WO2023171014A1 - Matériau de formation de film isolant, procédé de fabrication de dispositif à semi-conducteur et dispositif à semi-conducteur - Google Patents

Matériau de formation de film isolant, procédé de fabrication de dispositif à semi-conducteur et dispositif à semi-conducteur Download PDF

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Publication number
WO2023171014A1
WO2023171014A1 PCT/JP2022/037511 JP2022037511W WO2023171014A1 WO 2023171014 A1 WO2023171014 A1 WO 2023171014A1 JP 2022037511 W JP2022037511 W JP 2022037511W WO 2023171014 A1 WO2023171014 A1 WO 2023171014A1
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group
insulating film
forming material
film forming
organic
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PCT/JP2022/037511
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English (en)
Japanese (ja)
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香織 小林
大作 松川
聡 米田
憲哉 足立
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Ｈｄマイクロシステムズ株式会社
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Publication of WO2023171014A1 publication Critical patent/WO2023171014A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/60—Attaching or detaching leads or other conductive members, to be used for carrying current to or from the device in operation

Definitions

  • the present disclosure relates to an insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device.
  • Non-Patent Document 1 discloses an example of three-dimensional mounting of a semiconductor chip.
  • hybrid bonding technology used in W2W (Wafer-to-Wafer) bonding is used to perform fine bonding of wiring between devices. is being considered.
  • Patent Document 1 discloses an example of a technique that can lower the bonding temperature by using a cyclic olefin resin.
  • the heat resistance of the organic material is insufficient, and the organic material may deteriorate due to exposure to high temperatures during C2W bonding. Therefore, there is a risk that a bonding failure may occur at the interface between the substrate and the insulating film.
  • the present inventors have considered the use of an insulating material containing a polyimide precursor, which is an organic material with excellent heat resistance, from the viewpoint of suppressing bonding defects and deterioration of organic materials due to the generation of voids as described above. did.
  • the metal e.g., copper
  • the metal contained in the electrodes to be bonded is diffused into the insulating film formed of the insulating material. There is a problem that resistance tends to decrease.
  • the present disclosure has been made in view of the above, and provides an insulating film forming material capable of forming an insulating film with excellent insulation reliability when performing hybrid bonding, a method for manufacturing a semiconductor device using the insulating film forming material, and the same.
  • An object of the present invention is to provide a semiconductor device including an insulating film formed from an insulating film forming material.
  • a polyimide precursor that is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide;
  • B a polymerizable monomer; Hybrid bonding, wherein the content of the compound containing an alkylene oxide chain and (meth)acrylic group classified as the polymerizable monomer (B) is less than 20 parts by mass based on 100 parts by mass of the polyimide precursor (A).
  • the polymerizable monomer (B) is a compound containing an alkylene oxide chain and a (meth)acrylic group, a compound containing an alicyclic structure and a (meth)acrylic group, and an aromatic ring structure and a (meth)acrylic group.
  • the insulating film forming material according to ⁇ 1> containing at least one selected from the group consisting of compounds containing.
  • ⁇ 4> The insulation according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the polymerizable monomer (B) is 30 parts by mass or less based on 100 parts by mass of the polyimide precursor (A).
  • the insulating film forming material according to any one of the above.
  • R 1 , R 2 , R 8 and R 10 each independently have a carbon number of 1 to 4
  • R 3 to R 7 and R 9 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • s is an integer from 0 to 8
  • t is an integer from 0 to 4
  • r is an integer from 0 to 4
  • u is an integer from 0 to 3.
  • D The insulating film forming material according to any one of ⁇ 1> to ⁇ 6>, further comprising a photopolymerization initiator.
  • ⁇ 8> The insulating film forming material according to any one of ⁇ 1> to ⁇ 7>, wherein the polyimide precursor (A) contains a compound having a structural unit represented by the following general formula (1).
  • X represents a tetravalent organic group
  • Y represents a divalent organic group
  • R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group.
  • E The insulating film forming material according to ⁇ 8>, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E).
  • 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.
  • R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom
  • n each independently represents an integer of 0 to 4.
  • 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
  • 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.
  • 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 insulating film forming material according to any one of ⁇ 1> to ⁇ 11> is used for producing at least one of the first organic insulating film and the second organic insulating film, and the following steps ( A method for manufacturing a semiconductor device, which manufactures a semiconductor device through steps 1) to (5).
  • Step (1) A first semiconductor substrate having a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body is prepared.
  • Step (2) A second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body is prepared.
  • Step (3) Cutting the second semiconductor substrate into pieces to obtain a plurality of semiconductor chips each including an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode. do.
  • Step (4) Bonding the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip to each other.
  • Step (5) Joining the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.
  • a first semiconductor substrate having a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body, a semiconductor chip having a semiconductor chip substrate body, an organic insulating film portion and a second electrode provided on one surface of the semiconductor chip substrate body;
  • the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded to each other, and the first electrode of the first semiconductor substrate and the first organic insulating film portion of the semiconductor chip are bonded to each other.
  • a semiconductor device wherein at least one of the first organic insulating film and the organic insulating film portion is an organic insulating film formed by curing the insulating film forming material according to any one of ⁇ 1> to ⁇ 11>.
  • an insulating film forming material capable of forming an insulating film with excellent insulation reliability when performing hybrid bonding, a method for manufacturing a semiconductor device using the insulating film forming material, and a semiconductor device formed from the insulating film forming material.
  • a semiconductor device including an insulating film can be provided.
  • FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device manufactured by a method for manufacturing a semiconductor device according to an embodiment of the present invention.
  • FIG. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in FIG.
  • FIG. 3 is a diagram showing in more detail the bonding method in the method of manufacturing the semiconductor device shown in FIG.
  • FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing the steps after the step shown in FIG. 2 in order.
  • FIG. 5 is a diagram showing an example in which the method for manufacturing a semiconductor device according to an embodiment of the present invention is applied to Chip-to-Wafer (C2W).
  • (A) is a top view showing samples produced in each example and comparative example
  • (B) is a cross-sectional view taken along the line AA in (A).
