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CN115023453A - Paste resin composition, highly thermally conductive material, and semiconductor device - Google Patents

Paste resin composition, highly thermally conductive material, and semiconductor device Download PDF

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Publication number
CN115023453A
CN115023453A CN202180011544.6A CN202180011544A CN115023453A CN 115023453 A CN115023453 A CN 115023453A CN 202180011544 A CN202180011544 A CN 202180011544A CN 115023453 A CN115023453 A CN 115023453A
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resin composition
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metal
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paste resin
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Inventor
渡部直辉
阿部弓依
高本真
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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    • 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • C08G59/40—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 curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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

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

Abstract

The paste resin composition of the present invention comprises: (A) a (meth) acryloyl group-containing compound having a 2-or more-functional group, wherein the number of repeating units of a linear or branched oxyalkylene group is 2 or more; and (B) metal-containing particles comprising silver-containing particles or copper-containing particles.

Description

Paste resin composition, highly thermally conductive material, and semiconductor device
Technical Field
The invention relates to a paste resin composition, a highly heat conductive material and a semiconductor device.
Background
There is known a technique for manufacturing a semiconductor device using a thermosetting resin composition containing metal particles in order to improve heat dissipation of the semiconductor device. By containing metal particles having a thermal conductivity higher than that of the resin in the thermosetting resin composition, the thermal conductivity of the cured product can be improved.
As a specific example of application to a semiconductor device, a technique of bonding/joining a semiconductor element and a substrate (support member) using a thermosetting resin composition containing metal particles is known, as in patent documents 1 and 2 below.
Patent document 1 discloses a thermosetting resin composition for bonding a semiconductor, which contains a (meth) acrylate compound having a predetermined structure, a radical initiator, fine silver particles, silver powder, and a solvent, and a semiconductor device in which a semiconductor element and a substrate are bonded with the composition. This document describes that the connection reliability with respect to temperature cycles after mounting can be improved (paragraph 0011).
Patent document 2 discloses a paste resin composition containing an imide acrylate compound, a radical initiator, a filler and a liquid rubber component, and a semiconductor device in which a semiconductor element and a base material are bonded with the composition. This document describes that generation of chip cracks or chip warpage can be suppressed by reducing stress in the paste resin composition (paragraph 0003).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-74132
Patent document 2: japanese patent laid-open No. 2000-239616
Disclosure of Invention
Technical problem to be solved by the invention
However, in the resin compositions described in patent documents 1 to 2, a semiconductor device in which a semiconductor element and a base material are bonded may not exhibit good conductivity for a long period of time, and there is room for improvement in long-term reliability.
Technical solution for solving technical problem
The present inventors have found that a semiconductor device exhibits good conductivity over a long period of time and is excellent in long-term reliability by using a (meth) acryloyl group-containing compound having a predetermined structure, and have completed the present invention.
The present invention can be as follows.
According to the present invention, there is provided a paste resin composition comprising:
(A) a (meth) acryloyl group-containing compound having a 2-or more-functional group, the number of repeating units of a linear or branched oxyalkylene group being 2 or more; and
(B) a metal-containing particle comprising a silver-containing particle or a copper-containing particle.
According to the present invention, there is provided a highly thermal conductive material obtained by sintering the paste resin composition.
According to the present invention, there is provided a semiconductor device comprising: a substrate; and a semiconductor element mounted on the substrate via an adhesive layer, wherein the adhesive layer is formed by sintering the paste resin composition.
Effects of the invention
According to the present invention, a paste resin composition which is suitable for bonding a semiconductor element and a base material and can provide a semiconductor device exhibiting good conductivity over a long period of time and excellent long-term reliability can be provided.
Drawings
Fig. 1 is a cross-sectional view schematically showing an example of a semiconductor device.
Fig. 2 is a cross-sectional view schematically showing an example of the semiconductor device.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and the description thereof is omitted as appropriate. Unless otherwise specified, "to" means "above" to "below".
The paste resin composition of the present embodiment contains: (A) a (meth) acryloyl group-containing compound having a 2-or more-functional group, wherein the number of repeating units of a linear or branched oxyalkylene group is 2 or more; and (B) a metal-containing particle containing a silver particle or a copper particle.
[ Compound (A) containing a (meth) acryloyl group ]
The (meth) acryloyl group-containing compound (a) is not particularly limited as long as it has a 2-or more-functional (meth) acryloyl group and the number of repeating units of a linear or branched oxyalkylene group is 2 or more, and the compound (a) can be used within a range in which the effects of the present invention can be exerted.
In the present embodiment, by using a paste resin composition containing the (meth) acryloyl group-containing compound (a) having such a structure, the stress of a material obtained by firing the composition is relaxed, and the toughness is also excellent (the fracture energy is high, and fracture is difficult). Therefore, it is considered that the semiconductor device in which the semiconductor element and the base material are bonded to each other by the paste resin composition of the present embodiment can suppress peeling of the bonded portion and the like, exhibit good conductivity over a long period of time, and have excellent long-term reliability.
