WO2020189445A1 - 熱伝導性組成物および半導体装置 - Google Patents

熱伝導性組成物および半導体装置 Download PDF

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WO2020189445A1
WO2020189445A1 PCT/JP2020/010568 JP2020010568W WO2020189445A1 WO 2020189445 A1 WO2020189445 A1 WO 2020189445A1 JP 2020010568 W JP2020010568 W JP 2020010568W WO 2020189445 A1 WO2020189445 A1 WO 2020189445A1
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conductive composition
thermally conductive
heat
resin
particles
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PCT/JP2020/010568
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English (en)
French (fr)
Japanese (ja)
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直輝 渡部
真 高本
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住友ベークライト株式会社
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Priority to JP2021507239A priority Critical patent/JP6927455B2/ja
Priority to CN202080023194.0A priority patent/CN113632219A/zh
Priority to KR1020217033312A priority patent/KR20210143812A/ko
Publication of WO2020189445A1 publication Critical patent/WO2020189445A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/06—Homopolymers or copolymers of esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
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    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
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    • H01—ELECTRIC ELEMENTS
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    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
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    • 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
    • H01L2224/26—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
    • H01L2224/32245—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 metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • 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
    • H01L2224/481—Disposition
    • H01L2224/48151—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
    • H01L2224/48221—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
    • H01L2224/48225—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
    • H01L2224/48227—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 connecting the wire to a bond pad of the item
    • H—ELECTRICITY
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    • 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
    • H01L2224/481—Disposition
    • H01L2224/48151—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
    • H01L2224/48221—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
    • H01L2224/48245—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 metallic
    • H01L2224/48247—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 metallic connecting the wire to a bond pad of the item
    • 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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    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01—ELECTRIC ELEMENTS
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    • 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 thermally conductive composition and a semiconductor device.
  • Patent Document 1 describes a thermosetting resin composition for semiconductor adhesion containing a (meth) acrylic acid ester compound, a radical initiator, silver fine particles, silver powder and a solvent (Claim 1 of Patent Document 1).
  • a thermosetting resin composition for semiconductor adhesion containing a (meth) acrylic acid ester compound, a radical initiator, silver fine particles, silver powder and a solvent (Claim 1 of Patent Document 1).
  • the bonding between the semiconductor element and the metal substrate can be realized by the silver fine particles heated at 200 ° C. (paragraphs 0001, 0007, etc.).
  • Patent Document 2 describes a resin paste composition containing an epoxy resin, a curing agent, a curing accelerator, a diluent, and silver powder (Table 1 of Patent Document 2).
  • the resin paste composition is cured at 150 ° C., and the semiconductor element and the support member can be adhered to each other by a cured product such as an epoxy resin (paragraph 0038, etc.).
  • the present inventor appropriately controls the thermal conductivity and the storage elasticity of the thermally conductive composition when the thermally conductive composition is used for adhering the semiconductor element and the supporting base material. By doing so, it was found that the thermal cycle characteristics of the semiconductor device can be improved.
  • the type in which the semiconductor element and the supporting base material are bonded by joining the heat-treated silver particles (hereinafter referred to as the sintering type) can increase the thermal conductivity, but on the contrary, the storage elastic modulus becomes high. Moreover, the thermal cycle characteristics may deteriorate.
  • the type in which the semiconductor element and the supporting base material are adhered by a cured component such as a cured epoxy resin (hereinafter referred to as a binder type) can suppress the storage elasticity to a low level, but on the contrary, the thermal conductivity is lowered. , There is a risk that the heat dissipation will decrease. That is, in the conventional sintering type and binder type, high thermal conductivity and low storage elastic modulus show a trade-off relationship, and both improvement of thermal conductivity and reduction of storage elastic modulus have not been sufficiently examined. There was.
  • Binder resin and Monomer and Including A thermally conductive composition in which the metal particles are sintered to form a particle-connected structure by heat treatment.
  • the thermal conductivity ⁇ (W / mK) measured according to the following procedure A and the storage elastic modulus E (GPa) at 25 ° C. measured according to the following procedure B are A thermally conductive composition satisfying the following formula (I) is provided. 0.35 ⁇ ⁇ / (E 2 ) ... Equation (I) (Procedure A)
  • the heat conductive composition is heated from 30 ° C. to 200 ° C. over 60 minutes and then heat-treated at 200 ° C.
  • the obtained heat-treated body is measured for thermal conductivity ⁇ (W / mK) at 25 ° C. by using a laser flash method.
  • the heat conductive composition is heated from 30 ° C. to 200 ° C. over 60 minutes and then heat-treated at 200 ° C. for 120 minutes to obtain a heat-treated body.
  • the storage elastic modulus E (MPa) at 25 ° C. is measured by using dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz.
  • thermoly conductive composition having excellent thermal cycle characteristics and heat dissipation, and a semiconductor device using the same are provided.