  • a or B may include either A or B, or may include both.
  • 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.
  • numerical ranges indicated using “ ⁇ ” include the numerical values written before and after " ⁇ " as minimum and maximum values, respectively.
  • 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.
  • the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
  • 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.
  • 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.
  • 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.
  • the thickness of a layer or film can be measured directly, it is measured using a micrometer.
  • 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.
  • the term "insulating film" is a concept that also includes an insulating layer.
  • (meth)acrylic group means “acrylic group” and "methacrylic group.”
  • 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.
  • the insulating film forming material of the present disclosure includes (A) a polyimide precursor that is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide; and (B) a polymerizable polyimide precursor.
  • the content of the compound containing an alkylene oxide chain and a (meth)acrylic group classified as the polymerizable monomer (B) is 20 parts by mass based on 100 parts by mass of the polyimide precursor (A). It is a material for forming an insulating film by hybrid bonding.
  • the insulating film forming material of the present disclosure can be used to insulate semiconductor chips when three-dimensionally mounting semiconductor chips by applying hybrid bonding technology to W2W (Wafer-to-Wafer) bonding, C2W (Chip-to-Wafer) bonding, etc. It is a material for forming a film.
  • W2W Wafer-to-Wafer
  • C2W Chip-to-Wafer
  • It is a material for forming a film.
  • the insulating film forming material of the present disclosure includes (A) a polyimide precursor and (B) a polymerizable monomer, and when heated etc., these components react to form a crosslinked structure, thereby forming a cured insulating film. It is formed.
  • the content of the compound containing an alkylene oxide chain and (meth)acrylic group classified as (B) a polymerizable monomer is less than 20 parts by mass with respect to 100 parts by mass of (A) polyimide precursor. It is presumed that the metal (for example, copper) contained in the electrodes to be bonded becomes difficult to diffuse into the insulating film, and the reduction in insulation resistance is suppressed, resulting in excellent insulation reliability.
  • the insulating film obtained by curing the insulating film forming material has a lower elastic modulus and is softer than a molded product made of an inorganic material. Therefore, when bonding insulating films together, the surface of one insulating film (hereinafter also referred to as "first insulating film") or the surface of the other insulating film (hereinafter also referred to as "second insulating film”) Even if foreign matter is present in the insulating film, the insulating film at the bonding interface is easily deformed, and the foreign matter tends to be contained within the insulating film without creating large voids in the insulating film. Furthermore, (A) an insulating film forming material containing a polyimide precursor tends to have higher heat resistance than an insulating film obtained by curing an insulating film forming material containing an acrylic resin, an epoxy resin, or the like.
  • the insulating film forming material of the present disclosure may be a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material.
  • the glass transition temperature of the insulating film formed by curing the insulating film forming material of the present disclosure is preferably 100°C to 400°C, more preferably 150°C to 350°C, from the viewpoint of bonding at low temperatures. .
  • the glass transition temperature of the insulating film is measured as follows. First, an insulating film forming material is heated in a nitrogen atmosphere for 2 hours at a predetermined curing temperature (for example, 150° C. to 375° C.) that allows a curing reaction to occur, to obtain an insulating film. The obtained insulating film was cut to create a rectangular parallelepiped of 5 mm x 50 mm x 3 mm, and a dynamic viscoelasticity measurement device (for example, RSA-G2 manufactured by TA Instruments) was used with a tension jig at a frequency of 1 Hz. Dynamic viscoelasticity is measured in a temperature range of 50°C to 350°C under the conditions of heating rate: 5°C/min.
  • the glass transition temperature (Tg) is defined as the temperature at the peak top of tan ⁇ , which is determined from the ratio of the storage modulus and loss modulus obtained by the above method.
  • the thermal expansion coefficient of the insulating film formed by curing is preferably 150 ppm/K or less, more preferably 100 ppm/K or less, and further preferably 70 ppm/K or less. preferable.
  • the coefficient of thermal expansion of the insulating film, which is a cured product, and the coefficient of thermal expansion of the electrode are the same or close to each other, so even if heat generation occurs during use of the semiconductor device, the insulating film and the electrode Damage to the semiconductor device due to the difference in coefficient of thermal expansion between the two can be suppressed.
  • Thermal expansion coefficient indicates the rate at which the length of the insulating film expands due to temperature rise, and the amount of change in the length of the insulating film at 100°C to 150°C is measured using a thermomechanical analyzer etc. It can be calculated by
  • the insulating film forming material of the present disclosure is a polyimide precursor (hereinafter referred to as "(A) component ).
  • Component (A) preferably contains a polyimide precursor having a polymerizable unsaturated bond.
  • the component (A) contained in the insulating film forming material is preferably a component that does not cause problems in polishing steps, bonding steps, and the like.
  • the polyimide precursor is a polyamic acid, a compound in which the hydrogen atoms of at least some of the carboxy groups in the polyamic acid are substituted with monovalent organic groups, or a polyamic acid in which at least some of the carboxy groups have a pH of 7 or more.
  • polyamide acid salts which are compounds that form a salt structure with a basic compound.
  • examples of compounds in which at least some of the hydrogen atoms of carboxy groups in polyamic acids are substituted with monovalent organic groups include polyamic acid esters, polyamic acid amides, and the like. It is preferable that the polyamic acid ester, polyamic acid amide, etc. have a polymerizable unsaturated bond.
  • component (A) contains a compound having 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.
  • X represents a tetravalent organic group
  • 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.
  • 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.
  • R 6 and R 7 may both be hydrogen atoms, one may be a hydrogen atom and the other may be a monovalent organic group described below, and both may be the same or different monovalent organic groups. It may be.
  • the combination of R 6 and R 7 of each structural unit may be the same or different. .
  • 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.
  • aromatic hydrocarbon group examples include a benzene ring, a naphthalene ring, and a phenanthrene ring.
  • each aromatic ring may have a substituent or may be unsubstituted.
  • substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, and amino groups.
  • 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.
  • 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.
  • 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.
