Resin composition and semiconductor device

Abstract

This disclosure provides a resin composition capable of improving the flowability of a resin composition and enhancing the crack resistance of the 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 having nitrogen and oxygen atoms (d1). The viscosity of the resin composition at 25°C is less than 400 Pa·s.

Description

Technical Field

[0001] This disclosure generally relates to resin compositions and semiconductor devices, and more specifically to resin compositions containing epoxy compounds and semiconductor devices having a sealing portion made of the resin composition. Background Technology

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

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent No. 6841285 Summary of the Invention

[0006] The present invention addresses the need to provide a resin composition that improves the fluidity of the resin composition when heated and improves the crack resistance of the cured product, and a semiconductor device having a sealing portion comprising the cured product containing the resin composition.

[0007] One embodiment of the resin composition disclosed herein comprises 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 nitrogen and oxygen atoms. The viscosity of the above resin composition at 25°C is less than 400 Pa·s.

[0008] One aspect of the semiconductor device disclosed herein includes a substrate, a semiconductor element mounted on the substrate, and a sealing portion filling the gap between the substrate and the semiconductor element. The sealing portion comprises a cured product of the resin composition. Attached Figure Description

[0009] Figure 1 This is a cross-sectional view of a semiconductor device in an embodiment of the present disclosure. Detailed Implementation

[0010] 1. Summary

[0011] The embodiments of this disclosure will be described. It should be noted that the following embodiments are only a part of the various embodiments of this disclosure. Furthermore, various modifications can be made to the following embodiments based on design, etc., as long as the purpose of this disclosure is achieved. The figures referred to below are schematic diagrams, and the size ratios of the constituent elements in the figures may not reflect the actual size ratios. Hereinafter, the mechanisms of action in the embodiments will sometimes be described, but such descriptions include speculative explanations, and this disclosure is not bound by the descriptions of the mechanisms of action.

[0012] The resin composition of the 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), which has ligands (L) having nitrogen and oxygen atoms. The viscosity of composition (X) at 25°C is 400 Pa·s or less.

[0013] According to the embodiment, the fluidity of composition (X) is improved. In particular, the viscosity of composition (X) can be reduced by heating composition (X), and in this state, the fluidity of composition (X) can be improved when it is formed while flowing. In addition, the crack resistance of the cured composition (X) can be improved.

[0014] Composition (X) can be used to fabricate semiconductor devices. More specifically, composition (X) can be used to fabricate sealing portions of semiconductor devices. In particular, when semiconductor elements are flip-chip mounted on a substrate, composition (X) can be suitably used to fabricate sealing portions filled by the semiconductor elements 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 the fabrication of the sealing portion, thereby improving the manufacturing efficiency of the semiconductor device and suppressing unfilled sealing portions. Furthermore, when the semiconductor device is subjected to loads such as those caused by impact or heat, cracks are less likely to form in the sealing portion, thus improving the reliability of the semiconductor device.

[0015] It should be noted that the use of composition (X) is not limited to sealing semiconductor devices. Composition (X) can be used for a variety of applications other than sealing semiconductor devices.

[0016] The implementation method will be described in more detail below.

[0017] 2. Composition

[0018] As described above, composition (X) contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and an aluminum complex (D).

[0019] As described above, the epoxy compound (A) is in a liquid state. Liquid means having fluidity at 25°C. The components contained in the epoxy compound (A) can be entirely liquid, or the epoxy compound (A) can contain both liquid and solid components, with the entire epoxy compound (A) being liquid through mixing these components. The liquid epoxy compound (A) imparts fluidity to the composition (X).

[0020] The viscosity of epoxy compound (A) at 25°C is preferably 100 Pa·s or less. More preferably, it is 50 Pa·s or less, and even more preferably 20 Pa·s or less. Furthermore, the viscosity of epoxy compound (A) at 25°C is, for example, 0.01 Pa·s or more. More preferably, it is 0.02 Pa·s or more.

[0021] 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 improved. As a result, the heat resistance and crack resistance of the cured composition (X) can be further improved.

[0022] The epoxy compound (A) includes, for example, at least one of the following: diglycidyl ether type epoxy resins selected from 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 epoxidation of phenolic resins obtained by reacting phenols with aldehydes, represented by o-cresol phenolic resins; glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acids with epichlorohydrin; glycidyl amine type epoxy resins obtained by reacting amine compounds such as aminodiphenylmethane and isocyanuric acid with epichlorohydrin; and organosilicon modified epoxy resins (a1).

