WO2020067186A1 - Film-shaped adhesive, adhesive sheet, semiconductor device, and production method for semiconductor device - Google Patents

Film-shaped adhesive, adhesive sheet, semiconductor device, and production method for semiconductor device Download PDF

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Publication number
WO2020067186A1
WO2020067186A1 PCT/JP2019/037648 JP2019037648W WO2020067186A1 WO 2020067186 A1 WO2020067186 A1 WO 2020067186A1 JP 2019037648 W JP2019037648 W JP 2019037648W WO 2020067186 A1 WO2020067186 A1 WO 2020067186A1
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Prior art keywords
adhesive
film
semiconductor element
film adhesive
semiconductor
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PCT/JP2019/037648
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French (fr)
Japanese (ja)
Inventor
由衣 國土
慎太郎 橋本
山本　和弘
奏美 中村
恒則 大平
紘平 谷口
昂平 平尾
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日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to SG11202102895VA priority Critical patent/SG11202102895VA/en
Priority to JP2020549304A priority patent/JP7435458B2/en
Priority to KR1020217008789A priority patent/KR102629864B1/en
Priority to CN201980062235.4A priority patent/CN112740380A/en
Publication of WO2020067186A1 publication Critical patent/WO2020067186A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/28—Metal sheet
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/32—Holders for supporting the complete device in operation, i.e. detachable fixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32135—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/32145—Disposition the layer connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
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    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
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    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/831—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus
    • H01L2224/83101—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector the layer connector being supplied to the parts to be connected in the bonding apparatus as prepeg comprising a layer connector, e.g. provided in an insulating plate member
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Definitions

  • the present invention relates to a film adhesive, an adhesive sheet, a semiconductor device, and a method for manufacturing the same.
  • a stacked MCP Multi Chip Package
  • semiconductor elements semiconductor elements (semiconductor chips) are stacked in multiple stages
  • higher speed, higher density, and higher integration of semiconductor packages are being promoted.
  • the use of copper as a wiring material for semiconductor chip circuits has increased the speed.
  • a lead frame made of copper or the like is being used.
  • copper has the property of being easily corroded, and from the viewpoint of cost reduction, the coating material for securing the insulation of the circuit surface tends to be simplified, so that the electrical characteristics of the semiconductor package are secured. It tends to be difficult.
  • copper ions generated by corrosion move inside the adhesive, and electric signals tend to be easily lost in the semiconductor chip or between the semiconductor chips.
  • Patent Literature 1 discloses a complex with a cation having a thermoplastic resin having an epoxy group and no carboxyl group and a heterocyclic compound having a tertiary nitrogen atom as a ring atom.
  • An adhesive sheet for manufacturing a semiconductor device, comprising an organic complex-forming compound, is disclosed.
  • the present inventors have made intensive studies and found that by combining a specific acrylic rubber and a specific component in a film adhesive, it is possible to sufficiently suppress copper ion permeation in the adhesive, and furthermore, the adhesive strength And found that the present invention was completed.
  • One aspect of the present invention is a film adhesive for bonding a semiconductor element and a support member on which the semiconductor element is mounted, wherein the film adhesive is a thermosetting resin, a curing agent, and an acrylic rubber.
  • the film adhesive is a thermosetting resin, a curing agent, and an acrylic rubber.
  • the acrylic rubber has few (or no) structural units derived from acrylonitrile.
  • an acrylic rubber having a small amount (or no containing unit) derived from acrylonitrile it may be possible to sufficiently suppress the permeation of copper ions in the adhesive.
  • the reason for such an effect is not necessarily clear, but the present inventors have found that acrylonitrile, which easily forms a complex with copper ions (having a high complex stability constant), has a small (or no) nitrile group in acrylonitrile. It is considered that the absorption of copper ions by the adhesive is weakened, and as a result, the permeation of copper ions in the adhesive is suppressed.
  • acrylic rubber having a small number of (or not including) structural units derived from acrylonitrile tends to hardly form a phase-separated structure, and the difficulty of the phase-separated structure has an effect on suppression of copper ion permeation in the adhesive. It is possible that they are giving.
  • the film adhesive which contains a heterocyclic compound, has a tendency to sufficiently suppress copper ion permeation in the adhesive and to have further excellent adhesive strength.
  • the heterocyclic compound may be an aromatic compound having three or more nitrogen atoms.
  • the heterocyclic compound may be at least one selected from the group consisting of a triazole compound and a tetrazole compound.
  • the heterocyclic compound may be used in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the thermosetting resin, the curing agent, and the acrylic rubber.
  • the film adhesive may further contain an inorganic filler, and the average particle size of the inorganic filler may be 1 ⁇ m or less.
  • the present invention provides an adhesive sheet comprising a base material and the above-mentioned film adhesive provided on one surface of the base material.
  • the substrate may be a dicing tape.
  • the present invention includes a semiconductor element, a support member for mounting the semiconductor element, and an adhesive member provided between the semiconductor element and the support member, for bonding the semiconductor element and the support member. And a semiconductor device which is a cured product of the above film adhesive.
  • the support member may include a member made of copper.
  • the present invention provides a method for manufacturing a semiconductor device, comprising a step of bonding a semiconductor element and a support member using the above-mentioned film adhesive.
  • the present invention provides a method of attaching a film-like adhesive of the above-mentioned adhesive sheet to a semiconductor wafer, and cutting the semiconductor wafer to which the film-like adhesive has been attached to form a plurality of individual pieces.
  • a method of manufacturing a semiconductor device comprising: a step of producing a semiconductor element with a film-like adhesive; and a step of bonding the semiconductor element with a film-like adhesive to a support member.
  • the method for manufacturing a semiconductor device may further include a step of heating the semiconductor element with the film-like adhesive bonded to the support member using a reflow furnace.
  • a film adhesive which can sufficiently suppress the permeation of copper ions in the adhesive and has excellent adhesive strength. Further, according to the present invention, an adhesive sheet and a semiconductor device using such a film-like adhesive are provided. Further, according to the present invention, there is provided a method of manufacturing a semiconductor device using a film adhesive or an adhesive sheet.
  • FIG. 2 is a schematic cross-sectional view illustrating one embodiment of a semiconductor device.
  • FIG. 6 is a schematic sectional view showing another embodiment of the semiconductor device.
  • a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other stages. Good.
  • the upper limit or the lower limit of the numerical ranges may be replaced with the values shown in the embodiments.
  • (meth) acrylate means acrylate or its corresponding methacrylate.
  • the same applies to other similar expressions such as a (meth) acryloyl group and a (meth) acrylic copolymer.
  • the film adhesive is a film adhesive for bonding a semiconductor element and a support member on which the semiconductor element is mounted, wherein the film adhesive is (A) a thermosetting resin, It contains (B) a curing agent, (C) an acrylic rubber, and (D) a heterocyclic compound, and has a high absorption peak derived from stretching vibration of a carbonyl group in an infrared absorption spectrum of the (C) acrylic rubber.
  • the P CO is, when the height of the peak derived from stretching vibration of the nitrile group was P CN, satisfies the condition of P CO and P CN is represented by the following formula (1), the thickness of the film-like adhesive 50 ⁇ m or less is there.
  • the film adhesive is obtained by converting an adhesive composition containing (A) a thermosetting resin, (B) a curing agent, (C) an acrylic rubber, and (D) a heterocyclic compound into a film. It can be obtained by molding.
  • the film-like adhesive and the adhesive composition may be capable of undergoing a semi-cured (B-stage) state and becoming a completely cured (C-stage) state after the curing treatment.
  • Thermosetting resin may be an epoxy resin from the viewpoint of adhesiveness.
  • the epoxy resin can be used without any particular limitation as long as it has an epoxy group in the molecule.
  • Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, and bisphenol F novolak epoxy resin.
  • Stilbene type epoxy resin triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, polyfunctional phenols And polycyclic aromatic diglycidyl ether compounds such as anthracene and anthracene.
  • the component (A) may be a cresol novolak type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol A type epoxy resin from the viewpoint of the tackiness and flexibility of the film.
  • the epoxy equivalent of the epoxy resin is not particularly limited, but may be 90 to 300 g / eq, 110 to 290 g / eq, or 110 to 290 g / eq.
  • the epoxy equivalent of the epoxy resin is in such a range, there is a tendency that the fluidity can be secured while maintaining the bulk strength of the film adhesive.
  • the component (B) may be a phenol resin that can be a curing agent for an epoxy resin.
  • the phenol resin can be used without any particular limitation as long as it has a phenolic hydroxyl group in the molecule.
  • examples of the phenol resin include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene and formaldehyde.
  • Novolak-type phenolic resin obtained by condensation or co-condensation with a compound having an aldehyde group of phenol group phenols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalene diol, phenol novolak, phenol and / or And phenol aralkyl resins and naphthol aralkyl resins synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. These may be used alone or in combination of two or more.
  • the phenol resin may be a phenol aralkyl resin or a naphthol aralkyl resin.
  • the hydroxyl equivalent of the phenol resin may be 70 g / eq or more or 70 to 300 g / eq.
  • the hydroxyl equivalent of the phenol resin is 70 g / eq or more, the storage elastic modulus of the film tends to be further improved, and when it is 300 g / eq or less, it is possible to prevent problems due to foaming, outgassing and the like. .
  • the ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the phenol resin is from 0.30 / 0.70 to 0.70 / 0.30 from the viewpoint of curability. , 0.35 / 0.65-0.65 / 0.35, 0.40 / 0.60-0.60 / 0.40, or 0.45 / 0.55-0.55 / 0.45 May be.
  • the equivalent ratio is 0.30 / 0.70 or more, more sufficient curability tends to be obtained.
  • the equivalent ratio is 0.70 / 0.30 or less, it is possible to prevent the viscosity from becoming too high, and to obtain more sufficient fluidity.
  • the total content of the components (A) and (B) is 5 to 50 parts by mass, 10 to 40 parts by mass based on 100 parts by mass of the total mass of the components (A), (B) and (C). It may be parts by weight, or 15 to 30 parts by weight.
  • the elastic modulus tends to be improved by crosslinking.
  • the total content of the component (A) and the component (B) is 50 parts by mass or less, the film handling property tends to be maintained.
  • Component (C) Acrylic Rubber
  • the component (C) is a rubber having a structural unit derived from a (meth) acrylate ester as a main component.
  • the content of the structural unit derived from the (meth) acrylate in the component (C) may be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total amount of the structural units.
  • the component (C) may include a structural unit derived from a (meth) acrylate having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, and a carboxyl group.
  • the component (C) may include a constituent unit derived from acrylonitrile as long as the condition of the formula (1) described below is satisfied, but it is more effective to suppress copper ion permeation in the adhesive.
  • the component (C) may not contain a constituent unit derived from acrylonitrile, since the component is possible and the embedding property is more excellent.
  • the carbonyl group is mainly derived from the constituent unit (meth) acrylate
  • the nitrile group is mainly derived from the constituent unit acrylonitrile.
  • the height of the absorption peak (P CO ) derived from the stretching vibration of the carbonyl group and the height of the peak (P CN ) derived from the stretching vibration of the nitrile group mean those defined in Examples.
  • a small P CN / P CO means that the component (C) has few constituent units derived from acrylonitrile. Therefore, the component (C) that does not include a structural unit derived from acrylonitrile can theoretically satisfy the condition of the formula (1).
  • P CN / P CO is less than 0.070, 0.065 or less, 0.060 or less, 0.055 or less, 0.050 or less, 0.040 or less, 0.030 or less, 0.020 or less, or It may be 0.010 or less.
  • P CN / P CO is less than 0.070, it may be possible to sufficiently suppress the permeation of copper ions in the adhesive. Further, as the value of P CN / P CO becomes smaller, the permeation of copper ions in the adhesive can be more sufficiently suppressed. Further, as the value of P CN / P CO decreases, the cohesive force of the component (C) decreases, and the embedding property tends to be more excellent.
  • the glass transition temperature (Tg) of the component (C) may be ⁇ 50 to 50 ° C. or ⁇ 30 to 30 ° C.
  • Tg of the component (C) is -50 ° C or more
  • the flexibility of the adhesive tends to be prevented from becoming too high. This makes it easier to cut the film adhesive during wafer dicing, thereby preventing the occurrence of burrs.
  • the Tg of the component (C) is 50 ° C. or lower, a decrease in the flexibility of the adhesive tends to be suppressed. This tends to make it easy to sufficiently fill voids when the film adhesive is attached to the wafer. Further, it is possible to prevent chipping at the time of dicing due to a decrease in the adhesive strength of the wafer.
  • the glass transition temperature (Tg) means a value measured using a DSC (thermal differential scanning calorimeter) (for example, Thermo Plus 2 manufactured by Rigaku Corporation).
  • the weight average molecular weight (Mw) of the component (C) may be 100,000 to 3,000,000 or 200,000 to 2,000,000.
  • Mw means a value measured by gel permeation chromatography (GPC) and converted using a calibration curve using standard polystyrene.
  • ⁇ ⁇ As a commercially available component (C) which does not contain a structural unit derived from acrylonitrile, for example, KH-CT-865 (manufactured by Hitachi Chemical Co., Ltd.) and the like are listed.
  • the content of the component (C) is 50 to 95 parts by mass, 60 to 90 parts by mass, or 70 to 85 parts by mass based on 100 parts by mass of the total of the components (A), (B) and (C). It may be parts by mass.
  • the content of the component (C) is in such a range, there is a tendency that permeation of copper ions in the adhesive can be more sufficiently suppressed.
  • the film adhesive by containing the component (D), has a tendency to sufficiently suppress copper ion permeation in the adhesive and to have further excellent adhesive strength.
  • the component (D) may be an aromatic compound having three or more nitrogen atoms, and may be at least one selected from the group consisting of a triazole compound and a tetrazole compound.
  • triazole compound examples include benzotriazole, benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, benzotriazole-1-methanol, carboxybenzotriazole, 3-mercaptotriazole, 5-mercaptotriazole; Substitutes and the like.
  • the triazole compound may be benzotriazole or 3-mercaptotriazole.
  • tetrazole compound examples include 5-methyltetrazole, 5-aminotetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole and the like. Is mentioned.
  • the tetrazole compound may be 5-methyltetrazole or 5-aminotetrazole.
  • the content of the component (D) may be 0.01 to 2 parts by mass based on 100 parts by mass of the total mass of the components (A), (B) and (C). When the content of the component (D) is in such a range, the content tends to be more excellent in terms of adhesive strength.
  • the content of the component (D) may be 0.03 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, or 0.3 parts by mass or more.
  • the content of the component (D) may be 2 parts by mass or less, 1.8 parts by mass or less, 1.5 parts by mass or less, or 1.2 parts by mass or less.
  • the film adhesive may further contain (E) an inorganic filler, (F) a coupling agent, (G) a curing accelerator, and the like.
  • Component (E) Inorganic filler
  • the component (E) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, and nitride.
  • the component (E) may be silica from the viewpoint of adjusting the melt viscosity.
  • the average particle size of the component (E) may be 1 ⁇ m or less.
  • the average particle size of the component (E) is from 0.01 to 1 ⁇ m, 0.01 to 0.8 ⁇ m, 0.03 to 0.5 ⁇ m, 0.03 to 0.3 ⁇ m, or 0.03 to 1 ⁇ m from the viewpoint of fluidity. It may be up to 0.1 ⁇ m.
  • the average particle size means a value obtained by converting from the BET specific surface area. As the average particle size of the component (E) becomes smaller, it becomes possible to more sufficiently suppress the permeation of copper ions in the adhesive.
  • the shape of the component (E) is not particularly limited, but may be spherical.
  • the content of the component (E) is 0.1 to 50 parts by mass, 0.1 to 30 parts by mass, based on 100 parts by mass of the total mass of the components (A), (B), and (C). Alternatively, it may be 0.1 to 20 parts by mass.
  • Component (F) Coupling Agent
  • the component (F) may be a silane coupling agent.
  • the silane coupling agent include ⁇ -ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltrimethoxysilane. Can be These may be used alone or in combination of two or more.
  • Component (G) Curing accelerator
  • the component (G) is not particularly limited, and a commonly used component can be used.
  • Examples of the component (G) include imidazoles and derivatives thereof, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more. Among them, the component (G) may be imidazoles and derivatives thereof from the viewpoint of reactivity.
  • imidazoles examples include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole and the like. These may be used alone or in combination of two or more.
  • the film adhesive may further contain other components.
  • Other components include, for example, pigments, ion scavengers, antioxidants, and the like.
  • the content of the component (F), the component (G), and other components is 0 to 30 parts by mass based on 100 parts by mass of the total mass of the components (A), (B), and (C). May be.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a film adhesive.
  • the film adhesive 1 (adhesive film) shown in FIG. 1 is obtained by molding an adhesive composition into a film.
  • the film adhesive 1 may be in a semi-cured (B stage) state.
  • Such a film adhesive 1 can be formed by applying an adhesive composition to a support film.
  • a varnish of the adhesive composition adheresive varnish
  • the component (A), the component (B), the component (C), the component (D), and other components added as necessary may be added to a solvent.
  • a mixed solution is mixed or kneaded to prepare an adhesive varnish, the adhesive varnish is applied to a support film, and the solvent is removed by heating and drying to form the film adhesive 1. .
  • the support film is not particularly limited as long as it can withstand the above-mentioned heating and drying, for example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, a polymethylpentene film, and the like. It may be.
  • the support film may be a multilayer film in which two or more kinds are combined, or may be one whose surface is treated with a release agent such as a silicone-based or silica-based release agent.
  • the thickness of the support film may be, for example, 10-200 ⁇ m or 20-170 ⁇ m.
