KR20210143224A - Semiconductor package, manufacturing method of semiconductor package, and thermally conductive composition used therefor - Google Patents

Abstract

The semiconductor package of the present invention includes a substrate, a semiconductor element provided on the substrate, and a heat spreader surrounding the semiconductor element, wherein the semiconductor element and the heat spreader are heat-treated to cause sintering of metal particles. It is joined with a thermally conductive material having a particle-connected structure.

Description

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

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

Up to now, various developments have been made in semiconductor packages including thermal conductors. As a technique of this kind, the technique described in patent document 1 is known, for example.

Patent Document 1 describes a semiconductor package in which a semiconductor element (heating element) mounted on an electronic circuit board and a heat sink are adhered via a thermally conductive double-sided tape (thermal conductive material composed of an adhesive) (Patent Document 1) Example 7 of Fig. 16).

Patent Document 1: International Publication No. 2015/072428

However, as a result of this inventor examining, the semiconductor package of the said patent document 1 WHEREIN: It became clear that there exists room for improvement in the point of a heat dissipation characteristic.

At present, since the amount of heat generated by a semiconductor element (heating body) is increasing with higher performance, a further improvement in heat dissipation characteristics is required for a semiconductor package.

As a result of examination in consideration of such circumstances, even if an acrylic adhesive or a thermoreversible gel dispersed with boron nitride, alumina or zinc oxide is used as a thermally conductive material for bonding a semiconductor element and a heat dissipating member such as a heat spreader, thermoelectric It was found that the city was not sufficiently obtained.

As a result of further investigation, the present inventor improved the thermal conductivity of the thermally conductive material by using a thermally conductive material having a particle-connected structure formed by sintering of metal particles by heat treatment, thereby forming a semiconductor element and a heat-dissipating member. Since bonding was possible, it discovered that the heat dissipation characteristic in a semiconductor package could be improved, and came to complete this invention.

According to the present invention,

A semiconductor package comprising a substrate, a semiconductor element provided on the substrate, and a heat spreader surrounding the semiconductor element, wherein the semiconductor element and the heat spreader are joined with a thermally conductive material,

The thermally conductive material has a particle connection structure formed by causing metal particles to sinter by heat treatment, the semiconductor package is provided.

In addition, according to the present invention,

A semiconductor package comprising a substrate, a semiconductor element provided on the substrate, and a heat spreader surrounding the semiconductor element, wherein the semiconductor element and the heat spreader are joined with a thermally conductive material, wherein the thermally conductive material As a thermally conductive composition used to form,

metal particles,

binder resin,

contains a monomer;

A thermally conductive composition is provided to form a particle-connected structure by causing the metal particles to sinter by heat treatment.

In addition, according to the present invention,

A step of installing a semiconductor element on one surface of the substrate so that the other surface faces;

a step of applying a thermally conductive composition containing metal particles to the surface of one side of the semiconductor element;

disposing a heat spreader so as to be in contact with the thermally conductive composition and to cover at least one surface of the semiconductor element;

and heat-treating a structure including the substrate, the semiconductor device, the thermally conductive composition, and the heat spreader,

In the heat treatment step, there is provided a method of manufacturing a semiconductor package in which the semiconductor element and the heat spreader are joined through a thermally conductive material including a particle connection structure formed by causing the metal particles to sinter. .

ADVANTAGE OF THE INVENTION According to this invention, the semiconductor package excellent in heat dissipation characteristic, the manufacturing method of a semiconductor package, and the thermally conductive composition used for this are provided.

The above-mentioned and other objects, features, and advantages will become clearer with reference to the preferred embodiment described below and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an example of the semiconductor package which concerns on this embodiment.
2 : shows the SEM image in the cross section of the particle|grain connection structure of Example 1. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described using drawings. In addition, in all the drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably. In addition, the drawing is schematic and does not correspond with the actual dimensional ratio.

The outline of the semiconductor package of this embodiment is demonstrated.

1 : is sectional drawing which shows typically an example of the semiconductor package of this embodiment.

The semiconductor package 100 of this embodiment is equipped with the board|substrate 10, the semiconductor element 20, the heat spreader 30, and the thermally conductive material 50. As shown in FIG. The semiconductor element 20 is provided on the board|substrate 10, the heat spreader 30 surrounds the periphery of the semiconductor element 20, and the thermally conductive material 50 is the semiconductor element 20 and the heat spreader ( 30) is connected.

In such a semiconductor package 100 , the thermally conductive material 50 has a particle-connected structure formed by sintering (sintering) of metal particles by heat treatment.

The particle connection structure in the thermally conductive material 50 is at least one cross section when the thermally conductive material 50 is cut with respect to the stacking direction of the semiconductor element 20 and the heat spreader 30 by scanning electron microscopy or the like. It can be observed using various microscopes.

In a 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 in which the interface is lost. By such a connection structure of the metal particles, it is possible to improve the thermal conductivity of the thermally conductive material 50 .

Moreover, in at least a part of the adhesive surface of the thermal conductive material 50 and the semiconductor element 20, or the adhesive surface of the thermal conductive material 50 and the heat spreader 30, the thermal conductive material 50 is among them. It may have a bonding structure with the surface of the semiconductor device 20 or the surface of the heat spreader 30 through the metal particles.

According to the present embodiment, as the thermal conductive material, by using one having a particle connection structure formed by sintering of metal particles by heat treatment, the thermal conductivity of the thermal conductive material is improved, and the semiconductor element and the heat dissipation member are joined. Therefore, the heat dissipation characteristics of the semiconductor package can be improved.

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 spreader 30 , and a thermally conductive material 50 .

The semiconductor element 20 may be, for example, a logic chip or a memory chip, or an LSI chip in which a memory circuit and a logic circuit are mixed. The semiconductor element 20 may be configured in 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 flip-chip connected to the substrate 10 . In this case, the semiconductor element 20 is solder-connected to the substrate 10 via the solder ball 60 . The gap between the semiconductor element 20 and the substrate 10 may be filled with the underfill material 70 . Although a well-known thing can be used for the underfill material 70, a sealing material may be sufficient as it, or a die-attaching material may be sufficient as it.

As the board|substrate 10, a printed circuit board etc. are used, for example. One or two or more semiconductor elements 20 may be mounted on one surface of the substrate 10 . In addition, electronic components other than the semiconductor element 20 or a heat source may be mounted on one surface of the substrate 10 . In addition, the other surface (surface on the side opposite to one surface) of the board|substrate 10 may have a connection structure connectable to another board|substrate. As a connection structure, a solder ball, a pin connector, etc. are mentioned, for example.