From the viewpoint of the effect of the present invention, the number of repeating units of the oxyalkylene group may be 2 or more, preferably 4 or more, more preferably 4 to 30, and particularly preferably 8 to 30.
The oxyalkylene group includes a linear or branched oxyalkylene group having 2 to 10 carbon atoms, preferably a linear or branched oxyalkylene group having 2 to 8 carbon atoms, and more preferably a linear or branched oxyalkylene group having 2 to 5 carbon atoms.
In the present embodiment, the (meth) acryloyl group containing compound (a) preferably contains at least one selected from compounds represented by the following general formula (1).
Figure BDA0003769535590000031
In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the plurality of R may be the same or different.
X represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a mercapto group, a carboxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The plurality of xs present may be the same or different.
m may represent an integer of 2 to 10, preferably an integer of 2 to 8, and more preferably an integer of 2 to 5.
n may be an integer of 4 to 30 inclusive, and preferably an integer of 8 to 30 inclusive.
Examples of the (meth) acryloyl group-containing compound (a) include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol #200 di (meth) acrylate (n: 4), polyethylene glycol #400 di (meth) acrylate (n: 9), polyethylene glycol #600 di (meth) acrylate (n: 14), polyethylene glycol #1000 di (meth) acrylate (n: 23), and the like.
From the viewpoint of the effect of the present invention, the (meth) acryloyl group containing compound (a) may be contained in an amount of 0.1 to 15% by weight or less, preferably 0.5 to 10% by weight, and more preferably 1.0 to 8% by weight, of the total nonvolatile components of the paste resin composition.
In addition, a (meth) acryloyl group containing compound other than the (meth) acryloyl group containing compound (a), such as a monofunctional (meth) acrylic monomer having only one (meth) acryloyl group in one molecule, may be contained together with the (meth) acryloyl group containing compound (a) within a range not affecting the effect of the present invention.
[ Metal-containing particles (B) ]
The metal-containing particles (B) can be sintered (sintering) by an appropriate heat treatment to form a particle connection structure (sintered structure).
The metal-containing particles (B) can contain silver-containing particles or copper-containing particles.
In particular, by containing silver-containing particles in the paste resin composition, particularly by containing silver particles having a small particle size and a large specific surface area, a sintered structure is easily formed even when heat treatment is performed at a relatively low temperature (about 180 ℃). The preferred particle size will be described later.
The shape of the metal-containing particles (B) is not particularly limited. The preferred shape is spherical, but may be non-spherical, such as ellipsoidal, flat, plate-like, flake-like, needle-like, and the like.
(the "spherical shape" is not limited to a perfect true sphere, but includes a shape with a slight unevenness on the surface, etc.. the same applies hereinafter in this specification)
The metal-containing particles (B) may be (i) particles substantially composed of only a metal, or (ii) particles composed of a metal and a component other than a metal. Further, (i) and (ii) may be used in combination as the metal-containing particles.
In the present embodiment, it is particularly preferable that the metal-containing particles (B) contain metal-coated resin particles in which the surface of the resin particles is coated with a metal. Therefore, a paste resin composition can be prepared which can give a cured product having more excellent thermal conductivity and more excellent storage elastic modulus.
Since the metal-coated resin particles have a metal surface and a resin inside, they have good thermal conductivity and are more flexible than particles made of metal alone. Therefore, by using the metal-coated resin particles, the thermal conductivity and the storage elastic modulus can be easily designed to appropriate values.
Generally, in order to improve thermal conductivity, it may be considered to increase the amount of the metal-containing particles. However, in general, since the metal is "hard", if the amount of the metal-containing particles is too large, the elastic modulus after sintering may become too large. By using the metal-containing particles partially or entirely as the metal-coated resin particles, it is possible to easily design a paste resin composition that can give a cured product having a desired thermal conductivity and storage elastic modulus.
In the metal-coated resin particle, the metal layer may cover at least a part of the surface of the resin particle. Of course, the metal may cover the entire surface of the resin particle.
Specifically, in the metal-coated resin particle, the metal layer covers preferably 50% or more, more preferably 75% or more, and still more preferably 90% or more of the surface of the resin particle. It is particularly preferable that in the metal-coated resin particle, the metal layer covers substantially the entire surface of the resin particle.
From another viewpoint, when the metal-coated resin particles are cut in a certain cross section, it is preferable that the metal layer is confirmed around the cross section.
From another viewpoint, the mass ratio of resin/metal in the metal-coated resin particles is, for example, 90/10 to 10/90, preferably 80/20 to 20/80, and more preferably 70/30 to 30/70.
