阅读说明：本技术 密封用树脂组合物和半导体装置 (Resin composition for sealing and semiconductor device ) 是由 伊东昌治 于 2020-03-12 设计创作，主要内容包括：本发明的密封用树脂组合物含有：成分(A),选自3-氨基-1,2,4-三唑和4-氨基-1,2,4-三唑中的1种以上的化合物；和成分(B),环氧树脂。(The sealing resin composition of the present invention contains: component (A), at least 1 compound selected from the group consisting of 3-amino-1, 2, 4-triazole and 4-amino-1, 2, 4-triazole; and component (B), an epoxy resin.)

1. A resin composition for sealing, characterized in that,

comprises the following components (A) and (B),

(A) 1 or more compounds selected from 3-amino-1, 2, 4-triazole and 4-amino-1, 2, 4-triazole;

(B) and (3) epoxy resin.

2. The resin composition for sealing according to claim 1,

the component (B) is 1 or more than 2 selected from triphenylmethane type epoxy resin, biphenyl aralkyl type multifunctional epoxy resin, o-cresol type difunctional epoxy resin, biphenyl type difunctional epoxy resin and bisphenol type difunctional epoxy resin.

3. The sealing resin composition according to claim 1 or 2, further comprising an inorganic filler as the component (C).

4. The resin composition for sealing according to any one of claims 1 to 3,

further contains a silane coupling agent as a component (D).

5. The resin composition for sealing according to any one of claims 1 to 4,

the content of the component (a) is 0.01 to 1% by mass based on the entire sealing resin composition.

6. A semiconductor device is characterized in that a semiconductor element,

a semiconductor device sealed with a cured product of the sealing resin composition according to any one of claims 1 to 5.

Technical Field

The present invention relates to a sealing resin composition and a semiconductor device.

Background

As a resin composition for sealing electronic components, there is a composition described in patent document 1 (jp 62-25118 a). This document describes a sealing resin composition containing an epoxy resin, a novolak-type phenol resin, a predetermined amount of 2-vinyl-4, 6-diaminos-triazine, and a predetermined amount of an inorganic filler, as a technique for providing a sealing resin composition which is excellent in resistance to electrolytic corrosion caused by metal ions or ionic halogens and excellent in moisture resistance, while maintaining the advantages of conventional compositions. This document describes that when a predetermined amount of 2-vinyl-4, 6-diamino-s-triazine is blended, a sealing resin composition which is resistant to galvanic corrosion and has excellent moisture resistance can be obtained.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 62-25118

Disclosure of Invention

Technical problem to be solved by the invention

As a result of conducting research on the technique described in patent document 1, the inventors of the present invention have found that there is room for improvement in the adhesion to metal members and in the reliability of semiconductor devices obtained using the sealing resin composition described in the above document.

The invention provides a resin composition for sealing, which has excellent adhesion with metal parts and can obtain a semiconductor device with excellent reliability.

Means for solving the problems

According to the present invention, there is provided a sealing resin composition containing the following components (a) and (B):

(A) 1 or more compounds selected from 3-amino-1, 2, 4-triazole and 4-amino-1, 2, 4-triazole;

(B) and (3) epoxy resin.

Further, according to the present invention, a semiconductor device in which a semiconductor element is sealed with a cured product of the sealing resin composition of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a sealing resin composition which has excellent adhesion to a metal member and can provide a semiconductor device having excellent reliability can be provided.

Drawings

Fig. 1 is a sectional view showing a structure of a semiconductor device according to an embodiment.

Fig. 2 is a sectional view showing a structure of a semiconductor device according to an embodiment.

Detailed Description

Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and the description thereof is omitted as appropriate. The drawings are schematic and do not necessarily correspond to actual dimensional ratios. In the present embodiment, each component of the composition may contain 2 or more kinds alone or in combination.

(sealing resin composition)

In the present embodiment, the sealing resin composition contains the following components (a) and (B).

(A) 1 or more compounds selected from 3-amino-1, 2, 4-triazole and 4-amino-1, 2, 4-triazole

(B) Epoxy resin

(component (A))

The component (A) is an aminotriazole compound, specifically 1 or more compounds selected from the group consisting of 3-amino-1, 2, 4-triazole and 4-amino-1, 2, 4-triazole.