[0023] The epoxy compound (A) preferably contains a silicone-modified epoxy resin (a1). In this case, the flowability of the composition (X) can be further improved. Furthermore, the silicone-modified epoxy resin (a1) does not easily lower the glass transition temperature of the cured composition (X), and it is less likely to cause weight loss of the cured product under heating. This is believed to be because the silicone-modified epoxy resin (a1) has a silicone backbone with high heat resistance, and the silicon-oxygen bonding in the silicone backbone makes the molecular chains of the silicone-modified epoxy resin (a1) flexible, thereby reducing the viscosity of the composition (X).

[0024] When the epoxy compound (A) contains a silicone-modified epoxy resin (a1), the amount of silicone-modified epoxy resin (a1) relative to 100 parts by weight of the epoxy compound (A) is preferably 5 parts by weight or more and 30 parts by weight or less. If this amount is 5 parts by weight or more, the flowability of the composition (X) can be further improved. This amount is more preferably 7 parts by weight or more, and even more preferably 10 parts by weight or more. If this amount is 30 parts by weight or less, it has the advantage of being able to further suppress the weight loss when the composition (X) is heated and cured. This amount is more preferably 25 parts by weight or less, and even more preferably 20 parts by weight or less.

[0025] Preferably, the epoxy compound (A) contains at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, p-aminophenol type epoxy resin, and naphthalene type epoxy resin. In this case, the curability of the composition (X) can be particularly improved.

[0026] The epoxy compound (A) may contain commercially available products. For example, the epoxy compound (A) may contain at least one selected from bisphenol F type epoxy resin (trade name: YDF-8170C, epoxy equivalent: 155-165 g / eq) manufactured by NIPPONSTEEL Chemical & Material Co., Ltd., bisphenol A type epoxy resin (trade name: YD-128, epoxy equivalent: 184-194 g / eq) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and multifunctional epoxy resin (trade name: jER-630, epoxy equivalent: 90-105 g / eq) manufactured by Mitsubishi Chemical Co., Ltd.

[0027] 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 improved. 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.

[0028] As described above, the aromatic amine (B) is in a liquid state. The aromatic amine (B) may contain entirely liquid components, or it may contain both liquid and solid components, with the aromatic amine (B) being entirely liquid by mixing these components. The liquid aromatic amine (B) imparts fluidity to the composition (X).

[0029] The aromatic amine (B) preferably contains an aromatic amine (C1) having two or more amino groups in one molecule. In this case, the reactivity between the epoxy compound (A) and the aromatic amine (B) can be further improved. As a result, the curability of the composition (X) is further improved, and the heat resistance of the cured composition (X) can be further improved.

[0030] Aromatic amines (B) include, for example, aromatic amines with one aromatic ring selected from aliphatic aromatic amines such as m-phenylenediamine, m-phenylenediamine, 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 dimethylthiotoluene diamine, as well as 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4 At least one of the following: '-methylenebis(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 aromatic amines having two aromatic rings such as polytetramethylene oxide di-p-aminobenzoate, condensates of aromatic diamines with epichlorohydrin, and reaction products of aromatic diamines with styrene.

[0031] The aromatic amine (B) is particularly preferably composed of at least one of diethyltoluenediamine and dimethylthiotoluenediamine. In this case, the storage stability of the composition (X) can be further improved.

[0032] Aromatic amine (B) may contain commercially available products. For example, aromatic amine (B) may contain at least one product selected from Nippon Kayaku Co., Ltd.'s amine curing agent (trade name: KAYAHARD AA, amine active hydrogen equivalent: 63.5 g / eq) and ADEKA Co., Ltd.'s modified aromatic amine curing agent (trade name: EH-105L, amine active hydrogen equivalent: 61 g / eq).

[0033] 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 epoxide (A) and the aromatic amine (B) can be improved. It should be noted that the amine active hydrogen equivalent refers to 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 preferably, for example, 30 g / eq. or more. The amine active hydrogen equivalent of the aromatic amine (B) is preferably, for example, 100 g / eq. or less.

[0034] The equivalence ratio of the 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. Therefore, the glass transition temperature of the cured product is moderately increased, and the crack resistance of the cured product is also improved. This equivalence ratio is more preferably 0.7 or more, and even more preferably 0.8 or more. This equivalence ratio is also more preferably 1.3 or less.

[0035] Inorganic filler material (C) can help reduce the coefficient of linear expansion of the cured material, thereby helping to suppress warping and breakage of semiconductor devices. Inorganic filler material (C) can also help improve the thermal conductivity of the cured material, thereby improving the heat dissipation of semiconductor devices.

