WO2016121806A1 - ペースト状接着剤組成物、半導体装置、半導体装置の製造方法、および放熱板の接着方法 - Google Patents

ペースト状接着剤組成物、半導体装置、半導体装置の製造方法、および放熱板の接着方法 Download PDF

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Publication number
WO2016121806A1
WO2016121806A1 PCT/JP2016/052295 JP2016052295W WO2016121806A1 WO 2016121806 A1 WO2016121806 A1 WO 2016121806A1 JP 2016052295 W JP2016052295 W JP 2016052295W WO 2016121806 A1 WO2016121806 A1 WO 2016121806A1
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Prior art keywords
adhesive composition
paste
heating
compound
paste adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/052295
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English (en)
French (fr)
Japanese (ja)
Inventor
安雄 下邊
竜一 村山
康二 牧原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to SG11201705967TA priority Critical patent/SG11201705967TA/en
Priority to EP16743409.1A priority patent/EP3252123A4/en
Priority to US15/546,147 priority patent/US10259976B2/en
Priority to CN201680007771.0A priority patent/CN107207941B/zh
Priority to JP2016528923A priority patent/JP6137410B2/ja
Publication of WO2016121806A1 publication Critical patent/WO2016121806A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • 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 groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07 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
    • 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
    • H01L24/02—Bonding areas ; Manufacturing methods related thereto
    • H01L24/07—Structure, shape, material or disposition of the bonding areas after the connecting process
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • H01L2224/26—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
    • 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
    • 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
    • H01L2224/481—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
    • 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
    • H01L2224/481—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
    • 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
    • H01L2224/73—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
    • 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 paste adhesive composition, a semiconductor device, a method for manufacturing a semiconductor device, and a method for bonding a heat sink.
  • Patent Document 1 describes a thermosetting resin composition containing (A) plate-type silver fine particles, (B) silver powder having an average particle diameter of 0.5 to 30 ⁇ m, and (C) a thermosetting resin. Has been.
  • the present inventor has examined the generation of sintering in metal particles from the viewpoint of improving thermal conductivity, etc., when producing an adhesive layer using a paste-like adhesive composition containing metal particles. .
  • Metal particles (A); A compound (B) which is polymerized by heating; Including The metal particles (A) are sintered by heat treatment to form a particle connection structure,
  • the dynamic viscoelasticity measurement is performed under the condition of a measurement frequency of 1 Hz, the temperature range where the shear elastic modulus is 5,000 Pa or more and 100,000 Pa or less is 10 ° C. or more in the temperature range of 140 ° C. to 180 ° C.
  • a paste-like adhesive composition is provided in which the sample obtained by removing the metal particles (A) and heating at 180 ° C. for 2 hours has an acetone insoluble content of 5% by weight or less.
  • a substrate A semiconductor element mounted on the base material via an adhesive layer which is a heat treatment body of the paste adhesive composition described above, A semiconductor device is provided.
  • a step of mounting a semiconductor element on a substrate via the paste adhesive composition described above; Heating the paste adhesive composition; A method for manufacturing a semiconductor device is provided.
  • the present invention it is possible to improve the uniformity of sintering of the metal particles in the center portion and the peripheral portion in the surface direction of the adhesive layer.
  • FIG. 8 is a cross-sectional view showing a modification of the semiconductor device shown in FIG. 1.
  • the paste adhesive composition according to the present embodiment includes metal particles (A) and a compound (B) that is polymerized by heating.
  • the metal particles (A) are sintered by heat treatment to form a particle connection structure.
  • the paste-like adhesive composition has a shear elastic modulus of 5,000 Pa or more and 100,000 Pa or less in a temperature range of 140 ° C. to 180 ° C. when dynamic viscoelasticity measurement is performed at a measurement frequency of 1 Hz. It has a certain temperature range of 10 ° C. or more.
  • the paste-like adhesive composition has an acetone insoluble content of 5% by weight or less in a sample obtained by heating at 180 ° C. for 2 hours after removing the metal particles (A).
  • the sintering proceeds uniformly at the center and the peripheral part in the surface direction of the adhesive layer. It may be difficult to do so.
  • a large-area adhesive layer is formed as a die attach layer for adhering a large-area semiconductor element having a side of 5 mm or more
  • the sintering progresses in the central portion and the peripheral portion of the adhesive layer. There was concern that the degree of variation would become more prominent.
  • the present inventor examined a paste-like adhesive composition capable of improving the uniformity of sintering in the central portion and the peripheral portion in the surface direction of the adhesive layer.
  • the present inventor has included the compound (B) that is polymerized by heating with the metal particles (A) in the paste adhesive composition, the viscoelastic behavior of the paste adhesive composition, and a predetermined value. It was newly found out that the uniformity of sintering of the metal particles (A) can be improved by controlling the acetone insoluble matter measured under the above conditions as described above.
  • the paste adhesive composition according to the present embodiment is realized based on such new knowledge. For this reason, according to this embodiment, it becomes possible to improve the uniformity of the sintering of the metal particles in the center portion and the peripheral portion in the surface direction of the adhesive layer.