The "metal" in the metal-coated resin particles is as described above. Silver is particularly preferred.
Examples of the "resin" in the metal-coated resin particles include silicone resins, (meth) acrylic resins, phenol resins, polystyrene resins, melamine resins, polyamide resins, polytetrafluoroethylene resins, and the like. Of course, other resins may be used. The resin may be used alone, or two or more kinds of resins may be used in combination.
From the viewpoint of elastic properties and heat resistance, the resin is preferably a silicone resin or a (meth) acrylic resin.
The silicone resin may be particles composed of an organopolysiloxane obtained by polymerizing organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, dimethyldichlorosilane, and the like. Further, the silicone resin may have a structure in which the organopolysiloxane is further three-dimensionally crosslinked as a basic skeleton.
The (meth) acrylic resin may contain, as a main component, a resin obtained by polymerizing a (meth) acrylate-containing monomer in an amount of 50 wt% or more, preferably 70 wt% or more, and more preferably 90 wt% or more. Examples of the (meth) acrylic ester include at least one compound selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-propyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate. The monomer component of the acrylic resin may contain a small amount of another monomer. Examples of the other monomer components include styrene monomers. As for the metal-coated (meth) acrylic resin, reference may be made to the description of japanese patent application laid-open No. 2017-126463, and the like.
Various functional groups can be introduced into silicone resins and (meth) acrylic resins. The functional group that can be introduced is not particularly limited. Examples thereof include epoxy group, amino group, methoxy group, phenyl group, carboxyl group, hydroxyl group, alkyl group, vinyl group, mercapto group and the like.
The resin particle portion in the metal-coated resin particle may contain various additive components such as a low stress modifier and the like. Examples of the low-stress modifier include liquid synthetic rubbers such as butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane (polyurethane) rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, and liquid polybutadiene. In particular, when the resin particles partially contain a silicone resin, the elastic properties of the metal-coated resin particles can be improved by containing a low-stress modifier.
The shape of the resin particle portion in the metal-coated resin particle is not particularly limited. The preferred shape is spherical, but may be a different shape other than spherical, such as flat, plate, needle, etc. When the metal-coated resin particles are formed in a spherical shape, the resin particles to be used are preferably also in a spherical shape.
The specific gravity of the metal-coated resin particles is not particularly limited, and the lower limit is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. The upper limit of the specific gravity is, for example, 10 or less, preferably 9 or less, and more preferably 8 or less. The appropriate specific gravity is preferable in terms of dispersibility of the metal-coated resin particles themselves, uniformity when the resin particles and the other metal-containing particles are coated with the metal, and the like.
When the metal-coated resin particles are used, the proportion of the metal-coated resin particles in the entire metal-containing particles (B) is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and still more preferably 5 to 40% by mass. By appropriately adjusting this ratio, heat dissipation can be further improved while suppressing a decrease in adhesion due to heat cycle.
Incidentally, in the case where the proportion of the metal-coated resin particles in the entirety of the metal-containing particles (B) is not 100 mass%, the metal-containing particles other than the metal-coated resin particles are, for example, particles substantially composed of only a metal.
Median particle diameter D of the metal-containing particles (B) (in the case of using a plurality of metal-containing particles in combination, the entirety) 50 For example, the particle size is 0.001 to 1000 μm, preferably 0.01 to 100 μm, and more preferably 0.1 to 20 μm. By mixing D 50 The appropriate value makes it easy to maintain a balance among thermal conductivity, sinterability, resistance to thermal cycles, and the like. In addition, by mixing D 50 If the value is set to an appropriate value, the workability of coating/bonding may be improved.
The particle size distribution (horizontal axis: particle diameter, vertical axis: frequency) of the metal-containing particles may be unimodal or multimodal.
Median diameter D of particles consisting essentially of metal only 50 For example, 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. Therefore, the thermal conductivity can be further improved.
Further, the median diameter D of the particles substantially composed of only the metal 50 For example, 7.0 μm or less, preferably 5.0 μm or less, and more preferably 4.0 μm or less. Therefore, the sinterability can be further improved, the uniformity of sintering can be further improved, and the like.
Median particle diameter D of the metal-containing particles (B) 50 For example, 0.5 μm or more, preferably 1.5 μm or more, and more preferably 2.0 μm or more. Therefore, the storage elastic modulus E' can be easily set to an appropriate value.
Further, the median particle diameter D of the metal-containing particles (B) 50 For example, 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less. Therefore, it is easy to sufficiently improve the thermal conductivity.
Median particle diameter D of the metal-containing particles (B) 50 For example, it can be determined by performing particle image measurement using a flow type particle image analysis device FPIA (registered trademark) -3000 manufactured by Sysmex Corporation. More specifically, the particle size of the metal-containing particles (B) can be determined by using the apparatus to wet-measure the volume-based median particle size.
