WO2022070362A1 - 樹脂組成物、半導体装置の製造方法、硬化物及び半導体装置 - Google Patents

樹脂組成物、半導体装置の製造方法、硬化物及び半導体装置 Download PDF

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Publication number
WO2022070362A1
WO2022070362A1 PCT/JP2020/037322 JP2020037322W WO2022070362A1 WO 2022070362 A1 WO2022070362 A1 WO 2022070362A1 JP 2020037322 W JP2020037322 W JP 2020037322W WO 2022070362 A1 WO2022070362 A1 WO 2022070362A1
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Prior art keywords
group
insulating film
resin composition
organic insulating
semiconductor
Prior art date
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Ceased
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PCT/JP2020/037322
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English (en)
French (fr)
Japanese (ja)
Inventor
聡 米田
豊 生田目
智章 柴田
香織 小林
仁 小野関
直也 鈴木
敏央 野中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HD MicroSystems Ltd
Resonac Corp
Original Assignee
Showa Denko Materials Co Ltd
HD MicroSystems Ltd
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Application filed by Showa Denko Materials Co Ltd, HD MicroSystems Ltd filed Critical Showa Denko Materials Co Ltd
Priority to PCT/JP2020/037322 priority Critical patent/WO2022070362A1/ja
Priority to US18/029,102 priority patent/US20240018306A1/en
Priority to JP2022554021A priority patent/JP7853216B2/ja
Priority to KR1020237010875A priority patent/KR20230075457A/ko
Priority to PCT/JP2021/035672 priority patent/WO2022071329A1/ja
Priority to TW110136323A priority patent/TW202229408A/zh
Publication of WO2022070362A1 publication Critical patent/WO2022070362A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08F290/145—Polyamides; Polyesteramides; 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
    • 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
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • 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
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • 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
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • 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
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • 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

  • the present disclosure relates to a resin composition, a method for manufacturing a semiconductor device, a cured product, and a semiconductor device.
  • Non-Patent Document 1 discloses an example of three-dimensional mounting of a semiconductor chip.
  • Patent Document 1 discloses an example of a technique capable of lowering the bonding temperature by using a cyclic olefin resin.
  • SoICTM System on Integrated Chips
  • the heat resistance of the organic material is not sufficient, and the organic material is altered by being exposed to a high temperature at the time of C2W bonding. There is a risk that bonding defects may occur at the interface between the substrate and the insulating film.
  • the present disclosure has been made in view of the above, and a resin composition capable of producing a semiconductor device having an insulating film having excellent heat resistance and suppressing the generation of voids at the bonding interface, and the above-mentioned resin composition were used. It is an object of the present invention to provide a semiconductor device provided with a method for manufacturing a semiconductor device, a cured product obtained by curing the above-mentioned resin composition, and an insulating film in which the generation of voids at a bonding interface is suppressed and the heat resistance is excellent. ..
  • Step (1) A first semiconductor substrate having the first substrate main body and the first organic insulating film and the first electrode provided on one surface of the first substrate main body is prepared.
  • Step (2) A second semiconductor substrate having the second substrate main body, the second organic insulating film provided on one surface of the second substrate main body, and a plurality of second electrodes is prepared.
  • Step (3) The second semiconductor substrate is individualized to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode. do.
  • Step (4) 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.
  • Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined.
  • 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 resin composition according to ⁇ 3>, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E).
  • C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, and an ester bond (—O—).
  • -C ( O)-)
  • R independently represents an alkyl group, an alkoxy group, an alkyl halide group, a phenyl group or a halogen atom
  • n independently represents an integer of 0 to 4, respectively.
  • Sylylene bond (-Si ( RA ) 2- ;
  • the two RAs independently represent a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O- (Si ( RB )). 2 - O-) n ;
  • the two RBs independently represent a hydrogen atom, an alkyl group or a phenyl group, and n represents 1 or an integer of 2 or more) or a combination of at least two divalents. Represents the group of.
  • the monovalent organic group in the R 6 and the 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 content of the (B) solvent is 50 parts by mass to 10000 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor according to any one of ⁇ 1> to ⁇ 6>.
  • Resin composition. ⁇ 8> The solvent according to any one of ⁇ 1> to ⁇ 7>, which comprises at least one selected from the group consisting of the compounds represented by the following formulas (3) to (6). Resin composition.
  • R 1 , R 2 and R 8 are independently alkyl groups having 1 to 4 carbon atoms, and R 3 to R 7 are independently hydrogen atoms or carbons, respectively. It is an alkyl group of the number 1 to 4, s is an integer of 0 to 8, t is an integer of 0 to 4, and r is an integer of 0 to 4.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the cured product obtained by curing the resin composition has a 5% thermogravimetric reduction temperature of 200 ° C. or higher.
  • ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, which further contains (C) a photopolymerization initiator and (D) a polymerizable monomer.
  • ⁇ 13> A through hole for arranging a plurality of terminal electrodes in an organic insulating film provided on one surface of a substrate body by a photolithography method, which is a negative type photosensitive resin composition or a positive type photosensitive resin composition.
  • the resin composition according to any one of ⁇ 1> to ⁇ 12> for use in providing a plurality of the above.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, wherein the cured product obtained by being cured has a tensile elastic modulus of 7.0 GPa or less at 25 ° C.
  • ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 14>, wherein the cured product has a coefficient of thermal expansion of 100 ppm / K or less.
  • the resin composition according to any one of ⁇ 1> to ⁇ 15> is used for producing at least one of the first organic insulating film and the second organic insulating film, and the following steps (1). )-A method for manufacturing a semiconductor device for manufacturing a semiconductor device through the process (5).
  • Step (1) A first semiconductor substrate having a first substrate main body and the first organic insulating film and the first electrode provided on one surface of the first substrate main body is prepared.
  • Step (2) A second semiconductor substrate having the second substrate main body, the second organic insulating film provided on one surface of the second substrate main body, and a plurality of second electrodes is prepared.
  • Step (3) The second semiconductor substrate is individualized to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode. do.
  • Step (4) 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.
  • Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined.
  • the first organic insulating film and the organic insulating film portion are bonded together at a temperature at which the temperature difference between the semiconductor chip and the first semiconductor substrate is within 10 ° C.
  • the thickness of the organic insulating film formed by joining the first organic insulating film and the organic insulating film portion is 0.1 ⁇ m or more in ⁇ 16> or ⁇ 17>.
  • the step (1) includes a step of polishing the one side of the first semiconductor substrate, and the step (2) includes a step of polishing the one side of the second semiconductor substrate.
  • the polishing rate of the first organic insulating film is 0.1 to 5 times the polishing rate of the first electrode, and the polishing rate of the second organic insulating film is the above.
  • ⁇ 20> The method for manufacturing a semiconductor device according to any one of ⁇ 16> to ⁇ 19>, wherein the thickness of the second insulating film is larger than the thickness of the first insulating film.
  • ⁇ 21> The method for manufacturing a semiconductor device according to any one of ⁇ 16> to ⁇ 19>, wherein the thickness of the second insulating film is smaller than the thickness of the first insulating film.
  • ⁇ 22> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 23> A first semiconductor substrate having a first substrate main body, the first organic insulating film provided on one surface of the first substrate main body, and a first electrode.
  • a semiconductor chip having a semiconductor chip substrate main body, an organic insulating film portion provided on one surface of the semiconductor chip substrate main body, and a second electrode.
  • the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded to the first electrode of the first semiconductor substrate and the first electrode of the semiconductor chip.
  • the two electrodes are joined,
  • a resin composition capable of producing a semiconductor device having an insulating film excellent in heat resistance and suppressing the generation of voids at a bonding interface a method for manufacturing a semiconductor device using the above-mentioned resin composition, and the above-mentioned. It is possible to provide a semiconductor device provided with a cured product obtained by curing the resin composition of No. 1 and an insulating film having an insulating film excellent in heat resistance, in which the generation of voids at the bonding interface is suppressed.
  • FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device manufactured by the method for manufacturing a semiconductor device according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing in order a method for manufacturing the semiconductor device shown in FIG.
  • FIG. 3 is a diagram showing in more detail the joining method in the manufacturing method of the semiconductor device shown in FIG.
  • FIG. 4 is a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing steps after the steps 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 a Chip-to-Wafer (C2W).
  • C2W Chip-to-Wafer
  • a or B may include either A or B, and may include both.
  • the term “process” includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
  • the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. ..
  • each component may contain a plurality of applicable substances.
  • the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
  • the term "layer” or “membrane” is used only in a part of the region, in addition to the case where the layer or the membrane is formed in the entire region when the region is observed. The case where it is formed is also included.
  • the thickness of the layer or film is a value given as an arithmetic mean value obtained by measuring the thickness of five points of the target layer or film.
  • the thickness of the layer or the film can be measured using a micrometer or the like. In the present disclosure, if the thickness of the layer or membrane can be directly measured, it is measured using a micrometer.
  • the measurement may be performed by observing the cross section of the measurement target using an electron microscope.