The component (a) preferably contains 3-amino-1, 2, 4-triazole, and more preferably 3-amino-1, 2, 4-triazole from the viewpoint of improving adhesion to metal parts and from the viewpoint of ease of handling.

The content of the component (a) in the sealing resin composition is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, and even more preferably 0.04 mass% or more with respect to the entire sealing resin composition, from the viewpoint of stably improving the adhesion between the sealing material and the metal member. The content of the component (a) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less, based on the entire sealing resin composition, from the viewpoint of excellent fluidity and storage stability of the sealing resin composition.

(component (B))

The epoxy resin of the component (B) is a compound having 2 or more epoxy groups in 1 molecule, and may be a monomer, an oligomer or a polymer.

The epoxy resin is specifically selected from: crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin and the like; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; multifunctional epoxy resins such as triphenylmethane type epoxy resins and alkyl-modified triphenol methane type epoxy resins; phenol aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene skeleton and phenol aralkyl type epoxy resins having a biphenylene skeleton; naphthol type epoxy resins such as dihydroxynaphthalene type epoxy resins and epoxy resins obtained by glycidyletherifying a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; 1 or more than 2 of bridge ring hydrocarbon compound modified phenol epoxy resin such as dicyclopentadiene modified phenol epoxy resin.

From the viewpoint of improving the adhesion to the metal member, the component (B) is preferably 1 or 2 or more selected from the group consisting of triphenylmethane type epoxy resins, biphenyl aralkyl type polyfunctional epoxy resins, o-cresol type bifunctional epoxy resins, biphenyl type bifunctional epoxy resins and bisphenol type bifunctional epoxy resins.

From the same viewpoint, the component (B) is preferably 1 or 2 or more selected from the group consisting of tris (hydroxyphenyl) methane type epoxy resins, phenol aralkyl type epoxy resins containing a biphenylene skeleton, o-cresol novolac type epoxy resins and 3,3 ', 5, 5' -tetramethylbiphenol diglycidyl ether type epoxy resins.

The content of the component (B) in the sealing resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, based on the entire sealing resin composition, from the viewpoint of obtaining appropriate fluidity during molding and improving filling properties and moldability.

In addition, from the viewpoint of improving the reliability of a device obtained using the sealing resin composition, the content of the component (B) in the sealing resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably 10% by mass or less, relative to the entire sealing resin composition.

The sealing resin composition preferably does not contain a maleimide compound. The sealing resin composition is formed to contain the components (a) and (B) and not contain a maleimide compound, whereby the adhesion between the sealing material obtained using the sealing resin composition and the metal member can be improved, and the curability of the sealing resin composition at low temperature can also be improved.

Here, the maleimide compound is specifically a compound having 2 or more maleimide groups. Further, it is preferable that the maleimide compound is not intentionally added to the sealing resin composition, and the content of the maleimide compound in the sealing resin composition is preferably substantially 0 mass%, for example, not more than the detection limit.

The sealing resin composition may contain components other than the components (a) and (B). For example, the sealing resin composition may contain one or both of the following components (C) and (D).

(C) Inorganic filler

(D) Silane coupling agent

(component (C))

The component (C) is an inorganic filler. As the inorganic filler, a material generally used in a resin composition for sealing a semiconductor can be used. The component (C) may be a surface-treated material.

Specific examples of the component (C) include: silica such as fused silica, crystalline silica, amorphous silica, or the like; alumina; talc; titanium oxide; silicon nitride; aluminum nitride. These inorganic fillers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The component (C) preferably contains silica from the viewpoint of excellent versatility. Examples of the shape of the silica include spherical silica and crushed silica.

The average particle diameter (d) of the component (C) is determined from the viewpoint of improving moldability and adhesion₅₀) Preferably 5 μm or more, more preferably 10 μm or more, and preferably 80 μm or less, more preferably 50 μm or less, and further preferably 40 μm or less.

The particle size distribution of the component (C) can be obtained by measuring the particle size distribution of the particles on a volume basis using a commercially available laser diffraction particle size distribution measuring apparatus (for example, SALD-7000, manufactured by Shimadzu corporation).

