CN111801397B - Paste adhesive composition and semiconductor device - Google Patents

Paste adhesive composition and semiconductor device Download PDF

Info

Publication number
CN111801397B
CN111801397B CN201980016231.2A CN201980016231A CN111801397B CN 111801397 B CN111801397 B CN 111801397B CN 201980016231 A CN201980016231 A CN 201980016231A CN 111801397 B CN111801397 B CN 111801397B
Authority
CN
China
Prior art keywords
adhesive composition
paste adhesive
silver particles
monomer
minutes
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.)
Active
Application number
CN201980016231.2A
Other languages
Chinese (zh)
Other versions
CN111801397A (en
Inventor
西孝行
笼宫耕喜
日下庆一
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
Publication of CN111801397A publication Critical patent/CN111801397A/en
Application granted granted Critical
Publication of CN111801397B publication Critical patent/CN111801397B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic 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 subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Die Bonding (AREA)
  • Powder Metallurgy (AREA)

Abstract

The paste adhesive composition of the present invention comprises silver particles and a monomer, wherein the interface between the silver particles disappears by heat treatment to form a silver particle linked structure, the silver particles comprise flaky silver particles and spherical silver particles, the paste adhesive composition is heated from a temperature of 30 ℃ to a temperature of 200 ℃ at a heating rate of 10 ℃/min, then is heat-treated at a temperature of 200 ℃ for 60 minutes, then is heated from a temperature of 200 ℃ to a temperature of 450 ℃ at a heating time of 10 ℃/min, and then is heat-treated at a temperature of 450 ℃ for 10 minutes, when the 100 fraction of the weight reduction rate of the paste adhesive composition after heat-treating at a temperature of 200 ℃ for 60 minutes with respect to the paste adhesive composition before heating is W1 [% ], and the 100 fraction of the weight reduction rate of the paste adhesive composition after heat-treating at a temperature of 450 ℃ for 10 minutes is W2%, (W2-W1)/W2 is 0.20-0.90. As the measurement conditions, the measurement method was a Thermogravimetry-differential Thermal Analysis (TG-DTA) apparatus, and the atmosphere was an atmospheric atmosphere.