  • the "(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 resin composition of the present disclosure contains (A) a polyimide precursor and (B) a solvent, and is a first organic insulating film in a method for manufacturing a semiconductor device including the following steps (1) to (5). And a resin composition for use in producing at least one insulating film of the second organic insulating film.
  • a first semiconductor substrate having the first substrate main body and the first organic insulating film and the first electrode provided on one surface of the first substrate main body is prepared.
  • Step (2) A second semiconductor substrate having the second substrate main body, the second organic insulating film provided on one surface of the second substrate main body, and a plurality of second electrodes is prepared.
  • Step (3) The second semiconductor substrate is individualized to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode. And the process to do Step (4) 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. Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined. Specific examples of each of the above-mentioned steps (1) to (5) will be described in the section of the method for manufacturing a semiconductor device described later.
  • the insulating film which is a cured product obtained by curing a resin composition containing a polyimide precursor, has a lower elastic modulus and is softer than a molded product made of an inorganic material. Therefore, when foreign matter or the like is present on the surface of the first organic insulating film or the surface of the second organic insulating film when the first organic insulating film and the second organic insulating film, one of which is the insulating film, are bonded together. Even if the insulating film is present, the insulating film at the bonding interface is easily deformed, and foreign matter can be included in the insulating film without forming large voids in the insulating film.
  • the cured product obtained by curing the resin composition containing the polyimide precursor has higher heat resistance than the cured product obtained by curing the resin composition containing acrylic resin, epoxy resin and the like.
  • the resin composition of the present disclosure is excellent in reliability in the manufacturing process of the semiconductor device and can realize a high yield.
  • Modifications of the resin composition of the present disclosure include (A) a polyimide precursor and (B) a solvent, and are used for producing a cured product which is polished together with an electrode by a chemical mechanical polishing (CMP) method. It may be a resin composition for use.
  • CMP chemical mechanical polishing
  • the modified resin composition when the electrode made of a metal such as copper and the insulating film which is a cured product obtained by curing the resin composition are polished by the CMP method, the thickness of the electrode and the insulating film are used. It is easy to adjust the thickness of the material.
  • the surface of the insulating film can be easily adjusted to a position slightly lower than the surface of the electrode, and preferably the height difference between the surface of the insulating film and the surface of the electrode can be easily adjusted to 1 nm to 50 nm. Therefore, the modified resin composition has excellent CMP adaptability.
  • the 5% thermogravimetric reduction temperature of the cured product obtained by curing the resin composition of the present disclosure is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, from the viewpoint of heat resistance of the cured product. Further, the upper limit of the 5% thermogravimetric reduction temperature of the cured product is not particularly limited, and may be, for example, 450 ° C. or lower.
  • the 5% thermogravimetric reduction temperature of the cured product is measured as follows. First, the resin composition is heated at 375 ° C. for 1 hour or more in a nitrogen atmosphere to obtain a cured product. 10 mg of the obtained cured product was placed in a thermogravimetric measuring device (for example, TGA-50 manufactured by Shimadzu Corporation), and the temperature was raised from 25 ° C. to 500 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere, and the weight was increased. The temperature at which the temperature is reduced by 5% from that before the temperature rise is defined as the 5% thermogravimetric reduction temperature.
  • a thermogravimetric measuring device for example, TGA-50 manufactured by Shimadzu Corporation
  • the glass transition temperature of the cured product obtained by curing the resin composition of the present disclosure is preferably 100 ° C. to 400 ° C., more preferably 150 ° C. to 350 ° C. from the viewpoint of bonding at a low temperature.
  • the glass transition temperature of the cured product is measured as follows. First, the resin composition is heated at 375 ° C. for 2 hours in a nitrogen atmosphere to obtain a cured product. The obtained cured product is cut to prepare a rectangular body of 5 mm ⁇ 50 mm ⁇ 3 mm, and a dynamic viscoelasticity measuring device (for example, manufactured by TA Instrument, RSA-G2) is used with a tensile jig, and the frequency is 1 Hz. The dynamic viscoelasticity is measured in the temperature range of 50 ° C. to 350 ° C. under the condition of heating rate: 5 ° C./min.
  • the glass transition temperature (Tg) is the temperature of the peak top portion in tan ⁇ obtained from the ratio of the storage elastic modulus and the loss elastic modulus obtained by the above method.
  • a dynamic viscoelastic modulus with respect to a storage elastic modulus at a temperature 100 ° C. lower than the glass transition temperature (Tg) of the cured product obtained by dynamic viscoelasticity measurement is performed.
  • the ratio of the storage elastic modulus at a temperature 100 ° C. higher than the glass transition temperature (Tg) of the obtained cured product is preferably 0.005 to 0.02.
  • the method for measuring the storage elastic modulus can be measured by the method described in the description of the method for measuring the glass transition temperature.
  • the resin composition of the present disclosure may be a negative type photosensitive resin composition or a positive type photosensitive resin composition. Further, in the negative type photosensitive resin composition or the positive type photosensitive resin composition, a plurality of terminal electrodes are arranged on the first organic insulating film provided on one surface of the first substrate main body in the step (1). A plurality of through holes for arranging a plurality of terminal electrodes in the second organic insulating film provided on one surface of the second substrate main body in the step (2). It may be used for at least one of the provisions.
  • the resin composition of the present disclosure is cured from the viewpoint of more preferably reducing bonding defects by including the foreign substances in the insulating film without further forming large voids when the foreign substances adhere to the bonding interface.
  • the tensile elastic modulus of the cured product at 25 ° C. is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, further preferably 3.0 GPa or less, and 2.0 GPa or less. It is particularly preferable, and it is even more preferable that it is 1.5 GPa or less.
  • the cured product obtained by curing the resin composition of the present disclosure has a lower tensile elastic modulus than an inorganic material such as silicon dioxide (SiO 2 ). In the present disclosure, the tensile modulus is a value measured at 25 ° C. based on JIS K 7161 (1994).
  • the storage elastic modulus at 300 ° C. may be 0.5 GPa to 0.001 GPa or 0.1 GPa to 0.01 GPa.
  • the coefficient of thermal expansion of the cured product obtained by curing is preferably 100 ppm / K or less, and more preferably 70 ppm / K or less.
  • the coefficient of thermal expansion of the insulating film, which is a cured product, and the coefficient of thermal expansion of the electrodes are equal to or close to each other. Damage to the semiconductor device due to the difference in the coefficient of thermal expansion from the above can be suppressed.
  • the coefficient of thermal expansion indicates the rate at which the length of the cured product expands due to temperature rise per temperature, and the amount of change in the length of the cured product from 100 ° C to 150 ° C is measured using a thermomechanical analyzer or the like. It can be calculated by doing.
  • the resin composition of the present disclosure contains (A) a polyimide precursor (hereinafter, also referred to as “component (A)”).
  • component (A) is preferably a polyimide precursor capable of producing a cured product exhibiting high properties (for example, heat resistance), and as such a polyimide precursor, a polyimide precursor having a polymerizable unsaturated bond. It is preferable to include.
  • the component (A) contained in the resin composition is preferably a component that does not cause a problem in a polishing step, a bonding step, or the like.
  • the (A) polyimide precursor means a compound corresponding to either a polyamic acid or a compound in which the hydrogen atom of at least a part of the carboxy group in the polyamic acid is replaced with a monovalent organic group.
  • the component (A) preferably contains a compound having a structural unit represented by the following general formula (1). As a result, there is a tendency to obtain a semiconductor device having an insulating film showing high reliability.
  • X represents a tetravalent organic group and Y represents a divalent organic group.
  • R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group.
  • the polyimide precursor may have a plurality of structural units represented by the above general formula (1), and X, Y, R 6 and R 7 in the plurality of structural units may be the same or different. May be.
  • the combination of R 6 and R 7 is not particularly limited as long as they are independently hydrogen atoms or monovalent organic groups.
  • 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 later, 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 further preferably 6 to 12 carbon atoms. ..
  • the tetravalent organic group represented by X may contain an aromatic ring.
  • the aromatic ring include an aromatic hydrocarbon group (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), an aromatic heterocyclic group (for example, the number of atoms constituting the heterocycle is 5 to 20), and the like. 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, a phenanthrene ring and the like.
  • each aromatic ring may have a substituent or may be unsubstituted.
  • substituent of the aromatic ring include an alkyl group, a fluorine atom, an alkyl halide group, a hydroxyl group, an amino group and the like.
  • the tetravalent organic group represented by X contains a benzene ring
  • the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, and preferably contains 1 to 3 benzene rings.
  • each benzene ring may be linked by a single bond, or may be an alkylene group, a halogenated alkylene group, a carbonyl group, or a sulfonyl group.
  • siloxane bond (-O- (Si (RB) 2 - O-) n ;
  • the two RBs independently represent a hydrogen atom, an alkyl group or a phenyl group, where n is 1 or an integer of 2 or more. It may be bonded by a linking group such as), a composite linking group in which at least two of these linking groups are combined, or the like.
  • the two benzene rings may be bonded at two points by at least one of a single bond and a linking group to form a 5-membered ring or a 6-membered ring containing a linking group between the two benzene rings.
  • the -COOR 6 group and the -CONH- group are in the ortho position with each other, and the -COOR 7 group and the -CO- group are preferably in the ortho position with each other.