  • the paste adhesive composition according to the present embodiment includes metal particles (A) and a compound (B) that is polymerized by heating.
  • the paste adhesive composition according to this embodiment is a die attach paste used for forming a die attach layer for adhering a semiconductor element to another structure, for example.
  • the other structure is not particularly limited, and examples thereof include a substrate such as a wiring board or a lead frame, a semiconductor element, a heat sink, and a magnetic shield.
  • the paste adhesive composition can also be used, for example, to form an adhesive layer that adheres a heat sink to these other structures.
  • it is preferable that the said other structure is equipped with the film which promotes adhesion
  • the paste adhesive composition according to this embodiment has a shear elastic modulus of 5,000 Pa or more and 100,000 in a temperature range of 140 ° C. to 180 ° C. when dynamic viscoelasticity measurement is performed under the condition of a measurement frequency of 1 Hz. It has a temperature range W of 10 ° C. or more which is 000 Pa or less.
  • a paste adhesive composition and sintering the metal particles (A) by a heat treatment under a low temperature condition of less than 200 ° C. as will be described later the sintering of the metal particles (A) is performed. Can be more uniformly advanced in the center portion and the peripheral portion in the surface direction of the adhesive layer.
  • the paste adhesive composition has a shear elastic modulus of 5,000 Pa or more and 100,000 Pa or less in a temperature range of 140 ° C. to 180 ° C. when dynamic viscoelasticity measurement is performed.
  • the temperature width W is 10 ° C. or more.
  • the temperature width W is more preferably 15 ° C. or more, particularly preferably 20 ° C. or more, and further preferably 25 ° C. or more. preferable.
  • the upper limit value of the temperature width W is not particularly limited, and can be set to 40 ° C. or less, but more preferably 35 ° C. or less from the viewpoint of productivity of the semiconductor device.
  • the dynamic viscoelasticity measurement for the paste-like adhesive composition is performed using, for example, a rheometer (HAAKE RheoWin, manufactured by Thermo Scientific), a measurement frequency of 1 Hz, a heating rate of 5 ° C./min, and a measuring temperature range of 25
  • the reaction can be carried out at a temperature of from ° C to 250 ° C.
  • the viscoelastic behavior of the paste-like adhesive composition including the temperature range W can be controlled by adjusting, for example, the types and blending ratios of the components contained in the paste-like adhesive composition.
  • the type and blending ratio of the compound (B) that is polymerized by heating are particularly important.
  • adjusting the temperature range W for example, adjusting the type and blending ratio of the curing agent (C) in accordance with the metal particles (A) and the compound (B). It is possible to configure the paste adhesive composition so that the compound (B) can be linearly polymerized when heat-treated by appropriately selecting the types and blending ratios of these components. It is assumed that it is very important to control within a desired range.
  • the paste-like adhesive composition according to the present embodiment has an acetone insoluble content of 5% by weight or less in a sample obtained by heating at 180 ° C. for 2 hours after removing the metal particles (A). .
  • the paste-like adhesive composition having an acetone insoluble content of 5% by weight or less after heating it is estimated that a linear polymerization reaction proceeds instead of three-dimensional crosslinking for the compound (B) polymerized by heating.
  • the acetone insoluble matter can be measured as follows. First, the metal particles (A) are removed from the paste-like adhesive composition by centrifugation and filtration with a 115 mesh (aperture 125 ⁇ m) filter. Next, the paste-like adhesive composition from which the metal particles (A) have been removed is heated at 180 ° C. for 2 hours to obtain a measurement sample. Next, about 100 g of a measurement sample is precisely weighed and put into a sealed container containing about 900 g of acetone at a liquid temperature of 25 ° C., and the inside of the sealed container is obtained using about 100 g of acetone solution obtained by shaking for 20 minutes.
  • the acetone solution obtained by rinsing is sieved with a JIS standard sieve having a mesh size of 115 (mesh size: 125 ⁇ m). Then about 100 g of acetone is passed through the sieve. Next, after the residue on the sieve is air-dried, the weight of the residue is measured. From the measurement result, the ratio (wt%) of the residual to the whole measurement sample is calculated, and this is defined as acetone insoluble matter (wt%).
  • the above-mentioned acetone-insoluble component of the paste adhesive composition can be controlled by adjusting, for example, the types and blending ratios of the components contained in the paste adhesive composition.
  • the type and blending ratio of the compound (B) that is polymerized by heating are particularly important.
  • adjusting the type and blending ratio of the curing agent (C) in accordance with the metal particles (A) and the compound (B) can also be a factor affecting the acetone insoluble matter.
  • the paste-like adhesive composition according to this embodiment is obtained by, for example, increasing the temperature of a coating film obtained by applying this from 25 ° C. to 250 ° C. at a rate of temperature increase of 5 ° C./min, and then at 250 ° C. for 2 hours.
  • membrane obtained by heating by it is preferable that the heat conductivity of the thickness direction is 15 W / mK or more.
  • the thermal conductivity in the thickness direction is more preferably 50 W / mK or more, and particularly preferably 60 W / mK or more.
