Resin composition and semiconductor device

Abstract

The present disclosure provides a resin composition that can improve the fluidity of the resin composition and enhance the crack resistance of a cured product. The resin composition contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an aluminum complex (d1) having nitrogen atoms and oxygen atoms. The viscosity of the resin composition at 25°C is 400 Pa·s or less.

Description

Resin composition and semiconductor device

[0001] The present disclosure generally relates to a resin composition and a semiconductor device, and more particularly to a resin composition containing an epoxy compound and a semiconductor device including an encapsulant made from the resin composition.

[0002] Patent Document 1 discloses that, in order to provide an encapsulating resin composition having excellent fluidity while maintaining heat resistance, the encapsulating resin composition contains an epoxy resin, a curing agent having at least one amino group, at least one of a metal complex and a metal compound other than the metal complex, and an inorganic filler, and the total content of the metal complex and at least one of the metal compound other than the metal complex is 0.1 parts by mass or less per 100 parts by mass of the epoxy resin. The patent document discloses that the metal complex and at least one of the metal compound other than the metal complex is at least one of an aluminum chelate complex and an aluminum alkoxide compound.

[0003] Patent No. 6841285

[0004] The object of the present disclosure is to provide a resin composition that can increase the fluidity of the resin composition when heated and increase the crack resistance of the cured product, and a semiconductor device that has an encapsulating portion that includes a cured product of this resin composition.

[0005] A resin composition according to one embodiment of the present disclosure includes a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an aluminum complex (d1) having a ligand (L) having a nitrogen atom and an oxygen atom, and the resin composition has a viscosity of 400 Pa s or less at 25°C.

[0006] A semiconductor device according to one aspect of the present disclosure includes a substrate, a semiconductor element mounted on the substrate, and a sealing portion filling a gap between the substrate and the semiconductor, the sealing portion including a cured product of the resin composition.

[0007] FIG. 1 is a cross-sectional view of a semiconductor device according to an embodiment of the present disclosure.

[0008] 1. Overview An embodiment of the present disclosure will be described. Note that the following embodiments are merely a portion of various embodiments of the present disclosure. Furthermore, the following embodiments can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. The figures referred to below are schematic diagrams, and the dimensional ratios of the components in the figures do not necessarily reflect the actual dimensional ratios. Although the mechanism of action in the embodiments may be described below, this description of the mechanism of action includes an explanation based on speculation, and the present disclosure is not bound by the description of the mechanism of action.

[0009] A resin composition according to an embodiment (hereinafter also referred to as composition (X)) contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an aluminum complex (D). The aluminum complex (D) contains an aluminum complex (d1) having a ligand (L) having a nitrogen atom and an oxygen atom. The viscosity of composition (X) at 25°C is 400 Pa s or less.

[0010] According to the embodiment, the fluidity of the composition (X) is improved. In particular, the viscosity of the composition (X) is reduced by heating the composition (X), and the fluidity of the composition (X) can be improved when the composition (X) is molded while being flowed in this state. Furthermore, the crack resistance of the cured product of the composition (X) can be improved.

[0011] Composition (X) can be used to fabricate a semiconductor device. More specifically, composition (X) can be used to fabricate a sealing portion included in a semiconductor device. In particular, composition (X) can be suitably used to fabricate a sealing portion in which a semiconductor element is filled into a substrate when the semiconductor element is flip-chip mounted on the substrate. That is, composition (X) can be suitably used as an underfill material. In this case, composition (X) easily flows between the semiconductor element and the substrate during fabrication of the sealing portion, thereby improving the manufacturing efficiency of the semiconductor device and preventing the sealing portion from being left unfilled. Furthermore, cracks are less likely to occur in the sealing portion when the semiconductor device is subjected to a load such as an impact or heat, thereby improving the reliability of the semiconductor device.

[0012] The use of the composition (X) is not limited to the encapsulation of semiconductor elements, but the composition (X) can be used for various purposes other than the encapsulation of semiconductor elements.

[0013] The embodiments will be described in more detail below.

[0014] 2. Composition As described above, the composition (X) contains the liquid epoxy compound (A), the liquid aromatic amine compound (B), the inorganic filler (C), and the aluminum complex (D).

[0015] As described above, the epoxy compound (A) is liquid. Liquid means that the epoxy compound (A) has fluidity at 25°C. All components contained in the epoxy compound (A) may be liquid, or the epoxy compound (A) may contain liquid components and solid components, and the epoxy compound (A) may be liquid as a whole by mixing the components. The liquid epoxy compound (A) can impart fluidity to the composition (X).

[0016] The viscosity of the epoxy compound (A) at 25°C is preferably 100 Pa s or less. A viscosity of 50 Pa s or less is more preferable, and a viscosity of 20 Pa s or less is even more preferable. The viscosity of the epoxy compound (A) at 25°C is, for example, 0.01 Pa s or more. A viscosity of 0.02 Pa s or more is even more preferable.