Description

Paste adhesive composition and semiconductor device
Technical Field
The present invention relates to a paste adhesive composition and a semiconductor device.
Background
As a paste adhesive composition used for bonding each member of a semiconductor device, an electric component, and an electronic component, two types of paste adhesive compositions, i.e., an adhesive type and a sintering type, have been used.
The adhesive paste adhesive composition is a composition in which conductive metal particles such as silver particles are dispersed in a liquid thermosetting resin, and exhibits electrical conductivity and thermal conductivity by heating to cure the resin and pressure-bonding the metal particles.
In the adhesive paste adhesive composition, adhesiveness and adherence to an adherend are exhibited by curing a liquid thermosetting resin. Further, since the paste adhesive composition shrinks due to curing, the frequency of the metal particles contacting each other becomes higher than before curing, and the number of contact points between the metal particles increases. Thus, the cured product of the paste adhesive composition exhibits electrical and thermal conductivity.
In the adhesive paste adhesive composition, the cured thermosetting resin is adhered to an adherend. Therefore, such an adhesive paste adhesive composition has adhesiveness not only to metals such as copper, silver, gold, nickel, and palladium but also to adherends other than metals such as bare silicon. On the other hand, in the adhesive paste adhesive composition, the metal particles are in contact with each other via a cured product of the thermosetting resin. Therefore, the adhesive paste adhesive composition may have a smaller contact area between the silver particles and a poorer thermal conductivity than the sintered paste adhesive composition.
The sintered paste adhesive composition is a composition in which metal particles are dispersed in a volatile dispersion medium, and the dispersion medium is volatilized by heat treatment to secure conduction of the metal particles by sintering.
In the sintering type paste adhesive composition, the dispersion medium is volatilized by heating, thereby aggregating the metal particles dispersed therein. And the interfaces between the metal particles in the aggregate disappear by the action of heat, in other words, the metal particles sinter to form a metal particle-bonded structure. In the sintering type paste adhesive composition, not all of the dispersion medium volatilizes, and a small amount of monomer contained in the dispersion medium does not volatilize and remains, and the remaining monomer functions to bond the metal particle connecting structure to the adherend. Then, by volatilization of the dispersion, an attractive force is generated between the connection structure of the metal particles and the adherend, and these are joined. When the adherend is a metal such as silver or gold, the interface between the metal particles and the adherend disappears and the metal particles are firmly bonded to the adherend.
The sintered paste adhesive composition can exhibit higher thermal conductivity than an adhesive by forming a metal particle connection structure. On the other hand, when a sintering paste adhesive composition is used as the adhesive, a monomer remains between the metal particle bonded structure formed by heating and the adherend, but the monomer is present in a trace amount, and therefore, the adhesion between the metal particle bonded structure and the adherend may not be sufficiently obtained. Further, since the adhesiveness between the adherend and the metal particle connecting structure is affected by the kind or combination of the metal material and the metal particles constituting the adherend, when the compatibility between the material of the adherend and the metal particles is poor, the adhesiveness between the adherend and the metal particle connecting structure may be weak, and peeling may occur therebetween.
For example, patent document 1 describes an adhesive paste adhesive composition. Patent document 1 describes a thermosetting resin composition for bonding a semiconductor, which has excellent heat dissipation properties and can bond a semiconductor element to a metal substrate satisfactorily by containing a specific acrylic resin, a radical initiator, specific silver fine particles, a specific silver powder, and a solvent.
Further, for example, patent document 2 describes a sintering type paste adhesive composition. Patent document 2 describes a paste which is composed of a specific alloy powder, a glass frit and an organic vehicle and has excellent adhesion to a substrate, solder wettability, migration resistance, oxidation resistance and electrical adhesiveness.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2014-074132
Patent document 2: japanese laid-open patent publication No. H06-139813
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have studied heat dissipation properties of a paste adhesive composition, adhesion to bare silicon, and adhesion to metal in a semiconductor device in which a bare silicon and a copper lead frame are connected via the paste adhesive composition. As a result, it was found that the adhesive composition described in patent document 1 has insufficient heat dissipation properties, and the adhesive composition described in patent document 2 has insufficient adhesion to bare silicon or metal.
The present invention has been made in view of the above-mentioned problems, and provides a paste adhesive composition having appropriate adhesion to an adherend such as bare silicon or metal and improved heat dissipation properties.
Technical solution for solving technical problem
In order to obtain a paste adhesive composition having appropriate adhesion to various adherends such as bare silicon and metal and a cured product thereof having excellent thermal conductivity, the present inventors considered to produce a mixed type paste adhesive composition having both of the characteristics of the conventional adhesive type and the sintered type. As a result, it has been found that the above-mentioned problems can be solved by using the adhesive composition described below, the adhesive composition comprises silver particles and a monomer, the silver particles form a silver particle connection structure through heat treatment, heating the paste adhesive composition from 30 ℃ to 200 ℃ at a heating rate of 10 ℃/min, then heat-treated at 200 ℃ for 60 minutes, and then heated from 200 ℃ to 450 ℃ at a heating time of 10 ℃/minute, when the paste adhesive composition is heat-treated at a temperature of 450 ℃ for 10 minutes, the ratio of the weight loss of the paste adhesive composition after heat-treatment at a temperature of 200 ℃ for 60 minutes to the weight loss of the paste adhesive composition before temperature rise is W1 [% ], and the ratio of the weight loss of the paste adhesive composition after heat-treatment at a temperature of 450 ℃ for 10 minutes is W2 [% ], (W2-W1)/W2 are within a specific numerical range. Specifically, it was found that when curing is performed by using such an adhesive composition, the monomer is appropriately volatilized, the monomer and the main agent are appropriately cured, and the silver particles form a connected structure.
The present inventors have also found that, in such an adhesive composition, the monomer base compound is appropriately cured, and therefore, even when a silver particle-linked structure is formed, peeling of a cured product of the obtained paste adhesive composition from an adherend can be suppressed. Thus, the mixed type paste adhesive composition has excellent adhesion to bare silicon and metals such as copper, silver, nickel, and palladium, as in the adhesive type paste adhesive composition.
Also, when the monomer is properly volatilized, the silver particles generate attraction between each other. Here, the silver particles have a specific particle size distribution, and thus the silver particles are properly in contact with each other, and a silver particle connection structure can be formed. Thus, the hybrid paste adhesive composition can improve thermal conductivity as in the case of a sintered paste adhesive composition.
As described above, the present invention has been completed based on the following findings: the paste adhesive composition containing silver particles and a monomer and having a value in the range of (W2-W1)/W2 of a specific value has an appropriate adhesion to bare silicon and a metal such as copper, silver, nickel, palladium, etc., and a cured product thereof has a good thermal conductivity.
According to the present invention, there is provided a paste adhesive composition comprising silver particles and a monomer, wherein an interface between the silver particles disappears by heat treatment to form a silver particle linked structure, the silver particles include flaky silver particles and spherical silver particles, the paste adhesive composition is heated from a temperature of 30 ℃ to a temperature of 200 ℃ at a heating rate of 10 ℃/min under the following measurement conditions, then the paste adhesive composition is heat-treated at a temperature of 200 ℃ for 60 minutes, then the paste adhesive composition is heat-treated at a temperature of 10 ℃/min from a temperature of 200 ℃ to a temperature of 450 ℃ for 10 minutes, and when the paste adhesive composition is heat-treated at a temperature of 200 ℃ for 60 minutes and then at a temperature of 450 ℃ for 10 minutes, the paste adhesive composition before heating is given a weight loss ratio of 100 fraction W1 [% ], and the paste adhesive composition is heat-treated at a temperature of 450 ℃ for 10 minutes of 100% W2%, (W2-W1)/W2 is 0.20-0.90.
Further, according to the present invention, there can be provided a semiconductor device including: a substrate; and a semiconductor element: and a bonding layer formed by sintering the paste adhesive composition and mounted on the substrate.
Effects of the invention
The invention provides a paste adhesive composition which exhibits proper adhesion to bare silicon and metals such as copper, silver, nickel, palladium, etc., and can improve heat dissipation.
Drawings
The above and other objects, features and advantages will become more apparent from the following description of the preferred embodiments taken in conjunction with the accompanying drawings described below.
Fig. 1 is a cross-sectional view showing an example of an electronic device according to the present embodiment.
Fig. 2 is a cross-sectional view showing an example of the electronic device according to the present embodiment.
Detailed Description
Hereinafter, the present embodiment will be described with reference to the drawings as appropriate. In all the drawings, the same components are denoted by the same reference numerals, and the description thereof is omitted.
The paste adhesive composition of the present embodiment contains silver particles and a monomer, the interfaces between the silver particles disappear by heat treatment to form a silver particle connection structure, the silver particles include flaky silver particles and spherical silver particles, the paste adhesive composition is heated from a temperature of 30 ℃ to a temperature of 200 ℃ at a heating rate of 10 ℃/min under the following measurement conditions, then is heat-treated at a temperature of 200 ℃ for 60 minutes, then is heated from a temperature of 200 ℃ to a temperature of 450 ℃ at a heating time of 10 ℃/min, and then is heat-treated at a temperature of 450 ℃ for 10 minutes, when the 100 fraction of the weight reduction rate of the paste adhesive composition after heat-treating at a temperature of 200 ℃ for 60 minutes with respect to the paste adhesive composition before heating is W1 [% ], and the 100 fraction of the weight reduction rate of the paste adhesive composition after heat-treating at a temperature of 450 ℃ for 10 minutes is W2%), (W2-W1)/W2 is 3 to 14. Further, as the measurement conditions, a Thermogravimetry-differential Thermal Analysis (TG-DTA) apparatus was used, and the atmosphere was an atmospheric atmosphere.
The present inventors considered to produce a conventional adhesive-type and sintered-type mixed-type paste adhesive composition in order to exhibit appropriate adhesion to bare silicon and metals such as copper, silver, nickel, and palladium and to improve thermal conductivity during curing.
As a result, it was found that when the paste adhesive composition is heat-treated under the above conditions, when the 100 fraction of the weight loss of the paste adhesive composition after heat-treatment at 200 ℃ for 60 minutes is W1 [% ], and the 100 fraction of the weight loss of the paste adhesive composition after heat-treatment at 450 ℃ for 10 minutes is W2 [% ], it is preferable that (W2-W1)/W2 be within a specific numerical range. Thus, when the paste adhesive composition is cured, the monomer and the main component can be cured like in the adhesive type paste adhesive composition, and the monomer can be volatilized as in the case of the sintered type paste adhesive composition.
By appropriately curing the monomer and the base compound, even when strong attraction such as formation of a silver particle-linked structure occurs between silver particles, peeling of a cured product of the paste adhesive composition from an adherend can be suppressed. Thus, the mixed type paste adhesive composition has appropriate adhesion to various adherends such as bare silicon and metals such as copper, nickel, and palladium, like the adhesive type paste adhesive composition. The paste adhesive composition of the present embodiment also has appropriate adhesion to metals such as silver and gold.
Then, the monomer is volatilized by the heat treatment, thereby generating attraction between the silver particles. Here, the silver particles have a specific particle size distribution, and thus the silver particles can appropriately collide with each other. Therefore, the interface between the silver particles disappears, and a silver particle connection structure having high thermal conductivity is formed, whereby the thermal conductivity of the cured product of the obtained adhesive composition is improved.
The behavior of the monomer and the main agent will be described below, wherein the temperature is raised from 30 ℃ to 200 ℃ at a temperature raising rate of 10 ℃/min, followed by heat treatment at 200 ℃ for 60 minutes, followed by temperature raising from 200 ℃ to 450 ℃ for a temperature raising time of 10 ℃/min, followed by heat treatment at 450 ℃ for 10 minutes.
First, when the temperature was raised from 30 ℃ to 200 ℃ at a temperature raising rate of 10 ℃/min and then heat-treated at 200 ℃ for 60 minutes, the components causing no curing reaction were volatilized in the monomer and the base compound. Also, the components causing the curing reaction are sufficiently cured.
Subsequently, the temperature was raised from 200 ℃ to 450 ℃ at a temperature raising time of 10 ℃/min, and then, heat treatment was carried out at 450 ℃ for 10 min, whereby the monomers and the main agent were completely decomposed in the portion causing the curing reaction.
As described above, the molecular (W2-W1) represents the mass fraction of the cured monomer or main agent. W2 in the denominator represents the sum of the mass fractions of the cured monomer and the main agent and the mass fraction of the volatilized monomer. Therefore, (W2-W1)/W2 represents the ratio of the monomer to the cured monomer to the main agent.