  • the upper limit value of the thermal conductivity in the thickness direction is not particularly limited, but can be, for example, 200 W / mK or less.
  • the thermal conductivity in the thickness direction can be controlled by adjusting, for example, the types and blending ratios of the components contained in the paste adhesive composition.
  • the paste-like adhesive composition according to this embodiment is obtained by, for example, increasing the temperature of a coating film obtained by applying this from 25 ° C. to 250 ° C. at a rate of temperature increase of 5 ° C./min, and then at 250 ° C. for 2 hours. It is preferable that the volume resistivity in the plane direction is 25 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less with respect to the film obtained by heating in step 1. Thereby, the electroconductivity of the contact bonding layer obtained using a paste-form adhesive composition can be improved.
  • the volume resistivity in the plane direction is more preferably 15 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less, and particularly preferably 8 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less.
  • the volume resistivity in the plane direction can be controlled, for example, by adjusting the types and blending ratios of the components contained in the paste adhesive composition.
  • the lower limit value of the volume resistivity in the surface direction is not particularly limited, but is, for example, 0.01 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or more.
  • the paste adhesive composition according to this embodiment preferably has a 5% weight loss temperature of 100 ° C. or higher and 180 ° C. or lower.
  • the 5% weight reduction temperature is particularly preferably 100 ° C. or more and 160 ° C. or less from the viewpoint of improving the balance of stability over time and sinterability.
  • the 5% weight reduction temperature can be controlled, for example, by adjusting the types and blending ratios of the components contained in the paste adhesive composition.
  • TG / DTA thermogravimetric / differential thermal analysis
  • Metal particles (A) The metal particles (A) contained in the paste adhesive composition are sintered to form a particle connection structure by heat treatment of the paste adhesive composition. That is, in the adhesive layer obtained by heating the paste adhesive composition, the metal particles (A) are fused to each other. Thereby, about the adhesive bond layer obtained by heating a paste-form adhesive composition, the heat conductivity, electroconductivity, the adhesiveness to a base material, a semiconductor element, a heat sink, etc. can be improved.
  • the shape of the metal particles (A) is not particularly limited, and examples thereof include a spherical shape, a flake shape, and a scale shape. In the present embodiment, it is more preferable that the metal particles (A) include spherical particles. Thereby, the sinterability of a metal particle (A) can be improved. Moreover, it can contribute to the improvement of the uniformity of sintering. Moreover, from a viewpoint of reducing cost, the aspect in which a metal particle (A) contains flake shaped particle
  • the metal particles (A) can contain, for example, 90% by weight or more and 100% by weight or less, and 95% by weight or more of the whole metal particles (A) by combining, for example, spherical particles and flaky particles. More preferred. Thereby, the uniformity of sintering can be improved more effectively. Further, from the viewpoint of further improving the uniformity of sintering, it is more preferable that the metal particles (A) contain, for example, 90% by weight or more and 100% by weight or less of spherical particles as a whole. It is more preferable to include the above.
  • the metal particles (A) include, for example, one or more selected from the group consisting of Ag (silver), Au (gold), and Cu (copper). Thereby, the sinterability of the metal particles (A) can be improved, and the thermal conductivity and conductivity of the adhesive layer obtained using the paste adhesive composition can be effectively improved.
  • the metal particles (A) can contain metal components other than Ag, Au, and Cu for the purpose of, for example, promoting sintering or reducing costs.
  • the metal particles (A) can contain, for example, carbon. Carbon contained in the metal particles (A) functions as a sintering aid when sintering occurs in the metal particles (A). For this reason, it becomes possible to improve the sinterability of a metal particle (A).
  • the case where the metal particles (A) contain carbon includes the case where they are contained inside the metal particles (A) and the case where they are physically or chemically adsorbed on the surfaces of the metal particles (A). .
  • a lubricant containing carbon is attached to the metal particles (A) can be mentioned.
  • lubricants examples include higher fatty acids, higher fatty acid metal salts, higher fatty acid amides, and higher fatty acid esters.
  • the content of the lubricant is preferably 0.01% by mass or more and 5% by mass or less with respect to the entire metal particles (A). This makes it possible to suppress a decrease in thermal conductivity while effectively functioning carbon as a sintering aid.
  • the lower limit of the average particle diameter (D 50 ) of the metal particles (A) is, for example, 0.1 ⁇ m or more.
  • the upper limit of the average particle diameter of the metal particles (A) (D 50) is 10 ⁇ m or less.
  • the average particle diameter (D 50 ) of the metal particles (A) is not less than the above lower limit value, it is possible to suppress an excessive increase in specific surface area and to suppress a decrease in thermal conductivity due to contact thermal resistance. Further, the average particle size of the metal particles (A) (D 50) is more than the above upper limit, it is possible to improve the sintering property between the metal particles (A).
  • the average particle size (D 50 ) of the metal particles (A) is more preferably 0.6 ⁇ m or more and 2.7 ⁇ m or less, and 0.6 ⁇ m.