The heat spreader 30 should just be comprised with the member which radiates heat|fever from the heat generating body, such as the semiconductor element 20, and can be comprised with a metal material, for example. As a metal material, copper, aluminum, stainless steel etc. are mentioned, for example. These may be used independently and may be used in combination of 2 or more type. The heat spreader 30 may have a high thermal conductivity material other than a metal material, and may contain graphite etc. inside it, for example.

The heat spreader 30 may be comprised by the single layer using the metal layer which consists of the said metal material, or may be comprised by the laminated structure in which multiple layers were laminated|stacked. Moreover, although the said metal material may be exposed at least among the surfaces of the heat spreader 30, the surface joined with the thermal conductive material 50 may be plated with another metal. For example, the plating film can be constituted of nickel, gold, an alloy containing these as a main component, or these laminated films. Thereby, the rust prevention property of the heat spreader 30 can be improved.

The shape of the heat spreader 30 is not particularly limited as long as it has a cover structure that covers the semiconductor element 20 . The heat spreader 30 is constituted by a case in which a surface facing the semiconductor element 20 is opened. Specifically, the heat spreader 30 includes a plate-shaped portion having a surface opposite to one surface of the semiconductor element 20 , and protruding from the other surface of the plate-shaped portion so as to cover the circumference of the side surface of the semiconductor element 20 . , you may have a side wall part provided around the plate-shaped member.

The cross-sectional structure of the heat spreader 30 may have, for example, a substantially U-shape when viewed from a cross section in the stacking direction of the semiconductor element 20 and the heat spreader 30 .

A part of the heat spreader 30 may be adhered to the substrate 10 via an adhesive. For example, the tip of the side wall portion of the heat spreader 30 may be adhered to one surface of the substrate 10 with an adhesive. A known adhesive 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 spreader 30 opposite to the one surface to bond them.

The thermally conductive material 50 has a particle-connected structure formed by causing metal particles to sinter by heat treatment. The thermally conductive material 50 may be formed using a thermally conductive composition having a particle-connected structure formed by sintering of metal particles by heat treatment. The detail of this thermally conductive composition is mentioned later.

The metal particles may include particles made of a metal. The said metal particle may also contain the particle|grain which consists of a metal comprised by 1 or more types chosen from the group which consists of silver, gold|metal|money, and copper, for example.

Moreover, the lower limit of the thermal conductivity of the thermally conductive material 50 is 10 W/mK or more, for example, Preferably it is 15 W/mK or more, More preferably, it is 20 W/mK or more. Accordingly, the heat dissipation characteristics of the semiconductor package 100 may 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, for example, and 150 W/mK or less may be sufficient as it. Thermal conductivity is obtained by measuring in the thickness direction at 25 degreeC using the laser flash method.

The lower limit of the average particle diameter D ₅₀ of the particles made of the metal is, for example, 0.8 µm or more, preferably 1.0 µm or more, and more preferably 1.2 µm or more. Thereby, thermal conductivity can be improved. On the other hand, the _{upper limit of the average particle diameter D 50} of the particles made of the 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 sintering property in between metal particles can be improved. Moreover, the improvement of the uniformity of sintering can be aimed at. The average particle diameter D ₅₀ of the particles made of the metal, will be used as the average particle size D ₅₀ of the particles.

The upper limit of the standard deviation of the particle size of the particles made of the metal is 2.0 µm or less, preferably 1.9 µm or less, and more preferably 1.8 µm or less. Thereby, the uniformity at the time of sintering can be improved. In addition, the lower limit of the standard deviation of the particle diameter of the particle|grains which consists of said metal is although it does not specifically limit, For example, 0.1 micrometer or more and 0.3 micrometer or more may be sufficient.

Moreover, the said metal particle may also contain the metal-coat resin particle comprised with the metal formed in the surface of the resin particle and the resin particle. Although this metal particle can contain either one of a metal-coat resin particle and the particle|grains which consists of a metal, it is more preferable to contain both.

By using the metal coat resin particle, although the detailed mechanism is not certain, adhesiveness with the surface of the other surface side of the heat spreader 30 by which the nickel plating process was carried out can be improved.

Although the thermally conductive material 50 may be comprised only with the particle|grain connection structure of metal particle|grains, it may have the particle|grain connection structure and resin which exists in the structure. Thereby, while the thermal conductivity is improved, the storage elastic modulus can be reduced.

The upper limit of the storage elastic modulus in 25 degreeC of the thermal conductive material 50 is 10.0 GPa or less, for example, Preferably it is 9 GPa or less, More preferably, it is 8 GPa or less. Thereby, since the thermal conductive material 50 can be made low elastic, generation|occurrence|production of the crack by stress strain, and the fall of adhesiveness can be suppressed. The upper limit of the storage elastic modulus at 25°C of the thermal 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 implement|achieved. The storage modulus is obtained by measuring by dynamic viscoelasticity measurement (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 one 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 adhere to the heat spreader 30 via the thermally conductive material 90 . A well-known material can be used for the thermally conductive material 90, for example, grease may be used.

The heat sink 80 should just be comprised from the member excellent in heat dissipation, for example, the material used by the heat spreader 30 may be used. The heat sink 80 may have a plurality of fins.

Hereinafter, each component of the thermally conductive composition of this embodiment is demonstrated in detail.

The thermally conductive composition includes a substrate, a semiconductor element 20 provided on the substrate 10 , and a heat spreader 30 surrounding the semiconductor element 20 , and the semiconductor element 20 and the heat spreader In the semiconductor package in which (30) is joined with the thermally conductive material (50), it is used in order to form the thermally conductive material (50).

In the thermally conductive composition, metal particles cause sintering by heat treatment to form a particle-connected structure, thereby forming the thermally conductive material 50 .

The thermally conductive composition of this embodiment contains binder resin and a monomer with the said metal particle.

Although the detailed mechanism is not certain, when the monomer volatilizes and the volume of the composition shrinks due to heating, stress is applied in the direction in which the metal particles approach each other, the interface between the metal particles disappears, and a connection structure of the metal particles is formed. I think it will And it is thought that, at the time of such sintering of metal particles, a binder resin, or binder resin, and resin hardened|cured material, such as a hardening|curing agent and a monomer, remain|survive in the inside or outer periphery of a connection structure. Moreover, the case where the force which a some metal particle aggregates by hardening reaction generate|occur|produces is also conceivable.