In the present embodiment, the main component is an optional component.
In the present embodiment, the lower limit of (W2-W1)/W2 is 0.20 or more, for example, preferably 0.30 or more, more preferably 0.35 or more, still more preferably 0.40 or more, still more preferably 0.45 or more, and particularly preferably 0.50 or more. This can exhibit appropriate adhesion to bare silicon or metal.
In the present embodiment, the upper limit of (W2-W1)/W2 is 0.90 or less, for example, preferably 0.85 or less, more preferably 0.80 or less, still more preferably 0.75 or less, still more preferably 0.70 or less, and particularly preferably 0.65 or less. Thereby, the monomer can be appropriately volatilized. Therefore, an attractive force is generated between the silver particles, the silver particles collide with each other, the interface between the silver particles disappears, and a silver particle connection structure having high thermal conductivity can be formed. With this, heat dissipation can be improved.
The present inventors have studied a method in which (W2-W1)/W2 falls within the above numerical range. As a result, it was found that it is important to appropriately set the compounding composition of the paste adhesive composition to control (W2-W1)/W2. Specifically, the composition of the paste adhesive composition includes the content of the volatile raw material component and the content of the cured raw material component controlled by selecting the types of the monomer, the main agent, the radical polymerization initiator, and the curing agent and adjusting the contents.
First, each raw material component of the paste adhesive composition of the present embodiment will be explained.
(silver particles)
The paste adhesive composition of the present embodiment contains silver particles.
In the paste adhesive composition of the present embodiment, the silver particles are attracted to each other by appropriate volatilization of the monomer described later, and the silver particles collide with each other. This eliminates the interface between the silver particles, and forms a silver particle connection structure having high thermal conductivity, thereby improving thermal conductivity.
The paste adhesive composition of the present embodiment also contains, for example, a monomer and a main component which remain after curing. As a result, the monomer and the base compound are cured and shrunk, and the force of aggregation of the silver particles can be exerted, as in the case of the adhesive paste adhesive composition.
The silver particle-bonded structure is not particularly limited, and the lower limit of the inter-Chip (Chip-Chip) thermal diffusivity measured by a gold-plated silicon Chip is preferably 0.26cm, for example2A silver particle connecting structure of sec or more.
The upper limit of the inter-chip thermal diffusivity measured by a silicon chip is not limited, and may be, for example, 1.0cm2And/sec or less.
As a method for measuring the inter-chip thermal diffusivity using a silicon chip, for example, the following method can be used: 2 silicon chips each having a length of 10mm × a width of 10mm × a thickness of 350 μm were prepared, one of the silicon chips was coated with a paste adhesive composition so as to have a thickness of 20 ± 5 μm, the other silicon chip was stacked thereon, the temperature was increased from 25 ℃ to 175 ℃ over 30 minutes, and then the paste adhesive composition was cured to form a cured product by heat treatment at 175 ℃ for 60 minutes, and then the thermal diffusivity was measured by a laser flash method on a test piece in which the silicon chip, the cured product of the paste adhesive composition, and the silicon chip were stacked in this order.
The present inventors have studied a method in which silver particles appropriately collide with each other when the above-mentioned (W2-W1)/W2 is within a specific numerical range in order to exhibit appropriate adhesion to an adherend such as bare silicon or metal and to improve thermal conductivity. As a result, it was found that the properties of the silver particles are important to select appropriately. Here, as the properties of the silver particles, specifically, there can be mentioned particle diameter D in which the shape, aspect ratio, tap density, and cumulative frequency of volume-based particle size distribution of the silver particles become 50%50Average particle diameter, specific surface area, particle diameter peak value, and the like. The detailed mechanism is not clear, but by appropriately selecting these properties, a preferable silver particle connection structure can be formed by setting the frequency of collision of the silver particles with each other, the pressure generated at the time of collision, and the like to appropriate values. Therefore, the thermal conductivity of the paste adhesive composition can be improved when it is a cured product.
As the silver particles, plate-like silver particles and spherical silver particles are included. Thereby, the spherical silver particles enter the gaps of the flake silver particles, and the frequency of collision of the silver particles with each other can be further increased.
Hereinafter, representative properties of the flake silver particles and the spherical silver particles will be described.
(flaky silver particles)
The upper limit of the aspect ratio of the flaky silver particles is, for example, preferably 10.0 or less, more preferably 8.0 or less, further preferably 6.0 or less, further preferably 5.0 or less, and particularly preferably 4.5 or less. This enables the silver particles to be aggregated into a planar shape by the application of a pulling force. Therefore, the frequency of collision of the silver particles with each other can be increased, and the thermal conductivity can be increased.
The lower limit of the aspect ratio of the silver flakes is, for example, preferably 2.0 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. This makes it possible to form gaps between the flaky silver particles, into which spherical silver particles enter. Therefore, the frequency of collision of the silver particles with each other can be increased, and the thermal conductivity can be increased.
In the present embodiment, the aspect ratio of the silver particles is determined by (major axis)/(minor axis) of the silver particles. The major and minor diameters of the silver particles can be evaluated by direct observation using, for example, a Scanning Electron Microscope (SEM) or a Transmission Electron Microscope (TEM). Hereinafter, a method of evaluation by a scanning electron microscope will be described. First, the silver particles were fixed on a sample stage of a scanning electron microscope, and the shape was observed with the observation magnification increased to the maximum extent that only 1 particle entered the visual field, and the shape was observed from the direction of the largest surface of the observation area of the silver particles. Next, the sample stage was rotated to observe the silver particles from the smallest observation area. In the above observation, a minimum circle inscribed in a plane having the largest observation area of the silver particles is set, and its diameter is measured to define the "major axis" of the particles. The interval of parallel lines drawn so that the surface having the smallest observation area for the silver particles is closest to the surface having the smallest observation area for the silver particles and the silver particles are sandwiched therebetween is defined as "short diameter". This operation was performed on 100 silver particles arbitrarily sampled and an average value was calculated, thereby obtaining an aspect ratio.
The lower limit of the tap density of the flaky silver particles is, for example, preferably 4.1g/cm3Above, more preferably 4.5g/cm3Above, more preferably 5.0g/cm3Above, more preferably 5.1g/cm3The above. This enables the silver flake particles to be packed more densely. Therefore, the filling density of the silver particles can be increased, and the thermal conductivity can be improved.
The upper limit of the tap density of the silver flake particles may be, for example, 10g/cm3Hereinafter, the concentration may be set to 8g/cm3. This makes it possible to form gaps between the flaky silver particles, into which spherical silver particles enter. Therefore, the frequency of collision of the silver particles with each other can be increased, and the thermal conductivity can be increased.
Particle diameter D in which cumulative frequency of volume-based particle size distribution of flaky silver particles is 50%50The lower limit of (B) is, for example, preferably larger than 4.0. mu.m, more preferably 4.5 μm or larger, still more preferably 5.0 μm or larger, and still more preferably 5.5 μm or larger. This makes it possible to appropriately form gaps between the flaky silver particles, into which spherical silver particles enter. Therefore, the thermal conductivity can be further improved.
And, the cumulative frequency of the volume-based particle size distribution of the flaky silver particles is 50% of the particle diameter D50The upper limit of (B) is, for example, preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. This can increase the frequency of collision of the silver particles with each other. Therefore, the thermal conductivity can be further improved.
In the present embodiment, the cumulative frequency of the volume-based particle size distribution of the silver particles is 50% of the particle diameter D50For example, the particle size distribution of the particles can be measured on a volume basis by a commercially available laser diffraction particle size distribution measuring apparatus (for example, SALD-7000, manufactured by Shimadzu corporation), and the particle size can be determined from the cumulative 50% particle size.
The lower limit of the average particle diameter of the silver flake particles is, for example, preferably 3.0 μm or more, more preferably 5.0 μm or more, still more preferably 7.0 μm or more, and still more preferably 9.0 μm or more. This enables uniform and dense filling of silver particles. Therefore, the thermal conductivity can be further improved.
The upper limit of the average particle diameter of the silver flake particles is, for example, preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and still more preferably 25 μm or less. This can increase the frequency of collision of the silver particles with each other. Therefore, the thermal conductivity can be further improved.
The lower limit of the specific surface area of the plate-like silver particles is preferably 0.80m, for example2A ratio of the total amount of the components to the total amount of the components is 0.70m or less2A ratio of 0.50m or less per gram2The ratio of the carbon atoms to the carbon atoms is less than g. Thus, by the individual silver particles occupying a large volume, even if the frequency of contact of the silver particles with each other is small, a conductive path can be formed. Therefore, the thermal conductivity can be improved.
The upper limit of the specific surface area of the plate-like silver particles is preferably 0.10m, for example2A value of at least one per gram, more preferably 0.20m2More than g. This increases the interface area of the silver particles, thereby increasing the frequency of collision of the silver particles with each other. Therefore, the thermal conductivity can be improved.
(spherical silver particles)
The upper limit of the aspect ratio of the spherical silver particles is, for example, preferably 1.5 or less, more preferably 1.3 or less, and still more preferably 1.2 or less. Thereby, the spherical silver particles properly enter the gaps between the flaky silver particles. Therefore, the frequency of collision of the silver particles with each other can be increased, and the thermal conductivity can be increased.
The lower limit of the aspect ratio of the spherical silver particles may be, for example, 1.0 or more, or 1.01 or more.
The lower limit of the tap density of the spherical silver particles is preferably 4.0g/cm, for example3Above, more preferably 4.5g/cm3Above, more preferably 5.0g/cm3Above, more preferably 5.1g/cm3The above. This enables the gaps between the silver flakes to be embedded more densely. Therefore, the silver particles can be increasedThe packing density of the particles and the thermal conductivity can be improved.
The upper limit of the tap density of the spherical silver particles may be, for example, 10g/cm3Hereinafter, the concentration may be set to 8g/cm3。
Particle diameter D in which the cumulative frequency of the volume-based particle size distribution of spherical silver particles is 50%50The upper limit of (B) is, for example, preferably 4.0 μm or less, more preferably 3.0 μm or less, still more preferably 2.0 μm or less, yet more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less. Thereby, the spherical silver particles enter the gaps of the flake silver particles, and the frequency of collision of the silver particles with each other can be increased. Therefore, the thermal conductivity can be improved.
And, the cumulative frequency of the volume-based particle size distribution of the spherical silver particles is 50% of the particle diameter D50The lower limit of (B) is, for example, preferably 0.1 μm or more, more preferably 0.2 μm or more. D of substantially spherical silver particles50When the amount is small, the silver particles can be filled with high density, but it is preferable from the viewpoint that the workability of the silver particles can be improved by being equal to or more than the lower limit value.
The upper limit of the average particle diameter of the spherical silver particles is, for example, preferably 2.3 μm or less, more preferably 2.0 μm or less, and still more preferably 1.8 μm or less. Thereby, the spherical silver particles enter the gaps of the flake silver particles, and the frequency of collision of the silver particles with each other can be increased. Therefore, the thermal conductivity can be improved.
The lower limit of the average particle diameter of the spherical silver particles is, for example, preferably 0.1 μm or more, and more preferably 0.2 μm or more.
The lower limit of the specific surface area of the spherical silver particles is preferably 0.30m, for example2A value of at least one per gram, more preferably 0.40m2A molar ratio of 0.50m or more2A value of 0.70m or more per gram, more preferably2A value of at least one of,/g, particularly preferably 0.90m2More than g. This increases the interface area of the silver particles, thereby increasing the frequency of collision of the silver particles with each other. Therefore, the thermal conductivity can be improved.
And, as the specific surface area of the spherical silver particlesLimit value, for example, preferably 2.00m2A ratio of 1.75m or less per gram2A ratio of 1.50m or less per gram2The ratio of the carbon atoms to the carbon atoms is less than g. Thus, by the individual silver particles occupying a large volume, even if the frequency of contact of the silver particles with each other is small, a conductive path can be formed. Therefore, the thermal conductivity can be improved.
The lower limit of the content of the silver particles in the paste adhesive composition is, for example, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 65 parts by mass or more, and still more preferably 70 parts by mass or more, per 100 parts by mass of the paste adhesive composition.