  • the thickness is particularly preferably 2.0 ⁇ m or more.
  • the average particle diameter (D 50 ) of the metal particles (A) can be measured using, for example, a commercially available laser particle size distribution meter (for example, SALD-7000 manufactured by Shimadzu Corporation).
  • the maximum particle size of the metal particles (A) is not particularly limited, but can be, for example, 1 ⁇ m or more and 50 ⁇ m or less, more preferably 3 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 4 ⁇ m or more and 18 ⁇ m or less. . This makes it possible to more effectively improve the balance between the uniformity of sintering and the dispensing property.
  • the above upper limit value and lower limit value can be appropriately combined to determine the average particle diameter (D 50 ) and the like of the metal particles (A).
  • the content of the metal particles (A) in the paste adhesive composition is, for example, preferably 80% by weight or more, and more preferably 85% by weight or more with respect to the entire paste adhesive composition. Thereby, it becomes possible to improve the sinterability of the metal particles (A) and contribute to the improvement of thermal conductivity and conductivity.
  • the content of the metal particles (A) in the paste adhesive composition is preferably, for example, 95% by weight or less, and preferably 90% by weight or less, with respect to the entire paste adhesive composition. Particularly preferred. Thereby, it can contribute to improvement of the application
  • content with respect to the whole paste-form adhesive composition refers to content with respect to the whole component except a solvent of a paste-form adhesive composition, when a solvent is included.
  • the compound (B) polymerized by heating is, for example, one selected from a compound (B1) having only one radical polymerizable double bond in the molecule and a compound (B2) having only one epoxy group in the molecule. Or two or more can be included. Thereby, when the paste-like adhesive composition is heat-treated, the compound (B) can be linearly polymerized. For this reason, the uniformity of sintering and the balance of dispensing properties can be improved. Among those exemplified above, it is more preferable that at least the compound (B1) is included from the viewpoint of reducing the volume resistivity of the adhesive layer obtained by using the paste adhesive composition.
  • the compound (B1) having only one radical polymerizable double bond in the molecule is, for example, a compound having only one (meth) acryl group in the molecule, a compound having only one vinyl group in the molecule, or an allyl group One or more selected from a compound having only one in the molecule, a compound having only one maleimide group in the molecule, and a compound having only one maleic acid group in the molecule.
  • numerator the (meth) acrylic acid ester etc. which have only one (meth) acryl group in a molecule
  • numerator can be included, for example.
  • the (meth) acrylic acid ester contained in the compound (B1) having only one radical polymerizable double bond in the molecule is represented by, for example, the compound represented by the following formula (1) and the following formula (2). 1 type, or 2 or more types selected from the compound to be made can be included. Thereby, the uniformity of sintering can be improved more effectively.
  • R 11 is hydrogen or a methyl group
  • R 12 is a monovalent organic group having 1 to 20 carbon atoms including an OH group.
  • R 12 may contain one or more of an oxygen atom, a nitrogen atom, and a phosphorus atom.
  • the compound represented by the above formula (1) is not particularly limited.
  • 1,4-cyclohexanedimethanol monoacrylate 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl Methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydro Phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-acryloyl Carboxymethyl ethyl acid phosphate, and 2-methacryloyloxypropyl ethyl can Acid containing one or more selected from phosphates.
  • a compound having a cyclic structure in R 12 as exemplified by 1,4-cyclohexanedimethanol monoacrylate, or a compound in R 12 as exemplified by 2-methacryloyloxyethyl succinic acid is exemplified.
  • the case where a compound containing a carboxyl group is contained in can be adopted as an example of a preferred embodiment.
  • R 21 is hydrogen or a methyl group
  • R 22 is a monovalent organic group having 1 to 20 carbon atoms that does not contain an OH group.
  • R 22 may contain one or more of an oxygen atom, a nitrogen atom, and a phosphorus atom.
  • the compound represented by the above formula (2) is not particularly limited.
  • a compound containing a cyclic structure in R 22 as exemplified by 2-ethylhexyl methacrylate, n-lauryl acrylate, and n-lauryl methacrylate.
  • R 22 contains a compound in which R 22 is a linear or branched alkyl group can be employed as an example of a preferred embodiment.
  • the compound (B1) having only one radical polymerizable double bond in the molecule metal
  • the acrylate ester contains both the compound represented by the above formula (1) and the compound represented by the above formula (2).
  • the compound (B1) may contain only one of the compound represented by the above formula (1) and the compound represented by the above formula (2).
  • the compound (B2) having only one epoxy group in the molecule includes, for example, n-butyl glycidyl ether, versatic acid glycidyl ester, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, butyl phenyl glycidyl ether, and cresyl glycidyl ether. 1 type, or 2 or more types selected from can be included. Among these, from the viewpoint of improving the balance of sintering uniformity, thermal conductivity, conductivity, and the like, an example of a preferred embodiment that includes at least cresyl glycidyl ether is given.
  • an embodiment that includes the compound (B2) and does not include the compound (B3) having two or more epoxy groups in the molecule can be employed.