  • Mixing or kneading can be performed by using an ordinary stirrer, a mill, a three-roller, a disperser such as a ball mill, or the like, and appropriately combining these.
  • the solvent used for the preparation of the adhesive varnish is not limited as long as each component can be uniformly dissolved, kneaded or dispersed, and conventionally known solvents can be used.
  • a solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, xylene, and the like.
  • the solvent may be methyl ethyl ketone, cyclohexanone, etc. in terms of drying speed and cost.
  • a known method can be used, and examples thereof include a knife coat method, a roll coat method, a spray coat method, a gravure coat method, a bar coat method, and a curtain coat method.
  • a known method can be used, and examples thereof include a knife coat method, a roll coat method, a spray coat method, a gravure coat method, a bar coat method, and a curtain coat method.
  • the heating and drying conditions are not particularly limited as long as the used solvent is sufficiently volatilized, but the heating and drying can be performed by heating at 50 to 150 ° C. for 1 to 30 minutes.
  • the thickness of the film-like adhesive is 50 ⁇ m or less, the distance between the semiconductor element and the supporting member on which the semiconductor element is mounted becomes short, so that problems due to copper ions tend to occur easily. Since the film-like adhesive according to the present embodiment can sufficiently suppress the permeation of copper ions in the adhesive, the thickness can be reduced to 50 ⁇ m or less.
  • the thickness of the film adhesive 1 may be 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less.
  • the lower limit of the thickness of the film adhesive 1 is not particularly limited, but may be, for example, 1 ⁇ m or more.
  • the copper ion transmission time of the film adhesive 1 in the semi-cured (B stage) state may be more than 80 minutes, and is 85 minutes or more, 90 minutes or more, 100 minutes or more, 150 minutes or more, 200 minutes or more, or 250 minutes. Minutes or more.
  • the copper ion transmission time is longer than 80 minutes, it is predicted that even if a defect such as insufficient curing occurs during the fabrication of a semiconductor device, a defect caused by the copper ion hardly occurs.
  • the copper ion transmission time of the film adhesive 1 (that is, the cured product of the film adhesive) in the completely cured (C stage) state may be more than 100 minutes, and is 120 minutes or more, 140 minutes or more, 160 minutes or more. , 180 minutes or more, 200 minutes or more, or 250 minutes or more. Problems due to copper ions tend to occur during high-temperature treatment such as a reflow process. For this reason, it is expected that a defect caused by copper ions is less likely to occur when the completely cured (C stage) state is longer than 100 minutes.
  • FIG. 2 is a schematic sectional view showing an embodiment of the adhesive sheet.
  • the adhesive sheet 100 shown in FIG. 2 includes a base material 2 and a film adhesive 1 provided on the base material 2.
  • FIG. 3 is a schematic sectional view showing another embodiment of the adhesive sheet.
  • the adhesive sheet 110 shown in FIG. 3 includes a base material 2, a film adhesive 1 provided on the base material 2, and a cover film provided on a surface of the film adhesive 1 opposite to the base material 2. 3 is provided.
  • the substrate 2 is not particularly limited, but may be a substrate film.
  • the base film may be the same as the above-mentioned support film.
  • the cover film 3 is used to prevent the film adhesive from being damaged or contaminated, and may be, for example, a polyethylene film, a polypropylene film, or a surface release agent-treated film.
  • the thickness of the cover film 3 may be, for example, 15 to 200 ⁇ m or 70 to 170 ⁇ m.
  • the adhesive sheets 100 and 110 can be formed by applying an adhesive composition to a base film in the same manner as in the method for forming a film adhesive described above.
  • the method for applying the adhesive composition to the substrate 2 may be the same as the method for applying the adhesive composition to the support film described above.
  • the adhesive sheet 110 can be obtained by further laminating the cover film 3 on the film adhesive 1.
  • the adhesive sheets 100 and 110 may be formed by using a film adhesive prepared in advance.
  • the adhesive sheet 100 can be formed by laminating under a predetermined condition (for example, room temperature (20 ° C.) or a heated state) using a roll laminator, a vacuum laminator, or the like. Since the adhesive sheet 100 can be manufactured continuously and is excellent in efficiency, it may be formed using a roll laminator in a heated state.
  • the adhesive sheet is a dicing / die bonding integrated adhesive sheet in which the base material 2 is a dicing tape.
  • the laminating step for the semiconductor wafer is performed only once, so that the work efficiency can be improved.
  • the dicing tape examples include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film.
  • the dicing tape may have been subjected to a surface treatment such as a primer application, a UV treatment, a corona discharge treatment, a polishing treatment, an etching treatment and the like, as necessary.
  • the dicing tape may have adhesiveness.
  • Such a dicing tape may be one in which the above-mentioned plastic film is provided with adhesiveness, or one in which an adhesive layer is provided on one surface of the above-mentioned plastic film.
  • the pressure-sensitive adhesive layer may be either a pressure-sensitive type or a radiation-curable type, and has a sufficient adhesive strength so that the semiconductor element does not scatter during dicing, and does not damage the semiconductor element in the subsequent semiconductor element pickup step.
  • a pressure-sensitive type or a radiation-curable type
  • the thickness of the dicing tape may be 60 to 150 ⁇ m or 70 to 130 ⁇ m from the viewpoints of economy and handling of the film.
  • FIG. 4 is a schematic sectional view showing another embodiment of the adhesive sheet.
  • FIG. 5 is a schematic sectional view showing another embodiment of the adhesive sheet.
  • the adhesive sheet 120 shown in FIG. 4 includes the dicing tape 7, the adhesive layer 6, and the film adhesive 1 in this order.
  • the adhesive sheet 130 shown in FIG. 5 includes the dicing tape 7 and the film adhesive 1 provided on the dicing tape 7.
  • the adhesive sheet 120 can be obtained, for example, by providing the adhesive layer 6 on the dicing tape 7 and further laminating the film adhesive 1 on the adhesive layer 6.
  • the adhesive sheet 130 can be obtained, for example, by laminating the dicing tape 7 and the film adhesive 1.
  • the film adhesive and the adhesive sheet may be used in the manufacture of a semiconductor device.
  • the film adhesive and the dicing tape may be applied to a semiconductor wafer or a semiconductor element (semiconductor chip) that has already been cut into pieces at a temperature of 0 ° C. or less.
  • a semiconductor element with a film adhesive is obtained by cutting with a rotary blade, laser or stretching, and then the semiconductor element with a film adhesive is used as an organic substrate, a lead frame, or another semiconductor element. It may be used for manufacturing a semiconductor device including a step of bonding on top.
  • Examples of the semiconductor wafer include single crystal silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.
  • Film adhesives and adhesive sheets include semiconductor elements such as ICs and LSIs, lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resins and epoxy resins; A resin impregnated and cured with an epoxy resin or the like; can be used as a die bonding adhesive for bonding a semiconductor mounting support member such as ceramics such as alumina.
  • the film adhesive and the adhesive sheet are also suitably used as an adhesive for bonding the semiconductor elements to each other in a Stacked-PKG having a structure in which a plurality of semiconductor elements are stacked.
  • one of the semiconductor elements serves as a support member on which the semiconductor element is mounted.
  • the film adhesive and the adhesive sheet are, for example, a protective sheet for protecting the back surface of the semiconductor element of the flip-chip type semiconductor device, and for sealing between the surface of the semiconductor element of the flip-chip type semiconductor device and the adherend. It can also be used as a sealing sheet or the like.
  • a semiconductor device manufactured using a film adhesive will be specifically described with reference to the drawings.
  • semiconductor devices having various structures have been proposed, and the application of the film adhesive according to the present embodiment is not limited to the semiconductor devices having the structures described below.
  • FIG. 6 is a schematic sectional view showing one embodiment of a semiconductor device.
  • the semiconductor device 200 shown in FIG. 6 includes a semiconductor element 9, a support member 10 on which the semiconductor element 9 is mounted, and an adhesive member provided between the semiconductor element 9 and the support member 10 to adhere the semiconductor element 9 and the support member 10. (Cured film adhesive 1c).
  • a connection terminal (not shown) of the semiconductor element 9 is electrically connected to an external connection terminal (not shown) via a wire 11 and is sealed by a sealing material 12.
  • FIG. 7 is a schematic sectional view showing another embodiment of the semiconductor device.
  • the first-stage semiconductor element 9a is bonded to the support member 10 on which the terminals 13 are formed by an adhesive member (cured product 1c of a film-like adhesive).
  • the semiconductor element 9b in the second stage is further adhered thereon by an adhesive member (cured product 1c of a film adhesive).
  • the connection terminals (not shown) of the first-stage semiconductor element 9a and the second-stage semiconductor element 9b are electrically connected to external connection terminals via wires 11, and are sealed with a sealing material 12.
  • the film adhesive according to the present embodiment can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.
  • the semiconductor device (semiconductor package) shown in FIGS. 6 and 7 includes, for example, a film-like adhesive interposed between a semiconductor element and a support member or between a semiconductor element and a semiconductor element, and heat-pressing them to form a semiconductor device. And then, if necessary, a wire bonding step, a sealing step with a sealing material, a heating and melting step including reflow with solder, and the like.
  • the heating temperature in the thermocompression bonding step is usually 20 to 250 ° C.
  • the load is usually 0.1 to 200 N
  • the heating time is usually 0.1 to 300 seconds.
  • the support member or It may be a method of attaching to a semiconductor element.
  • the support member may include a member made of copper.
  • a member made of copper is used as a constituent member of the semiconductor device. Even so, the effect of copper ions generated from the member can be reduced, and the occurrence of electrical trouble due to copper ions can be sufficiently suppressed.
  • the member made of copper for example, a lead frame, a wiring, a wire, a heat radiating material, and the like can be mentioned.
  • the influence of copper ions can be reduced. It is.
  • the method for manufacturing a semiconductor device using the dicing / die bonding integrated adhesive sheet shown in FIG. 4 is not limited to the method for manufacturing a semiconductor device described below.
  • a semiconductor wafer is pressure-bonded to the film-like adhesive 1 in the adhesive sheet 120 (integrated dicing / die-bonding adhesive sheet), and the semiconductor wafer is adhered and held and fixed (mounting step).
  • This step may be performed while pressing with a pressing means such as a pressure roll.
  • dicing of the semiconductor wafer is performed.
  • the semiconductor wafer is cut into a predetermined size, and a plurality of individualized semiconductor elements (semiconductor chips) with a film adhesive are manufactured.
  • Dicing can be performed, for example, from the circuit surface side of the semiconductor wafer according to a conventional method.
  • a cutting method called full cut in which a dicing tape is cut, a method in which a semiconductor wafer is cut in half by cutting it in half and cooled and pulled, and a cutting method using a laser can be adopted.
  • the dicing apparatus used in this step is not particularly limited, and a conventionally known dicing apparatus can be used.
  • the semiconductor element is picked up.
  • the pickup method is not particularly limited, and various conventionally known methods can be employed. For example, there is a method in which individual semiconductor elements are pushed up from the dicing / die-bonding integrated adhesive sheet side by a needle, and the pushed up semiconductor elements are picked up by a pickup device.
  • the pickup is performed after irradiating the pressure-sensitive adhesive layer with the radiation.
  • the adhesive force of the pressure-sensitive adhesive layer to the film-like adhesive is reduced, and the peeling of the semiconductor element is facilitated.
  • pickup can be performed without damaging the semiconductor element.
  • the semiconductor element with a film-like adhesive formed by dicing is bonded to a support member for mounting the semiconductor element via the film-like adhesive.
  • the bonding may be performed by crimping.
  • the conditions for die bonding are not particularly limited, and can be set as appropriate as needed. Specifically, for example, the bonding can be performed at a die bonding temperature of 80 to 160 ° C., a bonding load of 5 to 15 N, and a bonding time of 1 to 10 seconds.
  • a step of thermally curing the film adhesive may be provided.
  • thermally curing the film adhesive bonding the support member and the semiconductor element by the bonding step it is possible to bond and fix more firmly.
  • pressure may be applied at the same time to perform curing.
  • the heating temperature in this step can be appropriately changed depending on the components of the film adhesive.
  • the heating temperature may be, for example, 60 to 200 ° C.
  • the temperature or the pressure may be changed stepwise.
  • a wire bonding step of electrically connecting the tip of the terminal portion (inner lead) of the support member and the electrode pad on the semiconductor element with a bonding wire is performed.
  • the bonding wire for example, a gold wire, an aluminum wire, a copper wire or the like is used.
  • the temperature at which wire bonding is performed may be in the range of 80 to 250 ° C or 80 to 220 ° C.
  • the heating time may be from a few seconds to a few minutes.
  • the connection may be performed by using the vibration energy by the ultrasonic wave and the compression energy by the applied pressure in a state of being heated within the above temperature range.
  • a sealing step of sealing the semiconductor element with a sealing resin is performed.
  • This step is performed to protect the semiconductor element or the bonding wire mounted on the support member.
  • This step is performed by molding a sealing resin with a mold.
  • the sealing resin for example, an epoxy resin may be used. The substrate and the residue are buried by heat and pressure at the time of sealing, so that separation at the bonding interface due to bubbles can be prevented.
  • the sealing resin that is insufficiently cured in the sealing step is completely cured. Even when the film adhesive is not thermally cured in the sealing step, the film adhesive is thermally cured together with the curing of the sealing resin in the present step, so that the adhesive can be fixed.
  • the heating temperature in this step can be appropriately set depending on the type of the sealing resin, and may be, for example, in the range of 165 to 185 ° C., and the heating time may be about 0.5 to 8 hours.
  • the semiconductor element with the film adhesive bonded to the support member is heated using a reflow furnace.
  • a resin-sealed semiconductor device may be surface-mounted on the support member.
  • a method of surface mounting for example, reflow soldering in which solder is supplied to a printed wiring board in advance and then heated and melted by warm air or the like and soldered is used.
  • the heating method include hot air reflow and infrared reflow.
  • the heating method may be a method of heating the whole or a method of heating a local part.
  • the heating temperature may be, for example, in the range of 240-280 ° C.
  • Curing agent (B1) HE-100C-30 (trade name, manufactured by Air Water Co., Ltd., phenylaralkyl-type phenol resin, hydroxyl equivalent: 174 g / eq, softening point 77 ° C.)
  • the highest absorbance peak was a peak point between the two points between 1670 cm -1 and 1860 cm -1. 1670cm and -1 and a linear baseline between the two points between 1860 cm -1, and a baseline point that it is the same wave number and the peak point on the base line, the difference in absorbance of the baseline point and the peak point.
  • the height (P CO ) of the absorption peak derived from the stretching vibration of the carbonyl group was used.
  • E Inorganic filler (E1) SC2050-HLG (trade name, manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size 0.50 ⁇ m) (E2) YA050C-HHG (trade name, manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size 0.05 ⁇ m)
  • G Curing accelerator (G1) 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole manufactured by Shikoku Chemicals Co., Ltd.)
  • ⁇ Preparation of film adhesive> The produced adhesive varnish was filtered through a 100-mesh filter, and degassed under vacuum.
  • the applied adhesive varnish was dried by heating at 90 ° C. for 5 minutes, and then at 130 ° C. for 5 minutes in two stages, to obtain Comparative Examples 1-1 and 1-2 and Examples 1-1 and 1 in the B-stage state. -2 and Comparative Examples 2-1 and 2-2 and Examples 2-1 to 2-7 were obtained.
  • the thickness of the film adhesive was adjusted to 10 ⁇ m depending on the amount of the adhesive varnish applied.
  • NMP N-methyl-2-pyrrolidone
  • Comparative Example 1-1 and Examples 1-1 and 1-2 and Comparative Example 2-1 and Examples 2-1 to 2-7 in the B-stage state are further heated at 170 ° C. for one hour. After drying, film adhesives of Comparative Example 1-1 and Examples 1-1 and 1-2 and Comparative Example 2-1 and Examples 2-1 to 2-7 in a C-stage state were produced.
  • the obtained dicing sample was cut using a full-auto dicer DFD-6361 (manufactured by Disco Corporation).
  • the cutting was performed by a step cutting method using two blades, and dicing blades ZH05-SD3500-N1-xx-DD and ZH05-SD4000-N1-xx-BB (both manufactured by Disco Corporation) were used.
  • the cutting conditions were a blade rotation speed of 4000 rpm, a cutting speed of 50 mm / sec, and a chip size of 7.5 mm ⁇ 7.5 mm.
  • the cutting was performed in the first stage so that the semiconductor wafer remained about 30 ⁇ m, and then in the second stage so that the dicing tape had a cut of about 20 ⁇ m.
  • the semiconductor chip obtained by the cutting was thermocompression-bonded on a solder resist (Taiyo Holdings Co., Ltd., trade name: AUS-308).
  • the pressure bonding conditions were a temperature of 120 ° C., a time of 1 second, and a pressure of 0.1 MPa.
  • the sample obtained by crimping was placed in a dryer and cured at 170 ° C. for 1 hour.
  • the semiconductor chip press-bonded to the solder resist is cured, and the semiconductor chip and the solder resist are hardened and die-shared by pulling the semiconductor chip with a universal bond tester (trade name: Series 4000, manufactured by Nordson Advance Technology Co., Ltd.).
  • the strength was measured and evaluated as the adhesive strength.
  • the measurement condition was a stage temperature of 250 ° C. The results are shown in Tables 5 and 6.
  • the film adhesive having an acrylic rubber satisfying the requirement of the formula (1) has a higher copper ion content than the film adhesive having an acrylic rubber not satisfying the requirement of the formula (1).