[0017] The epoxy compound (A) preferably contains a compound having two or more epoxy groups in one molecule. In this case, the reactivity of the epoxy compound (A) with the aromatic amine (B) can be further enhanced. As a result, the heat resistance and crack resistance of the cured product of the composition (X) can be further enhanced.

[0018] The epoxy compound (A) contains at least one selected from the group consisting of, for example, diglycidyl ether type epoxy resins such as p-aminophenol type epoxy resins, naphthalene type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol S type epoxy resins, and hydrogenated bisphenol A type epoxy resins; epoxy resins obtained by epoxidizing novolak resins obtained by reacting phenols with aldehydes, such as orthocresol novolak type epoxy resins; glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; glycidylamine type epoxy resins obtained by reacting amine compounds such as aminodiphenylmethane and isocyanuric acid with epichlorohydrin; and silicone-modified epoxy resins (a1).

[0019] The epoxy compound (A) preferably contains a silicone-modified epoxy resin (a1). In this case, the fluidity of the composition (X) can be further enhanced. Furthermore, the silicone-modified epoxy resin (a1) is less likely to lower the glass transition temperature of the cured product of the composition (X) and is less likely to cause weight loss of the cured product under heating. This is thought to be because the silicone skeleton of the silicone-modified epoxy resin (a1) has high heat resistance, and the bond between silicon and oxygen in the silicone skeleton flexibly modifies the molecular chain of the silicone-modified epoxy resin (a1), thereby lowering the viscosity of the composition (X).

[0020] When the epoxy compound (A) contains a silicone-modified epoxy resin (a1), the amount of the silicone-modified epoxy resin (a1) is preferably 5 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the epoxy compound (A). When this amount is 5 parts by mass or more, the fluidity of the composition (X) can be further increased. When this amount is 7 parts by mass or more, more preferably 10 parts by mass or more. When this amount is 30 parts by mass or less, there is an advantage that weight loss when the composition (X) is heated and cured can be further suppressed. When this amount is 25 parts by mass or less, more preferably 20 parts by mass or less.

[0021] It is also preferred that the epoxy compound (A) contains at least one selected from the group consisting of bisphenol A epoxy resins, bisphenol F epoxy resins, p-aminophenol epoxy resins, and naphthalene epoxy resins, in which case the curability of the composition (X) can be particularly enhanced.

[0022] The epoxy compound (A) may contain a commercially available product. For example, the epoxy compound (A) may contain at least one selected from the group consisting of bisphenol F epoxy resin (product name: YDF-8170C, epoxy equivalent: 155 to 165 g / eq) manufactured by Nippon Steel Chemical & Material Co., Ltd., bisphenol A epoxy resin (product name: YD-128, epoxy equivalent: 184 to 194 g / eq) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and multifunctional epoxy resin (product name: jER-630, epoxy equivalent: 90 to 105 g / eq) manufactured by Mitsubishi Chemical Corporation.

[0023] The epoxy equivalent of the epoxy compound (A) is, for example, 40 g / eq. or more and 1000 g / eq. or less. In this case, the reactivity of the epoxy compound (A) with the aromatic amine (B) can be enhanced. The epoxy equivalent of the epoxy compound (A) is preferably 50 g / eq. or more. The epoxy equivalent of the epoxy compound (A) is preferably 300 g / eq. or less.

[0024] As described above, the aromatic amine (B) is liquid. All components contained in the aromatic amine (B) may be liquid, or the aromatic amine (B) may contain liquid components and solid components, and the aromatic amine (B) may be liquid as a whole by mixing the components. The liquid aromatic amine (B) can impart fluidity to the composition (X).

[0025] The aromatic amine (B) preferably contains an aromatic amine (C1) having two or more amino groups per molecule. In this case, the reactivity of the epoxy compound (A) with the aromatic amine (B) can be further enhanced. As a result, the curability of the composition (X) can be further enhanced, and the heat resistance of the cured product of the composition (X) can be further enhanced.

[0026] Examples of the aromatic amine (B) include aliphatic aromatic amines such as m-xylylenediamine, aromatic amines having one aromatic ring such as metaphenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole, and dimethylthiotoluenediamine, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenediamine, and the like. The compound contains at least one member selected from the group consisting of aromatic amines having two aromatic rings, such as bis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, and polytetramethylene oxide diparaaminobenzoate, condensates of aromatic diamines and epichlorohydrin, and reaction products of aromatic diamines and styrene.

[0027] It is particularly preferable that the aromatic amine (B) contains at least one of diethyltoluenediamine and dimethylthiotoluenediamine, in which case the storage stability of the composition (X) can be further improved.

[0028] The aromatic amine (B) may contain a commercially available product. For example, the aromatic amine (B) may contain at least one selected from the group consisting of an amine curing agent manufactured by Nippon Kayaku Co., Ltd. (product name: KAYAHARD AA, amine active hydrogen equivalent: 63.5 g / eq) and a modified aromatic amine curing agent manufactured by ADEKA Corporation (product name: EH-105L, amine active hydrogen equivalent: 61 g / eq).