  • the phrase “not including the compound (B3)” refers to a case where the content of the compound (B3) is 0.01% by weight or less with respect to the entire compound (B) polymerized by heating, for example.
  • the content of the compound (B3) is more than 0.01% by weight of the whole compound (B) and 60% by weight or less. It is mentioned as an example of a preferable aspect from a viewpoint of improving the balance of the uniformity of sintering and the dispensing property.
  • the compound (B) that is polymerized by heating preferably does not contain, for example, a compound having two or more radical polymerizable double bonds in the molecule or a compound having two or more epoxy groups in the molecule. Thereby, it becomes possible to polymerize the said compound (B) in linear form, and it can contribute to the improvement of the uniformity of sintering.
  • the compound (B) may include a compound having two or more radical polymerizable double bonds in the molecule or a compound having two or more epoxy groups in the molecule. When a compound having two or more radically polymerizable double bonds in the molecule or a compound having two or more epoxy groups in the molecule is included, the total content of these compounds is 0 weight of the entire compound (B).
  • the content of the compound (B) polymerized by heating contained in the paste adhesive composition is preferably 5% by weight or more, for example, 8% by weight or more with respect to the entire paste adhesive composition. More preferred is 10% by weight or more. Thereby, the uniformity of sintering can be improved more effectively. Moreover, it can also contribute to the improvement of the mechanical strength and the like of the adhesive layer.
  • the content of the compound (B) contained in the paste adhesive composition is preferably 20% by weight or less, for example, 18% by weight or less with respect to the entire paste adhesive composition. More preferably, it is particularly preferably 15% by weight or less. Thereby, it becomes possible to contribute to the improvement of the sinterability of the metal particles (A).
  • the paste adhesive composition can include, for example, a curing agent (C).
  • the curing agent (C) is not particularly limited as long as it accelerates the polymerization reaction of the compound (B) that is polymerized by heating. Thereby, the polymerization reaction of the said compound (B) can be accelerated
  • the curing agent (C) is not included in the paste adhesive composition.
  • the paste-like adhesive composition does not contain a curing agent (C), for example, when the content of the curing agent (C) is 0.01 parts by weight or less with respect to 100 parts by weight of the compound (B) polymerized by heating. Point to.
  • the curing agent (C) can include, for example, a compound having a tertiary amino group.
  • the compound (B) polymerized by heating contains a compound having an epoxy group in the molecule, the compound (B) can be promoted to be linearly polymerized.
  • Examples of compounds having a tertiary amino group include tertiary amines such as benzyldimethylamine (BDMA), imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24), pyrazole, 3,5 -Pyrazoles such as dimethylpyrazole and pyrazoline, triazoles such as triazole, 1,2,3-triazole, 1,2,4-triazole and 1,2,3-benzotriazole, imidazoline, 2-methyl-2-imidazoline And imidazolines such as 2-phenylimidazoline, and one or more selected from these can be included.
  • BDMA benzyldimethylamine
  • imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24)
  • pyrazole 3,5 -Pyrazoles such as dimethylpyrazole and pyrazoline
  • triazoles such as triazole, 1,2,3-triazole
  • the compound (B) that is polymerized by heating contains a compound having an epoxy group in the molecule, it is possible to selectively promote homo ring-opening polymerization of the epoxy group.
  • an example of a preferable embodiment that includes at least an imidazole is given.
  • the curing agent (C) can contain, for example, a radical polymerization initiator.
  • a radical polymerization initiator for example, when the compound (B) polymerized by heating contains a compound having a radical polymerizable double bond in the molecule, the compound (B) can be promoted to be polymerized.
  • radical polymerization initiators include octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl -2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t- Butylperoxy-2-ethylhexanoate, m-toluyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dic Milperoxid
  • the paste-like adhesive composition of the present embodiment has a compound having an epoxy group (a compound having only one epoxy group in the molecule (B2), a compound having two or more epoxy groups in the molecule (B3 ) Etc.) can be included as a curing agent (C).
  • a compound having an epoxy group a compound having only one epoxy group in the molecule (B2), a compound having two or more epoxy groups in the molecule (B3 ) Etc.
  • a curing agent (C) can be included as a curing agent (C).
  • compounds such as bisphenol A, bisphenol F, bisphenol S, biphenol, and phenylphenol, phenol novolac type resins, and the like can be included as the curing agent (C).
  • the content of the curing agent (C) contained in the paste adhesive composition can be, for example, 25 parts by weight or less with respect to 100 parts by weight of the compound (B) polymerized by heating.
  • the compound (B) includes a compound (B1) having only one radical polymerizable double bond in the molecule, 100 weight of the compound (B) from the viewpoint of improving the uniformity of sintering.
  • the content of the curing agent (C) with respect to parts is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 1 part by weight or less.
  • curing agent (C) contained in a paste-form adhesive composition can be 0 weight part or more with respect to 100 weight part of said compounds (B). From the viewpoint of improving the mechanical properties of the paste adhesive composition, for example, the content of the curing agent (C) with respect to 100 parts by weight of the compound (B) can be 0.1 parts by weight or more.