From the viewpoint of improving moldability and adhesion, the maximum particle diameter of the component (C) is preferably 10 μm or more, more preferably 20 μm or more, and preferably 100 μm or less, more preferably 80 μm or less, and further preferably 50 μm or less.

In addition, the specific surface area of the component (C) is preferably 1m from the viewpoint of improving moldability and adhesiveness²A value of at least g, more preferably 3m²A total of 20m or more and²a ratio of 10m or less per gram²The ratio of the carbon atoms to the carbon atoms is less than g.

From the viewpoint of improving the low moisture absorption and low thermal expansion properties of the sealing material formed using the sealing resin composition, and more effectively improving the moisture resistance reliability and reflow resistance of the obtained semiconductor device, the content of the component (C) in the sealing resin composition is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 65 mass% or more with respect to the entire sealing resin composition.

From the viewpoint of more effectively improving the flowability and filling property at the time of molding of the sealing resin composition, the content of the component (C) in the sealing resin composition may be, for example, 97% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less, based on the entire sealing resin composition.

(component (D))

The component (D) is a silane coupling agent.

Examples of the component (D) include aminosilanes such as epoxysilane, mercaptosilane, and phenylaminosilane. From the viewpoint of improving the adhesion between the sealing material and the metal member, the component (D) is preferably an epoxy silane or an aminosilane, and more preferably a secondary aminosilane. From the same viewpoint, the component (D) is preferably 1 or more selected from the group consisting of phenylaminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

The content of the component (D) in the sealing resin composition is preferably 0.01 mass% or more, and more preferably 0.05 mass% or more, based on the entire sealing resin composition, from the viewpoint that the sealing resin composition can obtain preferable fluidity during molding.

The content of the component (D) in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, based on the entire sealing resin composition, from the viewpoint of suppressing thickening of the resin viscosity.

(curing agent)

The sealing resin composition may further contain a curing agent. The curing agent can be roughly classified into 3 types, for example, an addition polymerization type curing agent, a catalyst type curing agent, and a condensation type curing agent, and 1 or 2 or more of these can be used.

Examples of the addition polymerization type curing agent include: polyamine compounds including aliphatic polyamines such as Diethylenetriamine (DETA), triethylenetetramine (TETA), and m-xylylenediamine (MXDA), aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS), Dicyandiamide (DICY), and organic acid dihydrazide; acid anhydrides including alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), and aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA) and Benzophenone Tetracarboxylic Dianhydride (BTDA); phenolic resin curing agents such as novolak-type phenolic resins and polyvinyl phenols; polythiol compounds such as polysulfides, thioesters and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins.

Examples of the catalyst-type curing agent include: tertiary amine compounds such as Benzyldimethylamine (BDMA) and 2,4, 6-tris-dimethylaminomethylphenol (DMP-30); imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI 24); BF (BF) generator₃Lewis acids such as complexes, etc.

Examples of the condensation type curing agent include: a phenolic resin; urea resins such as methylol group-containing urea resins; melamine resins such as methylol group-containing melamine resins, and the like.

Among these, a phenol resin curing agent is preferable from the viewpoint of improving the balance among flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. As the phenolic resin curing agent, any of monomers, oligomers, and polymers having 2 or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and the molecular structure thereof are not limited.

Examples of the phenolic resin curing agent used as the curing agent include: novolak-type phenol resins such as phenol novolak resin, cresol novolak resin, and bisphenol novolak resin; polyvinyl phenol; multifunctional phenol resins such as phenol/hydroxybenzaldehyde resins and triphenol methane type phenol resins; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl type phenol resins such as phenol aralkyl resins having at least one of a phenylene skeleton and a biphenylene skeleton, and naphthol aralkyl resins having at least one of a phenylene skeleton and a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F, and these may be used alone in 1 kind or in combination with 2 or more kinds. Among these, from the viewpoint of improving the insulating properties of a semiconductor device obtained using the sealing resin composition, 1 or 2 or more selected from the group consisting of a triphenolmethane-type phenol resin, a biphenylaralkyl-type phenol resin, a novolak-type phenol resin, a phenol aralkyl-type resin having a biphenylene skeleton and a phenol aralkyl-type/formaldehyde polycondensate having a biphenylene skeleton are more preferably used.