[0029] The amine active hydrogen equivalent of the aromatic amine (B) is, for example, 20 g / eq. or more and 500 g / eq. or less. In this case, the reactivity between the epoxy compound (A) and the aromatic amine (B) can be enhanced. The amine active hydrogen equivalent means the mass (g) of the aromatic amine (B) containing 1 mole of amine active hydrogen. The amine active hydrogen equivalent of the aromatic amine (B) is, for example, preferably 30 g / eq. or more. The amine active hydrogen equivalent of the aromatic amine (B) is, for example, preferably 100 g / eq. or less.

[0030] The equivalent ratio of the amine active hydrogen of the aromatic amine (B) to the epoxy group of the epoxy compound (A) is preferably 0.6 or more and 1.4 or less. In this case, the epoxy compound (A) and the aromatic amine (B) can react efficiently. This allows the glass transition temperature of the cured product to be appropriately increased, and the crack resistance of the cured product to be improved. This equivalent ratio is more preferably 0.7 or more, and even more preferably 0.8 or more. It is also more preferable that this equivalent ratio is 1.3 or less.

[0031] The inorganic filler (C) can contribute to a low linear expansion coefficient of the cured product, thereby contributing to suppressing warpage and breakage of the semiconductor device. The inorganic filler (C) can also contribute to improving the thermal conductivity of the cured product, thereby improving the heat dissipation properties of the semiconductor device.

[0032] The inorganic filler (C) may contain one or more materials selected from the group consisting of silica such as fused silica, synthetic silica, crystalline silica, and hollow silica; metal oxides such as alumina and titanium oxide; silicates such as talc, calcined clay, uncalcined clay, mica, and glass; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, and calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride. The fused silica may be either fused spherical silica or fused crushed silica.

[0033] The inorganic filler (C) preferably contains silica, which can particularly contribute to increasing the elasticity, decreasing the linear expansion coefficient, and decreasing the dielectric loss tangent of the cured product.

[0034] The particle shape of the inorganic filler (C) is not particularly limited and may be crushed, needle-like, scaly, spherical, etc. In order to improve the dispersibility of the inorganic filler (C) in the composition (X) and to control the viscosity of the composition (X), the particle shape of the inorganic filler (C) is preferably spherical.

[0035] The particles of the inorganic filler (C) are preferably surface-treated with a surface treatment agent. In this case, the dispersibility of the inorganic filler (C) in the composition (X) can be improved. This can suppress a decrease in the fluidity of the composition (X) due to the inorganic filler (C). The surface treatment agent contains at least one selected from the group consisting of, for example, silane-based compounds, titanium-based compounds, aluminum chelates, and aluminum / zirconium-based compounds.

[0036] The silane-based compound contains at least one selected from the group consisting of, for example, a silane compound having an amino group, an epoxy silane, a mercapto silane, an alkyl silane, a ureido silane, and a vinyl silane.

[0037] Specifically, examples of the silane-based compound include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropylmethyldimethoxysilane. thoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyltrimethoxysilane, γ-(N,N-di γ-(N,N-dimethyl)aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl) The compound contains at least one selected from the group consisting of anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane.

[0038] The average particle diameter of the inorganic filler (C) is, for example, 0.1 μm or more and 70 μm or less. In this case, the composition (X) can have good fluidity. The average particle diameter of the inorganic filler (C) is more preferably 0.3 μm or more. It is also more preferably 20 μm or less. The average particle diameter is a volume-based median diameter calculated from the particle size distribution measured by a laser diffraction / scattering method, and can be measured using a commercially available laser diffraction / scattering particle size distribution measuring device.

[0039] The inorganic filler (C) preferably contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and not more than 15 μm and a second inorganic filler (C2) having an average particle size of not more than 0.1 μm. In this case, an increase in viscosity of the composition (X) due to the inorganic filler (C) can be further suppressed. This allows the composition (X) to have better fluidity.

[0040] The average particle size of the first inorganic filler (C1) is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The average particle size of the first inorganic filler (C1) is more preferably 5 μm or less, and more preferably 2 μm or less. The average particle size of the second inorganic filler (C2) is more preferably 5 nm or more, and more preferably 10 nm or more. The average particle size of the second inorganic filler (C2) is more preferably 80 nm or less, and more preferably 60 nm or less.

[0041] When the inorganic filler (C) contains a first inorganic filler (C1) and a second inorganic filler (C2), the amount of the second inorganic filler (C2) is preferably 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the first inorganic filler (C1). In this case, the increase in viscosity of the composition (X) can be further suppressed. It is more preferable that the amount of the second inorganic filler (C2) is 2 parts by mass or more. It is also more preferable that the amount of the second inorganic filler (C2) is 8 parts by mass or less.

[0042] The first inorganic filler (C1) may contain silica or may contain only silica, and the second inorganic filler (C2) may also contain silica or may contain only silica.