  • the paste adhesive composition can contain, for example, a polymerization inhibitor (D).
  • a polymerization inhibitor (D) a compound that suppresses the polymerization reaction of the compound contained in the paste adhesive composition is used. Thereby, the storage characteristic of a paste-form adhesive composition can be improved more.
  • the polymerization inhibitor (D) is not particularly limited, but examples thereof include hydroquinones exemplified by hydroquinone, p-tert-butylcatechol, and mono-tert-butylhydroquinone, hydroquinone monomethyl ether, and di-p-cresol.
  • the content of the polymerization inhibitor (D) in the paste adhesive composition is preferably 0.0001 parts by weight or more, for example, 0.001 part by weight with respect to 100 parts by weight of the compound (B) polymerized by heating. More preferably, it is at least part. Thereby, it becomes possible to contribute to the improvement of the uniformity of sintering. Moreover, the storage characteristic of a paste-form adhesive composition can be improved more effectively.
  • the content of the polymerization inhibitor (D) in the paste adhesive composition is preferably 0.5 parts by weight or less with respect to 100 parts by weight of the compound (B), for example, 0.1 weight. It is more preferable to set it as a part or less. Thereby, the mechanical strength etc. of an adhesive bond layer can be improved.
  • the paste adhesive composition according to the present embodiment can contain a solvent, for example.
  • the solvent is not particularly limited, but 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, ethylene glycol mono Propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl methoxybutanol, ⁇ -terpineol, ⁇ -terpineol, hexylene glycol, benzyl alcohol, 2 -
  • FIG. 1 is a cross-sectional view showing a semiconductor device 100 according to this embodiment.
  • the semiconductor device 100 according to this embodiment includes a base material 30 and a semiconductor element 20 mounted on the base material 30 via a die attach layer 10 that is a heat treatment body of a paste adhesive composition. .
  • the semiconductor element 20 and the base material 30 are electrically connected through, for example, a bonding wire 40 or the like. Further, the semiconductor element 20 is sealed with, for example, a sealing resin 50.
  • the film thickness of the die attach layer 10 is not specifically limited, For example, they are 5 micrometers or more and 100 micrometers or less.
  • the base material 30 is, for example, a lead frame.
  • the semiconductor element 20 is mounted on the die pad 32 (30) via the die attach layer 10. Further, the semiconductor element 20 is electrically connected to the outer lead 34 (30) through, for example, the bonding wire 40.
  • the base material 30 which is a lead frame is composed of, for example, a 42 alloy, Cu frame.
  • the base material 30 may be an organic substrate or a ceramic substrate. As the organic substrate, for example, a substrate known to those skilled in the art to which an epoxy resin, a cyanate resin, a maleimide resin or the like is applied is suitable. Further, the surface of the substrate 30 may be coated with silver or the like in order to improve the adhesiveness with the paste adhesive composition.
  • the planar shape of the semiconductor element 20 is not particularly limited, but is rectangular, for example.
  • a rectangular semiconductor element 20 having a chip size of 0.5 mm ⁇ or more and 15 mm ⁇ or less can be employed.
  • a semiconductor chip 20 using a rectangular large chip having sides of 5 mm or more can be cited.
  • the area of the die attach layer is also increased, it may be difficult to uniformly sinter the metal particles in the central portion and the peripheral portion of the die attach layer.
  • even when such a large chip is used, by forming the die attach layer using the paste adhesive composition described above, the center and peripheral portions of the die attach layer are formed. The uniformity of the sintering of the metal particles can be made very good.
  • FIG. 2 is a cross-sectional view showing a modification of the semiconductor device 100 shown in FIG.
  • the base material 30 is, for example, an interposer.
  • a plurality of solder balls 52 are formed on the other surface of the base material 30 that is an interposer opposite to the one surface on which the semiconductor element 20 is mounted.
  • the semiconductor device 100 is connected to another wiring board via the solder balls 52.
  • the semiconductor device 100 can be manufactured as follows, for example. First, the paste-like adhesive composition including the metal particles (A) and the compound (B) that is polymerized by heating, wherein the metal particles (A) are sintered by heat treatment to form a particle connection structure. Then, the semiconductor element 20 is mounted on the base material 30. Next, the paste adhesive composition is heated. As a result, the semiconductor device 100 is manufactured.
  • the paste-like adhesive composition including the metal particles (A) and the compound (B) that is polymerized by heating, wherein the metal particles (A) are sintered by heat treatment to form a particle connection structure.
  • the semiconductor element 20 is mounted on the base material 30.
  • the paste adhesive composition is heated.
  • the semiconductor device 100 is manufactured.
  • a method for manufacturing the semiconductor device 100 will be described in detail.
  • the semiconductor element 20 is mounted on the base material 30 through the paste adhesive composition described above.
  • the semiconductor element 20 is mounted on the coating film made of the paste adhesive composition.
  • a method of apply coating a paste-form adhesive composition
  • dispensing, the printing method, and the inkjet method are mentioned.