  • the transmission time was long (comparison of Comparative Example 1-2 and Examples 1-1 and 1-2 with Comparative Example 1-1 and comparison with Comparative Example 2-2 and Examples 2-1 to 2-7) Comparison with Example 2-2). This is presumed to be due to the fact that the use of an acrylic rubber having a small (or no) nitrile group having a high complex stability constant with copper ions weakened the ability of the film adhesive to take in copper ions. Also, from the comparison between Example 1-1 and Example 2-1 and the comparison between Example 1-2 and Example 2-2, the smaller the average particle diameter of the inorganic filler, the smaller the copper ion transmission time. It turns out that it tends to be longer.
  • the film adhesive containing various heterocyclic compounds had further improved adhesive strength as compared with the film adhesive containing no heterocyclic compound (Comparative Example 1). -2 and Examples 1-1 and 1-2, and Comparative Example 2-2 and Examples 2-1 to 2-7).
  • the film adhesive of the present invention was able to sufficiently suppress the permeation of copper ions in the adhesive, and was also excellent in adhesive strength.
  • SYMBOLS 1 Film adhesive, 2 ... Base material, 3 ... Cover film, 6 ... Adhesive layer, 7 ... Dicing tape, 9, 9a, 9b ... Semiconductor element, 10 ... Support member, 11 ... Wire, 12 ... Sealing Material, 13 terminals, 100, 110, 120, 130 adhesive sheet, 200, 210 semiconductor device.

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Abstract

Disclosed is a film-shaped adhesive for adhering together a semiconductor element and a support member upon which the semiconductor element is placed. The film-shaped adhesive includes a thermosetting resin, a curing agent, an acrylic rubber, and a heterocyclic compound. In the infrared absorption spectrum of the acrylic rubber, PCO and PCN satisfy the condition in formula (1), where PCO is the height of an absorption peak derived from carbonyl stretching vibrations and PCN is the height of a peak derived from nitrile stretching vibrations. The thickness of the film-shaped adhesive is 50 μm or less.　(1): PCN/PCO<0.070

Description

フィルム状接着剤、接着シート、並びに半導体装置及びその製造方法Film adhesive, adhesive sheet, semiconductor device and method of manufacturing the same
　本発明は、フィルム状接着剤、接着シート、並びに半導体装置及びその製造方法に関する。 The present invention relates to a film adhesive, an adhesive sheet, a semiconductor device, and a method for manufacturing the same.
　近年、半導体素子（半導体チップ）を多段に積層したスタックドＭＣＰ（Ｍｕｌｔｉ　Ｃｈｉｐ　Ｐａｃｋａｇｅ）が普及しており、携帯電話、携帯オーディオ機器用のメモリ半導体パッケージ等として搭載されている。また、携帯電話等の多機能化に伴い、半導体パッケージの高速化、高密度化、高集積化等も推し進められている。これに伴い、半導体チップ回路の配線材料として銅を使用することによって高速化が図られている。また、複雑な搭載基板への接続信頼性の向上、半導体パッケージからの排熱促進の観点から、銅を素材としたリードフレーム等が使用されつつある。 In recent years, a stacked MCP (Multi Chip Package) in which semiconductor elements (semiconductor chips) are stacked in multiple stages has become widespread, and is mounted as a memory semiconductor package for a mobile phone, a portable audio device, or the like. In addition, with the increase in functions of mobile phones and the like, higher speed, higher density, and higher integration of semiconductor packages are being promoted. Along with this, the use of copper as a wiring material for semiconductor chip circuits has increased the speed. In addition, from the viewpoint of improving the reliability of connection to a complicated mounting substrate and promoting heat dissipation from a semiconductor package, a lead frame made of copper or the like is being used.
　しかし、銅は腐食し易い特性をもち、また、低コスト化の観点から、回路面の絶縁性を確保するためのコート材も簡略化される傾向にあるため、半導体パッケージの電気的特性を確保し難くなる傾向にある。特に、半導体チップを多段積層する半導体パッケージでは、腐食により発生した銅イオンが接着剤内部を移動し、半導体チップ内又は半導体チップ／半導体チップ間での電気信号のロスが起こり易い傾向にある。 However, copper has the property of being easily corroded, and from the viewpoint of cost reduction, the coating material for securing the insulation of the circuit surface tends to be simplified, so that the electrical characteristics of the semiconductor package are secured. It tends to be difficult. In particular, in a semiconductor package in which semiconductor chips are stacked in multiple stages, copper ions generated by corrosion move inside the adhesive, and electric signals tend to be easily lost in the semiconductor chip or between the semiconductor chips.
　また、高機能化という観点から、複雑な搭載基板へ半導体素子を接続することが多く、接続信頼性を向上するために銅を素材としたリードフレームが好まれる傾向にある。このような場合においても、リードフレームから発生する銅イオンによる電気信号のロスが問題となることがある。 In addition, from the viewpoint of high functionality, semiconductor elements are often connected to complicated mounting substrates, and lead frames made of copper tend to be preferred in order to improve connection reliability. Even in such a case, a loss of an electric signal due to copper ions generated from the lead frame may cause a problem.
　さらに、銅を素材とする部材を使用した半導体パッケージにおいては、その部材から銅イオンが発生し、電気的な不具合を起こす可能性が高く、充分な耐ＨＡＳＴ性が得られないことがある。 Furthermore, in a semiconductor package using a member made of copper, there is a high possibility that copper ions are generated from the member, causing an electrical failure, and sufficient HAST resistance may not be obtained.
　電気信号のロス等を防ぐ観点から、半導体パッケージ内で発生する銅イオンを捕捉する接着剤の検討が行われている。例えば、特許文献１には、エポキシ基を有し、且つ、カルボキシル基を有さない熱可塑性樹脂と、３級の窒素原子を環原子に含む複素環化合物を有し、陽イオンと錯体を形成する有機系錯体形成化合物とを有する半導体装置製造用の接着シートが開示されている。 接着 From the viewpoint of preventing loss of electric signals, etc., an adhesive for capturing copper ions generated in a semiconductor package is being studied. For example, Patent Literature 1 discloses a complex with a cation having a thermoplastic resin having an epoxy group and no carboxyl group and a heterocyclic compound having a tertiary nitrogen atom as a ring atom. An adhesive sheet for manufacturing a semiconductor device, comprising an organic complex-forming compound, is disclosed.
　しかしながら、従来の接着剤では、接着剤内の銅イオン透過の抑制の点において充分でなく、未だ改善の余地がある。 However, conventional adhesives are not sufficient in terms of suppressing copper ion permeation in the adhesive, and there is still room for improvement.
特開２０１３－０２６５６６号公報JP 2013-026566 A
　そこで、本発明は、接着剤内の銅イオン透過を充分に抑制することが可能であり、さらに接着力にも優れるフィルム状接着剤を提供することを主な目的とする。 Accordingly, it is a main object of the present invention to provide a film-like adhesive which can sufficiently suppress the permeation of copper ions in the adhesive and has excellent adhesive strength.
　本発明者らが鋭意検討したところ、フィルム状接着剤に特定のアクリルゴムと特定の成分とを組み合わせることによって、接着剤内の銅イオン透過を充分に抑制することが可能であり、さらに接着力にも優れることを見出し、本発明を完成するに至った。 The present inventors have made intensive studies and found that by combining a specific acrylic rubber and a specific component in a film adhesive, it is possible to sufficiently suppress copper ion permeation in the adhesive, and furthermore, the adhesive strength And found that the present invention was completed.
　本発明の一側面は、半導体素子と半導体素子を搭載する支持部材とを接着するためのフィルム状接着剤であって、フィルム状接着剤が、熱硬化性樹脂と、硬化剤と、アクリルゴムと、複素環式化合物とを含有し、アクリルゴムの赤外吸収スペクトルにおいて、カルボニル基の伸縮振動に由来する吸収ピークの高さをＰＣＯ、ニトリル基の伸縮振動に由来するピークの高さをＰＣＮとしたとき、ＰＣＯ及びＰＣＮが下記式（１）の条件を満たし、フィルム状接着剤の厚みが５０μｍ以下である、フィルム状接着剤を提供する。
　ＰＣＮ／ＰＣＯ＜０．０７０　（１） One aspect of the present invention is a film adhesive for bonding a semiconductor element and a support member on which the semiconductor element is mounted, wherein the film adhesive is a thermosetting resin, a curing agent, and an acrylic rubber. , A heterocyclic compound, and in the infrared absorption spectrum of the acrylic rubber, the height of the absorption peak derived from the stretching vibration of the carbonyl group is P CO , and the height of the peak derived from the stretching vibration of the nitrile group is P when the CN, P CO and P CN satisfies the following condition expression (1), the thickness of the film adhesive is 50μm or less, to provide a film-like adhesive.
P CN / P CO <0.070 (1)
　式（１）の条件を満たすということは、アクリルゴムにおいて、アクリロニトリルに由来する構成単位が少ない（又は含まない）ということを意味する。アクリロニトリルに由来する構成単位が少ない（又は含まない）アクリルゴムを用いることによって、接着剤内の銅イオン透過を充分に抑制することが可能となり得る。このような効果を奏する理由は必ずしも定かではないが、本発明者らは、銅イオンと錯形成し易い（錯体安定度定数の高い）アクリロニトリルのニトリル基が少ない（又は含まない）ことからフィルム状接着剤の銅イオンの取り込みが弱くなり、結果として、接着剤内の銅イオン透過が抑制されるためであると考えている。また、アクリロニトリルに由来する構成単位が少ない（又は含まない）アクリルゴムは相分離構造を形成し難い傾向にあり、相分離構造のし難さが、接着剤内の銅イオン透過の抑制に影響を与えている可能性も考えられる。 を 満 た す Satisfying the condition of the formula (1) means that the acrylic rubber has few (or no) structural units derived from acrylonitrile. By using an acrylic rubber having a small amount (or no containing unit) derived from acrylonitrile, it may be possible to sufficiently suppress the permeation of copper ions in the adhesive. The reason for such an effect is not necessarily clear, but the present inventors have found that acrylonitrile, which easily forms a complex with copper ions (having a high complex stability constant), has a small (or no) nitrile group in acrylonitrile. It is considered that the absorption of copper ions by the adhesive is weakened, and as a result, the permeation of copper ions in the adhesive is suppressed. In addition, acrylic rubber having a small number of (or not including) structural units derived from acrylonitrile tends to hardly form a phase-separated structure, and the difficulty of the phase-separated structure has an effect on suppression of copper ion permeation in the adhesive. It is possible that they are giving.
　フィルム状接着剤は、複素環式化合物を含有することによって、接着剤内の銅イオン透過を充分に抑制するとともに、さらに接着力に優れる傾向にある。複素環式化合物は、３以上の窒素原子を有する芳香族化合物であってよい。複素環式化合物は、トリアゾール化合物及びテトラゾール化合物からなる群より選ばれる少なくも１種であってよい。複素環式化合物は、熱硬化性樹脂、硬化剤、及びアクリルゴムの総質量１００質量部に対して、０．０１～２質量部であってよい。 The film adhesive, which contains a heterocyclic compound, has a tendency to sufficiently suppress copper ion permeation in the adhesive and to have further excellent adhesive strength. The heterocyclic compound may be an aromatic compound having three or more nitrogen atoms. The heterocyclic compound may be at least one selected from the group consisting of a triazole compound and a tetrazole compound. The heterocyclic compound may be used in an amount of 0.01 to 2 parts by mass based on 100 parts by mass of the thermosetting resin, the curing agent, and the acrylic rubber.
　フィルム状接着剤は、無機フィラーをさらに含有していてもよく、無機フィラーの平均粒径は１μｍ以下であってよい。 The film adhesive may further contain an inorganic filler, and the average particle size of the inorganic filler may be 1 μm or less.
　別の側面において、本発明は、基材と、基材の一方の面上に設けられた上述のフィルム状接着剤とを備える、接着シートを提供する。基材は、ダイシングテープであってよい。 In another aspect, the present invention provides an adhesive sheet comprising a base material and the above-mentioned film adhesive provided on one surface of the base material. The substrate may be a dicing tape.
　別の側面において、本発明は、半導体素子と、半導体素子を搭載する支持部材と、半導体素子及び支持部材の間に設けられ、半導体素子及び支持部材を接着する接着部材とを備え、接着部材が、上述のフィルム状接着剤の硬化物である、半導体装置を提供する。支持部材は、銅を素材とする部材を含んでいてよい。 In another aspect, the present invention includes a semiconductor element, a support member for mounting the semiconductor element, and an adhesive member provided between the semiconductor element and the support member, for bonding the semiconductor element and the support member. And a semiconductor device which is a cured product of the above film adhesive. The support member may include a member made of copper.
　別の側面において、本発明は、上述のフィルム状接着剤を用いて、半導体素子と支持部材とを接着する工程を備える、半導体装置の製造方法を提供する。 In another aspect, the present invention provides a method for manufacturing a semiconductor device, comprising a step of bonding a semiconductor element and a support member using the above-mentioned film adhesive.
　別の側面において、本発明は、半導体ウェハに、上述の接着シートのフィルム状接着剤を貼り付ける工程と、フィルム状接着剤を貼り付けた半導体ウェハを切断することによって、複数の個片化されたフィルム状接着剤付き半導体素子を作製する工程と、フィルム状接着剤付き半導体素子を支持部材に接着する工程とを備える、半導体装置の製造方法を提供する。半導体装置の製造方法は、支持部材に接着されたフィルム状接着剤付き半導体素子に対して、リフロー炉を用いて加熱する工程をさらに備えていてもよい。 In another aspect, the present invention provides a method of attaching a film-like adhesive of the above-mentioned adhesive sheet to a semiconductor wafer, and cutting the semiconductor wafer to which the film-like adhesive has been attached to form a plurality of individual pieces. A method of manufacturing a semiconductor device, comprising: a step of producing a semiconductor element with a film-like adhesive; and a step of bonding the semiconductor element with a film-like adhesive to a support member. The method for manufacturing a semiconductor device may further include a step of heating the semiconductor element with the film-like adhesive bonded to the support member using a reflow furnace.
　本発明によれば、接着剤内の銅イオン透過を充分に抑制することが可能であり、さらに接着力にも優れるフィルム状接着剤が提供される。また、本発明によれば、このようなフィルム状接着剤を用いた接着シート及び半導体装置が提供される。さらに、本発明によれば、フィルム状接着剤又は接着シートを用いた半導体装置の製造方法が提供される。 According to the present invention, there is provided a film adhesive which can sufficiently suppress the permeation of copper ions in the adhesive and has excellent adhesive strength. Further, according to the present invention, an adhesive sheet and a semiconductor device using such a film-like adhesive are provided. Further, according to the present invention, there is provided a method of manufacturing a semiconductor device using a film adhesive or an adhesive sheet.
フィルム状接着剤の一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of a film adhesive. 接着シートの一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of an adhesive sheet. 接着シートの他の一実施形態を示す模式断面図である。It is a schematic cross section showing another embodiment of an adhesive sheet. 接着シートの他の一実施形態を示す模式断面図である。It is a schematic cross section showing another embodiment of an adhesive sheet. 接着シートの他の一実施形態を示す模式断面図である。It is a schematic cross section showing another embodiment of an adhesive sheet. 半導体装置の一実施形態を示す模式断面図である。FIG. 2 is a schematic cross-sectional view illustrating one embodiment of a semiconductor device. 半導体装置の他の一実施形態を示す模式断面図である。FIG. 6 is a schematic sectional view showing another embodiment of the semiconductor device.
　以下、図面を適宜参照しながら、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（ステップ等も含む）は、特に明示した場合を除き、必須ではない。各図における構成要素の大きさは概念的なものであり、構成要素間の大きさの相対的な関係は各図に示されたものに限定されない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including steps and the like) are not essential unless otherwise specified. The size of the components in each drawing is conceptual, and the relative relationship between the sizes of the components is not limited to that shown in each drawing.
　本明細書における数値及びその範囲についても同様であり、本発明を制限するものではない。本明細書において「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 数 値 The same applies to numerical values and ranges in the present specification, and do not limit the present invention. In this specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other stages. Good. Further, in the numerical ranges described in this specification, the upper limit or the lower limit of the numerical ranges may be replaced with the values shown in the embodiments.
　本明細書において、（メタ）アクリレートは、アクリレート又はそれに対応するメタクリレートを意味する。（メタ）アクリロイル基、（メタ）アクリル共重合体等の他の類似表現についても同様である。 に お い て In the present specification, (meth) acrylate means acrylate or its corresponding methacrylate. The same applies to other similar expressions such as a (meth) acryloyl group and a (meth) acrylic copolymer.
　一実施形態に係るフィルム状接着剤は、半導体素子と半導体素子を搭載する支持部材とを接着するためのフィルム状接着剤であって、フィルム状接着剤が、（Ａ）熱硬化性樹脂と、（Ｂ）硬化剤と、（Ｃ）アクリルゴムと、（Ｄ）複素環式化合物とを含有し、（Ｃ）アクリルゴムの赤外吸収スペクトルにおいて、カルボニル基の伸縮振動に由来する吸収ピークの高さをＰＣＯ、ニトリル基の伸縮振動に由来するピークの高さをＰＣＮとしたとき、ＰＣＯ及びＰＣＮが下記式（１）の条件を満たし、フィルム状接着剤の厚みが５０μｍ以下である。
　ＰＣＮ／ＰＣＯ＜０．０７０　（１） The film adhesive according to one embodiment is a film adhesive for bonding a semiconductor element and a support member on which the semiconductor element is mounted, wherein the film adhesive is (A) a thermosetting resin, It contains (B) a curing agent, (C) an acrylic rubber, and (D) a heterocyclic compound, and has a high absorption peak derived from stretching vibration of a carbonyl group in an infrared absorption spectrum of the (C) acrylic rubber. the P CO is, when the height of the peak derived from stretching vibration of the nitrile group was P CN, satisfies the condition of P CO and P CN is represented by the following formula (1), the thickness of the film-like adhesive 50μm or less is there.