  • -COOR 6 groups and -CONH- groups are preferably located at ortho positions
  • -COOR 7 groups and -CO- groups are preferably located at ortho positions.
  • tetravalent organic group represented by X include groups represented by the following formulas (A) to (F).
  • 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.
  • 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.
  • 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.
  • C preferably contains an ether bond, more preferably an ether bond. Further, C may have a structure represented
  • 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.
  • 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-dimethyltramethylene group
  • 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.
  • 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.
  • tetravalent organic group represented by X may be groups represented by the following formulas (J) to (O).
  • 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.
  • 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.
  • 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.
  • divalent aromatic group represented by Y include groups represented by the following formulas (G) to (I).
  • a group represented by the following formula (H) is preferable from the viewpoint of obtaining an insulating film that has excellent flexibility and further suppresses the generation of voids at the bonding interface. is more preferably a group containing an ether bond, and even more preferably an ether bond.
  • R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom
  • n each independently represents an integer of 0 to 4.
  • 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.
  • 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 an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, or the like.
  • the alkyl group represented by R in formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. , more preferably an alkyl group having 1 or 2 carbon atoms.
  • Specific examples of the alkyl group represented by R in formulas (G) to (I) include 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 (I) 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 (I) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, and s-butoxy group. , t-butoxy group and the like.
  • the halogenated alkyl group represented by R in formulas (G) to (I) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, and 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 halogenated alkyl groups represented by R in formulas (G) to (I) include at least one hydrogen atom contained in the alkyl groups represented by R in formulas (G) to (I). 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.
  • n is each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • divalent aliphatic group represented by Y examples include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a divalent group having a polysiloxane structure. Examples include the following groups.
  • the linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms. More preferably, the number is 1 to 10 alkylene groups.
  • Specific examples of the alkylene group represented by Y include tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 2-methylpentamethylene group. , 2-methylhexamethylene group, 2-methylheptamethylene group, 2-methyloctamethylene group, 2-methylnonamethylene group, 2-methyldecamethylene group, and the like.
  • the cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, more preferably a cycloalkylene group having 3 to 6 carbon atoms.
  • Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.
  • the unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and An alkylene oxide structure of 1 to 4 is more preferred.
  • 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.
  • 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.
  • 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.
  • substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, and a hydroxy group.
  • 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" ), and the group represented by formula (I) is preferably a group represented by formula (I') below.
  • 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.
  • X is a group represented by formula (E)
  • Y is a group represented by formula (G).
  • a combination of groups in which X is a group represented by formula (E) and Y is a group represented by formula (H); X is a group represented by formula (E), and Y is a group represented by formula Examples include combinations of groups represented by (I).
  • R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, such as a group represented by the following general formula (2), an ethyl group, It is more preferable that it is either an isobutyl group or a t-butyl group, and it is even more preferable that it contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2). It is particularly preferable to include a group represented by (2).
  • the i-line transmittance is high, and even when curing at a low temperature of 400°C or less. It tends to form a good insulating film.
  • Specific examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, etc. Among them, ethyl group, Isobutyl and t-butyl groups are preferred.
  • 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.
  • 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.
  • 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.
  • R 6 and R 7 are 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:
  • the component (A) contains a compound having a structural unit represented by the above-mentioned general formula (1), it is expressed by the general formula (2) based on the sum of R 6 and R 7 of all structural units contained in the compound.
  • the proportion of R 6 and R 7 which are the groups to be used, is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more.
  • the upper limit is not particularly limited, and may be 100 mol%.
  • 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.
  • 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.
  • q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.
  • the content of the structural unit represented by the general formula (1) contained in the compound having the structural unit represented by the general formula (1) is preferably 60 mol% or more based on the total structural units, More preferably 70 mol% or more, and even more preferably 80 mol% or more.
  • the upper limit of the above-mentioned content is not particularly limited, and may be 100 mol%.
  • Component (A) may be synthesized using a tetracarboxylic dianhydride and a diamine compound.
  • X corresponds to a residue derived from a tetracarboxylic dianhydride
  • Y corresponds to a residue derived from a diamine compound.
  • component (A) may be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride.
  • diamine compounds include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m- Phenylene diamine, p-xylylene diamine, m-xylylene diamine, 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'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,4'-diaminomino
  • diamine compound m-phenylenediamine, 4,4'-diaminodiphenyl ether and 1,3-bis(3-aminophenoxy)benzene are preferred.
  • the diamine compounds may be used alone or in combination of two or more.
  • a compound having a structural unit represented by general formula (1) and in which at least one of R 6 and R 7 in general formula (1) is a monovalent organic group is, for example, the following (a) or It can be obtained by the method (b).
  • a 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.
  • 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.
  • the reaction is carried out in an organic solvent to introduce an ester group.
  • 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.
  • 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, ⁇ -butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and among others, 3-methoxy-N,N- Dimethylpropionamide is preferred.
  • a polyimide precursor may be synthesized by allowing a dehydration condensation agent to act on a polyamic acid solution together with a compound represented by R-OH.
  • the dehydration condensation agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).
  • DCC N,N'-dicyclohexylcarbodiimide
  • DIC 1,3-diisopropylcarbodiimide
  • the above-mentioned compound contained in component (A) 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 forming a diester derivative such as thionyl chloride. It can be obtained by reacting a diamine compound represented by H 2 N-Y-NH 2 with the acid chloride.
  • the above-mentioned compound contained in component (A) is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then converting it into a carbodiimide compound.
  • component (A) It can be obtained by reacting a diamine compound represented by H 2 N—Y—NH 2 with a diester derivative in the presence of H 2 N—Y—NH 2 .
  • the above-mentioned compound contained in component (A) is produced by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H 2 N-Y-NH 2 to form a polyamide acid. After that, the polyamic acid is isoimidized in the presence of a dehydration condensation agent such as trifluoroacetic anhydride, and then a compound represented by R-OH is allowed to act thereon.
  • a dehydration condensation agent such as trifluoroacetic anhydride
  • 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.
  • X is the same as X in general formula (1), and specific examples and preferred examples are also the same.