  • the paste adhesive composition is heat-treated. At this time, sintering occurs in the metal particles (A) in the paste adhesive composition, and a particle connection structure is formed between the metal particles (A). As a result, the die attach layer 10 is formed on the substrate 30.
  • heat treatment can be performed while applying pressure to the paste-like adhesive composition.
  • the paste adhesive composition is heated under a temperature condition of 200 ° C. or higher.
  • a heating step (hereinafter also referred to as second heat treatment) can be performed.
  • the progress of the sintering of the metal particles (A) is caused to be a binder component (polymerized by heating). It can suppress more reliably that it is prevented by a compound (B)) etc. For this reason, it becomes possible to sinter the metal particles (A) more uniformly and sufficiently at the periphery and the center of the die attach layer.
  • the heating is performed for a certain time under a temperature condition of a temperature T 2 of 200 ° C. or more.
  • a heat treatment and a second heat treatment can be performed.
  • T 1 can be, for example, 120 ° C. or more and less than 200 ° C.
  • T 2 can be, for example, 200 ° C. or higher and 350 ° C. or lower.
  • the processing time for the first heat treatment temperatures T 1 may be, for example, be at least 20 minutes 90 minutes or less.
  • the processing time of the second heat treatment temperature T 2 may be, for example, 180 minutes or less 30 minutes or more.
  • the paste-like adhesive composition is heated for a certain time under the temperature condition of the temperature T 3.
  • the object may be heat treated.
  • treats before reaching the 200 ° C. of the heating step as the first heat treatment to handle the process of heat treatment at a temperature T 3 was heated to a temperature T 3 from 200 ° C. as a second heat treatment Can do.
  • T 3 can be, for example, 200 ° C. or higher and 350 ° C. or lower.
  • the semiconductor element 20 and the base material 30 are electrically connected using the bonding wire 40.
  • the semiconductor element 20 is sealed with a sealing resin 50.
  • the semiconductor device 100 can be manufactured as described above.
  • a heat sink may be bonded to the semiconductor device.
  • the heat sink can be bonded to the semiconductor device via an adhesive layer which is a heat treatment body of the paste adhesive composition.
  • the heat sink can be bonded as follows, for example. First, a heat sink is bonded to the semiconductor device via the paste adhesive composition described above. Next, the paste adhesive composition is heat-treated.
  • the heat treatment for the paste adhesive composition can be performed, for example, in the same manner as the step of forming the die attach layer 10 by heat treating the paste adhesive composition in the method for manufacturing the semiconductor device 100 described above.
  • a paste adhesive composition was prepared for each example and each comparative example. This preparation was performed by mixing each component uniformly according to the composition shown in Table 1, Table 2, and Table 3. In addition, the detail of the component shown in Table 1, Table 2, and Table 3 is as follows. Moreover, the compounding ratio of each component in Table 1, Table 2, and Table 3 indicates the compounding ratio (% by weight) of each component with respect to the entire paste adhesive composition.
  • Compound that is polymerized by heating (B))
  • Compound 1 1,4-cyclohexanedimethanol monoacrylate (CHDMMA (product name), manufactured by Nippon Kasei Co., Ltd.)
  • Compound 2 Phenoxyethyl methacrylate (light ester PO, manufactured by Kyoeisha Chemical Co., Ltd.)
  • Compound 3 2-ethylhexyl methacrylate (light ester EH, manufactured by Kyoeisha Chemical Co., Ltd.)
  • Compound 4 Meta-para-cresyl glycidyl ether (m, p-CGE (product name), manufactured by Sakamoto Pharmaceutical Co., Ltd.)
  • Compound 5 Bisfer F type epoxy resin (SB-403S, manufactured by Nippon Kayaku Kogyo Co., Ltd.)
  • Compound 6 Polyethylene glycol # 200 dimethacrylate (Light Ester 4EG, manufactured by Kyoeisha Chemical Co., Ltd.)
  • Compound 7 1,
  • Hardener 1 Dicumyl peroxide (Perkadox BC, manufactured by Kayaku Akzo Co., Ltd.)
  • Curing agent 2 Imidazole (2PHZ-PW, manufactured by Shikoku Chemicals Co., Ltd.)
  • Curing agent 3 Bisphenol F (DIC-BPF, manufactured by DIC Corporation)
  • the coating film obtained by applying the obtained paste adhesive composition was increased from 25 ° C. to 250 ° C. at a rate of temperature increase of 5 ° C./min in a nitrogen atmosphere having a residual oxygen concentration of less than 1000 ppm. After the heating, heat treatment was performed at 250 ° C. for 2 hours. As a result, the metal particles (A) in the coating film were sintered to form a particle connection structure.
  • the acetone insoluble content of the obtained paste-form adhesive composition was measured as follows. First, the metal particles (A) were removed from the paste-like adhesive composition by centrifugal separation and filtration with a 115 mesh (aperture 125 ⁇ m) filter. Next, the paste-like adhesive composition from which the metal particles (A) were removed was heated at 180 ° C. for 2 hours to obtain a measurement sample. Next, about 100 g of a measurement sample is precisely weighed and put into a sealed container containing about 900 g of acetone at a liquid temperature of 25 ° C., and the inside of the sealed container is obtained using about 100 g of acetone solution obtained by shaking for 20 minutes.