  • tetravalent organic group represented by X include groups represented by the following formulas (A) to (F).
  • the group represented by the following formula (E) is preferable, and the group represented by the following formula (E) is represented by C. 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. The present disclosure is not limited to the following specific examples.
  • a and B are each independently a divalent group that is not coupled to a single bond or benzene ring. However, both A and B are not single bonds. Divalent groups that are not conjugated to the benzene ring include methylene group, methylene halide group, methylmethylene halide group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), and silylene bond.
  • (-Si ( RA ) 2- each of the two RAs independently represents a hydrogen atom, an alkyl group or a phenyl group
  • a and B are independently preferable to have a methylene group, a bis (trifluoromethyl) methylene group, a difluoromethylene group, an ether bond, a sulfide bond and the like, and an ether bond is more preferable.
  • C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, and an ester bond (—O—).
  • -C ( O)-)
  • C (Si (RB) 2 - O-) n ;
  • the two RBs 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.
  • C preferably contains an ether bond, and is preferably an ether bond. Further, C may have a structure represented by the following formula (C1).
  • the alkylene group represented by C in the 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 having 1 carbon atom. Alternatively, it is more preferably 2 alkylene groups.
  • alkylene group represented by C in the formula (E) include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a 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,
  • the halogenated alkylene group represented by C in the formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 5 carbon atoms. It is preferable that it is a halogenated alkylene group having 1 to 3 carbon atoms.
  • the halogenated alkylene group represented by C in the formula (E) at least one hydrogen atom contained in the alkylene group represented by C in the above formula (E) is a fluorine atom, a chlorine atom or the like. Examples thereof include an alkylene group substituted with a halogen atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group and the like are preferable.
  • the alkyl group represented by RA or RB contained in the silylene bond or the 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 an alkyl group having 1 or 2 carbon atoms is further preferable.
  • Specific examples of the alkyl group represented by RA or RB 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. Can be mentioned.
  • the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 12 to 18 carbon atoms. ..
  • the divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group.
  • a divalent aromatic hydrocarbon group for example, the number of carbon atoms constituting the aromatic ring is 6 to 20
  • a divalent aromatic heterocyclic group for example, forming a heterocycle
  • the number of atoms is 5 to 20) and the like, and a divalent aromatic hydrocarbon group is preferable.
  • divalent aromatic group represented by Y include groups represented by the following formulas (G) to (I).
  • the group represented by the following formula (H) is preferable, and the group represented by the following formula (H) is represented by D from the viewpoint of obtaining an insulating film having excellent flexibility and more suppressed generation of voids at the bonding interface. Is more preferably a group containing an ether bond, and even more preferably an ether bond.
  • R independently represents an alkyl group, an alkoxy group, an alkyl halide group, a phenyl group or a halogen atom
  • n independently represents an integer of 0 to 4, respectively.
  • D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, and an ester bond (—O—).
  • D may have a structure represented by the above formula (C1).
  • the specific example of D in the formula (H) is the same as the specific example of C in the formula (E).
  • the D in the 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, and the like.
  • the alkyl group represented by R in the formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. , It is more preferably an alkyl group having 1 or 2 carbon atoms.
  • Specific examples of the alkyl group represented by R in the formulas (G) to (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an s-butyl group. Examples thereof include a t-butyl group.
  • the alkoxy group represented by R in the formulas (G) to (I) is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. , It is more preferable that it is an alkoxy group having 1 or 2 carbon atoms.
  • Specific examples of the alkoxy group represented by R in the formulas (G) to (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group and an s-butoxy group. , T-butoxy group and the like.
  • the alkyl halide group represented by R in the formulas (G) to (I) is preferably an alkyl halide group having 1 to 5 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. It is more preferable that it is an alkyl halide group having 1 or 2 carbon atoms.
  • the halogenated alkyl group represented by R in the formulas (G) to (I) at least one hydrogen atom contained in the alkyl group represented by R in the formulas (G) to (I).
  • examples thereof include an alkyl group substituted with a halogen atom such as a fluorine atom and a chlorine atom.
  • a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group and the like are preferable.
  • n in the formulas (G) to (I) is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0, respectively.
  • 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. The basics of.
  • 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 carbon. More preferably, it is an alkylene group having a number of 1 to 10.
  • Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a 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, 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 and a cyclohexylene group.
  • the alkylene oxide structure having 1 to 10 carbon atoms is preferable, the alkylene oxide structure having 1 to 8 carbon atoms is more preferable, and the alkylene oxide structure having 1 to 8 carbon atoms is more preferable.
  • the alkylene oxide structure of 1 to 4 is more preferable.
  • the polyethylene oxide structure or the polypropylene oxide structure is preferable as the polyalkylene oxide structure.
  • the alkylene group in the alkylene oxide structure may be linear or branched.
  • the unit structure in the polyalkylene oxide structure may be one kind or two or more kinds.
  • 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 thereof include a divalent group having a polysiloxane structure.
  • Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and an n-.
  • Examples thereof include an octyl group, a 2-ethylhexyl group and an n-dodecyl group. Among these, a methyl group is preferable.
  • the aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of the substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, a hydroxy group and the like. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, a benzyl group and the like.
  • 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 kind or two or more kinds.
  • the silicon atom constituting the divalent group having a polysiloxane structure represented by Y is an NH group in the general formula (1) via an alkylene group such as a methylene group and an ethylene group and an arylene group such as a phenylene group. May be combined with.
  • the group represented by the formula (I) is preferably a group represented by the following formula (I').
  • R independently represents an alkyl group, an alkoxy group, an alkyl halide 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 the general formula (1) is not particularly limited.
  • X is a group represented by the formula (E) and Y is represented by the formula (H).
  • R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, and is a group represented by the following general formula (2), an ethyl group, or the like. It is more preferably either an isobutyl group or a t-butyl group, further preferably containing an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and the following general formula. It is particularly preferable to include the group represented by (2).
  • the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), so that the i-ray transmittance is high and even when cured at a low temperature of 400 ° C. or lower. It tends to form a good cured product.
  • the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like, and among them, an ethyl group and an ethyl group. Isobutyl groups 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 the 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 the like, and a methyl group is preferable.
  • R 8 to R 10 in the general formula (2) a combination of R 8 and R 9 is a hydrogen atom, and R 10 is a hydrogen atom or a methyl group is preferable.
  • R x in the 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 a linear or branched alkylene group.
  • the number of carbon atoms in Rx 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 general formula (2), and both R 6 and R 7 are in the general formula (2). It is more preferable that it is a group represented.
  • the component (A) contains a compound having a structural unit represented by the above-mentioned general formula (1), it is represented by the general formula (2) with respect to the total of R 6 and R 7 of all structural units contained in the compound.
  • the ratio of R 6 and R 7 to be formed is preferably 60 mol% or more, more preferably 70 mol% or more, still 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 the 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, and q represents an integer of 1 to 10.
  • Q in the general formula (2') 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 with respect to all the structural units. 70 mol% or more is more preferable, and 80 mol% or more is further preferable.
  • the upper limit of the above-mentioned content rate is not particularly limited, and may be 100 mol%.
  • the component (A) may be synthesized by 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.
  • the component (A) may be synthesized using tetracarboxylic dianhydride instead of tetracarboxylic dianhydride.
  • tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride.
  • diamine compound examples include 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-.
  • a compound having a structural unit represented by the general formula (1) and having at least one of R 6 and R 7 in the general formula (1) being a monovalent organic group is, for example, the following general formula (8).
  • the tetracarboxylic acid dianhydride represented by (1) and the compound represented by R-OH are reacted in an organic solvent such as N-methyl-2-pyrrolidone to form a diester derivative, and then the diester derivative and H2N are obtained.
  • the diamine compound represented by Y-NH 2 is subjected to a condensation reaction, or the tetracarboxylic acid dianhydride is reacted with the diamine compound represented by H2N -Y-NH 2 in an organic solvent.
  • a polyamic acid it can be obtained by obtaining a polyamic acid, adding a compound represented by R-OH, reacting in an organic solvent, and introducing an ester group.
  • Y in the diamine compound represented by H 2 N Y—NH 2 is the same as Y in the 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 preferable examples are the same as in the case of R 6 and R 7 in the general formula (1).
  • the tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H2NY — NH2 , and the compound represented by R—OH may be used alone. Often, two or more types may be combined.
  • the above-mentioned compound contained in the component (A) is obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then thionyl chloride or the like. It can be obtained by reacting the chlorinating agent of the above to convert it into an acid chloride, and then reacting the diamine compound represented by H2NY-NH 2 with the acid chloride.
  • the above-mentioned compound contained in the component (A) is prepared as a diester derivative by allowing a compound represented by R-OH to act on a tetracarboxylic acid dianhydride represented by the following general formula (8) to obtain a carbodiimide compound.
  • the above-mentioned compound contained in the component (A) is a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a diamine compound represented by H2NY - NH2 . Then, the polyamic acid is isoimided in the presence of trifluoroacetic anhydride, and then a compound represented by R-OH is allowed to act on the polyamic acid.