In the present embodiment, the content of the curing agent in the sealing resin composition is, for example, 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more, with respect to the entire sealing resin composition, from the viewpoint of achieving excellent fluidity during molding and improving filling properties and moldability.

In the semiconductor device obtained using the sealing resin composition, the content of the curing agent in the sealing resin composition is preferably 25% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less with respect to the entire sealing resin composition, from the viewpoint of improving moisture resistance reliability and reflow resistance.

The sealing resin composition may contain components other than the above components, and may contain, for example, 1 or more of various additives such as a curing accelerator, a fluidity imparting agent, a release agent, an ion scavenger, a low stress component, a flame retardant, a colorant, and an antioxidant. The sealing resin composition may further contain 1 or more of 2-hydroxy-N-1H-1, 2, 4-triazol-3-ylbenzamide and 3-amino-5-mercapto-1, 2, 4-triazole, for example.

Among them, the curing accelerator may contain, for example, a compound selected from: phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphate betaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; amidine and tertiary amine exemplified by 1, 8-diazabicyclo [5.4.0] undecene-7, benzyldimethylamine and 2-methylimidazole, and nitrogen atom-containing compounds such as quaternary salts of the amidine and amine; 1 or 2 or more kinds of polyhydroxy naphthalene compounds such as 2, 3-dihydroxy naphthalene. Among these, compounds containing a phosphorus atom are more preferable from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, compounds having a latent property such as tetra-substituted phosphonium compounds, phosphate betaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds are more preferably contained.

The content of the curing accelerator in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, based on the entire sealing resin composition, from the viewpoint of improving the curing characteristics of the sealing resin composition.

In addition, the content of the curing accelerator in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, based on the entire sealing resin composition, from the viewpoint of obtaining preferable fluidity during molding of the sealing resin composition.

The release agent may contain, for example, a compound selected from: natural waxes such as carnauba wax; synthetic waxes such as montanic acid ester wax, oxidized polyethylene wax and the like; higher fatty acids such as zinc stearate and metal salts thereof; paraffin wax; and 1 or more than 2 of carboxylic acid amides such as erucamide.

From the viewpoint of improving the releasability of the cured product of the sealing resin composition, the content of the release agent in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, and is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.5% by mass or less, based on the entire sealing resin composition.

Specific examples of the ion scavenger include hydrotalcite.

From the viewpoint of improving the reliability of the sealing material, the content of the ion scavenger in the sealing resin composition is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and preferably 1.0 mass% or less, more preferably 0.5 mass% or less, with respect to the entire sealing resin composition.

Specific examples of the low-stress component include silicones such as silicone oil, silicone rubber, silicone elastomer, and silicone resin; acrylonitrile butadiene rubber.

From the viewpoint of improving the reliability of the sealing material, the content of the low-stress component in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, relative to the entire sealing resin composition.

Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate and phosphazene.

The content of the flame retardant in the sealing resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, relative to the entire sealing resin composition, from the viewpoint of improving the flame retardancy of the sealing material.

Specific examples of the colorant include carbon black and red iron oxide.

The content of the colorant in the sealing resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 2% by mass or less, more preferably 1% by mass or less, relative to the entire sealing resin composition, from the viewpoint of excellent color tone of the sealing material.

Specific examples of the antioxidant include hindered phenol compounds, hindered amine compounds, and thioether compounds.

Next, the physical properties of the sealing resin composition or the cured product thereof will be described.

The sealing resin composition of the present embodiment is cured on a copper plate at 175 ℃ for 180 seconds to obtain a cured product, and further heated at 175 ℃ for 3 hours, wherein the shear strength (die shear strength) between the copper plate and the cured product is preferably 10MPa or more, more preferably 12MPa or more at room temperature (25 ℃ C.). By setting in this manner, for example, even when an element having a large heat generation is used as a semiconductor device or when a device exposed to a higher temperature condition is manufactured, higher reliability can be ensured.

From the same viewpoint, when a cured product is obtained by curing the copper plate under the above conditions and further heated under the above conditions, the shear strength between the copper plate and the cured product is preferably 0.95MPa or more, more preferably 1.0MPa or more, and still more preferably 1.1MPa or more at 260 ℃.