The upper limit of the content of the silver particles in the paste adhesive composition may be, for example, 99 parts by mass or less, or 90 parts by mass or less, based on 100 parts by mass of the paste adhesive composition.
When the content of the silver particles is not less than the upper limit and not more than the lower limit, an appropriate silver particle connection structure can be formed. Therefore, heat dissipation can be improved.
The upper limit of the amount of the flaky silver particles in the silver particles is, for example, preferably 65 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and still more preferably 50 parts by mass or less, based on 100 parts by mass of the total of the flaky silver particles and the spherical silver particles.
The lower limit of the amount of the flaky silver particles in the silver particles is, for example, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and particularly preferably 35 parts by mass or more, based on 100 parts by mass of the total of the flaky silver particles and the spherical silver particles.
When the content of the flaky silver particles is within the above numerical range, the interface between the flaky silver particles and the spherical silver particles is appropriately disappeared and the thermal conductivity can be improved.
(monomer)
The paste adhesive composition of the present embodiment generates attraction between silver particles by volatilization of the monomer, and is cured to be largely shrunk by curing of the monomer. This can form a silver particle connection structure in which the interface between silver particles disappears, and improve the heat dissipation of the cured product.
Specific examples of the monomer used in the adhesive composition of the present embodiment include a diol monomer, an acrylic monomer, an epoxy monomer, and a maleimide monomer. As the monomer, a combination of 1 or 2 or more of the above specific examples can be used.
The diol monomer is a monomer that does not solidify but volatilizes. And is a monomer that generates an attractive force between silver particles when volatilized. The diol monomer of the present embodiment has a higher boiling point than other monomers. Therefore, when the paste adhesive composition contains the diol monomer and the other monomer, the diol monomer is further volatilized after the other monomer is volatilized in the temperature increasing step. The silver particles are coagulated with each other by volatilization of the other monomer, and the silver particles are further coagulated with each other by volatilization of the glycol monomer. This promotes the formation of a silver particle connection structure.
The acrylic monomer and the maleimide monomer are polymerized by a radical polymerization initiator described later. In addition, the acrylic monomer and the maleimide monomer are volatilized by heat in the curing step of the paste adhesive composition. The paste adhesive composition can be cured and shrunk greatly by polymerization or volatilization of an acrylic monomer, a maleimide monomer, or the like.
The epoxy monomer can be reacted with a curing agent described later to cure and shrink. The epoxy monomer is volatilized by heat in the curing step of the paste adhesive composition. The paste adhesive composition can be cured and shrunk greatly by the reaction of the epoxy monomer with the curing agent and the volatilization of the epoxy monomer.
In the above specific examples, the monomer preferably contains a diol monomer, for example. Thus, when the paste adhesive composition is used, the glycol monomer can be volatilized after the monomer and the main component are cured and shrunk to bring the silver particles close to each other when the paste adhesive composition is heated. Therefore, a silver particle connection structure more suitable for improving heat dissipation can be formed.
The monomer used in combination with the diol monomer is preferably an acrylic monomer. Thus, the acrylic monomer is appropriately volatilized to bring (W2-W1)/W2 into a desired numerical range, and an appropriate silver particle-linked structure can be formed.
[ diol monomer ]
Specifically, the diol monomer of the present embodiment is a 2-membered alcohol having 2 hydroxyl groups in the structure, and the 2 hydroxyl groups are bonded to different carbon atoms; a compound obtained by alcohol condensation of 2 or more of the 2-valent alcohol; the hydroxyl group of the compound obtained by condensation of the alcohol is substituted with an organic group having 1 to 30 carbon atoms and is an alkoxy group.
Specific examples of the glycol monomer include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-hexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-allyl ether, ethylene glycol mono-phenyl ether, ethylene glycol mono-benzyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, diethylene glycol mono-hexyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-benzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol mono-n-butyl ether, tetraethylene glycol mono-butyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-butyl ether, diethylene glycol mono-, Propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-butyl ether, and the like. As the diol monomer, 1 or a combination of 2 or more of the above specific examples can be used.
As the diol monomer, for example, tripropylene glycol mono-n-butyl ether or ethylene glycol mono-n-butyl acetate is preferably used in the above-mentioned specific examples. Thus, when the paste adhesive composition is used, the glycol monomer can be volatilized after the monomer and the main component are cured and shrunk to bring the silver particles close to each other when the paste adhesive composition is heated. Therefore, a silver particle connection structure more suitable for improving heat dissipation can be formed.
The lower limit of the content of the diol monomer is, for example, preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more, still more preferably 3.0 parts by mass or more, and still more preferably 4.0 parts by mass or more, per 100 parts by mass of the paste adhesive composition. Thus, by volatilization of the diol monomer, an attractive force is generated between the silver particles as appropriate, and a silver particle connection structure more suitable for improving heat dissipation can be formed.
The upper limit of the content of the diol monomer may be, for example, 10 parts by mass or less, 8 parts by mass or less, or 6 parts by mass or less with respect to 100 parts by mass of the paste adhesive composition.
The lower limit of the boiling point of the diol monomer is, for example, preferably 100 ℃ or higher, more preferably 130 ℃ or higher, still more preferably 150 ℃ or higher, yet more preferably 170 ℃ or higher, and particularly preferably 190 ℃ or higher. This allows the diol monomer to volatilize after the monomer and the main agent are cured and shrunk to bring the silver particles close to each other.
The upper limit of the boiling point of the diol monomer may be, for example, 400 ℃ or lower, or 350 ℃ or lower.
In the present embodiment, the boiling point of the diol monomer means the boiling point at atmospheric pressure (101.3 kPa).
[ acrylic acid monomer ]
The acrylic monomer of the present embodiment is a monomer having a (meth) acrylic group in its structure. Here, (meth) acrylic group means acrylic group and methacrylic group (methacrylate group).
The acrylic monomer of the present embodiment may be a monofunctional acrylic monomer having only 1 (meth) acrylic group in its structure, or may be a polyfunctional acrylic monomer having 2 or more (meth) acrylic groups in its structure.
In addition, in the present embodiment, the acrylic group includes an acrylate group.
Specific examples of the monofunctional acrylic monomer include 2-phenoxyethyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, n-tridecyl (meth) acrylate, n-octadecyl (meth) acrylate, isostearyl (meth) acrylate, ethoxydiglycol (meth) acrylate, butoxydiglycol (meth) acrylate, methoxytriglycol (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropyldiglycol (meth) acrylate, and mixtures thereof, Cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenol ethylene oxide-modified (meth) acrylate, phenylphenol ethylene oxide-modified (meth) acrylate, isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternary compound, glycidyl (meth) acrylate, neopentyl glycol (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 2- (meth) acryloyloxyacetic acid phosphate and the like. As the monofunctional acrylic monomer, 1 or a combination of 2 or more of the above specific examples can be used.
As the monofunctional acrylic monomer, 2-phenoxyethyl methacrylate is preferably used among the above-mentioned specific examples. This allows the acrylic monomer to be appropriately polymerized to improve the adhesion, and the paste adhesive composition to be appropriately cured and shrunk to allow the silver particles to approach each other.
In the present embodiment, the (meth) acrylate represents an acrylate or a methacrylate. And, methacrylic acid means acrylic acid and methacrylic acid. And, (meth) acryloyl represents acryloyl and methacryloyl.
Specific examples of the polyfunctional acrylic monomer include ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propoxylated bisphenol a di (meth) acrylate, hexane-1, 6-diol bis (2-meth) acrylate, 4,4 '-isopropylidenediphenol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-bis ((meth) acryloyloxy) -2,2,3,3,4,4,5, 5-octafluorohexane, 1, 4-bis ((meth) acryloyloxy) butane, 1, 6-bis ((meth) acryloyloxy) hexane, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, N' -di (meth) acryloylethylenediamine, N-di (meth) acrylate, N-di (meth) octylene, N-isopropylidenediphenol di (meth) acrylate, N-3-butylene glycol di (meth) acrylate, N-bis (meth) acrylate, N-acryloyloxy) 2,3, 3-bis (meth) acrylate, 4-octyleneglycol di (meth) acrylate, N-di (meth) acrylate, N-acryloylethylenediamine, N-or a mixture thereof, N, N' - (1, 2-dihydroxyethylene) bis (meth) acrylamide, 1, 4-bis ((meth) acryloyl) piperazine, or the like.
The lower limit of the content of the acrylic monomer in the paste adhesive composition is, for example, preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more, per 100 parts by mass of the paste adhesive composition.
The upper limit of the content of the acrylic monomer in the paste adhesive composition is, for example, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less, per 100 parts by mass of the paste adhesive composition.
When the content of the acrylic monomer in the paste adhesive composition is within the above numerical range, the paste adhesive composition can be appropriately cured and shrunk by polymerization of the monofunctional acrylic monomer and the polyfunctional acrylic monomer. Further, the silver particle connection structure can be appropriately formed by volatilization of the monofunctional acrylic monomer and the polyfunctional acrylic monomer.
As the 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. As the acrylic monomer, for example, a polyfunctional acrylic monomer is preferably used alone.
[ epoxy monomer ]
The epoxy monomer of the present embodiment is a monomer having an epoxy group in its structure.
The epoxy monomer of the present embodiment may be a monofunctional epoxy monomer having only 1 epoxy group in its structure, or may be a polyfunctional epoxy monomer having 2 or more epoxy groups in its structure.
Specific examples of the monofunctional epoxy monomer include 4-tert-butylphenyl glycidyl ether, m/p-tolyl glycidyl ether, phenyl glycidyl ether, and tolyl glycidyl ether. As the monofunctional epoxy monomer, 1 or a combination of 2 or more of the above specific examples can be used.
Specific examples of the polyfunctional epoxy monomer include bisphenol compounds such as bisphenol a, bisphenol F, and biphenol, and derivatives thereof; diols having an alicyclic structure such as hydrogenated bisphenol a, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, and cyclohexanediol, or derivatives thereof; 2-functional epoxy monomers obtained by epoxidizing aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, and decanediol, or derivatives thereof; a 3-functional epoxy monomer having a trihydroxyphenylmethane skeleton, an aminophenol skeleton; and polyfunctional epoxy monomers obtained by epoxidizing phenol novolac type resins, cresol novolac type resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, and the like. As the polyfunctional epoxy monomer, 1 or a combination of 2 or more of the above specific examples can be used.
[ Maleimide monomer ]
The maleimide monomer of the present embodiment is a monomer having a maleimide ring in its structure.
The maleimide monomer of the present embodiment may be a monofunctional maleimide monomer having only 1 maleimide ring in its structure, or may be a polyfunctional maleimide monomer having 2 or more maleimide rings in its structure.
Specific examples of the maleimide monomer include polytetramethylene ether glycol-bis (2-maleimide acetate).
(other Components)
The paste adhesive composition of the present embodiment may contain, in addition to the above raw material components, for example, a base compound, a radical polymerization initiator, a curing agent, a curing accelerator, a low-stress agent, a silane coupling agent, and the like.
Hereinafter, typical components will be described.
(Main agent)
The paste adhesive composition of the present embodiment is cured and shrunk by curing the main component. The paste adhesive composition contains the main agent, so that the monomer has an appropriate branched shape by polymerization, and the swelling of the cured product of the paste adhesive composition can be suppressed by moisture absorption.
The paste adhesive composition of the present embodiment is also cured and shrunk by curing the main component. Thus, the paste adhesive composition can greatly agglomerate silver particles and exhibit high thermal conductivity. Further, the cure shrinkage by curing of the main agent is smaller than that by curing of the monomer.
Specific examples of such a main agent include acrylic resins such as acrylic oligomers and acrylic polymers; epoxy resins such as epoxy oligomers and epoxy polymers; allyl resins such as allyl oligomers and allyl polymers. As the main agent, 1 kind or a combination of 2 or more kinds of the above-mentioned specific examples can be used. As the main agent, an epoxy resin is preferable in the above specific example. Thus, the monomer and the main agent can be cured and shrunk appropriately by combining with the epoxy monomer of the monomer.
The acrylic resin can be cured and shrunk by polymerization using a radical polymerization initiator described later, similarly to the acrylic monomer. In addition, polymerization of the acrylic resin is produced by introducing acrylic monomers.
The epoxy resin can be cured and shrunk by reacting with a curing agent described later, similarly to the epoxy monomer. In addition, the curing reaction of the epoxy resin is generated by introducing an acrylic monomer.
The allyl resin can be cured and shrunk by polymerization using a radical polymerization initiator described later, similarly to the acrylic resin and the acrylic monomer. Furthermore, the polymerization of the allyl resin is produced by the introduction of acrylic monomers.