  • the thermally conductive composition of the present embodiment contains metal particles, a binder resin, and a monomer, and the metal particles undergo syntaration by heat treatment to form a particle-connected structure.
  • ⁇ and E satisfy the following formula (I). 0.35 ⁇ ⁇ / (E 2 ) ... Equation (I)
  • the adhesive layer formed by curing the thermally conductive composition has a higher thermal conductivity than the binder type because the particle connecting structure (sintering structure) of the metal particles is formed. It is considered that the storage elastic modulus is lower than that of the sintering type because it is high and the resin component such as the binder resin remains.
  • metal-coated resin particles in which the surface of the resin particles is coated with metal as the metal particles, it is possible to appropriately reduce the storage elastic modulus while suppressing the decrease in the sinterability of the metal particles. ,Conceivable. Since this adhesive layer can bond the semiconductor element and the supporting base material by bonding metal particles or a binder resin, good adhesion can be realized.
  • the lower limit of ⁇ / (E 2 ) is 0.35 or more, preferably 0.37 or more, and more preferably 0.40 or more. As a result, the thermal cycle characteristics can be improved.
  • the upper limit of ⁇ / (E 2 ) may be, for example, 3.0 or less, 2.0 or less, or 1.5 or less.
  • the lower limit of the thermal conductivity of the heat-treated body of the heat conductive composition in the thickness direction at 25 ° C. is, for example, 10 W / mK or more, preferably 15 W / mK or more, and more preferably 20 W / mK or more.
  • the upper limit of the thermal conductivity of the heat-treated body of the heat conductive composition may be, for example, 200 W / mK or less, or 150 W / mK or less.
  • the upper limit of the storage elastic modulus E (GPa) is, for example, 15.0 GPa or less, preferably 8.5 GPa or less, and more preferably 7.0 GPa or less. This makes it possible to further enhance the thermal cycle characteristics.
  • the lower limit of the storage elastic modulus E (GPa) is not particularly limited, but may be, for example, 0.1 GPa or more, or 0.5 GPa or more.
  • the resin content in the heat-treated body obtained by the following procedure is, for example, 10% by mass or more and 30% by mass or less, preferably 12% by mass or more and 29% by mass or less, based on 100% by mass of the heat-treated body. ..
  • the heat conductive composition is heated from 30 ° C. to 200 ° C. over 60 minutes and then heat-treated at 200 ° C. for 120 minutes to obtain a heat-treated body.
  • the resin content can be calculated by measuring the weight of the obtained heat-treated body and subtracting the weight of silver contained from the weight.
  • the resin component subject to the resin content include a resin component derived from a binder resin and a resin component derived from metal-coated resin particles, and one or both of these may be included.
  • the combined use of a sintering type composition system and a binder type composition system, the use of metal-coated resin particles, and the appropriate selection of metal particles such as their particle size and content are the above-mentioned ⁇ . / (E 2 ), ⁇ , and the residual amount of the resin can be mentioned as factors for setting the desired numerical range.
  • the thermally conductive composition of the present embodiment can be used for various purposes, but can be applied to applications where heat dissipation and adhesiveness of electronic components such as semiconductor elements are required.
  • the thermally conductive composition can be used to intervene between an electronic component such as a semiconductor element and a metal member such as a lead frame to form an adhesive layer for adhering them. ..
  • Such an adhesive layer is composed of a heat-treated body of a heat conductive composition.
  • the thermal cycle characteristics in the semiconductor device can be improved by using the adhesive layer composed of the heat-treated body of the heat conductive composition.
  • high heat dissipation of the semiconductor element can be realized.
  • the high heat dissipation can be stably realized.
  • the thermally conductive composition of the present embodiment contains the binder resin and the monomer together with the metal particles.
  • the monomer volatilizes and the volume of the composition shrinks due to heating stress is applied in the direction in which the metal particles approach each other, the interface between the metal particles disappears, and the connected structure of the metal particles Is considered to be formed.
  • the binder resin or the cured resin product of the binder resin and the curing agent, the monomer, or the like remains inside or the outer periphery of the connecting structure during the syntaring of such metal particles. It is also conceivable that the curing reaction produces a force that causes a plurality of metal particles to aggregate.
  • an adhesive layer containing a particle-connected structure of metal particles and a resin component composed of a binder resin, a cured product thereof, resin particles in the metal-coated resin particles, and the like is realized. it can.
  • the thermally conductive composition of the present embodiment contains metal particles.
  • the metal particles can be sintered by heat treatment to form a particle connecting structure (sintering structure).
  • metal particles metal-coated resin particles, particles made of metal, or the like can be used.
  • the metal particles may contain either metal-coated resin particles or particles made of metal, but it is more preferable to include both.
  • the metal-coated resin particles By using the metal-coated resin particles, it is possible to appropriately reduce the storage elastic modulus while suppressing the decrease in the sinterability of the metal particles. By using the particles made of the metal, it is possible to appropriately increase the thermal conductivity while improving the sinterability of the metal particles.
