Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/90—Bond pads, in general
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • 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
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
  • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
  • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
  • H10W70/69—Insulating materials thereof
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/01—Manufacture or treatment
  • H10W72/019—Manufacture or treatment of bond pads
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
  • H10W72/073—Connecting or disconnecting of die-attach connectors
  • H10W72/07331—Connecting techniques
  • H10W72/07337—Connecting techniques using a polymer adhesive, e.g. an adhesive based on silicone or epoxy
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W90/00—Package configurations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W99/00—Subject matter not provided for in other groups of this subclass

Definitions

• This 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 semiconductor chips.
• Patent Document 1 discloses an example of a technology that can lower the bonding temperature by using a cyclic olefin resin.
• the heat resistance of the organic material is insufficient, and the insulating film is exposed to high temperatures during hybrid bonding, which can cause the organic material to change in quality, resulting in poor bonding at the interface between the substrate and the insulating film.
• the inventors are considering using a polyimide precursor as a hybrid bonding material because of its excellent heat resistance.
• a polyimide precursor as a hybrid bonding material because of its excellent heat resistance.
• metals such as copper to metals and insulating film to insulating film in the same process
• poor metal-metal bonding for example, gaps at the bonding interface
• the inventors have focused on the fact that the difference in coefficient of linear expansion (CTE) between an insulating film formed using a polyimide precursor and metal is the cause of poor metal-metal bonding, and have been investigating a method of mixing a filler with a polyimide precursor to suppress poor metal-metal bonding.
• CTE coefficient of linear expansion
• a filler when used, the photosensitive properties of the insulating film-forming material tend to decrease. Therefore, an insulating film-forming material that has photosensitive properties and can reduce the linear expansion coefficient of the insulating film is desirable.
• the present disclosure has been made in consideration of the above, and aims to provide an insulating film forming material that has photosensitive properties and can reduce the linear expansion coefficient of an insulating film, a method for manufacturing a semiconductor device using the insulating film forming material, and a semiconductor device that is formed from an insulating film forming material that has photosensitive properties and has an insulating film with a reduced linear expansion coefficient.
• X represents a tetravalent organic group
• Y represents a divalent organic group
• R6 and R7 each independently represent a hydrogen atom or a monovalent organic group
• at least one of R6 and R7 has a polymerizable unsaturated bond.
• ⁇ 3> The insulating film forming material according to ⁇ 1> or ⁇ 2>, further comprising (D) a polymerizable monomer and (E) a photopolymerization initiator.
• ⁇ 4> The insulating film forming material according to any one of ⁇ 1> to ⁇ 3>, wherein the filler has an average particle size of 10 nm to 100 nm.
• ⁇ 5> The insulating film forming material according to any one of ⁇ 1> to ⁇ 4>, wherein the filler has been subjected to a surface treatment.
• ⁇ 6> The insulating film forming material according to any one of ⁇ 1> to ⁇ 5>, wherein the solvent includes a non-amide solvent.
• ⁇ 7> The insulating film forming material according to ⁇ 6>, wherein the non-amide solvent contains a cyclic ester compound.
• ⁇ 8> The insulating film forming material according to any one of ⁇ 1> to ⁇ 7>, for forming an insulating film used in hybrid bonding.
• a method for manufacturing a semiconductor device comprising: forming at least one of a first organic insulating film and a second organic insulating film using the insulating film forming material according to ⁇ 8>; and bonding the first organic insulating film and the second organic insulating film.
• a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body; a semiconductor chip having a semiconductor chip substrate body and a second organic insulating film 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 second organic insulating film of the semiconductor chip are bonded to each other, and the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are bonded to each other, At least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing a photosensitive insulating film forming material containing (A) a polyimide precursor and (C) a filler, and the insulating film has an i-line transmittance of 5% to 40%.
• an insulating film forming material that has photosensitive properties and can reduce the linear expansion coefficient of an insulating film
• a method for manufacturing a semiconductor device using the insulating film forming material and a semiconductor device that is formed from an insulating film forming material that has photosensitive properties and has an insulating film with a reduced linear expansion coefficient.
• FIG. 1 is a cross-sectional view showing a schematic example of a semiconductor device manufactured by a method for manufacturing a semiconductor device according to an embodiment of the present invention.
• 2A to 2C are diagrams sequentially showing a method for manufacturing the semiconductor device shown in FIG. 3A to 3C are diagrams showing in more detail the bonding method in the method of manufacturing the semiconductor device shown in FIG. 4A to 4D are views showing a method for manufacturing the semiconductor device shown in FIG. 1, sequentially illustrating steps subsequent to the step shown in FIG.
• 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).
• C2W Chip-to-Wafer
• the terms “layer” and “film” include cases where the layer or film is formed over the entire area when the area in which the layer or film is present is observed, as well as cases where the layer or film is formed over only a portion of the area.
• the thickness of a layer or film is determined as the arithmetic mean value of thicknesses measured at five points on the layer or film of interest.
• the thickness of the layer or film can be measured using a micrometer or the like.
• when the thickness of the layer or film can be measured directly it is measured using a micrometer.
• the thickness of one layer or the total thickness of multiple layers it may be measured by observing the cross section of the measurement target using an electron microscope.
• the term "(meth)acrylic group” means “acrylic group” and “methacrylic group”
• the term “(meth)acrylate” means “acrylate” and “methacrylate”
• the term “(meth)acryloyl” means “acryloyl” and “methacryloyl”.
• the term “insulating film” is a concept that also encompasses an insulating layer.
• the number of carbon atoms in the functional group means the total number of carbon atoms including the number of carbon atoms in the substituent.
• the insulating film-forming material of the present disclosure includes (A) a polyimide precursor, (B) a solvent, and (C) a filler, and the insulating film obtained by molding the insulating film-forming material has an i-line transmittance of 5% to 40%, and is a photosensitive material.
• the insulating film forming material of the present disclosure has photosensitive properties and can reduce the linear expansion coefficient of the insulating film.