[0043] It is particularly preferred that the first inorganic filler (C1) contains silica surface-treated with at least one selected from the group consisting of phenylaminosilane compounds, phenylsilane compounds, epoxysilane compounds, and methacrylsilane compounds. In this case, the fluidity of composition (X) can be further improved, and the storage stability of composition (X) can be further enhanced. In composition (X) containing epoxy compound (A), aromatic amine compound (B), and inorganic filler (C), if inorganic filler (C) is treated with a surface treatment agent, the storage stability may be reduced. However, if the first inorganic filler (C1) contains silica surface-treated with any of the above-mentioned silane compounds, the reduction in the storage stability of composition (X) can be suppressed. The phenylaminosilane compound includes, for example, N-phenyl-3-aminopropyltrimethoxysilane. The phenylsilane compound includes, for example, phenyltrimethoxysilane. The epoxy silane compound contains at least one compound selected from the group consisting of, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The methacryl silane compound contains at least one compound selected from the group consisting of, for example, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.

[0044] The total proportion of the first inorganic filler (C1) and the second inorganic filler (C2) relative to the inorganic filler (C) is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more. The inorganic filler (C) may contain only the first inorganic filler (C1) and the second inorganic filler (C2).

[0045] The proportion of the inorganic filler (C) is preferably 40% by mass or more and 80% by mass or less relative to the total amount of the composition (X). When the proportion of the inorganic filler (C) is 40% by mass or more, the linear expansion coefficient of the composition (X) can be further reduced. This can improve the crack resistance of the cured product of the composition (X). When the proportion of the inorganic filler (C) is 80% by mass or less, the composition (X) can have good fluidity. The proportion of the inorganic filler (C) is more preferably 42% by mass or more, and even more preferably 45% by mass or more. The proportion of the inorganic filler (C) is more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0046] The aluminum complex (D) can improve the fluidity of the composition (X). Furthermore, when the aluminum complex (D) contains an aluminum complex (d1) having a ligand (L) having a nitrogen atom and an oxygen atom, the crack resistance of a cured product of the composition (X) can be enhanced.

[0047] The aluminum complex (d1) contains, for example, an aluminum chelate complex (d11) having a ligand (L1) containing a structure represented by the following formula (1): Here, the term "containing" means that the ligand (L1) contains the structure represented by formula (1) as a part of the overall structure of the ligand (L1).

[0048]

[0049] The reason why the aluminum complex (d1) improves the crack resistance of the cured product is not clear, but it is presumed to be as follows. If radicals remain in the cured product, the deterioration of the cured product caused by the radicals will progress, which may reduce the flexibility of the cured product. However, the ligand (L) having a nitrogen atom and an oxygen atom reacts with the radicals in the cured product, thereby suppressing the remaining radicals in the cured product. Therefore, it is thought that the progression of deterioration of the cured product caused by the radicals is suppressed, and as a result, the flexibility of the cured product is less likely to decrease.

[0050] For example, it is presumed that the ligand (L1) containing the structure shown in the above formula (1) reacts with a radical according to the following reaction: ・are radicals that remain in the cured product.

[0051]

[0052] The ligand (L1) containing the structure shown in formula (1) has, for example, the structure shown in formula (11) below. That is, the aluminum complex (d1) contains, for example, an aluminum chelate complex (d11) having a ligand (L1) having the structure shown in formula (11) below. R in formula (11) is a phenyl group or a naphthyl group. When R is a phenyl group or a naphthyl group, the aluminum complex (d1) can be well dissolved in the liquid aromatic amine compound (B). This contributes to the homogenization of composition (X) and can contribute to improving the fluidity of composition (X).

[0053]

[0054] When the ligand (L1) has a structure represented by formula (11), the aluminum chelate complex (d11) has, for example, a structure represented by the following formula (2): That is, the aluminum chelate complex (d11) contains, for example, an aluminum chelate complex having a structure represented by the following formula (2): R in formula (2) is a phenyl group or a naphthyl group.

[0055]

[0056] The ratio of the aluminum complex (D) to the total of the epoxy compound (A) and the aromatic amine compound (B) is preferably 0.03% by mass or more and 1.2% by mass or less. If this ratio is 0.03% by mass or more, the fluidity of the composition (X) can be further improved. If this ratio is 0.05% by mass or more, it is more preferable, and if it is 0.10% by mass or more, it is even more preferable. If this ratio is 1.2% by mass or less, there is an advantage that deterioration of the storage stability of the composition (X) can be suppressed. If this ratio is 1.0% by mass or less, it is more preferable, and if it is 0.8% by mass or less, it is even more preferable.

[0057] The ratio of the aluminum complex (d1) to the total of the epoxy compound (A) and the aromatic amine compound (B) is preferably 0.03% by mass or more and 1.2% by mass or less. If this ratio is 0.03% by mass or more, the crack resistance of the cured product can be further improved. If this ratio is 0.05% by mass or more, it is more preferable, and if it is 0.10% by mass or more, it is even more preferable. If this ratio is 1.2% by mass or less, there is an advantage that deterioration of the storage stability of the composition (X) can be suppressed. If this ratio is 1.0% by mass or less, it is more preferable, and if it is 0.8% by mass or less, it is even more preferable.