  • the metal-coated resin particles are composed of resin particles and a metal formed on the surface of the resin particles. That is, the metal-coated resin particles may be particles in which the surface of the resin particles is coated with a metal layer.
  • the term "covering the surface of the resin particles with a metal layer” refers to a state in which the metal layer covers at least a part of the surface of the resin particles, and covers the entire surface of the resin particles.
  • the present invention is not limited to, and may include, for example, a mode in which the metal layer partially covers the surface or a mode in which the entire surface is covered when viewed from a specific cross section.
  • the metal layer preferably covers the entire surface surface when viewed from a specific cross section, and more preferably covers the entire surface surface of the particles.
  • the metal in the metal-coated resin particles can include, for example, one or more selected from the group consisting of silver, gold, nickel, and tin. These may be used alone or in combination of two or more. Alternatively, an alloy containing these metals as a main component may be used. Among these, silver can be used from the viewpoint of sintering property and thermal conductivity.
  • the resin material constituting the resin particles (core resin particles) in the metal-coated resin particles examples include silicone, acrylic, phenol, polystyrene, melamine, polyamide, and polytetrafluoroethylene. These may be used alone or in combination of two or more. Resin particles can be composed of polymers using these. The polymer may be a homopolymer or a copolymer containing these as a main component. From the viewpoint of elastic properties and heat resistance, silicone resin particles or acrylic resin particles may be used as the resin particles.
  • the silicone resin particles may be particles composed of organopolysiloxane obtained by polymerizing organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, and dimethyldichlorosilane, and have a structure in which the organopolysiloxane is further three-dimensionally crosslinked. Silicone resin particles as the basic skeleton may be used.
  • various functional groups can be introduced into the structure of the silicone resin particles, and the functional groups that can be introduced include an epoxy group, an amino group, a methoxy group, a phenyl group, a carboxyl group, a hydroxyl group, an alkyl group, and a vinyl group. Examples thereof include, but are not limited to, mercapto groups.
  • another low stress modifier may be added to the silicone resin particles as long as the characteristics are not impaired.
  • low-stress modifiers that can be used in combination include butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, liquid synthetic rubber such as liquid polybutadiene, and the like. , Not limited to these.
  • the shape of the resin particles is not particularly limited and may be spherical, but may be irregular shapes other than spherical, for example, flat, plate-shaped, or needle-shaped.
  • the shape of the metal-coated resin particles is formed spherically, it is preferable that the shape of the resin particles used is also spherical.
  • the spherical shape is not limited to a perfect true sphere, but also includes a shape close to a sphere such as an ellipse and a shape having some irregularities on the surface.
  • the lower limit of the specific gravity of the metal-coated resin particles is, for example, 2 or more, preferably 2.5 or more, and further preferably 3 or more. As a result, the thermal conductivity and conductivity of the adhesive layer can be further improved. Further, the upper limit of the specific gravity of the metal-coated resin particles is, for example, 10 or less, preferably 9 or less, and more preferably 8 or less. Thereby, the dispersibility of the particles can be improved.
  • the specific gravity may be the specific gravity of the metal particles including the metal-coated resin particles and the particles made of metal.
  • the metal-coated resin particles may be monodisperse particles or polydisperse particles. Further, the metal-coated resin particles may have one peak in the particle size frequency distribution, or may have two or more peaks.
  • the particles made of the above metal may be particles made of one or more kinds of metal materials, and the core portion and the surface layer portion may be made of the same or different metal materials.
  • the metallic material can include, for example, one or more selected from the group consisting of silver, gold, and copper. These may be used alone or in combination of two or more. Alternatively, an alloy containing these metals as a main component may be used. Among these, silver can be used from the viewpoint of sintering property and thermal conductivity.
  • the shape of the particles made of the metal may be, for example, spherical or flaky.
  • the particles made of the metal may contain either one or both of spherical particles and flake-shaped particles.
  • the metal particles includes silver-coated silicone resin particles as the metal-coated resin particles, and silver particles as particles made of metal.
  • silver-coated acrylic resin particles may be used from the viewpoint of elastic properties.
  • particles containing a metal component other than silver, such as gold particles and copper particles can be used in combination for the purpose of promoting syntaring or reducing the cost.
  • the lower limit of the average particle diameter D 50 of the metal-coated resin particles may be, for example, 0.5 ⁇ m or more, preferably 1.5 ⁇ m or more, and more preferably 2.0 ⁇ m or more. Thereby, the storage elastic modulus can be reduced.
  • the upper limit of the average particle diameter D 50 of the metal-coated resin particles may be, for example, 20 ⁇ m or less, 15 ⁇ m or less, or 10 ⁇ m or less. Thereby, the thermal conductivity can be enhanced.