  • Compounds represented by R-OH used in the synthesis of the above-mentioned compounds contained in component (A) include compounds in which a hydroxy group is bonded to R x of a group represented by general formula (2), and compounds represented by general formula ( It may also be a compound in which a hydroxy group is bonded to the terminal methylene group of the group represented by 2').
  • Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and acrylic.
  • Examples include 2-hydroxypropyl acid, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. -hydroxyethyl and 2-hydroxyethyl acrylate are preferred.
  • the weight average molecular weight of component (A) is preferably 10,000 to 200,000, more preferably 10,000 to 100,000.
  • the weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.
  • the insulating film forming material of the present disclosure may further contain a dicarboxylic acid, and the (A) polyimide precursor contained in the insulating film forming material is such that some of the amino groups in the (A) polyimide precursor are in the dicarboxylic acid. It may have a structure formed by reacting with a carboxy group. For example, when synthesizing a polyimide precursor, a portion of the amino groups of the diamine compound and the carboxy groups of the dicarboxylic acid may be reacted.
  • the dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula.
  • the methacrylic group derived from the dicarboxylic acid is added to the (A) polyimide precursor. can be introduced.
  • the insulating film forming material of the present disclosure may contain a resin component other than the component (A).
  • resin components other than component (A) include polyimide resins, novolac resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, and polychlorinated resins. Examples include vinyl resin. Among these, it is preferable that the resin components other than the component (A) include a polyimide resin. Resin components other than component (A) may be used alone or in combination of two or more.
  • 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).
  • X a compound having a structural unit represented by the following general formula (X).
  • X represents a tetravalent organic group
  • 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.
  • 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 content of component (A) relative to the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 90% by mass. More preferably, the amount is from % by mass to 100% by mass.
  • the resin component other than the component (A) preferably a polyimide resin
  • the proportion of (preferably polyimide resin) may be 15% by mass to 50% by mass, or 10% by mass to 20% by mass.
  • the insulating film forming material of the present disclosure includes (B) a polymerizable monomer (hereinafter also referred to as "component (B)").
  • Component (B) preferably has at least one group containing a polymerizable unsaturated double bond, and from the viewpoint of being suitably polymerizable in combination with a photopolymerization initiator, component (B) contains at least one (meth)acrylic group. It is more preferable to have one. From the viewpoint of improving crosslinking density and photosensitivity, it is preferable to have 2 to 6 groups, and more preferably 2 to 4 groups containing polymerizable unsaturated double bonds.
  • the polymerizable monomers may be used alone or in combination of two or more.
  • the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,4-butane Diol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, (meth)acryloyloxyethyl iso
  • Component (B) is a compound containing an alkylene oxide chain and a (meth)acrylic group (hereinafter also referred to as “compound (1)”), a compound containing an alicyclic structure and a (meth)acrylic group (hereinafter referred to as “compound (1)”), (2)), and a compound containing an aromatic ring structure and a (meth)acrylic group (hereinafter also referred to as “compound (3)”).
  • compound (1) does not need to contain both an alicyclic structure and an aromatic ring structure
  • compound (2) does not need to contain both an alkylene oxide chain and an aromatic ring structure.
  • Compound (3) may contain an alkylene oxide chain.
  • the alkylene oxide chain in component (B) means a group consisting of an alkylene group and an oxygen atom bonded to the alkylene group (excluding the oxygen atom contained in the (meth)acryloyloxy group).
  • component (B) contains compound (1) and compound (2).
  • the insulating film forming material contains the compound (1), the thermocompression bondability between the substrate and the insulating film tends to improve.
  • the insulating film forming material contains the compound (2), the insulation reliability of the insulating film tends to be more excellent.
  • Examples of the compound (1) include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.
  • Examples of the compound (2) include tricyclodecane dimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and 1,3-adamantanedimethanol di(meth)acrylate.
  • Examples of the compound (3) include EO-modified bisphenol A di(meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxymethacrylate.
  • Component (B) may contain a polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group.
  • the polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N , N-dimethylacrylamide and N-methylolacrylamide.
  • Component (B) is not limited to a compound having a group containing a polymerizable unsaturated double bond, and may be a compound having a polymerizable group other than an unsaturated double bond group (for example, an oxirane ring). .
  • the content of component (B) may be 30 parts by mass or less, and may be 25 parts by mass or less, from the viewpoint of insulation reliability of the insulating film, with respect to 100 parts by mass of component (A). 20 parts by mass or less, 18 parts by mass or less, or 15 parts by mass or less.
  • the content of component (B) is 30 parts by mass or less per 100 parts by mass of component (A)
  • unreacted polymerizable monomer (B) is less likely to be generated after curing. This makes it difficult for the metal (for example, copper) contained in the electrodes and the like to be bonded to diffuse into the insulating film, and it is presumed that the reduction in insulation resistance is suppressed, resulting in excellent insulation reliability.
  • the lower limit of the content of component (B) may be 1 part by mass or more, or 3 parts by mass or more, based on 100 parts by mass of component (A).
  • the content of compound (1) is less than 20 parts by mass, and when the insulating film forming material of the present disclosure contains compound (1), the content of compound (1) is (A ) may be 0.5 parts by mass to 15 parts by mass, 1 part by mass to 12 parts by mass, or 2 parts by mass to 8 parts by mass, based on 100 parts by mass of the component.
  • the content of compound (2) may be 2 parts by mass to 20 parts by mass, and 5 parts by mass, based on 100 parts by mass of component (A). The amount may be from 8 parts to 12 parts by weight, or from 8 parts to 12 parts by weight.
  • the ratio of the content of compound (1) and the content of compound (2) (compound (1): compound (2)) is , may be 1:20 to 20:20, may be 1:20 to 16:20, or may be 2:20 to 15:20, based on mass.
  • the insulating film forming material of the present disclosure may contain a (C) solvent (hereinafter also referred to as "component (C)").
  • Component (C) preferably contains at least one selected from the group consisting of compounds represented by the following formulas (3) to (7), for example.
  • Component (C) may be used alone or in combination of two or more.