P CN / P CO <0.070 (1)
　フィルム状接着剤は、（Ａ）熱硬化性樹脂と、（Ｂ）硬化剤と、（Ｃ）アクリルゴムと、（Ｄ）複素環式化合物とを含有する、接着剤組成物を、フィルム状に成形することによって得ることができる。フィルム状接着剤及び接着剤組成物は、半硬化（Ｂステージ）状態を経て、硬化処理後に完全硬化（Ｃステージ）状態となり得るものであってよい。 The film adhesive is obtained by converting an adhesive composition containing (A) a thermosetting resin, (B) a curing agent, (C) an acrylic rubber, and (D) a heterocyclic compound into a film. It can be obtained by molding. The film-like adhesive and the adhesive composition may be capable of undergoing a semi-cured (B-stage) state and becoming a completely cured (C-stage) state after the curing treatment.
（Ａ）成分：熱硬化性樹脂
　（Ａ）成分は、接着性の観点から、エポキシ樹脂であってよい。エポキシ樹脂は、分子内にエポキシ基を有するものであれば、特に制限なく用いることができる。エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、スチルベン型エポキシ樹脂、トリアジン骨格含有エポキシ樹脂、フルオレン骨格含有エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ビフェニル型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、多官能フェノール類、アントラセン等の多環芳香族類のジグリシジルエーテル化合物などが挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、（Ａ）成分は、フィルムのタック性、柔軟性などの観点から、クレゾールノボラック型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、又はビスフェノールＡ型エポキシ樹脂であってもよい。 Component (A): Thermosetting resin The component (A) may be an epoxy resin from the viewpoint of adhesiveness. The epoxy resin can be used without any particular limitation as long as it has an epoxy group in the molecule. Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, and bisphenol F novolak epoxy resin. , Stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, polyfunctional phenols And polycyclic aromatic diglycidyl ether compounds such as anthracene and anthracene. These may be used alone or in combination of two or more. Among these, the component (A) may be a cresol novolak type epoxy resin, a bisphenol F type epoxy resin, or a bisphenol A type epoxy resin from the viewpoint of the tackiness and flexibility of the film.
　エポキシ樹脂のエポキシ当量は、特に制限されないが、９０～３００ｇ／ｅｑ、１１０～２９０ｇ／ｅｑ、又は１１０～２９０ｇ／ｅｑであってよい。エポキシ樹脂のエポキシ当量がこのような範囲にあると、フィルム状接着剤のバルク強度を維持しつつ、流動性を確保することができる傾向にある。 The epoxy equivalent of the epoxy resin is not particularly limited, but may be 90 to 300 g / eq, 110 to 290 g / eq, or 110 to 290 g / eq. When the epoxy equivalent of the epoxy resin is in such a range, there is a tendency that the fluidity can be secured while maintaining the bulk strength of the film adhesive.
（Ｂ）成分：硬化剤
　（Ｂ）成分は、エポキシ樹脂の硬化剤となり得るフェノール樹脂であってよい。フェノール樹脂は、分子内にフェノール性水酸基を有するものであれば特に制限なく用いることができる。フェノール樹脂としては、例えば、フェノール、クレゾール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール等のフェノール類及び／又はα－ナフトール、β－ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド等のアルデヒド基を有する化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック型フェノール樹脂、アリル化ビスフェノールＡ、アリル化ビスフェノールＦ、アリル化ナフタレンジオール、フェノールノボラック、フェノール等のフェノール類及び／又はナフトール類とジメトキシパラキシレン又はビス（メトキシメチル）ビフェニルから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂などが挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、フェノール樹脂は、フェノールアラルキル樹脂又はナフトールアラルキル樹脂であってもよい。 Component (B): Curing Agent The component (B) may be a phenol resin that can be a curing agent for an epoxy resin. The phenol resin can be used without any particular limitation as long as it has a phenolic hydroxyl group in the molecule. Examples of the phenol resin include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde. Novolak-type phenolic resin obtained by condensation or co-condensation with a compound having an aldehyde group of phenol group, phenols such as allylated bisphenol A, allylated bisphenol F, allylated naphthalene diol, phenol novolak, phenol and / or And phenol aralkyl resins and naphthol aralkyl resins synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. These may be used alone or in combination of two or more. Among these, the phenol resin may be a phenol aralkyl resin or a naphthol aralkyl resin.
　フェノール樹脂の水酸基当量は、７０ｇ／ｅｑ以上又は７０～３００ｇ／ｅｑであってよい。フェノール樹脂の水酸基当量が７０ｇ／ｅｑ以上であると、フィルムの貯蔵弾性率がより向上する傾向にあり、３００ｇ／ｅｑ以下であると、発泡、アウトガス等の発生による不具合を防ぐことが可能となる。 The hydroxyl equivalent of the phenol resin may be 70 g / eq or more or 70 to 300 g / eq. When the hydroxyl equivalent of the phenol resin is 70 g / eq or more, the storage elastic modulus of the film tends to be further improved, and when it is 300 g / eq or less, it is possible to prevent problems due to foaming, outgassing and the like. .
　エポキシ樹脂のエポキシ当量とフェノール樹脂の水酸基当量との比（エポキシ樹脂のエポキシ当量／フェノール樹脂の水酸基当量）は、硬化性の観点から、０．３０／０．７０～０．７０／０．３０、０．３５／０．６５～０．６５／０．３５、０．４０／０．６０～０．６０／０．４０、又は０．４５／０．５５～０．５５／０．４５であってよい。当該当量比が０．３０／０．７０以上であると、より充分な硬化性が得られる傾向にある。当該当量比が０．７０／０．３０以下であると、粘度が高くなり過ぎることを防ぐことができ、より充分な流動性を得ることができる。 The ratio of the epoxy equivalent of the epoxy resin to the hydroxyl equivalent of the phenol resin (the epoxy equivalent of the epoxy resin / the hydroxyl equivalent of the phenol resin) is from 0.30 / 0.70 to 0.70 / 0.30 from the viewpoint of curability. , 0.35 / 0.65-0.65 / 0.35, 0.40 / 0.60-0.60 / 0.40, or 0.45 / 0.55-0.55 / 0.45 May be. When the equivalent ratio is 0.30 / 0.70 or more, more sufficient curability tends to be obtained. When the equivalent ratio is 0.70 / 0.30 or less, it is possible to prevent the viscosity from becoming too high, and to obtain more sufficient fluidity.
　（Ａ）成分及び（Ｂ）成分の合計の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の総質量１００質量部に対して、５～５０質量部、１０～４０質量部、又は１５～３０質量部であってよい。（Ａ）成分及び（Ｂ）成分の合計の含有量が５質量部以上であると、架橋によって弾性率が向上する傾向にある。（Ａ）成分及び（Ｂ）成分の合計の含有量が５０質量部以下であると、フィルム取扱い性を維持できる傾向にある。 The total content of the components (A) and (B) is 5 to 50 parts by mass, 10 to 40 parts by mass based on 100 parts by mass of the total mass of the components (A), (B) and (C). It may be parts by weight, or 15 to 30 parts by weight. When the total content of the components (A) and (B) is 5 parts by mass or more, the elastic modulus tends to be improved by crosslinking. When the total content of the component (A) and the component (B) is 50 parts by mass or less, the film handling property tends to be maintained.
（Ｃ）成分：アクリルゴム
　（Ｃ）成分は、（メタ）アクリル酸エステルに由来する構成単位を主成分として有するゴムである。（Ｃ）成分における（メタ）アクリル酸エステルに由来する構成単位の含有量は、構成単位全量を基準として、例えば、７０質量％以上、８０質量％以上、又は９０質量％以上であってよい。（Ｃ）成分は、エポキシ基、アルコール性又はフェノール性水酸基、カルボキシル基等の架橋性官能基を有する（メタ）アクリル酸エステルに由来する構成単位を含むものであってよい。（Ｃ）成分は、後述の式（１）の条件を満たす範囲で、アクリルニトリルに由来する構成単位を含むものであってもよいが、接着剤内の銅イオン透過をよりに抑制することが可能であり、埋込性にもより優れることから、（Ｃ）成分は、アクリルニトリルに由来する構成単位を含まないものであってよい。 Component (C): Acrylic Rubber The component (C) is a rubber having a structural unit derived from a (meth) acrylate ester as a main component. The content of the structural unit derived from the (meth) acrylate in the component (C) may be, for example, 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total amount of the structural units. The component (C) may include a structural unit derived from a (meth) acrylate having a crosslinkable functional group such as an epoxy group, an alcoholic or phenolic hydroxyl group, and a carboxyl group. The component (C) may include a constituent unit derived from acrylonitrile as long as the condition of the formula (1) described below is satisfied, but it is more effective to suppress copper ion permeation in the adhesive. The component (C) may not contain a constituent unit derived from acrylonitrile, since the component is possible and the embedding property is more excellent.
　（Ｃ）成分の赤外吸収スペクトルにおいて、カルボニル基の伸縮振動に由来する吸収ピークの高さをＰＣＯ、ニトリル基の伸縮振動に由来するピークの高さをＰＣＮとしたとき、ＰＣＯ及びＰＣＮが下記式（１）の条件を満たす。
　ＰＣＮ／ＰＣＯ＜０．０７０　（１） In the infrared absorption spectrum of the component (C), when the height P CO absorption peak derived from stretching vibration of the carbonyl group, the height of the peak derived from stretching vibration of the nitrile group was P CN, P CO and PCN satisfies the condition of the following equation (1).
P CN / P CO <0.070 (1)
　ここで、カルボニル基は主に構成単位である（メタ）アクリル酸エステルに由来するものであり、ニトリル基は主に構成単位であるアクリルニトリルに由来するものである。なお、カルボニル基の伸縮振動に由来する吸収ピークの高さ（ＰＣＯ）及びニトリル基の伸縮振動に由来するピークの高さ（ＰＣＮ）は、実施例で定義されるものを意味する。 Here, the carbonyl group is mainly derived from the constituent unit (meth) acrylate, and the nitrile group is mainly derived from the constituent unit acrylonitrile. The height of the absorption peak (P CO ) derived from the stretching vibration of the carbonyl group and the height of the peak (P CN ) derived from the stretching vibration of the nitrile group mean those defined in Examples.
　ＰＣＮ／ＰＣＯが小さいことは、（Ｃ）成分において、アクリルニトリルに由来する構成単位が少ないことを意味する。そのため、アクリルニトリルに由来する構成単位を含まない（Ｃ）成分は、理論上、式（１）の条件を満たし得る。 A small P CN / P CO means that the component (C) has few constituent units derived from acrylonitrile. Therefore, the component (C) that does not include a structural unit derived from acrylonitrile can theoretically satisfy the condition of the formula (1).
　ＰＣＮ／ＰＣＯは、０．０７０未満であり、０．０６５以下、０．０６０以下、０．０５５以下、０．０５０以下、０．０４０以下、０．０３０以下、０．０２０以下、又は０．０１０以下であってよい。ＰＣＮ／ＰＣＯが０．０７０未満であると、接着剤内の銅イオン透過を充分に抑制することが可能となり得る。また、ＰＣＮ／ＰＣＯの値が小さくなるにつれて、接着剤内の銅イオン透過をより充分に抑制することができる。また、ＰＣＮ／ＰＣＯの値が小さくなるにつれて、（Ｃ）成分の凝集力が低下するため、埋込性もより優れる傾向にある。 P CN / P CO is less than 0.070, 0.065 or less, 0.060 or less, 0.055 or less, 0.050 or less, 0.040 or less, 0.030 or less, 0.020 or less, or It may be 0.010 or less. When P CN / P CO is less than 0.070, it may be possible to sufficiently suppress the permeation of copper ions in the adhesive. Further, as the value of P CN / P CO becomes smaller, the permeation of copper ions in the adhesive can be more sufficiently suppressed. Further, as the value of P CN / P CO decreases, the cohesive force of the component (C) decreases, and the embedding property tends to be more excellent.
　（Ｃ）成分のガラス転移温度（Ｔｇ）は、－５０～５０℃又は－３０～３０℃であってよい。（Ｃ）成分のＴｇが－５０℃以上であると、接着剤の柔軟性が高くなり過ぎることを防ぐことができる傾向にある。これにより、ウェハダイシング時にフィルム状接着剤を切断し易くなり、バリの発生を防ぐことが可能となる。（Ｃ）成分のＴｇが５０℃以下であると、接着剤の柔軟性の低下を抑制できる傾向にある。これによって、フィルム状接着剤をウェハに貼り付ける際に、ボイドを充分に埋め込み易くなる傾向にある。また、ウェハの接着力の低下によるダイシング時のチッピングを防ぐことが可能となる。ここで、ガラス転移温度（Ｔｇ）は、ＤＳＣ（熱示差走査熱量計）（例えば、株式会社リガク製、Ｔｈｅｒｍｏ　Ｐｌｕｓ　２）を用いて測定した値を意味する。 The glass transition temperature (Tg) of the component (C) may be −50 to 50 ° C. or −30 to 30 ° C. When the Tg of the component (C) is -50 ° C or more, the flexibility of the adhesive tends to be prevented from becoming too high. This makes it easier to cut the film adhesive during wafer dicing, thereby preventing the occurrence of burrs. When the Tg of the component (C) is 50 ° C. or lower, a decrease in the flexibility of the adhesive tends to be suppressed. This tends to make it easy to sufficiently fill voids when the film adhesive is attached to the wafer. Further, it is possible to prevent chipping at the time of dicing due to a decrease in the adhesive strength of the wafer. Here, the glass transition temperature (Tg) means a value measured using a DSC (thermal differential scanning calorimeter) (for example, Thermo Plus 2 manufactured by Rigaku Corporation).
　（Ｃ）成分の重量平均分子量（Ｍｗ）は、１０万～３００万又は２０万～２００万であってよい。（Ｃ）成分のＭｗがこのような範囲にあると、フィルム形成性、フィルム状における強度、可撓性、タック性等を適切に制御することができるとともに、リフロー性に優れ、埋め込み性を向上することができる。ここで、Ｍｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、標準ポリスチレンによる検量線を用いて換算した値を意味する。 The weight average molecular weight (Mw) of the component (C) may be 100,000 to 3,000,000 or 200,000 to 2,000,000. When the Mw of the component (C) is within such a range, the film formability, the strength in the form of a film, the flexibility, the tackiness, and the like can be appropriately controlled, and the reflow property is excellent and the embedding property is improved. can do. Here, Mw means a value measured by gel permeation chromatography (GPC) and converted using a calibration curve using standard polystyrene.
　アクリルニトリルに由来する構成単位を含まない（Ｃ）成分の市販品としては、例えば、ＫＨ－ＣＴ－８６５（日立化成株式会社製）等が挙げられる。 市 販 As a commercially available component (C) which does not contain a structural unit derived from acrylonitrile, for example, KH-CT-865 (manufactured by Hitachi Chemical Co., Ltd.) and the like are listed.
　（Ｃ）成分の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の総質量１００質量部に対して、５０～９５質量部、６０～９０質量部、又は７０～８５質量部であってよい。（Ｃ）成分の含有量がこのような範囲にあると、接着剤内の銅イオン透過をより充分に抑制できる傾向にある。 The content of the component (C) is 50 to 95 parts by mass, 60 to 90 parts by mass, or 70 to 85 parts by mass based on 100 parts by mass of the total of the components (A), (B) and (C). It may be parts by mass. When the content of the component (C) is in such a range, there is a tendency that permeation of copper ions in the adhesive can be more sufficiently suppressed.
（Ｄ）複素環式化合物
　フィルム状接着剤は、（Ｄ）成分を含有することによって、接着剤内の銅イオン透過を充分に抑制するとともに、さらに接着力に優れる傾向にある。（Ｄ）成分は、３以上の窒素原子を有する芳香族化合物であってよく、トリアゾール化合物及びテトラゾール化合物からなる群より選ばれる少なくも１種であってよい。 (D) Heterocyclic compound The film adhesive, by containing the component (D), has a tendency to sufficiently suppress copper ion permeation in the adhesive and to have further excellent adhesive strength. The component (D) may be an aromatic compound having three or more nitrogen atoms, and may be at least one selected from the group consisting of a triazole compound and a tetrazole compound.
　トリアゾール化合物としては、例えば、ベンゾトリアゾール、ベンゾトリアゾール－１－アセトニトリル、ベンゾトリアゾール－５－カルボン酸、ベンゾトリアゾール－１－メタノール、カルボキシベンゾトリアゾール、３－メルカプトトリアゾール、５－メルカプトトリアゾール；これらのアミノ基置換体等が挙げられる。トリアゾール化合物は、ベンゾトリアゾール又は３－メルカプトトリアゾールであってよい。 Examples of the triazole compound include benzotriazole, benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, benzotriazole-1-methanol, carboxybenzotriazole, 3-mercaptotriazole, 5-mercaptotriazole; Substitutes and the like. The triazole compound may be benzotriazole or 3-mercaptotriazole.
　テトラゾール化合物としては、例えば、５－メチルテトラゾール、５－アミノテトラゾール、１－メチル－５－アミノ－テトラゾール、１－メチル－５－メルカプト－１Ｈ－テトラゾール、１－カルボキシメチル－５－アミノ－テトラゾール等が挙げられる。テトラゾール化合物は、５－メチルテトラゾール又は５－アミノテトラゾールであってよい。 Examples of the tetrazole compound include 5-methyltetrazole, 5-aminotetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole and the like. Is mentioned. The tetrazole compound may be 5-methyltetrazole or 5-aminotetrazole.