In the present embodiment, oligomers having a weight average molecular weight of less than 1 ten thousand are represented as the polymers, and polymers having a weight average molecular weight of 1 ten thousand or more are represented as the polymers. And, the resin means includes oligomers and polymers.
[ acrylic resin ]
As the acrylic resin, a liquid acrylic resin having 2 or more acrylic groups in 1 molecule can be used.
As the acrylic resin, specifically, an acrylic resin obtained by polymerizing or copolymerizing the above-mentioned acrylic monomer can be used. The method of polymerization or copolymerization is not limited, and a known method using a general polymerization initiator and a chain transfer agent, such as solution polymerization, can be used. Further, as the acrylic resin, 1 kind may be used alone, or 2 or more kinds different in structure may be used.
[ epoxy resin ]
As the epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule can be used.
Specific examples of the epoxy resin include triphenol methane type epoxy resins; hydrogenated bisphenol a type liquid epoxy resin; bisphenol F type liquid epoxy resins such as bisphenol F diglycidyl ether; o-cresol novolac type epoxy resins, and the like. As the epoxy resin, 1 or a combination of 2 or more of the above specific examples can be used. The epoxy resin is preferably, for example, a hydrogenated bisphenol a type liquid epoxy resin or a bisphenol F type liquid epoxy resin among the above specific examples. As the bisphenol F type liquid epoxy resin, for example, bisphenol-F-diglycidyl ether is preferably used. This improves the workability of the paste adhesive composition and enables the paste adhesive composition to be appropriately cured and shrunk.
[ allyl resin ]
As the allyl resin, a liquid allyl resin having 2 or more allyl groups in 1 molecule can be used.
Specific examples of the allyl resin include allyl resins obtained by reacting a dicarboxylic acid, allyl alcohol, and a compound having an allyl group.
Specific examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. As the dicarboxylic acid, 1 or a combination of 2 or more of the above specific examples can be used.
Specific examples of the compound having an allyl group include polyethers, polyesters, polycarbonates, polyacrylates, polymethacrylates, polybutadienes, butadiene acrylonitrile copolymers, and the like having an allyl group. As the compound having an allyl group, 1 or a combination of 2 or more of the above-mentioned specific examples can be used.
The lower limit of the content of the main component in the paste adhesive composition is, for example, preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 3 parts by mass or more, per 100 parts by mass of the paste adhesive composition. This enables the monomer and the main agent to be cured and shrunk appropriately, and adhesion to various adherends to be improved.
The upper limit of the content of the main component in the paste adhesive composition is, for example, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less, per 100 parts by mass of the paste adhesive composition. This can prevent the host agent from entering between the silver particles too much and interfering with the formation of the silver particle connection structure.
The upper limit of the weight average molecular weight Mw of the main agent is, for example, preferably less than 10000, more preferably 5000 or less, and still more preferably 1000 or less. This enables the paste adhesive composition to be appropriately cured and shrunk.
The lower limit of the weight average molecular weight Mw of the epoxy resin is, for example, preferably 100 or more, and more preferably 150 or more. Thus, the paste adhesive composition can exhibit an appropriate adhesive force via the base compound.
(radical polymerization initiator)
As the radical polymerization initiator, specifically, an azo compound, a peroxide, or the like can be used. As the radical polymerization initiator, 1 or a combination of 2 or more of the above-mentioned specific examples can be used. As the radical polymerization initiator, for example, a peroxide is preferably used in the above-mentioned specific examples.
Specific examples of the above-mentioned peroxide include bis (1-phenyl-1-methylethyl) peroxide, 1-bis (peroxy-1, 1-dimethylethyl) cyclohexane, methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, 1-bis (peroxy-tert-hexyl) cyclohexane, 1-bis (peroxy-tert-butyl) -2-methylcyclohexane, 1-bis (peroxy-tert-butyl) cyclohexane, 2-bis (peroxy-tert-butyl) butane, n-butyl-4, 4-bis (peroxy-tert-butyl) valerate, 2-bis (4, 4-bis (peroxy-tert-butyl) cyclohexane) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, p-tert-butyl hydroperoxide, n-butyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, di (2-tert-butylperoxyisopropyl) benzene, bisisopropylphenyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, tert-butylisopropylphenyl peroxide, di-tert-butyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne, diisobutyl peroxide, di (3,5, 5-trimethylhexanoyl) peroxide, dilauroyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, Di (2-ethylhexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, cumylphenyl peroxyneodecanoate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, tert-hexyl neodecanoate, tert-butyl peroxyneoheptanoate, tert-hexyl peroxypivalate, 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate, 2, 5-dimethyl-2, 5-di (2-diethylhexanoyl-peroxy) hexane, tert-butyl peroxy2-ethylhexanoate, tert-hexyl peroxyisopropylmonocarbonate, tert-butyl peroxymaleate, tert-butyl peroxy3, 5, 5-trimethylhexanoate, tert-butyl peroxyisopropylmonocarbonate, tert-butyl peroxy2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2, 5-dimethyl-2, 5-di (peroxybenzoyl) hexane, tert-butyl peroxypyruvate, tert-butyl peroxy-3-methylbenzoate, tert-butyl peroxybenzoate, tert-butyl peroxyallylmonocarbonate, 3',4,4' -tetra (tert-butylperoxycarbonyl) benzophenone, and the like. As the peroxide, 1 or a combination of 2 or more of the above specific examples can be used. As the peroxide, bis (1-phenyl-1-methylethyl) peroxide is preferably used among the above-mentioned specific examples.
(curing agent)
When the paste adhesive composition of the present embodiment contains an epoxy monomer as a monomer or an epoxy resin as a main agent, for example, it preferably contains a curing agent. This can solidify and shrink the monomer and the main agent to agglomerate the silver particles.
As the curing agent, for example, a phenol curing agent or an imidazole curing agent can be used. The following description is made in detail.
[ phenol curing agent ]
Specific examples of the phenolic resin curing agent include novolak phenolic resins such as phenol novolak resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenol novolak resin; polyvinyl phenol; multifunctional phenol resins such as triphenylmethane phenol resins; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; phenol aralkyl type phenol resins such as phenol aralkyl resins having a phenylene skeleton and/or a biphenylene skeleton and naphthol aralkyl resins having a phenylene skeleton and/or a biphenylene skeleton; bisphenol compounds such as bisphenol a and bisphenol F (dihydroxydiphenylmethane); and compounds having a biphenylene skeleton such as 4,4' -biphenol. The phenolic resin curing agent may contain 1 or 2 or more selected from the above specific examples.
As the phenolic resin, for example, a phenol aralkyl resin is preferably used among the above-mentioned specific examples. Further, as the phenol aralkyl resin, for example, a condensation product of phenol-p-xylylene ether is preferably used.
[ imidazole-based curing agent ]
Specific examples of the imidazole-based curing agent include 2-phenyl-1H-imidazole-4, 5-dimethanol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methylimidazole, 2-phenylimidazole, 2, 4-diamino-6- [ 2-methylimidazolyl- (1) ] -ethyl-s-triazine, 2-undecylimidazole, 2-heptadecylimidazole, 2, 4-diamino-6- [ 2-methylimidazolyl- (1) ] -ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-methylimidazolium isocyanurate adduct, 1-cyanoethyl-2-phenylimidazolium trimellitate (trimellitate), 1-cyanoethyl-2-undecylimidazolium trimellitate, and the like. As the imidazole-based curing agent, 1 or a combination of 2 or more of the above specific examples can be used.
The lower limit of the content of the curing agent in the paste adhesive composition is, for example, preferably 1 part by mass or more, and more preferably 2 parts by mass or more, based on 100 parts by mass of the total amount of the epoxy monomer and the epoxy resin in the paste adhesive composition.
The upper limit of the content of the curing agent in the paste adhesive composition is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the epoxy monomer and the epoxy resin in the paste adhesive composition.
When the content of the curing agent in the paste adhesive composition is within the above numerical range, the paste adhesive composition can be cured and shrunk appropriately. Further, it is also preferable from the viewpoint of not inhibiting the formation of the silver particle connection structure.
(curing accelerators)
The paste adhesive composition of the present embodiment may contain, for example, a curing accelerator for accelerating the reaction between an epoxy monomer or an epoxy resin and a curing agent.
Specific examples of the curing accelerator include compounds containing a phosphorus atom such as organic phosphines, tetra-substituted phosphonium compounds, phosphate betaine (phosphobetaine) compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; amidine or tertiary amine such as dicyandiamide (dicyandiamide), 1, 8-diazabicyclo [5.4.0] undecene-7, benzyldimethylamine and the like; and nitrogen atom-containing compounds such as the amidines and quaternary ammonium salts of the tertiary amines. As the curing accelerator, 1 or a combination of 2 or more of the above-mentioned specific examples can be used.
(Low-stress agent)
The paste adhesive composition of the present embodiment may contain, for example, a low stress agent.
Specific examples of the low-stress agent include organosilicon compounds such as silicone oil and silicone rubber; polybutadiene compounds such as polybutadiene maleic anhydride adducts; acrylonitrile butadiene copolymer compounds, and the like. The low-stress agent may be blended with 1 or 2 or more of the above specific examples.
(silane coupling agent)
The paste adhesive composition of the present embodiment may contain, for example, a silane coupling agent in order to improve the adhesion between the paste adhesive composition and the base material.
Specific examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; styryl silanes such as p-styryl trimethoxysilane; methacrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and 3-methacryloxypropyltriethoxysilane; acrylic silanes such as 3- (trimethoxysilyl) propyl methacrylate and 3-acryloxypropyltrimethoxysilane; aminosilanes such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, and N-phenyl-gamma-aminopropyltrimethoxysilane; an isocyanurate silane; an alkylsilane; urea silanes such as 3-ureido (ureide) propyltrialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silane such as 3-isocyanatopropyltriethoxysilane, and the like. As the silane coupling agent, 1 or a combination of 2 or more of the above specific examples can be used.
(method for producing paste adhesive composition)
A method for producing the paste adhesive composition of the present embodiment will be described.
The method for producing a paste adhesive composition includes a mixing step of mixing the above raw material components to prepare a mixture, and a defoaming step of removing air contained in the mixture.
(mixing Process)
In the mixing step, the raw material components are mixed to prepare a mixture.
The mixing method is not limited, and for example, a three-roll mill, a mixer, or the like can be used. Thereby, the raw material components are mixed to obtain a mixture.
(defoaming step)
In the defoaming step, air contained in the mixture is removed.
The method of removing the air contained in the mixture is not limited, and for example, the removal can be performed by leaving the mixture under vacuum. Thus, a paste adhesive composition was obtained.
(paste adhesive composition)
The curing conditions of the paste adhesive composition of the present embodiment can be, for example, sufficiently cured by raising the temperature from near room temperature (20 ℃ to 30 ℃ inclusive) to 100 ℃ to 300 ℃ at a temperature rise rate of 0.5 ℃/min to 30 ℃/min inclusive, and by heat-treating at the temperature after the temperature rise for 10 minutes to 2 hours inclusive.
When the paste adhesive composition of the present embodiment is heated from 25 ℃ to 175 ℃ over 30 minutes and is heat-treated at 175 ℃ for 30 minutes, the thermal conductivity in the thickness direction of the obtained cured product is CT [ W/(m · K) ], and the viscosity of the paste adhesive composition of the present embodiment at a temperature of 25 ℃ and a rotational frequency of 2.5rpm is η [ Pa · s ], the lower limit value of CT/η is, for example, preferably 2.3[ W/(m · K · Pa · s) ] or more, and more preferably 2.4[ W/(m · K · Pa · s) ] or more. When CT/eta is within the above numerical range, a silver particle connection structure is formed, and heat dissipation such as thermal diffusivity between chips can be improved.
The upper limit of CT/η may be, for example, 20[ W/(m · K · Pa · s) ] or less, or 10[ W/(m · K · Pa · s) ] or less.
In the present embodiment, the value of CT/η can be controlled by appropriately selecting the type and content of the raw material components contained in the paste adhesive composition, for example. Among these, factors for setting the CT/η to a desired numerical range include, for example, the shape of the silver particles, the specific surface area of the silver particles, the content of the silver particles, the types of the monomer, the main agent, the curing agent, and the radical polymerization initiator, and the content of the volatile component determined by the content.
Although the detailed mechanism is not clear, it is presumed that when CT/η is within the above numerical range, the monomer and the base compound interposed between the silver particles are in a preferable amount, and the silver particle-linked structure can be appropriately formed.
(use)
The application of the paste adhesive composition of the present embodiment will be described.
The paste adhesive composition of the present embodiment can be adhered to a plurality of adherends and has excellent heat dissipation properties. Specific examples of the adherend include semiconductor elements such as ICs and LSIs; base materials such as lead frames, BGA substrates, mounting substrates, and semiconductor chips; heat radiating members such as heat sinks and heat radiating fins.
The paste adhesive composition of the present embodiment can be suitably used for, for example, a semiconductor device such as a semiconductor package.
Specific examples of the semiconductor Package include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Scale Package), Chip Size Package, QFN (Quad Flat Non-leaded Package), SON (micro-miniature Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead frame), Lead frame, FCBGA (Flip Chip; Flip Chip), MAPGBGA (Mold Array Process BGA; Molded Array Process), eWLBGA BGA (Ball Grid Array), LF-In type eBGA (Fan-In) and Fan-Out type WLB (Fan-WLOUTPB).