  • R 1 , R 2 , R 8 and R 10 are each independently an alkyl group having 1 to 4 carbon atoms
  • R 3 to R 7 and R 9 are each independently an alkyl group having 1 to 4 carbon atoms.
  • 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
  • u is an integer from 0 to 3.
  • 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.
  • 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.
  • 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.
  • 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 (C) 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 The compound represented by formula (7) may be used, or from the viewpoint of reducing the reproductive toxicity and environmental load of the insulating film forming material, the compound represented by formula (5) may be used.
  • component (C) include the following compounds.
  • component (C) that may be included in the insulating film forming material of the present disclosure is not limited to the above-mentioned compounds, and may be other solvents.
  • Component (C) may be an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, or the like.
  • Solvents for esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone. , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkoxy acetates such as methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g.
  • 3-Alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (e.g.
  • 2-alkoxypropionate alkyl esters e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate
  • 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.
  • 2-alkoxypropionate alkyl esters e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Prop
  • Ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene.
  • Examples include glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.
  • Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone (NMP), and 3-methoxy-N,N-dimethylpropionamide.
  • Examples of hydrocarbon solvents include limonene and the like.
  • Examples of aromatic hydrocarbon solvents include toluene, xylene, anisole, and the like.
  • Examples of the sulfoxide solvent include dimethyl sulfoxide.
  • Preferred examples of the solvent for component (C) include 3-methoxy-N,N-dimethylpropionamide, ⁇ -butyrolactone, cyclopentanone, and ethyl lactate.
  • the content of NMP may be 1% by mass or less based on the total amount of the insulating film forming material; It may be 3% by mass or less based on the total amount.
  • the content of component (C) is preferably 1 part by mass to 10,000 parts by mass, and preferably 50 parts by mass to 10,000 parts by mass, per 100 parts by mass of component (A). It is more preferable.
  • Component (C) is at least one solvent (1) selected from the group consisting of compounds represented by formulas (3) to (7), as well as ester solvents, ether solvents, and ketone solvents. , a hydrocarbon solvent, an aromatic hydrocarbon solvent, and a sulfoxide solvent. Further, the content of the solvent (1) may be 5% by mass to 100% by mass, or even 5% by mass to 50% by mass, based on the total of the solvent (1) and the solvent (2). good. The content of the solvent (1) may be 10 parts by mass to 1000 parts by mass, 10 parts by mass to 100 parts by mass, 10 parts by mass to 100 parts by mass, based on 100 parts by mass of component (A). It may be 50 parts by mass.
  • the insulating film forming material of the present disclosure further includes (D) a photopolymerization initiator (hereinafter also referred to as (D) component). Further, the insulating film forming material of the present disclosure may further include (E) a thermal polymerization initiator (hereinafter also referred to as (E) component). Preferred forms of component (D) and component (E) will be described below.
  • the insulating film forming material of the present disclosure preferably contains (D) a photopolymerization initiator.
  • component (D) examples include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4 Benzophenones such as '-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone, etc.
  • benzophenone N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4 Benzophenones such as '-dimethoxybenzophen
  • Acetophenone derivatives such as acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, etc.
  • Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone; benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl- ⁇ -methoxyethyl acetal; benzoin, benzoin methyl ether, benzoin Benzoin derivatives such as 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-pheny
  • the content of component (D) is 0% based on 100 parts by mass of component (A) from the viewpoint that photocrosslinking tends to be uniform in the film thickness direction. .1 part by weight to 25 parts by weight is preferable, 1 part to 20 parts by weight is more preferable, 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.
  • 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.
  • 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
  • the content of component (E) may be 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor, The amount may be 1 part by mass to 15 parts by mass, or 5 parts by mass to 10 parts by mass.
  • the insulating film forming material of the present disclosure may contain (F) a polymerization inhibitor (hereinafter also referred to as "component (F)") from the viewpoint of ensuring good storage stability.
  • a polymerization inhibitor hereinafter also referred to as "component (F)”
  • the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.
  • component (F) include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl- 2-naphthylamine, cuperone, 2,5-torquinone, tannic acid, parabenzylaminophenol, nitrosamines, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2 , 3-dioxide, hindered phenol compounds, and the like.
  • the polymerization inhibitors may be used alone or in combination of two or more. By combining two or more polymerization inhibitors, it tends to be easier to adjust the photosensitive characteristics due to the difference in reactivity.
  • the hindered phenol compound may have both the function of a polymerization inhibitor and the function of an antioxidant described below, or it may have either one of the functions.
  • the hindered phenol compound is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5- di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di- t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis [3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], 2,
  • the content of component (F) is 100% of component (A) from the viewpoint of storage stability of the insulating film forming material and heat resistance of the obtained cured product. It is preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.01 parts by mass to 10 parts by mass, and preferably 0.05 parts by mass to 5 parts by mass. More preferred.
  • the insulating film forming material of the present disclosure may further contain an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust preventive, or a nitrogen-containing compound.
  • 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.
  • 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.
  • the content of the antioxidant is preferably 0.1 parts by mass to 20 parts by mass, and 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of component (A).
  • the amount is more preferably from .1 parts by weight to 10 parts by weight, and even more preferably from 0.1 parts by weight to 5 parts by weight.
  • the insulating film forming material of the present disclosure may include a coupling agent.
  • the coupling agent reacts with component (A) and crosslinks, or the coupling agent itself polymerizes. This tends to further improve the adhesiveness between the obtained cured product and the substrate.
  • 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
  • the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, and 0.3 parts by mass, based on 100 parts by mass of component (A). Parts by weight to 10 parts by weight are more preferable, and 1 part to 10 parts by weight are even more preferable.
  • the insulating film forming material of the present disclosure may include at least one of a surfactant and a leveling agent.
  • 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.
  • surfactant or leveling agent examples include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.
  • the surfactants and leveling agents may be used alone or in combination of two or more.
  • the total content of the surfactant and leveling agent is 0.01 parts by mass to 100 parts by mass of component (A).
  • the amount is preferably 10 parts by weight, more preferably 0.05 parts to 5 parts by weight, and even more preferably 0.05 parts to 3 parts by weight.