By heat-treating the thermally conductive composition, an adhesive layer (thermal conductive material 50) comprising a particle connection structure of metal particles, a binder resin, a cured product thereof, and a resin component composed of resin particles in metal coat resin particles, etc. can be realized

In addition, the lower limit of the thermal conductivity λ measured by the following procedure A using the thermally conductive composition is, for example, 10 W/mK or more, preferably 15 W/mK or more, and more preferably 20 W/mK or more. Accordingly, the heat dissipation characteristics of the semiconductor package 100 may be improved. On the other hand, the upper limit of the thermal conductivity of the thermal conductivity λ may be, for example, 200 W/mK or less, or 150 W/mK or less.

(Sequence A)

The said thermally conductive composition is heated up over 60 minutes from 30 degreeC to 200 degreeC, Then, it heat-processes at 200 degreeC for 120 minutes, and obtains the heat treatment body of thickness 1mm. With respect to the obtained heat treatment body, the thermal conductivity λ (W/mK) at 25°C is measured using a laser flash method.

The upper limit of the storage elastic modulus E at 25°C measured by the following procedure B using the thermally conductive composition is, for example, 10 GPa or less, preferably 9 GPa or less, and more preferably 8 GPa or less. Thereby, since the thermal conductive material 50 can be made low elastic, generation|occurrence|production of the crack by stress strain, and the fall of adhesiveness can be suppressed. The upper limit of the storage elastic modulus E in 25 degreeC is, for example, 1 GPa or more, Preferably, 2 GPa or more, More preferably, 3 GPa or more may be sufficient. Thereby, the thermally conductive material 50 excellent in durability can be implement|achieved. The storage modulus is obtained by measuring by dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz.

(metal particles)

The thermally conductive composition of this embodiment contains a metal particle. This metal particle can generate|occur|produce sintering by heat processing, and can form a particle|grain connection structure (sintering structure).

As the metal particles, metal coating resin particles, metal particles, and the like can be used. Although the said metal particle can contain either one of a metal-coat resin particle and the particle|grains which consists of a metal, it is more preferable to contain both.

By using the said metal coat resin particle, it is possible to reduce the storage elastic modulus suitably, suppressing the fall of the sinterability of a metal particle. By using the particle|grains which consist of the said metal, it is possible to raise thermal conductivity suitably, improving the sinterability of a metal particle.

The said metal coat resin particle is comprised from the metal formed in the surface of a resin particle and a resin particle. That is, the said metal coat resin particle may be the particle|grains which the metal layer coat|covered the surface of the resin particle.

In this specification, the metal layer covering the surface of the resin particle refers to a state in which the metal layer covers at least a part of the surface of the resin particle, and is not limited to the embodiment covering the entire surface of the resin particle, e.g. For example, the aspect in which the metal layer partially covers the surface, and the aspect which covers the whole surface at the time of seeing from a specific cross section may also be included.

Among these, 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 more preferably covers the entire surface of the particle.

The metal in the metal coat resin particles may include, for example, at least one selected from the group consisting of silver, gold, nickel, and tin. These may be used independently and may be used in combination of 2 or more type. Or you may use the alloy which has these metals as a main component. Among these, from a viewpoint of sintering property and thermal conductivity, silver can be used.

Examples of the resin material constituting the resin particles (core resin particles) in the metal coat resin particles include silicone, acryl, phenol, polystyrene, melamine, polyamide, and polytetrafluoroethylene. These may be used independently and may be used in combination of 2 or more type. A resin particle can be comprised from the polymer using these. A homopolymer may be sufficient as a polymer, and the copolymer which has these as a main component may be sufficient as it.

From the viewpoint of elastic properties and heat resistance, silicone resin particles or acrylic resin particles may be used as the resin particles.

The silicone resin particles may be particles composed of an organopolysiloxane obtained by polymerizing an organochlorosilane such as methylchlorosilane, trimethyltrichlorosilane, or dimethyldichlorosilane, and the organopolysiloxane may be The silicone resin particle|grains which made the structure which further three-dimensionally bridge|crosslinked polysiloxane as a basic frame|skeleton may be sufficient.

In addition, various functional groups can be introduced into the structure of the silicone resin particles, and examples of the functional groups that can be introduced include an epoxy group, an amino group, a methoxy group, a phenyl group, a carboxyl group, a hydroxyl group, an alkyl group, a vinyl group, a mercapto group, etc. It is not limited to these.

In addition, in this embodiment, you may add another low-stress modifier to this silicone resin particle in the range which does not impair a characteristic. Examples of other low-stress modifiers that can be used in combination include butadienestyrene rubber, butadieneacrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, liquid polyol. Although liquid synthetic rubbers, such as lyitadiene, etc. are mentioned, It is not limited to these.

The shape of the said resin particle is not specifically limited, Although a spherical shape may be sufficient, tooth shapes other than a spherical shape, for example, flat shape (flake shape), plate shape, and needle shape may be sufficient. When forming the shape of a metal coat resin particle in a spherical shape, it is preferable that the shape of the resin particle to be used is also spherical. In addition, the spherical shape is not limited to a perfect sphere as mentioned above, A shape close to a spherical shape, such as an ellipse, a shape with some unevenness|corrugation on the surface, etc. are also included.

The lower limit of the specific gravity of the metal coat resin particles is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. Thereby, the thermal conductivity and electroconductivity as an adhesive layer can be improved further. Moreover, the upper limit of the specific gravity of the said metal coat resin particle is 10 or less, for example, It is preferable that it is 9 or less, It is more preferable that it is 8 or less. Thereby, the dispersibility of particle|grains can be improved. The specific gravity may be the specific gravity of the metal particles containing the metal coating resin particles and the metal particles.

Monodisperse particle|grains may be sufficient as the said metal coat resin particle, and polydisperse particle|grains may be sufficient as it. Moreover, the said metal coat resin particle may have one peak in particle diameter frequency distribution, and may have two or more several peak.

The particle|grains which consist of said metal may just be the particle|grains which consist of 1 type, or 2 or more types of metal materials, and the core part and surface layer part may be comprised with the same or different types of metal materials. The metal material may include, for example, at least one selected from the group consisting of silver, gold, and copper. These may be used independently and may be used in combination of 2 or more type. Or you may use the alloy which has these metals as a main component. Among these, from a viewpoint of sintering property and thermal conductivity, silver can be used.

The shape of the particle|grains which consists of the said metal may be spherical, for example may be sufficient, and flake shape may be sufficient as it. The particle|grains which consist of the said metal may contain any one or both of spherical particle|grains and flaky particle|grains.