[0036] The inorganic filler material (C) may contain, for example, one or more of the following: silica such as fused silica, synthetic silica, crystalline silica, and hollow silica; metal oxides such as alumina and titanium dioxide; 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 fragmented silica.

[0037] The inorganic filler material (C) is particularly preferably containing silica. In this case, silica can particularly contribute to the high elasticity, low coefficient of linear expansion, and low dielectric loss tangent of the cured material.

[0038] The particle shape of the inorganic filler material (C) can be fragmented, needle-like, flake-like, spherical, etc., without particular limitation. In order to improve the dispersibility of the inorganic filler material (C) in the composition (X) and control the viscosity of the composition (X), the particle shape of the inorganic filler material (C) is preferably spherical.

[0039] The particles of the inorganic filler material (C) are preferably surface-treated with a surface treatment agent. In this case, the dispersibility of the inorganic filler material (C) in the composition (X) can be improved. This suppresses the reduction in the flowability of the composition (X) caused by the inorganic filler material (C). The surface treatment agent contains, for example, at least one selected from silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds.

[0040] The silane compound contains, for example, at least one selected from silane compounds having an amino group, epoxy silanes, mercaptosilanes, alkyl silanes, ureosilanes, and vinyl silanes.

[0041] Specifically, silane compounds include, for example, those selected from vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyl 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-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 At least one of the following: γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, and γ-mercaptopropylmethyldimethoxysilane.

[0042] The average particle size of the inorganic filler material (C) is, for example, 0.1 μm or more and 70 μm or less. In this case, the composition (X) can have good flowability. The average particle size of the inorganic filler material (C) is more preferably 0.3 μm or more. The average particle size of the inorganic filler material (C) is even more preferably 20 μm or less. It should be noted that the average particle size is the median particle size of the volume reference calculated based on the particle size distribution measured by laser diffraction and scattering, and can be measured using a commercially available laser diffraction and scattering particle size distribution measuring device.

[0043] The inorganic filler (C) preferably contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and less than 15 μm, and a second inorganic filler (C2) having an average particle size of less than 0.1 μm. In this case, the viscosity increase of the composition (X) caused by the inorganic filler (C) can be suppressed in one step. As a result, the composition (X) can have better flowability.

[0044] The average particle size of the first inorganic filler material (C1) is more preferably 0.3 μm or more, and even more preferably 0.5 μm or more. The average particle size of the first inorganic filler material (C1) is more preferably 5 μm or less, and even more preferably 2 μm or less. The average particle size of the second inorganic filler material (C2) is more preferably 5 nm or more, and even more preferably 10 nm or more. The average particle size of the second inorganic filler material (C2) is more preferably 80 nm or less, and even more preferably 60 nm or less.

[0045] When the inorganic filler material (C) contains a first inorganic filler material (C1) and a second inorganic filler material (C2), the amount of the second inorganic filler material (C2) is preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the first inorganic filler material (C1). In this case, the viscosity increase of the composition (X) can be further suppressed. The amount of the second inorganic filler material (C2) is more preferably 2 parts by mass or more. The amount of the second inorganic filler material (C2) is also more preferably 8 parts by mass or less.

[0046] The first inorganic filler material (C1) may contain silicon dioxide or contain only silicon dioxide. The second inorganic filler material (C2) may also contain silicon dioxide or contain only silicon dioxide.

[0047] The first inorganic filler material (C1) particularly preferably contains silica that has been surface-treated with at least one selected from phenylaminosilane compounds, phenylsilane compounds, epoxysilane compounds, and methacryloxysilane compounds. In this case, the flowability of the composition (X) can be further improved, and the storage stability of the composition (X) can be further improved. In the composition (X) containing an epoxy compound (A), an aromatic amine compound (B), and an inorganic filler material (C), if the inorganic filler material (C) is treated with a surface treatment agent, the storage stability may sometimes decrease. However, if the first inorganic filler material (C1) contains silica that has been surface-treated with any of the aforementioned silane compounds, the decrease in the storage stability of the composition (X) can be suppressed. Phenylaminar silane compounds include, for example, N-phenyl-3-aminopropyltrimethoxysilane. Phenylsilane compounds include, for example, phenyltrimethoxysilane. Epoxysilane compounds, for example, contain at least one selected from 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Methacrylsilane compounds, for example, contain at least one selected from 3-methacryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltriethoxysilane.