• the reason for this is not clear, but it can be considered as follows.
• the insulating film formed from the insulating film-forming material of the present disclosure has an i-line transmittance of 5% or more, degradation of photosensitive characteristics can be suppressed, and an insulating film-forming material with high resolution can be obtained, for example.
• the insulating film forming material contains the filler (C) together with the polyimide precursor (A), the linear expansion coefficient of the insulating film tends to be reduced compared to when the filler (C) is not used.
• the insulating film forming material of the present disclosure has a linear expansion coefficient of the insulating film after curing of 60 ppm/K or less, more preferably 50 ppm/K or less, and even more preferably 45 ppm/K or less. This makes it possible to suitably suppress poor bonding between metals.
• the lower limit of the insulating film is not particularly limited, and may be, for example, 20 ppm/K or more, or 25 ppm/K or more.
• the linear expansion coefficient indicates the rate at which the length of an insulating film expands due to an increase in temperature per unit temperature, and can be calculated by measuring the change in length of the insulating film at temperatures between 50°C and 100°C using a thermomechanical analyzer or the like.
• the i-line transmittance of the insulating film obtained by molding the insulating film-forming material of the present disclosure is 5% to 40%, and may be, for example, 10% to 40%, or may be 12% to 30%.
• the i-line transmittance of the insulating film can be adjusted by, for example, (A) the type of polyimide precursor, (B) the type of solvent, (C) the type of filler, and the like.
• the method for measuring the i-line transmittance is as follows.
• the insulating film forming material is applied onto a glass substrate by spin coating or the like, the coating is dried at 100°C for 2 minutes, and then dried at 110°C for 2 minutes to form a resin film, and the i-line transmittance of the resin film is measured using a spectrophotometer (for example, a U-3900H spectrophotometer manufactured by Hitachi High-Tech Science Corporation). The obtained value is regarded as the i-line transmittance of the insulating film.
• a spectrophotometer for example, a U-3900H spectrophotometer manufactured by Hitachi High-Tech Science Corporation.
• the insulating film forming material of the present disclosure may be a material for forming an insulating film used in hybrid bonding.
• the insulating film forming material of the present disclosure may be a material that is applied to techniques such as W2W (Wafer-to-Wafer) bonding and C2W (Chip-to-Wafer) bonding.
• W2W Wide-to-Wafer
• C2W Chip-to-Wafer
• the insulating film-forming material of the present disclosure contains (A) a polyimide precursor (hereinafter also referred to as “component (A)”).
• the component (A) is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide.
• the polyamic acid ester and polyamic acid amide are compounds in which hydrogen atoms of at least some of the carboxyl groups in a polyamic acid are substituted with monovalent organic groups
• the polyamic acid salt is a compound in which at least some of the carboxyl groups in a polyamic acid form a salt structure with a basic compound having a pH of over 7.
• the component (A) may have a polymerizable unsaturated bond.
• the (A) component preferably contains a compound having a structural unit represented by the following general formula (1). This tends to result in a semiconductor device having an insulating film that exhibits high reliability.
• X represents a tetravalent organic group
• Y represents a divalent organic group
• R6 and R7 each independently represent a hydrogen atom or a monovalent organic group
• at least one of R6 and R7 has a polymerizable unsaturated bond.
• the polyimide precursor may have a plurality of structural units represented by the above general formula (1), and X, Y, R6 and R7 in the plurality of structural units may be the same or different.
• R 6 and R 7 are each independently a hydrogen atom or a monovalent organic group, the combination is not particularly limited.
• R 6 and R 7 may be a hydrogen atom and the remaining may be a monovalent organic group described below, or they may be the same or different monovalent organic groups.
• the combinations 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 contain an aromatic ring.
• the aromatic ring include aromatic hydrocarbon groups (e.g., aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., heterocyclic rings having 5 to 20 atoms).
• the tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring.
• each aromatic ring may have a substituent or may be unsubstituted.
• substituent of the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group.
• the tetravalent organic group represented by X contains a benzene ring
• the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably contains one to three benzene rings, and even more preferably contains one or two benzene rings.
• the benzene rings may be linked by a single bond, or may be linked by a linking group such as an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A ) 2 -; each of the two R A's independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B ) 2 -O-) n ; each of the two R B's independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more), or a composite linking group formed by combining at least two of these linking groups.
• the two benzene rings may be linked by a single bond, or may be linked by a linking group such as an
• the --COOR 6 group and the --CONH-- group are preferably located at the ortho position relative to each other, and the --COOR 7 group and the --CO-- group are preferably located at the ortho position relative to each other.
• tetravalent organic group represented by X include groups represented by the following formulae (A) to (F).
• a group represented by the following formula (E) is preferred, and in the following formula (E), C is more preferably a group containing an ether bond, and even more preferably an ether bond.
• the following formula (F) is a structure in which C in the following formula (E) is a single bond. It should be noted that the present disclosure is not limited to the following specific examples.
• a and B are each independently a single bond or a divalent group not conjugated with a benzene ring. However, A and B cannot both be single bonds.
• the divalent group not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A ) 2 -; each of the two R A's independently represents a hydrogen atom, an alkyl group, or a phenyl group).
• a and B are each independently preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.
• C preferably contains an ether bond, and is preferably an ether bond.
• C may include 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 even more preferably an alkylene group having 1 or 2 carbon atoms.
• alkylene group represented by C in formula (E) examples include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethyl branched alkylene groups such as ethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene 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, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms.
• Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in formula (E) is substituted with a halogen atom such as a fluorine atom or a chlorine atom.
• a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.
• the alkyl group represented by R A or R B contained in the silylene bond or siloxane bond is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.
• Specific examples of the alkyl group represented by R A or R B include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and the like.
• tetravalent organic group represented by X may be groups represented by the following formulae (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 a preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X.
• the skeleton of the divalent organic group represented by Y may be a structure in which two bonding positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups).
• the divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group.
• divalent aromatic group examples include a divalent aromatic hydrocarbon group (e.g., an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (e.g., a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.