[0058] The aluminum complex (D) may contain only the aluminum complex (d1), or may contain, in addition to the aluminum complex (d1), a component other than the aluminum complex (d1) (hereinafter, also referred to as aluminum complex (d2)). The aluminum complex (d2) can also improve the fluidity of the composition (X).

[0059] The aluminum complex (d2) contains, for example, at least one selected from the group consisting of aluminum trisacetylacetonate and aluminum bisethylacetoacetate monoacetylacetonate.

[0060] When the aluminum complex (D) contains the aluminum complex (d2), the ratio of the aluminum complex (d2) to the aluminum complex (D) is preferably 1% by mass or more and 80% by mass or less. In this case, the fluidity of the composition (X) can be further improved. This ratio is more preferably 3% by mass or more, and even more preferably 5% by mass or more. When this ratio is 80% by mass or less, there is an advantage that deterioration of the storage stability of the composition (X) can be suppressed. This ratio is more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0061] The composition (X) may contain rubber particles (E). When the composition (X) contains the rubber particles (E), the crack resistance of the cured product can be further improved.

[0062] The rubber particles (E) preferably contain at least one of silicone rubber particles and butadiene rubber particles, which can further enhance the crack resistance of the cured product.

[0063] The silicone rubber particles may include, but are not limited to, silicone-based core-shell particles, specifically, commercially available products such as Kane Ace (registered trademark) MX-962 manufactured by Kaneka Corporation. The butadiene rubber particles may include, but are not limited to, butadiene-based core-shell particles, specifically, commercially available products such as Kane Ace (registered trademark) MX-136 manufactured by Kaneka Corporation.

[0064] The ratio of rubber particles (E) to composition (X) is preferably 0.1% by mass or more and 3.0% by mass or less. If the ratio is 0.1% by mass or more, the crack resistance of the cured product can be particularly improved. If this ratio is 0.3% by mass or more, it is more preferable, and if it is 0.5% by mass or more, it is even more preferable. If the ratio of rubber particles (E) is 3.0% by mass or less, there is an advantage that the viscosity of composition (X) is less likely to increase. If this ratio is 2.5% by mass or less, it is more preferable, and if it is 2.0% by mass or less, it is even more preferable.

[0065] The composition (X) may contain an organic phosphorus compound (F). When the composition (X) contains the organic phosphorus compound (F), the storage stability of the composition (X) can be further improved.

[0066] The organic phosphorus compound (F) contains at least one compound selected from the group consisting of, for example, triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, and tris(tetraalkylphenyl)phosphine.

[0067] The ratio of the organic phosphorus compound (F) to the composition (X) is preferably 0.03% by mass or more and 0.70% by mass or less. If the ratio is 0.03% by mass or more, the storage stability of the composition (X) can be further improved. If this ratio is 0.05% by mass or more, it is more preferable, and if it is 0.10% by mass or more, it is even more preferable. If the ratio of the organic phosphorus compound (F) is 0.70% by mass or less, there is an advantage that a decrease in the glass transition temperature of the cured product is suppressed, that is, a decrease in the heat resistance of the cured product can be suppressed. If this ratio is 0.60% by mass or less, it is more preferable, and if it is 0.50% by mass or less, it is even more preferable.

[0068] The composition (X) may contain additives other than the above components, if necessary. The additives are preferably contained in an amount that does not excessively impair the above-mentioned properties of the composition (X) and the curing agent.

[0069] The additive may include at least one selected from the group consisting of, for example, a resin modifier, an antioxidant, a curing aid, a coupling agent, a colorant, a thixotropic agent, an ion trapping agent, an antifoaming agent, a leveling agent, and an antioxidant.

[0070] It is preferred that the composition (X) contains no solvent or only a trace amount of solvent that is unavoidably mixed in.

[0071] The viscosity of composition (X) at 25°C is 400 Pa·s or less. Therefore, composition (X) can have good fluidity during molding. This viscosity is more preferably 100 Pa·s or less, and even more preferably 50 Pa·s or less. Furthermore, the viscosity of composition (X) at 25°C may be, for example, 0.01 Pa·s or more, or even 0.02 Pa·s or more. This viscosity of composition (X) can be achieved by appropriately setting the composition of composition (X) within the range described above. The method for measuring viscosity will be explained in the Examples section.

[0072] 1 shows an example of a semiconductor device 1. The composition (X) in this embodiment is for semiconductor encapsulation. That is, the encapsulation portion 5 in the semiconductor device 1 can be produced from the composition (X). The encapsulation portion 5 is a component that protects the semiconductor element 3 in the semiconductor device 1 by covering a part or all of the semiconductor element 3.

[0073] Composition (X) can be used as an underfill material. The underfill material is a material for producing a sealing portion 5 that fills the gap between a substrate 2 and a semiconductor element 3 surface-mounted on the substrate 2. That is, in this case, the semiconductor device 1 includes a substrate 2, a semiconductor element 3 mounted on the substrate 2, and a sealing portion 5 that fills the gap between the substrate 2 and the semiconductor element 3, and the sealing portion 5 includes a cured product of composition (X).