One aspect of the said metal particle is a silver-coated silicone resin particle as said metal-coat resin particle, and a particle|grain which consists of a metal contains a silver particle.

You may use a silver coat acrylic resin particle other than a silver coat silicone resin particle from a viewpoint of an elastic characteristic. In addition to silver particles, it is possible to use together particles containing a metal component other than silver, such as gold particles and copper particles, for the purpose of, for example, promoting sintering or reducing the cost.

The lower limit of the average particle diameter D ₅₀ of the metal coat 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 size D ₅₀ of the metal coating resin particles is, for example, and even less than 20μm, and even 15μm or less, or may be less than 10μm. Thereby, thermal conductivity can be improved. The average particle diameter D ₅₀ of the metal coat resin particles, silicone resin particles and the coat will also be used as the average particle diameter D ₅₀ of the coat of acrylic resin particles.

The lower limit of the average particle diameter D ₅₀ of the particles made of the metal is, for example, 0.8 µm or more, preferably 1.0 µm or more, and more preferably 1.2 µm or more. Thereby, thermal conductivity can be improved. On the other hand, the _{upper limit of the average particle diameter D 50} of the particles made of the 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 sintering property in between metal particles can be improved. Moreover, the improvement of the uniformity of sintering can be aimed at. The average particle diameter D ₅₀ of the particles made of the metal, will be used as the average particle size D ₅₀ of the particles.

In addition, particles made of a metal, and may include a combination of two or more having different particle diameter D _50. Thereby, sintering property can be improved.

Further, the average particle size D ₅₀ of the metal particles is, for example, Sysmex Co., Ltd. flow type particle image analyzer FPIA (registered trademark) using a -3000 can be determined by performing a particle image measurement. More specifically, the particle diameter of a metal particle can be determined by measuring a volume-based median diameter using the said apparatus.

Content of the said metal coat resin particle is 1 mass % - 50 mass % with respect to the whole metal particle (100 mass %), Preferably 3 mass % - 45 mass %, More preferably, 5 mass % -40 mass %. By using more than the said lower limit, a storage elastic modulus can be reduced. Thermal conductivity can be improved by using below the said upper limit.

In this specification, "-" represents that an upper limit and a lower limit are included unless otherwise indicated.

Content of the said metal particle is 1 mass % - 98 mass % with respect to the whole thermal conductive composition (100 mass %), Preferably it is 30 mass % - 95 mass %, More preferably, it is 50 mass % - 90 mass % . Thermal conductivity can be improved by setting it as more than the said lower limit. By carrying out below the said upper limit, applicability|paintability and workability|operativity at the time of a paste can be improved.

(binder resin)

The thermally conductive composition contains a binder resin.

The binder resin may include at least one selected from the group consisting of an epoxy resin, an acrylic resin, and an allyl resin. These may be used independently and may be used in combination of 2 or more type.

As the binder resin, specifically, an acrylic resin such as an acrylic oligomer or an acrylic polymer; epoxy resins such as epoxy oligomers and epoxy polymers; Allyl resins, such as an allyl oligomer and an allyl polymer, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

In addition, let the thing with a weight average molecular weight less than 10,000 an oligomer, and let a thing with a weight average molecular weight 10,000 or more a polymer.

As said epoxy resin, you may use the epoxy resin which has two or more epoxy groups in a molecule|numerator. This epoxy resin may be liquid at 25 degreeC. Thereby, the handling property of a thermally conductive composition can be improved. Moreover, the cure shrinkage can be adjusted suitably.

Specific examples of the epoxy resin include, for example, a trisphenol methane type epoxy resin; hydrogenated bisphenol A liquid epoxy resin; bisphenol F-type liquid epoxy resins such as bisphenol-F-diglycidyl ether; orthocresol novolak-type epoxy resins and the like. These may be used independently and may be used in combination of 2 or more type.

Among these, hydrogenated bisphenol A liquid epoxy resin or bisphenol F liquid epoxy resin may be used. As the bisphenol F-type liquid epoxy resin, for example, bisphenol-F-diglycidyl ether can be used.

As said acrylic resin, you may use the acrylic resin which has two or more acrylic groups in a molecule|numerator. This acrylic resin may be liquid at 25 degreeC.

As said acrylic resin, what specifically (co)polymerized an acrylic monomer can be used. Here, the method of (co)polymerization is not limited, A well-known method using a general polymerization initiator and a chain transfer agent, such as solution polymerization, can be used.

As the allyl resin, an allyl resin having two or more allyl groups in one molecule may be used. This allyl resin may be liquid at 25 degreeC.

Specific examples of the allyl resin include an allyl ester resin obtained by reacting dicarboxylic acid, allyl alcohol, and a compound having an allyl group.

Here, as said 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, tetrahydro Phthalic acid, hexahydrophthalic acid, etc. are mentioned. Moreover, as a compound provided with the said allyl group, specifically, polyether, polyester, polycarbonate, polyacrylate, polymethacrylate, polybutadiene, butadiene acrylonitrile having an allyl group synthesis; and the like.

The lower limit of the content of the binder resin is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the thermally conductive composition. Thereby, adhesiveness to a to-be-adhered body can be improved. On the other hand, the upper limit of content of the said binder resin is 15 mass parts or less with respect to 100 mass parts of thermal conductive compositions, Preferably it is 12 mass parts or less, More preferably, it is 10 mass parts or less. Thereby, the fall of thermal conductivity can be suppressed.

(monomer)

The said thermally conductive composition contains a monomer.

The monomer may include one or two or more selected from the group consisting of a glycol monomer, an acrylic monomer, an epoxy monomer, and a maleimide monomer. These may be used independently and may be used in combination of 2 or more type.

By using the said monomer, the volatilization state of the said thermally conductive composition at the time of heat processing can be adjusted. Moreover, by selecting suitably the combination of binder resin and a hardening|curing agent, the said monomer and these may be made to harden-react, and a cure shrinkage state may be adjusted.

Specific examples of the glycol monomer include: a dihydric alcohol having two hydroxyl groups in the molecule, wherein the two hydroxyl groups are bonded to different carbon atoms; a compound obtained by condensing two or more of the dihydric alcohols; The thing in which the hydrogen atom in the hydroxyl group of the alcohol-condensed compound was substituted with C1-C30 organic group, and became an alkoxy group, etc. are mentioned.