An example of a semiconductor device using the paste adhesive composition of the present embodiment will be described below.
Fig. 1 is a cross-sectional view showing an example of a semiconductor device according to the present embodiment.
The semiconductor device 100 of the present embodiment includes a base 30 and a semiconductor element 20 mounted on the base 30 via an adhesive layer 10 which is a cured product of a paste adhesive composition. That is, the adhesive layer 10 is formed by curing a paste adhesive composition.
The semiconductor element 20 and the base 30 are electrically connected via a bonding wire 40 or the like, for example. The semiconductor element 20 is sealed with a sealing resin 50, for example.
The lower limit of the thickness of the adhesive layer 10 is, for example, preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more. This can improve the heat capacity of the cured product of the paste adhesive composition and improve the heat dissipation properties.
The upper limit of the thickness of the adhesive layer 10 may be, for example, 100 μm or less, or may be 50 μm or less.
In fig. 1, the substrate 30 is, for example, a lead frame. At this time, the semiconductor element 20 is mounted on the die pad (die pad)32 or the base 30 via the adhesive layer 10. The semiconductor element 20 is electrically connected to the outer lead 34 (base 30) via a bonding wire 40, for example. The base 30 as a lead frame is made of, for example, 42 alloy or Cu frame.
The substrate 30 may be an organic substrate or a ceramic substrate. The organic substrate is preferably made of, for example, an epoxy resin, a cyanate resin, a maleimide resin, or the like.
The surface of the substrate 30 may be coated with a metal such as silver or gold. This can improve the adhesion between the adhesive layer 10 and the base material 30.
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.
In the semiconductor device 100 of the present modification example, the substrate 30 is, for example, an Interposer (Interposer). The substrate 30 as an interposer has, for example, a plurality of solder balls 52 formed on one surface of the substrate opposite to the surface on which the semiconductor element 20 is mounted. At this time, the semiconductor device 100 is connected to another wiring board via the solder ball 52.
(method of manufacturing semiconductor device)
An example of the method for manufacturing a semiconductor device according to the present embodiment will be described.
First, a paste adhesive composition is applied to the base 30, and then the semiconductor element 20 is disposed thereon. That is, the base 30, the paste adhesive composition, and the semiconductor element 20 are stacked in this order. The method of applying the paste adhesive composition is not limited, and specifically, a dispensing method (dispensing), a printing method, an ink jet method, or the like can be used.
Subsequently, the paste adhesive composition is pre-cured and post-cured to obtain a cured product. The heat treatment such as the pre-curing and the post-curing aggregates the silver particles in the paste adhesive composition, and the heat conductive layer in which the interfaces between the plurality of silver particles disappear is formed in the adhesive layer 10. Thereby, the base material 30 and the semiconductor element 20 are bonded via the adhesive layer 10. Next, the semiconductor element 20 and the substrate 30 are electrically connected by using the bonding wire 40. Next, the semiconductor element 20 is sealed with a sealing resin 50. Thereby, a semiconductor device can be manufactured.
The present invention has been described above with reference to the embodiments, but the present invention is not limited to the above embodiments, and the configuration thereof may be modified within a range not changing the gist of the present invention.
[ examples ]
The present invention will be described in detail with reference to examples below, but the present invention is not limited to the examples.
< ingredient of raw Material >
First, the raw material components used in examples and comparative examples will be described in detail.
(monomer)
The following monomers were used as monomers.
Diol monomer 1: tripropylene glycol mono-n-butyl ether (BFTG, boiling point at atmospheric pressure (101.3kPa) 274 ℃ C., manufactured by Nippon emulsifier Co.)
Diol monomer 2: ethylene glycol Mono-n-butyl acetate (BCSA with a boiling point of 192 ℃ under atmospheric pressure (101.3kPa) manufactured by Tokyo chemical Co., Ltd.)
Monofunctional acrylic monomer 1: 2-Phenoxyethyl methacrylate (PO, Co., Ltd.)
Monofunctional acrylic monomer 2: 1, 4-cyclohexanedimethanol monoacrylate (CHDMMA, manufactured by Nippon chemical industries Co., Ltd.)
Polyfunctional acrylic monomer 1: ethylene glycol dimethacrylate (manufactured by Kyoeisha chemical Co., Ltd., EG)
Monofunctional epoxy monomer 1: 4-tert-butylphenyl glycidyl ether (manufactured by Nippon Chemicals Co., Ltd., TGE-H)
(Main agent)
The following main agents were used as the main agents.
Epoxy polymer 1: bisphenol-F-diglycidyl ether (RE-303 SL, manufactured by Nippon Chemicals Co., Ltd., epoxy equivalent of 160g/eq)
Epoxy polymer 2: bisphenol-F-diglycidyl ether (RE-403S, epoxy equivalent of 165g/eq, manufactured by Nippon Chemicals Co., Ltd.)
Epoxy polymer 3: hydrogenated bisphenol A type liquid epoxy resin (YX-8000, epoxy equivalent 210g/eq, Mitsubishi chemical corporation)
(curing agent)
The following curing agents were used as the curing agents.
Phenol curing agent 1: dihydroxy diphenylmethane (DIC-BPF, DIC Co., Ltd.)
Phenol curing agent 2: 4,4' -biphenol (sea Enterprise Co., Ltd., product of Ltd., BP pulverizate)
Phenol curing agent 3: phenol-p-xylene dimethyl ether polycondensate (MEH-7800 SS, manufactured by Minghe chemical Co., Ltd.)
Imidazole curing agent 1: 2-phenyl-1H-imidazole-4, 5-dimethanol (2 PHZ-PW, manufactured by Siguo chemical industries Co., Ltd.)
Imidazole curing agent 2: 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P 4MHZ, manufactured by Sicountry chemical industries Co., Ltd.)
(radical polymerization initiator)
The following initiators were used as radical polymerization initiators.
Peroxide 1: bis (1-phenyl-1-methylethyl) peroxide (Kayaku Akzo Co., Ltd., PERCADOX BC, manufactured by Ltd.)
(curing accelerators)
Curing accelerator 1: dicyandiamide (EH-3636 AS, manufactured by Asahi Denka Co., Ltd.)
(silane coupling agent)
Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane (KBM-403E, manufactured by shin-Etsu chemical Co., Ltd.)
Silane coupling agent 2: 3- (trimethoxysilyl) propyl methacrylate (KBM-503P, manufactured by shin-Etsu chemical Co., Ltd.)
Silane coupling agent 3: n-phenyl-gamma-aminopropyltrimethoxysilane (KBM-573, manufactured by shin-Etsu chemical Co., Ltd.)
(silver particles)
As the silver particles, silver particles shown in table 1 below were used. In the present embodiment, the particle size peak represents a particle size peak of a volume-based particle size distribution of the silver particles.
[ Table 1]
Figure BDA0002657623520000271
< preparation of paste adhesive composition >
Paste adhesive compositions of examples and comparative examples were prepared. As a production method, each raw material component was kneaded at room temperature by a three-roll mill in the blending amount shown in table 2 below.
< evaluation >
The paste adhesive compositions of the examples and comparative examples were evaluated by the following methods.
(weight loss ratio)
The paste adhesive compositions of examples and comparative examples were evaluated for weight loss by the following method.
Thermogravimetry (TG-DTA) was carried out for the paste adhesive compositions of the examples and comparative examples. The thermogravimetric conditions were carried out by raising the temperature from 30 ℃ to 200 ℃ at a temperature raising rate of 10 ℃/min, followed by heat treatment at 200 ℃ for 60 minutes, followed by raising the temperature from 200 ℃ to 450 ℃ at a temperature raising time of 10 ℃/min, followed by heat treatment at 450 ℃ for 10 minutes.
Further, the measurement was performed under the atmospheric air.
The 100 fraction of the weight loss rate of the paste adhesive composition after heat treatment at 200 ℃ for 60 minutes with respect to the paste adhesive compositions of examples and comparative examples before temperature rise was W1 [% ].
The 100 fraction of the weight loss rate of the paste adhesive composition after heat treatment at 450 ℃ for 10 minutes with respect to the paste adhesive compositions of examples and comparative examples before temperature rise was W2 [% ].
Then, (W2-W1)/W2 were calculated from the measured W1 and W2. The evaluation results are shown in table 2 below.
W1 and W2 are positive values or 0 values. For example, when the weight of the paste adhesive composition after the heat treatment at 200 ℃ for 60 minutes is 90% of the weight of the paste adhesive composition before the temperature rise, the weight loss rate is 10%.
(thermal conductivity)
The paste adhesive compositions of the examples and comparative examples were evaluated for thermal conductivity by the following methods.
The paste adhesive compositions of examples and comparative examples were heated from 25 ℃ to 175 ℃ over 30 minutes and heat-treated at 175 ℃ for 30 minutes, whereby cured products of the paste adhesive compositions having a thickness of 1mm were obtained. Next, the thermal diffusivity α of the cured product in the thickness direction was measured by a laser flash method. The measurement temperature was set to 25 ℃.
The specific heat Cp is measured by Differential Scanning Calorimetry (DSC), and the density ρ is measured in accordance with JIS-K-6911. From these values, the thermal conductivity CT was calculated according to the following equation.
The evaluation results are shown in table 2 below. The unit is W/(m.K).
(formula) thermal conductivity CT [ W/(m.K)]＝α[mm2/sec]×Cp[J/kg·K]×ρ[g/cm3]
(inter-chip thermal diffusivity)
The paste adhesive compositions of examples and comparative examples were evaluated for inter-chip thermal diffusivity by the following method. The details are as follows.
First, 2 pieces of back-side gold-plated silicon chips having a length of 10mm, a width of 10mm and a thickness of 350 μm were prepared. One silicon chip was coated with the paste adhesive composition so as to have a thickness of 20. + -. 5 μm, and the other silicon chip was laminated thereon. That is, a laminate was prepared in which a silicon chip, a paste adhesive composition, and a silicon chip were sequentially laminated.
Then, the temperature was increased from 25 ℃ to 175 ℃ over 30 minutes, and then heat-treated at 175 ℃ for 60 minutes to cure the paste adhesive composition of the laminate to obtain a cured product. Thus, a test piece was prepared by bonding 2 silicon chips to each other via a cured product of the paste adhesive composition.
Next, the thermal diffusivity of the test piece in the thickness direction was measured by a laser flash method, and this was used as the evaluation result of the thermal diffusivity between chips. The temperature for measuring the thermal diffusivity was set to 25 ℃. The evaluation results are shown in table 2 below. Furthermore, the unit is cm2And/sec. Among them, the higher the value of the inter-chip thermal diffusivity, the better the evaluation result.
(viscosity)
The paste adhesive compositions of the examples and comparative examples were evaluated for viscosity by the following method.
The paste adhesive compositions of examples and comparative examples were evaluated for viscosity η by means of an E-type viscometer using a cone with a cone angle of 3 °. The measurement conditions were set at a temperature of 25 ℃ and a rotational frequency of 2.5 rpm. The evaluation results are shown in table 2 below. In addition, the unit is Pa · s.
And calculating CT/eta from the thermal conductivity CT and the viscosity eta. The evaluation results are shown in table 2 below. The unit is W/(m.K.Pa.s).
(Tight-contact property)
The paste adhesive compositions of examples and comparative examples were evaluated for adhesion to Cu and Si by the following methods. The description is made in detail.
First, a lead frame (copper frame) and a silicon chip (length 2mm × width 2mm) were prepared. Next, the paste adhesive compositions of examples and comparative examples were applied to a silicon chip so that the application thickness became 20 ± 5 μm, and a lead frame was disposed. That is, a laminate was produced by sequentially laminating a silicon chip, a paste adhesive composition, and a lead frame. The surface of the lead frame in contact with the paste adhesive composition is made of copper.
Subsequently, the temperature was raised from 30 ℃ to 175 ℃ for 60 minutes under the atmospheric air, and then the paste adhesive composition of the laminate was cured at 175 ℃ for 120 minutes to prepare a cured product.
Next, the chip shear strength (die shear strength) of the silicon chip and the copper lead frame bonded to each other with the cured product interposed therebetween was measured. The measurement was performed at a temperature of 260 ℃ for 20 seconds as a measurement condition. Using the obtained chip shear strength, evaluation was performed on the following criteria. The evaluation results are shown in table 2 below.
O: the shear strength of the chip is more than 10N/(2mm multiplied by 2 mm).
X: the shear strength of the chip is less than 10N/(2mm multiplied by 2 mm).
(observation of silver particle bonding Structure)
Regarding the semiconductor devices using the paste adhesive compositions of the examples and comparative examples, the cross section of the cured product of the paste adhesive composition was observed with a Scanning Electron Microscope (SEM), and it was confirmed whether or not the silver particle-linked structure was formed in the cured product. Detailed methods are disclosed below.
First, a copper lead frame (hereinafter, also referred to as copper LF) and a silicon chip (length 2mm × width 2mm, thickness 0.35mm) were prepared. Next, the paste adhesive compositions of examples and comparative examples were applied to a silicon chip to a coating thickness of 25 ± 10 μm, and a copper lead frame was placed thereon. That is, a laminate was prepared by sequentially laminating a silicon chip, a paste adhesive composition, and a copper lead frame. The surface of the copper lead frame in contact with the paste adhesive composition is made of copper.
Subsequently, the temperature was increased from 25 ℃ to 175 ℃ over 30 minutes under the air, and then heat-treated at 175 ℃ for 60 minutes, thereby curing the paste adhesive composition of the laminate to produce a cured product. Subsequently, the cross section of the cured product was observed by SEM. The evaluation results are shown in table 2 below, in which the case where the silver particle connection structure was formed was indicated by "o" and the case where the silver particle connection structure was not formed was indicated by "x".
[ Table 2]
Figure BDA0002657623520000311
As shown in table 2, it was confirmed that the paste adhesive compositions of the examples exhibit proper adhesion to bare silicon and copper and can improve heat dissipation properties such as thermal diffusivity between chips, as compared with the paste adhesive compositions of the comparative examples.
This application claims priority based on japanese patent application No. 2018-036597, filed 3/1 in 2018, the disclosure of which is incorporated herein in its entirety.