  • a compound represented by R-OH is allowed to act on a part of the tetracarboxylic acid dianhydride in advance to partially esterify the tetracarboxylic acid dianhydride and H2NY - NH2 . You may react with the diamine compound which is made.
  • X is the same as the X in the general formula (1), and the specific example and the preferable example are also the same.
  • Examples of the compound represented by R—OH used for the synthesis of the above-mentioned compound contained in the component (A) include a compound in which a hydroxy group is bonded to R x of the group represented by the general formula (2), and a general formula (A). It may be a compound in which a hydroxy group is bonded to a terminal methylene group of the group represented by 2').
  • 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, and acrylic.
  • Examples thereof include 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like. Among them, 2 hydroxyacrylate. -Hydroxyethyl and 2-hydroxyethyl acrylate are preferred.
  • the molecular weight of the component (A) is not particularly limited, and for example, the weight average molecular weight is preferably 10,000 to 200,000, more preferably 10,000 to 100,000.
  • the weight average molecular weight can be measured, for example, by a gel permeation chromatography method and can be determined by conversion using a standard polystyrene calibration curve.
  • the resin composition of the present disclosure may contain a resin component other than the component (A).
  • the resin composition of the present disclosure includes a polyimide resin, a novolak resin, an acrylic resin, a polyether nitrile resin, a polyether sulfone resin, an epoxy resin, a polyethylene terephthalate resin, a polyethylene naphthalate resin, and a polyvinyl chloride. It may contain other resins such as resins. Other resins may be used alone or in combination of two or more.
  • the content of the component (A) with respect to the total amount of the resin component is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 90% by mass. It is more preferably% to 100% by mass.
  • the resin composition of the present disclosure contains (B) a solvent (hereinafter, also referred to as “component (B)”).
  • component (B) contains, for example, at least one selected from the group consisting of the compounds represented by the following formulas (3) to (6) from the viewpoint of reducing the reproductive toxicity and environmental load of the resin composition. Is preferable.
  • R 1 , R 2 and R 8 are independently alkyl groups having 1 to 4 carbon atoms, and R 3 to R 7 are independently hydrogen atoms or carbons, respectively. It is an alkyl group of the number 1 to 4. s is an integer of 0 to 8, t is an integer of 0 to 4, and r is an integer of 0 to 4.
  • the alkyl group having 1 to 4 carbon atoms of 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 of 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 of R 4 and R 5 is preferably a methyl group or an ethyl group.
  • the alkyl group having 1 to 4 carbon atoms of 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 component (B) may be, for example, at least one of the compounds represented by the formulas (4), (5) and (6), or may be a compound represented by the formula (5). ..
  • component (B) include the following compounds.
  • the component (B) contained in the resin composition of the present disclosure is not limited to the above-mentioned compound, and may be another solvent.
  • the component (B) may be a solvent for esters, a solvent for ethers, a solvent for ketones, a solvent for hydrocarbons, a solvent for aromatic hydrocarbons, a solvent for sulfoxides, and the like.
  • Ester solvents 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, and ⁇ -butyrolactone.
  • ⁇ -caprolactone, ⁇ -valerolactone methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate and other alkyl alkoxyacetates (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate and ethyl ethoxyacetate), 3-alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxypropionate).
  • 3-alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
  • 2-alkoxypropionate alkyl esters such as ethyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, etc.)
  • Methyl 2-alkoxy-2-methylpropionate, 2-ethoxy-2 such as propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate), methyl 2-methoxy-2-methylpropionate, etc.
  • -Ethyl 2-alkoxy-2-methylpropionate such as ethyl methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. Can be mentioned.
  • ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene.
  • examples thereof include glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • Examples of the solvent for the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone (NMP) and the like.
  • Examples of the hydrocarbon solvent include limonene and the like.
  • Examples of the solvent for aromatic hydrocarbons include toluene, xylene, anisole and the like.
  • Examples of the solvent for sulfoxides include dimethyl sulfoxide and the like.
  • Examples of the solvent for the component (B) include ⁇ -butyrolactone, cyclopentanone, ethyl lactate and the like.
  • the content of NMP may be 1% by mass or less with respect to the total amount of the resin composition, and may be the total amount of the component (A). On the other hand, it may be 3% by mass or less.
  • the content of the component (B) is preferably 50 parts by mass to 10000 parts by mass with respect to 100 parts by mass of the component (A).
  • the component (B) is at least one solvent (1) selected from the group consisting of compounds represented by the formulas (3) to (6), as well as a solvent for esters, a solvent for ethers, and a solvent for ketones.
  • At least one of the solvent (2) which is at least one selected from the group consisting of a solvent for hydrocarbons, a solvent for aromatic hydrocarbons, and a solvent for sulfoxides.
  • the content of the solvent (1) may be 5% by mass to 100% by mass or 5% by mass to 50% by mass with respect to 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, or 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the component (A). It may be 50 parts by mass.
  • the resin composition of the present disclosure preferably further contains (C) a photopolymerization initiator and (D) a polymerizable monomer (hereinafter, also referred to as (C) component and (D) component, respectively). Further, the resin composition of the present disclosure may further contain (E) a thermal polymerization initiator (hereinafter, also referred to as a component (E)).
  • C photopolymerization initiator
  • D polymerizable monomer
  • E a thermal polymerization initiator
  • the resin composition of the present disclosure preferably contains (C) a photopolymerization initiator.
  • component (C) examples include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Mihiler ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-.
  • Benzoin derivatives such as methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, propyl benzoin; 1-phenyl-1,2-butandion-2- (O-methoxycarbonyl) oxime, 1-phenyl-1, 2-Phenyldione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- ( O-benzoyl) oxime, 1,3-diphenylpropantrion-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrion-2- (O-benzoyl) oxime, 1,2-octanedione, Oxym derivatives such as 1- [4- (phenylthio) pheny
  • the content of the component (C) is 0. 1 part by mass to 20 parts by mass is preferable, 0.1 part by mass to 10 parts by mass is more preferable, and 0.1 part by mass to 6 parts by mass is further preferable.
  • the resin composition of the present disclosure may contain an antireflection agent that suppresses reflected light from the substrate direction from the viewpoint of improving the photosensitive characteristics.
  • the resin composition of the present disclosure preferably contains (D) a polymerizable monomer.
  • the component (D) preferably has at least one group containing a polymerizable unsaturated double bond, and contains at least a (meth) acrylic group from the viewpoint that it can be suitably polymerized when used in combination with a photopolymerization initiator. It is more preferable to have one. From the viewpoint of improving the crosslink density and the photosensitivity, it is preferable to have 2 to 6 groups containing a polymerizable unsaturated double bond, and more preferably 2 to 4 groups.
  • the polymerizable monomer may be used alone or in combination of two or more.
  • the polymerizable monomer having a (meth) acrylic group is not particularly limited, and for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol diacrylate.
  • the polymerizable monomer other than the polymerizable monomer having a (meth) acrylic group is not particularly limited, and is, for example, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N. , N-dimethylacrylamide and N-methylolacrylamide.
  • the component (D) is not limited to a compound having a group containing a polymerizable unsaturated double bond, and may be a compound having a polymerizable group (for example, an oxylan ring) other than the unsaturated double bond group. ..
  • the content of the component (D) is not particularly limited, and may be 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 1 part by mass to 75 parts by mass, more preferably 1 part by mass to 50 parts by mass.
  • the resin composition of the present disclosure preferably contains (E) a thermal polymerization initiator from the viewpoint of improving the physical properties of the cured product.
  • component (E) examples include a ketone peroxide such as methyl ethyl ketone peroxide, 1,1-di (t-hexyl peroxide) -3,3,5-trimethylcyclohexane, and 1,1-di (t-hexyl peroxide).
  • a ketone peroxide such as methyl ethyl ketone peroxide, 1,1-di (t-hexyl peroxide) -3,3,5-trimethylcyclohexane, and 1,1-di (t-hexyl peroxide).
  • Cyclohexane, peroxyketal such as 1,1-di (t-butylperoxy) cyclohexane, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, p-menthan hydroperoxide, diisopropylbenzenehydroperoxide Hydroperoxides such as, dicumyl peroxides, dialkyl peroxides such as di-t-butyl peroxides, diacyl peroxides such as dilauroyl peroxides and dibenzoyl peroxides, di (4-t-butylcyclohexyl) peroxydicarbonates, di (2-).
  • peroxyketal such as 1,1-di (t-butylperoxy) cyclohexane, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, p-menthan hydroperoxide, diisopropylbenz
  • Ethylhexyl) Peroxydicarbonate such as peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate, 1,1,3,3- Examples thereof include peroxyesters such as tetramethylbutylperoxy-2-ethylhexanoate and bis (1-phenyl-1-methylethyl) peroxides.
  • the thermal polymerization initiator may be used alone or in combination of two or more.
  • the content of the component (E) may be 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor. It may be 5 parts by mass to 15 parts by mass, or 5 parts by mass to 10 parts by mass.
  • the resin composition 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 a radical polymerization inhibitor, a radical polymerization inhibitor and the like.
  • component (F) examples include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-.