• a divalent aromatic hydrocarbon group e.g., an aromatic ring having 6 to 20 carbon atoms
• a divalent aromatic heterocyclic group e.g., a heterocyclic ring having 5 to 20 atoms
• divalent aromatic group represented by Y include groups represented by the following formulae (G) and (H).
• the group represented by the following formula (H) is preferred, and among these, in the following formula (H), D is more preferably a group containing a single bond or an ether bond, even more preferably a group containing a single bond or an ether bond, particularly preferably a group containing an ether bond, and extremely 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.
• D may also be a structure represented by formula (C1) above.
• Specific examples of D in formula (H) are the same as the specific examples of C in formula (E). It is preferable that each D in formula (H) independently represents a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group and an alkylene group, or the like.
• the alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.
• Specific examples of the alkyl group represented by R in formulae (G) to (H) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
• the alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms.
• Specific examples of the alkoxy group represented by R in formulae (G) to (H) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.
• the halogenated alkyl group represented by R in Formulae (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms.
• Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom.
• a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.
• n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
• divalent aliphatic group represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups having a polyalkylene oxide structure.
• the linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.
• alkylene group represented by Y examples include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.
• the cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms.
• Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group, a cyclohexylene group, and the like.
• the unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms.
• the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure.
• the alkylene group in the alkylene oxide structure may be linear or branched.
• the unit structure in the polyalkylene oxide structure may be of one type or two or more types.
• the divalent organic group represented by Y may be a divalent group having a polysiloxane structure.
• Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
• alkyl group having 1 to 20 carbon atoms bonded to a silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a 2-ethylhexyl group, an n-dodecyl group, etc.
• a methyl group is preferable.
• the aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent.
• 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 a phenyl group, a naphthyl group, and a benzyl group. Of these, a phenyl group is preferred.
• the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or of two or more types.
• the silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.
• the group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H'), formula (H'') or formula (H'''). From the viewpoint of having a flexible skeleton and excellent bonding properties, it is more preferably a group represented by the following formula (H') or formula (H'').
• each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom.
• R is preferably an alkyl group, and more preferably a methyl group.
• the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited.
• Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include a combination in which X is a group represented by formula (E) and Y is a group represented by formula (H).
• R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group, with the proviso that at least one of them has a polymerizable unsaturated bond.
• the monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and further preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2).
• at least one of R 6 and R 7 is a group represented by general formula (2).
• the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-ray transmittance is high, and a good cured product tends to be formed even when cured at a low temperature of 400° C. or less.
• the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a part of the unsaturated double bond portion is eliminated by a base or the like.
• 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 carbon number of the aliphatic hydrocarbon group represented by R 8 to R 10 in general formula (2) is 1 to 3, and preferably 1 or 2.
• 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, etc., and a methyl group is preferred.
• R 8 to R 10 in the general formula (2) a combination in which R 8 and R 9 are hydrogen atoms and R 10 is a hydrogen atom or a methyl group is preferred.
• R x is a divalent linking group, and is 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 further preferably 2 or 3.
• R6 and R7 are a group represented by general formula (2), and it is more preferable that both of R6 and R7 are groups represented by general formula (2).
• the ratio of R6 and R7 which are groups represented by the general formula (2), to the sum of R6 and R7 of all structural units contained in the compound 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 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 the following general formula (2'):
• R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; q represents an integer of 1 to 10.
• q is an integer from 1 to 10, preferably an integer from 2 to 5, and more preferably 2 or 3.
• the content of the structural unit represented by general formula (1) contained in the compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, based on the total structural units.
• the upper limit of the aforementioned content is not particularly limited, and may be 100 mol%.
• the polyimide precursor (A) may be synthesized using a tetracarboxylic dianhydride and a diamine compound.
• X corresponds to a residue derived from the tetracarboxylic dianhydride
• Y corresponds to a residue derived from the diamine compound.
• the polyimide precursor (A) may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.
• tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, carboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-
• 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride and 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride are preferred, and 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride is more preferred from the viewpoint of bonding at lower temperatures.
• the tetracarboxylic dianhydrides may be used alone or in combination of two or more kinds.
• diamine compound examples include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4, 4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,4'
• diamine compound 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene are preferred.
• 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis ⁇ 4-(4'-aminophenoxy)phenyl ⁇ propane are more preferred from the viewpoint of having a flexible skeleton and excellent adhesiveness.
• the diamine compounds may be used alone or in combination of two or more kinds.
• a compound having a structural unit represented by general formula (1) in which at least one of R6 and R7 in general formula (1) is a monovalent organic group can be obtained, for example, by the following method (a) or (b).
• a tetracarboxylic dianhydride preferably a tetracarboxylic dianhydride represented by the following general formula (8)
• R-OH a compound represented by R-OH
• diester derivative is subjected to a condensation reaction with a diamine compound represented by H 2 N-Y-NH 2 .
• a tetracarboxylic dianhydride is reacted with a diamine compound represented by H 2 N-Y-NH 2 in an organic solvent to obtain a polyamic acid solution, and a compound represented by R-OH is added to the polyamic acid solution and reacted 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 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 or in combination of two or more.
• the organic solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropanamide, and among these, 3-methoxy-N,N-dimethylpropanamide is preferred.
• a polyimide precursor may be synthesized by reacting a dehydration condensation agent with a polyamic acid solution together with the compound represented by R-OH.
• the dehydration condensation agent preferably 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 the polyimide precursor (A) can be 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, then reacting the diester with a chlorinating agent such as thionyl chloride to convert it into an acid chloride, and then reacting a diamine compound represented by H 2 N-Y-NH 2 with the acid chloride.
• the above-mentioned compound contained in the polyimide precursor (A) can be 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 reacting the diamine compound represented by H 2 N-Y-NH 2 with the diester derivative in the presence of a carbodiimide compound.