Specific examples of the glycol monomer include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, and ethylene glycol monomethyl ether. Isopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol Colmonoallyl ether, ethylene glycol monophenyl ether, ethylene glycol 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 Col 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, tetraethylene glycol monoethyl, tetraethylene glycol mono n-butyl, 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 and the like. These may be used independently and may be used in combination of 2 or more type. Among them, from the viewpoint of volatility, tripropylene glycol mono-n-butyl ether or ethylene glycol mono-n-butyl acetate can be used.

The lower limit of the boiling point of the glycol monomer is, for example, preferably 100°C or higher, more preferably 130°C or higher, still more preferably 150°C or higher, still more preferably 170°C or higher, and 190°C or higher. Especially preferred. Moreover, as an upper limit of the boiling point of a glycol monomer, 400 degrees C or less may be sufficient and 350 degrees C or less may be sufficient, for example.

In addition, the boiling point of a glycol monomer shows the boiling point in atmospheric pressure (101.3 kPa).

As said acryl monomer, the monomer provided with a (meth)acryl group in a molecule|numerator is mentioned.

Here, the (meth)acryl group represents an acryl group and a methacryl group.

The said acryl monomer may be a monofunctional acryl monomer provided with only one (meth)acryl group in a molecule|numerator, and the polyfunctional acryl monomer provided with two or more (meth)acryl groups in a molecule|numerator may be sufficient as it.

As the monofunctional acrylic monomer, specifically, 2-phenoxyethyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert- butyl ( Meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, n-tridecyl (meth) acrylate , n-stearyl (meth) acrylate, isostearyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene Glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, cyclo Hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol Lycol (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, phenylphenol ethylene oxide modified (meth) acrylate, isobornyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, die Ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate quaternary, glycidyl (meth)acrylate, neopentyl glycol (meth)acrylic acid benzoic acid ester, 1,4-cyclohexane Dimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy Cypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- ( and meth)acryloyloxyethyl-2-hydroxyethylphthalic acid and 2-(meth)acryloyloxyethyl acid phosphate.

Specific examples of the polyfunctional acrylic monomer include ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, hexane-1, 6-diolbis (2-methyl (meth) acrylate), 4,4'-isopropylidene diphenol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 6-bis((meth)acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, 1,4-bis((meth)acryloyloxy)view Tane, 1,6-bis ((meth) acryloyloxy) hexane, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di ( meth)acrylate, N,N'-di(meth)acryloylethylenediamine, N,N'-(1,2-dihydroxyethylene)bis(meth)acrylamide, or 1,4-bis( (meth)acryloyl)piperazine etc. are mentioned.

As an acrylic monomer, a monofunctional acrylic monomer or a polyfunctional acrylic monomer may be used independently, and a monofunctional acrylic monomer and a polyfunctional acrylic monomer may be used together. As an acryl monomer, it is preferable to use independently a polyfunctional acryl monomer, for example.

The said epoxy monomer is a monomer provided with an epoxy group in a molecule|numerator.

The said epoxy monomer may be a monofunctional epoxy monomer provided with only one epoxy group in a molecule|numerator, and the polyfunctional epoxy monomer provided with two or more epoxy groups in a molecule|numerator may be sufficient as it.

Specific examples of the monofunctional epoxy monomer include 4-tert-butylphenyl glycidyl ether, m,p-cresyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, and the like. can be heard

Specific examples of the polyfunctional epoxy monomer include bisphenol compounds or derivatives thereof such as bisphenol A, bisphenol F, and biphenol; diol or derivatives thereof having an alicyclic structure such as hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol and cyclohexanediethanol; bifunctional ones obtained by epoxidizing aliphatic diols such as butanediol, hexanediol, octanediol, nonadiol and decanediol or derivatives thereof; trifunctional thing which has trihydroxyphenylmethane skeleton and aminophenol skeleton; The polyfunctional thing etc. which epoxidized phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, etc. are mentioned.

The said maleimide monomer is a monomer provided with a maleimide ring in a molecule|numerator.

The said maleimide monomer may be a monofunctional maleimide monomer provided with only one maleimide ring in a molecule|numerator, and the polyfunctional maleimide monomer provided with two or more maleimide rings in a molecule|numerator may be sufficient as it.

Specific examples of the maleimide monomer include polytetramethylene ether glycol-di(2-maleimide acetate).

The lower limit of the content of the monomer is, for example, 0.5 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 2.0 parts by mass or more with respect to 100 parts by mass of the thermally conductive composition. On the other hand, the upper limit of content of the said monomer is 10 mass parts or less with respect to 100 mass parts of thermal conductive compositions, Preferably it is 7 mass parts or less, More preferably, it is 5 mass parts or less.

(hardener)

The said thermally conductive composition may also contain a hardening|curing agent as needed.

The said hardening|curing agent has a reactive group which reacts with the functional group in a monomer or binder resin. As a reactive group, you may use what reacts with functional groups, such as an epoxy group, a maleimide group, and a hydroxyl group, for example.

Specifically, when the monomer is an epoxy monomer or/and the binder resin contains an epoxy resin, a phenol resin curing agent or an imidazole curing agent may be used as the curing agent.

Specific examples of the phenol resin-based curing agent include novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenyl novolac resin; polyvinylphenol; polyfunctional phenol resins such as triphenylmethane type phenol resins; modified phenol resins such as terpene-modified phenol resins and dicyclopentadiene-modified phenol resins; phenol aralkyl type phenol resins such as phenol aralkyl resins having a phenylene skeleton and/or biphenylene skeleton, and naphthol aralkyl resins having phenylene and/or biphenylene skeletons; bisphenol compounds (phenol resins having a bisphenol F skeleton) such as bisphenol A and bisphenol F (dihydroxydiphenylmethane); The compound etc. which have biphenylene frame|skeleton, such as 4,4'- biphenol, are mentioned. These may be used independently and may be used in combination of 2 or more type.

Among these, a phenol aralkyl resin may be used, and a phenol-para-xylylene dimethyl ether polycondensate may be used as a phenol aralkyl resin.

Specific examples of the imidazole-based curing agent include 2-phenyl-1H-imidazole-4,5-dimethanol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methylimidazole, 2-Phenylimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, 2-undecylimidazole, 2-heptadecylimida Sol, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid addition Water, 2-methylimidazole isocyanuric acid adduct, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, etc. can be heard These may be used independently and may be used in combination of 2 or more type.

As for content of the said hardening|curing agent, 5 mass parts - 50 mass parts may be sufficient with respect to 100 mass parts of said binder resins in a thermally conductive composition, and 20 mass parts - 40 mass parts may be sufficient.