  • Examples thereof include 2-naphthylamine, cuperon, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosoamines and the like.
  • the polymerization inhibitor may be used alone or in combination of two or more. By combining two or more polymerization inhibitors, it tends to be easy to adjust the photosensitive characteristics due to the difference in reactivity.
  • the content of the component (F) is 100 parts by mass of the component (A) from the viewpoint of storage stability of the resin composition and heat resistance of the obtained cured product.
  • it is preferably 0.01 part by mass to 30 parts by mass, more preferably 0.01 part by mass to 10 parts by mass, and further preferably 0.05 part by mass to 5 parts by mass. ..
  • the resin composition of the present disclosure may further contain an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor or a nitrogen-containing compound.
  • the resin composition of the present disclosure may contain an antioxidant from the viewpoint of suppressing deterioration of adhesiveness by capturing oxygen radicals and peroxide radicals generated by high temperature storage, reflow treatment and the like. Since the resin composition of the present disclosure contains an antioxidant, it is possible to suppress the oxidation of the electrode during the insulation reliability test.
  • antioxidants include N, N'-bis [2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy] ethyl] oxamid, N, N'-.
  • the content of the antioxidant is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A), and 0. It is more preferably 1 part by mass to 10 parts by mass, and further preferably 0.1 part by mass to 5 parts by mass.
  • the resin composition of the present disclosure may contain a coupling agent.
  • the coupling agent reacts with the component (A) to crosslink, or the coupling agent itself polymerizes. Thereby, there is a tendency that the adhesiveness between the obtained cured product and the substrate can be further improved.
  • the coupling agent are not particularly limited.
  • the coupling agent 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] phthalamide acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzen
  • Ring agents such as aluminumtris (ethylacetacetate), aluminumtris (acetylacetonate), ethylacetacetate aluminum diisopropylate; and the like.
  • the coupling agent may be used alone or in combination of two or more.
  • the content of the coupling agent is preferably 0.1 part by mass to 20 parts by mass, preferably 0.3 parts by mass with respect to 100 parts by mass of the component (A). Up to 10 parts by mass is more preferable, and 1 part by mass to 10 parts by mass is further preferable.
  • the resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent.
  • a surfactant and a leveling agent By containing at least one of a surfactant and a leveling agent in the resin composition, coatability (for example, suppression of striation (unevenness of film thickness)), improvement of adhesiveness, compatibility of compounds in the resin composition, etc. are improved. 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 surfactant and the leveling agent may be used alone or in combination of two or more.
  • the total content of the surfactant and the leveling agent is 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the component (A). It is preferably by mass, more preferably 0.05 parts to 5 parts by mass, and even more preferably 0.05 parts by mass to 3 parts by mass.
  • the resin composition of the present disclosure may contain a rust inhibitor from the viewpoint of suppressing corrosion of metals such as copper and copper alloys and from the viewpoint of suppressing discoloration of the metal.
  • a rust preventive agent include azole compounds and purine derivatives.
  • azole compound examples include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-.
  • purine derivative examples include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, and the like.
  • the rust inhibitor may be used alone or in combination of two or more.
  • the content of the rust preventive is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 1 part by mass to 5 parts by mass, and further preferably 0.5 part by mass to 3 parts by mass.
  • the content of the rust inhibitor is 0.1 part by mass or more, discoloration of the surface of copper or copper alloy is suppressed when the resin composition of the present disclosure is applied on the surface of copper or copper alloy. Will be done.
  • the resin composition of the present disclosure may contain a nitrogen-containing compound from the viewpoint of promoting the imidization reaction of the component (A) to obtain a highly reliable cured product.
  • nitrogen-containing compound examples include 2- (methylphenylamino) ethanol, 2- (ethylanilino) ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, and N-.
  • the nitrogen-containing compound may be used alone or in combination of two or more.
  • the nitrogen-containing compound preferably contains a compound represented by the following formula (17).
  • R 31A to R 33A are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups, monovalent aliphatic hydrocarbon groups having a hydroxy group, or monovalent aromatic groups. Yes, at least one (preferably one) of R 31A to R 33A is a monovalent aromatic group.
  • R 31A to R 33A may form a ring structure between adjacent groups. 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 and a phenyl group.
  • the hydrogen atom of the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than the 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. It is preferably a family group.
  • the monovalent aliphatic hydrocarbon group of R 31A to R 33A preferably has 1 to 10 carbon atoms, and 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 has one or more hydroxy groups bonded to the monovalent aliphatic hydrocarbon group of R 31A to R 33A . It is preferably a group to which one to three hydroxy groups are bonded, and more preferably. Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a methylol group and a hydroxyethyl group, and among them, a hydroxyethyl group is preferable.
  • Examples of the monovalent aromatic group of R 31A to R 33A of the formula (17) include a monovalent aromatic hydrocarbon group, a monovalent aromatic heterocyclic group and the like, and a monovalent aromatic hydrocarbon. Groups are preferred.
  • the monovalent aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, and 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 group of R 31A to R 33A of the formula (17) may have a substituent.
  • a group similar to the group can be mentioned.
  • the content of the nitrogen-containing compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A), and is stable in storage. From the viewpoint of sex, it is more preferably 0.3 parts by mass to 15 parts by mass, and further preferably 0.5 part by mass to 10 parts by mass.
  • the resin composition of the present disclosure contains a component (A) and a component (B), and if necessary, a component (C) to a component (F), an antioxidant, a coupling agent, a surfactant, a leveling agent, and an anti-corrosion agent. It may contain a rust agent, a nitrogen-containing compound and the like, and may contain other components and unavoidable impurities as long as the effects of the present disclosure are not impaired. For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the resin composition of the present disclosure.
  • component and (B) component At least one selected from the group consisting of components (A) to (F) and antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors and nitrogen-containing compounds. It may consist of.
  • the semiconductor device of the present disclosure includes a first semiconductor substrate having a first substrate main body, the first organic insulating film and a first electrode provided on one surface of the first substrate main body, a semiconductor chip substrate main body, and the above.
  • a semiconductor chip having an organic insulating film portion provided on one surface of a semiconductor chip substrate main body and a second electrode is provided, and the first organic insulating film of the first semiconductor substrate and the organic insulating film of the semiconductor chip are provided.
  • the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined to each other, and at least one of the first organic insulating film and the organic insulating film portion is present. It is a semiconductor device which is an insulating film obtained by curing the disclosed resin composition.
  • 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 obtained by curing the resin composition of the present disclosure, the semiconductor device of the present disclosure suppresses the generation of voids at the bonding interface of the insulating film. And has excellent heat resistance of the insulating film. Further, the semiconductor device of the present disclosure is manufactured through steps (1) to (5).
  • a semiconductor device is manufactured using the resin composition of the present disclosure. Specifically, a semiconductor device can be manufactured by going through steps (1) to (5) using the resin composition of the present disclosure.
  • the cured product of the present disclosure is obtained by curing the resin composition of the present disclosure.
  • the cured product is used, for example, as an insulating film for a semiconductor device.
  • FIG. 1 is a cross-sectional view schematically showing an example of the semiconductor device of the present disclosure.
  • the semiconductor device 1 is an example of a semiconductor package, for example, a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar portion 30, and a rewiring 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 has a three-dimensional mounting structure in which the second semiconductor chip 20 is mounted downward. There is.
  • the second semiconductor chip 20 is a semiconductor chip such as an LSI or a memory, and is a chip component having a smaller area in a plan view than the first semiconductor chip 10.
  • the second semiconductor chip 20 is Chip-to-Chip (C2C) bonded to the back surface of the first semiconductor chip 10.
  • the first semiconductor chip 10 and the second semiconductor chip 20 are finely bonded to each other by hybrid bonding, which will be described in detail later, so that the respective terminal electrodes and the insulating films around them are firmly and without displacement.
  • the pillar portion 30 is a connecting 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 to the lower surface of the pillar portion 30.
  • the plurality of pillars 31 may have a cylindrical shape having a diameter of 3 ⁇ m or more and 20 ⁇ m or less (in one example, a diameter of 5 ⁇ m), or may be arranged so that the distance between the centers of the pillars 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) in which a hole is made in a mold and soldered.
  • the pillar portion 30 has, for example, a thickness similar to that of the second semiconductor chip 20, and is arranged on the lateral side of the second semiconductor chip 20 in the horizontal direction.
  • a plurality of solder balls may be arranged in place 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 having a terminal pitch conversion function, which is a function of the package substrate, and is made of polyimide, copper wiring, or the like on the insulating film under the second semiconductor chip 20 and on the lower surface of the pillar portion 30. It is a layer in which a rewiring pattern is formed.
  • the rewiring layer 40 is formed in a state where the first semiconductor chip 10, the second semiconductor chip 20, and the like are turned upside down (see (d) in FIG. 4).
  • the rewiring layer 40 electrically connects the terminal electrode on the lower surface of the second semiconductor chip 20 and the terminal electrode of the first semiconductor chip 10 via the pillar portion 30 to the terminal electrode 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 rewiring layer 40 and the substrate 50, an inorganic interposer or the like is used between the rewiring layer 40 and the substrate 50 to electrically connect the rewiring layer 40 and the substrate 50. You may make a connection.