　（Ｄ）成分の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の総質量１００質量部に対して、０．０１～２質量部であってよい。（Ｄ）成分の含有量がこのような範囲であることによって、接着力の観点でより優れる傾向にある。（Ｄ）成分の含有量は、０．０３質量部以上、０．０５質量部以上、０．１質量部以上又は０．３質量部以上であってよい。（Ｄ）成分の含有量は、２質量部以下、１．８質量部以下、１．５質量部以下、又は１．２質量部以下であってよい。 The content of the component (D) may be 0.01 to 2 parts by mass based on 100 parts by mass of the total mass of the components (A), (B) and (C). When the content of the component (D) is in such a range, the content tends to be more excellent in terms of adhesive strength. The content of the component (D) may be 0.03 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, or 0.3 parts by mass or more. The content of the component (D) may be 2 parts by mass or less, 1.8 parts by mass or less, 1.5 parts by mass or less, or 1.2 parts by mass or less.
　フィルム状接着剤（接着剤組成物）は、（Ｅ）無機フィラー、（Ｆ）カップリング剤、（Ｇ）硬化促進剤等をさらに含有していてもよい。 The film adhesive (adhesive composition) may further contain (E) an inorganic filler, (F) a coupling agent, (G) a curing accelerator, and the like.
（Ｅ）成分：無機フィラー
　（Ｅ）成分としては、例えば、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、窒化アルミニウム、ホウ酸アルミウィスカ、窒化ホウ素、シリカ等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、（Ｅ）成分は、溶融粘度の調整の観点から、シリカであってもよい。 Component (E): Inorganic filler Examples of the component (E) include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, and nitride. Aluminum, aluminum borate whiskers, boron nitride, silica, and the like. These may be used alone or in combination of two or more. Among these, the component (E) may be silica from the viewpoint of adjusting the melt viscosity.
　（Ｅ）成分の平均粒径は、１μｍ以下であってよい。（Ｅ）成分の平均粒径は、流動性の観点から、０．０１～１μｍ、０．０１～０．８μｍ、０．０３～０．５μｍ、０．０３～０．３μｍ、又は０．０３～０．１μｍであってよい。ここで、平均粒径は、ＢＥＴ比表面積から換算することによって求められる値を意味する。（Ｅ）成分の平均粒径が小さくなるにつれて、接着剤内の銅イオン透過をより一層充分に抑制することが可能となる。 The average particle size of the component (E) may be 1 μm or less. The average particle size of the component (E) is from 0.01 to 1 μm, 0.01 to 0.8 μm, 0.03 to 0.5 μm, 0.03 to 0.3 μm, or 0.03 to 1 μm from the viewpoint of fluidity. It may be up to 0.1 μm. Here, the average particle size means a value obtained by converting from the BET specific surface area. As the average particle size of the component (E) becomes smaller, it becomes possible to more sufficiently suppress the permeation of copper ions in the adhesive.
　（Ｅ）成分の形状は、特に制限されないが、球状であってよい。 形状 The shape of the component (E) is not particularly limited, but may be spherical.
　（Ｅ）成分の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の総質量１００質量部に対して、０．１～５０質量部、０．１～３０質量部、又は０．１～２０質量部であってよい。 The content of the component (E) is 0.1 to 50 parts by mass, 0.1 to 30 parts by mass, based on 100 parts by mass of the total mass of the components (A), (B), and (C). Alternatively, it may be 0.1 to 20 parts by mass.
（Ｆ）成分：カップリング剤
　（Ｆ）成分は、シランカップリング剤であってよい。シランカップリング剤としては、例えば、γ－ウレイドプロピルトリエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、３－フェニルアミノプロピルトリメトキシシラン、３－（２－アミノエチル）アミノプロピルトリメトキシシラン等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。 Component (F): Coupling Agent The component (F) may be a silane coupling agent. Examples of the silane coupling agent include γ-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltrimethoxysilane. Can be These may be used alone or in combination of two or more.
（Ｇ）成分：硬化促進剤
　（Ｇ）成分は、特に限定されず、一般に使用されるものを用いることができる。（Ｇ）成分としては、例えば、イミダゾール類及びその誘導体、有機リン系化合物、第二級アミン類、第三級アミン類、第四級アンモニウム塩等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。これらの中でも、反応性の観点から（Ｇ）成分はイミダゾール類及びその誘導体であってもよい。 Component (G): Curing accelerator The component (G) is not particularly limited, and a commonly used component can be used. Examples of the component (G) include imidazoles and derivatives thereof, organic phosphorus compounds, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more. Among them, the component (G) may be imidazoles and derivatives thereof from the viewpoint of reactivity.
　イミダゾール類としては、例えば、２－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－メチルイミダゾール等が挙げられる。これらは、１種を単独で又は２種以上を組み合わせて用いてもよい。 Examples of the imidazoles include 2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole and the like. These may be used alone or in combination of two or more.
　フィルム状接着剤（接着剤組成物）は、その他の成分をさらに含有していてもよい。その他の成分としては、例えば、顔料、イオン補捉剤、酸化防止剤等が挙げられる。 The film adhesive (adhesive composition) may further contain other components. Other components include, for example, pigments, ion scavengers, antioxidants, and the like.
　（Ｆ）成分、（Ｇ）成分、及びその他の成分の含有量は、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の総質量１００質量部に対して、０～３０質量部であってよい。 The content of the component (F), the component (G), and other components is 0 to 30 parts by mass based on 100 parts by mass of the total mass of the components (A), (B), and (C). May be.
　図１は、フィルム状接着剤の一実施形態を示す模式断面図である。図１に示すフィルム状接着剤１（接着フィルム）は、接着剤組成物をフィルム状に成形したものである。フィルム状接着剤１は、半硬化（Ｂステージ）状態であってよい。このようなフィルム状接着剤１は、接着剤組成物を支持フィルムに塗布することによって形成することができる。接着剤組成物のワニス（接着剤ワニス）を用いる場合は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分、並びに必要に応じて添加される他の成分を溶剤中で混合し、混合液を混合又は混練して接着剤ワニスを調製し、接着剤ワニスを支持フィルムに塗布し、溶剤を加熱乾燥して除去することによってフィルム状接着剤１を形成することができる。 FIG. 1 is a schematic cross-sectional view showing one embodiment of a film adhesive. The film adhesive 1 (adhesive film) shown in FIG. 1 is obtained by molding an adhesive composition into a film. The film adhesive 1 may be in a semi-cured (B stage) state. Such a film adhesive 1 can be formed by applying an adhesive composition to a support film. When a varnish of the adhesive composition (adhesive varnish) is used, the component (A), the component (B), the component (C), the component (D), and other components added as necessary may be added to a solvent. , A mixed solution is mixed or kneaded to prepare an adhesive varnish, the adhesive varnish is applied to a support film, and the solvent is removed by heating and drying to form the film adhesive 1. .
　支持フィルムは、上記の加熱乾燥に耐えるものであれば特に限定されないが、例えば、ポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、ポリイミドフィルム、ポリエーテルイミドフィルム、ポリエーテルナフタレートフィルム、ポリメチルペンテンフィルム等であってよい。支持フィルムは、２種以上を組み合わせた多層フィルムであってもよく、表面がシリコーン系、シリカ系等の離型剤などで処理されたものであってもよい。支持フィルムの厚みは、例えば、１０～２００μｍ又は２０～１７０μｍであってよい。 The support film is not particularly limited as long as it can withstand the above-mentioned heating and drying, for example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, a polymethylpentene film, and the like. It may be. The support film may be a multilayer film in which two or more kinds are combined, or may be one whose surface is treated with a release agent such as a silicone-based or silica-based release agent. The thickness of the support film may be, for example, 10-200 μm or 20-170 μm.
　混合又は混練は、通常の撹拌機、らいかい機、三本ロール、ボールミル等の分散機を用い、これらを適宜組み合わせて行うことができる。 Mixing or kneading can be performed by using an ordinary stirrer, a mill, a three-roller, a disperser such as a ball mill, or the like, and appropriately combining these.
　接着剤ワニスの調製に用いられる溶剤は、各成分を均一に溶解、混練または分散できるものであれば制限はなく、従来公知のものを使用することができる。このような溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎメチルピロリドン、トルエン、キシレン等が挙げられる。溶剤は、乾燥速度及び価格の点でメチルエチルケトン、シクロヘキサノン等であってよい。 溶 剤 The solvent used for the preparation of the adhesive varnish is not limited as long as each component can be uniformly dissolved, kneaded or dispersed, and conventionally known solvents can be used. Examples of such a solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, xylene, and the like. The solvent may be methyl ethyl ketone, cyclohexanone, etc. in terms of drying speed and cost.
　接着剤ワニスを支持フィルムに塗布する方法としては、公知の方法を用いることができ、例えば、ナイフコート法、ロールコート法、スプレーコート法、グラビアコート法、バーコート法、カーテンコート法等が挙げられる。加熱乾燥の条件は、使用した溶剤が充分に揮散する条件であれば特に制限はないが、５０～１５０℃で、１～３０分間加熱して行うことができる。 As a method of applying the adhesive varnish to the support film, a known method can be used, and examples thereof include a knife coat method, a roll coat method, a spray coat method, a gravure coat method, a bar coat method, and a curtain coat method. Can be The heating and drying conditions are not particularly limited as long as the used solvent is sufficiently volatilized, but the heating and drying can be performed by heating at 50 to 150 ° C. for 1 to 30 minutes.
　フィルム状接着剤の厚みが５０μｍ以下であると、半導体素子と半導体素子を搭載する支持部材との距離が近くなるため、銅イオンによる不具合が発生し易くなる傾向にある。本実施形態に係るフィルム状接着剤は、接着剤内の銅イオン透過を充分に抑制することが可能であることから、その厚みを５０μｍ以下とすることが可能となる。フィルム状接着剤１の厚みは、４０μｍ以下、３０μｍ以下、２０μｍ以下、又は１５μｍ以下であってもよい。フィルム状接着剤１の厚みの下限は、特に制限されないが、例えば、１μｍ以上とすることができる。 (4) If the thickness of the film-like adhesive is 50 μm or less, the distance between the semiconductor element and the supporting member on which the semiconductor element is mounted becomes short, so that problems due to copper ions tend to occur easily. Since the film-like adhesive according to the present embodiment can sufficiently suppress the permeation of copper ions in the adhesive, the thickness can be reduced to 50 μm or less. The thickness of the film adhesive 1 may be 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less. The lower limit of the thickness of the film adhesive 1 is not particularly limited, but may be, for example, 1 μm or more.
　半硬化（Ｂステージ）状態におけるフィルム状接着剤１の銅イオン透過時間は、８０分超であってよく、８５分以上、９０分以上、１００分以上、１５０分以上、２００分以上、又は２５０分以上であってもよい。銅イオン透過時間が８０分超であることによって、半導体装置作製時に硬化不足等の不良が発生した場合であっても、銅イオンに起因する不具合はより発生し難いことが予測される。 The copper ion transmission time of the film adhesive 1 in the semi-cured (B stage) state may be more than 80 minutes, and is 85 minutes or more, 90 minutes or more, 100 minutes or more, 150 minutes or more, 200 minutes or more, or 250 minutes. Minutes or more. When the copper ion transmission time is longer than 80 minutes, it is predicted that even if a defect such as insufficient curing occurs during the fabrication of a semiconductor device, a defect caused by the copper ion hardly occurs.
　完全硬化（Ｃステージ）状態におけるフィルム状接着剤１（すなわち、フィルム状接着剤の硬化物）の銅イオン透過時間は、１００分超であってよく、１２０分以上、１４０分以上、１６０分以上、１８０分以上、２００分以上、又は２５０分以上であってもよい。銅イオンによる不具合は、リフロー工程等の高温処理時に発生し易い傾向にある。そのため、完全硬化（Ｃステージ）状態が１００分超であることによって、銅イオンに起因する不具合はより発生し難いことが予測される。 The copper ion transmission time of the film adhesive 1 (that is, the cured product of the film adhesive) in the completely cured (C stage) state may be more than 100 minutes, and is 120 minutes or more, 140 minutes or more, 160 minutes or more. , 180 minutes or more, 200 minutes or more, or 250 minutes or more. Problems due to copper ions tend to occur during high-temperature treatment such as a reflow process. For this reason, it is expected that a defect caused by copper ions is less likely to occur when the completely cured (C stage) state is longer than 100 minutes.
　図２は、接着シートの一実施形態を示す模式断面図である。図２に示す接着シート１００は、基材２と、基材２上に設けられたフィルム状接着剤１とを備える。図３は、接着シートの他の一実施形態を示す模式断面図である。図３に示す接着シート１１０は、基材２と、基材２上に設けられたフィルム状接着剤１と、フィルム状接着剤１の基材２とは反対側の面に設けられたカバーフィルム３とを備える。 FIG. 2 is a schematic sectional view showing an embodiment of the adhesive sheet. The adhesive sheet 100 shown in FIG. 2 includes a base material 2 and a film adhesive 1 provided on the base material 2. FIG. 3 is a schematic sectional view showing another embodiment of the adhesive sheet. The adhesive sheet 110 shown in FIG. 3 includes a base material 2, a film adhesive 1 provided on the base material 2, and a cover film provided on a surface of the film adhesive 1 opposite to the base material 2. 3 is provided.
　基材２は、特に制限されないが、基材フィルムであってよい。基材フィルムは、上述の支持フィルムと同様のものであってよい。 The substrate 2 is not particularly limited, but may be a substrate film. The base film may be the same as the above-mentioned support film.
　カバーフィルム３は、フィルム状接着剤の損傷又は汚染を防ぐために用いられ、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、表面はく離剤処理フィルム等であってよい。カバーフィルム３の厚みは、例えば、１５～２００μｍ又は７０～１７０μｍであってよい。 The cover film 3 is used to prevent the film adhesive from being damaged or contaminated, and may be, for example, a polyethylene film, a polypropylene film, or a surface release agent-treated film. The thickness of the cover film 3 may be, for example, 15 to 200 μm or 70 to 170 μm.
　接着シート１００、１１０は、上述のフィルム状接着剤を形成する方法と同様に、接着剤組成物を基材フィルムに塗布することによって形成することができる。接着剤組成物を基材２に塗布する方法は、上述の接着剤組成物を支持フィルムに塗布する方法と同様であってよい。 The adhesive sheets 100 and 110 can be formed by applying an adhesive composition to a base film in the same manner as in the method for forming a film adhesive described above. The method for applying the adhesive composition to the substrate 2 may be the same as the method for applying the adhesive composition to the support film described above.
　接着シート１１０は、さらにフィルム状接着剤１にカバーフィルム３を積層させることによって得ることができる。 The adhesive sheet 110 can be obtained by further laminating the cover film 3 on the film adhesive 1.
　接着シート１００、１１０は、予め作製したフィルム状接着剤を用いて形成してもよい。この場合、接着シート１００は、ロールラミネーター、真空ラミネーター等を用いて所定条件（例えば、室温（２０℃）又は加熱状態）でラミネートすることによって形成することができる。接着シート１００は、連続的に製造ができ、効率に優れることから、加熱状態でロールラミネーターを用いて形成してもよい。 (4) The adhesive sheets 100 and 110 may be formed by using a film adhesive prepared in advance. In this case, the adhesive sheet 100 can be formed by laminating under a predetermined condition (for example, room temperature (20 ° C.) or a heated state) using a roll laminator, a vacuum laminator, or the like. Since the adhesive sheet 100 can be manufactured continuously and is excellent in efficiency, it may be formed using a roll laminator in a heated state.
　接着シートの他の実施形態は、基材２がダイシングテープであるダイシング・ダイボンディング一体型接着シートである。ダイシング・ダイボンディング一体型接着シートを用いると、半導体ウェハへのラミネート工程が１回となることから、作業の効率化が可能である。 Another embodiment of the adhesive sheet is a dicing / die bonding integrated adhesive sheet in which the base material 2 is a dicing tape. When the dicing / die-bonding integrated adhesive sheet is used, the laminating step for the semiconductor wafer is performed only once, so that the work efficiency can be improved.
　ダイシングテープとしては、例えば、ポリテトラフルオロエチレンフィルム、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、ポリメチルペンテンフィルム、ポリイミドフィルム等のプラスチックフィルムなどが挙げられる。また、ダイシングテープは、必要に応じて、プライマー塗布、ＵＶ処理、コロナ放電処理、研磨処理、エッチング処理等の表面処理が行われていてもよい。ダイシングテープは、粘着性を有するものであってもよい。このようなダイシングテープは、上述のプラスチックフィルムに粘着性を付与したものであってよく、上述のプラスチックフィルムの片面に粘着剤層を設けたものであってよい。粘着剤層は、感圧型又は放射線硬化型のいずれであってもよく、ダイシング時には半導体素子が飛散しない充分な粘着力を有し、その後の半導体素子のピックアップ工程においては半導体素子を傷つけない程度の低い粘着力を有するものであれば特に制限されず、従来公知のものを使用することができる。 Examples of the dicing tape include plastic films such as polytetrafluoroethylene film, polyethylene terephthalate film, polyethylene film, polypropylene film, polymethylpentene film, and polyimide film. The dicing tape may have been subjected to a surface treatment such as a primer application, a UV treatment, a corona discharge treatment, a polishing treatment, an etching treatment and the like, as necessary. The dicing tape may have adhesiveness. Such a dicing tape may be one in which the above-mentioned plastic film is provided with adhesiveness, or one in which an adhesive layer is provided on one surface of the above-mentioned plastic film. The pressure-sensitive adhesive layer may be either a pressure-sensitive type or a radiation-curable type, and has a sufficient adhesive strength so that the semiconductor element does not scatter during dicing, and does not damage the semiconductor element in the subsequent semiconductor element pickup step. There is no particular limitation as long as it has a low adhesive strength, and a conventionally known one can be used.