[0048] The total proportion of the first inorganic filler material (C1) and the second inorganic filler material (C2) relative to the inorganic filler material (C) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The inorganic filler material (C) may contain only the first inorganic filler material (C1) and the second inorganic filler material (C2).

[0049] The proportion of inorganic filler (C) relative to the total amount of composition (X) is preferably 40% by mass or more and 80% by mass or less. If the proportion of inorganic filler (C) is 40% by mass or more, the coefficient of linear expansion of composition (X) can be further reduced. This improves the crack resistance of the cured composition (X). If the proportion of inorganic filler (C) is 80% by mass or less, composition (X) can have good flowability. The proportion of inorganic filler (C) is more preferably 42% by mass or more, and even more preferably 45% by mass or more. The proportion of inorganic filler (C) is more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0050] The aluminum complex (D) can improve the flowability of the composition (X). Furthermore, by including the aluminum complex (D) with an aluminum complex (d1) having a ligand (L) having nitrogen and oxygen atoms, the crack resistance of the cured composition (X) can be improved.

[0051] The aluminum complex (d1) contains an aluminum chelate (d11) having a ligand (L1) comprising, for example, the structure shown in formula (1) below. It should be noted that "comprising" here means that the ligand (L1) comprises the structure shown in formula (1) as part of the overall structure of the ligand (L1).

[0052] [Chemical Formula 1]

[0053]

[0054] The rationale for improving the crack resistance of cured products through aluminum complexes (d1) is unclear, but the following speculation is made: If free radicals remain in the cured product, degradation caused by free radicals will occur, potentially reducing the product's flexibility. However, ligands (L) with nitrogen and oxygen atoms react with free radicals in the cured product, thereby inhibiting the presence of residual free radicals. Therefore, it is believed that the degradation of the cured product caused by free radicals is suppressed, thus reducing the product's flexibility.

[0055] For example, it is speculated that the ligand (L1) containing the structure shown in formula (1) above reacts with a free radical via the following reaction. It should be noted that X in the following... · These are the free radicals remaining in the solidified material.

[0056] [Chemical Formula 2]

[0057]

[0058] The ligand (L1) comprising 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 (d11) having a ligand (L1) having the structure shown in formula (11) below. R in formula (11) is phenyl or naphthyl. If R is phenyl or naphthyl, the aluminum complex (d1) is well soluble in liquid aromatic amine compound (B). This contributes to the homogenization of composition (X) and helps to improve the flowability of composition (X).

[0059] [Chemical Formula 3]

[0060]

[0061] When the ligand (L1) has the structure shown in formula (11), the aluminum chelate (d11) has, for example, the structure shown in formula (2) below. That is, the aluminum chelate (d11) contains an aluminum chelate having, for example, the structure shown in formula (2) below. R in formula (2) is phenyl or naphthyl.

[0062] [Chemical Formula 4]

[0063]

[0064] 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 flowability of the composition (X) can be further improved. This ratio is more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more. If this ratio is 1.2% by mass or less, it has the advantage of suppressing the deterioration of the storage stability of the composition (X). This ratio is more preferably 1.0% by mass or less, and even more preferably 0.8% by mass or less.

[0065] 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. This ratio is more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more. If this ratio is 1.2% by mass or less, it has the advantage of suppressing the deterioration of the storage stability of the composition (X). This ratio is more preferably 1.0% by mass or less, and even more preferably 0.8% by mass or less.

[0066] The aluminum complex (D) may contain only the aluminum complex (d1), or it may contain other components besides the aluminum complex (d1) (hereinafter also referred to as the aluminum complex (d2)). The aluminum complex (d2) can also improve the flowability of the composition (X).

[0067] The aluminum complex (d2) contains, for example, at least one selected from aluminum triacetylacetonate and aluminum diacetylacetonate monoacetylacetonate.

[0068] When the aluminum complex (D) contains aluminum complex (d2), the ratio of aluminum complex (d2) to aluminum complex (D) is preferably 1% by mass or more and 80% by mass or less. In this case, the flowability 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. If this ratio is 80% by mass or less, it has the advantage of being able to suppress the deterioration of the storage stability of the composition (X). This ratio is more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0069] The composition (X) may contain rubber particles (E). If the composition (X) contains rubber particles (E), the crack resistance of the cured product can be further improved.

[0070] The rubber particles (E) preferably contain at least one of silicone rubber particles and butadiene rubber particles. In this case, the crack resistance of the cured product can be further improved.

