Epoxy resin composition, cured product, semiconductor device, and method for manufacturing semiconductor device

Abstract

Provided is an epoxy resin composition having good adhesion. Also provided are a cured product formed from the epoxy resin composition, a semiconductor device comprising the cured product, and a method for producing the semiconductor device.　The epoxy resin composition includes an epoxy resin (A), a curing agent (B), and an inorganic filler (C). The content of a naphthalene-type epoxy resin with respect to the epoxy resin (A) (100 mass%) is 51 mass% or more, and the content of the inorganic filler (C) is 40-90 mass%.

Description

Epoxy resin composition, cured product, semiconductor device, and method for manufacturing semiconductor device

[0001] The present invention relates to an epoxy resin composition, a cured product, a semiconductor device, and a method for manufacturing a semiconductor device.

[0002] In recent years, in data communication, performance improvements such as high speed, high efficiency, and large capacity have been demanded. Along with this, the requirements for space saving and high speed in semiconductor packages have become even more stringent. As one method for realizing miniaturization of semiconductor packages, three-dimensional stacking technology (3D stacking) of semiconductors has advanced. As an important technology to support its realization, TSV (Through-Silicon Via, through-silicon via) technology is known.

[0003] In TSV technology, a form is adopted in which a plurality of chips are stacked as one semiconductor package using TSVs that penetrate the inside of the semiconductor chip in the thickness direction. Each stacked semiconductor chip exhibits its function when the TSVs of each other are physically and electrically connected. Usually, a copper material is used for the TSV itself and the connection portion between TSVs. By adopting TSV technology, it becomes possible to stack a plurality of semiconductor chips, achieve high integration, and accommodate many functions in a compact space. In addition, since power supply is performed through TSVs, it leads to power saving of the semiconductor device.

[0004] In the manufacture of a semiconductor device having a structure in which a plurality of semiconductor chips are stacked, a method is adopted in which the entire stacked semiconductor chip is filled with a curable resin composition and subjected to compression molding, thereby simultaneously performing sealing between semiconductor chips, sealing between semiconductor chips and wafers, and molding of the semiconductor device. The composition used in such a method is called an underfill material for multilayer semiconductors.

[0005] Epoxy resin compositions are primarily used as underfill materials for multilayer semiconductors. These underfill materials require high filling properties (e.g., low viscosity) to fill the narrow gaps between stacked semiconductor chips. Furthermore, to ensure reliable sealing after filling, properties such as high curability, no cracking during sealing (good crack resistance), and minimal warping of the semiconductor package after sealing (low warping) are required.

[0006] Patent Document 1 discloses an epoxy resin composition comprising a polyfunctional epoxy resin, a phenolic resin, an inorganic filler, and a curing accelerator, which is used in BGA-type semiconductors, which are semiconductor packages requiring high-density mounting. It also states that by using this epoxy resin composition, the package exhibits excellent warp resistance, fluidity and moldability, solder heat resistance during mounting, resin crack resistance, adhesion, and moisture resistance after mounting, thus ensuring long-term reliability.

[0007] Japanese Patent Application Publication No. 11-147940

[0008] However, when these epoxy resin compositions were used as underfill materials for multilayer semiconductors, there was a problem in that the cured material would peel off from the copper TSVs and the connections between TSVs. When the cured material peels off, the reliability of the semiconductor device may be significantly reduced.

[0009] Therefore, an object of the present invention is to provide an epoxy resin composition that provides a cured product that is less prone to peeling from TSVs and connection portions between TSVs due to its good adhesion to copper materials. Another object is to provide a cured product of the epoxy resin composition, a semiconductor device equipped with the cured product, and a method for manufacturing the same. Hereinafter, the adhesion to copper materials may be simply referred to as "adhesion."

[0010] The inventors of this invention, after diligent research to achieve the above objectives, discovered that the above problems can be solved by incorporating specific components into an epoxy resin composition. This invention was completed based on these findings.