　ダイシングテープの厚みは、経済性及びフィルムの取扱い性の観点から、６０～１５０μｍ又は７０～１３０μｍであってよい。 厚 み The thickness of the dicing tape may be 60 to 150 μm or 70 to 130 μm from the viewpoints of economy and handling of the film.
　このようなダイシング・ダイボンディング一体型接着シートとしては、例えば、図４に示される構成を有するもの、図５に示される構成を有するもの等が挙げられる。図４は、接着シートの他の一実施形態を示す模式断面図である。図５は、接着シートの他の一実施形態を示す模式断面図である。図４に示す接着シート１２０は、ダイシングテープ７、粘着剤層６、及びフィルム状接着剤１をこの順に備える。図５に示す接着シート１３０は、ダイシングテープ７と、ダイシングテープ７上に設けられたフィルム状接着剤１とを備える。 接着 As such an integrated dicing / die-bonding adhesive sheet, for example, a sheet having the configuration shown in FIG. 4 and a sheet having the configuration shown in FIG. 5 are exemplified. FIG. 4 is a schematic sectional view showing another embodiment of the adhesive sheet. FIG. 5 is a schematic sectional view showing another embodiment of the adhesive sheet. The adhesive sheet 120 shown in FIG. 4 includes the dicing tape 7, the adhesive layer 6, and the film adhesive 1 in this order. The adhesive sheet 130 shown in FIG. 5 includes the dicing tape 7 and the film adhesive 1 provided on the dicing tape 7.
　接着シート１２０は、例えば、ダイシングテープ７上に粘着剤層６を設け、さらに粘着剤層６上にフィルム状接着剤１を積層させることによって得ることができる。接着シート１３０は、例えば、ダイシングテープ７とフィルム状接着剤１とを貼り合わせることによって得ることができる。 The adhesive sheet 120 can be obtained, for example, by providing the adhesive layer 6 on the dicing tape 7 and further laminating the film adhesive 1 on the adhesive layer 6. The adhesive sheet 130 can be obtained, for example, by laminating the dicing tape 7 and the film adhesive 1.
　フィルム状接着剤及び接着シートは、半導体装置の製造に用いられるものであってよく、半導体ウェハ又はすでに小片化されている半導体素子（半導体チップ）に、フィルム状接着剤及びダイシングテープを０℃～９０℃で貼り合わせた後、回転刃、レーザー又は伸張による分断でフィルム状接着剤付き半導体素子を得た後、当該フィルム状接着剤付き半導体素子を、有機基板、リードフレーム、又は他の半導体素子上に接着する工程を含む半導体装置の製造に用いられるものであってよい。 The film adhesive and the adhesive sheet may be used in the manufacture of a semiconductor device. The film adhesive and the dicing tape may be applied to a semiconductor wafer or a semiconductor element (semiconductor chip) that has already been cut into pieces at a temperature of 0 ° C. or less. After bonding at 90 ° C., a semiconductor element with a film adhesive is obtained by cutting with a rotary blade, laser or stretching, and then the semiconductor element with a film adhesive is used as an organic substrate, a lead frame, or another semiconductor element. It may be used for manufacturing a semiconductor device including a step of bonding on top.
　半導体ウェハとしては、例えば、単結晶シリコン、多結晶シリコン、各種セラミック、ガリウムヒ素等の化合物半導体などが挙げられる。 Examples of the semiconductor wafer include single crystal silicon, polycrystalline silicon, various ceramics, and compound semiconductors such as gallium arsenide.
　フィルム状接着剤及び接着シートは、ＩＣ、ＬＳＩ等の半導体素子と、４２アロイリードフレーム、銅リードフレーム等のリードフレーム；ポリイミド樹脂、エポキシ樹脂等のプラスチックフィルム；ガラス不織布等基材にポリイミド樹脂、エポキシ樹脂等のプラスチックを含浸、硬化させたもの；アルミナ等のセラミックス等の半導体搭載用支持部材などとを貼り合せるためのダイボンディング用接着剤として用いることができる。 Film adhesives and adhesive sheets include semiconductor elements such as ICs and LSIs, lead frames such as 42 alloy lead frames and copper lead frames; plastic films such as polyimide resins and epoxy resins; A resin impregnated and cured with an epoxy resin or the like; can be used as a die bonding adhesive for bonding a semiconductor mounting support member such as ceramics such as alumina.
　フィルム状接着剤及び接着シートは、複数の半導体素子を積み重ねた構造のＳｔａｃｋｅｄ－ＰＫＧにおいて、半導体素子と半導体素子とを接着するための接着剤としても好適に用いられる。この場合、一方の半導体素子が、半導体素子を搭載する支持部材となる。 The film adhesive and the adhesive sheet are also suitably used as an adhesive for bonding the semiconductor elements to each other in a Stacked-PKG having a structure in which a plurality of semiconductor elements are stacked. In this case, one of the semiconductor elements serves as a support member on which the semiconductor element is mounted.
　フィルム状接着剤及び接着シートは、例えば、フリップチップ型半導体装置の半導体素子の裏面を保護する保護シート、フリップチップ型半導体装置の半導体素子の表面と被着体との間を封止するための封止シート等としても用いることできる。 The film adhesive and the adhesive sheet are, for example, a protective sheet for protecting the back surface of the semiconductor element of the flip-chip type semiconductor device, and for sealing between the surface of the semiconductor element of the flip-chip type semiconductor device and the adherend. It can also be used as a sealing sheet or the like.
　フィルム状接着剤を用いて製造された半導体装置について、図面を用いて具体的に説明する。なお、近年は様々な構造の半導体装置が提案されており、本実施形態に係るフィルム状接着剤の用途は、以下に説明する構造の半導体装置に限定されるものではない。 半導体 A semiconductor device manufactured using a film adhesive will be specifically described with reference to the drawings. In recent years, semiconductor devices having various structures have been proposed, and the application of the film adhesive according to the present embodiment is not limited to the semiconductor devices having the structures described below.
　図６は、半導体装置の一実施形態を示す模式断面図である。図６に示す半導体装置２００は、半導体素子９と、半導体素子９を搭載する支持部材１０と、半導体素子９及び支持部材１０の間に設けられ、半導体素子９及び支持部材１０を接着する接着部材（フィルム状接着剤の硬化物１ｃ）とを備える。半導体素子９の接続端子（図示せず）はワイヤ１１を介して外部接続端子（図示せず）と電気的に接続され、封止材１２によって封止されている。 FIG. 6 is a schematic sectional view showing one embodiment of a semiconductor device. The semiconductor device 200 shown in FIG. 6 includes a semiconductor element 9, a support member 10 on which the semiconductor element 9 is mounted, and an adhesive member provided between the semiconductor element 9 and the support member 10 to adhere the semiconductor element 9 and the support member 10. (Cured film adhesive 1c). A connection terminal (not shown) of the semiconductor element 9 is electrically connected to an external connection terminal (not shown) via a wire 11 and is sealed by a sealing material 12.
　図７は、半導体装置の他の一実施形態を示す模式断面図である。図７に示す半導体装置２１０において、一段目の半導体素子９ａは、接着部材（フィルム状接着剤の硬化物１ｃ）によって、端子１３が形成された支持部材１０に接着され、一段目の半導体素子９ａ上にさらに接着部材（フィルム状接着剤の硬化物１ｃ）によって二段目の半導体素子９ｂが接着されている。一段目の半導体素子９ａ及び二段目の半導体素子９ｂの接続端子（図示せず）は、ワイヤ１１を介して外部接続端子と電気的に接続され、封止材１２によって封止されている。このように、本実施形態に係るフィルム状接着剤は、半導体素子を複数重ねる構造の半導体装置にも好適に使用できる。 FIG. 7 is a schematic sectional view showing another embodiment of the semiconductor device. In the semiconductor device 210 shown in FIG. 7, the first-stage semiconductor element 9a is bonded to the support member 10 on which the terminals 13 are formed by an adhesive member (cured product 1c of a film-like adhesive). The semiconductor element 9b in the second stage is further adhered thereon by an adhesive member (cured product 1c of a film adhesive). The connection terminals (not shown) of the first-stage semiconductor element 9a and the second-stage semiconductor element 9b are electrically connected to external connection terminals via wires 11, and are sealed with a sealing material 12. Thus, the film adhesive according to the present embodiment can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.
　図６及び図７に示す半導体装置（半導体パッケージ）は、例えば、半導体素子と支持部材との間又は半導体素子と半導体素子との間にフィルム状接着剤を介在させ、これらを加熱圧着して両者を接着させ、その後、必要に応じてワイヤーボンディング工程、封止材による封止工程、はんだによるリフローを含む加熱溶融工程等を経ることによって得られる。加熱圧着工程における加熱温度は、通常、２０～２５０℃、荷重は、通常、０．１～２００Ｎであり、加熱時間は、通常、０．１～３００秒間である。 The semiconductor device (semiconductor package) shown in FIGS. 6 and 7 includes, for example, a film-like adhesive interposed between a semiconductor element and a support member or between a semiconductor element and a semiconductor element, and heat-pressing them to form a semiconductor device. And then, if necessary, a wire bonding step, a sealing step with a sealing material, a heating and melting step including reflow with solder, and the like. The heating temperature in the thermocompression bonding step is usually 20 to 250 ° C., the load is usually 0.1 to 200 N, and the heating time is usually 0.1 to 300 seconds.
　半導体素子と支持部材との間又は半導体素子と半導体素子との間にフィルム状接着剤を介在させる方法としては、上述したように、予めフィルム状接着剤付半導体素子を作製した後、支持部材又は半導体素子に貼り付ける方法であってよい。 As a method of interposing a film adhesive between the semiconductor element and the support member or between the semiconductor element and the semiconductor element, as described above, after preparing a semiconductor element with a film adhesive in advance, the support member or It may be a method of attaching to a semiconductor element.
　支持部材は、銅を素材とする部材を含むものであってよい。本実施形態に係る半導体装置は、フィルム状接着剤の硬化物１ｃによって半導体素子と支持部材とが接着されているため、半導体装置の構成部材として銅を素材とする部材を用いている場合であっても、当該部材から発生する銅イオンの影響を低減することができ、銅イオンに起因する電気的な不具合の発生を充分に抑制することができる。 The support member may include a member made of copper. In the semiconductor device according to the present embodiment, since the semiconductor element and the support member are bonded by the cured product 1c of the film adhesive, a case where a member made of copper is used as a constituent member of the semiconductor device. Even so, the effect of copper ions generated from the member can be reduced, and the occurrence of electrical trouble due to copper ions can be sufficiently suppressed.
　ここで、銅を素材とする部材としては、例えば、リードフレーム、配線、ワイヤ、放熱材等が挙げられるが、いずれの部材に銅を用いた場合でも、銅イオンの影響を低減することが可能である。 Here, as the member made of copper, for example, a lead frame, a wiring, a wire, a heat radiating material, and the like can be mentioned. However, even when copper is used for any member, the influence of copper ions can be reduced. It is.
　次に、図４に示すダイシング・ダイボンディング一体型接着シートを用いた場合における半導体装置の製造方法の一実施形態について説明する。なお、ダイシング・ダイボンディング一体型接着シートによる半導体装置の製造方法は、以下に説明する半導体装置の製造方法に限定されるものではない。 Next, one embodiment of a method of manufacturing a semiconductor device using the dicing / die bonding integrated adhesive sheet shown in FIG. 4 will be described. The method for manufacturing a semiconductor device using the dicing / die bonding integrated adhesive sheet is not limited to the method for manufacturing a semiconductor device described below.
　まず、接着シート１２０（ダイシング・ダイボンディング一体型接着シート）におけるフィルム状接着剤１に半導体ウェハを圧着し、これを接着保持させて固定する（マウント工程）。本工程は、圧着ロール等の押圧手段によって押圧しながら行ってもよい。 First, a semiconductor wafer is pressure-bonded to the film-like adhesive 1 in the adhesive sheet 120 (integrated dicing / die-bonding adhesive sheet), and the semiconductor wafer is adhered and held and fixed (mounting step). This step may be performed while pressing with a pressing means such as a pressure roll.
　次に、半導体ウェハのダイシングを行う。これにより、半導体ウェハを所定のサイズに切断して、複数の個片化されたフィルム状接着剤付き半導体素子（半導体チップ）を製造する。ダイシングは、例えば、半導体ウェハの回路面側から常法に従って行うことができる。また、本工程では、例えば、ダイシングテープまで切込みを行なうフルカットと呼ばれる切断方式、半導体ウェハに半分切込みを入れて冷却化引っ張ることにより分断する方式、レーザーによる切断方式等を採用できる。本工程で用いるダイシング装置としては、特に限定されず、従来公知のものを用いることができる。 Next, dicing of the semiconductor wafer is performed. Thus, the semiconductor wafer is cut into a predetermined size, and a plurality of individualized semiconductor elements (semiconductor chips) with a film adhesive are manufactured. Dicing can be performed, for example, from the circuit surface side of the semiconductor wafer according to a conventional method. In this step, for example, a cutting method called full cut, in which a dicing tape is cut, a method in which a semiconductor wafer is cut in half by cutting it in half and cooled and pulled, and a cutting method using a laser can be adopted. The dicing apparatus used in this step is not particularly limited, and a conventionally known dicing apparatus can be used.
　ダイシング・ダイボンディング一体型接着シートに接着固定された半導体素子を剥離するために、半導体素子のピックアップを行う。ピックアップの方法としては特に限定されず、従来公知の種々の方法を採用できる。例えば、個々の半導体素子をダイシング・ダイボンディング一体型接着シート側からニードルによって突き上げ、突き上げられた半導体素子をピックアップ装置によってピックアップする方法等が挙げられる。 半導体 In order to peel off the semiconductor element bonded and fixed to the dicing / die bonding integrated adhesive sheet, the semiconductor element is picked up. The pickup method is not particularly limited, and various conventionally known methods can be employed. For example, there is a method in which individual semiconductor elements are pushed up from the dicing / die-bonding integrated adhesive sheet side by a needle, and the pushed up semiconductor elements are picked up by a pickup device.
　ここでピックアップは、粘着剤層が放射線（例えば、紫外線）硬化型の場合、該粘着剤層に放射線を照射した後に行う。これにより、粘着剤層のフィルム状接着剤に対する粘着力が低下し、半導体素子の剥離が容易になる。その結果、半導体素子を損傷させることなく、ピックアップが可能となる。 ピ ッ ク ア ッ プ Here, when the pressure-sensitive adhesive layer is of a radiation (for example, ultraviolet) curable type, the pickup is performed after irradiating the pressure-sensitive adhesive layer with the radiation. Thereby, the adhesive force of the pressure-sensitive adhesive layer to the film-like adhesive is reduced, and the peeling of the semiconductor element is facilitated. As a result, pickup can be performed without damaging the semiconductor element.
　次に、ダイシングによって形成されたフィルム状接着剤付き半導体素子を、フィルム状接着剤を介して半導体素子を搭載するための支持部材に接着する。接着は圧着によって行われてよい。ダイボンドの条件としては、特に限定されず、適宜必要に応じて設定することができる。具体的には、例えば、ダイボンド温度８０～１６０℃、ボンディング荷重５～１５Ｎ、ボンディング時間１～１０秒の範囲内で行うことができる。 Next, the semiconductor element with a film-like adhesive formed by dicing is bonded to a support member for mounting the semiconductor element via the film-like adhesive. The bonding may be performed by crimping. The conditions for die bonding are not particularly limited, and can be set as appropriate as needed. Specifically, for example, the bonding can be performed at a die bonding temperature of 80 to 160 ° C., a bonding load of 5 to 15 N, and a bonding time of 1 to 10 seconds.
　必要に応じて、フィルム状接着剤を熱硬化させる工程を設けてもよい。上記接着工程によって支持部材と半導体素子とを接着しているフィルム状接着剤を熱硬化させることによって、より強固に接着固定が可能となる。熱硬化を行う場合、圧力を同時に加えて硬化させてもよい。本工程における加熱温度は、フィルム状接着剤に構成成分によって適宜変更することができる。加熱温度は、例えば、６０～２００℃であってよい。なお、温度又は圧力は、段階的に変更しながら行ってもよい。 工程 If necessary, a step of thermally curing the film adhesive may be provided. By thermally curing the film adhesive bonding the support member and the semiconductor element by the bonding step, it is possible to bond and fix more firmly. When performing thermosetting, pressure may be applied at the same time to perform curing. The heating temperature in this step can be appropriately changed depending on the components of the film adhesive. The heating temperature may be, for example, 60 to 200 ° C. The temperature or the pressure may be changed stepwise.
　次に、支持部材の端子部（インナーリード）の先端と半導体素子上の電極パッドとをボンディングワイヤーで電気的に接続するワイヤーボンディング工程を行う。ボンディングワイヤーとしては、例えば、金線、アルミニウム線、銅線等が用いられる。ワイヤーボンディングを行う際の温度は、８０～２５０℃又は８０～２２０℃の範囲内であってよい。加熱時間は数秒～数分間であってよい。結線は、上記温度範囲内で加熱された状態で、超音波による振動エネルギーと印加加圧とによる圧着エネルギーの併用によって行われてもよい。 Next, a wire bonding step of electrically connecting the tip of the terminal portion (inner lead) of the support member and the electrode pad on the semiconductor element with a bonding wire is performed. As the bonding wire, for example, a gold wire, an aluminum wire, a copper wire or the like is used. The temperature at which wire bonding is performed may be in the range of 80 to 250 ° C or 80 to 220 ° C. The heating time may be from a few seconds to a few minutes. The connection may be performed by using the vibration energy by the ultrasonic wave and the compression energy by the applied pressure in a state of being heated within the above temperature range.