  • the average particle diameter D 50 of the metal coated resin particles may be used as the average particle diameter D 50 of the silver-coated silicone resin particles or silver-coated acrylic resin particles.
  • the lower limit of the average particle diameter D 50 of the particles made of the metal is, for example, 0.8 ⁇ m or more, preferably 1.0 ⁇ m or more, and more preferably 1.2 ⁇ m or more. Thereby, the thermal conductivity can be enhanced.
  • the upper limit of the average particle diameter D 50 of the particles made of the metal is, for example, 7.0 ⁇ m or less, preferably 5.0 ⁇ m or less, and more preferably 4.0 ⁇ m or less. Thereby, the sinterability between the metal particles can be improved. In addition, the uniformity of sintering can be improved.
  • the average particle diameter D 50 of the particles composed of the metal may be used as the average particle diameter D 50 of the silver particles.
  • the average particle diameter D 50 of the metal particles for example, using a Sysmex Corporation flow particle image analyzer FPIA (registered trademark) -3000 can be determined by performing a particle image measurement. More specifically, the particle size of the metal particles can be determined by measuring the volume-based median diameter using the above device.
  • FPIA registered trademark
  • the content of the metal-coated resin particles is, for example, 1% by mass to 50% by mass, preferably 3% by mass to 45% by mass, and more preferably 5% by mass to 40% by mass with respect to the entire metal particles (100% by mass). It is mass%.
  • the content of the metal particles is 1% by mass to 98% by mass, preferably 30% by mass to 95% by mass, and more preferably 50% by mass to 90% by mass with respect to the entire heat conductive composition (100% by mass). %.
  • the thermal conductivity can be enhanced.
  • the value to the above upper limit or less By setting the value to the above upper limit or less, the coatability and the work-made product at the time of pasting can be improved.
  • "to" means that an upper limit value and a lower limit value are included unless otherwise specified.
  • the heat conductive composition contains a binder resin.
  • the binder resin may contain one or more selected from the group consisting of epoxy resin, acrylic resin, and allyl resin. These may be used alone or in combination of two or more.
  • binder resin examples include acrylic resins such as acrylic oligomers and acrylic polymers; epoxy resins such as epoxy oligomers and epoxy polymers; and allyl resins such as allyl oligomers and allyl polymers. These may be used alone or in combination of two or more.
  • an epoxy resin having two or more epoxy groups in the molecule may be used.
  • This epoxy resin may be liquid at 25 ° C. Thereby, the handleability of the heat conductive composition can be improved. Moreover, the curing shrinkage can be appropriately adjusted.
  • epoxy resin examples include, for example, trisphenol methane type epoxy resin; hydrogenated bisphenol A type liquid epoxy resin; bisphenol F type liquid epoxy resin such as bisphenol-F-diglycidyl ether; orthocresol novolac type epoxy resin, and the like. Can be mentioned. These may be used alone or in combination of two or more. Among these, hydrogenated bisphenol A type liquid epoxy resin or bisphenol F type liquid epoxy resin may be used. As the bisphenol F type liquid epoxy resin, for example, bisphenol-F-diglycidyl ether can be used.
  • an acrylic resin having two or more acrylic groups in the molecule may be used.
  • This acrylic resin may be liquid at 25 ° C.
  • the acrylic resin one obtained by (co) polymerizing an acrylic monomer can be used.
  • the method of (co) polymerization is not limited, and a known method using a general polymerization initiator and chain transfer agent such as solution polymerization can be used.
  • allyl resin an allyl resin having two or more allyl groups in one molecule may be used.
  • This allyl resin may be liquid at 25 ° C.
  • the allyl resin examples include an allyl ester resin obtained by reacting a dicarboxylic acid, an allyl alcohol, and a compound having an allyl group.
  • the dicarboxylic acid specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, Examples thereof include tetrahydrophthalic acid and hexahydrophthalic acid.
  • the compound having an allyl group include polyether having an allyl group, polyester, polycarbonate, polyacrylate, polymethacrylate, polybutadiene, and a butadiene acrylonitrile copolymer.
  • the lower limit of the content of the binder resin is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more with respect to 100 parts by mass of the heat conductive composition. As a result, the adhesion to the adherend can be improved.
  • the upper limit of the content of the binder resin is, for example, 15 parts by mass or less, preferably 12 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the heat conductive composition. As a result, it is possible to suppress a decrease in thermal conductivity.
  • the thermally conductive composition contains a monomer.
  • the monomer may contain one or more selected from the group consisting of glycol monomers, acrylic monomers, epoxy monomers and maleimide monomers. These may be used alone or in combination of two or more.
  • the volatilization state of the above-mentioned heat conductive composition after heat treatment can be adjusted.
  • the above-mentioned monomers may be subjected to a curing reaction to adjust the curing shrinkage state.
  • glycol monomer a dihydric alcohol having two hydroxy groups in the molecule and the two hydroxy groups bonded to different carbon atoms; two or more alcohol condensations of the dihydric alcohol.