The upper limit of the shear strength is not limited, and is, for example, 30MPa or less at room temperature or 260 ℃.

Further, the sealing resin composition of the present embodiment is cured on a nickel plate at 175 ℃ for 180 seconds to obtain a cured product, and when the cured product is further heated at 175 ℃ for 3 hours, the shear strength between the nickel plate and the cured product is preferably 5.0MPa or more, more preferably 7.0MPa or more, further preferably 7.5MPa or more, and further preferably 10MPa or more at room temperature. By setting in this manner, for example, even when an element having a large heat generation is used as a semiconductor device or when a device exposed to a higher temperature condition is manufactured, higher reliability can be ensured.

From the same viewpoint, when a cured product is obtained by curing a nickel plate under the above conditions and further heated under the above conditions, the shear strength between the nickel plate and the cured product is preferably 0.5MPa or more, more preferably 0.7MPa or more, and still more preferably 1.0MPa or more at 260 ℃.

The upper limit of the shear strength is not limited, and is, for example, 30MPa or less at room temperature or 260 ℃.

The method for measuring the shear strength will be described later in the first example.

Next, the shape of the sealing resin composition will be described.

In the present embodiment, the shape of the sealing resin composition can be selected according to the molding method of the sealing resin composition, and examples thereof include a granular shape such as a tablet shape, a powder shape, and a pellet shape; and (4) sheet-shaped.

The sealing resin composition can be produced, for example, by mixing the above components in a known manner, melt-kneading the mixture with a kneading machine such as a roll, kneader or extruder, cooling the mixture, and pulverizing the cooled mixture. Further, the resin composition for sealing may be obtained in the form of particles or flakes by pulverizing and molding. For example, the sealing resin composition may be formed into a pellet form by compression molding. Further, for example, a sheet-like sealing resin composition can be obtained by a vacuum extruder. Further, the dispersion degree, fluidity, and the like of the obtained resin composition for sealing can be appropriately adjusted.

The sealing resin composition obtained in the present embodiment contains the components (a) and (B), and therefore has excellent adhesion to metal members. More specifically, according to the present embodiment, the adhesion between the sealing material and the member made of Ag, Ni, Cu, or an alloy containing 1 or more of these elements can be improved.

Further, by using the sealing resin composition obtained in the present embodiment, a semiconductor device having excellent reliability can be obtained.

(semiconductor device)

The semiconductor device of the present embodiment is a device in which a semiconductor element is sealed with a cured product of the sealing resin composition of the present embodiment. Specific examples of the semiconductor element include an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, a solid-state imaging element, and the like. The semiconductor element is preferably an element that does not involve the input and output of light, other than an optical semiconductor element such as a light receiving element and a light emitting element (e.g., a light emitting diode).

The base material of the semiconductor device is, for example, a wiring board such as an Interposer (Interposer) or a lead frame. The semiconductor element is electrically connected to the base material by wire bonding, flip chip bonding, or the like.

Examples of the semiconductor device obtained by sealing a semiconductor element by seal molding using the sealing resin composition include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array Package), LF-BGA (Lead frame Ball Grid Array Package), FCBGA (Flip Chip Ball Grid Array Package), BGA (Ball Grid Array Package), and ebb (Embedded Ball Grid Array Package), BGA (die Array Package), and BGA (Ball Grid Array Package), Fan-In eWLB, Fan-Out eWLB, and the like.

Hereinafter, the description will be more specifically made with reference to the drawings.

Fig. 1 and 2 are cross-sectional views each showing a structure of a semiconductor device. However, in this embodiment, the structure of the semiconductor device is not limited to the structure shown in fig. 1 and 2.

First, the semiconductor device 100 shown in fig. 1 includes a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 for sealing the semiconductor element 20.

The sealing material 50 is composed of a cured product obtained by curing the sealing resin composition of the present embodiment.

Fig. 1 illustrates a case where the substrate 30 is a circuit substrate. At this time, as shown in fig. 1, a plurality of solder balls 60, for example, are formed on the other surface of the substrate 30 opposite to the surface on which the semiconductor element 20 is mounted. The semiconductor element 20 is mounted on the substrate 30, and is electrically connected to the substrate 30 via a wire 40. On the other hand, the semiconductor element 20 may be flip-chip mounted on the substrate 30. Here, the lead wire 40 may be an Ag wire, a Ni wire, a Cu wire, an Au wire, or an Al wire, for example, and the lead wire 40 is preferably made of Ag, Ni, or Cu or an alloy containing 1 or more of these, but is not particularly limited.