　次に、封止樹脂によって半導体素子を封止する封止工程を行う。本工程は、支持部材に搭載された半導体素子又はボンディングワイヤーを保護するために行われる。本工程は、封止用の樹脂を金型で成型することにより行う。封止樹脂としては、例えばエポキシ系の樹脂であってよい。封止時の熱及び圧力によって基板及び残渣が埋め込まれ、接着界面での気泡による剥離を防止することができる。 Next, a sealing step of sealing the semiconductor element with a sealing resin is performed. This step is performed to protect the semiconductor element or the bonding wire mounted on the support member. This step is performed by molding a sealing resin with a mold. As the sealing resin, for example, an epoxy resin may be used. The substrate and the residue are buried by heat and pressure at the time of sealing, so that separation at the bonding interface due to bubbles can be prevented.
　次に、後硬化工程において、封止工程で硬化不足の封止樹脂を完全に硬化させる。封止工程において、フィルム状接着剤が熱硬化されない場合でも、本工程において、封止樹脂の硬化とともにフィルム状接着剤を熱硬化させて接着固定が可能になる。本工程における加熱温度は、封止樹脂の種類よって適宜設定することができ、例えば、１６５～１８５℃の範囲内であってよく、加熱時間は０．５～８時間程度であってよい。 Next, in the post-curing step, the sealing resin that is insufficiently cured in the sealing step is completely cured. Even when the film adhesive is not thermally cured in the sealing step, the film adhesive is thermally cured together with the curing of the sealing resin in the present step, so that the adhesive can be fixed. The heating temperature in this step can be appropriately set depending on the type of the sealing resin, and may be, for example, in the range of 165 to 185 ° C., and the heating time may be about 0.5 to 8 hours.
　次に、支持部材に接着されたフィルム状接着剤付き半導体素子に対して、リフロー炉を用いて加熱する。本工程では支持部材上に、樹脂封止した半導体装置を表面実装してもよい。表面実装の方法としては、例えば、プリント配線板上に予めはんだを供給した後、温風等によって加熱溶融し、はんだ付けを行うリフローはんだ付けなどが挙げられる。加熱方法としては、例えば、熱風リフロー、赤外線リフロー等が挙げられる。また、加熱方法は、全体を加熱するものであってもよく、局部を加熱するものであってもよい。加熱温度は、例えば、２４０～２８０℃の範囲内であってよい。 Next, the semiconductor element with the film adhesive bonded to the support member is heated using a reflow furnace. In this step, a resin-sealed semiconductor device may be surface-mounted on the support member. As a method of surface mounting, for example, reflow soldering in which solder is supplied to a printed wiring board in advance and then heated and melted by warm air or the like and soldered is used. Examples of the heating method include hot air reflow and infrared reflow. Further, the heating method may be a method of heating the whole or a method of heating a local part. The heating temperature may be, for example, in the range of 240-280 ° C.
　半導体素子を多層に積層する場合には、ワイヤーボンディング工程等の熱履歴が多くなり、フィルム状接着剤と半導体素子との界面に存在する気泡による剥離への影響は大きなものとなり得る。しかしながら、本実施形態に係るフィルム状接着剤は、特定のアクリルゴムを用いることによって、凝集力が低下し、埋込性が向上する傾向にある。そのため、半導体装置内に気泡を巻き込み難く、封止工程における気泡を容易に拡散させることができ、接着界面での気泡による剥離を防止することができる。 に は When semiconductor elements are stacked in multiple layers, the thermal history of the wire bonding step and the like increases, and the effect of air bubbles existing at the interface between the film adhesive and the semiconductor element on peeling can be significant. However, the use of a specific acrylic rubber in the film adhesive according to the present embodiment tends to reduce cohesion and improve embedding. Therefore, bubbles are hardly entrained in the semiconductor device, bubbles can be easily diffused in the sealing step, and peeling due to bubbles at the bonding interface can be prevented.
　以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれらに限定されるものではない。 The present invention will be specifically described below based on examples, but the present invention is not limited thereto.
［フィルム状接着剤の作製］
（実施例及び比較例）
＜接着剤ワニスの調製＞
　表１及び表２に示す品名及び組成比（単位：質量部）で、（Ａ）熱硬化性樹脂としてのエポキシ樹脂、（Ｂ）硬化剤としてのフェノール樹脂、及び（Ｅ）無機フィラーからなる組成物にシクロヘキサノンを加え、撹拌混合した。これに、表１及び表２に示す（Ｃ）アクリルゴムを加えて撹拌し、さらに表１及び表２に示す（Ｄ）複素環式化合物、（Ｆ）カップリング剤、及び（Ｇ）硬化促進剤を加えて、各成分が均一になるまで撹拌して、接着剤ワニスを調製した。なお、表１及び表２に示す（Ｃ）成分及び（Ｅ）成分の数値は、固形分の質量部を意味する。 [Preparation of film adhesive]
(Examples and Comparative Examples)
<Preparation of adhesive varnish>
With the product name and composition ratio (unit: parts by mass) shown in Tables 1 and 2, a composition comprising (A) an epoxy resin as a thermosetting resin, (B) a phenol resin as a curing agent, and (E) an inorganic filler. Cyclohexanone was added to the mixture and mixed with stirring. To this, (C) acrylic rubber shown in Tables 1 and 2 was added and stirred, and further, (D) heterocyclic compound, (F) coupling agent, and (G) curing acceleration shown in Tables 1 and 2 The agent was added, and the mixture was stirred until each component became uniform to prepare an adhesive varnish. In addition, the numerical values of the components (C) and (E) shown in Tables 1 and 2 mean parts by mass of the solid content.
（Ａ）熱硬化性樹脂
（Ａ１）ＹＤＣＮ－７００－１０（商品名、新日鉄住金化学株式会社製、ｏ－クレゾールノボラック型エポキシ樹脂、エポキシ当量：２０９ｇ／ｅｑ） (A) Thermosetting resin (A1) YDCN-700-10 (trade name, Nippon Steel & Sumikin Chemical Co., Ltd., o-cresol novolak type epoxy resin, epoxy equivalent: 209 g / eq)
（Ｂ）硬化剤
（Ｂ１）ＨＥ－１００Ｃ－３０（商品名、エア・ウォーター株式会社製、フェニルアラルキル型フェノール樹脂、水酸基当量：１７４ｇ／ｅｑ、軟化点７７℃） (B) Curing agent (B1) HE-100C-30 (trade name, manufactured by Air Water Co., Ltd., phenylaralkyl-type phenol resin, hydroxyl equivalent: 174 g / eq, softening point 77 ° C.)
（Ｃ）アクリルゴム
（Ｃ１）ＳＧ－Ｐ３改良品（ＳＧ－Ｐ３（商品名、ナガセケムテックス株式会社製）のアクリルゴムにおいて、アクリルニトリルに由来する構成単位を除いたもの、アクリルゴムの重量平均分子量：６０万、アクリルゴムの理論Ｔｇ：１２℃、ＰＣＮ／ＰＣＯ＝０．００１）
（Ｃ２）ＳＧ－Ｐ３溶剤変更品（ＳＧ－Ｐ３（商品名、ナガセケムテックス株式会社製、アクリルゴムのメチルエチルケトン溶液）の溶剤を変更したもの、アクリルゴムの重量平均分子量：８０万、アクリルゴムの理論Ｔｇ：１２℃、ＰＣＮ／ＰＣＯ＝０．０７０） (C) Acrylic rubber (C1) Acrylic rubber of SG-P3 improved product (SG-P3 (trade name, manufactured by Nagase ChemteX Corporation), excluding structural units derived from acrylonitrile, weight average of acrylic rubber) Molecular weight: 600,000, theoretical Tg of acrylic rubber: 12 ° C., PCN / PCO = 0.001)
(C2) A modified solvent of SG-P3 solvent (SG-P3 (trade name, manufactured by Nagase ChemteX Corporation, methyl ethyl ketone solution of acrylic rubber)), the weight average molecular weight of acrylic rubber: 800,000, acrylic rubber Theoretical Tg: 12 ° C., P CN / P CO = 0.070)
（ＩＲスペクトルの測定）
　（Ｃ１）及び（Ｃ２）のＰＣＮ／ＰＣＯは以下の方法によって算出した。まず、（Ｃ１）及び（Ｃ２）から溶剤を除去したものをＫＢｒ錠剤法によって、透過ＩＲスペクトルを測定し、縦軸を吸光度、横軸を波数（ｃｍ－１）で表示した。ＩＲスペクトルの測定には、ＦＴ－ＩＲ６３００（日本分光株式会社製、光源：高輝度セラミック光源、検出器：ＤＬＡＴＧＳ）を使用した。 (Measurement of IR spectrum)
P CN / P CO of (C1) and (C2) was calculated by the following method. First, transmission IR spectra of (C1) and (C2) obtained by removing the solvent were measured by the KBr tablet method, and the vertical axis was represented by absorbance and the horizontal axis was represented by wavenumber (cm −1 ). For the measurement of the IR spectrum, FT-IR6300 (manufactured by JASCO Corporation, light source: high-intensity ceramic light source, detector: DLATGS) was used.
（カルボニル基の伸縮振動に由来する吸収ピークの高さＰＣＯ）
　１６７０ｃｍ－１と１８６０ｃｍ－１との２点の間で最も吸光度の高いピークをピーク点とした。１６７０ｃｍ－１と１８６０ｃｍ－１との２点間の直線をベースラインとし、このベースライン上でピーク点と同波数である点をベースライン点とし、ベースライン点とピーク点との吸光度の差をカルボニル基の伸縮振動に由来する吸収ピークの高さ（ＰＣＯ）とした。 (Height P CO absorption peak derived from stretching vibration of carbonyl group)
The highest absorbance peak was a peak point between the two points between 1670 cm -1 and 1860 cm -1. 1670cm and -1 and a linear baseline between the two points between 1860 cm -1, and a baseline point that it is the same wave number and the peak point on the base line, the difference in absorbance of the baseline point and the peak point The height (P CO ) of the absorption peak derived from the stretching vibration of the carbonyl group was used.
（ニトリル基の伸縮振動に由来するピークの高さＰＣＮ）
　ＰＣＯを求めたものと同一のＩＲスペクトルにおいて、２２７０ｃｍ－１と２２２０ｃｍ－１との２点の間で最も吸光度の高いピークをピーク点とした。２２７０ｃｍ－１と２２２０ｃｍ－１との２点間の直線をベースラインとし、このベースライン上でピーク点と同波数である点をベースライン点とし、ベースライン点とピーク点との吸光度の差をニトリル基の伸縮振動に由来するピークの高さ（ＰＣＮ）とした。 (Height P CN of a peak derived from stretching vibration of the nitrile group)
In the same IR spectrum as those seeking P CO, and the peak point a high peak most absorbance between two points between 2270 cm -1 and 2220cm -1. 2270cm and -1 and a linear baseline between the two points of the 2220Cm -1, and a baseline point that it is the same wave number and the peak point on the base line, the difference in absorbance of the baseline point and the peak point The peak height ( PCN ) derived from the stretching vibration of the nitrile group was used.
（Ｄ）複素環式化合物
（Ｄ１）ベンゾトリアゾール
（Ｄ２）５－アミノテトラゾール
（Ｄ３）５－メチルテトラゾール
（Ｄ４）３－メルカプトトリアゾール (D) Heterocyclic compound (D1) Benzotriazole (D2) 5-aminotetrazole (D3) 5-methyltetrazole (D4) 3-mercaptotriazole
（Ｅ）無機フィラー
（Ｅ１）ＳＣ２０５０－ＨＬＧ（商品名、アドマテックス株式会社製、シリカフィラー分散液、平均粒径０．５０μｍ）
（Ｅ２）ＹＡ０５０Ｃ－ＨＨＧ（商品名、アドマテックス株式会社製、シリカフィラー分散液、平均粒径０．０５μｍ） (E) Inorganic filler (E1) SC2050-HLG (trade name, manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size 0.50 μm)
(E2) YA050C-HHG (trade name, manufactured by Admatechs Co., Ltd., silica filler dispersion, average particle size 0.05 μm)
（Ｆ）カップリング剤
（Ｆ１）Ａ－１８９（商品名、日本ユニカー株式会社製、γ－メルカプトプロピルトリメトキシシラン）
（Ｆ２）Ａ－１１６０（商品名、日本ユニカー株式会社製、γ－ウレイドプロピルトリエトキシシラン） (F) Coupling agent (F1) A-189 (trade name, manufactured by Nippon Unicar, γ-mercaptopropyltrimethoxysilane)
(F2) A-1160 (trade name, manufactured by Nippon Unicar Co., Ltd., γ-ureidopropyltriethoxysilane)
（Ｇ）硬化促進剤
（Ｇ１）２ＰＺ－ＣＮ（商品名、四国化成工業株式会社製、１－シアノエチル－２－フェニルイミダゾール） (G) Curing accelerator (G1) 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole manufactured by Shikoku Chemicals Co., Ltd.)
＜フィルム状接着剤の作製＞
　作製した接着剤ワニスを１００メッシュのフィルターでろ過し、真空脱泡した。基材フィルムとして、厚さ３８μｍの離型処理を施したポリエチレンテレフタレート（ＰＥＴ）フィルムを用意し、真空脱泡後の接着剤ワニスをＰＥＴフィルム上に塗布した。塗布した接着剤ワニスを、９０℃で５分間、続いて１３０℃で５分間の２段階で加熱乾燥し、Ｂステージ状態にある比較例１－１、１－２及び実施例１－１、１－２並びに比較例２－１、２－２及び実施例２－１～２－７のフィルム状接着剤を得た。フィルム状接着剤においては、接着剤ワニスの塗布量によって、厚み１０μｍになるように調整した。 <Preparation of film adhesive>
The produced adhesive varnish was filtered through a 100-mesh filter, and degassed under vacuum. As a substrate film, a polyethylene terephthalate (PET) film having a thickness of 38 μm and subjected to release treatment was prepared, and an adhesive varnish after vacuum defoaming was applied on the PET film. The applied adhesive varnish was dried by heating at 90 ° C. for 5 minutes, and then at 130 ° C. for 5 minutes in two stages, to obtain Comparative Examples 1-1 and 1-2 and Examples 1-1 and 1 in the B-stage state. -2 and Comparative Examples 2-1 and 2-2 and Examples 2-1 to 2-7 were obtained. The thickness of the film adhesive was adjusted to 10 μm depending on the amount of the adhesive varnish applied.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［銅イオン透過時間の測定］
＜Ａ液の調製＞
　無水硫酸銅（ＩＩ）２．０ｇを蒸留水１０２０ｇに溶解させ、完全に硫酸銅が溶解するまで撹拌し、銅イオン濃度がＣｕ元素換算で濃度５００ｍｇ／ｋｇである硫酸銅水溶液を調製した。得られた硫酸銅水溶液をＡ液とした。 [Measurement of copper ion transmission time]
<Preparation of solution A>
2.0 g of anhydrous copper (II) sulfate was dissolved in 1020 g of distilled water, and stirred until copper sulfate was completely dissolved to prepare an aqueous copper sulfate solution having a copper ion concentration of 500 mg / kg in terms of Cu element. The obtained aqueous solution of copper sulfate was used as solution A.
＜Ｂ液の調製＞
　無水硫酸ナトリウム１．０ｇを蒸留水１０００ｇに溶解させ、完全に硫酸ナトリウムが溶解するまで撹拌した。これにさらにＮ－メチル－２－ピロリドン（ＮＭＰ）を１０００ｇ加え、撹拌した。その後、室温になるまで空冷して硫酸ナトリウム水溶液を得た。得られた溶液をＢ液とした。 <Preparation of solution B>
1.0 g of anhydrous sodium sulfate was dissolved in 1000 g of distilled water, and the mixture was stirred until sodium sulfate was completely dissolved. Further, 1000 g of N-methyl-2-pyrrolidone (NMP) was added thereto, followed by stirring. Thereafter, the mixture was air-cooled to room temperature to obtain an aqueous sodium sulfate solution. The obtained solution was used as solution B.
＜銅イオン透過時間の測定＞
　上記で作製した比較例１－１及び実施例１－１、１－２並びに比較例２－１及び実施例２－１～２－７のフィルム状接着剤（厚み：１０μｍ）を、それぞれ直径約３ｃｍの円状に切り抜いた。次に、厚み１．５ｍｍ、外径約３ｃｍ、内径１．８ｃｍのシリコンパッキンシートを２枚用意した。円状に切り抜いたフィルム状接着剤を２枚のシリコンパッキンシートで挟み、これを容積５０ｍＬの２つのガラス製セルのフランジ部で挟み、ゴムバンドで固定した。 <Measurement of copper ion transmission time>
The film-shaped adhesives (thickness: 10 μm) of Comparative Example 1-1 and Examples 1-1 and 1-2 and Comparative Example 2-1 and Examples 2-1 to 2-7 produced above were each coated with a diameter of about 10 μm. A 3 cm circle was cut out. Next, two silicon packing sheets having a thickness of 1.5 mm, an outer diameter of about 3 cm, and an inner diameter of 1.8 cm were prepared. The film-shaped adhesive cut in a circular shape was sandwiched between two silicon packing sheets, sandwiched between flange portions of two glass cells having a capacity of 50 mL, and fixed with a rubber band.