Claims (9)

1. A paste adhesive composition characterized by:
the paste adhesive composition contains silver particles and a monomer, the interface between the silver particles disappears due to heat treatment to form a silver particle connection structure,
the silver particles include flake silver particles and spherical silver particles,
under the following measurement conditions, when the paste adhesive composition is heated from 30 ℃ to 200 ℃ at a heating rate of 10 ℃/min, then heat-treated at 200 ℃ for 60 minutes, then heated from 200 ℃ to 450 ℃ for a heating time of 10 ℃/min, and then heat-treated at 450 ℃ for 10 minutes, the paste adhesive composition before heating is set to have a weight loss rate of 100W 1 [% ] after heat-treating at 200 ℃ for 60 minutes and a weight loss rate of 100W 2 [% ] after heat-treating at 450 ℃ for 10 minutes, wherein (W2-W1)/W2 is 0.40-0.75,
(measurement conditions)
The measurement method: a thermogravimetric (Thermogravimetry-Differential Thermal Analysis: TG-DTA) device;
atmosphere: an atmosphere of air.
2. The paste adhesive composition as claimed in claim 1, wherein:
the thermal conductivity in the thickness direction of a cured product obtained by heating the paste adhesive composition from 25 ℃ to 175 ℃ over a period of 30 minutes and then heat-treating the resultant composition at 175 ℃ for 30 minutes is represented by CT [ W/(m.K) ],
when the viscosity of the paste adhesive composition at a temperature of 25 ℃ and a rotational frequency of 2.5rpm is defined as eta Pa s,
CT/eta is 2.3[ W/(mK Pa s) ] or more.
3. The paste adhesive composition as claimed in claim 1 or 2, wherein:
the cumulative frequency of the volume-based particle size distribution of the spherical silver particles is 50% of the particle diameter D50Is 0.1 to 4.0 μm.
4. The paste adhesive composition as claimed in claim 1 or 2, wherein:
the cumulative frequency of the volume-based particle size distribution of the flaky silver particles is 50% of the particle diameter D50Greater than 4.0 μm and not more than 30 μm.
5. The paste adhesive composition as claimed in claim 1 or 2, wherein:
the monomer comprises a diol monomer having a hydroxyl group,
the diol monomer is a 2-membered alcohol having 2 hydroxyl groups in the structure, and the 2 hydroxyl groups are bonded to different carbon atoms; a compound obtained by alcohol condensation of 2 or more of the 2-membered alcohols; the hydroxyl group of the compound obtained by condensation of the alcohol is substituted with an organic group having 1 to 30 carbon atoms and is an alkoxy group.
6. The paste adhesive composition as set forth in claim 5, wherein:
the monomer also includes an epoxy monomer or an acrylic monomer.
7. The paste adhesive composition as claimed in claim 1 or 2, wherein:
the paste adhesive composition further comprises a main agent,
the main agent is more than 1 selected from epoxy resin, acrylic resin and allyl resin.
8. The paste adhesive composition as claimed in claim 1 or 2, wherein:
the paste adhesive composition further comprises a curing agent,
the curing agent is a phenol curing agent or an imidazole curing agent.
9. A semiconductor device is characterized by comprising:
a substrate; and
a semiconductor element mounted on the substrate via an adhesive layer,
the adhesive layer is formed by sintering the paste adhesive composition according to any one of claims 1 to 8.
CN201980016231.2A 2018-03-01 2019-02-22 Paste adhesive composition and semiconductor device Active CN111801397B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2018-036597 2018-03-01
JP2018036597 2018-03-01
PCT/JP2019/006717 WO2019167824A1 (en) 2018-03-01 2019-02-22 Paste adhesive composition and semiconductor device