• the above-mentioned compound contained in the polyimide precursor (A) can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H 2 N-Y-NH 2 to form a polyamic acid, then isoimidizing the polyamic acid in the presence of a dehydrating condensing agent such as trifluoroacetic anhydride, and then reacting the polyamic acid with a compound represented by R-OH.
• a dehydrating condensing agent such as trifluoroacetic anhydride
• a compound represented by R-OH may be reacted in advance with a part of the tetracarboxylic dianhydride to react the partially esterified tetracarboxylic dianhydride with the diamine compound represented by H 2 N-Y-NH 2 .
• X is the same as X in general formula (1), and specific examples and preferred examples are also the same.
• the compound represented by R-OH used in the synthesis of the above-mentioned compound contained in the polyimide precursor (A) may be a compound in which a hydroxy group is bonded to R x of the group represented by the general formula (2), a compound in which a hydroxy group is bonded to the terminal methylene group of the group represented by the general formula (2'), etc.
• Specific examples of the compound represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc., among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.
• the weight average molecular weight of the polyimide precursor (A) is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000.
• the weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated 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 may have a structure in which a part of the amino group in the (A) polyimide precursor reacts with a carboxy group in the dicarboxylic acid.
• the polyimide precursor when synthesizing the polyimide precursor, a part of the amino group of a diamine compound may react with a carboxy group of the dicarboxylic acid.
• the dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula:
• a methacryl group derived from the dicarboxylic acid can be introduced into the polyimide precursor (A) by reacting a part of the amino group of the diamine compound with a carboxy group of the dicarboxylic acid.
• the insulating film forming material of the present disclosure may contain a polyimide resin in addition to the polyimide precursor (A).
• a polyimide resin in addition to the polyimide precursor (A).
• the polyimide resin referred to here 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 the insulating film forming material using the polyimide precursor.
• the polyimide resin is not particularly limited as long as it is a polymeric compound having a plurality of structural units including imide bonds, and it is preferable that the polyimide resin contains, for example, a compound having a structural unit represented by the following general formula (X). This tends to result in a semiconductor device having an insulating film that exhibits high reliability.
• X represents a tetravalent organic group
• Y represents a divalent organic group.
• Preferred examples of the substituents X and Y in general formula (X) are the same as the preferred examples of the substituents X and Y in general formula (1) described above.
• the ratio of the polyimide resin to the total of the polyimide precursor and the polyimide resin may be 15% by mass to 50% by mass, or 10% by mass to 20% by mass.
• the insulating film forming material of the present disclosure may contain other resins in addition to the (A) polyimide precursor and polyimide resin.
• the other resins include novolac resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polyvinyl chloride resins, etc., from the viewpoint of heat resistance.
• the other resins may be used alone or in combination of two or more.
• the content of the polyimide precursor (A) relative to the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
• the insulating film forming material of the present disclosure may or may not contain a resin component such as a cyclic olefin resin such as benzocyclobutene, or an epoxy resin.
• a resin component such as a cyclic olefin resin such as benzocyclobutene, or an epoxy resin.
• the content of the cyclic olefin resin and the content of the epoxy resin are each independently preferably 30% by mass or less, more preferably 0% by mass to 10% by mass, and even more preferably 0% by mass to 5% by mass, based on the total amount of the insulating film forming material of the present disclosure.
• the insulating film forming material of the present disclosure contains a solvent (B) (hereinafter also referred to as “component (B)”).
• the component (B) is not particularly limited, and examples thereof include ester-based solvents, ketone-based solvents, carbonate-based solvents, heterocyclic compound-based solvents, and amide-based solvents.
• the ester-based solvents, ketone-based solvents, carbonate-based solvents, and amide-based solvents may each independently have a cyclic structure or may not have a cyclic structure.
• the component (B) may be used alone or in combination of two or more types.
• the component (B) preferably contains a non-amide solvent other than an amide solvent, and more preferably contains no amide solvent and is composed of a non-amide solvent.
• the non-amide solvent is not particularly limited as long as it is a compound that does not contain an amide group, and examples thereof include the above-mentioned ester solvents, ketone solvents, carbonate solvents, and heterocyclic compound solvents.
• the non-amide solvent is preferably an ester solvent such as a cyclic ester compound.
• the component (B) may contain, for example, at least one compound selected from the group consisting of compounds represented by the following formulas (3) to (10).
• the component (B) may be used alone or in combination of two or more types.
• R 1 , R 2 , R 8 , R 10 , R 11 , R 13 , and R 14 are each independently an alkyl group having 1 to 4 carbon atoms
• R 3 to R 7 , R 9 , and R 12 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• s is an integer of 0 to 8
• t is an integer of 0 to 4
• r is an integer of 0 to 4
• u is an integer of 0 to 3
• v is an integer of 0 to 3
• w is an integer of 0 to 4
• x is an integer of 0 to 5.
• the alkyl group having 1 to 4 carbon atoms represented by R2 is preferably a methyl group or an ethyl group.
• t is preferably 0, 1 or 2, and more preferably 1.
• the alkyl group having 1 to 4 carbon atoms for R3 is preferably a methyl group, an ethyl group, a propyl group, or a butyl group.
• the alkyl group having 1 to 4 carbon atoms for R4 and R5 is preferably a methyl group or an ethyl group.
• the alkyl group having 1 to 4 carbon atoms for R 6 to R 8 is preferably a methyl group or an ethyl group.
• r is preferably 0 or 1, and more preferably 0.
• the alkyl group having 1 to 4 carbon atoms for R 9 and R 10 is preferably a methyl group or an ethyl group.
• u is preferably 0 or 1, and more preferably 0.
• the alkyl group having 1 to 4 carbon atoms represented by R 11 is preferably a methyl group or an ethyl group. u is preferably 0 or 1, and more preferably 0.
• the alkyl group having 1 to 4 carbon atoms for R 12 is preferably a methyl group or an ethyl group.
• the alkyl group having 1 to 4 carbon atoms for R 13 is preferably a methyl group or an ethyl group.
• w is preferably 0 or 1, and more preferably 0.