  • the acetone solution obtained by washing was sieved with a JIS standard sieve having a mesh size of 115 (mesh size 125 ⁇ m). Next, about 100 g of acetone was passed through the entire sieve. The residue on the sieve was then air dried and the weight of the residue was measured. From the measurement results, the ratio (% by weight) of the residue to the entire measurement sample was calculated, and this was defined as acetone insoluble matter (% by weight). In Tables 1 to 3, when the acetone insoluble content was 5% by weight or less, “5 or less” and those exceeding 5% by weight were shown as “5 excess”.
  • the volume resistivity was measured as follows. First, after applying the obtained paste-like adhesive composition, it was heated from 25 ° C. to 250 ° C. at a heating rate of 5 ° C./min in a nitrogen atmosphere, and then heated at 250 ° C. for 2 hours. Thus, a sample (width 4 mm, length 40 mm, thickness 40 ⁇ m) was obtained. Next, the volume resistivity in the planar direction of the sample was measured according to JIS K 6911. The results are shown in Tables 1 to 3.
  • Example 6 (5% weight loss temperature)
  • the 5% weight loss temperature of the paste adhesive composition was measured. The measurement was performed by performing TG / DTA (thermogravimetric / differential thermal analysis) measurement on a paste adhesive composition 10 mg under the condition of a heating rate of 5 ° C./min. Measurements were carried out under conditions of a nitrogen atmosphere and an air atmosphere. As a result, the 5% weight loss temperature was 130 ° C. for both.
  • TG / DTA thermogravimetric / differential thermal analysis
  • dispensing property was evaluated as follows. First, the obtained paste-like adhesive fat composition was packed in a syringe, a needle having a nozzle diameter of 200 ⁇ m was attached, and the paste was applied in a dot shape with an automatic dispenser. Then, the thread-drawing property at the time of coating was visually observed, ⁇ when no threading or dot deformation was observed, ⁇ when either threading or dot deformation was not observed, both were observed Was marked with x.
  • a semiconductor device 1 was manufactured as follows. First, a 10 mm ⁇ 10 mm ⁇ 350 ⁇ mt back-sided rectangular silicon chip was mounted on an Ag-plated copper frame (11 mm ⁇ 11 mm ⁇ 150 ⁇ mt) via the paste adhesive composition obtained above. To obtain a laminate. Next, the laminate was heated from 25 ° C. to 250 ° C. at a heating rate of 5 ° C./min in a nitrogen atmosphere having a residual oxygen concentration of less than 1000 ppm, and then heated at 250 ° C. for 2 hours. As a result, the metal particles (A) in the paste adhesive composition were sintered to form a die attach layer having a thickness of 60 ⁇ m. In this way, the semiconductor device 1 was obtained.
  • Examples 1 to 15 it can be seen that good results were obtained in both the uniformity evaluation of the sintering and the evaluation of the dispensing property. In particular, in Examples 1 to 13, particularly good dispensing property evaluation results were obtained. On the other hand, in Comparative Examples 1 to 5, no good results were obtained in the uniformity evaluation of sintering. In Examples 1 to 15, good results were obtained as compared with Comparative Examples 1 to 5 from the viewpoints of thermal conductivity and conductivity. Thus, according to the Example, it turns out that the die attach layer excellent in the balance of heat conductivity and electroconductivity is realized.

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PCT/JP2016/052295 2015-01-29 2016-01-27 ペースト状接着剤組成物、半導体装置、半導体装置の製造方法、および放熱板の接着方法 Ceased WO2016121806A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
SG11201705967TA SG11201705967TA (en) 2015-01-29 2016-01-27 Paste-like adhesive composition, semiconductor device, method for manufacturing semiconductor device, and method for bonding heatsink
EP16743409.1A EP3252123A4 (en) 2015-01-29 2016-01-27 Paste adhesive composition, semiconductor device, method for manufacturing semiconductor device, and method for bonding heat radiation plate
US15/546,147 US10259976B2 (en) 2015-01-29 2016-01-27 Paste-like adhesive composition, semiconductor device, method for manufacturing semiconductor device, and method for bonding heatsink
CN201680007771.0A CN107207941B (zh) 2015-01-29 2016-01-27 膏状粘合剂组合物、半导体装置、半导体装置的制造方法和散热板的粘合方法
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JP2018095682A (ja) * 2016-12-08 2018-06-21 住友ベークライト株式会社 ペースト状接着剤組成物および電子装置
JP2018098272A (ja) * 2016-12-08 2018-06-21 住友ベークライト株式会社 ペースト状接着剤組成物および電子装置
JP2020204043A (ja) * 2016-12-08 2020-12-24 住友ベークライト株式会社 ペースト状接着剤組成物および電子装置
JP2019065354A (ja) * 2017-10-02 2019-04-25 リンテック株式会社 フィルム状焼成材料、及び支持シート付フィルム状焼成材料
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