[0071] Organosilicon rubber particles may contain, for example, organosilicon-based core-shell particles. Specifically, they may contain commercially available products such as Kaneka Corporation's trade name Kane Ace (registered trademark) MX-962, but are not limited to these. Butadiene rubber particles may contain, for example, butadiene-based core-shell particles. Specifically, they may contain commercially available products such as Kaneka Corporation's trade name Kane Ace (registered trademark) MX-136, but are not limited to these.

[0072] 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 high. This ratio is more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. If the ratio of rubber particles (E) is 3.0% by mass or less, it has the advantage of not easily causing an increase in the viscosity of composition (X). This ratio is more preferably 2.5% by mass or less, and even more preferably 2.0% by mass or less.

[0073] Composition (X) may contain an organophosphorus compound (F). If composition (X) contains an organophosphorus compound (F), the storage stability of composition (X) can be further improved.

[0074] Organophosphorus compounds (F) contain, for example, at least one selected from triphenylphosphine, diphenyl(p-tolyl)phosphine, tri(alkylphenyl)phosphine, tri(dialkylphenyl)phosphine, tri(trialkylphenyl)phosphine and tri(tetraalkylphenyl)phosphine.

[0075] The ratio of organophosphorus compound (F) to 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 composition (X) can be further improved. This ratio is more preferably 0.05% by mass or more, and even more preferably 0.10% by mass or more. If the ratio of organophosphorus compound (F) is 0.70% by mass or less, it has the advantage of suppressing the decrease in the glass transition temperature of the cured product, that is, suppressing the decrease in the heat resistance of the cured product. This ratio is more preferably 0.60% by mass or less, and even more preferably 0.50% by mass or less.

[0076] The composition (X) may contain additives other than those described above, as needed. Preferably, the additives are contained within a range that does not excessively impair the aforementioned properties related to the composition (X) and the curing agent.

[0077] The additives may contain at least one selected from resin modifiers, antioxidants, curing aids, coupling agents, colorants, thixotropic agents, ion scavengers, defoamers, leveling agents, and antioxidants.

[0078] The preferred composition (X) is solvent-free or contains only trace amounts of solvent that are unavoidably mixed in.

[0079] The viscosity of composition (X) at 25°C is 400 Pa·s or less. Therefore, composition (X) exhibits good flowability during molding. More preferably, this viscosity is 100 Pa·s or less, and even more preferably 50 Pa·s or less. Furthermore, the viscosity of composition (X) at 25°C is, for example, 0.01 Pa·s or more, and can be 0.02 Pa·s or more. The 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 is described in the Examples section.

[0080] 3. Semiconductor devices

[0081] exist Figure 1 An example of a semiconductor device 1 is shown. The composition (X) in the embodiment is used for semiconductor sealing. That is, the sealing portion 5 in the semiconductor device 1 can be made from the composition (X). The sealing portion 5 is a component that protects the semiconductor element 3 by covering part or all of the semiconductor element 3 in the semiconductor device 1.

[0082] Composition (X) can be used as an underfill material. The underfill material is a material used to create a sealing portion 5 that fills the gap between the substrate 2 and the 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, the sealing portion 5 containing a cured product of composition (X).

[0083] The substrate 2 includes, for example, an insulating substrate such as a glass epoxy board, a polyimide substrate, a polyester substrate, or a ceramic substrate, and conductive wiring 21 superimposed on the insulating substrate. The conductive wiring 21 includes, for example, electrode pads. The substrate 2 is, for example, a mother substrate, a packaging substrate, or an interposer substrate.

[0084] Semiconductor element 3 can be any suitable surface-mount component. Semiconductor element 3 has bump electrodes 31 on the surface opposite to substrate 2. Semiconductor element 3 can be a bare die, a packaged component, or a wafer-level package. Semiconductor element 3 can be, for example, a flip-chip type chip such as BGA (Ball Grid Array), LGA (Pad Grid Array), or CSP (Chip Scale Package). Semiconductor element 3 can also be a PoP (PoP) type chip.

[0085] Semiconductor element 3 is surface-mounted on substrate 2. Specifically, the surface of semiconductor element 3 with bump electrodes 31 faces substrate 2, and the bump electrodes 31 of semiconductor element 3 are joined to the electrode pads of conductor wiring 21 in substrate 2 via solder bumps 4, and the bump electrodes 31 and electrode pads are electrically connected via solder bumps 4. It should be noted that as long as the semiconductor element 3 is mounted on substrate 2 with a gap between it and substrate 2, the connection method between semiconductor element 3 and substrate 2 is not limited to the above method.