[0074] The substrate 2 includes an insulating substrate such as a glass epoxy substrate, a polyimide substrate, a polyester substrate, or a ceramic substrate, and conductive wiring 21 overlaid on the insulating substrate. The conductive wiring 21 includes, for example, electrode pads. The substrate 2 is, for example, a motherboard, a package substrate, or an interposer substrate.

[0075] The semiconductor element 3 may be any suitable surface-mount type element. The semiconductor element 3 has bump electrodes 31 on the surface facing the substrate 2. The semiconductor element 3 may be a bare chip, a packaged component, or a wafer-level package. The semiconductor element 3 may be a flip-chip type chip such as a BGA (ball grid array), an LGA (land grid array), or a CSP (chip-size package). The semiconductor element 3 may also be a PoP (package-on-package) type chip.

[0076] A semiconductor element 3 is surface-mounted on the substrate 2. More specifically, the surface of the semiconductor element 3 having bump electrodes 31 faces the substrate 2, the bump electrodes 31 on the semiconductor element 3 are joined to the electrode pads of the conductor wiring 21 on the substrate 2 by solder bumps 4, and the bump electrodes 31 are electrically connected to the electrode pads by the solder bumps 4. Note that the manner of connection between the semiconductor element 3 and the substrate 2 is not limited to the above, as long as the semiconductor element 3 is mounted on the substrate 2 so that a gap is left between the semiconductor element 3 and the substrate 2.

[0077] The sealing portion 5 fills the gap between the semiconductor element 3 and the substrate 2 , so that the bump electrodes 31 , the solder bumps 4 and the electrode pads of the conductor wiring 21 are embedded in the sealing portion 5 .

[0078] In the embodiment, the composition (X) may have a high glass transition temperature, and therefore the semiconductor device 1 may have high heat resistance.

[0079] An example of a method for manufacturing the semiconductor device 1 will now be described. First, the substrate 2, the semiconductor element 3, and the composition (X) are prepared.

[0080] A semiconductor element 3 is surface-mounted on a substrate 2. Specifically, the surface of the semiconductor element 3 having the bump electrodes 31 is placed opposite the substrate 2, and solder bumps 4 are interposed between the bump electrodes 31 on the semiconductor element 3 and the electrode pads of the conductor wiring 21 on the substrate 2. The solder contained in the solder bumps 4 is a lead-free solder with a melting point of 210°C or higher, such as Sn-3.5Ag (melting point 221°C), Sn-2.5Ag-0.5Cu-1Bi (melting point 214°C), Sn-0.7Cu (melting point 227°C), or Sn-3Ag-0.5Cu (melting point 217°C). In this state, the solder bumps 4 are heated and melted by an appropriate heating method such as reflow heating, and then solidified. The heating temperature is set appropriately depending on the solder bumps 4 so that the solder bumps 4 melt, but for example, the maximum heating temperature is 180°C or higher and 300°C or lower. As a result, the conductor wiring 21 and the electrode pads are joined by the solder bumps 4, and the conductor wiring 21 and the electrode pads are electrically connected by the solder bumps 4.

[0081] Next, composition (X) is injected into the gap between the semiconductor element 3 and the substrate 2 using a dispenser or the like. The composition (X) flows through the gap between the semiconductor element 3 and the substrate 2 due to capillary action. When causing the composition (X) to flow, the viscosity of the composition (X) may be reduced by heating the composition (X), if necessary. In this case, the heating temperature of the composition (X) is, for example, 80°C or higher and 130°C or lower. This allows the composition (X) to fill the gap between the semiconductor element 3 and the substrate 2. In the embodiment, the fluidity of the composition (X) can be increased when the composition (X) is heated as described above. Therefore, the composition (X) can be successfully filled into the gap between the semiconductor element 3 and the substrate 2. In this state, the composition (X) is cured by heating. The heating conditions in this case are appropriately set depending on the composition of the composition (X), but are, for example, a heating temperature of 80°C or higher and 180°C or lower, and a heating time of 60 minutes or higher and 300 minutes or lower. As a result, a sealing portion 5 containing the cured product of the composition (X) is produced in the gap between the semiconductor element 3 and the substrate 2 .

[0082] In the embodiment, since the composition (X) can have high fluidity, it is possible to suppress the occurrence of unfilled portions of the composition (X) and the sealing portion 5 between the semiconductor element 3 and the substrate 2 .

[0083] The method for manufacturing the semiconductor device 1 is not limited to the above.

[0084] 4. Aspects The composition (X) according to the first aspect of the present disclosure contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an aluminum complex (d1) having a ligand (L) having a nitrogen atom and an oxygen atom. The viscosity of the composition (X) at 25°C is 400 Pa s or less.

[0085] According to this embodiment, the fluidity of the composition (X) can be increased, and the crack resistance of the cured product can be improved.

[0086] In the second embodiment, the aluminum complex (d1) in the first embodiment contains an aluminum chelate complex (d11) having a ligand (L1) containing a structure represented by formula (1).

[0087]

[0088] In the third embodiment, in the second embodiment, the ligand (L1) has a structure shown in the following formula (11), and R in formula (11) is a phenyl group or a naphthyl group.