  • the circuit board 60 mounts the first semiconductor chip 10 and the second semiconductor chip 20 on it, and is electrically connected to the substrate 50 connected to the first semiconductor chip 10, the second semiconductor chip 20, the electronic component 51, and the like. It is a substrate having a plurality of through electrodes to be formed inside.
  • the terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 are electrically connected to the terminal electrodes 61 provided on the back surface of the circuit board 60 by the plurality of through electrodes.
  • FIG. 2 is a diagram showing in order a method for manufacturing the semiconductor device shown in FIG.
  • FIG. 3 is a diagram showing in more detail the bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in FIG. 2.
  • FIG. 4 is a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing steps after the steps shown in FIG. 2 in order.
  • the semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n).
  • B A step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20.
  • C A step of polishing the first semiconductor substrate 100.
  • D A step of polishing the second semiconductor substrate 200.
  • E A step of disassembling the second semiconductor substrate 200 and acquiring a plurality of semiconductor chips 205.
  • F A step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with respect to the terminal electrodes 103 of the first semiconductor substrate 100.
  • (G) A step of bonding the insulating film 102 of the first semiconductor substrate 100 and the insulating film portions 202b of the plurality of semiconductor chips 205 to each other (see (b) in FIG. 3).
  • (H) A step of joining the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of each of the plurality of semiconductor chips 205 (see (c) in FIG. 3).
  • (I) A step of forming a plurality of pillars 300 (corresponding to pillars 31) between a plurality of semiconductor chips 205 on the connection surface of the first semiconductor substrate 100.
  • (J) A step of molding a resin 301 on a connection surface of a first semiconductor substrate 100 so as to cover the semiconductor chip 205 and the pillar 300 to obtain a semi-finished product M1.
  • (K) A step of grinding and thinning the resin 301 side of the semi-finished product M1 molded in the step (j) to obtain the semi-finished product M2.
  • (L) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in the step (k).
  • (M) A step of cutting the semi-finished product M3 on which the wiring layer 400 is formed in the step (l) along the cutting line A so as to be each semiconductor device 1.
  • (N) A step of inverting the semiconductor device 1a individualized in the step (m) and installing it on the substrate 50 and the circuit board 60 (see FIG. 1).
  • step (1) corresponds to the above-mentioned steps (a) and (c)
  • step (2) corresponds to the above-mentioned steps (b) and (d)
  • step (3) corresponds to step (e)
  • step (4) corresponds to step (g)
  • step (5) corresponds to step (h).
  • the resin composition of the present disclosure comprises a first organic insulating film and a second organic insulating in a method for manufacturing a semiconductor device including at least one step corresponding to the step (f) and the steps (i) to (n). It may be a resin composition for use in producing at least one insulating film of the film.
  • the 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 in which an integrated circuit including a semiconductor element and wiring connecting them is formed.
  • a plurality of terminal electrodes 103 made of copper, aluminum, or the like are designated on one surface 101a of the first substrate main body 101 made of silicon or the like.
  • An insulating film 102 (first insulating film), which is a cured product obtained by curing the resin composition of the present disclosure while being provided at intervals, is provided.
  • a plurality of terminal electrodes 103 may be provided after the insulating film 102 is provided on one surface 101a of the first substrate main body 101, or a plurality of terminal electrodes 103 may be provided on one surface 101a of the first substrate main body 101 and then the insulating film. 102 may be provided.
  • a predetermined interval is provided between the plurality of terminal electrodes 103 in order to form the pillar 300 in a step described later, and another terminal electrode (not shown) connected to the pillar 300 is provided between the plurality of terminal electrodes 103. It is formed.
  • the step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate corresponding to a plurality of second semiconductor chips 20 and having an integrated circuit including semiconductor elements and wirings connecting them.
  • a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc. are placed on one surface 201a of the second substrate main body 201 made of silicon or the like.
  • an insulating film 202 (second insulating film) which is a cured product obtained by curing the resin composition of the present disclosure is provided.
  • a plurality of terminal electrodes 203 may be provided after the insulating film 202 is provided on one surface 201a of the second substrate main body 201, or a plurality of terminal electrodes 203 may be provided on one surface 201a of the second substrate main body 201 and then the insulating film 202. May be provided.
  • the insulating films 102 and 202 used in the steps (a) and (b) are not limited to the structure in which both the insulating films 102 and 202 are cured products obtained by curing the resin composition of the present disclosure, and at least one of the insulating films 102 and 202 is the present. It may be a cured product obtained by curing the disclosed resin composition.
  • a resin composition containing an organic material such as polyimide, polyamideimide, benzocyclobutene (BCB), polybenzoxazole (PBO), and PBO precursor is cured without containing a polyimide precursor.
  • a cured product made of polyimide can be mentioned.
  • the tensile elastic modulus of the insulating films 102 and 202 at 25 ° C. is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, further preferably 3.0 GPa or less, and 2.0 GPa or less. The following is particularly preferable, and 1.5 GPa or less is even more preferable.
  • the coefficient of thermal expansion of the insulating films 102 and 202 is preferably 100 ppm / K or less, and more preferably 70 ppm / K or less.
  • the thickness of the insulating films 102 and 202 is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m. As a result, the processing time can be shortened in the subsequent polishing step while ensuring the uniformity of the film thickness of the insulating film.
  • the polishing rate of the insulating film 102 is 0.1 to 5 times the polishing rate of the terminal electrode 103 from the viewpoint of facilitating the work in the step (c) and the step (d) and simplifying these steps. It is preferable that the polishing rate of the insulating film 202 satisfies at least one (preferably satisfying both) of 0.1 to 5 times the polishing rate of the terminal electrode 203. stomach.
  • the polishing rate of the insulating film 102 or 202 is 200 nm / min or less (four times or less of the polishing rate of copper). It is more preferably 100 nm / min or less (twice or less of the polishing rate of copper), and even more preferably 50 nm / min or less (equal to or less than the polishing rate of copper).
  • the insulating film is obtained by curing the resin composition.
  • the method for producing the above-mentioned insulating film includes, for example, a step of applying ( ⁇ ) a resin composition on a substrate and drying it to form a resin film, and a step of heat-treating the resin film.
  • ⁇ ) A step of forming a film with a certain film thickness on a film that has been subjected to a mold release treatment using a resin composition and then transferring the resin film to a substrate by a laminating method, and a resin film formed on the substrate after the transfer.
  • Examples of the method for applying the resin composition include a spin coating method, an inkjet method, and a slit coating method.
  • the rotation speed is 300 rpm (rotation per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, the acceleration is 500 rpm / sec to 15,000 rpm / sec, and the rotation time is 30 seconds to 300 seconds.
  • the resin composition may be spin-coated.
  • a drying step may be included after the resin composition is applied to a support, a film, or the like. Drying may be performed using a hot plate, an oven, or the like.
  • the drying temperature is preferably 75 ° C. to 130 ° C., and more preferably 90 ° C. to 120 ° C. from the viewpoint of improving the flatness of the insulating film.
  • the drying time is preferably 30 seconds to 5 minutes. Drying may be performed twice or more. Thereby, a resin film obtained by forming the above-mentioned resin composition into a film can be obtained.
  • the chemical discharge rate is 10 ⁇ L / sec to 400 ⁇ L / sec
  • the chemical discharge portion height is 0.1 ⁇ m to 1.0 ⁇ m
  • the stage speed (or the chemical discharge portion speed) is 1.0 mm / sec to 50.0 mm.
  • the resin composition may be slit-coated at the above.
  • the formed resin film may be heat-treated.
  • the heating temperature is preferably 150 ° C. to 450 ° C., more preferably 150 ° C. to 350 ° C.
  • the heating temperature is within the above range, it is possible to suitably produce an insulating film while suppressing damage to the substrate, device, etc. and realizing energy saving in the process.
  • the heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
  • the atmosphere of the heat treatment may be in the atmosphere or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the resin film.
  • Examples of the device used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, and the like.
  • the insulating film 202 is provided on one surface 201a of the second substrate main body 201, and then a plurality of terminal electrodes 203 are provided.
  • a step of heat-treating the pattern resin film may be used. Thereby, a cured pattern insulating film can be obtained.
  • a step of applying a resin composition other than the resin composition of the present disclosure on the substrate for example, a step of applying a resin composition other than the resin composition of the present disclosure on the substrate.
  • the process of forming a resin film by drying, and the resin composition of the present disclosure, which is a negative-type photosensitive resin composition or a positive-type photosensitive resin composition, is applied onto the resin film, and after drying, pattern exposure is performed and a developing solution is applied.
  • a method including a step of developing to obtain a pattern resin film and a step of heat-treating the pattern resin film may be used. Thereby, a cured pattern insulating film can be obtained.
  • the pattern exposure exposes a predetermined pattern through, for example, a photomask.
  • the activated light beam to be irradiated include i-ray, ultraviolet rays such as wide band, visible light, and radiation, and i-ray is preferable.
  • a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine and the like can be used as the exposure apparatus.