  • the compound; the hydrogen atom in the hydroxyl group of the alcohol-condensed compound is replaced with an organic group having 1 to 30 carbon atoms to form an alkoxy group.
  • glycol monomer examples include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, and ethylene glycol monoisobutyl.
  • Ethylene ethylene glycol monohexyl ether, ethylene glycol mono2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monon-propyl Ether, Diethylene glycol monoisopropyl ether, Diethylene glycol monon-butyl ether, Diethylene glycol monoisobutyl ether, Diethylene glycol monohexyl ether, Diethylene glycol mono2-ethylhexyl ether, Diethylene glycol monobenzyl ether, Triethylene glycol, Triethylene glycol monomethyl ether, Triethylene glycol monoethyl Ether, Triethylene Glycol Mono n-Butyl Ether, Tetraethylene Glycol, Tetratylene Glycol Monomethyl, Tetratylene Glycol Monoethy
  • the lower limit of the boiling point of the glycol monomer is, for example, preferably 100 ° C. or higher, more preferably 130 ° C. or higher, further preferably 150 ° C. or higher, and even more preferably 170 ° C. or higher. , 190 ° C. or higher is particularly preferable.
  • the upper limit of the boiling point of the glycol monomer may be, for example, 400 ° C. or lower, or 350 ° C. or lower.
  • the boiling point of the glycol monomer indicates the boiling point under atmospheric pressure (101.3 kPa).
  • the acrylic monomer examples include a monomer having a (meth) acrylic group in the molecule.
  • the (meth) acrylic group refers to an acrylic group and a methacrylic group.
  • the acrylic monomer may be a monofunctional acrylic monomer having only one (meth) acrylic group in the molecule, or a polyfunctional acrylic monomer having two or more (meth) acrylic groups in the molecule. Good.
  • the monofunctional acrylic monomer examples include 2-phenoxyethyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and isoamyl.
  • polyfunctional acrylic monomer examples include ethylene glycol di (meth) acrylate, trimethylpropantri (meth) atacrylate, propoxylated bisphenol A di (meth) acrylate, and hexane-1,6-diol bis (2-methyl).
  • acrylic monomer a monofunctional acrylic monomer or a polyfunctional acrylic monomer may be used alone, or a monofunctional acrylic monomer and a polyfunctional acrylic monomer may be used in combination.
  • acrylic monomer for example, it is preferable to use a polyfunctional acrylic monomer alone.
  • the epoxy monomer is a monomer having an epoxy group in the molecule.
  • the epoxy monomer may be a monofunctional epoxy monomer having only one epoxy group in the molecule, or a polyfunctional epoxy monomer having two or more epoxy groups in the molecule.
  • the monofunctional epoxy monomer examples include 4-tert-butylphenylglycidyl ether, m, p-cresylglycidyl ether, phenylglycidyl ether, and cresylglycidyl ether.
  • polyfunctional epoxy monomer examples include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol or derivatives thereof; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, and the like.
  • Diols having an alicyclic structure such as sidilohexane diethanol or derivatives thereof; aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol or epoxidized derivatives thereof; Trifunctional ones having a trihydroxyphenylmethane skeleton and an aminophenol skeleton; and polyfunctional ones obtained by epoxidizing phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin and the like.
  • the maleimide monomer is a monomer having a maleimide ring in the molecule.
  • the maleimide monomer may be a monofunctional maleimide monomer having only one maleimide ring in the molecule, or a polyfunctional maleimide monomer having two or more maleimide rings in the molecule.
  • Specific examples of the maleimide monomer include polytetramethylene ether glycol-di (2-maleimide acetate).
  • the lower limit of the content of the monomer is, for example, 0.5 parts by mass or more, preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more with respect to 100 parts by mass of the heat conductive composition. ..
  • the upper limit of the content of the monomer is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the heat conductive composition.
  • the thermally conductive composition may contain a curing agent, if necessary.
  • the curing agent has a reactive group that reacts with a functional group in a monomer or a binder resin.
  • the reactive group for example, one that reacts with a functional group such as an epoxy group, a maleimide group, or a hydroxyl group may be used.
  • the monomer contains an epoxy monomer and / or the binder resin contains an epoxy resin
  • a phenol resin-based curing agent or an imidazole-based curing agent may be used as the curing agent.
  • phenol resin-based curing agent examples include novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenyl novolak resin; polyvinylphenol; and polyfunctionality such as triphenylmethane-type phenol resin.