The proportion of the metal-containing particles (B) (the total of these in the case of using a plurality of metal-containing particles) in the entire paste resin composition is, for example, 1 to 98 mass%, preferably 30 to 95 mass%, and more preferably 50 to 90 mass%. By setting the proportion of the metal-containing particles to 1 mass% or more, the thermal conductivity is easily improved. By setting the proportion of the metal-containing particles (B) to 98 mass% or less, the workability of coating/bonding can be improved.
The metal-containing particles (B) substantially consisting of only metal can be obtained, for example, from Dowa Hightech co., ltd., fuda foil powder industries, and the like. The metal-coated resin particles can be obtained, for example, from mitsubishi aggregate co, hydrochemical industries co, kam corporation, and the like.
[ thermosetting resin (C) ]
The paste resin composition of the present embodiment may further contain a thermosetting resin (C). In the present embodiment, the thermosetting resin (C) does not include the (meth) acryloyl group containing compound (a).
The thermosetting resin (C) generally contains a group which is polymerized/crosslinked by the action of an active chemical species such as a radical and/or a chemical structure which reacts with the curing agent (D) described later. The thermosetting resin (C) contains one or more of epoxy group, oxetanyl group, group containing olefinic carbon-carbon double bond, hydroxyl group, isocyanate group, maleimide structure, and the like.
As the thermosetting resin (C), an epoxy resin can be preferably mentioned.
The epoxy resin may be a compound having only one epoxy group in one molecule, or may be a compound having two or more epoxy groups in one molecule.
Examples of the epoxy resin include: 2-functional or crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, and hydroquinone type epoxy resins; novolac-type epoxy resins such as cresol novolac-type epoxy resin, phenol novolac-type epoxy resin, and naphthol novolac-type epoxy resin; phenol aralkyl type epoxy resins such as phenol aralkyl type epoxy resins containing a phenylene skeleton, phenol aralkyl type epoxy resins containing a biphenylene skeleton, and naphthol aralkyl type epoxy resins containing a phenylene skeleton; 3-functional epoxy resins such as triphenol methane type epoxy resins and alkyl-modified triphenol methane type epoxy resins; modified phenol epoxy resins such as dicyclopentadiene-modified phenol epoxy resin and terpene-modified phenol epoxy resin; and heterocyclic ring-containing epoxy resins such as triazine nucleus-containing epoxy resins.
Further, the epoxy group-containing compound may include a monofunctional epoxy group-containing compound such as 4-tert-butylphenyl glycidyl ether, m-tolyl glycidyl ether, p-tolyl glycidyl ether, phenyl glycidyl ether, and tolyl glycidyl ether.
The paste resin composition of the present embodiment may contain only one thermosetting component, or may contain two or more thermosetting components.
In the present embodiment, the thermosetting resin (C) is preferably used in combination with the (meth) acryloyl group-containing compound (a). The ratio (mass ratio) when these are used in combination is not particularly limited, and for example, the thermosetting resin (C)/the (meth) acryloyl group-containing compound (a) is 95/5 to 50/50, and the thermosetting resin (C)/the (meth) acryloyl group-containing compound (a) is 90/10 to 60/40.
As the thermosetting resin (C), an epoxy resin is preferable. The epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, or the like.
The amount of the thermosetting resin (C) in the paste resin composition of the present embodiment is, for example, 3 to 20% by mass, preferably 5 to 15% by mass, based on the entire nonvolatile components.
[ curing agent (D) ]
The paste resin composition of the present embodiment may further contain a curing agent (D).
Examples of the curing agent (D) include a curing agent having a reactive group that reacts with the thermosetting resin (C). The curing agent (D) contains, for example, a reactive group that reacts with a functional group such as an epoxy group, a maleimide group, or a hydroxyl group contained in the thermosetting resin (C).
The curing agent (D) preferably contains a phenol curing agent and/or an imidazole curing agent. These curing agents are particularly preferable when the thermosetting component contains an epoxy group.
The phenolic curing agent may be a low molecular compound or a high molecular compound (i.e., a phenol resin).
Examples of the phenolic curing agent of the low-molecular compound include: bisphenol compounds (phenol resins having a bisphenol F skeleton) such as bisphenol a and bisphenol F (dihydroxydiphenylmethane); and compounds having a biphenylene skeleton such as 4, 4' -biphenol.
Specific examples of the phenolic resin include: novolak-type phenol resins such as phenol novolak resins, cresol novolak resins, bisphenol novolak resins, and phenol-diphenol novolak resins; 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.
When the curing agent (D) is used, only one kind may be used, or two or more kinds may be used in combination.
When the paste resin composition of the present embodiment contains the curing agent (D), the amount of the thermosetting resin (C) is, for example, 10 to 150 parts by mass, preferably 20 to 100 parts by mass, based on 100 parts by mass of the resin.