Moreover, content of the said hardening|curing agent may be 1 mass parts - 40 mass parts with respect to 100 mass parts of epoxy resins in a thermally conductive composition, or a total of 100 mass parts of an epoxy resin and an epoxy monomer, 10 mass parts - 35 mass may be provided.

(Radical polymerization initiator)

The said thermally conductive composition may also contain a radical polymerization initiator.

As said radical polymerization initiator, an azo compound, a peroxide, etc. can be used.

As the peroxide, specifically, bis(1-phenyl-1-methylethyl)peroxide, 1,1-bis(1,1-dimethylethylperoxy)cyclohexane, methylethylketone peroxide, cyclohexene Cein peroxide, acetylacetone peroxide, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)-2-methylcyclohexane, 1,1-di (tert-butylperoxy)cyclohexane, 2,2-di(tert-butylperoxy)butane, n-butyl-4,4-di(tert-butylperoxy)valerate, 2,2-di (4,4-di(tert-butylperoxy)cyclohexane)propane, p-methane hydroperoxide, diisopropylbenzenehydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide , cumene hydroperoxide, tert-butyl hydroperoxide, di (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) ) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine, diisobutyl peroxide, di (3, 5,5-Trimethylhexanoyl) peroxide, dilauryl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) Peroxide, din-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, disec-butylperoxydicarbonate, cumylperoxyneodecanate, 1, 1,3,3-tetramethylbutylperoxyneodecanate, tert-hexylneodecanate, tert-butylperoxyneoheptanate, tert-hexylperoxypivalate, 1,1,3,3-tetramethylvu Tylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di(2-diethylhexanoylperoxy)hexane, tert-butylperoxy-2-ethylhexanate, tert-hexylper Oxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylhexanate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy -2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxyacetate, tert-peroxy-3 -methylbenzoate, tert-butylperoxybenzoate, tert-butylperoxyallyl monocarbonate, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

(curing accelerator)

The said thermally conductive composition may also contain a hardening accelerator.

The curing accelerator may accelerate the reaction between the binder resin or the monomer and the curing agent.

Specific examples of the curing accelerator include phosphorus atom-containing compounds such as organic phosphine, tetrasubstituted phosphonium compound, phosphobetaine compound, adduct of phosphine compound and quinone compound, and adduct of phosphonium compound and silane compound. ; amidines and tertiary amines such as dicyandiamide, 1,8-diazabicyclo[5.4.0]undecene-7, and benzyldimethylamine; Nitrogen atom-containing compounds, such as quaternary ammonium salt of the said amidine or the said tertiary amine, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

(Silane coupling agent)

The said thermally conductive composition may also contain a silane coupling agent.

The said silane coupling agent can improve the adhesiveness of the adhesive layer using a thermally conductive composition, and a base material or a semiconductor element.

Specific examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl epoxysilanes such as trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; styryl silanes such as p-styryl trimethoxy silane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. of methacrylsilane; acrylsilanes such as 3-(trimethoxysilyl)propyl methacrylic acid and 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminosilanes such as aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-γ-aminopropyltrimethoxysilane sign; isocyanurate silane; alkyl silanes; ureidosilanes such as 3-ureidopropyltrialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, etc. can be used. These may be used independently and may be used in combination of 2 or more type.

(plasticizer)

The said thermally conductive composition may also contain a plasticizer. By adding a plasticizer, reduction in stress can be realized.

Specific examples of the plasticizer include silicone compounds such as silicone oil and silicone rubber; polybutadiene compounds such as polybutadiene maleic anhydride adducts; An acrylonitrile butadiene copolymerization compound etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

(Other ingredients)

The said thermally conductive composition may contain other components other than the component mentioned above as needed. As another component, a solvent is mentioned, for example.

Although it does not specifically limit as said solvent, For example, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, ethylene glycol monomethyl ether, ethylene glycol Lycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether ter, propylene glycol monobutyl ether, methyl methoxybutanol, α-terpineol, β-terpineol, hexylene glycol, benzyl alcohol, 2-phenylethyl alcohol, isopalmityl alcohol, iso alcohols such as stearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, butyl propylene triglycol, or glycerin; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl) ketones such as -2-cyclohexen-1-one) or diisobutyl ketone (2,6-dimethyl-4-heptanone); 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, esters such as propylene glycol monomethyl ether acetate, 1,2-diacetoxyethane, tributyl phosphate, tricresyl phosphate or tripentyl phosphate; Tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether , ethers such as 1,2-bis(2-diethoxy)ethane or 1,2-bis(2-methoxyethoxy)ethane; esters such as acetic acid 2-(2-butoxyethoxy)ethane; ether alcohols such as 2-(2-methoxyethoxy)ethanol; hydrocarbons such as toluene, xylene, n-paraffin, isoparaffin, dodecylbenzene, terepine oil, kerosene or light oil; nitriles such as acetonitrile or propionitrile; amides such as acetamide or N,N-dimethylformamide; It may include one or two or more selected from silicone oils such as low molecular weight volatile silicone oil or volatile organically modified silicone oil.

By using the solvent, the fluidity of the thermally conductive composition can be controlled. For example, the workability of the thermally conductive composition in the form of a paste can be improved. Moreover, sintering can be accelerated|stimulated by the shrinkage|contraction at the time of heating. Among the solvents, by using a solvent having a relatively high boiling point, preferably by using a solvent having a boiling point higher than the curing temperature, generation of voids in the adhesive layer obtained by heat-treating the thermally conductive composition can be suppressed. The boiling point of this high boiling point solvent may be 180 degreeC - 450 degreeC, and 200 degreeC - 400 degreeC may be sufficient, for example.

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 above-mentioned raw material components is used. Although a well-known method can be used for mixing, for example, 3 rolls, a mixer, etc. can be used.

In addition, you may further perform defoaming with respect to the obtained mixture. Defoaming may leave a mixture still in vacuum, for example.

Next, the manufacturing method of the semiconductor package 100 of this embodiment is demonstrated.

An example of the semiconductor package 100 of this embodiment can be manufactured using the above-mentioned thermally conductive composition.

The manufacturing method of the semiconductor package 100 includes a step of installing the semiconductor element 20 on one surface of a substrate 10 so that the other surface faces it, and one surface side (opposite side to the other surface) of the semiconductor element 20 . A step of applying the thermally conductive composition containing metal particles to the surface, a step of disposing a heat spreader 30 so as to cover at least one surface of the semiconductor element 20 while in contact with the thermally conductive composition, and a substrate ( 10), you may include the process of heat-processing the structure containing the semiconductor element 20, a thermally conductive composition, and the heat spreader 30.