The sealing material 50 seals the semiconductor element 20 so as to cover, for example, the other surface of the semiconductor element 20 opposite to the one surface of the counter substrate 30. In the example shown in fig. 1, the sealing material 50 is formed so as to cover the other surface and the side surface of the semiconductor element 20.

In the present embodiment, the sealing material 50 is composed of a cured product of the sealing resin composition. Therefore, in the semiconductor device 100, the sealing material 50 has excellent adhesion to the lead 40, and thus the semiconductor device 100 has excellent reliability.

The sealing material 50 can be formed by sealing and molding the sealing resin composition by a known method such as a transfer molding method or a compression molding method.

Fig. 2 is a cross-sectional view showing the structure of the semiconductor device 100 according to the present embodiment, and shows an example different from fig. 1. The semiconductor element 100 shown in fig. 2 uses a lead frame as the substrate 30. In this case, the semiconductor element 20 is mounted on, for example, the die pad 32 of the substrate 30, and is electrically connected to the external lead 34 via the wire 40. The sealing material 50 is composed of a cured product of the sealing resin composition of the present embodiment, as in the example shown in fig. 1.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than the above-described configurations may be adopted.

Examples

Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. However, the present embodiment is not limited to the description of the examples.

Examples 1 to 7 and comparative examples 1 to 7

(preparation of sealing resin composition)

For each example and each comparative example, a resin composition for sealing was prepared in the following manner, respectively.

First, the components shown in table 1 were mixed by a mixer. Next, the obtained mixture was roll-kneaded, cooled, and pulverized to obtain a sealing resin composition as a powder or granule.

The details of each component in table 1 are as follows. The blending ratio of each component shown in table 1 represents the blending ratio (mass%) of the entire resin composition.

(raw materials)

(inorganic Filler)

(C) Inorganic filler 1: fused spherical silica, FB series, available from Denko corporation (average particle diameter 27.2 μm, specific surface area 1.5 m)²G, upper limit cut-off 75 μm)

(C) Inorganic filler 2: fused silica, FMT-05, manufactured by Fumetita corporation

(C) Inorganic filler 3: fused spherical silica, FB-105, available from Denko corporation (average particle diameter 10.6 μm, specific surface area 5).1m²G, upper limit cut-off 71 μm)

(C) Inorganic filler 4: 99.35% by mass of fused spherical silica S30-71 (manufactured by Meiguang Co., Ltd.) (average particle diameter: 23.1 μm, specific surface area: 1.75 m) was surface-treated with 0.65% by mass of KBM-903 (. gamma. -aminopropyltriethoxysilane)²G, upper limit cut-off 75 μm)

(C) Inorganic filler 5: fused spherical silica, TS13-006, manufactured by Meiguang corporation (average particle diameter 28 μm, specific surface area 2.5 m)²G, upper limit cut-off 75 μm)

(C) Inorganic filler 6: fused spherical silica ES series manufactured by Tokai Minerals (average particle diameter 28.0 μm, specific surface area 1.0 m)²G, upper limit cut-off 75 μm)

(C) Inorganic filler 7: fused silica, FMT-15C, manufactured by Fumetai corporation (C) inorganic filler 8: fused spherical silica, FB series, available from Denko corporation (average particle diameter 31 μm, specific surface area 1.6 m)²/g)

(C) Inorganic filler 9: 99.35% by mass of amorphous silica (ES-355, manufactured by Tokai Minerals Co.) was surface-treated with 0.65% by mass of gamma-aminopropyltriethoxysilane

(C) Inorganic filler 10: spherical alumina, CB-60C, manufactured by Showa Denko K.K

(C) Inorganic filler 11: silazane-treated microsilica, SC-2500-SQ, manufactured by ADMATECHS

(C) Inorganic filler 12: fused spherical silica, SC-2500-SQ manufactured by ADMATECHS

(C) Inorganic filler 13: fused spherical silica, SC-5500-SQ manufactured by ADMATECHS

(C) Inorganic filler 14: alumina manufactured by ADMATECHS

(C) Inorganic filler 15: fused spherical silica, fumed silica (REOLOSIL) CP102, manufactured by Deshan corporation

(silane coupling agent)

(D) Silane coupling agent 1: phenylaminopropyl trimethoxysilane, CF-4083, manufactured by Torredo Corning Co., Ltd

(D) Silane coupling agent 2: gamma-glycidoxypropyltrimethoxysilane, manufactured by GPS-M, JNC

(D) Silane coupling agent 3: 3-mercaptopropyltrimethoxysilane, manufactured by JNC Co Ltd

(epoxy resin)

(B) Epoxy resin 1: tris (hydroxyphenyl) methane-type epoxy resin, E1032H60, Mitsubishi chemical corporation

(B) Epoxy resin 2: phenylaralkyloxy epoxy resin having biphenylene skeleton, NC3000, manufactured by Nippon Kabushiki Kaisha

(B) Epoxy resin 3: o-cresol novolac epoxy resin, YDCN-800-62, available from Nissi iron chemical Co., Ltd

(B) Epoxy resin 4: o-cresol novolac epoxy resin, YDCN-800-65, available from Nissi iron chemical Co., Ltd

(B) Epoxy resin 5: o-cresol novolac epoxy resin, N685EXP-S, DIC

(B) Epoxy resin 6: 3,3 ', 5, 5' -Tetramethylbiphenol diglycidyl ether type epoxy resin, YX4000HK, manufactured by Mitsubishi chemical corporation

(B) Epoxy resin 7: phenol aralkyl type epoxy resin having biphenylene skeleton, NC3000L, manufactured by Nippon Kabushiki Kaisha

(curing agent)

Curing agent 1: triphenolmethane-type phenol resin, MEH-7500, manufactured by Michelson chemical Co., Ltd

Curing agent 2: phenol aralkyl type resin containing biphenylene skeleton, MEH-7851SS, MIKANGCHE CHEMICAL Co., Ltd

Curing agent 3: phenol aralkyl type/formaldehyde polycondensate containing biphenylene skeleton, produced by Kogyo Kabushiki Kaisha

Curing agent 4: novolac type phenol resin, PR-51714, manufactured by Sumitomo Bakelite Co., Ltd

Curing agent 5: novolac type phenol resin, PR-55617, manufactured by Sumitomo Bakelite Co., Ltd

(curing accelerators)

Curing accelerator 1: 4-hydroxy-2- (triphenylphosphonium) phenolate

Curing accelerator 2: tetraphenylphosphonium-4, 4' -sulfonyldiphenol salts

Curing accelerator 3: triphenylphosphine, PP-360 micropowder, K.I Chemical Industry Co., LTD

Curing accelerator 4: adduct of tetraphenylphosphonium and bis (naphthalene-2, 3-dioxo) phenylsilicate, product of Sumitomo bakelite Co., Ltd

Curing accelerator 5: 2, 3-dihydroxynaphthalene, manufactured by AIR WATER

Curing accelerator 6: 4-hydroxy-2- (triphenylphosphonium) phenolate, K.I Chemical Industry Co., manufactured by LTD

(mold releasing agent)

Mold release agent 1: carnauba WAX, C-WAX, manufactured by Toyo chemical Co., Ltd

And (2) release agent: montan acid ester wax, Licowax E, manufactured by JAPONICA CORPORATION

And (3) release agent: carnauba wax, TOWAX-132, manufactured by TOYACHE CHEMICAL CO., LTD

And (4) release agent: erucamide, Alflow P-10, manufactured by Nichisu oil Co., Ltd

And (5) release agent: oxidized polyethylene wax, Licowax PED191 manufactured by JAPONIC corporation

(ion scavenger)

Ion scavenger 1: magnesium/aluminum/hydroxide/carbonate/hydrate, DHT-4H, from Kyowa Chemicals K.K.

(flame retardant)

Flame retardant 1: aluminum hydroxide, CL-303, manufactured by Sumitomo chemical Co., Ltd

(additives)

Additive 1: 2-hydroxy-N-1H-1, 2, 4-triazol-3-ylbenzamide manufactured by ADEKA Inc

Additive 2: 3-amino-5-mercapto-1, 2, 4-triazole, ASTA-P, NIPPON CARBIDE INDUSTRIES CO., INC

(A) Additive 3: 3-amino-1, 2, 4-triazoles

(coloring agent)

Colorant 1: carbon Black, carbon #5, manufactured by Mitsubishi chemical corporation

Colorant 2: carbon Black, ERS-2001, manufactured by Toyo carbon Co., Ltd

(Low-stress agent)

Low-stress agent 1: silicone resin, KR-480, manufactured by shin-Etsu chemical industries, Ltd

Low-stress agent 2: silicone elastomer, CF-2152, manufactured by Torildo Corning Co., Ltd

Low-stress agent 3: acrylonitrile butadiene rubber, CTBN1008SP, product of Ud Kyoho K.K

Low-stress agent 4: silicone oil, FZ-3730, manufactured by Donglidao Corning Co., Ltd

Low-stress agent 5: molten reactant A obtained in production example 1

Production example 1

66.1 parts by mass of an epoxy resin represented by the following formula (8) (bisphenol A type epoxy resin, manufactured by Nippon epoxy resin Co., Ltd., JeR (registered trademark) YL6810, softening point 45 ℃ C., epoxy equivalent 172) was heated and melted at 140 ℃, and 33.1 parts by mass of organopolysiloxane 1 (organopolysiloxane represented by the following formula (7)) and 0.8 part by mass of triphenylphosphine were added and melt-mixed for 30 minutes to obtain a molten reactant A.

(in the above formula (7), the average value of n7 is 7.5.)

(evaluation)

Using the resin compositions obtained in the respective examples, evaluation samples were prepared in the following manner, and the adhesion and reliability of the obtained samples were evaluated in the following manner.

(Adhesivity)

The sealing resin compositions obtained in the respective examples were measured for shear strength of cured after plastic sealing (PMC) as an index of adhesion by the following method.

The sealing resin compositions obtained in the respective examples were molded using a low-pressure transfer molding machine ("AV-600-50-TF", manufactured by Hill-Tokyo Seiki Seisaku-Sho Ltd.)10 test copper lead frames or nickel plates having a temperature of 175 deg.C, an injection pressure of 10MPa and a curing time of 180 seconds were molded into a 9X 29mm stripThe adhesion strength test piece of (1).

Then, the samples cured at 175 ℃ for 3 hours were measured for shear strength at Room Temperature (RT) or 260 ℃ using an automatic weld strength measuring apparatus (model DAGE4000, manufactured by Nordson Advanced Technology k.k.), to determine the shear strength (MPa).

(reliability: temperature cycle test)

The sealing resin compositions obtained in the respective examples were molded into TO-220 (package size: 114 mm. times.30 mm, thickness: 1.3mm, no chip mounted, lead frame made of Cu or Ni plated product) using a low pressure transfer molding machine ("MSL-06M" manufactured by APIC YAMADA CORPORATION) at a mold temperature of 175 ℃ under an injection pressure of 10MPa for a curing time of 180 seconds, and cured at 175 ℃ for 4 hours TO prepare semiconductor devices for testing. The sealed test semiconductor device was subjected to a 100-cycle temperature cycle test at-40 to 150 ℃ to determine the presence or absence of a package crack or part-to-part separation. The measurement results are shown in "number of failures/number of samples" in Table 1. The "defective number/sample number" was 4/10 or less and was judged as acceptable.

[ Table 1]

As is clear from table 1, when example 1 and comparative example 1, example 2 and comparative example 2, example 3 and comparative example 3, example 4 and comparative example 4, example 5 and comparative example 5, example 6 and comparative example 6, and example 7 and comparative example 7 were compared with each other, the sealing resin compositions obtained in the respective examples were excellent in adhesion to metal members. Further, by using the sealing resin compositions obtained in the respective examples, a semiconductor device having excellent reliability can be obtained.

The present application claims priority based on japanese application laid-open at 27/3/2019, japanese application laid-open at 2019-.

Description of the reference numerals

20: semiconductor element, 30: substrate, 32: chip pad, 34: external lead, 40: wire, 50: sealing material, 60: solder ball, 100: a semiconductor device is provided.