[0086] The sealing portion 5 is filled in the gap between the semiconductor element 3 and the substrate 2, so the bump electrode 31, the solder bump 4 and the electrode pad of the conductor wiring 21 are buried by the sealing portion 5.

[0087] In this embodiment, since the composition (X) can have a high glass transition temperature, the semiconductor device 1 can have high heat resistance.

[0088] An example of a method for manufacturing semiconductor device 1 will be described. First, the aforementioned substrate 2, semiconductor element 3, and composition (X) are prepared.

[0089] Semiconductor element 3 is surface-mounted onto substrate 2. Specifically, the surface of semiconductor element 3 with bump electrode 31 is positioned opposite substrate 2, and solder bump 4 is positioned between the bump electrode 31 of semiconductor element 3 and the electrode pad of conductor wiring 21 in substrate 2. The solder contained in solder bump 4 is, for example, 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, solder bump 4 is heated to melt by a suitable heating method such as reflow heating, and then solidified. The heating temperature is appropriately set according to solder bump 4 to melt solder bump 4, for example, the maximum heating temperature is 180°C or higher and 300°C or lower. Thus, the conductor wiring 21 and the electrode pad are joined by the solder bump 4, and the conductor wiring 21 and the electrode pad are electrically connected by the solder bump 4.

[0090] Next, the 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 within the gap due to capillary action. While the composition (X) is flowing, its viscosity can be reduced by heating it as needed. In this case, the heating temperature of the composition (X) is, for example, 80°C or higher and 130°C or lower. This fills the gap between the semiconductor element 3 and the substrate 2 with the composition (X). In this embodiment, as described above, the flowability of the composition (X) can be improved when heated. Therefore, the composition (X) can be well 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 according to the composition (X), for example, a heating temperature of 80°C or higher and 180°C or lower, and a heating time of 60 minutes or more and 300 minutes or less. This creates a sealing portion 5 containing the cured composition (X) in the gap between the semiconductor element 3 and the substrate 2.

[0091] In this embodiment, since the composition (X) has high fluidity, it is possible to suppress the unfilling of the composition (X) and the sealing portion 5 between the semiconductor element 3 and the substrate 2.

[0092] It should be noted that the manufacturing method of semiconductor device 1 is not limited to the above-described method.

[0093] 4. Method

[0094] The composition (X) of the first aspect of this disclosure comprises 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 nitrogen and oxygen atoms. The composition (X) has a viscosity of less than 400 Pa·s at 25°C.

[0095] According to this method, the fluidity of the composition (X) can be improved, and the crack resistance of the cured product can be improved.

[0096] In the second embodiment, based on the first embodiment, the aluminum complex (d1) contains an aluminum chelate (d11) having a ligand (L1) comprising the structure shown in formula (1).

[0097] [Chemical Formula 5]

[0098]

[0099] In the third approach, based on the second approach, the ligand (L1) has the structure shown in the following formula (11), where R in formula (11) is phenyl or naphthyl.

[0100] [Chemical Formula 6]

[0101]

[0102] In the fourth embodiment, based on the third embodiment, the aluminum complex (d11) contains the aluminum chelate shown in formula (2). In formula (2), each R is independently phenyl or naphthyl.

[0103] [Chemical Formula 7]

[0104]

[0105] In the fifth embodiment, based on any of the embodiments from 1 to 4, the inorganic filler material (C) contains a first inorganic filler material (C1) having an average particle size of more than 0.1 μm and less than 15 μm, and a second inorganic filler material (C2) having an average particle size of less than 0.1 μm. The amount of the second inorganic filler material (C2) is more than 1 part by mass and less than 10 parts by mass relative to 100 parts by mass of the first inorganic filler material (C1).

[0106] According to this method, the flowability of composition (X) can be further improved.

[0107] In the sixth embodiment, based on any of the embodiments from 1 to 5, the first inorganic filler material (C1) contains silicon dioxide that has been surface-treated using at least one selected from phenylaminosilane compounds, phenylsilane compounds, epoxysilane compounds, and methacryloxysilane compounds.

[0108] According to this method, the flowability and storage stability of composition (X) can be further improved.

[0109] In the seventh embodiment, based on any of the embodiments from the first to the sixth, the epoxy compound (A) contains an organosilicon-modified epoxy resin (a1).

[0110] According to this method, the flowability of composition (X) can be further improved.

[0111] In the eighth method, based on the seventh method, the amount of silicone-modified epoxy resin (a1) is 5 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of epoxy compound (A).

[0112] According to this method, the flowability of composition (X) can be further improved.