[0089]

[0090] In a fourth embodiment, in the third embodiment, the aluminum complex (d11) contains an aluminum chelate complex represented by formula (2): In formula (2), each R is independently a phenyl group or a naphthyl group.

[0091]

[0092] In a fifth aspect, in any one of the first to fourth aspects, the inorganic filler (C) contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and not more than 15 μm, and a second inorganic filler (C2) having an average particle size of 0.1 μm or less, and the amount of the second inorganic filler (C2) is 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the first inorganic filler (C1).

[0093] According to this embodiment, the fluidity of the composition (X) can be further increased.

[0094] In a sixth aspect, in any one of the first to fifth aspects, the first inorganic filler (C1) contains silica that has been surface-treated with at least one compound selected from the group consisting of a phenylaminosilane compound, a phenylsilane compound, an epoxysilane compound, and a methacrylsilane compound.

[0095] According to this embodiment, the fluidity and storage stability of the composition (X) can be further improved.

[0096] In a seventh aspect, in any one of the first to sixth aspects, the epoxy compound (A) contains a silicone-modified epoxy resin (a1).

[0097] According to this embodiment, the fluidity of the composition (X) can be further increased.

[0098] In an eighth aspect, in the seventh aspect, the amount of the silicone-modified epoxy resin (a1) is 5 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the epoxy compound (A).

[0099] According to this embodiment, the fluidity of the composition (X) can be further increased.

[0100] In a ninth aspect, in any one of the first to eighth aspects, the composition (X) further contains rubber particles (E).

[0101] According to this embodiment, the crack resistance of the cured product can be improved.

[0102] In a tenth aspect, in the ninth aspect, the rubber particles (E) contain at least one of butadiene rubber particles and silicone rubber particles.

[0103] According to this embodiment, the crack resistance of the cured product can be further improved.

[0104] In an eleventh aspect, in any one of the first to tenth aspects, the composition (X) further contains an organic phosphorus compound (F).

[0105] According to this embodiment, the fluidity of the composition can be further increased.

[0106] In a twelfth aspect, in any one of the first to eleventh aspects, the composition (X) is for semiconductor encapsulation.

[0107] In a thirteenth aspect, in any one of the first to twelfth aspects, the composition (X) is an underfill material.

[0108] A semiconductor device (1) according to a fourteenth aspect includes a substrate (2), a semiconductor element (3) mounted on the substrate (2), and a sealing portion (5) filling a gap between the substrate (2) and the semiconductor element (3). The sealing portion (5) contains a cured product of the resin composition according to any one of the first to thirteenth aspects.

[0109] Specific examples of the embodiments will be described below, but the present disclosure is not limited to these examples.

[0110] 1. Preparation of Compositions Compositions were prepared by mixing the components shown in the table. Details of the components in the table are as follows: - Epoxy compound #1: Manufactured by Nippon Steel Chemical & Material Co., Ltd. Product name: YDF8170. Liquid bisphenol F type epoxy resin. Epoxy equivalent: 160 g / eq. - Epoxy compound #2: Manufactured by Momentive Performance Materials Japan, LLC. Product name: TSL9906. Liquid silicone-modified epoxy resin (siloxane oligomer with glycidoxypropyl groups at both ends). Epoxy equivalent: 181 g / eq. - Curing agent: Manufactured by Nippon Kayaku Co., Ltd. Product name: KAYAHARD A-A. Liquid aromatic amine resin. Amine active hydrogen equivalent: 63.5 g / eq. - Silica #1: Silica with an average particle size of 0.4 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Silica #2: Silica with an average particle size of 0.4 μm, surface-treated with phenyltrimethoxysilane. - Silica #3: Silica with an average particle size of 0.4 μm, surface-treated with 3-glycidoxypropyltrimethoxysilane. - Silica #4: Silica with an average particle size of 0.4 μm, surface-treated with 3-methacryloxypropyltrimethoxysilane. - Silica #5: Silica with an average particle size of 0.7 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Silica #6: Silica with an average particle size of 1.0 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Silica #7: Manufactured by Admatechs Co., Ltd. Product name: YA-010A-JER. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 and silica with an average particle size of 10 nm. Silica concentration: 25% by mass. - Aluminum complex #1: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Product name Q1301. Aluminum N-nitrosophenylhydroxylamine. - Aluminum complex #2: Manufactured by Kawaken Fine Chemicals Co., Ltd. Product name Aluminum Chelate A. Aluminum tris(acetylacetonate). - Organic phosphorus compound: triphenylphosphine. - Rubber particles #1: Manufactured by Kaneka Corporation Product name MX-139. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 g / eg and core-shell rubber particles with a polybutadiene rubber core. Concentration of rubber particles: 33% by mass.- Rubber particles #2: manufactured by Kaneka Corporation. Product name MX-965. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 g / eg and core-shell rubber particles with a silicone rubber core. Rubber particle concentration: 25% by mass. - Coupling agent: manufactured by Momentive Performance Materials Japan LLC. Product name SILQUEST A-187 SILANE. 3-glycidoxypropyltrimethoxysilane.