(curing accelerators)
The paste resin composition of the present embodiment may further contain a curing accelerator.
Typically, the curing accelerator is a curing accelerator that accelerates the reaction of the thermosetting resin (C) and the curing agent (D).
Specific examples of the curing accelerator include: phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine (phosphobetaine) compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, and the like; amidines and tertiary amines such as dicyanodiamine, 1, 8-diazabicyclo [5.4.0] undecene-7 and benzyldimethylamine; and nitrogen atom-containing compounds such as the amidines and quaternary ammonium salts of the tertiary amines.
When the curing accelerator is used, only one kind may be used, or two or more kinds may be used in combination.
When the paste resin composition of the present embodiment contains a curing accelerator, the amount of the thermosetting resin (C) is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the composition.
(silane coupling agent)
The paste resin composition of the present embodiment may further contain a silane coupling agent. Therefore, the adhesion can be further improved.
Examples of the silane coupling agent include known silane coupling agents, and specific examples thereof include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane;
epoxy silanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropyloxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane and 3-epoxypropoxypropyltriethoxysilane; styryl silanes such as p-styryl trimethoxysilane;
methacryloylsilanes 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;
a isocyanurate silane;
an alkylsilane;
ureido silanes such as 3-ureidopropyltrialkoxysilane;
mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
isocyanate silane such as 3-isocyanatopropyltriethoxysilane, and the like.
When the silane coupling agent is used, only one kind may be used, or two or more kinds may be used in combination.
When the paste resin composition of the present embodiment contains the silane coupling agent, the amount of the thermosetting component (the total amount of the (meth) acryloyl group-containing compound (a) and the thermosetting resin (C)) is, for example, 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass, based on 100 parts by mass.
(plasticizer)
The paste resin composition of the present embodiment may contain a plasticizer. By the plasticizer, the storage elastic modulus is easily designed to be small. Further, it is easy to further suppress the decrease in adhesive strength due to thermal cycle.
Specific examples of the plasticizer include polyester compounds, silicone compounds such as silicone oils and silicone rubbers, polybutadiene compounds such as polybutadiene maleic anhydride adducts, and acrylonitrile-butadiene copolymer compounds.
When the plasticizer is used, only one kind may be used, or two or more kinds may be used in combination.
When the paste resin composition of the present embodiment contains a plasticizer, the amount of the thermosetting component (the total amount of the (meth) acryloyl group-containing compound (a) and the thermosetting resin (C)) is, for example, 5 to 50 parts by mass, preferably 10 to 30 parts by mass, based on 100 parts by mass.
(free radical initiator)
The paste resin composition of the present embodiment may contain a radical initiator.
The radical initiator may inhibit insufficient curing, may sufficiently perform a curing reaction at a relatively low temperature (e.g., 180 ℃), or may further improve the adhesive strength.
Examples of the radical initiator include peroxides and azo compounds.
Examples of the peroxide include organic peroxides such as diacyl peroxide, dialkyl peroxide, and peroxyketal, and more specifically, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxyketals such as 1, 1-bis (t-butylperoxy) cyclohexane and 2, 2-bis (4, 4-bis (t-butylperoxy) cyclohexyl) propane;
hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide;
dialkyl peroxides such as bis (2-t-butylperoxyisopropyl) benzene, diisopropylphenyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, and di-t-butyl peroxide;
diacyl peroxides such as dibenzoyl peroxide and bis (4-methylbenzoyl) peroxide;
peroxydicarbonates such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate;
peroxy esters such as 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate and t-butylperoxy-2-ethylhexanoate.
Examples of the azo compound include 2,2 ' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2 ' -azobis (2-cyclopropylpropionitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), and the like.
When a radical initiator is used, only one kind may be used, or two or more kinds may be used in combination.
When the paste resin composition of the present embodiment contains a radical initiator, the amount of the thermosetting component (the total amount of the (meth) acryloyl group-containing compound (a) and the thermosetting resin (C)) is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass, and more preferably 0.5 to 5 parts by mass, based on 100 parts by mass.
(solvent)
The paste resin composition of the present embodiment may further contain a solvent. The solvent can adjust the fluidity of the paste resin composition, for example, and improve workability in forming an adhesive layer on a substrate.
Typically, the solvent is an organic solvent.
Examples of the organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl methoxybutanol, α -terpineol, β -terpineol, hexylene glycol, benzyl alcohol, 2-phenylethyl alcohol, isopalmitol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, butyl tripropylene glycol (butyl propylene glycol), and glycerol;
ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5, 5-trimethyl-2-cyclohexene-1-one), and diisobutyl ketone (2, 6-dimethyl-4-heptanone);
esters such as ethyl acetate, butyl acetate, diethyl phthalate, dibutyl phthalate, acetoxyethane, methyl butyrate, methyl hexanoate, methyl octanoate, methyl decanoate, methyl cellosolve acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 1, 2-diacetoxyethane, tributyl phosphate, tricresyl phosphate, and tripentyl phosphate;
ethers such as tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1, 2-bis (2-diethoxy) ethane, 1, 2-bis (2-methoxyethoxy) ethane and the like;
ester ethers such as 2- (2-butoxyethoxy) ethane acetate;
ether alcohols such as 2- (2-methoxyethoxy) ethanol;
hydrocarbons such as toluene, xylene, n-alkane, iso-alkane, dodecylbenzene, turpentine, kerosene, and light oil;
nitriles such as acetonitrile and propionitrile;
amides such as acetamide and N, N-dimethylformamide;
and silicone oils such as low-molecular-weight volatile silicone oils and volatile organic-modified silicone oils.
When a solvent is used, only one solvent may be used, or two or more solvents may be used in combination.
When a solvent is used, the amount thereof is not particularly limited. The amount of the surfactant to be used may be appropriately adjusted based on the desired fluidity or the like. For example, the solvent is used in an amount such that the concentration of the nonvolatile component in the paste resin composition is 50 to 90 mass%.
(Properties of composition)
The paste resin composition of the present embodiment is preferably paste at 20 ℃. That is, the paste resin composition of the present embodiment can be applied to a substrate or the like at 20 ℃ as a paste. Therefore, the paste resin composition of the present embodiment can be preferably used as an adhesive for semiconductor devices or the like.
Of course, the paste resin composition of the present embodiment may be in the form of varnish having a relatively low viscosity, depending on the process to be applied.
< high thermal conductivity Material >
The paste resin composition of the present embodiment can be fired to obtain a highly thermally conductive material.
By changing the shape of the high thermal conductive material, the material can be applied to various members requiring heat dissipation in the fields of automobiles and motors.
< semiconductor device >
The paste resin composition of the present embodiment can be used to manufacture a semiconductor device. For example, a semiconductor device can be manufactured by using the paste resin composition of the present embodiment as an "adhesive" between a substrate and a semiconductor element.
In other words, the semiconductor device of the present embodiment includes, for example: a substrate; and a semiconductor element mounted on the substrate via an adhesive layer obtained by sintering the paste resin composition by heat treatment.
In the semiconductor device of the present embodiment, the adhesiveness and the like of the adhesive layer are less likely to be deteriorated by thermal cycle. That is, the semiconductor device of the present embodiment has high reliability.
Examples of the semiconductor element include an IC, an LSI, a power semiconductor element (power semiconductor), and various other elements.
Examples of the substrate include various semiconductor chips, lead frames, BGA substrates, mounting substrates, heat spreaders (heat sinks), and heat sinks (heat sinks).
An example of the semiconductor device is described below with reference to the drawings.
Fig. 1 is a cross-sectional view showing an example of a semiconductor device.
The semiconductor device 100 includes: a substrate 30; and a semiconductor element 20 mounted on the substrate 30 via an adhesive layer 10 (die bond material) which is a heat-treated body of a paste resin composition.
The semiconductor element 20 and the base 30 are electrically connected to each other via a bonding wire (bonding wire)40, for example. The semiconductor element 20 is sealed with, for example, a sealing resin 50.
The thickness of the adhesive layer 10 is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 20 μm or more. Therefore, the stress absorbing ability of the paste resin composition can be improved, and the heat cycle resistance can be improved.
The thickness of the adhesive layer 10 is, for example, 100 μm or less, preferably 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 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, Cu frame, or the like.
The substrate 30 may be an organic substrate or a ceramic substrate. Examples of the organic substrate include organic substrates made of epoxy resin, cyanate resin, maleimide resin, and the like.
The surface of the substrate 30 may be covered with a metal such as silver or gold. This improves the adhesion between the adhesive layer 10 and the substrate 30.
Fig. 2 is a cross-sectional view showing an example of the semiconductor device 100 different from that of fig. 1.
In the semiconductor device 100 of fig. 2, the substrate 30 is, for example, an interposer (interposer). A plurality of solder balls 52 are formed, for example, on the surface of the base 30 as an interposer 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.
An example of a method for manufacturing a semiconductor device will be described.
First, a paste resin composition is applied to a substrate 30, and then a semiconductor element 20 is disposed thereon. That is, the substrate 30, the paste resin composition, and the semiconductor element 20 are stacked in this order.
The method of applying the paste resin composition is not particularly limited. Specifically, a dispensing method (dispensing), a printing method, an ink jet method, and the like can be given.