Publications (2)

Publication Number Publication Date
CN111801397A CN111801397A (en) 2020-10-20
CN111801397B true CN111801397B (en) 2021-08-20

Family

ID=67805046

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980016231.2A Active CN111801397B (en) 2018-03-01 2019-02-22 Paste adhesive composition and semiconductor device

Country Status (3)

Country Link
CN (1) CN111801397B (en)
TW (1) TWI799521B (en)
WO (1) WO2019167824A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022202434A1 (en) * 2021-03-24 2022-09-29 住友ベークライト株式会社 Conductive paste, and semiconductor device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008166841A (en) * 2008-03-10 2008-07-17 Hitachi Chem Co Ltd Adhesive, and semiconductor device
CN103563063A (en) * 2011-05-31 2014-02-05 住友电木株式会社 Resin composition, semiconductor device using same, and method of manufacturing semiconductor device
CN104112490A (en) * 2014-06-25 2014-10-22 广东风华高新科技股份有限公司 Electrode slurry and preparation method
WO2017006854A1 (en) * 2015-07-08 2017-01-12 住友ベークライト株式会社 Thermally conductive composition, semiconductor device, process for producing semiconductor device, and method for bonding heat sink plate
WO2018034234A1 (en) * 2016-08-19 2018-02-22 住友ベークライト株式会社 Die attach paste and semiconductor device

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104575671B (en) * 2014-12-09 2016-10-05 华南理工大学 A kind of ultraviolet curing urethane base conductive silver paste and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008166841A (en) * 2008-03-10 2008-07-17 Hitachi Chem Co Ltd Adhesive, and semiconductor device
CN103563063A (en) * 2011-05-31 2014-02-05 住友电木株式会社 Resin composition, semiconductor device using same, and method of manufacturing semiconductor device
CN104112490A (en) * 2014-06-25 2014-10-22 广东风华高新科技股份有限公司 Electrode slurry and preparation method
WO2017006854A1 (en) * 2015-07-08 2017-01-12 住友ベークライト株式会社 Thermally conductive composition, semiconductor device, process for producing semiconductor device, and method for bonding heat sink plate
WO2018034234A1 (en) * 2016-08-19 2018-02-22 住友ベークライト株式会社 Die attach paste and semiconductor device

Also Published As

Publication number Publication date
WO2019167824A1 (en) 2019-09-06
TW201945502A (en) 2019-12-01
TWI799521B (en) 2023-04-21
CN111801397A (en) 2020-10-20

Similar Documents

Publication Publication Date Title
JP6319530B1 (en) Die attach paste and semiconductor device
WO2011158753A1 (en) Resin paste composition
JP5664673B2 (en) Resin paste composition
CN111801397B (en) Paste adhesive composition and semiconductor device
TWI828881B (en) Thermoconductive composition and semiconductor device
WO2019111778A1 (en) Pasty adhesive composition and semiconductor device
JP6566177B1 (en) Paste adhesive composition and semiconductor device
CN111788275B (en) Paste adhesive composition and semiconductor device
CN114341288B (en) Thermally conductive composition and semiconductor device
JP7395979B2 (en) Conductive paste and semiconductor devices
CN113631675A (en) Semiconductor package, method for manufacturing semiconductor package, and thermally conductive composition used therefor
TW202135098A (en) Conductive paste and semiconductor device
CN113930167B (en) Paste adhesive composition and semiconductor device
TWI841706B (en) Semiconductor package, manufacturing method of semiconductor package and thermoconductive composition used for the same
WO2022202434A1 (en) Conductive paste, and semiconductor device
TW202330828A (en) Electrically conductive paste, cured product, sintering accelerator, and sintering acceleration method
TW202227561A (en) Silver-containing paste and joined body
JP2023016331A (en) Conductive paste and semiconductor device
TW202138507A (en) Paste resin composition, high heat-conductive material, and semiconductor device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant