TW202100703A - Semiconductor package, manufacturing method of semiconductor package and thermoconductive composition used for the same - Google Patents

Abstract

A semiconductor package of the present invention is provided with: a substrate; a semiconductor element provided on the substrate; and a heat spreader surrounding the periphery of the semiconductor element, wherein the semiconductor element and the heat spreader are bonded with a thermally conductive material having a particle connecting structure in which metal particles are formed through sintering by heat treatment.

Description

Semiconductor package, manufacturing method of semiconductor package, and thermal conductive composition used therefor

The present invention relates to a semiconductor package, a method of manufacturing a semiconductor package, and a thermally conductive composition used therefor.

So far, various developments have been made in semiconductor packages with thermal conductors. As these techniques, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes a semiconductor package in which a semiconductor element (heater) and a heat sink mounted on an electronic circuit board are connected via a thermally conductive double-sided tape (a thermally conductive material composed of an adhesive) (patent Example 7 of Document 1, Figure 16).

Patent Document 1: International Publication No. 2015/072428

However, as a result of research conducted by the present inventors, it is clear that the semiconductor package described in Patent Document 1 has room for improvement in terms of heat dissipation characteristics.

At present, the amount of heat generated by semiconductor elements (heating elements) has increased with higher performance. Therefore, semiconductor packages are required to further improve heat dissipation characteristics. According to the results of research on this situation, it was found that even if a thermoplastic gel dispersed with acrylic adhesive, boron nitride, aluminum oxide, or zinc oxide is used as a thermal conductive material for bonding heat dissipation members such as semiconductor elements and heat sinks, It is also unable to obtain sufficient thermal conductivity.

As a result of further research, the inventors found that by using a particle-connected structure formed by sintering metal particles by heat treatment as a thermally conductive material, the thermal conductivity of the thermally conductive material can be improved, and the semiconductor element and heat can be integrated The components are joined, and therefore the heat dissipation characteristics in the semiconductor package can be improved, thereby completing the present invention.

According to the present invention, a semiconductor package is provided, which includes a substrate, a semiconductor element provided on the substrate, and a heat sink surrounding the semiconductor element, and the semiconductor element and the heat sink are joined by a thermally conductive material. In the package, the aforementioned thermally conductive material has a particle connection structure formed by sintering metal particles by heat treatment.

In addition, according to the present invention, there is provided a thermally conductive composition used to form the thermally conductive material in a semiconductor package, the semiconductor package having a substrate, a semiconductor element disposed on the substrate, and heat dissipation surrounding the semiconductor element And use a thermally conductive material to join the aforementioned semiconductor element and the aforementioned heat sink. The thermally conductive composition contains: Metal particles Adhesive resin; and monomer, The metal particles are sintered by heat treatment to form a particle connection structure.

Furthermore, according to the present invention, there is provided a method for manufacturing a semiconductor package, which includes: The step of arranging semiconductor elements on one side of the substrate so that the other side of the substrate is on the opposite side; The step of coating a thermally conductive composition containing metal particles on the surface of one side of the aforementioned semiconductor element; The step of arranging a heat sink in contact with the aforementioned thermally conductive composition and covering at least one side of the aforementioned semiconductor element; The step of heating the structure including the aforementioned substrate, semiconductor element, thermally conductive composition and aforementioned heat sink, In the step of the heating treatment, the semiconductor element and the heat sink are joined via a thermally conductive material containing a particle connection structure formed by sintering the metal particles. [Invention Effect]

According to the present invention, a semiconductor package with excellent heat dissipation characteristics, a method for manufacturing the semiconductor package, and a thermally conductive composition for the semiconductor package are provided.

Hereinafter, the embodiments of the present invention will be described using drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description is appropriately omitted. In addition, the drawing is a schematic drawing and does not match the actual size ratio.

The outline of the semiconductor package of this embodiment will be described. FIG. 1 is a cross-sectional view schematically showing an example of the semiconductor package of this embodiment.

The semiconductor package 100 of this embodiment includes a substrate 10, a semiconductor element 20, a heat sink 30, and a thermally conductive material 50. The semiconductor element 20 is provided on the substrate 10, the heat sink 30 surrounds the semiconductor element 20, and the thermal conductive material 50 joins the semiconductor element 20 and the heat sink 30. In this type of semiconductor package 100, the thermally conductive material 50 has a particle connection structure formed by sintering metal particles by heat treatment.

Regarding the particle connection structure in the thermally conductive material 50, at least one cross section when the thermally conductive material 50 is cut in the stacking direction of the semiconductor element 20 and the heat sink 30 can be observed with various microscopes such as a scanning electron microscope.

In the predetermined region of the cross section of the thermally conductive material 50, there is a structure in which a plurality of metal particles are connected in a state where the interface disappears. With the connection structure of such metal particles, the thermal conductivity of the thermally conductive material 50 can be improved.

In addition, in at least a part of the bonding surface of the thermally conductive material 50 and the semiconductor element 20 or the bonding surface of the thermally conductive material 50 and the heat sink 30, the thermally conductive material 50 can pass through the metal particles and the surface of the semiconductor element 20 or the heat sink. The surface of 30 has a joining structure.

According to this embodiment, by using as the thermally conductive material a particle-connected structure formed by sintering metal particles by heat treatment, the thermal conductivity of the thermally conductive material can be improved, and the semiconductor element and the heat dissipation member can be joined, thereby improving Heat dissipation characteristics in semiconductor packages.

Hereinafter, the semiconductor package 100 will be described in detail.

The semiconductor package 100 of FIG. 1 includes a substrate 10, a semiconductor element 20, a heat sink 30 and a thermally conductive material 50.

The semiconductor device 20 may be, for example, a logic chip, a memory chip, or an LSI chip formed by mixing a memory circuit and a logic circuit. The semiconductor element 20 may be constituted by a BGA type package.

The semiconductor element 20 is mounted on the substrate 10 and is electrically connected to the substrate 10. The semiconductor element 20 may be connected to the substrate 10 via a flip chip. In this case, the semiconductor element 20 is soldered to the substrate 10 via the solder balls 60. An underfill material 70 may be filled in the gap between the semiconductor element 20 and the substrate 10. Known underfill material 70 can be used, but it may be a sealing material or a chip adhesive material.

For the substrate 10, a printed circuit board or the like can be used, for example. One or two or more semiconductor elements 20 may be mounted on one surface of the substrate 10. Moreover, electronic components and heat source bodies other than the semiconductor element 20 may be mounted on one surface of the substrate 10. On the other hand, the other surface of the substrate 10 (the surface on the side opposite to one of the surfaces) may have a connection structure capable of connecting with other substrates. As the connection structure, for example, solder balls, pin connectors, and the like can be given.

The heat sink 30 may be formed of a member that radiates heat from a heating element such as the semiconductor element 20, and for example, may be formed of a metal material. As a metal material, copper, aluminum, stainless steel, etc. are mentioned, for example. These can be used alone or in combination of two or more kinds. The heat sink 30 may have a material with high thermal conductivity other than a metal material, for example, graphite or the like may be contained inside.

The heat sink 30 may use a metal layer composed of the above-mentioned metal material, and may be composed of a single layer thereof, or may be composed of a laminated structure in which a plurality of layers are laminated. In addition, at least the surface of the heat sink 30 that is joined to the thermally conductive material 50 may expose the above-mentioned metal materials, but other metals may also be used for electroplating. For example, the plating film can be formed of nickel, gold, alloys containing these as main components, or these laminated films. Thereby, the rust resistance of the radiator 30 can be improved.

The shape of the heat sink 30 is not particularly limited as long as it is a cover structure covering the semiconductor element 20. The heat sink 30 is constituted by a case with an opening on the surface facing the semiconductor element 20. Specifically, the heat sink 30 may have: a plate-shaped portion having the other surface facing the semiconductor element 20; and a side wall portion protruding from the other surface of the plate-shaped portion to cover the semiconductor element 20 The way around the side of the plate is set around the plate-shaped member. Regarding the cross-sectional structure of the heat sink 30, when viewed from the cross section in the stacking direction of the semiconductor element 20 and the heat sink 30, for example, it may have a substantially "U" shape.

A part of the heat sink 30 may be bonded to the substrate 10 via an adhesive. For example, the tip of the side wall of the heat sink 30 may be bonded to one surface of the substrate 10 using an adhesive. As the adhesive, a known one can be used.

The thermally conductive material 50 is interposed between one surface of the semiconductor element 20 and the other surface of the heat sink 30 facing the one surface, and joins them.

The thermally conductive material 50 has a particle connection structure formed by sintering metal particles by heat treatment. The thermally conductive material 50 can be formed using a thermally conductive composition having a particle connection structure formed by sintering metal particles by heat treatment. The details of the thermally conductive composition will be described later.

The above-mentioned metal particles may include particles made of metal. The above-mentioned metal particles may include, for example, particles composed of a metal composed of one or more selected from the group consisting of silver, gold, and copper.

In addition, the lower limit of the thermal conductivity of the thermally conductive material 50 is, for example, 10 W/mK or more, preferably 15 W/mK or more, and more preferably 20 W/mK or more. Thereby, the heat dissipation characteristics of the semiconductor package 100 can be improved. On the other hand, the upper limit of the thermal conductivity of the thermally conductive material 50 may be 200 W/mK or less, or may be 150 W/mK or less, for example. The thermal conductivity can be obtained by measuring in the thickness direction at 25°C using the laser flash method.

The lower limit of the average particle diameter D ₅₀ of the particles made of metal is, for example, 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. This can improve thermal conductivity. On the other hand, the upper limit of the average particle diameter D ₅₀ of the particles made of metal is, for example, 7.0 μm or less, preferably 5.0 μm or less, and more preferably 4.0 μm or less. Thereby, the sinterability between metal particles can be improved. In addition, it is possible to improve the uniformity of sintering. The average particle diameter D _{50 of the} aforementioned metal-made particles can be used as the average particle diameter D _{50 of} silver particles.

The upper limit of the standard deviation of the particle diameter of the particles made of metal is 2.0 μm or less, preferably 1.9 μm or less, and more preferably 1.8 μm or less. This can improve the uniformity during sintering. On the other hand, the lower limit of the standard deviation of the particle diameter of the particles made of metal is not particularly limited, but may be, for example, 0.1 μm or more and 0.3 μm or more.

Furthermore, the metal particles may include metal-coated resin particles composed of resin particles and a metal formed on the surface of the resin particles. The metal particles can include any one of metal-coated resin particles and particles made of metal, but it is more preferable to include both. By using metal-coated resin particles, although the detailed mechanism is unclear, it is possible to improve the adhesion with the surface of the heat sink 30 on the other side of the nickel-plated heat sink 30.

The thermally conductive material 50 may be composed of only a particle-connected structure of metal particles, but may also have a particle-connected structure and resin existing in the structure. Thereby, the thermal conductivity can be improved while reducing the storage elastic modulus.

The upper limit of the storage elastic modulus at 25°C of the thermally conductive material 50 is, for example, 10.0 GPa or less, preferably 9 GPa or less, and more preferably 8 GPa or less. This can reduce the elasticity of the thermally conductive material 50, and therefore can suppress the generation of cracks due to stress and strain and the decrease in adhesion. The upper limit of the storage elastic modulus at 25°C of the thermally conductive material 50 may be, for example, 1 GPa or more, preferably 2 GPa or more, and more preferably 3 GPa or more. Thereby, the thermally conductive material 50 excellent in durability can be realized. The storage elastic modulus can be obtained by measuring the dynamic viscoelasticity (DMA) at a frequency of 1 Hz.

The thermally conductive material 50 may be formed on at least a part or the entire surface of the semiconductor element 20.

As shown in FIG. 1, the semiconductor package 100 may further include a heat sink 80 and a thermally conductive material 90.

The heat sink 80 can be connected to the heat sink 30 via the thermally conductive material 90. As the thermally conductive material 90, a known material can be used, for example, grease can be used.

The heat sink 80 may be formed of a member having excellent heat dissipation properties. For example, a material used in the heat sink 30 may also be used. The heat sink 80 may have a plurality of fins.

Hereinafter, each component of the thermally conductive composition of this embodiment will be described in detail.

The aforementioned thermally conductive composition is used to form a thermally conductive material 50 in a semiconductor package. The semiconductor package includes a substrate, a semiconductor element 20 provided on the substrate 10, and a heat sink 30 surrounding the semiconductor element 20, and uses the thermally conductive material 50 The semiconductor element 20 and the heat sink 30 are joined. The above-mentioned thermally conductive composition is one that sinters metal particles by heat treatment to form a particle-connected structure, whereby the thermally conductive material 50 can be formed.

The thermally conductive composition of this embodiment contains the aforementioned metal particles, binder resin, and monomers. Although the detailed mechanism is not clear, it is thought that if the volume of the composition shrinks due to the volatilization of monomers due to heating, stress is applied in the direction in which the metal particles approach each other, and the interface between the metal particles disappears, forming a connection structure of the metal particles. In addition, it is considered that when such metal particles are sintered, the binder resin, or the resin cured product such as the binder resin and the curing agent or monomer, remains inside or outside the connection structure. Furthermore, it is believed that the hardening reaction generates a force such as agglomeration of a plurality of metal particles.

By heat-treating the above-mentioned thermally conductive composition, it is possible to achieve a combination of "particle-connected structure of metal particles" and "resin components composed of binder resin, its hardened product, and resin particles in metal-coated resin particles." Next layer (thermally conductive material 50).

Furthermore, using the thermally conductive composition, the lower limit of the thermal conductivity λ measured in the following step A is, for example, 10 W/mK or more, preferably 15 W/mK or more, and more preferably 20 W/mK or more. Thereby, the heat dissipation characteristics of the semiconductor package 100 can be improved. On the other hand, the upper limit of the thermal conductivity of the thermal conductivity λ may be 200 W/mK or less, or 150 W/mK or less, for example. (Step A) It took 60 minutes to raise the temperature of the thermally conductive composition from 30°C to 200°C, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body with a thickness of 1 mm. For the obtained heat-treated body, use the laser flash method to measure the thermal conductivity λ (W/mK) at 25°C.

Using the thermally conductive composition, the upper limit of the storage elastic modulus E at 25°C measured in the following step B is, for example, 10 GPa or less, preferably 9 GPa or less, and more preferably 8 GPa or less. This can reduce the elasticity of the thermally conductive material 50, and therefore can suppress the generation of cracks due to stress and strain and the decrease in adhesion. The upper limit of the storage elastic modulus E at 25°C may be, for example, 1 GPa or more, preferably 2 GPa or more, and more preferably 3 GPa or more. Thereby, the thermally conductive material 50 excellent in durability can be realized. The storage elastic modulus can be obtained by measuring the dynamic viscoelasticity (DMA) at a frequency of 1 Hz.

(Metal particles) The thermally conductive composition of this embodiment contains metal particles. The metal particles can be sintered by heat treatment to form a particle connection structure (sintered structure).

The metal particles can use metal-coated resin particles, particles made of metal, and the like. The above-mentioned metal particles may include any of metal-coated resin particles and particles composed of metal, but it is more preferable to include both.

By using the above-mentioned metal-coated resin particles, it is possible to appropriately reduce the storage elastic modulus while suppressing the decrease in the sinterability of the metal particles. By using the above-mentioned particles made of metal, the sinterability of the metal particles can be improved, and the thermal conductivity can be appropriately increased.

The metal-coated resin particles are composed of resin particles and a metal formed on the surface of the resin particles. That is, the metal-coated resin particles may be particles obtained by coating the surface of the resin particles with a metal layer.

In this specification, the surface of the metal layer-coated resin particle refers to the state where the metal layer covers at least a part of the surface of the resin particle, and is not limited to covering the entire surface of the resin particle. For example, it may include a metal layer partially covering the surface. State, covering the whole surface when viewed from a specific section. Among them, from the viewpoint of thermal conductivity, it is preferable that the metal layer covers the entire surface when viewed from a specific cross-section, and it is more preferable to cover the entire surface of the particles.

The metal in the metal-coated resin particles can include, for example, one or more selected from the group consisting of silver, gold, nickel, and tin. These can be used alone or in combination of two or more kinds. Alternatively, alloys containing these metals as main components can be used. Among them, silver can be used from the viewpoint of sinterability and thermal conductivity.

Regarding the resin material constituting the resin particles (core resin particles) in the metal-coated resin particles, for example, silicone, acrylic, phenol, polystyrene, melamine, polyamide, polytetrafluoroethylene, etc. can be cited. These can be used alone or in combination of two or more kinds. The resin particles can be composed of polymers using these. The polymer may be a homopolymer or a copolymer with these as main components. From the standpoint of elastic properties and heat resistance, silicone resin particles and acrylic resin particles can be used as the resin particles.

The above-mentioned polysiloxane resin particles may be particles composed of organopolysiloxane obtained by polymerizing organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, dimethyldichlorosilane, etc., or may be A polysiloxane resin particle with a structure formed by further three-dimensional crosslinking of the organopolysiloxane as the basic skeleton.

In addition, various functional groups can be introduced into the structure of the silicone resin particles. Examples of functional groups that can be introduced include epoxy groups, amino groups, methoxy groups, phenyl groups, carboxyl groups, hydroxyl groups, alkyl groups, and vinyl groups. , Mercapto groups, etc., but are not limited to these. In addition, in this embodiment, other low-stress modifiers can be added to the silicone resin particles within a range that does not impair the characteristics. As other low-stress modifiers that can be used simultaneously, butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid Liquid synthetic rubbers such as organopolysiloxane and liquid polybutadiene are not limited to these.

The shape of the resin particles is not particularly limited, and may be spherical, but may also have a different shape other than spherical, for example, flat (flake), plate, or needle. In the case where the shape of the metal-coated resin particles is formed into a spherical shape, it is preferable that the shape of the resin particles used is also spherical. In addition, as described above, the sphere is not limited to a perfect sphere, but also includes a shape close to a sphere such as an ellipse, and a shape with a number of irregularities on the surface.

The lower limit of the specific gravity of the metal-coated resin particles is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. This can further improve the thermal conductivity and electrical conductivity of the adhesive layer. In addition, the upper limit of the specific gravity of the metal-coated resin particles is, for example, 10 or less, preferably 9 or less, and more preferably 8 or less. Thereby, the dispersibility of particles can be improved. The aforementioned specific gravity may be the specific gravity of metal particles including metal-coated resin particles and particles made of metal.

The metal-coated resin particles may be monodisperse particles or polydisperse particles. In addition, in the particle size frequency distribution, the metal-coated resin particles may have one peak or two or more peaks.

The particles composed of metal may be particles composed of one or more types of metal materials, and the core part and the surface layer part may be composed of the same or different types of metal materials. The metal material can include, for example, one or more selected from the group consisting of silver, gold, and copper. These can be used alone or in combination of two or more kinds. Alternatively, alloys containing these metals as main components can be used. Among them, silver can be used from the viewpoint of sinterability and thermal conductivity.

The shape of the particles made of metal may be spherical or flake-like, for example. The above-mentioned particles made of metal can include either or both of spherical particles and plate-shaped particles.

Regarding one aspect of the metal particles, the metal-coated resin particles include silver-coated silicone resin particles and metal-made particles include silver particles. In addition to silver-coated silicone resin particles, silver-coated acrylic resin particles can also be used from the viewpoint of elastic properties. In addition to silver particles, particles containing metal components other than silver, such as gold particles, copper particles, etc., can be used at the same time for the purpose of promoting sintering or reducing costs.

The lower limit of the average particle diameter D ₅₀ of the metal-coated resin particles may be, for example, 0.5 μm or more, preferably 1.5 μm or more, and more preferably 2.0 μm or more. Thereby, the storage elastic modulus can be reduced. On the other hand, the upper limit of the average particle diameter D ₅₀ of the metal-coated resin particles may be, for example, 20 μm or less, 15 μm or less, or 10 μm or less. This can improve thermal conductivity. The metallic coating resin particles having an average particle diameter D ₅₀ may be used as a silver coating polyethylene silicone particles, acrylic resin coating the silver particles having an average particle diameter D _50.

The lower limit of the average particle diameter D ₅₀ of the particles made of metal is, for example, 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. This can improve thermal conductivity. On the other hand, the upper limit of the average particle diameter D ₅₀ of the particles made of metal is, for example, 7.0 μm or less, preferably 5.0 μm or less, and more preferably 4.0 μm or less. Thereby, the sinterability between metal particles can be improved. In addition, it is possible to improve the uniformity of sintering. The average particle diameter D _{50 of the} aforementioned metal-made particles can be used as the average particle diameter D _{50 of} silver particles. And, on the particles made of a metal, it may comprise ₅₀ or more kinds of those having different particle sizes D. This can improve the sinterability.

In addition, the average particle diameter D _{50 of the} metal particles can be determined by, for example, particle image measurement using a flow-type particle image analyzer FPIA (registered trademark)-3000 manufactured by Sysmex Corporation. More specifically, the particle diameter of the metal particles can be determined by measuring the volume-based median diameter using the above-mentioned device.

The content of the metal-coated resin particles is, for example, 1% by mass to 50% by mass, preferably 3% by mass to 45% by mass, more preferably 5% by mass to 40% by mass relative to the entire metal particles (100% by mass) . The storage elastic modulus can be reduced by setting it to be higher than the above lower limit. By setting it below the above upper limit value, the thermal conductivity can be improved. In this specification, unless otherwise specified, "~" means that the upper limit and the lower limit are included.

The content of the metal particles is 1% to 98% by mass relative to the entire thermally conductive composition (100% by mass), preferably 30% to 95% by mass, and more preferably 50% to 90% by mass. By setting it as the above-mentioned lower limit or more, thermal conductivity can be improved. By setting it below the above upper limit value, it is possible to improve coatability and workability at the time of sticking.

(Adhesive resin) The said thermally conductive composition contains binder resin. The said binder resin can contain 1 or more types chosen from the group which consists of an epoxy resin, an acrylic resin, and an allyl resin. These can be used alone or in combination of two or more kinds.

Specific examples of the above-mentioned binder resin include: acrylic resins such as acrylic oligomers and acrylic polymers; epoxy resins such as epoxy oligomers and epoxy polymers; allyl oligomers and allyl Allyl resins such as base polymers. These can be used alone or in combination of two or more kinds. In addition, those with a weight average molecular weight of less than 10,000 are defined as oligomers, and those with a weight average molecular weight of 10,000 or more are defined as polymers.

As said epoxy resin, the epoxy resin which has 2 or more epoxy groups in a molecule|numerator can be used. The epoxy resin can be liquid at 25°C. Thereby, the handleability of the thermally conductive composition can be improved. In addition, the hardening shrinkage can be appropriately adjusted.

Regarding specific examples of the aforementioned epoxy resins, for example, trisphenol methane type epoxy resins; hydrogenated bisphenol A type liquid epoxy resins; bisphenol F type liquid epoxy resins such as bisphenol-F-dieglycidyl ether Oxygen resin; o-cresol novolac type epoxy resin, etc. These can be used alone or in combination of two or more kinds. Among them, hydrogenated bisphenol A type liquid epoxy resin or bisphenol F type liquid epoxy resin can be used. As the bisphenol F type liquid epoxy resin, for example, bisphenol-F-dieglycidyl ether can be used.

As the above-mentioned acrylic resin, an acrylic resin having two or more acrylic groups in the molecule can be used. The acrylic resin may be liquid at 25°C. As the acrylic resin, specifically, those obtained by (co)polymerizing an acrylic monomer can be used. Here, the method of (co)polymerization is not limited, and a known method using general polymerization initiators and chain transfer agents, such as solution polymerization, can be used.

As the allyl resin, an allyl resin having two or more allyl groups in one molecule can be used. The allyl resin can be liquid at 25°C.

As said allyl resin, specifically, the allyl ester resin obtained by reacting dicarboxylic acid, allyl alcohol, and the compound which has an allyl group is mentioned. Here, as the above-mentioned dicarboxylic acid, specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc. In addition, as the compound having the above allyl group, specifically, polyether, polyester, polycarbonate, polyacrylate, polymethacrylate, polybutadiene, butadiene having an allyl group can be mentioned. Acrylonitrile copolymer, etc.

The lower limit of the content of the binder resin with respect to 100 parts by mass of the thermally conductive composition is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. Thereby, the adhesiveness with the adherend can be improved. On the other hand, with respect to 100 parts by mass of the thermally conductive composition, the upper limit of the content of the binder resin is, for example, 15 parts by mass or less, preferably 12 parts by mass or less, and more preferably 10 parts by mass or less. This can suppress a decrease in thermal conductivity.

(monomer) The said thermally conductive composition contains a monomer. Regarding the above-mentioned monomers, one or two or more selected from the group consisting of diol monomers, acrylic monomers, epoxy monomers, and maleimide monomers can be included. These can be used alone or in combination of two or more kinds. By using the above-mentioned monomer, the volatilization state of the above-mentioned thermally conductive composition when heat-treated can be adjusted. In addition, by appropriately selecting the combination with the binder resin and the curing agent, the above-mentioned monomer can undergo a curing reaction with these, and the curing shrinkage state can be adjusted.

Specific examples of the above-mentioned diol monomer include: a diol having two hydroxyl groups in the molecule, and the two hydroxyl groups are bonded to different carbon atoms; the diol and two or more A compound obtained by condensation of an alcohol; a compound obtained by condensation of the alcohol with a hydrogen atom in the hydroxyl group being substituted with an organic group having 1 to 30 carbon atoms to form an alkoxy group.

As the above-mentioned glycol monomer, specifically, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol Mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, ethylene two Alcohol monobenzyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n Butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monobenzyl ether, triethylene glycol, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol mono-n-butyl ether, 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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-butyl ether, etc. These can be used alone or in combination of two or more kinds. Among them, from the viewpoint of volatility, tripropylene glycol mono-n-butyl ether or ethylene glycol mono-n-butyl acetate can be used.

As the lower limit of the boiling point of the aforementioned diol monomer, for example, 100°C or higher is preferred, 130°C or higher is more preferred, 150°C or higher is more preferred, 170°C or higher is even more preferred, and 190°C or higher is particularly preferred. In addition, as the upper limit of the boiling point of the diol monomer, for example, it may be 400°C or lower, or 350°C or lower. In addition, the boiling point of the diol monomer means the boiling point under atmospheric pressure (101.3 kPa).

As said acrylic monomer, the monomer which has a (meth)acrylic group in a molecule|numerator is mentioned. Here, the (meth)acrylic group means an acrylic group and a methacrylic group. The acrylic monomer may be a monofunctional acrylic monomer having only one (meth)acrylic group in the molecule, or a multifunctional acrylic monomer having two or more (meth)acrylic groups in the molecule.

As the above-mentioned monofunctional acrylic monomer, specifically, 2-phenoxyethyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate can be mentioned. Butyl ester, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-laurel (meth)acrylate Esters, n-tridecyl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxy Diethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 2-ethylhexyl diethylene glycol (meth)acrylate, methoxy polyethylene glycol ( Meth) acrylate, methoxydipropylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Phenoxyethyl, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenol ethylene oxide modified (meth)acrylate, benzene Base phenol ethylene oxide modification (meth)acrylate, (meth)isobornyl acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylate Base) dimethylaminoethyl acrylate quaternary compound, glycidyl (meth)acrylate, neopentyl glycol (meth)acrylate benzoate, 1,4-cyclohexanedimethanol mono(methyl) ) Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate Propyl ester, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxyethyl phthalic acid, 2- (Methyl)acryloxyethyl-2-hydroxyethylphthalic acid and 2-(meth)acryloxyethyl acid phosphate, etc.

Specific examples of the multifunctional acrylic monomer include ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propoxylated bisphenol A bis(meth) Acrylate, hexane-1,6-diol bis(2-(meth)acrylate), 4,4'-isopropylidene diphenol bis(meth)acrylate, 1,3-butanedi Alcohol di(meth)acrylate, 1,6-bis((meth)acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, 1,4- Bis((meth)acryloxy)butane, 1,6-bis((meth)acryloxy)hexane, triethylene glycol di(meth)acrylate, neopentyl glycol di( Meth)acrylate, neopentyl glycol di(meth)acrylate, N,N'-bis(meth)acryloylethylenediamine, N,N'-(1,2-dihydroxyethylene)bis (Meth)acrylamide or 1,4-bis((meth)acryloyl)piperidin, etc.

As the acrylic monomer, a monofunctional acrylic monomer or a multifunctional acrylic monomer can be used alone, or a monofunctional acrylic monomer and a multifunctional acrylic monomer can be used together. As the acrylic monomer, for example, it is preferable to use a multifunctional acrylic monomer alone.

The above-mentioned epoxy monomer is a monomer having an epoxy group in the molecule. The epoxy monomer may be a monofunctional epoxy monomer having only one epoxy group in the molecule, or a multifunctional epoxy monomer having two or more epoxy groups in the molecule.

As the above-mentioned monofunctional epoxy monomer, specifically, 4-tertiary butylphenyl glycidyl ether, m-cresol glycidyl ether, p-cresol glycidyl ether, Phenyl glycidyl ether, cresyl glycidyl ether, etc.

Specific examples of the above-mentioned polyfunctional epoxy monomer include: bisphenol compounds such as bisphenol A, bisphenol F, and biphenol or derivatives thereof; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol Phenol, cyclohexanediol, cyclohexanedimethanol, cyclohexanedimethanol, and other diols with alicyclic structure or their derivatives; using butanediol, hexanediol, octanediol, nonanediol Aliphatic diols such as decanediol, or derivatives of these difunctional ones obtained by epoxidation; those having tri-functional trihydroxyphenylmethane skeleton and aminophenol skeleton; using novolak resin, cresol phenolic Varnish resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins and other polyfunctional ones obtained by epoxidation.

The above-mentioned maleimide monomer is a monomer having a maleimide ring in the molecule. The above-mentioned maleimide monomer may be a monofunctional maleimide monomer having only one maleimide ring in the molecule, or it may have two or more in the molecule The multifunctional maleimide monomer of the maleimide ring. Specific examples of the maleimide monomer include polytetramethylene ether glycol-bis(2-maleimide acetate) and the like.

The lower limit of the content of the above-mentioned monomer with respect to 100 parts by mass of the thermally conductive composition is, for example, 0.5 parts by mass or more, preferably 1.0 parts by mass or more, and more preferably 2.0 parts by mass or more. On the other hand, with respect to 100 parts by mass of the thermally conductive composition, the upper limit of the content of the monomer is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less.

(hardener) If necessary, the above-mentioned thermally conductive composition may contain a hardening agent. The above-mentioned hardener has a reactive group that reacts with the monomer and the functional group in the binder resin. As the reactive group, for example, an epoxy group, a maleimide group, a hydroxyl group, etc. reacted with a functional group can be used.

Specifically, in the case where the monomer contains an epoxy monomer or/and the binder resin contains an epoxy resin, a phenol resin-based curing agent or an imidazole-based curing agent can be used as the above-mentioned curing agent.

Specific examples of the phenol resin curing agent include novolac type phenol resins such as novolak resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenol novolak resin; polyvinyl phenol; three Multifunctional phenol resins such as phenylmethane type phenol resin; modified phenol resins such as terpene modified phenol resin, dicyclopentadiene modified phenol resin, etc.; phenol aromatic with phenylene skeleton and/or biphenylene skeleton Phenol aralkyl type phenol resins such as alkyl resins and naphthol aralkyl resins with phenylene and/or biphenylene skeletons; bisphenol compounds such as bisphenol A and bisphenol F (dihydroxydiphenylmethane) (Phenolic resin with bisphenol F skeleton); 4,4'-biphenol and other compounds with biphenylene skeleton. These can be used alone or in combination of two or more kinds. Among them, a phenol aralkyl resin can be used, and as a phenol aralkyl resin, a phenol•para-stubble dimethyl ether condensation polymer can be used.

As the imidazole curing agent, specifically, 2-phenyl-1H-imidazole-4,5-dimethanol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methyl Imidazole, 2-Phenylimidazole, 2,4-Diamine-6-[2-Methylimidazolyl-(1)]-Ethyl-Symmetric Tris, 2-Undecylimidazole, 2-Heptadecylimidazole , 2,4-Diamine-6-[2-Methylimidazolyl-(1)]-ethyl-symmetric triisocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct Product, 2-methylimidazole isocyanuric acid adduct, 1,2,4- trimellitic acid 1-cyanoethyl-2-phenylimidazolium, 1,2,4- trimellitic acid 1- Cyanoethyl-2-undecylimidazolium and the like. These can be used alone or in combination of two or more kinds.

The content of the curing agent may be, for example, 5 parts by mass to 50 parts by mass, or 20 parts by mass to 40 parts by mass relative to 100 parts by mass of the binder resin in the thermally conductive composition. In addition, the content of the curing agent may be, for example, 1 part by mass to 40 parts by mass, or may be 100 parts by mass of epoxy resin in the thermally conductive composition or 100 parts by mass of the total of epoxy resin and epoxy monomer 10 parts by mass to 35 parts by mass.

(Free radical polymerization initiator) The above-mentioned thermally conductive composition may contain a radical polymerization initiator. As the radical polymerization initiator, azo compounds, peroxides, and the like can be used.

Specific examples of the above-mentioned peroxide include bis(1-phenyl-1-methylethyl) peroxide, 1,1-bis(1,1-dimethylethylperoxy) ring Hexane, methyl ethyl ketone peroxide, cyclohexane peroxide, acetone peroxide, 1,1-bis(tertiary hexylperoxy) cyclohexane, 1,1-bis(tertiary) Butylperoxy)-2-methylcyclohexane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2-bis(tertiarybutylperoxy)butane, n-butyl -4,4-bis(tertiary butylperoxy) valerate, 2,2-bis(4,4-bis(tertiary butylperoxy)cyclohexane) propane, p-methane hydroperoxide, Diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tertiary butyl hydroperoxide, two (2-tri -Butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane, tertiary butyl isopropyl Phenyl peroxide, di-tertiary butyl peroxide, 2,5-dimethyl 2,5-di(tertiary butyl peroxy) hexane, diisobutyl peroxide, di(3 ,5,5-Trimethylhexyl) peroxide, dilauryl peroxide, bis(3-methylbenzyl) peroxide, benzyl(3-methylbenzyl) peroxide Base) peroxide, dibenzyl peroxide, bis(4-methylbenzyl) peroxide, di-n-propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, Di(2-ethylhexyl)peroxydicarbonate, di-secondary butylperoxydicarbonate, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl Peroxy neodecanoate, tertiary hexyl neodecanoate, tertiary butyl peroxy neoheptanoate, tertiary hexyl peroxy pivalate, 1,1,3,3-tetramethyl butyl peroxy Oxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-diethylhexylperoxy)hexane, tertiary butylperoxy-2-ethylhexyl Ester, tertiary hexylperoxyisopropyl monocarbonate, tertiary butylperoxymaleic acid, tertiary butylperoxy 3,5,5-trimethylhexanoate, tertiary butyl Peroxyisopropyl monocarbonate, tertiary butylperoxy-2-ethylhexyl monocarbonate, tertiary hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzene Methyl peroxy) hexane, tertiary butyl peroxypyruvate, tertiary peroxy-3-methyl benzoate, tertiary butyl peroxybenzoate, tertiary butyl peroxy allyl Monocarbonate, 3,3',4,4'-tetra(tertiary butylperoxy hydroxy) diphenyl ketone, etc. These may be used alone or in combination of two or more kinds.

(Hardening accelerator) The above-mentioned thermally conductive composition may contain a hardening accelerator. The above-mentioned hardening accelerator can promote the reaction between the binder resin or monomer and the hardening agent.

Specific examples of the curing accelerator include: organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds Compounds containing phosphorus atoms; dicyandiamine, 1,8-diazebicyclo[5.4.0]undecene-7, benzyldimethylamine and other amidino and tertiary amines; the above amidino or the above tertiary Nitrogen-containing compounds such as quaternary ammonium salts of amines. These can be used alone or in combination of two or more kinds.

(Silicane coupling agent) The said thermally conductive composition may contain a silane coupling agent. The above-mentioned silane coupling agent can improve the adhesion between the adhesive layer using the thermally conductive composition and the substrate or semiconductor element.

As the silane coupling agent, specifically, vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane; 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane can be used. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-epoxy Propoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane and other siloxane oxides; p-styryl trimethoxy silane and other styryl silanes; 3-methyl Acrylicoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methyl Methacryloxysilanes such as acryloxypropyltriethoxysilane; Acrylic silanes such as 3-(trimethoxysilyl)propyl methacrylate and 3-acryloxypropyltrimethoxysilane ; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-γ-amine Amino silanes such as propyl trimethoxysilane; triisocyanate silane; alkyl silanes; ureido silanes such as 3-ureidopropyl trialkoxy silane; 3-mercaptopropyl methyl dimethoxy silane, 3 -Mercapto propyl trimethoxy silane and other mercapto silanes; 3-isocyanate propyl triethoxy silane and other isocyanate silanes. These can be used alone or in combination of two or more kinds.

(Plasticizer) The said thermally conductive composition may contain a plasticizer. By adding a plasticizer, the stress can be reduced. As the above-mentioned plasticizer, specifically, polysiloxane compounds such as silicone oil and silicone rubber; polybutadiene compounds such as polybutadiene maleic anhydride adducts; acrylonitrile butadiene Diene copolymer compounds, etc. These can be used alone or in combination of two or more kinds.

(Other ingredients) In addition to the above-mentioned components, the above-mentioned thermally conductive composition may also contain other components as needed. As other components, for example, a solvent can be mentioned.

The solvent is not particularly limited, but for example, it can contain selected from ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, ethylene glycol monomethyl ether, and ethylene glycol. Alcohol 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, hexanediol, benzyl alcohol, 2-phenylethanol, isopalmitol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, butyl glycerol or glycerol and other alcohols; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3, Ketones such as 5,5-trimethyl-2-cyclohexene-1-one) or diisobutyl ketone (2,6-dimethyl-4-heptanone); ethyl acetate, butyl acetate, Diethyl phthalate, dibutyl phthalate, acetoxyethane, methyl butyrate, methyl caproate, methyl caprylate, methyl decanoate, methyl cellulose acetate, ethylene glycol monobutyl ether Acetate, propylene glycol monomethyl ether acetate, 1,2-diethoxyethane, tributyl phosphate, tricresyl phosphate, or tripentyl phosphate and other esters; tetrahydrofuran, dipropyl ether, ethylene two Alcohol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis(2-diethoxy)ethane or 1,2-bis( 2-Methoxyethoxy) ethane and other ethers; acetic acid 2-(2 butoxyethoxy) ethane and other ester ethers; 2-(2-methoxyethoxy) ethanol and other ether alcohols Hydrocarbons such as toluene, xylene, n-alkane, isoalkane, dodecylbenzene, turpentine, kerosene or light oil; nitrile such as acetonitrile or propionitrile; acetamide or N,N-dimethylformamide Isobaric amines; one or more of silicone oils such as low molecular weight volatile silicone oil or volatile organic modified silicone oil.

By using the above-mentioned solvent, the fluidity of the above-mentioned thermally conductive composition can be controlled. For example, the workability of the above-mentioned thermally conductive composition in paste form can be improved. In addition, the shrinkage during heating can promote sintering. Among the solvents, a solvent having a relatively high boiling point, preferably a solvent having a boiling point higher than the curing temperature, can be used to suppress the generation of voids in the adhesive layer obtained by heat-treating the thermally conductive composition. The boiling point of the high boiling point solvent may be, for example, 180°C to 450°C, or 200°C to 400°C.

Hereinafter, the manufacturing method of the thermally conductive composition of this embodiment is demonstrated. As a manufacturing method of the said thermally conductive composition, the method of mixing the said raw material component can be used. For mixing, a known method can be used, but for example, three rolls, a mixer, etc. can be used. In addition, the obtained mixture can be further defoamed. Regarding defoaming, for example, the mixture can be left standing under vacuum.

Next, a method of manufacturing the semiconductor package 100 of this embodiment will be described.

An example of the semiconductor package 100 of this embodiment can be manufactured using the above-mentioned thermally conductive composition. The method of manufacturing the semiconductor package 100 may include: arranging a semiconductor element 20 on one side of the substrate 10 with the other side of the substrate on the opposite side; applying the above-mentioned thermal conductive composition containing metal particles to the semiconductor element 20 Steps on the surface of one side (the side opposite to the other side); Steps of contacting the thermally conductive composition and arranging the heat sink 30 to cover at least one side of the semiconductor element 20; For the step of including the substrate 10 and the semiconductor element 20. The step of heating the thermally conductive composition and the structure of the heat sink 30,

The semiconductor package 100 can include the step of joining the semiconductor element 10 and the heat sink 30 through a thermally conductive material 50 containing a particle connection structure formed by sintering metal particles in the step of heating treatment.

Furthermore, the manufacturing method of the semiconductor package 100 may include a step of drying the above-mentioned thermally conductive composition after the step of coating and before the step of disposing. This can improve the leveling properties.

In addition, in the step of coating, a dispenser can be used to coat the thermally conductive composition. This can improve workability.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be used. In addition, the present invention is not limited to the above-mentioned embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are also included in the present invention. [Example]

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited at all by the description of these examples.

＜Thermally conductive composition＞ Based on the blending amounts shown in Table 1 below, the raw material components were mixed to obtain a varnish. According to the blending amounts shown in Table 1 below, the obtained varnish, solvent, and metal particles were blended, and kneaded at room temperature using a three-roll mill to produce a paste-like thermal conductive composition.

Below, the information of the raw material components in Table 1 is shown. (Adhesive resin) •Epoxy resin 1: Bisphenol F type liquid epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE-303S)

(hardener) • Hardener 1: Phenolic resin with bisphenol F skeleton (solid at room temperature 25°C, manufactured by DIC Corporation, DIC-BPF) • Hardener 2: m-cresol-based glycidyl ether, p-cresol-based glycidyl ether (manufactured by Sakamoto Yakuhin kogyo Co., Ltd., mp-CGE) (Acrylic monomer) •Acrylic monomer 1: (meth)acrylic monomer (ethylene glycol dimethacrylate, manufactured by KYOEISHA CHEMICAL Co., LTD., Light Ester EG) • Acrylic monomer 2: Polyolefin glycol dimethacrylate (manufactured by NOF CORPORATION, PDE-600)

(Plasticizer) • Plasticizer 1: Allyl resin (manufactured by KANTO CHEMICAL CO., INC., a polymer of 1,2-cyclohexanedicarboxylic acid bis(2-propenyl) and propane-1,2-diol)

(Silicane coupling agent) • Silane coupling agent 1: 3-(trimethoxysilyl) propyl methacrylate (manufactured by Shin-Etsu Chemica. Co., Ltd., KBM-503P) • Silane coupling agent 2: 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Chemica. Co., Ltd., KBM-403E)

(Hardening accelerator) • Imidazole hardener 1: 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by SHIKOKU CHEMICALS CORPORATION, 2PHZ-PW)

(Polymerization initiator) • Radical polymerization initiator 1: Dicumyl peroxide (manufactured by Kayaku Akzo Corporation, Perkadox BC)

(Solvent) • Solvent 1: Butyl glycerol (BFTG)

(Metal particles) •Silver particles 1: Silver powder (manufactured by DOWA HIGHTECH CO., LTD., AG-DSB-114, spherical, D ₅₀ : 1μm) •Silver particles 2: Silver powder (Fukuda Metal Foil & Powder Co., Ltd. Manufacture, HKD-16, flake, D ₅₀ : 2μm) • Silver-coated resin particles 1: Silver-plated acrylic resin particles (manufactured by SANNO Co., Ltd., SANSILVER-8D, spherical, D ₅₀ : 8μm, monodisperse particles , Specific gravity: 2.4, the weight ratio of silver is 50wt%, and the weight ratio of resin is 50wt%) •Silver particles 3: Silver powder (TC-88, manufactured by TOKURIKI HONTEN CO., LTD., flake, D ₅₀ : 3μm)

[Table 1] unit Reference example 1 Example 1 Example 2 Example 3 Varnish Adhesive resin Epoxy 1 Mass parts 50.0 50.0 50.0 50.0 hardener Hardener 1 20.0 20.0 20.0 10.0 Hardener 2 30.0 Acrylic monomer Acrylic monomer 1 20.0 20.0 Acrylic monomer 2 20.0 Plasticizer Plasticizer 1 20.0 20.0 20.0 Silane coupling agent Silane coupling agent 1 1.5 1.5 1.5 Silane coupling agent 2 0.5 0.5 0.5 Hardening accelerator Hardening accelerator 1 1.0 1.0 1.0 1.0 Polymerization initiator Free radical polymerization initiator 1 3.5 3.5 3.5 Thermal conductive composition Slurry Varnish Varnish quality% 12.8 12.8 12.8 15.0 Solvent Solvent 1 6.2 6.2 6.2 Metal particles Silver particles 1 43.0 27.1 32.4 63.8 Silver particles 2 38.0 23.9 28.6 Silver particles 3 21.2 Silver coated resin particles 1 30.0 20.0 total 100.0 100.0 100.0 100.0 Storage elastic modulus@25℃ GPa 10400 5100 3000 7000 Chip shear strength@260℃ N/2mm×2mm 6.7 35 17 26

Using the obtained thermally conductive composition, the following physical properties were measured, and evaluation items were evaluated.

(Thermal conductivity) It took 60 minutes to heat up the obtained thermally conductive composition from 30°C to 200°C, followed by heat treatment at 200°C for 120 minutes to obtain a heat-treated body with a thickness of 1 mm. Next, the laser flash method was used to measure the thermal diffusion coefficient α in the thickness direction of the heat-treated body. In addition, the measurement temperature was set to 25°C. Furthermore, the specific heat Cp was measured by differential scanning calorimetry (DSC) measurement, and the density ρ was measured in accordance with JIS-K-6911. Using these values, the thermal conductivity λ was calculated based on the following formula. The evaluation results are shown in Table 1 below. In addition, the unit is W/(m•K). Thermal conductivity λ[W/(m•K)]=α[m ² /sec]×Cp[J/kg•K]×ρ[g/cm ³ ] The thermal conductivity of Example 1 and Reference Example 1 are both 20W /(M•K) above, it can be used without any problems in actual use.

(Storage elastic modulus) It took 60 minutes to heat up the obtained thermally conductive composition from 30°C to 200°C, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body. For the obtained heat-treated body, using a measuring device (manufactured by Hitachi High-Tech Science Corporation, DMS6100), the storage elastic modulus E (MPa) at 25°C was measured by dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz ).

(Observation of particle connection structure) Prepared copper lead frame and silicon wafer (length 2mm x width 2mm, thickness 0.35mm). Next, the obtained thermally conductive composition was coated on a silicon wafer so that the coating thickness became 25±10 μm, and a copper lead frame was placed on it. A laminated body was produced in which a silicon wafer, a thermally conductive composition, and a copper lead frame were sequentially laminated. Then, it took 60 minutes to heat the obtained laminate from 30°C to 200°C in the atmosphere, and then heat treatment at 200°C for 120 minutes to harden the thermally conductive composition in the laminate to obtain thermal conductivity material. Next, using a scanning electron microscope (SEM), the cross section of the heat-treated body of the thermally conductive composition in the laminate was observed, and the state was evaluated.

In Example 1, as shown in FIG. 2, it was confirmed that a silver particle connection structure was formed. In addition, in the cross-sectional image (Figure 2), it was also confirmed that the silver particle connecting structure includes a plurality of substantially circular resin particles, and the metal layer (silver layer) on the surface of the resin particle and the silver particle connecting structure link. Furthermore, it was confirmed that the cured product of the binder resin was present in a portion other than the silver inside the silver particle connecting structure to cover the silver.

(Shear strength of wafer) The obtained thermal conductive composition was coated on a nickel-plated copper substrate, and a silicon wafer (2mm×2mm) with a nickel-plated surface was mounted on it. Then, the temperature was raised to 30°C to 200°C in an oven for 60 minutes, and then heated at 200°C for 120 minutes to harden it. The sample was placed on a hot plate heated to 260°C, and the wafer shear strength (N/2mm×2mm) was measured using DAGE-4000 (manufactured by Nordson Corporation).

In Examples 1 to 3, aggregation failure occurred inside the thermally conductive material, and in Reference Example 1, interfacial peeling occurred at the interface between the thermally conductive material and the lead frame.

Using the thermally conductive compositions of Examples 1 to 3, semiconductor packages were obtained in the following manner. On one surface of the substrate, a semiconductor element is provided such that the other surface of the substrate is on the opposite side. The thermally conductive composition containing metal particles is coated on the surface of one side of the semiconductor element. The heat sink is placed in contact with the thermally conductive composition and covers one side of the semiconductor element. Heat treatment is performed on the structure including the substrate, semiconductor element, thermal conductive composition and heat sink. The semiconductor element and the heat sink are joined through a thermally conductive material containing a particle-connected structure formed by sintering metal particles in the thermally conductive composition by heat treatment to obtain a semiconductor package.

As Comparative Example 1, an acrylic adhesive was used instead of the thermally conductive composition of Example 1, and a semiconductor package was obtained.

The semiconductor packages of Examples 1 to 3 and Comparative Example 1 were used as evaluation samples, and the surface of the semiconductor element was measured for thermal diffusivity by a laser flash method. Examples 1 to 3 show higher thermal diffusivity than Comparative Example 1, and it was found that the semiconductor packages of Examples 1 to 3 can have structures with excellent heat dissipation characteristics. In addition, compared with Comparative Example 1, in the semiconductor packages of Examples 1 to 3, the bonding interface between the thermally conductive material and the semiconductor element and the bonding interface between the thermally conductive material and the heat sink both showed high bonding strength. Value.

It was found that compared with Reference Example 1, the thermally conductive materials of Examples 1 to 3 have superior wafer shear strength. By using the thermally conductive materials of Examples 1 to 3 as the TIM1 material, a semiconductor package with excellent heat dissipation characteristics can be realized.

This application claims priority based on Japanese Patent Application No. 2019-052739 filed on March 20, 2019, and uses all the contents disclosed therein.

100: Semiconductor packaging 10: substrate 20: Semiconductor components 30: radiator 50: Thermal conductivity material 60: Solder ball 70: Underfill material 80: Heat Exchange 90: Thermal conductivity material

The above-mentioned purpose and other purposes, features and advantages will be made clearer by the preferred embodiments described below and the accompanying drawings below.

[Figure] 1 is a cross-sectional view schematically showing an example of the semiconductor package of this embodiment. [Fig. 2] A SEM image showing a cross section of the particle connection structure of Example 1. [Fig.

100: Semiconductor packaging

10: substrate

20: Semiconductor components

30: radiator

50: Thermal conductivity material

60: Solder ball

70: Underfill material

80: Heat Exchange

90: Thermal conductivity material

Claims (22)

A semiconductor package is provided with a substrate, a semiconductor element provided on the substrate, and a heat spreader surrounding the semiconductor element, and the semiconductor element and the heat spreader are joined by a thermally conductive material, The aforementioned thermally conductive material has a particle connection structure formed by sintering metal particles by heat treatment. Such as the semiconductor package of claim 1, in which, The storage elastic modulus at 25°C of the aforementioned thermally conductive material measured by dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz is 1 GPa or more and 10 GPa or less. Such as the semiconductor package of claim 1, in which, The thermal conductivity of the aforementioned thermally conductive material measured by the laser flash method is 10W/mK or more at 25°C. The semiconductor package of claim 1, wherein the metal particles include particles made of metal, and the particle size D ₅₀ at a cumulative 50% of the volume-based cumulative distribution of the particles made of metal is 0.8 μm or more and 7.0 μm the following. Such as the semiconductor package of claim 4, in which, The standard deviation of the particle diameter of the aforementioned metal particles is 2.0 μm or less. The semiconductor package as described in item 4 of the request, wherein the metal particles are made to include ₅₀ or more kinds of those having different particle sizes D. Such as the semiconductor package of claim 4, in which, The aforementioned particles made of metal include spherical particles and flake-shaped particles. Such as the semiconductor package of claim 1, in which, The metal particles include metal-coated resin particles composed of resin particles and a metal formed on the surface of the resin particles. Such as the semiconductor package of any one of Claims 1 to 8, wherein: The metal particles include particles composed of the following metal, and the metal is composed of one or more selected from the group consisting of silver, gold, and copper. A thermally conductive composition used to form a thermally conductive material in a semiconductor package. The semiconductor package includes a substrate, a semiconductor element provided on the substrate, and a heat sink surrounding the semiconductor element, and the thermal conductive material is used to combine The semiconductor element and the heat sink are joined, and the thermally conductive composition contains: Metal particles Adhesive resin; and monomer, The metal particles are sintered by heat treatment to form a particle connection structure. Such as the thermal conductivity composition of claim 10, in which, Using this thermally conductive composition, the thermal conductivity λ measured in the following step A is 10W/mK or more, (Step A) It took 60 minutes to heat up the thermally conductive composition from 30°C to 200°C, followed by heat treatment at 200°C for 120 minutes to obtain a heat-treated body with a thickness of 1 mm. For the heat-treated body obtained, the laser flash method was used to measure the temperature at 25°C. The thermal conductivity λ (W/mK). Such as the thermal conductivity composition of claim 10, in which, Using this thermally conductive composition, the storage elastic modulus E at 25°C measured in the following step B is 1 GPa or more and 10 GPa or less, (Step B) It took 60 minutes to heat up the thermally conductive composition from 30°C to 200°C, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body. The heat-treated body obtained was measured using dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz. Storage elastic modulus E (MPa) at 25°C. Such as the thermal conductivity composition of claim 10, in which, The aforementioned metal particles include particles composed of one or more metal materials selected from the group consisting of silver, gold, and copper. Such as the thermal conductivity composition of claim 10, in which, The said binder resin contains 1 or more types chosen from the group which consists of an epoxy resin, an acrylic resin, and an allyl resin. Such as the thermal conductivity composition of claim 10, which contains a hardener. Such as the thermal conductivity composition of claim 10, in which, The aforementioned monomer includes one or more selected from the group consisting of a diol monomer, an acrylic monomer, an epoxy monomer, and a maleimide monomer. The thermal conductive composition of claim 10, which contains a radical polymerization initiator. Such as the thermal conductivity composition of claim 10, which contains a silane coupling agent. The thermally conductive composition according to any one of claims 10 to 18, which contains a plasticizer. A manufacturing method of semiconductor package, which includes: The step of arranging semiconductor elements on one side of the substrate so that the other side of the substrate is on the opposite side; The step of coating a thermally conductive composition containing metal particles on the surface of one side of the aforementioned semiconductor element; The step of arranging a heat sink in a manner in contact with the aforementioned thermal conductive composition and covering at least one side of the aforementioned semiconductor element; The step of heating the structure including the aforementioned substrate, semiconductor element, thermally conductive composition and aforementioned heat sink, In the step of the heating treatment, the semiconductor element and the heat sink are joined via a thermally conductive material containing a particle connection structure formed by sintering the metal particles. According to claim 20, the method of manufacturing a semiconductor package includes a step of drying the aforementioned thermally conductive composition after the aforementioned step of coating and before the aforementioned step of arranging. Such as the method of manufacturing a semiconductor package of claim 20 or 21, wherein: In the aforementioned coating step, a dispenser is used to coat the aforementioned thermally conductive composition.

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