　次に、一方のガラス製セルにＡ液を５０ｇ注入した後、他方のガラス製セルにＢ液を５０ｇ注入した。各セルにカーボン電極として、Ｍａｒｓ　Ｃａｒｂｏｎ（ステッドラー有限合資会社製、φ２ｍｍ／１３０ｍｍ）を挿入した。Ａ液側を陽極、Ｂ液側を陰極として、陽極と直流電源（株式会社エーアンドディ製、直流電源装置ＡＤ－９７２３Ｄ）とを接続した。また、陰極と直流電源とを、電流計（三和電気計器株式会社製、Ｄｅｇｉｔａｌ　ｍｕｌｔｉｍｅｔｅｒ　ＰＣ－７２０Ｍ）を介して直列に接続した。室温下、印加電圧２４．０Ｖにて電圧を印加し、印加した後から電流値の計測を開始した。測定は電流値が１５μＡを超えるまで行い、電流値が１０μＡとなった時間を銅イオン透過時間とした。結果を表３及び表４に示す。本評価では、透過時間が長いほど、銅イオン透過が抑制されているといえる。 (5) Next, after injecting 50 g of the solution A into one glass cell, 50 g of the solution B was injected into the other glass cell. A Mars @ Carbon (manufactured by Staedtler GmbH, φ2 mm / 130 mm) was inserted into each cell as a carbon electrode. The anode was connected to a DC power supply (DC power supply AD-9723D, manufactured by A & D Corporation) with the liquid A side as the anode and the liquid B side as the cathode. The cathode and the DC power supply were connected in series via an ammeter (Digital multimeter PC-720M manufactured by Sanwa Electric Instruments Co., Ltd.). A voltage was applied at room temperature at an applied voltage of 24.0 V, and measurement of the current value was started after the application. The measurement was performed until the current value exceeded 15 μA, and the time when the current value reached 10 μA was defined as the copper ion transmission time. The results are shown in Tables 3 and 4. In this evaluation, it can be said that the longer the permeation time, the more suppressed the copper ion permeation.
　Ｂステージ状態にある比較例１－１及び実施例１－１、１－２並びに比較例２－１及び実施例２－１～２－７のフィルム状接着剤をさらに１７０℃、１時間で加熱乾燥し、Ｃステージ状態にある比較例１－１及び実施例１－１、１－２並びに比較例２－１及び実施例２－１～２－７のフィルム状接着剤を作製した。 The film adhesives of Comparative Example 1-1 and Examples 1-1 and 1-2 and Comparative Example 2-1 and Examples 2-1 to 2-7 in the B-stage state are further heated at 170 ° C. for one hour. After drying, film adhesives of Comparative Example 1-1 and Examples 1-1 and 1-2 and Comparative Example 2-1 and Examples 2-1 to 2-7 in a C-stage state were produced.
　Ｂステージ状態にあるフィルム状接着剤をＣステージ状態にあるフィルム状接着剤に変更した以外は、Ｂステージ状態にあるフィルム状接着剤を用いたときの銅イオン透過時間の測定と同様にして、銅イオンの透過時間を測定した。なお、Ｃステージ状態にあるフィルム状接着剤を用いた場合、測定は電流値が５μＡを超えるまで行い、電流値が１μＡとなった時間を銅イオン透過時間とした。結果を表３及び表４に示す。本評価では、透過時間が長いほど、銅イオン透過が抑制されているといえる。 Except that the film adhesive in the B stage state was changed to the film adhesive in the C stage state, in the same manner as the measurement of the copper ion transmission time when using the film adhesive in the B stage state, The permeation time of copper ions was measured. When the film adhesive in the C-stage state was used, the measurement was performed until the current value exceeded 5 μA, and the time when the current value reached 1 μA was defined as the copper ion transmission time. The results are shown in Tables 3 and 4. In this evaluation, it can be said that the longer the permeation time, the more suppressed the copper ion permeation.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
［接着力の評価］
＜半導体装置の作製＞
　ダイシングテープ（日立化成株式会社製、厚み１１０μｍ）を用意し、作製した比較例１－２及び実施例１－１、１－２並びに比較例２－２及び実施例２－１～２－７のフィルム状接着剤（厚み１０μｍ）を貼り付けて、ダイシングテープ及びフィルム状接着剤を備えるダイシング－ダイボンディング一体型接着シートを作製した。ダイシング－ダイボンディング一体型接着シートのフィルム状接着剤側に４００μｍ厚の半導体ウェハを、ステージ温度７０℃でラミネートし、ダイシングサンプルを作製した。 [Evaluation of adhesive strength]
<Production of semiconductor device>
A dicing tape (manufactured by Hitachi Chemical Co., Ltd., thickness 110 μm) was prepared and prepared for Comparative Example 1-2 and Examples 1-1 and 1-2 and Comparative Example 2-2 and Examples 2-1 to 2-7. A film-like adhesive (thickness: 10 μm) was adhered to produce an integrated dicing-die bonding adhesive sheet provided with a dicing tape and a film-like adhesive. A semiconductor wafer having a thickness of 400 μm was laminated at a stage temperature of 70 ° C. on the film adhesive side of the dicing-die bonding integrated adhesive sheet to prepare a dicing sample.
　フルオートダイサーＤＦＤ－６３６１（株式会社ディスコ製）を用いて、得られたダイシングサンプルを切断した。切断には、２枚のブレードを用いるステップカット方式で行い、ダイシングブレードＺＨ０５－ＳＤ３５００－Ｎ１－ｘｘ－ＤＤ、及びＺＨ０５－ＳＤ４０００－Ｎ１－ｘｘ－ＢＢ（いずれも株式会社ディスコ製）を用いた。切断条件は、ブレード回転数４０００ｒｐｍ、切断速度５０ｍｍ／ｓｅｃ、チップサイズ７．５ｍｍ×７．５ｍｍとした。切断は、半導体ウェハが３０μｍ程度残るように１段階目の切断を行い、次いで、ダイシングテープに２０μｍ程度の切り込みが入るように２段階目の切断を行った。 The obtained dicing sample was cut using a full-auto dicer DFD-6361 (manufactured by Disco Corporation). The cutting was performed by a step cutting method using two blades, and dicing blades ZH05-SD3500-N1-xx-DD and ZH05-SD4000-N1-xx-BB (both manufactured by Disco Corporation) were used. The cutting conditions were a blade rotation speed of 4000 rpm, a cutting speed of 50 mm / sec, and a chip size of 7.5 mm × 7.5 mm. The cutting was performed in the first stage so that the semiconductor wafer remained about 30 μm, and then in the second stage so that the dicing tape had a cut of about 20 μm.
　続いて、切断により得られた半導体チップをソルダーレジスト（太陽ホールディングス株式会社、商品名：ＡＵＳ－３０８）上に熱圧着した。圧着条件は、温度１２０℃、時間１秒、圧力０．１ＭＰａとした。続いて、圧着により得られたサンプルを乾燥機に入れ、１７０℃、１時間硬化させた。ソルダーレジストに圧着した半導体チップを硬化させ、万能ボンドテスター（ノードソン・アドバンス・テクノロジー株式会社製、商品名：シリーズ４０００）によって半導体チップを引っ掛けながら引っ張ることによって、半導体チップとソルダーレジストとの硬化後ダイシェア強度を測定し、接着力として評価した。測定条件はステージ温度を２５０℃とした。結果を表５及び表６に示す。 Subsequently, the semiconductor chip obtained by the cutting was thermocompression-bonded on a solder resist (Taiyo Holdings Co., Ltd., trade name: AUS-308). The pressure bonding conditions were a temperature of 120 ° C., a time of 1 second, and a pressure of 0.1 MPa. Subsequently, the sample obtained by crimping was placed in a dryer and cured at 170 ° C. for 1 hour. The semiconductor chip press-bonded to the solder resist is cured, and the semiconductor chip and the solder resist are hardened and die-shared by pulling the semiconductor chip with a universal bond tester (trade name: Series 4000, manufactured by Nordson Advance Technology Co., Ltd.). The strength was measured and evaluated as the adhesive strength. The measurement condition was a stage temperature of 250 ° C. The results are shown in Tables 5 and 6.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表３及び表４に示すとおり、式（１）の要件を満たすアクリルゴムを有するフィルム状接着剤は、式（１）の要件を満たさないアクリルゴムを有するフィルム状接着剤に比べて、銅イオン透過時間が長くなっていた（比較例１－２及び実施例１－１、１－２と比較例１－１との対比並びに比較例２－２及び実施例２－１～２－７と比較例２－２との対比）。これは銅イオンとの錯体安定度定数の高いニトリル基が少ない（又は含まない）アクリルゴムを使用することによって、フィルム状接着剤の銅イオンを取り込む力が弱まったためであると推察される。また、実施例１－１と実施例２－１との対比及び実施例１－２と実施例２－２との対比から、無機フィラーの平均粒径が小径であるほど、銅イオン透過時間が長くなる傾向があることが判明した。 As shown in Tables 3 and 4, the film adhesive having an acrylic rubber satisfying the requirement of the formula (1) has a higher copper ion content than the film adhesive having an acrylic rubber not satisfying the requirement of the formula (1). The transmission time was long (comparison of Comparative Example 1-2 and Examples 1-1 and 1-2 with Comparative Example 1-1 and comparison with Comparative Example 2-2 and Examples 2-1 to 2-7) Comparison with Example 2-2). This is presumed to be due to the fact that the use of an acrylic rubber having a small (or no) nitrile group having a high complex stability constant with copper ions weakened the ability of the film adhesive to take in copper ions. Also, from the comparison between Example 1-1 and Example 2-1 and the comparison between Example 1-2 and Example 2-2, the smaller the average particle diameter of the inorganic filler, the smaller the copper ion transmission time. It turns out that it tends to be longer.
　表５及び表６に示すとおり、各種複素環式化合物を含有するフィルム状接着剤は、複素環式化合物を含有しないフィルム状接着剤に比べて、さらに接着力が向上していた（比較例１－２と実施例１－１、１－２との対比及び比較例２－２と実施例２－１～２－７との対比）。 As shown in Tables 5 and 6, the film adhesive containing various heterocyclic compounds had further improved adhesive strength as compared with the film adhesive containing no heterocyclic compound (Comparative Example 1). -2 and Examples 1-1 and 1-2, and Comparative Example 2-2 and Examples 2-1 to 2-7).
　以上のとおり、本発明のフィルム状接着剤が、接着剤内の銅イオン透過を充分に抑制することが可能であり、さらに接着力にも優れることが確認された。 と お り As described above, it was confirmed that the film adhesive of the present invention was able to sufficiently suppress the permeation of copper ions in the adhesive, and was also excellent in adhesive strength.
　１…フィルム状接着剤、２…基材、３…カバーフィルム、６…粘着剤層、７…ダイシングテープ、９，９ａ，９ｂ…半導体素子、１０…支持部材、１１…ワイヤ、１２…封止材、１３…端子、１００，１１０，１２０，１３０…接着シート、２００，２１０…半導体装置。 DESCRIPTION OF SYMBOLS 1 ... Film adhesive, 2 ... Base material, 3 ... Cover film, 6 ... Adhesive layer, 7 ... Dicing tape, 9, 9a, 9b ... Semiconductor element, 10 ... Support member, 11 ... Wire, 12 ... Sealing Material, 13 terminals, 100, 110, 120, 130 adhesive sheet, 200, 210 semiconductor device.

Claims (12)

  1. 　半導体素子と前記半導体素子を搭載する支持部材とを接着するためのフィルム状接着剤であって、
    　前記フィルム状接着剤が、熱硬化性樹脂と、硬化剤と、アクリルゴムと、複素環式化合物とを含有し、
    　前記アクリルゴムの赤外吸収スペクトルにおいて、カルボニル基の伸縮振動に由来する吸収ピークの高さをＰＣＯ、ニトリル基の伸縮振動に由来するピークの高さをＰＣＮとしたとき、ＰＣＯ及びＰＣＮが下記式（１）の条件を満たし、
    　前記フィルム状接着剤の厚みが５０μｍ以下である、フィルム状接着剤。
    　ＰＣＮ／ＰＣＯ＜０．０７０　（１）     A film-like adhesive for bonding a semiconductor element and a supporting member on which the semiconductor element is mounted,
    The film adhesive contains a thermosetting resin, a curing agent, an acrylic rubber, and a heterocyclic compound,
    Wherein in the infrared absorption spectrum of the acrylic rubber, when the height of the P CO absorption peak derived from stretching vibration of the carbonyl group, the height of the peak derived from stretching vibration of the nitrile group was P CN, P CO and P CN satisfies the condition of the following formula (1),
    A film adhesive, wherein the thickness of the film adhesive is 50 μm or less.
    P CN / P CO <0.070 (1)
  2. 　前記複素環式化合物が、３以上の窒素原子を有する芳香族化合物である、請求項１の記載のフィルム状接着剤。 The film adhesive according to claim 1, wherein the heterocyclic compound is an aromatic compound having three or more nitrogen atoms.
  3. 　前記複素環式化合物が、トリアゾール化合物及びテトラゾール化合物からなる群より選ばれる少なくも１種である、請求項１又は２に記載のフィルム状接着剤。 The film adhesive according to claim 1 or 2, wherein the heterocyclic compound is at least one selected from the group consisting of a triazole compound and a tetrazole compound.
  4. 　前記複素環式化合物が、前記熱硬化性樹脂、前記硬化剤、及び前記アクリルゴムの総質量１００質量部に対して、０．０１～２質量部である、請求項１～３のいずれか一項に記載のフィルム状接着剤。 4. The method according to claim 1, wherein the amount of the heterocyclic compound is 0.01 to 2 parts by mass based on 100 parts by mass of the thermosetting resin, the curing agent, and the acrylic rubber. Item 10. The film adhesive according to item 8.
  5. 　無機フィラーをさらに含有し、前記無機フィラーの平均粒径が１μｍ以下である、請求項１～４のいずれか一項に記載のフィルム状接着剤。 The film adhesive according to any one of claims 1 to 4, further comprising an inorganic filler, wherein the inorganic filler has an average particle size of 1 μm or less.
  6. 　基材と、前記基材の一方の面上に設けられた請求項１～５のいずれか一項に記載のフィルム状接着剤とを備える、接着シート。 (4) An adhesive sheet, comprising: a substrate; and the film adhesive according to any one of claims 1 to 5 provided on one surface of the substrate.
  7. 　前記基材が、ダイシングテープである、請求項６に記載の接着シート。 The adhesive sheet according to claim 6, wherein the base material is a dicing tape.
  8. 　半導体素子と、前記半導体素子を搭載する支持部材と、前記半導体素子及び前記支持部材の間に設けられ、前記半導体素子及び前記支持部材を接着する接着部材とを備え、
    　前記接着部材が、請求項１～５のいずれか一項に記載のフィルム状接着剤の硬化物である、半導体装置。     A semiconductor element, a support member for mounting the semiconductor element, and an adhesive member provided between the semiconductor element and the support member, for bonding the semiconductor element and the support member,
    A semiconductor device, wherein the adhesive member is a cured product of the film adhesive according to any one of claims 1 to 5.
  9. 　前記支持部材が、銅を素材とする部材を含む、請求項８に記載の半導体装置。 The semiconductor device according to claim 8, wherein the supporting member includes a member made of copper.
  10. 　請求項１～５のいずれか一項に記載のフィルム状接着剤を用いて、半導体素子と支持部材とを接着する工程を備える、半導体装置の製造方法。 A method of manufacturing a semiconductor device, comprising a step of bonding a semiconductor element and a support member using the film adhesive according to any one of claims 1 to 5.
  11. 　半導体ウェハに、請求項６又は７に記載の接着シートの前記フィルム状接着剤を貼り付ける工程と、
    　前記フィルム状接着剤を貼り付けた前記半導体ウェハを切断することによって、複数の個片化されたフィルム状接着剤付き半導体素子を作製する工程と、
    　前記フィルム状接着剤付き半導体素子を支持部材に接着する工程と、
    を備える、半導体装置の製造方法。     A step of attaching the film-like adhesive of the adhesive sheet according to claim 6 to a semiconductor wafer,
    By cutting the semiconductor wafer to which the film adhesive is attached, a step of producing a plurality of individualized semiconductor elements with a film adhesive,
    Bonding the semiconductor element with the film adhesive to a support member,
    A method for manufacturing a semiconductor device, comprising:
  12. 　前記支持部材に接着された前記フィルム状接着剤付き半導体素子に対して、リフロー炉を用いて加熱する工程をさらに備える、請求項１１に記載の半導体装置の製造方法。 The method of manufacturing a semiconductor device according to claim 11, further comprising: heating the semiconductor element with a film-like adhesive bonded to the support member using a reflow furnace.
PCT/JP2019/037648 2018-09-26 2019-09-25 Film-shaped adhesive, adhesive sheet, semiconductor device, and production method for semiconductor device WO2020067186A1 (en)

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JP2020549304A JP7435458B2 (en) 2018-09-26 2019-09-25 Film adhesive, adhesive sheet, semiconductor device and manufacturing method thereof
KR1020217008789A KR102629864B1 (en) 2018-09-26 2019-09-25 Film adhesives, adhesive sheets, and semiconductor devices and methods for manufacturing the same
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JP2009094493A (en) * 2007-09-20 2009-04-30 Toray Ind Inc Adhesive composition for electronic components, and adhesive sheet for electronic components using the same
JP2010241951A (en) * 2009-04-06 2010-10-28 Hitachi Chem Co Ltd Transparent adhesive composition, transparent adhesive film and method for manufacturing the same, and display-mounting member and method for manufacturing the same
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