The semiconductor package 100 includes a semiconductor element 10 and a heat spreader 30 via a thermally conductive material 50 including a particle connection structure formed by sintering metal particles in a heat treatment process. ) may include a bonding process.

Moreover, the manufacturing method of the semiconductor package 100 may also include the process of drying the said thermally conductive composition after the process of application|coating and before the process of arrange|positioning. Thereby, leveling property can be improved.

Moreover, in the process of apply|coating, you may apply|coat a thermally conductive composition using a dispenser. Thereby, workability can be improved.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention, and various structures other than the above are employable. In addition, this invention is not limited to the above-mentioned embodiment, The deformation|transformation, improvement, etc. in the range which can achieve the objective of this invention are contained in this invention.

Example

Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples.

<Thermal conductive composition>

Each raw material component was mixed according to the compounding quantity shown in following Table 1, and the varnish was obtained.

The obtained varnish, solvent, and metal particles were blended according to the blending amounts shown in Table 1 below, and kneaded at room temperature with a three-roll mill to prepare a paste-like thermally conductive composition.

Hereinafter, the information of the raw material component of Table 1 is shown.

(binder resin)

・Epoxy resin 1: bisphenol F-type liquid epoxy resin (manufactured by Nippon Kayaku, RE-303S)

(hardener)

Curing agent 1: phenolic resin having a bisphenol F skeleton (solid at room temperature 25°C, made by DIC, DIC-BPF)

Curing agent 2: m, p-cresyl 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, Light Ester EG)

·Acrylic monomer 2: polyalkylene glycol dimethacrylate (Nichi Oil Co., Ltd., PDE-600)

(plasticizer)

Plasticizer 1: Allyl resin (manufactured by Kanto Chemical Co., Ltd., polymer of 1,2-cyclohexanedicarboxylic acid bis(2-propenyl) and propane-1,2-diol)

(Silane coupling agent)

· Silane coupling agent 1: methacrylic acid 3-(trimethoxysilyl)propyl (Shin-Etsu Chemical Co., Ltd., KBM-503P)

· Silane coupling agent 2: 3-glycidyloxypropyl trimethoxysilane (KBM-403E, manufactured by Shin-Etsu Chemical Co., Ltd.)

(curing accelerator)

・Imidazole curing agent 1: 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2PHZ-PW)

(Polymerization Initiator)

·Radical polymerization initiator 1: dicumyl peroxide (Kayaku Akuzo Co., Ltd., Percadox BC)

(solvent)

Solvent 1: Butyl propylene triglycol (BFTG)

(metal particles)

· Silver particle 1: silver powder (DOWA Hi-Tech, AG-DSB-114, spherical, D ₅₀ : 1 μm)

・Silver particle 2: silver powder (manufactured by Fukuda Kinzoku Hakubun Kogyo Co., _{Ltd., HKD-16, flake shape, D 50} : 2 μm)

・Silver coat resin particle 1: Silver plating acrylic resin particle (manufactured by Sano Corporation, SANSILVER-8D, spherical shape, D ₅₀ : 8 μm, monodisperse particle, specific gravity: 2.4, silver weight ratio 50 wt%, resin weight ratio 50 wt%)

・Silver particle 3: silver powder (TC-88, manufactured by Tokuriki Honden Co., _{Ltd., flaky, D 50} : 3 μm)

[Table 1]

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

(thermal conductivity)

The temperature of the obtained thermally conductive composition was raised over 60 minutes from 30 degreeC to 200 degreeC, then, it heat-processed at 200 degreeC for 120 minutes, and obtained the heat treatment body with a thickness of 1 mm. Next, the thermal diffusion coefficient α in the thickness direction of the heat treatment body was measured using the laser flash method. In addition, the measurement temperature was 25 degreeC.

Moreover, the specific heat Cp was measured by differential scanning calorimetry (DSC) measurement, and also the density (rho) was measured based on 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. Incidentally, the unit is W/(m·K).

Thermal conductivity λ [W/(m K)] = α [m ² /sec] × Cp [J/kg K] × ρ [g/cm ³ ]

Both of the thermal conductivity of Example 1 and Reference Example 1 were 20 W/(m·K) or more, and could be used practically without any problem.

(storage modulus)

The obtained thermally conductive composition was heated up over 60 minutes from 30 degreeC to 200 degreeC, Then, it heat-processed at 200 degreeC for 120 minutes, and obtained the heat treatment body. About the obtained heat treatment body, the storage elastic modulus E (MPa) in 25 degreeC was measured by the dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz using the measuring apparatus (The Hitachi High-tech Science company make, DMS6100).

(Observation of particle-linked structure)

A copper lead frame and a silicon chip (length 2 mm x width 2 mm, thickness 0.35 mm) were prepared. Next, the obtained thermally conductive composition was apply|coated to a silicon chip so that it might become an application|coating thickness of 25±10 micrometers, and the copper lead frame was arrange|positioned on it. A laminate was produced in which a silicon chip, a thermally conductive composition, and a copper lead frame were laminated in this order.

Next, the obtained laminate was heated from 30° C. to 200° C. over 60 minutes in the atmosphere, and then heat treated at 200° C. for 120 minutes to harden the thermally conductive composition in the laminate to obtain a thermally conductive material.

Next, using the scanning electron microscope (SEM), the cross section of the heat treatment body of the thermally conductive composition in a laminated body was observed, and the state was evaluated.

In Example 1, as shown in FIG. 2, it confirmed that the silver particle connection structure was formed. Moreover, in the cross-sectional image (FIG. 2), a plurality of substantially circular resin particles are included in the silver particle connection structure, and the metal layer (silver layer) on the surface of the resin particle and the silver particle connection structure are connected. Confirmed. Moreover, it was confirmed that the hardened|cured material of binder resin made it cover silver on parts other than silver, and existed inside the silver particle connection structure.

(Die Sheer Strength)

The obtained thermally conductive composition was apply|coated on the copper substrate of surface nickel plating, and the silicon chip (2 mm x 2 mm) of surface nickel plating was mounted on it. Then, it hardened by heating up to 30 degreeC - 200 degreeC over 60 minutes in oven, then heating at 200 degreeC for 120 minutes.

This sample was placed on a hot plate heated to 260° C., and the die shear strength (N/2 mm×2 mm) was measured using DAGE-4000 (manufactured by Nordson).

In Examples 1 to 3, cohesive 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 as follows.