  • 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.
  • rust preventive agents include azole compounds and purine derivatives.
  • 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( ⁇ , ⁇ -dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)
  • 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-azaa
  • the rust inhibitors may be used alone or in combination of two or more.
  • the content of the rust preventive agent is preferably 0.01 parts by mass to 10 parts by mass, and 0.01 parts by mass to 10 parts by mass, based on 100 parts by mass of component (A).
  • the amount is more preferably from .1 part by weight to 5 parts by weight, and even more preferably from 0.5 parts by weight to 3 parts by weight.
  • the content of the rust preventive agent is 0.1 parts by mass or more, when the insulating film forming material of the present disclosure is applied on the surface of copper or copper alloy, discoloration of the surface of copper or copper alloy is prevented. suppressed.
  • the insulating film forming material of the present disclosure may contain a nitrogen-containing compound from the viewpoint of accelerating the imidization reaction of component (A) and obtaining a highly reliable cured product.
  • 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
  • the nitrogen-containing compound includes a compound represented by the following 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.
  • 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.
  • 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.
  • the monovalent aliphatic hydrocarbon group having a hydroxy group of R 31A to R 33A is one or more hydroxy groups bonded to the monovalent aliphatic hydrocarbon group of R 31A to R 33A . It is preferable that the hydroxyl group is a bonded group, and a group that has one to three hydroxy groups bonded is more preferable. Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a methylol group, a hydroxyethyl group, and the like, with a hydroxyethyl group being preferred.
  • Examples of the monovalent aromatic group R 31A to R 33A in formula (17) include a monovalent aromatic hydrocarbon group, a monovalent aromatic heterocyclic group, etc. Groups are preferred.
  • the monovalent aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
  • Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a naphthyl group.
  • the monovalent aromatic groups R 31A to R 33A in formula (17) may have a substituent.
  • substituents 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.
  • the content of the nitrogen-containing compound is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of component (A). From the viewpoint of stability, the amount is more preferably 0.3 parts by mass to 15 parts by mass, and even more preferably 0.5 parts by mass to 10 parts by mass.
  • a semiconductor device of the present disclosure includes: a first semiconductor substrate having a first substrate body; the first organic insulating film and a first electrode provided on one surface of the first substrate body; a semiconductor chip substrate body; a semiconductor chip having an organic insulating film portion and a second electrode provided on one surface of a semiconductor chip substrate body, the first organic insulating film of the first semiconductor substrate and the organic insulating film of the semiconductor chip; the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined, and at least one of the first organic insulating film and the organic insulating film part is in contact with the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.
  • the semiconductor device of the present disclosure since at least one of the first organic insulating film and the organic insulating film portion is an insulating film formed by curing the insulating film forming material of the present disclosure, metal (for example, copper) becomes difficult to diffuse into the insulating film, and a decrease in insulation resistance is suppressed. Thereby, a semiconductor device including an insulating film with excellent insulation reliability can be obtained. Further, the semiconductor device of the present disclosure is manufactured, for example, through steps (1) to (5) described below.
  • the semiconductor device of the present disclosure is manufactured using the insulating film forming material of the present disclosure.
  • a semiconductor device can be manufactured through steps (1) to (5) using the insulating film forming material of the present disclosure.
  • Step (1) A first semiconductor substrate having a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body is prepared.
  • Step (2) A second semiconductor substrate having a second substrate body, the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body is prepared.
  • Step (3) Cutting the second semiconductor substrate into pieces to obtain a plurality of semiconductor chips each including an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode. .
  • Step (5) Joining the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip.
  • FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present disclosure.
  • 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 the second semiconductor chip 2 It has a three-dimensional mounting structure in which 0 is mounted downward.
  • the second semiconductor chip 20 is a semiconductor chip such as an LSI or a memory, and is a chip component having a smaller area in plan view than the first semiconductor chip 10.
  • the second semiconductor chip 20 is chip-to-chip (C2C) bonded to the back surface of the first semiconductor chip 10.
  • the first semiconductor chip 10 and the second semiconductor chip 20 are finely bonded to each other by hybrid bonding, the details of which will be described later, so that the respective terminal electrodes and the insulating films around the terminal electrodes are firmly and without misalignment.
  • the pillar part 30 is a connection part in which a plurality of pillars 31 made of metal such as copper (Cu) are sealed with 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 ⁇ m or more and 20 ⁇ m or less (in one example, a diameter of 5 ⁇ m), and may be arranged such that the distance between the centers of each pillar 31 is 15 ⁇ m 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.
  • connection electrode can be formed in the semiconductor device 1 without using a technique called TMV (Through Mold Via) in which a hole is made in a mold and a solder connection is made.
  • the pillar section 30 has, for example, the same thickness as the second semiconductor chip 20, and is arranged on the side of the second semiconductor chip 20 in the horizontal direction. Note that a plurality of solder balls may be arranged instead of the pillar portion 30, and the solder balls electrically connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40. You may.
  • the rewiring layer 40 is a wiring layer that has a terminal pitch conversion function, which is a function of a package substrate, and is made of polyimide, copper wiring, etc. on the insulating film on the lower side of the second semiconductor chip 20 and on the lower surface of the pillar section 30. This is a layer in which a rewiring pattern is formed.
  • the rewiring layer 40 is formed by turning the first semiconductor chip 10 (first semiconductor substrate 100), second semiconductor chip 20, etc. upside down (see (d) in FIG. 4).
  • the rewiring layer 40 electrically connects the terminal electrodes of the first semiconductor chip 10 via the terminal electrodes on the lower surface of the second semiconductor chip 20 and the pillar portion 30 to the terminal electrodes of the substrate 50.
  • the terminal pitch of the substrate 50 is wider than the terminal pitch of the pillar 31 and the terminal pitch of the second semiconductor chip 20.
  • various electronic components 51 may be mounted on the board 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.
  • 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.
  • FIG. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in FIG.
  • FIG. 3 is a diagram showing in more detail the bonding method (hybrid bonding) in the method of manufacturing the semiconductor device shown in FIG.
  • FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram sequentially showing steps after the step shown in FIG. 2.
  • the semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n).
  • (a) 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) One surface 101a side, which is the surface of the first semiconductor substrate 100, is polished using the CMP method so that each surface 103a of the terminal electrode 103 is at the same position or in a protruding position with respect to the surface 102a of the insulating film 102. (see FIG. 3(a)).
  • One surface 201a which is the surface of the second semiconductor substrate 200, is polished using a CMP method so that each surface 203a of the terminal electrode 203 is at the same position or in a protruding position with respect to the surface 202a of the insulating film 202. Polishing step (see FIG. 3(a)).
  • step (j) A step of molding resin 301 on the connection surface of first semiconductor substrate 100 so as to cover semiconductor chip 205 and pillar 300 to obtain semi-finished product M1 (see (b) of FIG. 4).
  • step (k) A process of grinding and thinning the resin 301 side of the semi-finished product M1 molded in step (j) to obtain a semi-finished product M2 (see (c) in FIG. 4).
  • step (l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k) (see (d) in FIG. 4).
  • step (m) A step of cutting the semi-finished product M3 on which the wiring layer 400 was formed in step (l) along the cutting line A to form each semiconductor device 1 (see (d) in FIG. 4).
  • step (n) A step of inverting the semiconductor device 1a individualized in step (m) and placing it on the substrate 50 and the circuit board 60 (see FIG. 1).
  • step (1) corresponds to the above-mentioned step (a) and step (c)
  • step (2) corresponds to the above-mentioned step (b) and step (d)
  • step (3) corresponds to step (e)
  • step (4) corresponds to step (g)
  • step (5) corresponds to step (h).
  • the insulating film forming material of the present disclosure may be an insulating film forming material for use in manufacturing at least one of a first organic insulating film and a second organic insulating film in a method for manufacturing a semiconductor device. .
  • Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate, corresponding to a plurality of first semiconductor chips 10 and on which an integrated circuit consisting of semiconductor elements and wiring connecting them is formed.
  • a plurality of terminal electrodes 103 made of copper, aluminum, etc. are placed on one surface 101a of the first substrate body 101 made of silicon etc. in a predetermined manner.
  • An insulating film 102 (first insulating film) is provided at intervals and is a cured product obtained by curing the insulating film forming material of the present disclosure.
  • the plural terminal electrodes 103 may be provided after the insulating film 102 is provided on the one surface 101a of the first substrate main body 101, or the plural terminal electrodes 103 may be provided on the one surface 101a of the first substrate main body 101 and then the insulating film is provided. 102 may be provided.
  • Step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate, on which an integrated circuit corresponding to a plurality of second semiconductor chips 20 and including semiconductor elements and wiring connecting them is formed.
  • a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc. are formed on one surface 201a of the second substrate main body 201 made of silicon or the like. are continuously provided, and an insulating film 202 (second insulating film) which is a cured product obtained by curing the insulating film forming material of the present disclosure is provided.
  • a plurality of terminal electrodes 203 may be provided after the insulating film 202 is provided on the one surface 201a of the second substrate main body 201, or a plurality of terminal electrodes 203 may be provided on the one surface 201a of the second substrate main body 201 and then the insulating film 202 is provided. may be provided.
  • the insulating films 102 and 202 used in step (a) and step (b) are not limited to a structure in which both are cured products obtained by curing the insulating film forming material of the present disclosure, and at least one of the insulating films 102 and 202 is The structure may be a cured product obtained by curing the insulating film forming material of the present disclosure.
  • FIG. 1 shows an example of C2C bonding
  • FIG. The present invention may be applied to bonding with 2W).
  • C2W a semiconductor wafer 410 (first substrate body) having a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes) is used.
  • 1 semiconductor substrate is prepared.
  • a plurality of semiconductor chips each having a substrate body 421 (second substrate body), an insulating film portion 422 (second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes).
  • semiconductor substrates (second semiconductor substrates) before being separated into individual pieces are prepared. Then, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before being singulated into semiconductor chips 420 are polished by CMP or the like in the same manner as in the above steps (c) and (d). . Thereafter, the second semiconductor substrate is subjected to the same singulation process as in step (e) to obtain a plurality of semiconductor chips 420.
  • 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).
  • 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 precision.
  • 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.
  • a semiconductor device 401 is obtained by bonding a plurality of semiconductor chips 420 to a semiconductor wafer 410 in the same manner.
  • 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.
  • At least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 is made of the insulating film of the present disclosure.
  • This is an insulating film that is a cured product obtained by curing the forming material. Therefore, a semiconductor device including an insulating film with excellent insulation reliability can be obtained.
  • the present invention is not limited to these configurations.
  • the first electrode and the second electrode may be through electrodes that penetrate the first semiconductor substrate and the second semiconductor substrate.
  • the method for manufacturing a semiconductor device of the present disclosure includes, for example, using the insulating film forming material of the present disclosure for producing at least one of a first organic insulating film and a second organic insulating film, and performing the following step (1)' It may be a method of manufacturing a semiconductor device through steps (5)'.
  • Step (1)' A first semiconductor substrate having a first substrate body and the first organic insulating film provided on one surface of the first substrate body is prepared.
  • Step (2)' A second semiconductor substrate having a second substrate body and the second organic insulating film provided on one surface of the second substrate body is prepared.
  • Step (3)' The second semiconductor substrate is cut into pieces to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film.
  • Step (4)' The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded together.
  • Step (5)' A through hole is provided in a part of the first semiconductor substrate and the second semiconductor substrate that are bonded together, and a through electrode is provided in the through hole.
  • a through hole may be provided by etching or the like, or a through electrode may be provided by electrolytic plating, electroless plating, sputtering, or the like.
  • Example 1 to 19 Comparative Example 1
  • Insulating film forming materials of Examples 1 to 19 and Comparative Example 1 were prepared as follows using the components and blending amounts shown in Tables 1 and 2. The unit of the amount of each component in Tables 1 and 2 is parts by mass. In addition, a blank column in Tables 1 and 2 means that the corresponding component was not blended.