Subsequently, the paste resin composition is thermally cured. The thermal curing is preferably carried out by pre-curing and post-curing. The paste resin composition is thermally cured to form a heat-treated product (cured product). By heat curing (heat treatment), the metal-containing particles in the paste resin composition are aggregated, and a structure in which the interface between a plurality of metal-containing particles disappears is formed in the adhesive layer 10. Accordingly, the base material 30 and the semiconductor element 20 are bonded via the adhesive layer 10. Next, the semiconductor element 20 and the base 30 are electrically connected by using the bonding wire 40. Next, the semiconductor element 20 is sealed with a sealing resin 50. Thus, a semiconductor device can be manufactured.
Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than the above-described configurations may be adopted. The present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within a range in which the object of the present invention can be achieved are included in the present invention.
Examples
Embodiments of the present invention will be described in detail based on examples and comparative examples. The present invention is not limited to the examples.
< preparation of paste resin composition >
First, the respective raw material components were mixed in the blending amounts shown in table-1 described later to obtain varnish.
Subsequently, the obtained varnish, solvent and metal-containing particles (including metal-coated resin particles) were mixed in the mixing amounts shown in table-1, and kneaded by a three-roll mill at room temperature. Thus, a paste resin composition was prepared.
The following shows the information of the raw material components in Table-1.
(thermosetting component)
Epoxy resin 1: bisphenol F type liquid epoxy resin (RE-303S, manufactured by Nippon Kabushiki Kaisha)
(curing agent)
Curing agent 1: phenol resin having bisphenol F skeleton (solid at room temperature 25 ℃ C., DIC-BPF manufactured by DIC Corporation)
(Compound containing (meth) acryloyl group)
Acrylic monomer 1: ethylene glycol dimethacrylate (manufactured by Kyori chemical Co., Ltd., LIGHT ESTER EG)
Acrylic monomer 2: polyethylene glycol #600 dimethacrylate (wherein n in the general formula (1) is 14) (manufactured by Nichisu oil Co., Ltd., PDE600)
Acrylic monomer 3: polyethylene glycol #600 dimethacrylate (wherein n in the general formula (1) is 14) (manufactured by Kyoho chemical Co., Ltd., LIGHT ESTER 14EG)
Acrylic monomer 4: polyethylene glycol #1000 diacrylate (n of the general formula (1) is 23) (manufactured by Xinzhongcun chemical Co., Ltd., A-1000)
(plasticizer)
Plasticizer 1: allyl resin (a polymer of bis (2-propenyl) 1, 2-cyclohexanedicarboxylate and propane-1, 2-diol, manufactured by Kanto chemical Co., Ltd.)
(curing accelerators)
Imidazole curing agent 1: 2-phenyl-1H-imidazole-4, 5-dimethanol (2 PHZ-PW, manufactured by Siguo Kasei Kogyo Co., Ltd.)
(polymerization initiator)
Radical polymerization initiator 1: diisopropylphenyl peroxide (Perkadox BC, manufactured by Kayaku Akzo Corporation)
(Metal-containing particles)
Silver particles 1: silver powder (HKD-38, manufactured by Futian Metal foil powder industries Co., Ltd., flakes, D) 50 ：4μm)
Silver-coated resin particles 1: silver-plated silicone resin particles (Heat-resistant/surface-treated 10 μm product, manufactured by Mitsubishi corporation, spherical, D) 50 : 10 μm, specific gravity: 2.3, the weight ratio of the silver is 50 wt%, and the weight ratio of the resin is 50 wt%)
(solvent)
Solvent 1: butyl tripropylene glycol (BFTG)
< determination of thermal conductivity λ >
The obtained paste resin composition was applied to a teflon plate, and the temperature was raised from 30 ℃ to 200 ℃ over 60 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ℃ for 120 minutes. Thus, a heat-treated product of a paste-like resin composition having a thickness of 1mm was obtained ("Teflon" is a registered trademark with respect to a fluororesin).
Next, the thermal diffusivity α in the thickness direction of the heat-treated body was measured by a laser flash method. The measurement temperature was 25 ℃.
The specific heat Cp is measured by Differential Scanning Calorimetry (DSC).
Further, the density ρ was measured according to JIS K6911.
Using these values, the thermal conductivity λ was calculated based on the following equation.
Thermal conductivity lambda [ W/(m.K)]＝α[m 2 /sec]×Cp[J/kg·K]×ρ[g/cm 3 ]
< determination of resistivity >
The obtained paste resin composition was applied to a glass plate, and the temperature was raised from 30 ℃ to 200 ℃ over 60 minutes under a nitrogen atmosphere, followed by heat treatment at 200 ℃ for 120 minutes. Thus, a heat-treated product of the paste resin composition having a thickness of 0.05mm was obtained. The resistance value of the surface of the heat-treated body was measured using an electrode having an electrode spacing of 40mm by a direct current four-electrode method based on a milliohm meter (manufactured by Hioki e.e. corporation).