[0111] 2. Evaluation The compositions were evaluated as follows, and the results are shown in the table below.

[0112] (1) Viscosity at 25° C. The viscosity of the composition at 25° C. was measured using a B-type rotational viscometer (TVB-10H, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm.

[0113] (2) Storage Stability The composition was subjected to a treatment of being exposed to a temperature of 40°C for 8 hours. The viscosity of the composition before this treatment (η0) and the viscosity of the composition after this treatment (η1) were measured using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., TVB-10H) at a temperature of 40°C and a rotation speed of 20 rpm. From these results, the viscosity increase rate ((η1-η0)×100 / η0) was calculated.

[0114] When this result is 100% or less, the storage stability can be evaluated as good, and when it is 50% or less, the storage stability can be evaluated as particularly good.

[0115] (3) Fluidity Two glass slides were placed facing each other with a gap of 50 μm between them, and the composition was poured between the glass slides at a temperature of 110° C. The composition was allowed to flow between the glass slides. The time from the start of pouring until the maximum movement distance of the composition between the glass slides reached 30 mm was measured.

[0116] If the result is 500 seconds or less, the fluidity can be evaluated as good, and if the result is 300 seconds or less, the fluidity can be evaluated as particularly good.

[0117] (4) Viscosity at 110°C The temperature dependency of the composition was measured using a rheometer (manufactured by Anton Paar, model number: MCR-102) under conditions of a rotation speed of 1 rpm, a gap of 300 μm, and a heating rate of 5°C / min, and the viscosity of the composition at 110°C was read from the results.

[0118] If this result is in the range of 0.4 Pa·s or less, the fluidity of the composition when heated can be evaluated as good, and if it is in the range of 0.2 Pa·s or less, the fluidity of the composition when heated can be evaluated as particularly good.

[0119] (5) Crack Resistance 10 mg of the composition was applied in an X-shape onto a silicon substrate measuring 25 mm × 25 mm × 775 μm. A silicon substrate measuring 7 mm × 7 mm × 775 μm was placed on the applied composition. In this state, the silicon substrate and composition were heated at 80 °C for 60 seconds and then cooled to 25 °C. As a result, the composition spread between the two silicon substrates, and a fillet of the composition protruded from the periphery of the silicon substrate measuring 7 mm × 7 mm × 775 μm. The silicon substrate and composition were heated at 100 °C for 2 hours and then at 165 °C for 2 hours to prepare a sample for evaluation. The sample was placed in a constant temperature bath at 175 °C for 500 hours, and then the appearance of the sample was evaluated. If the sample had two or fewer corner cracks, it could be evaluated as having particularly good crack resistance. The corner cracks are cracks that occur in the fillet of the cured composition near the corners of a substrate measuring 7 mm x 7 mm x 775 µm.

[0120]

[0121]

[0122] REFERENCE SIGNS LIST 1 semiconductor device 2 substrate 3 semiconductor element 5 sealing portion

Claims

1. A resin composition comprising a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an aluminum complex (d1) having a ligand (L) having a nitrogen atom and an oxygen atom, the resin composition having a viscosity of 400 Pa·s or less at 25°C.

2. The aluminum complex (d1) contains an aluminum chelate complex (d11) having a ligand (L1) having a structure represented by the following formula (1): The resin composition according to claim 1.

3. The ligand (L1) has a structure shown in the following formula (11), in which R is a phenyl group or a naphthyl group. The resin composition according to claim 2.

4. The aluminum chelate complex (d11) contains an aluminum chelate complex represented by the following formula (2), in which each R is independently a phenyl group or a naphthyl group. The resin composition according to claim 3.

5. The resin composition according to claim 1, wherein the inorganic filler (C) contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and not more than 15 μm, and a second inorganic filler (C2) having an average particle size of 0.1 μm or less, and the amount of the second inorganic filler (C2) is 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the first inorganic filler (C1).

6. The resin composition according to claim 5, wherein the first inorganic filler (C1) contains silica that has been surface-treated with at least one compound selected from the group consisting of a phenylaminosilane compound, a phenylsilane compound, an epoxysilane compound, and a methacrylsilane compound.

7. The resin composition according to claim 1, wherein the epoxy compound (A) contains a silicone-modified epoxy resin (a1).

8. The resin composition according to claim 7, wherein the amount of the silicone-modified epoxy resin (a1) is 5 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the epoxy compound (A).

9. The resin composition according to claim 1, further comprising rubber particles (E).

10. The resin composition according to claim 9, wherein the rubber particles (E) contain at least one of butadiene rubber particles and silicone rubber particles.

11. The resin composition according to claim 1, further comprising an organic phosphorus compound (F).

12. The resin composition according to claim 1, which is used for semiconductor encapsulation.

13. The resin composition according to claim 1, which is an underfill material.

14. A semiconductor device comprising: a substrate; a semiconductor element mounted on the substrate; and a sealing portion filling a gap between the substrate and the semiconductor element, the sealing portion comprising a cured product of a resin composition according to any one of claims 1 to 13.

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