  • Type phenol resin modified phenol resin such as terpen-modified phenol resin and dicyclopentadiene-modified phenol resin; phenol aralkyl type having phenylene skeleton and / or biphenylene skeleton, phenylene and / or naphthol aralkyl resin having biphenylene skeleton
  • Phenolic resins bisphenol compounds such as bisphenol A and bisphenol F (dihydroxydiphenylmethane) (phenol resins having a bisphenol F skeleton); compounds having a biphenylene skeleton such as 4,4'-biphenol and the like can be mentioned. These may be used alone or in combination of two or more. Among these, a phenol aralkyl resin may be used, and a phenol / paraxylylene dimethyl ether polycondensate may be used as the phenol aralkyl resin.
  • imidazole-based curing agent examples include 2-phenyl-1H-imidazole-4,5-dimethanol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methylimidazole, and 2-phenylimidazole.
  • 2,4-Diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 2-undecylimidazole, 2-heptadecylimidazole, 2,4-diamino-6- [2-methyl Imidazolyl- (1)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 1-cyanoethyl-2-phenylimidazolium trimerite, 1- Examples thereof include cyanoethyl-2-undecylimidazolium trimellitate. These may be used alone or in combination of two or more.
  • the content of the curing agent may be, for example, 5 parts by mass to 50 parts by mass or 20 parts by mass to 40 parts by mass with respect to 100 parts by mass of the binder resin in the heat conductive composition.
  • the content of the curing agent may be, for example, 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the epoxy resin in the heat conductive composition or 100 parts by mass of the total of the epoxy resin and the epoxy monomer. It may be 10 parts by mass to 35 parts by mass.
  • the thermally conductive composition may contain a radical polymerization initiator.
  • a radical polymerization initiator an azo compound, a peroxide or the like can be used.
  • peroxide examples include bis (1-phenyl-1-methylethyl) peroxide, 1,1-bis (1,1-dimethylethyl peroxy) cyclohexane, methylethylketone peroxide, cyclohexane peroxide, and acetylacetone peroxide.
  • the heat conductive composition may contain a curing accelerator.
  • the curing accelerator can accelerate the reaction between the binder resin or the monomer and the curing agent.
  • the curing accelerator include phosphorus atom-containing compounds such as organic phosphine, tetra-substituted phosphonium compound, phosphobetaine compound, adduct of phosphine compound and quinone compound, and adduct of phosphonium compound and silane compound; Amidines and tertiary amines such as dicyandiamide, 1,8-diazabicyclo [5.4.0] undecene-7, benzyldimethylamine; nitrogen atom-containing compounds such as the amidine or the quaternary ammonium salt of the tertiary amines. Be done. These may be used alone or in combination of two or more.
  • the thermally conductive composition may contain a silane coupling agent.
  • the silane coupling agent can improve the adhesion between the adhesion layer using the thermally conductive composition and the base material or the semiconductor element.
  • silane coupling agent examples include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3 -Epoxysilanes such as glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane Styrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, methacrylsilanes such as 3-methacryloxypropyltriethoxysilane; 3-
  • Acrylic silanes such as (trimethoxysilyl) propyl, 3-acryloxypropyltrimethoxysilane; N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxy Aminosilanes such as silanes; isocyanuratesilanes; alkylsilanes; ureidosilanes such as 3-ureidopropyltrialkoxysilanes; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilanes and 3-mercap
  • the thermally conductive composition may contain a plasticizer.
  • Low stress can be achieved by adding a plasticizer.
  • the plasticizer include silicone compounds such as silicone oil and silicone rubber; polybutadiene compounds such as polybutadiene maleic anhydride adduct; and acrylonitrile butadiene copolymer compounds. These may be used alone or in combination of two or more.
  • the heat conductive composition may contain other components in addition to the above-mentioned components, if necessary.
  • other components include solvents.
  • the solvent is not particularly limited, and is, for example, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol.
  • Ketones ethyl acetate, butyl acetate, diethyl phthalate, dibutyl phthalate, acetoxietan, methyl butyrate, methyl hexanoate, methyl octanate, methyl decanoate, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 1 , 2-Diacetoxyethane, tributyl phosphate, tricredyl phosphate or tripentyl phosphate and other esters; tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether , 1,2-bis (2-diethoxy) ethane or 1,2-bis (2-methoxyethoxy) ethane and other est
  • the fluidity of the heat conductive composition can be controlled, and for example, the workability of the paste-like heat conductive composition can be improved.
  • sintering can be promoted by shrinkage during heating.
  • the solvents by using a solvent having a relatively high boiling point, preferably a solvent having a boiling point higher than the curing temperature, voids are generated in the adhesive layer obtained by heat-treating the thermally conductive composition. Can be suppressed.
  • the boiling point of this high boiling point solvent may be, for example, 180 ° C. to 450 ° C., or 200 ° C. to 400 ° C.
  • thermoly conductive composition of the present embodiment a method for producing the thermally conductive composition of the present embodiment.
  • a method for producing the heat conductive composition a method of mixing the above-mentioned raw material components is used.
  • a known method can be used for mixing, and for example, a three-roll or a mixer can be used.
  • the obtained mixture may be further defoamed.