[0113] In the ninth embodiment, based on any of the embodiments from the first to the eighth, the composition (X) further contains rubber particles (E).

[0114] This method can improve the crack resistance of the cured material.

[0115] In the 10th method, based on the 9th method, the rubber particles (E) contain at least one of butadiene rubber particles and silicone rubber particles.

[0116] This method can further improve the crack resistance of the cured material.

[0117] In the 11th embodiment, based on any of the 1st to 10th embodiments, the composition (X) further contains an organophosphorus compound (F).

[0118] According to this method, the flowability of the composition can be further improved.

[0119] In the 12th embodiment, based on any of the 1st to 11th embodiments, the composition (X) is used for semiconductor sealing.

[0120] In the 13th embodiment, based on any of the 1st to 12th embodiments, the composition (X) is a bottom filler material.

[0121] The semiconductor device (1) of the 14th type includes a substrate (2), a semiconductor element (3) mounted on the substrate (2), and a sealing portion (5) filling the gap between the substrate (2) and the semiconductor element (3). The sealing portion (5) comprises a cured resin composition of any of the 1st to 13th types.

[0122] Example

[0123] The following describes specific embodiments of the implementation. It should be noted that this disclosure is not limited to these embodiments.

[0124] 1. Preparation of the composition

[0125] Mix the ingredients shown in the table to prepare a composition. Details of the ingredients in the table are described below.

[0126] - Epoxy Compound #1: Manufactured by NIPPON STEEL Chemical & Material Co., Ltd. Trade name: YDF8170. Liquid bisphenol F type epoxy resin. Epoxy equivalent: 160 g / eq.

[0127] - Epoxy Compound #2: Manufactured by Momentive Performance Materials Japan. Trade name: TSL9906. Liquid silicone-modified epoxy resin (siloxane oligomer with epoxypropoxypropyl groups at both ends). Epoxy equivalent: 181 g / eq.

[0128] - Curing agent: Manufactured by Nippon Kayaku Co., Ltd. Trade name: KAYAHARD AA. Liquid aromatic amine resin. Amine active hydrogen equivalent: 63.5 g / eq.

[0129] - Silica #1: Silica with an average particle size of 0.4 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane.

[0130] - Silica #2: Silica with an average particle size of 0.4 μm that has been surface-treated with phenyltrimethoxysilane.

[0131] - Silica #3: Silica with an average particle size of 0.4 μm, surface-treated with 3-epoxypropoxypropyltrimethoxysilane.

[0132] - Silica #4: Silica with an average particle size of 0.4 μm, surface-treated with 3-methacryloyloxypropyltrimethoxysilane.

[0133] - Silica #5: Silica with an average particle size of 0.7 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane.

[0134] - Silica #6: Silica with an average particle size of 1.0 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane.

[0135] - Silica #7: Manufactured by Admatechs Co., Ltd. Trade name YA-010A-JER. A mixture of bisphenol F type epoxy resin with an epoxy equivalent of 160 and silica with an average particle size of 10 nm. Silica concentration 25% by mass.

[0136] - Aluminum complex #1: Manufactured by Fujifilm and Kazuko Pure Chemicals Co., Ltd. Trade name: Q1301. N-Nitrophenylhydroxylamine aluminum.

[0137] - Aluminum complex #2: Manufactured by Kawaken Fine Chemicals Co., Ltd. Trade name: Alumichelate A. Trialuminum (acetylacetone).

[0138] - Organophosphorus compound: triphenylphosphine.

[0139] - Rubber Particles #1: Manufactured by Kaneka Co., Ltd. Trade name MX-139. A mixture of bisphenol F type epoxy resin with an epoxy equivalent of 160 g / eg and core-shell rubber particles with a polybutadiene rubber core. The concentration of rubber particles is 33% by mass.

[0140] - Rubber Particles #2: Manufactured by Kaneka Co., Ltd. Trade name MX-965. A mixture of bisphenol F type epoxy resin with an epoxy equivalent of 160 g / eg and core-shell type rubber particles with a silicone rubber core. The concentration of rubber particles is 25% by mass.

[0141] - Coupling agent: Manufactured by Momentive Performance Materials Japan. Trade name: SILQUEST A-187 SILANE. 3-Epoxypropoxypropyltrimethoxysilane.

[0142] 2. Evaluation

[0143] The composition was evaluated as follows. The results are shown in the table.

[0144] (1) Viscosity at 25℃

[0145] The viscosity of the composition at 25°C was measured using a Type B rotational viscometer (Toki Sangyo Co., Ltd., TVB-10H) at a rotational speed of 20 rpm.