[0011] In other words, the present invention provides an epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and an inorganic filler (C), wherein the epoxy resin (A) includes a naphthalene-type epoxy resin, the content of the naphthalene-type epoxy resin relative to the epoxy resin (A) (100% by mass) is 51% by mass or more, and the content of the inorganic filler (C) is 40% to 90% by mass.

[0012] The epoxy resin composition described above preferably contains 10% by mass or less of the phenolic curing agent relative to the curing agent (B) (100% by mass).

[0013] The epoxy resin composition described above preferably contains an acid anhydride-based curing agent as curing agent (B), and the content of the acid anhydride-based curing agent relative to curing agent (B) (100% by mass) is 50% by mass or more.

[0014] The epoxy resin composition described above preferably has a viscosity of 5 to 1000 Pa·s at 25°C.

[0015] The epoxy resin composition described above preferably has a glass transition temperature (Tg) of 130 to 200°C in its cured product.

[0016] The epoxy resin composition described above is preferably a liquid compression molding material.

[0017] The above epoxy resin composition is preferably an underfill material for multilayer semiconductors.

[0018] The present invention also provides a cured product of the above epoxy resin composition.

[0019] The present invention also provides a semiconductor device comprising the above-mentioned cured material.

[0020] The present invention also provides a semiconductor device comprising: a support; a semiconductor element disposed on the support; and a cured material that encapsulates the semiconductor element.

[0021] The present invention also provides a method for manufacturing a semiconductor device, comprising the steps of: supplying the epoxy resin composition onto a laminate comprising a support and a semiconductor element mounted on the support; filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body; curing the molded body to seal the semiconductor element and obtain a sealed body.

[0022] The epoxy resin composition of the present invention exhibits excellent adhesion. Therefore, semiconductor devices equipped with a cured product of the epoxy resin composition exhibit high reliability. The factors contributing to this "adhesion" are thought to be the interplay between (1) high adhesion between the cured product of the epoxy resin composition and the copper material, and (2) a small coefficient of thermal expansion of the cured product, i.e., a small rate of expansion due to temperature. In other words, the epoxy resin composition of the present invention exhibits high adhesion to copper materials when cured, and its low coefficient of thermal expansion results in high adhesion to copper materials.

[0023] This is a diagram illustrating one embodiment of the semiconductor device manufacturing method of the present invention. This is a diagram illustrating another embodiment of the semiconductor device manufacturing method of the present invention. This is a diagram illustrating one embodiment of the semiconductor device of the present invention. This is a diagram illustrating an example of a multilayer semiconductor structure in the semiconductor device of the present invention. This is a diagram illustrating another example of a multilayer semiconductor structure in the semiconductor device of the present invention. This is a diagram illustrating another example of a multilayer semiconductor structure in the semiconductor device of the present invention.

[0024] <Epoxy Resin Composition> The epoxy resin composition of the present invention is an epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and an inorganic filler (C), wherein the epoxy resin (A) includes a naphthalene-type epoxy resin, the content of the naphthalene-type epoxy resin relative to the epoxy resin (A) (100% by mass) is 51% by mass or more, and the content of the inorganic filler (C) is 40 to 90% by mass. The epoxy resin composition may further contain a curing accelerator (D) and a coupling agent (E).

[0025] Epoxy resin (A) The epoxy resin composition can impart high electrical insulation properties to its cured product by containing epoxy resin (A). The number of epoxy groups in epoxy resin (A) is not particularly limited as long as it is one or more, but it is preferable that it is two or more (i.e., a polyfunctional type epoxy resin). Epoxy resin (A) can be used alone or in combination of two or more types.

[0026] The epoxy resin (A) may be liquid or solid at room temperature (25°C), but from the viewpoint of the viscosity of the epoxy resin composition, it is preferable that it be liquid. Even if it is a solid epoxy resin, it can preferably be used if it becomes liquid as a mixture when used in combination with a liquid epoxy resin.