  • the mixture of each component was kneaded overnight at room temperature in a general solvent-resistant container, and then filtered under pressure using a 0.2 ⁇ m pore filter. The following evaluations were performed using the obtained insulating film forming material.
  • HAST test HAST (Highly Accelerated Temperature and The insulation reliability of the insulating film was evaluated by a Humidity Stress Test) test. After sputtering titanium and copper on one side of a silicon wafer (Si substrate with a SiO 2 film) and polyimide as shown in FIG. 6, a plurality of copper electrodes are formed by electroplating at the intervals shown in FIG. The unnecessary sputtered layer was removed. An insulating film formed by curing the insulating film forming material of each Example and Comparative Example between electrodes was produced under the following conditions. First, an insulating film forming material was spin-coated onto a silicon wafer using a spin coater coating device, and a drying process was performed to form a resin film.
  • the obtained resin film was exposed using a proximity exposure machine "Mask Aligner MA8" (manufactured by SUSS Microtech Co., Ltd.) at an exposure amount such that the residual film rate after development was approximately 80% or more. Ta. Thereafter, the resin film was cured by heating at 230° C. for a predetermined time in a nitrogen atmosphere in a clean oven, thereby producing an insulating film. Furthermore, the insulating film provided between the electrodes was treated under HAST conditions of 130° C., 85% RH, 3.3 V, 5 V, or 10 V for 300 hours. Further, under HAST conditions, the insulation resistance value of the insulation film was observed for 100 hours or 300 hours, and the insulation reliability in each Example and Comparative Example was evaluated based on the following criteria.
  • thermocompression bondability (Preparation of insulating film with chip)
  • the insulating film forming materials of Examples 1 to 19 and Comparative Example 1 were spin-coated onto a 6-inch silicon wafer or glass substrate using a spin coater coating device, and a drying process was performed to form a resin film.
  • the obtained resin film was exposed using a proximity exposure machine "Mask Aligner MA8" (manufactured by SUSS Microtech Co., Ltd.) at an exposure amount such that the residual film rate after development was approximately 80% or more. Ta. Thereafter, the resin film was cured by heating at 230° C.
  • thermocompression adhesion between the insulating films was evaluated as described below.
  • thermocompression bondability was evaluated multiple times and evaluated as (number of times the thermocompression bondability was good/number of times the thermocompression bondability was evaluated). Specifically, after thermocompression bonding, only the resin-coated chip is grabbed using tweezers, and when the resin-coated chip is lifted, the silicon wafer or glass substrate is lifted together with the resin-coated chip, and the thermocompression bondability is evaluated. was judged to be good. On the other hand, when the silicon wafer or glass substrate peeled off when the resin-coated chip was lifted using tweezers, and only the resin-coated chip was lifted, the evaluation of thermocompression bondability was determined to be poor. The results are shown in Tables 1 and 2.
  • first semiconductor substrate 411...Substrate body (first substrate body), 412...Insulating film (first insulating film), 413...Terminal electrode (first electrode), 420...Semiconductor chip (second semiconductor substrate) , 421... Substrate body (second substrate body), 422... Insulating film portion (second insulating film), 423... Terminal electrode (second electrode), A... Cutting line, H... Heat, M1 to M3... Semi-finished product, S1...Insulating bonding portion, S2...Electrode bonding portion, S3...Insulating bonding portion, S4...Electrode bonding portion.

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Abstract

L'invention concerne un matériau de formation de film isolant, destiné à former un film isolant par collage hybride et contenant : un précurseur de polyimide (A) qui est au moins une résine choisie dans le groupe constitué par l'acide polyamique , les esters d'acide polyamique, les sels d'acide polyamique et les amides d'acide polyamique ; et un monomère polymérisable (B). La quantité contenue d'un composé qui comprend un groupe (méth)acrylique et une chaîne oxyde d'alkylène classé comme monomère polymérisable (B) est inférieure à 20 parties en masse pour 100 parties en masse du précurseur de polyimide (A).
PCT/JP2022/037511 2022-03-09 2022-10-06 Matériau de formation de film isolant, procédé de fabrication de dispositif à semi-conducteur et dispositif à semi-conducteur WO2023171014A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018066395A1 (fr) * 2016-10-05 2018-04-12 東レ株式会社 Composition de résine, film durci, dispositif à semi-conducteur et procédé pour sa production
WO2020071201A1 (fr) * 2018-10-03 2020-04-09 日立化成デュポンマイクロシステムズ株式会社 Composition de résine photosensible, procédé de production d'un produit durci à motifs, produit durci, film isolant intercouche, couche de revêtement de recouvrement, film de protection de surface et composant électronique
WO2020071437A1 (fr) * 2018-10-03 2020-04-09 日立化成デュポンマイクロシステムズ株式会社 Composition de résine photosensible, procédé de fabrication de produit durci à motifs, produit durci, film isolant intercouche, couche de revêtement de couverture, film de protection de surface et composant électronique
JP2021197430A (ja) * 2020-06-12 2021-12-27 昭和電工マテリアルズ株式会社 半導体装置の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018066395A1 (fr) * 2016-10-05 2018-04-12 東レ株式会社 Composition de résine, film durci, dispositif à semi-conducteur et procédé pour sa production
WO2020071201A1 (fr) * 2018-10-03 2020-04-09 日立化成デュポンマイクロシステムズ株式会社 Composition de résine photosensible, procédé de production d'un produit durci à motifs, produit durci, film isolant intercouche, couche de revêtement de recouvrement, film de protection de surface et composant électronique
WO2020071437A1 (fr) * 2018-10-03 2020-04-09 日立化成デュポンマイクロシステムズ株式会社 Composition de résine photosensible, procédé de fabrication de produit durci à motifs, produit durci, film isolant intercouche, couche de revêtement de couverture, film de protection de surface et composant électronique
JP2021197430A (ja) * 2020-06-12 2021-12-27 昭和電工マテリアルズ株式会社 半導体装置の製造方法

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