• the alkyl group having 1 to 4 carbon atoms represented by R 14 is preferably a methyl group or an ethyl group.
• x is preferably 0 or 1, and more preferably 0.
• component (B) examples include the following compounds.
• Component (B) may contain, for example, ⁇ -butyrolactone or cyclohexanone, or may contain ⁇ -butyrolactone, from the viewpoint of increasing i-line transmittance.
• the content of N-methyl-2-pyrrolidone (NMP) may be 1 mass % or less based on the total amount of the insulating film forming material, and may be 3 mass % or less based on the total amount of component (A).
• the content of component (B) is preferably 1 part by mass to 10,000 parts by mass, and more preferably 50 parts by mass to 10,000 parts by mass, per 100 parts by mass of component (A).
• the hybrid insulating film-forming material of the present disclosure contains a filler (C) (hereinafter also referred to as "component (C)").
• the component (C) may be an organic filler, an inorganic filler, or an inorganic-organic composite filler.
• the component (C) may be used alone or in combination of two or more types.
• inorganic fillers include silica, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, zirconium silicate, calcium oxide, magnesium oxide, titanium oxide, silicon nitride, aluminum nitride, boron nitride, calcium titanate, barium titanate, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica.
• silica and alumina are particularly preferred, and silica is more preferred.
• the volume average particle diameter of the (C) component in the insulating film forming material or insulating film can be measured by a known method.
• the (C) component preferably an inorganic filler
• the (C) component is extracted from the insulating film forming material or insulating film using an organic solvent, nitric acid, aqua regia, etc., and thoroughly dispersed using an ultrasonic disperser or the like to prepare a dispersion.
• the volume average particle diameter of the (C) component preferably an inorganic filler
• the insulating film can be embedded in a transparent epoxy resin or the like, polished, and the cross section obtained is observed using a scanning electron microscope to obtain a volume-based particle size distribution, from which the volume average particle diameter of the (C) component can be measured.
• the volume average particle diameter can be measured by continuously observing two-dimensional cross sections of the insulating film using an FIB device (focused ion beam SEM) or the like and performing three-dimensional structural analysis.
• the (C) component has been subjected to a surface treatment. This tends to improve the dispersibility of the (C) component in the insulating film forming material of the present disclosure, and as a result, tends to have good photosensitive properties.
• the insulating film forming material of the present disclosure preferably contains a surface-treated inorganic filler, and more preferably contains at least one of surface-treated silica and surface-treated alumina.
• Surface treatments include hydrophobization treatments from the viewpoint of improving the dispersibility of component (C).
• a commercially available filler may be used as the surface-treated component (C).
• component (C) that has not been surface-treated may be surface-treated using various surface treatment agents such as the coupling agents described below.
• the content of the component (C) may be 5 parts by mass to 200 parts by mass, 10 parts by mass to 150 parts by mass, 10 parts by mass to 100 parts by mass, 15 parts by mass to 50 parts by mass, or 25 parts by mass to 50 parts by mass, relative to 100 parts by mass of the component (A).
• the content of component (C) means the content of the filler, which is the solid content excluding the dispersion solvent.
• the (C) component may be a filler dispersed in a dispersion solvent in order to suppress aggregation.
• the dispersion solvent is not particularly limited, and examples thereof include known solvents such as cyclohexanone and dimethylacetamide.
• the insulating film forming material of the present disclosure may contain, as necessary, at least one of (D) a polymerizable monomer, (E) a photopolymerization initiator, (F) a sensitizer, (G) a coupling agent, a thermal polymerization initiator, a polymerization inhibitor, an antioxidant, a surfactant, a leveling agent, a rust inhibitor, a nitrogen-containing compound, or a dicarboxylic acid.
• the insulating film forming material of the present disclosure may contain (D) a polymerizable monomer and (E) a photopolymerization initiator.
• the insulating film forming material of the present disclosure may contain (D) a polymerizable monomer (hereinafter also referred to as "(D) component").
• the (D) component preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of favorable polymerization when used in combination with (E) a photopolymerization initiator. From the viewpoint of improving crosslink density and improving photosensitivity, the (D) component preferably has 2 to 6 groups containing a polymerizable unsaturated double bond, and more preferably has 2 to 4 groups containing a polymerizable unsaturated double bond.
• the polymerizable monomers may be used alone or in combination of two or more.
• the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythr
• polyisocyanuric acid acrylate examples include taerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, 2-hydroxyethyl (meth)acrylate, 1,3-bis((meth)acryloyloxy)-2-hydroxypropane, ethylene oxide (EO)-modified bisphenol A diacrylate, and ethylene oxide (EO)-modified bisphenol A dimethacrylate
• Polymerizable monomers other than those having a (meth)acrylic group are not particularly limited, and examples include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide.
• Component (D) is not limited to compounds having a group containing a polymerizable unsaturated double bond, but may also be a compound having a polymerizable group other than an unsaturated double bond group (e.g., an oxirane ring).
• component (D) when the insulating film forming material of the present disclosure contains component (D), the content of component (D) is not particularly limited, but is preferably 1 part by mass to 100 parts by mass, more preferably 1 part by mass to 75 parts by mass, and even more preferably 1 part by mass to 50 parts by mass, per 100 parts by mass of component (A).
• the mass ratio of D2 to D1 may be 50/100 to 100/100, or 60/100 to 90/100.
• the insulating film forming material of the present disclosure may contain (E) a photopolymerization initiator (hereinafter also referred to as “component (E)”).
• component (E) is not particularly limited and may be, for example, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxycarbonyl oxime compounds such as 2-(O-benzoyl)oxime, 1-[4-(phenylthio)phenyl]oct
• the content of the oxime compound relative to the total amount of component (E) is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
• the total amount of component (E) is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 20 parts by mass, and even more preferably 2 parts by mass to 10 parts by mass, per 100 parts by mass of component (A).
• the insulating film forming material of the present disclosure may contain a sensitizer (F).