[0146] (2) Preservation stability

[0147] The composition was treated by setting at 40°C for 8 hours. Using a type B rotational viscometer (Toki Sangyo Co., Ltd., TVB-10H), the viscosity (η0) of the composition before treatment and the viscosity (η1) of the composition after treatment were measured at 40°C and 20 rpm. The viscosity increase rate ((η1-η0)×100 / η0) was calculated based on these results.

[0148] If the result is below 100%, it can be evaluated as having good preservation stability; if it is below 50%, it can be evaluated as having exceptionally good preservation stability.

[0149] (3) Liquidity

[0150] Two cover glass plates were placed face-to-face with a 50 μm gap and the temperature of the cover glass plates was set to 110°C. The composition was injected between the cover glass plates, allowing the composition to flow between them. The time from the start of injection until the maximum distance the composition traveled between the cover glass plates reached 30 mm was measured.

[0151] If the result is less than 500 seconds, it can be rated as good liquidity; if it is less than 300 seconds, it can be rated as exceptionally good liquidity.

[0152] (4) Viscosity at 110℃

[0153] The temperature dependence of the composition was determined using a rheometer (Anton Paar, model: MCR-102) at a rotation speed of 1 rpm, a gap of 300 μm, and a heating rate of 5 °C / min. The viscosity of the composition at 110 °C was then read from the results.

[0154] When the result is in the range of 0.4 Pa·s or less, the composition can be evaluated as having good flowability when heated; when it is in the range of 0.2 Pa·s or less, the composition can be evaluated as having particularly good flowability when heated.

[0155] (5) Crack resistance

[0156] 10 mg of the composition was coated in an X-shape on a silicon substrate with dimensions of 25 mm × 25 mm × 775 μm. A silicon substrate with dimensions of 7 mm × 7 mm × 775 μm was then placed on the coated composition. In this state, the silicon substrate and the composition were heated at 80°C for 60 seconds and then cooled to 25°C. As a result, the composition wetted and spread between the two silicon substrates, and the fillet overflow of the composition overflowed from the outer periphery of the 7 mm × 7 mm × 775 μm silicon substrate. The silicon substrate and the composition were heated at 100°C for 2 hours and then at 165°C for 2 hours to prepare an evaluation sample. The sample was then placed in a constant temperature bath at 175°C for 500 hours, and the appearance of the sample was evaluated. If the sample had 2 or fewer corner cracks, it could be evaluated as having particularly good crack resistance. It should be noted that corner cracks refer to cracks that occur near the corners of the cured composition of a substrate with dimensions of 7mm×7mm×775μm, at the rounded corner overflow portion.

[0157] [Table 1]

[0158]

[0159] [Table 2]

[0160]

[0161] Explanation of reference numerals in the attached figures

[0162] 1. Semiconductor device

[0163] 2 substrate

[0164] 3 Semiconductor components

[0165] 5. Sealing section

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), said ligand (L) having nitrogen and oxygen atoms, The viscosity of the resin composition at 25°C is below 400 Pa·s.

2. The resin composition according to claim 1, wherein, The aluminum complex (d1) contains an aluminum chelate (d11) having a ligand (L1) comprising the structure shown in formula (1). 。 3. The resin composition according to claim 2, wherein, The ligand (L1) has the structure shown in formula (11), where R in formula (11) is phenyl or naphthyl. 。 4. The resin composition according to claim 3, wherein, The aluminum chelate (d11) contains an aluminum chelate as shown in formula (2), where each R in formula (2) is independently phenyl or naphthyl. 。 5. The resin composition according to claim 1, wherein, The inorganic filler material (C) contains a first inorganic filler material (C1) having an average particle size of more than 0.1 μm and less than 15 μm, and a second inorganic filler material (C2) having an average particle size of less than 0.1 μm. The amount of the second inorganic filler (C2) is more than 1 part by mass and less than 10 parts by mass relative to 100 parts by mass of the first inorganic filler (C1).

6. The resin composition according to claim 5, wherein, The first inorganic filler material (C1) contains silica that has been surface-treated with at least one selected from phenylaminosilane compounds, phenylsilane compounds, epoxysilane compounds and methacryloxysilane compounds.

7. The resin composition according to claim 1, wherein The epoxy compound (A) contains an organosilicon-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 relative to 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 organophosphorus compound (F).

12. The resin composition according to claim 1, used for semiconductor sealing.

13. The resin composition according to claim 1, wherein it is a bottom filler material.

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

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