[0027] The epoxy resin (A) is not particularly limited, but examples include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bixylenol type epoxy resin, cyclohexane type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, and oxazolidone ring epoxy resin. Examples include epoxy resins containing epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, fluorene-type epoxy resins, biphenyl aralkyl epoxy resins, aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiroring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylmethane-type epoxy resins, aminophenol-type epoxy resins, and silicone-modified epoxy resins.

[0028] The above epoxy resin composition includes a naphthalene-type epoxy resin as epoxy resin (A). The naphthalene-type epoxy resin is not particularly limited as long as it has a naphthalene skeleton as a constituent unit of the resin and also has epoxy groups. By including a naphthalene-type epoxy resin, (1) adhesion is improved, and (2) the glass transition temperature of the cured product tends to be higher, resulting in high reliability.

[0029] The epoxy equivalent of epoxy resin (A) is not particularly limited, but is preferably 60 to 500 g / eq, more preferably 80 to 400 g / eq, even more preferably 100 to 300 g / eq, and most preferably 120 to 200 g / eq.

[0030] Specific examples of liquid epoxy resins include "YDF-8170" and "YDF-870GS" (both bisphenol F type epoxy resins), "YDF-8125" (bisphenol A type epoxy resin), "ZX-1658" and "ZX-1658GS" (both liquid 1,4-glycidylcyclohexane) from Nippon Steel Chemical & Material Co., Ltd.; "HP-4032," "HP-4032D," and "HP-4032SS" (all naphthalene type epoxy resins) from DIC Corporation; and "jER828US" and "jER828EL" (both bisphenol A type epoxy resins) and "jER8" from Mitsubishi Chemical Corporation. "06", "jER807" (both bisphenol F type epoxy resins), "jER152" (phenol novolac type epoxy resin), "jER630", "jER630LSD" (both aminophenol type epoxy resins), "YX7400N" (aliphatic epoxy resin / diglycidyl ether of polytetramethylene glycol); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) and "EX-171" (lauryl alcohol (EO) manufactured by Nagase ChemteX Corporation) １５Examples include glycidyl ether; "Adeka Resin EP-4005" and "Adeka Resin EP-4003S" (both bisphenol A type epoxy resins containing a polypropylene glycol structure) manufactured by ADEKA Corporation, "EP-3950L" (aminophenol type epoxy resin), and "EP3980S" (glycidylamine type epoxy resin); "AER9000" (PO-modified bisphenol type epoxy resin), "AER4001", "AER4004", and "AER4152" (all oxazolidone ring-containing epoxy resins) manufactured by Asahi Kasei Corporation; "DER852" and "DER858" (both oxazolidone ring-containing epoxy resins) manufactured by Dow Chemical Ltd.; "FAE-2500" and "EPPN-501HY" (both trisphenolmethane type epoxy resins) manufactured by Nippon Kayaku Co., Ltd.; and "Celoxide 2021P" (alicyclic epoxy resin) manufactured by Daicel Corporation.

[0031] Specific examples of solid epoxy resins include "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both naphthalene-type tetrafunctional epoxy resins), "N-690" (cresol novolac-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", and "HP-7200HHH" (all dicyclopentadi (Naphthylene ether type epoxy resin), "EXA850CRP", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (all naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenolmethane type epoxy resin), "NC-7000-L" (naphthol novolac type epoxy resin), "NC-3000-H", "NC-3000", "NC-3000-L", "NC-310 0 (all biphenyl-type epoxy resins); "ESN475V" (naphthol-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H" and "YL6121" (both biphenyl-type epoxy resins), "YX4000HK" (bixylenol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation. Examples include "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; and "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), "jER157S70" (bisphenol novolac-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), and "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation.

[0032] The epoxy resin composition described above may contain an alicyclic epoxy resin as epoxy resin (A), but it is preferable not to include it from the viewpoint of improving the toughness of the cured product.