  • a patterned resin film which is a patterned resin film
  • the resin composition of the present disclosure is a negative photosensitive resin composition
  • the unexposed portion is removed with a developing solution.
  • the organic solvent used as the negative type developer the good solvent of the photosensitive resin film can be used alone, or the good solvent and the poor solvent can be appropriately mixed and used as the developer.
  • Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, Cyclopentanone, cyclohexanone and the like can be mentioned.
  • the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water and the like.
  • the exposed portion is removed with a developing solution.
  • the solution used as the positive developer include tetramethylammonium hydroxide (TMAH) solution and sodium carbonate solution.
  • At least one of the negative type developer and the positive type developer may contain a surfactant.
  • the content of the surfactant is preferably 0.01 part by mass to 10 parts by mass, and more preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the developing solution.
  • the development time can be, for example, twice the time required for the photosensitive resin film to be immersed in a developing solution and the resin film to be completely dissolved.
  • the developing time may be adjusted according to the component (A) contained in the resin composition of the present disclosure, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, from the viewpoint of productivity. , 20 seconds to 5 minutes is more preferable.
  • the pattern resin film after development may be washed with a rinsing solution.
  • a rinsing solution distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like may be used alone or appropriately mixed, or these may be used in a stepwise combination. May be.
  • a photosensitive resin As an organic material constituting the insulating films 102 and 202 other than the cured product obtained by curing the resin composition of the present disclosure, a photosensitive resin, a thermosetting non-conductive film (NCF: NonConductive Film), or , Thermosetting resin may be used. This organic material may be an underfill material. Further, the organic material constituting the insulating films 102 and 202 may be a heat-resistant resin.
  • the step (c) is a step of polishing the first semiconductor substrate 100.
  • the CMP is such that each surface 103a of the terminal electrode 103 is at an equivalent position or a slightly higher (protruding) position with respect to the surface 102a of the insulating film 102.
  • the one side 101a which is the surface of the first semiconductor substrate 100, is polished by the method.
  • the first semiconductor substrate 100 can be polished by the CMP method under the condition that the terminal electrode 103 made of copper or the like is selectively deeply ground.
  • each surface 103a of the terminal electrode 103 may be polished by the CMP method so as to coincide with the surface 102a of the insulating film 102.
  • the polishing method is not limited to the CMP method, and a back grind or the like may be adopted.
  • the height difference between each surface 103a and the surface 102a may be 1 nm to 50 nm and 1 nm to 15 nm. It may be.
  • the step (d) is a step of polishing the second semiconductor substrate 200.
  • each surface 203a of the terminal electrode 203 is at the same position or slightly higher (protruding) position with respect to the surface 202a of the insulating film 202.
  • the one side 201a which is the surface of the second semiconductor substrate 200, is polished using the CMP method.
  • the second semiconductor substrate 200 is polished by the CMP method under the condition that the terminal electrode 203 made of copper or the like is selectively deeply ground.
  • each surface 203a of the terminal electrode 203 may be polished by the CMP method so as to coincide with the surface 202a of the insulating film 202.
  • the polishing method is not limited to the CMP method, and a back grind or the like may be adopted.
  • the height difference between each surface 203a and the surface 202a may be 1 nm to 50 nm, and 1 nm to 15 nm. It may be.
  • the insulating film 102 may be polished so that the thickness of the insulating film 102 and the thickness of the insulating film 202 are the same.
  • the thickness of the insulating film 202 is the thickness of the insulating film 102. It may be polished to be larger than the halfbeak.
  • the thickness of the insulating film 202 may be polished to be smaller than the thickness of the insulating film 102.
  • the insulating film 202 contains most of the foreign matter adhering to the bonding interface when the second semiconductor substrate 200 is fragmented or when the chip is mounted. It is possible to further reduce joint defects.
  • the thickness of the insulating film 202 is smaller than the thickness of the insulating film 102, the height of the mounted semiconductor chip 205, that is, the semiconductor device 1 can be reduced.
  • the step (e) is a step of disassembling the second semiconductor substrate 200 and acquiring a plurality of semiconductor chips 205.
  • the second semiconductor substrate 200 is separated into a plurality of semiconductor chips 205 by cutting means such as dicing.
  • the insulating film 202 may be coated with a protective material or the like, and then individualized.
  • the insulating film 202 of the second semiconductor substrate 200 is divided into the insulating film portion 202b corresponding to each semiconductor chip 205.
  • Examples of the dicing method for individualizing the second semiconductor substrate 200 include plasma dicing, stealth dicing, laser dicing and the like.
  • a thin film such as an organic film that can be removed by water, TMAH or the like, or a carbon film that can be removed by plasma or the like may be provided.
  • the step (f) is a step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with respect to the terminal electrodes 103 of the first semiconductor substrate 100.
  • the terminal electrodes 203 of the semiconductor chips 205 face each of the corresponding terminal electrodes 103 of the first semiconductor substrate 100.
  • Perform alignment For this alignment, an alliance mark or the like may be provided on the first semiconductor substrate 100.
  • the step (g) is a step of bonding the insulating film 102 of the first semiconductor substrate 100 and the insulating film portions 202b of the plurality of semiconductor chips 205 to each other.
  • the semiconductor chip 205 is aligned with the first semiconductor substrate 100 as shown in FIG. 2 (c).
  • the insulating film portion 202b of each of the plurality of semiconductor chips 205 is bonded to the insulating film 102 of the first semiconductor substrate 100 (see (b) in FIG. 3).
  • the insulating film portion of the plurality of semiconductor chips 205 and the insulating film 102 of the first semiconductor substrate 100 may be uniformly heated before joining.
  • the insulating film 102 and the insulating film portion 202b are separated from the terminal electrodes 103 and 203 due to the difference between the thermal expansion coefficient of the insulating film 102 and the insulating film portion 202b and the thermal expansion coefficient of the terminal electrodes 103 and 203.
  • the first semiconductor substrate 100 may be polished in step (c) so that the height of the insulating film 102 becomes equal to or higher than the height of the terminal electrode 103 due to thermal expansion due to heating, and the insulating film portion 202b may be polished.
  • the second semiconductor substrate 200 may be polished in the step (d) so that the height is equal to or higher than the height of the terminal electrode 203.
  • the temperature difference between the semiconductor chip 205 and the first semiconductor substrate 100 at the time of joining is preferably, for example, 10 ° C. or less.
  • the insulating film 102 and the insulating film portion 202b are bonded to form an insulating bonding portion S1, and the plurality of semiconductor chips 205 are mechanically strong against the first semiconductor substrate 100. Can be attached to.
  • the heat bonding is performed at a highly uniform temperature, it is difficult for positional deviation or the like to occur at the bonding location, and high-precision bonding can be performed.
  • the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of the semiconductor chip 205 are separated from each other and are not connected (however, they are aligned).
  • the semiconductor chip 205 may be bonded to the first semiconductor substrate 100 by another bonding method, for example, room temperature bonding or the like.
  • the thickness of the organic insulating film which is the insulating bonding portion to which the insulating film 102 and the insulating film portion 202b are bonded, is not particularly limited, and may be, for example, 0.1 ⁇ m or more, to suppress the influence of foreign substances and to design the device. From the viewpoint of the above, it may be 1 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 5 ⁇ m.
  • the step (h) is a step of joining the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of each of the plurality of semiconductor chips 205.
  • the step (h) as shown in (d) of FIG. 2, when the bonding of the step (g) is completed, heat H, pressure, or both are applied to the terminals of the first semiconductor substrate 100 as hybrid bonding.
  • the electrode 103 and each terminal electrode 203 of the plurality of semiconductor chips 205 are joined (see (c) in FIG. 3).
  • the annealing temperature in the step (g) is preferably 150 ° C. or higher and 400 ° C. or lower, and more preferably 200 ° C.
  • the electrode bonding in the step (h) may be performed after the bonding in the step (g), or may be performed at the same time as the bonding in the step (g).
  • a plurality of semiconductor chips 205 are electrically and mechanically installed at predetermined positions on the first semiconductor substrate 100 with high accuracy.
  • a product reliability test (connection test, etc.) may be performed at the semi-finished product stage shown in FIG. 2 (d), and only non-defective products may be used in the subsequent steps. Subsequently, a manufacturing method of an example of a semiconductor device using such a semi-finished product will be described with reference to FIG.
  • the step (i) is a step of forming a plurality of pillars 300 between the plurality of semiconductor chips 205 on the connection surface 100a of the first semiconductor substrate 100.
  • a large number of pillars 300 made of copper, for example, are formed between the plurality of semiconductor chips 205.
  • the pillar 300 can be formed from copper plating, a conductor paste, a copper pin, or the like.
  • the pillar 300 is formed so that one end is connected to a terminal electrode of the terminal electrode of the first semiconductor substrate 100 that is not connected to the terminal electrode 203 of the semiconductor chip 205, and the other end extends upward.
  • the pillar 300 has, for example, a diameter of 10 ⁇ m or more and 100 ⁇ m or less, and a height of 10 ⁇ m or more and 1000 ⁇ m or less. It should be noted that, for example, one or more and 10,000 or less pillars 300 may be provided between the pair of semiconductor chips 205.