• the sensitizer (F) include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, o-benzoylmethylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone, and other benzophenone derivatives.
• the component (F) may be used alone or in combination of two or more types.
• component (F) when the insulating film forming material of the present disclosure contains component (F), the content of component (F) is not particularly limited, but is preferably 0.01 parts by mass to 3 parts by mass, and more preferably 0.1 parts by mass to 1 part by mass, per 100 parts by mass of component (A).
• the insulating film forming material of the present disclosure may contain a coupling agent (G).
• the coupling agent (G) is not particularly limited, and examples thereof include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3- silane
• the method for preparing the insulating film forming material disclosed herein is not particularly limited, and it is sufficient to mix the aforementioned components.
• the semiconductor device disclosed herein comprises a first substrate body, a first semiconductor substrate having the first organic insulating film and a first electrode provided on one surface of the first substrate body, a semiconductor chip substrate body, and a semiconductor chip having a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film of the first semiconductor substrate is bonded to the second organic insulating film of the semiconductor chip, the first electrode of the first semiconductor substrate is bonded to the second electrode of the semiconductor chip, at least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing a photosensitive insulating film forming material containing (A) a polyimide precursor and (C) a filler, and the insulating film has an i-line transmittance of 5% to 40%.
• the semiconductor device of the present disclosure at least one of the first organic insulating film and the second organic insulating film is an insulating film formed by curing a photosensitive insulating film forming material containing (A) a polyimide precursor and (C) a filler. Furthermore, the insulating film has an i-line transmittance of 5% to 40%. As a result, the semiconductor device of the present disclosure includes an insulating film formed from an insulating film forming material having photosensitive properties and having a reduced linear expansion coefficient.
• the insulating film forming material used in the semiconductor device of the present disclosure may be a material having photosensitivity, containing (A) a polyimide precursor and (C) a filler, and having an i-line transmittance of 5% to 40%.
• the insulating film forming material may be the insulating film forming material of the present disclosure described above.
• the semiconductor device of the present disclosure can be manufactured, for example, by the manufacturing method of a semiconductor device described below.
• the i-line transmittance of the insulating film formed from the insulating film forming material used in the semiconductor device disclosed herein is 5% to 40%, and may be, for example, 10% to 40%, or 12% to 30%.
• the method for manufacturing a semiconductor device includes forming at least one of a first organic insulating film and a second organic insulating film using the insulating film forming material according to the present disclosure, and bonding the first organic insulating film and the second organic insulating film together. More specifically, the semiconductor device can be manufactured through the following steps (1) to (5). Step (1) A first semiconductor substrate is prepared, the first semiconductor substrate having a first substrate body, and the first organic insulating film and a first electrode provided on one surface of the first substrate body.
• Step (2) A second semiconductor substrate is prepared, the second semiconductor substrate having a second substrate body, and the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body.
• Step (1) is a step of applying an insulating film forming material to a first substrate body and removing a portion of the insulating film forming material applied to the first substrate body to form a via; a step of forming a first organic insulating film by curing the insulating film forming material in which the vias are formed in the first substrate body, and forming a first electrode by filling the vias with an electrode material, the step of preparing a first semiconductor substrate having the first organic insulating film and a first electrode provided on one surface of the first substrate body; may also include Step (2) is applying an insulating film forming material to a second substrate body and removing a portion of the insulating film forming material applied to the first substrate body to form a via; a step of forming a second organic insulating film by curing the insulating film forming material in which the vias are formed in the second substrate body, and forming a second electrode by filling the vias with an electrode material, the step of preparing a second semiconductor substrate having the
• step (1) is The method may include a step of forming a first electrode on a first substrate body and then forming a first organic insulating film around the first electrode, thereby preparing a first semiconductor substrate having the first organic insulating film and the first electrode provided on one surface of the first substrate body.
• step (2) is The method may include a step of forming a second electrode on the second substrate body and then forming a second organic insulating film around the second electrode, thereby preparing a second semiconductor substrate having the second organic insulating film and the second electrode provided on one surface of the second substrate body.
• the semiconductor device 1 is a cross-sectional view showing an example of a semiconductor device according to the present disclosure.
• the semiconductor device 1 is, for example, an example of a semiconductor package, and includes a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar portion 30, a redistribution layer 40, a substrate 50, and a circuit substrate 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 20 is mounted downward in a three-dimensional mounting structure.
• the second semiconductor chip 20 is a semiconductor chip such as an LSI or memory, and is a chip component with a smaller area in a planar view than the first semiconductor chip 10.
• the second semiconductor chip 20 is bonded to the back surface of the first semiconductor chip 10 by chip-to-chip (C2C) bonding.
• the first semiconductor chip 10 and the second semiconductor chip 20 are finely bonded to each other by their respective terminal electrodes and the insulating films around them, firmly and without misalignment, by hybrid bonding, the details of which will be described later.
• the pillar portion 30 is a connection portion in which a plurality of pillars 31 formed of a metal such as copper (Cu) are sealed with a resin 32.
• the plurality of pillars 31 are conductive members extending from the upper surface of the pillar portion 30 to the lower surface.
• the plurality of pillars 31 may have a cylindrical shape with a diameter of, for example, 3 ⁇ m to 20 ⁇ m (in one example, a diameter of 5 ⁇ m), and may be arranged so that the center-to-center distance between each pillar 31 is 15 ⁇ m or less.
• the plurality of pillars 31 flip-chip connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40.
• the semiconductor device 1 can form a connection electrode without using a technique called TMV (Through mold via), which is a technique of drilling holes in a mold and soldering the mold.
• TMV Through mold via
• the pillar portion 30 has a thickness approximately the same as that of the second semiconductor chip 20, for example, and is arranged on the side of the second semiconductor chip 20 in the horizontal direction. Note that multiple solder balls may be arranged instead of the pillar portions 30, and the lower terminal electrodes of the first semiconductor chip 10 and the upper terminal electrodes of the rewiring layer 40 may be electrically connected by the solder balls.