Measurement of storage elastic modulus E' at < 25 ℃ >
The obtained paste resin composition was applied to a teflon plate, and the temperature was raised from 30 ℃ to 200 ℃ over 60 minutes, followed by heat treatment at 200 ℃ for 120 minutes. Thus, a heat-treated body of a heat-conductive composition having a thickness of 0.3mm was obtained.
The obtained heat-treated body was peeled from the teflon plate, set on a measuring apparatus (DMS 6100, manufactured by hitachi heigh technologies) and subjected to dynamic viscoelasticity measurement (DMA) under conditions of a tensile mode and a frequency of 1 Hz. Thus, the storage elastic modulus E' (MPa) at 25 ℃ was measured.
< determination of the breaking Strength >
The obtained paste resin composition was applied to a Teflon plate, and the temperature was raised from 30 ℃ to 200 ℃ over 60 minutes, followed by heat treatment at 200 ℃ for 120 minutes. Thus, a heat-treated body of a heat-conductive composition having a thickness of 0.3mm and a width of 4mm was obtained. The breaking strength of each test specimen at 25 ℃ was measured using a tensile tester ("MST-1" manufactured by shimadzu corporation).
< determination of fracture Strain >
The breaking strain was calculated by dividing the elongation from the origin of elongation (distance between the initial jigs) to the breaking point of each test piece (displacement amount at breaking of the test piece) by the distance between the initial jigs.
< determination of fracture energy >
The energy at the breaking point was calculated by integrating the stress from the origin of elongation (distance between the initial jigs) to the breaking point of each test piece (amount of displacement at breaking of the test piece) by displacement. The obtained energy at break point was divided by the volume of the test piece to obtain the energy at break point per unit volume (mJ/mm) 3 )。
< evaluation of Heat cycle test/Presence of peeling >
A paste resin composition was applied onto a substrate having a silver-plated surface to form a coating film, and a 7X 7mm silicon chip having a gold-plated surface was placed on the coating film. Thereafter, the temperature was raised from 30 ℃ to 200 ℃ over 60 minutes, followed by heat treatment at 200 ℃ for 120 minutes. Thereby, the thermally conductive composition is cured, and the silicon chip is bonded to the substrate.
The bonded silicon chip/substrate was sealed with a sealing material EME-G700ML-C (manufactured by Sumitomo Bakelite Co., Ltd.). This was used as a sample for temperature cycle test.
The sample was placed in a high-temperature and high-humidity chamber at 60 ℃/60% RH for 48 hours, and then reflow treatment was performed at 260 ℃.
The samples after the reflow treatment were put into a temperature cycle tester TSA-72ES (manufactured by ESPEC CORP.) and subjected to 2000 cycles of (i)150 ℃/10 minutes, (ii)25 ℃/10 minutes, (iii) -65 ℃/10 minutes, and (iv)25 ℃/10 minutes.
Thereafter, the presence or absence of peeling was confirmed by SAT (ultrasonic testing). The case of non-peeling was evaluated as "good", and the case of peeling was evaluated as "poor".
[ Table 1]
TABLE-1
Figure BDA0003769535590000191
From the results in table-1, it is understood that by joining a semiconductor element and a substrate using the paste resin composition of the present invention, a semiconductor device exhibiting good conductivity over a long period of time and excellent long-term reliability can be obtained.
The present application claims priority based on Japanese application laid-open No. 2020-012506, filed on 29/1/2020, and the entire disclosure thereof is incorporated herein by reference.

Claims (7)

1. A paste resin composition, comprising:
(A) a (meth) acryloyl group-containing compound having a functionality of 2 or more, the number of repeating units of a linear or branched oxyalkylene group being 2 or more; and
(B) a metal-containing particle comprising a silver-containing particle or a copper-containing particle.
2. The paste resin composition according to claim 1, wherein:
the (meth) acryloyl group-containing compound (A) contains at least one compound selected from the group consisting of compounds represented by the following general formula (1),
Figure FDA0003769535580000011
in the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a plurality of R may be the same or different, X represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a mercapto group, a carboxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, a plurality of X may be the same or different, m represents an integer of 2 to 10, and n represents an integer of 4 to 30.
3. The paste resin composition according to claim 1 or 2, wherein:
further contains a thermosetting resin (C) excluding the (meth) acryloyl group-containing compound (A).
4. The paste resin composition according to claim 3, wherein:
the thermosetting resin (C) contains an epoxy resin.
5. The paste resin composition according to claim 3 or 4, wherein:
further contains a curing agent (D).
6. A high thermal conductivity material characterized by:
which is obtained by firing the paste resin composition according to any one of claims 1 to 5.
7. 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 obtained by sintering the paste resin composition according to any one of claims 1 to 5.
CN202180011544.6A 2020-01-29 2021-01-21 Paste resin composition, highly thermally conductive material, and semiconductor device Pending CN115023453A (en)

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