  • defoaming for example, the mixture may be allowed to stand under vacuum.
  • the semiconductor device of this embodiment will be described.
  • the semiconductor device includes a base material and a semiconductor element mounted on the base material via an adhesive layer obtained by heat-treating the heat conductive composition.
  • an adhesive layer having excellent heat dissipation and adhesion By using an adhesive layer having excellent heat dissipation and adhesion, a semiconductor device having excellent reliability can be realized.
  • the adhesive layer can be applied to various adherends.
  • the adherend include semiconductor elements such as ICs and LSIs; base materials such as lead frames, BGA substrates, mounting substrates, and semiconductor wafers; heat dissipation members such as heat spreaders and heat sinks.
  • FIG. 1 is a cross-sectional view showing an example of a semiconductor device according to the present embodiment.
  • the semiconductor device 100 according to the present embodiment comprises a base material 30 and a semiconductor element 20 mounted on the base material 30 via an adhesive layer 10 (diatack material) which is a heat-treated body of a heat conductive composition. Be prepared.
  • the semiconductor element 20 and the base material 30 are electrically connected via, for example, a bonding wire 40 or the like. Further, the semiconductor element 20 is sealed with, for example, a sealing resin 50.
  • the lower limit of the thickness of the adhesive layer 10 is, for example, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 20 ⁇ m or more. As a result, the heat capacity of the heat-treated body of the heat conductive composition can be improved, and the heat dissipation can be improved. Further, the upper limit of the thickness of the adhesive layer 10 may be, for example, 100 ⁇ m or less, or 50 ⁇ m or less.
  • the base material 30 is, for example, a lead frame.
  • the semiconductor element 20 is mounted on the die pad 32 or the base material 30 via the adhesive layer 10. Further, the semiconductor element 20 is electrically connected to the outer lead 34 (base material 30) via, for example, a bonding wire 40.
  • the base material 30 which is a lead frame is composed of, for example, 42 alloys and a Cu frame.
  • the base material 30 may be an organic substrate or a ceramic substrate.
  • the organic substrate is preferably composed of, for example, an epoxy resin, a cyanate resin, a maleimide resin, or the like.
  • the surface of the base material 30 may be coated with a metal such as silver or gold. Thereby, the adhesiveness between the adhesive layer 10 and the base material 30 can be improved.
  • FIG. 2 is a modification of FIG. 1 and is a cross-sectional view showing an example of the semiconductor device 100 according to the present embodiment.
  • the base material 30 is, for example, an interposer.
  • the base material 30 that is an interposer for example, a plurality of solder balls 52 are formed on the other surface on the opposite side to the one on which the semiconductor element 20 is mounted.
  • the semiconductor device 100 is connected to another wiring board via the solder ball 52.
  • the heat conductive composition is applied onto the base material 30, and then the semiconductor element 20 is arranged on the heat conductive composition. That is, the base material 30, the heat conductive composition, and the semiconductor element 20 are laminated in this order.
  • the method for applying the thermally conductive composition is not limited, and specifically, a dispensing method, a printing method, an inkjet method, or the like can be used.
  • the heat conductive composition is pre-cured and post-cured to obtain a heat-treated body (cured product).
  • ⁇ Thermal conductive composition Each raw material component was mixed according to the blending amount shown in Table 1 below to obtain a varnish. The obtained varnish, solvent, and metal particles were blended according to the blending amounts shown in Table 1 below, and kneaded with a three-roll mill at room temperature to prepare a paste-like thermally conductive composition.
  • (Plasticizer) -Plasticizer 1 Allyl resin (manufactured by Kanto Chemical Co., Inc., polymer of bis (2-propenyl) 1,2-cyclohexanedicarboxylic acid and propane-1,2-diol)
  • Silane coupling agent -Silane coupling agent 1: 3- (trimethoxysilyl) propyl methacrylate (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503P)
  • Silane coupling agent 2 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E)
  • (Curing accelerator) -Imidazole hardener 1 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by Shikoku Chemicals Corporation, 2PHZ-PW)
  • solvent butyl propylene triglycol (BFTG)
  • -Silver particle 1 Silver powder (manufactured by DOWA Hightech, AG-DSB-114, spherical, D 50 : 1 ⁇ m)
  • -Silver particle 2 Silver powder (manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd., HKD-16, flake-shaped, D 50 : 2 ⁇ m)
  • -Silver-coated resin particles 1 Silver-plated silicone resin particles (manufactured by Mitsubishi Materials, heat-resistant 2 ⁇ m product, spherical shape, d50: 2 ⁇ m, specific gravity: 4.3, silver weight ratio 80 wt%, resin weight ratio 20 wt%)
  • -Silver-coated resin particles 2 Silver-plated silicone resin particles (manufactured by Mitsubishi Materials, heat-resistant / surface-treated 2 ⁇ m product, spherical shape, D 50 : 2 ⁇ m, specific gravity: 4.3, silver weight ratio 80 wt%, resin weight ratio 20 wt%)
  • thermally conductive composition Using the obtained thermally conductive composition, the following physical properties were measured and the evaluation items were evaluated.