• the rewiring layer 40 is a wiring layer that has the function of terminal pitch conversion, which is a function of the package substrate, and is a layer in which a rewiring pattern is formed using polyimide and copper wiring, etc. on the insulating film on the lower side of the second semiconductor chip 20 and on the lower surface of the pillar portion 30.
• the rewiring layer 40 is formed in a state in which the first semiconductor chip 10 (first semiconductor substrate 100), the second semiconductor chip 20, etc. are inverted upside down (see FIG. 4(d)).
• the redistribution layer 40 electrically connects the terminal electrodes on the underside of the second semiconductor chip 20 and the terminal electrodes of the first semiconductor chip 10 via the pillar 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 substrate 50. If there is a large difference in the terminal pitch between the redistribution layer 40 and the substrate 50, an inorganic interposer or the like may be used between the redistribution layer 40 and the substrate 50 to electrically connect the redistribution layer 40 and the substrate 50.
• the circuit board 60 is a board on which the first semiconductor chip 10 and the second semiconductor chip 20 are mounted, and has a plurality of through electrodes inside that are electrically connected to the board 50 that is connected to the first semiconductor chip 10, the second semiconductor chip 20, and electronic components 51, etc.
• the terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 are electrically connected to terminal electrodes 61 provided on the rear surface of the circuit board 60 by the plurality of through electrodes.
• Figure 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in Figure 1.
• Figure 3 is a diagram showing in more detail a bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in Figure 2.
• Figure 4 is a diagram sequentially showing steps subsequent to the steps shown in Figure 2 in the method for manufacturing the semiconductor device shown in Figure 1.
• the semiconductor device 1 can be manufactured through, for example, the following steps (a) to (n).
• a polishing method such as a CMP method or polishing using a surface planer
• step (m) A step of cutting the semi-finished product M3 on which the wiring layer 400 has been formed in the step (l) along the cutting lines A so as to obtain individual semiconductor devices 1 (see FIG. 4(d)).
• step (n) A step of inverting the semiconductor device 1a individualized in the step (m) and placing it on the substrate 50 and the circuit board 60 (see FIG. 1).
• step (1) corresponds to the aforementioned steps (a) and (c)
• step (2) corresponds to the aforementioned steps (b) and (d)
• step (3) corresponds to step (e)
• step (4) corresponds to step (g)
• 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 producing at least one of the first organic insulating film and the second organic insulating film in the manufacturing method of a semiconductor device.
• Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate on which an integrated circuit consisting of semiconductor elements and wiring connecting them is formed, corresponding to a plurality of first semiconductor chips 10.
• a plurality of terminal electrodes 103 made of copper, aluminum, etc. are provided at predetermined intervals on one surface 101a of a first substrate body 101 made of silicon, etc., and an insulating film 102 (first insulating film) which is a hardened product obtained by hardening the insulating film forming material of the present disclosure is provided.
• the insulating film forming material is a photosensitive material such as a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material
• the insulating film 102 may be provided on one surface 101a of the first substrate body 101 before providing the plurality of terminal electrodes 103, or the insulating film 102 may be provided after providing the plurality of terminal electrodes 103 on one surface 101a of the first substrate body 101.
• the insulating film forming material is a non-photosensitive material
• multiple terminal electrodes 103 may be provided on one surface 101a of the first substrate body 101 before the insulating film 102 is provided.
• Step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate on which an integrated circuit having semiconductor elements and wiring connecting them is formed, corresponding to a plurality of second semiconductor chips 20.
• a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc. are continuously provided on one surface 201a of a second substrate body 201 made of silicon, etc., and an insulating film 202 (a second insulating film) which is a hardened product obtained by hardening the insulating film forming material of the present disclosure is provided.
• the insulating film forming material is a photosensitive material such as a negative-type photosensitive insulating film forming material or a positive-type photosensitive insulating film forming material
• the insulating film 202 may be provided on one surface 201a of the second substrate body 201 before the plurality of terminal electrodes 203 are provided, or the insulating film 202 may be provided after the plurality of terminal electrodes 203 are provided on one surface 201a of the second substrate body 201.
• the insulating film forming material is a non-photosensitive material
• multiple terminal electrodes 203 may be provided on one surface 201a of the second substrate body 201 before the insulating film 202 is provided.
• the insulating films 102 and 202 used in steps (a) and (b) are not limited to being both cured products obtained by curing the insulating film-forming material of the present disclosure, and at least one of the insulating films 102 and 202 may be a cured product obtained by curing the insulating film-forming material of the present disclosure.
• FIG. 1 shows an example of C2C bonding
• the present invention may be applied to chip-to-wafer (C2W) bonding as shown in FIG. 5.
• C2W chip-to-wafer
• a semiconductor wafer 410 first semiconductor substrate 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 prepared.
• a semiconductor substrate (second semiconductor substrate) before being singulated into a plurality of semiconductor chips 420 is prepared, having a substrate body 421 (second substrate body), an insulating film 422 (second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (second electrodes). Then, one surface of the semiconductor wafer 410 and one surface of the second semiconductor substrate before being singulated into the semiconductor chips 420 are polished by a polishing method such as a CMP method or polishing using a surface planer, as in the above steps (c) and (d). Thereafter, a singulation process similar to step (e) is performed on the second semiconductor substrate to obtain multiple semiconductor chips 420.
• a polishing method such as a CMP method or polishing using a surface planer
• the terminal electrodes 423 of the semiconductor chip 420 are aligned with the terminal electrodes 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film 422 of the semiconductor chip 420 are bonded to each other (step (g)), and the terminal electrodes 413 of the semiconductor wafer 410 and the terminal electrodes 423 of the semiconductor chip 420 are bonded to each other (step (h)), thereby obtaining the semi-finished product shown in FIG. 5B.
• the insulating film 412 and the insulating film 422 are bonded to each other to form an insulating bonded portion S3, and the semiconductor chip 420 is attached to the semiconductor wafer 410 mechanically and with high precision.