[0033] The content of epoxy resin (A) in the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 6% by mass or more. Also, is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 16% by mass or less. When the content of epoxy resin (A) is within the above range, a cured product with high electrical insulation properties tends to be obtained.

[0034] In the epoxy resin composition described above, the content of naphthalene-type epoxy resin relative to epoxy resin (A) (100% by mass) is not particularly limited as long as it is 51% by mass or more, but for example, it is more preferably 55% by mass or more, even more preferably 60% by mass or more, even more preferably 62% by mass or more, even more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. When the content of naphthalene-type epoxy resin is within the above range, adhesion is improved and the glass transition temperature of the cured product is improved, which tends to lead to higher reliability.

[0035] • Curing agent (B) The curing agent (B) is not particularly limited as long as it initiates, promotes, or accelerates the polymerization of the epoxy resin, but examples include acid anhydride-based curing agents and phenol-based curing agents. From the viewpoint of improving adhesion and the glass transition temperature of the cured product, it is preferable that the curing agent (B) includes an acid anhydride-based curing agent. The curing agent (B) can be used alone or in combination of two or more types.

[0036] Examples of the above acid anhydride-based curing agents include alkylated tetrahydrophthalic anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadoic anhydride. Examples of the above phenol-based curing agents include phenol novolac resins, cresol novolac resins, naphthol-modified phenol resins, dicyclopentadiene-modified phenol resins, and p-xylene-modified phenol resins.

[0037] Commercially available acid anhydride-based curing agents include "Ricacid HNA-100," "Ricacid MH-700," "Ricacid MH-700G," and "Ricacid MTA-15" from Shin Nippon Rika Co., Ltd.; "YH-306" and "YH-307" from Mitsubishi Chemical Corporation; and "HN-2000," "HN-2200," and "HN-5500" from Resona Co., Ltd. Commercially available phenol-based curing agents include "MEH-8005," "MEH-8000H," and "NEH-8015" from Meiwa Kasei Co., Ltd.; and "YLH903" from Mitsubishi Chemical Corporation.

[0038] The equivalent amount of the cured product of the curing agent (B) is not particularly limited, but is preferably 60 to 500 g / eq, more preferably 80 to 400 g / eq, even more preferably 100 to 300 g / eq, and particularly preferably 120 to 200 g / eq.

[0039] The content of the curing agent (B) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, even more preferably 5% by mass or more, and particularly preferably 6% by mass or more. Alternatively, it is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. When the content of the curing agent (B) is within the above range, adhesion tends to be better. Also, curability tends to be improved and moldability tends to be good.

[0040] The content of the curing agent (B) relative to the epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Also, is preferably 200% by mass or less, more preferably 180% by mass or less, even more preferably 160% by mass or less, even more preferably 140% by mass or less, and particularly preferably 120% by mass or less. When the content of the curing agent (B) is within the above range, adhesion tends to be better. Also, curability tends to be improved and moldability tends to be good.

[0041] The content of the acid anhydride-based curing agent relative to the curing agent (B) (100% by mass) in the epoxy resin composition described above is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. When the content of the acid anhydride-based curing agent is within the above range, the glass transition temperature of the cured product tends to improve further.

[0042] The content of the phenolic curing agent relative to the curing agent (B) (100% by mass) in the epoxy resin composition described above is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 6% by mass or less. Having the phenolic curing agent content within the above range tends to increase reliability by allowing for a higher glass transition temperature of the cured product.

[0043] • Inorganic filler (C) The inorganic filler (C) is not particularly limited, but it is preferable that it (1) has the property of suppressing volume shrinkage (curing shrinkage) caused by the curing reaction of the epoxy resin composition, (2) has the property of suppressing volume change (thermal shrinkage) due to heating of the cured product, that is, has the effect of lowering the coefficient of linear expansion when added, or (3) has both of the above properties.

