductor substrate is within 10°C. A method for manufacturing a semiconductor device according to any one of the items. In the manufactured semiconductor device, the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film is 0.1 μm or more. A method for manufacturing a semiconductor device according to any one of the items. Before bonding the first electrode and the second electrode and bonding the first organic insulating film and the first organic insulating film, 15. The method for manufacturing a semiconductor device according to claim 10, wherein at least one of the surface and the one surface side of the semiconductor chip is polished. 16. The method for manufacturing a semiconductor device according to claim 15, wherein the polishing includes chemical mechanical polishing. 17. The method of manufacturing a semiconductor device according to claim 16, wherein the polishing further includes mechanical polishing. 10. The first organic insulating film is thicker than the first electrode, and the second organic insulating film is thicker than the second electrode. The method for manufacturing a semiconductor device according to claim 17. a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body;
A semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body,
The first organic insulating film and the second organic insulating film are bonded, the first electrode and the second electrode are bonded,
A semiconductor device, wherein at least one of the first organic insulating film and the second organic insulating film is a cured product of the hybrid bonding insulating film forming material according to claim 8 or 9.