• the terminal electrodes 413 and the corresponding terminal electrodes 423 are bonded to each other to form an electrode bonded portion S4, and the terminal electrodes 413 and 423 are bonded mechanically and electrically.
• step (h) as shown in FIG. 2(d), after the bonding in step (g) is completed, heat H, pressure, or both are applied to bond the terminal electrode 103 of the first semiconductor substrate 100 to each of the terminal electrodes 203 of the semiconductor chips 205 as hybrid bonding (see FIG. 3(c)).
• the annealing temperature in step (g) is preferably 150° C. or higher and 400° C. or lower, and more preferably 200° C. or higher and 300° C. or lower.
• the insulating film forming material disclosed herein it is possible to set the annealing temperature low.
• the terminal electrode 103 and the corresponding terminal electrode 203 are bonded to form an electrode bonding portion S2, and the terminal electrode 103 and the terminal electrode 203 are mechanically and electrically firmly bonded to each other.
• the electrode bonding in step (h) may be performed after the bonding in step (g) or may be performed simultaneously with the bonding in step (g).
• multiple semiconductor chips 420 are bonded to semiconductor wafer 410 in a similar manner to obtain semiconductor device 401. Note that multiple semiconductor chips 420 may be bonded to semiconductor wafer 410 one by one by hybrid bonding, or may be bonded collectively to semiconductor wafer 410 by hybrid bonding.
• At least one of the insulating film 412 of the semiconductor wafer 410 and the insulating film 422 of the semiconductor chip 420 is an insulating film that is a cured product formed by curing the insulating film forming material of the present disclosure. Therefore, it is possible to reduce the difference in linear expansion coefficient between the insulating film and the terminal electrodes such as copper electrodes, and when the terminal electrodes are bonded together, it is possible to suppress poor bonding between the terminal electrodes caused by the difference in linear expansion coefficient between the insulating film and the terminal electrodes.
• the present invention is not limited to this configuration.
• the first electrode and the second electrode may be through electrodes that penetrate the first semiconductor substrate and the second semiconductor substrate.
• the method for manufacturing a semiconductor device according to the present disclosure may be, for example, a method for manufacturing a semiconductor device by using the insulating film-forming material according to the present disclosure in the preparation of at least one of a first organic insulating film and a second organic insulating film, and by carrying out the following steps (1)' to (5)'.
• Step (1)' A first semiconductor substrate is prepared, the first semiconductor substrate having a first substrate body and the first organic insulating film provided on one surface of the first substrate body.
• Step (2)' A second semiconductor substrate is prepared, the second semiconductor substrate having a second substrate body and the second organic insulating film provided on one surface of the second substrate body.
• Step (3)' The second semiconductor substrate is divided into individual pieces to obtain a plurality of semiconductor chips each having the second organic insulating film.
• Step (4)' The first organic insulating film of the first semiconductor substrate and the second organic insulating film of the semiconductor chip are bonded to each other.
• Step (5)' A through hole is provided in a part of the bonded first semiconductor substrate and second semiconductor substrate, and a through electrode is provided in the through hole.
• the method of providing the through holes and the method of providing the through electrodes are not particularly limited.
• the through holes may be provided by etching or the like, and the through electrodes may be provided by electrolytic plating, electroless plating, sputtering or the like.
• polymer A1 This reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor (hereinafter referred to as polymer A1).
• the weight average molecular weight of polymer A1 was determined by gel permeation chromatography (GPC) in terms of standard polystyrene.
• THF tetrahydrofuran
• DMF dimethylformamide
• polymer A2 polyimide precursor A2 (hereinafter referred to as polymer A2).
• the weight average molecular weight of Polymer A2 was determined in the same manner as for Polymer A1. The weight average molecular weight of Polymer A2 was 22,000.
• the obtained insulating film forming material was spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 100°C for 2 minutes, and then dried at 110°C for 2 minutes to form a photosensitive resin film having a dry thickness of 10 to 12 ⁇ m.
• the resulting photosensitive resin film was immersed in cyclopentanone and the developing time was set to twice the time required for the film to be completely dissolved.
• a photosensitive resin film was formed in the same manner as above, and the obtained photosensitive resin film was exposed to light using an i-line stepper NES2WA06 (manufactured by Nikon Corporation) at an exposure dose of 400 mJ/cm 2 .
• the resin film after exposure and baking was paddle-developed in cyclopentanone using Act8 for the above-mentioned developing time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
• PMEA propylene glycol monomethyl ether acetate
• the obtained patterned cured product was observed using an optical microscope, and the resolution was determined as the minimum diameter at which an opening was formed in which 55% or more of the substrate surface was exposed relative to the area of the via mask dimensions.
• the resolution was 30 ⁇ m or less, it was rated A, when the resolution was greater than 30 ⁇ m and less than 50 ⁇ m, it was rated B, and when the resolution was greater than 50 ⁇ m, it was rated C. If it was rated A or B, the resolution result was good.
• Table 1 The results are shown in Table 1.
• the obtained insulating film-forming material was used to form a cured film as follows, and then the thermal expansion coefficient was measured:
• the insulating film-forming material was spin-coated on a Si substrate, and dried by heating on a hot plate at 100° C. for 120 seconds, and then at 110° C. for 120 seconds, to form a resin film having a thickness of about 10 ⁇ m after curing.
• the obtained resin film was cured in a vertical diffusion furnace ⁇ -TF under a nitrogen atmosphere at a curing temperature of 200° C. for 2 hours to obtain a cured product having a film thickness of 10 ⁇ m.
• the obtained cured product was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and peeled off from the Si substrate.
• the obtained cured product was formed into a width of 10 mm using a razor to obtain a patterned cured product having a width of 10 mm.
• TMA tester TMA8310, manufactured by Rigaku Corporation
• the linear thermal expansion coefficient in the in-plane direction of the patterned cured product was measured from 50°C to 100°C under the conditions of an initial sample length of 10 mm, a load of 10 g, and a heating rate of 5°C/min.
• the results are shown in Table 1 as linear expansion coefficient (ppm/K).

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