On one surface of the substrate, a semiconductor element was installed so that the other surface was opposed. The thermally conductive composition containing metal particles was apply|coated to the surface of the one side of a semiconductor element. While in contact with the thermally conductive composition, a heat spreader was disposed so as to cover one surface of the semiconductor element. A structure comprising a substrate, a semiconductor device, a thermally conductive composition, and a heat spreader was heat treated. By heat treatment, the semiconductor element and the heat spreader were joined through the heat conductive material containing the particle|grain connection structure formed by causing sintering of the metal particles in the heat conductive composition, and the semiconductor package was obtained.

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

The semiconductor packages of Examples 1-3 and Comparative Example 1 were used as evaluation samples, and the thermal diffusion coefficient was measured with respect to the surface of a semiconductor element by the laser flash method. Since Examples 1-3 show a higher thermal diffusion coefficient than Comparative Example 1, it turned out that the semiconductor package of Examples 1-3 can have the structure excellent in the heat dissipation characteristic.

Further, in the semiconductor packages of Examples 1 to 3, as compared with Comparative Example 1, in any of the bonding interface between the thermally conductive material and the semiconductor element and the bonding interface between the thermally conductive material and the heat spreader, the adhesive strength is high. value was indicated.

It turned out that the heat conductive material of Examples 1-3 was excellent in die shear strength compared with the reference example 1. By using such a thermally conductive material of Examples 1 to 3 as the TIM1 material, a semiconductor package excellent in heat dissipation characteristics can be realized.

This application claims the priority on the basis of Japanese Patent Application No. 2019-052739 for which it applied on March 20, 2019, and uses all the indication here.

Claims (22)

A semiconductor package comprising a substrate, a semiconductor element provided on the substrate, and a heat spreader surrounding the semiconductor element, wherein the semiconductor element and the heat spreader are joined with a thermally conductive material,
The thermally conductive material, which has a particle connection structure formed by causing metal particles to sinter by heat treatment, the semiconductor package. The method according to claim 1,
The storage elastic modulus in 25 degreeC of the said thermally conductive material measured by the dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz is 1 GPa or more and 10.0 GPa or less, The semiconductor package. The method according to claim 1 or 2,
The semiconductor package in which the thermal conductivity in 25 degreeC of the said thermally conductive material measured using the laser flash method is 10 W/mK or more. 4. The method according to any one of claims 1 to 3,
The metal particles include particles made of a metal,
_{The semiconductor package, wherein the particle size D 50} at the time of 50% accumulation in the volume-based cumulative distribution of the particles made of the metal is 0.8 µm or more and 7.0 µm or less. 5. The method according to claim 4,
The standard deviation of the particle size of the particles made of the metal is 2.0 μm or less, the semiconductor package. 6. The method according to claim 4 or 5,
The semiconductor package of the particles made of the metal, including a combination of two or more having different particle diameter D _50. 7. The method according to any one of claims 4 to 6,
The semiconductor package in which the particle|grains which consist of the said metal contain spherical particle|grains and flake-shaped particle|grains. 8. The method according to any one of claims 1 to 7,
The said metal particle contains the metal-coat resin particle which consists of a resin particle and the metal formed on the surface of the said resin particle, The semiconductor package containing. 9. The method according to any one of claims 1 to 8,
The semiconductor package, wherein the metal particles include particles made of a metal composed of at least one selected from the group consisting of silver, gold, and copper. A semiconductor package comprising a substrate, a semiconductor element provided on the substrate, and a heat spreader surrounding the semiconductor element, wherein the semiconductor element and the heat spreader are joined with a thermally conductive material, wherein the thermally conductive material As a thermally conductive composition used to form,
metal particles,
binder resin,
contains a monomer;
By heat treatment, the metal particles cause sintering to form a particle-connected structure. 11. The method of claim 10,
The thermally conductive composition, wherein the thermal conductivity λ measured by the following procedure A using the thermally conductive composition is 10 W/mK or more.
(Sequence A)
The said thermally conductive composition is heated up over 60 minutes from 30 degreeC to 200 degreeC, Then, it heat-processes at 200 degreeC for 120 minutes, and obtains the heat treatment body of thickness 1mm. With respect to the obtained heat treatment body, the thermal conductivity λ (W/mK) at 25°C is measured using a laser flash method. 12. The method of claim 10 or 11,
The thermally conductive composition whose storage elastic modulus E at 25 degreeC measured by the following procedure B using the said thermally conductive composition is 1 GPa or more and 10.0 GPa or less.
(Sequence B)
The heat conductive composition is heated from 30° C. to 200° C. over 60 minutes, and then heat-treated at 200° C. for 120 minutes to obtain a heat-treated body. About the obtained heat treatment body, the storage elastic modulus E (MPa) in 25 degreeC is measured using the dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz. 13. The method according to any one of claims 10 to 12,
The metal particles include particles made of one or more metal materials selected from the group consisting of silver, gold, and copper, the thermally conductive composition. 14. The method according to any one of claims 10 to 13,
The binder resin, an epoxy resin, an acrylic resin, and an allyl resin comprising at least one selected from the group consisting of, a thermally conductive composition. 15. The method according to any one of claims 10 to 14,
A thermally conductive composition comprising a curing agent. 16. The method according to any one of claims 10 to 15,
The monomer is a glycol monomer, an acrylic monomer, an epoxy monomer, and a thermally conductive composition comprising at least one selected from the group consisting of a maleimide monomer. 17. The method according to any one of claims 10 to 16,
A thermally conductive composition comprising a radical polymerization initiator. 18. The method according to any one of claims 10 to 17,
A thermally conductive composition comprising a silane coupling agent. 19. The method according to any one of claims 10 to 18,
A thermally conductive composition comprising a plasticizer. A step of installing a semiconductor element on one surface of the substrate so that the other surface faces;
a step of applying a thermally conductive composition containing metal particles to the surface of one side of the semiconductor element;
disposing a heat spreader so as to be in contact with the thermally conductive composition and to cover at least one surface of the semiconductor element;
and heat-treating a structure including the substrate, the semiconductor device, the thermally conductive composition, and the heat spreader,
In the step of the heat treatment, the semiconductor element and the heat spreader are joined to each other via a thermally conductive material including a particle connection structure formed by causing the metal particles to sinter. 21. The method of claim 20,
The manufacturing method of the semiconductor package including the process of drying the said thermally conductive composition after the said apply|coating process and before the said arrange|positioning process. 22. The method of claim 20 or 21,
The manufacturing method of the semiconductor package which apply|coats the said thermally conductive composition using a dispenser in the said application|coating process.

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