  • the step (j) is a step of molding the resin 301 on the connection surface 100a of the first semiconductor substrate 100 so as to cover the plurality of semiconductor chips 205 and the plurality of pillars 300.
  • an epoxy resin or the like is molded to cover the plurality of semiconductor chips 205 and the plurality of pillars 300 as a whole.
  • the molding method include a compression mold, a transfer mold, a method of laminating a film-shaped epoxy film, and the like.
  • the semi-finished product M1 filled with the resin is formed.
  • the curing treatment may be performed after molding the epoxy resin or the like.
  • the step (i) and the step (j) are performed substantially at the same time, that is, when the pillar 300 is also formed at the timing of resin molding, the pillar is formed by using imprint which is a fine transfer and conductive paste or electrolytic plating. It may be formed.
  • Step (k) In the step (k), the semi-finished product M1 composed of the resin 301 molded in the step (j), the plurality of pillars 300, and the plurality of semiconductor chips 205 is ground from the resin 301 side to be thinned, and the semi-finished product M2 is obtained. It is a process.
  • the resin-molded first semiconductor substrate 100 or the like is thinned by polishing the upper part of the semi-finished product M1 with a grander or the like to obtain the semi-finished product M2. ..
  • the thickness of the semiconductor chip 205, the pillar 300 and the resin 301 is reduced to, for example, about several tens of ⁇ m, and the semiconductor chip 205 has a shape corresponding to the second semiconductor chip 20, and the pillar 300 and the resin are formed.
  • the shape of 301 corresponds to the pillar portion 30.
  • the step (l) is a step of forming the wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in the step (k).
  • a rewiring pattern is formed on the second semiconductor chip 20 and the pillar portion 30 of the ground semi-finished product M2 with polyimide, copper wiring or the like.
  • a semi-finished product M3 having a wiring structure in which the terminal pitches of the second semiconductor chip 20 and the pillar portion 30 are widened is formed.
  • the step (m) is a step of cutting the semi-finished product M3 on which the wiring layer 400 is formed in the step (l) along the cutting line A so as to become each semiconductor device 1.
  • the semiconductor device substrate is cut along the cutting line A so as to become each semiconductor device 1 by dicing or the like.
  • the semiconductor device 1a individualized in the step (m) is inverted and installed on the substrate 50 and the circuit board 60, and a plurality of the semiconductor devices 1 shown in FIG. 1 are acquired.
  • the insulating film 102 of the first semiconductor substrate 100 and the insulating film 202 of the second semiconductor substrate 200 cure the resin composition of the present disclosure. It is a cured product. Since the cured product obtained by curing the resin composition of the present disclosure has a lower elastic coefficient than an inorganic material such as silicon dioxide, the resin composition can be used for producing an insulating film for hybrid bonding to form a second semiconductor substrate. Even if foreign matter generated by dicing when the 200 is separated into the semiconductor chip 205 adheres to the insulating film, the insulating film around the foreign matter is easily deformed and the foreign matter is insulated without forming a large void in the insulating film.
  • the insulating film makes it possible to suppress the influence of foreign matter. Therefore, according to the manufacturing method according to the present embodiment, it is possible to reduce bonding defects while performing fine bonding between the first semiconductor substrate 100 and the semiconductor chip 205.
  • the resin composition of the present disclosure contains a material having a low elastic modulus or has a resin composition having high toughness, damage to the semiconductor device 1 manufactured by the above manufacturing method can be more reliably suppressed. Can be done.
  • the present invention is not limited to the above embodiment.
  • the step (i) of forming the pillar 300 in the step shown in FIG. 4, after the step (i) of forming the pillar 300, the step (j) of molding the resin 301 and the step (k) of grinding and thinning the resin 301 and the like are performed.
  • the step (j) of molding the resin 301 on the connection surface of the first semiconductor substrate 100 is first performed, and then the step (k) of grinding the resin 301 to a predetermined thickness to make it thinner.
  • the step (i) for forming the pillar 300 may be performed. In this case, the work of scraping the pillar 300 and the like can be reduced, and the material cost can be reduced because the scraped portion of the pillar 300 becomes unnecessary.
  • the semiconductor wafer 410 (first electrode) having the substrate main body 411 (first substrate main body), the insulating film 412 (first insulating film) provided on one surface of the substrate main body 411, and a plurality of terminal electrodes 413 (first electrode).
  • (1 semiconductor substrate) is prepared, and the substrate main body 421 (second substrate main body), the insulating film portion 422 (second insulating film) provided on one surface of the substrate main body 421, and a plurality of terminal electrodes 423 (second electrode) are prepared.
  • a semiconductor substrate (second semiconductor substrate) before fragmentation of a plurality of semiconductor chips 420 having the above is prepared. Then, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before being fragmented into the semiconductor chip 420 are polished by the CMP method or the like in the same manner as in the above steps (c) and (d). .. After that, the same fragmentation process as in step (e) is performed on the second semiconductor substrate to acquire a plurality of semiconductor chips 420.
  • the terminal electrode 423 of the semiconductor chip 420 is aligned with the terminal electrode 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 to each other (step (g)), and the terminal electrode 413 of the semiconductor wafer 410 and the terminal electrode 423 of the semiconductor chip 420 are bonded to each other. (Step (h)), the semi-finished product shown in FIG. 5 (b) is acquired.
  • the insulating film 412 and the insulating film portion 422 are joined to form the insulating bonding portion S3, and the semiconductor chip 420 is mechanically firmly and highly accurately attached to the semiconductor wafer 410.
  • the terminal electrode 413 and the corresponding terminal electrode 423 are bonded to each other to form an electrode bonding portion S4, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly bonded to each other.
  • the semiconductor device 401 is acquired by joining the plurality of semiconductor chips 420 to the semiconductor wafer 410, which is a semiconductor wafer, in the same manner.
  • the plurality of semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, but may be collectively bonded to the semiconductor wafer 410 by hybrid bonding.
  • the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 has the resin composition of the present disclosure, as in the method of manufacturing the semiconductor device 1 described above. It is an insulating film that is a cured product obtained by curing an object. Therefore, even if foreign matter generated by dicing during dicing into the semiconductor chip 420 adheres to the insulating film, the insulating film around the foreign matter is easily deformed, and the foreign matter is removed without forming a large void in the insulating film. It can be included in the insulating film. That is, the insulating film makes it possible to suppress the influence of foreign matter. Therefore, even in the above-mentioned manufacturing method according to C2W, it is possible to reduce bonding defects while finely bonding the semiconductor wafer 410 and the semiconductor chip 420, as in the case of C2C.
  • an inorganic material may be contained in a part of the insulating film 102 of the semiconductor substrate 110, the insulating film 202 of the semiconductor chip 205, and the like within the range in which the effect of the present invention is exhibited.

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PCT/JP2020/037322 2020-09-30 2020-09-30 樹脂組成物、半導体装置の製造方法、硬化物及び半導体装置 Ceased WO2022070362A1 (ja)

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US18/029,102 US20240018306A1 (en) 2020-09-30 2021-09-28 Resin composition, method for producing semiconductor device, cured product, semiconductor device, and method for synthesizing polyimide precursor
JP2022554021A JP7853216B2 (ja) 2020-09-30 2021-09-28 樹脂組成物、半導体装置の製造方法、硬化物、半導体装置及びポリイミド前駆体の合成方法
KR1020237010875A KR20230075457A (ko) 2020-09-30 2021-09-28 수지 조성물, 반도체 장치의 제조 방법, 경화물, 반도체 장치 및 폴리이미드 전구체의 합성 방법
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TW110136323A TW202229408A (zh) 2020-09-30 2021-09-29 樹脂組成物、半導體裝置的製造方法、硬化物、半導體裝置及聚醯亞胺前驅物的合成方法

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WO2024219502A1 (ja) * 2023-04-19 2024-10-24 Ｈｄマイクロシステムズ株式会社 絶縁膜形成材料、半導体装置の製造方法及び半導体装置
WO2024248064A1 (ja) * 2023-05-30 2024-12-05 株式会社ダイセル ポリマー及びそれを含む感光性樹脂組成物、銅ペースト、液状組成物、半導体デバイスの製造方法及び半導体接続用銅ピラーの製造方法
WO2024248066A1 (ja) * 2023-05-30 2024-12-05 株式会社ダイセル ポリマー及びそれを含む感光性樹脂組成物、銅ペースト、液状組成物、半導体デバイスの製造方法及び半導体接続用銅ピラーの製造方法
WO2024248065A1 (ja) * 2023-05-30 2024-12-05 株式会社ダイセル ポリマー及びそれを含む感光性樹脂組成物、銅ペースト、液状組成物、半導体デバイスの製造方法及び半導体接続用銅ピラーの製造方法
WO2025094691A1 (ja) * 2023-10-30 2025-05-08 Ｈｄマイクロシステムズ株式会社 絶縁膜形成材料、絶縁膜形成材料キット、半導体装置の製造方法及び半導体装置
WO2026070803A1 (ja) * 2024-09-27 2026-04-02 富士フイルム株式会社 接合体の製造方法、接合体、デバイスの製造方法、及び、樹脂組成物

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