  • the obtained thermally conductive composition was heated from 30 ° C. to 200 ° C. over 60 minutes and then heat-treated at 200 ° C. for 120 minutes to obtain a heat-treated body having a thickness of 1 mm.
  • the heat diffusion coefficient ⁇ in the thickness direction of the heat-treated body was measured by using a laser flash method. The measurement temperature was 25 ° C.
  • the specific heat Cp was measured by differential scanning calorimetry (DSC) measurement, and the density ⁇ measured according to JIS-K-6911 was measured. Using these values, the thermal conductivity ⁇ was calculated based on the following formula.
  • the evaluation results are shown in Table 2 below.
  • the unit is W / (m ⁇ K).
  • Thermal conductivity ⁇ [W / (m ⁇ K)] ⁇ [m 2 / sec] ⁇ Cp [J / kg ⁇ K] ⁇ ⁇ [g / cm 3 ]
  • the obtained thermally conductive composition was heated from 30 ° C. to 200 ° C. over 60 minutes, and then heat-treated at 200 ° C. for 120 minutes to obtain a heat-treated body.
  • the storage elastic modulus E (MPa) at 25 ° C. was measured by dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz using a measuring device (DMS6100 manufactured by Hitachi High-Tech Science Co., Ltd.).
  • a copper lead frame and a silicon chip (length 2 mm ⁇ width 2 mm, thickness 0.35 mm) were prepared. Next, the obtained heat conductive composition was applied to the silicon chip so as to have a coating thickness of 25 ⁇ 10 ⁇ m, and a copper lead frame was placed on the coating thickness. A laminate in which a silicon chip, a heat conductive composition, and a copper lead frame were laminated in this order was produced. Next, the obtained laminate was heated in the air from 30 ° C. to 200 ° C. for 60 minutes, and then heat-treated at 200 ° C. for 120 minutes to cure the thermally conductive composition in the laminate. .. Next, using a scanning electron microscope (SEM), the cross section of the heat-treated body of the heat-conductive composition in the laminated body was observed, and the state was evaluated.
  • SEM scanning electron microscope
  • the silver particle connecting structure was formed in all of Examples 1 to 7. It was also confirmed in the cross-sectional image that the silver particle connecting structure contained a plurality of substantially circular resin particles, and that the metal layer (silver layer) on the surface of the resin particles and the silver particle connecting structure were connected. Was done. Further, it was confirmed that the cured product of the binder resin exists in the silver particle connecting structure so as to cover the silver in a portion other than silver.
  • the obtained thermally conductive composition was heated from 30 ° C. to 200 ° C. over 60 minutes and then heat-treated at 200 ° C. for 120 minutes to obtain a heat-treated body.
  • the resin content derived from the binder resin and the silver-coated resin particles was measured as follows.
  • the resin content in the heat-treated body was defined as the resin content (mass%).
  • the resin content was calculated by measuring the weight of the obtained heat-treated body and subtracting the weight of silver contained from the weight.
  • Thermal cycle test The obtained thermally conductive composition was applied onto a silver-plated substrate, and a 3.5 ⁇ 3.5 mm silicon chip (only Comparative Example 1 was silver-plated on the surface, the others were not plated) was placed on the substrate, and 30 The temperature was raised from ° C. to 200 ° C. over 60 minutes, and then heat treatment was performed at 200 ° C. for 120 minutes to cure and bond.
  • the silicon chip / substrate after joining was sealed with a sealing material EME-G700ML-C (manufactured by Sumitomo Bakelite) to obtain a sample.
  • the obtained sample was placed in a high temperature and high humidity bath of 85 C / 60% RH, treated for 168 hours, and then subjected to a reflow treatment at 260 ° C.
  • the sample after the reflow treatment is put into a temperature cycle tester TSA-72ES (manufactured by ESPEC), and 2000 cycles are processed with 150 ° C. 10 minutes ⁇ 25 ° C. 10 minutes ⁇ -65 ° C. 10 minutes ⁇ 25 ° C. 10 minutes as one cycle. Was done. After that, the presence or absence of peeling was confirmed by SAT (ultrasonic flaw detection). In Table 1, those without peeling are marked with ⁇ , and those with peeling are marked with x.
  • thermally conductive compositions of Examples 1 to 7 were superior in temperature cycle property as compared with Comparative Example 1 and heat dissipation property as compared with Comparative Example 2.
  • the heat conductive composition of such an example it is possible to realize a semiconductor device that stably exhibits high heat dissipation and has excellent durability during use.

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PCT/JP2020/010568 2019-03-20 2020-03-11 熱伝導性組成物および半導体装置 WO2020189445A1 (ja)

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