[0044] As the inorganic filler (C), for example, silica (silicon dioxide), silicon carbide, silicon nitride, alumina (aluminum oxide), aluminum nitride, aluminum hydroxide, aluminum silicate, magnesium silicate, calcium silicate, calcium carbonate, barium sulfate, barium carbonate, titanium oxide, gypsum, potassium titanate, magnesium carbonate, zinc oxide, boron nitride, zirconia (zirconium oxide), and inorganic particles whose surfaces are treated with these can be mentioned. Among these, silica is preferable from the viewpoint of being able to lower the coefficient of thermal expansion (CTE) of the cured product. The inorganic filler (C) can be used alone or in combination of two or more kinds.

[0045] From the viewpoints of improving adhesion and making the viscosity of the epoxy resin composition within an appropriate range, the inorganic filler (C) is preferably one whose surface is treated with a coupling agent having a functional group such as an epoxy group, (meth)acryloyl group, or amino group (especially phenylamino group). Examples of the above coupling agent include silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane. For the surface treatment of the inorganic filler (C), one kind of the above coupling agent can be used alone or two or more kinds can be used in combination.

[0046] Examples of commercially available products of the inorganic filler (C) include "YA050C-SM1", "SE2200-SME", "SE1050-SMO", "SE101G-SMO", "SE605H-SMG" manufactured by Admatechs Co., Ltd.

[0047] The shape of the inorganic filler (C) is not particularly limited, and examples include spherical (true spherical, substantially true spherical, etc.), polyhedral, rod-shaped (cylindrical, prismatic, etc.), flat plate-shaped, flaky, and irregular-shaped. Among these, spherical is preferable from the viewpoint of being able to achieve a high filling amount.

[0048] The average particle size of the inorganic filler (C) is not particularly limited, but is preferably 1 nm to 10 μm, more preferably 5 nm to 7 μm, even more preferably 10 nm to 5 μm, even more preferably 10 nm to 3 μm, and particularly preferably 30 nm to 1 μm. Because the average particle size of the inorganic filler (C) is within the above range, the particle size is not too large, and the epoxy resin composition tends to have high filling properties even in narrow gaps. In addition, two or more fillers with different average particle sizes may be used in combination to adjust the viscosity of the epoxy resin composition. In this specification, the method for measuring the average particle size of the inorganic filler (C) is not particularly limited, but can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer (product name: LS 13 320, manufactured by Beckman Coulter, Inc.).

[0049] The epoxy resin composition preferably contains, as an inorganic filler (C), an inorganic filler (C1) having an average particle size of 0.2 to 10 μm and an inorganic filler (C2) having an average particle size of 1 nm or more and less than 200 nm. The average particle size of inorganic filler (C1) is preferably 0.25 to 7 μm, more preferably 0.3 to 5 μm, even more preferably 0.35 to 3 μm, and particularly preferably 0.4 to 1 μm. The average particle size of inorganic filler (C2) is preferably 5 to 150 nm, more preferably 10 to 120 nm, even more preferably 20 to 100 nm, and particularly preferably 30 to 80 nm.

[0050] From the viewpoint of gap-filling ability, the above epoxy resin composition preferably contains an inorganic filler (CX) with an average particle size of 3 μm or less as the inorganic filler (C). The average particle size of the inorganic filler (CX) is not particularly limited, but is more preferably 2 μm or less, even more preferably 1.5 μm or less, and particularly preferably 1 μm or less. The content of the inorganic filler (CX) relative to the inorganic filler (C) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably, for example, 30% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0051] The content of inorganic filler (C) in the above epoxy resin composition (100% by mass) is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 65% ​​by mass or more, and particularly preferably 70% by mass or more. Alternatively, it is preferably 90% by mass or less, more preferably 88% by mass or less, even more preferably 86% by mass or less, even more preferably 85% by mass or less, even more preferably 83% by mass or less, and particularly preferably 80% by mass or less. When the content of inorganic filler (C) is within the above range, the coefficient of thermal expansion (CTE) of the cured product tends to be lower. Also, the viscosity of the epoxy resin composition tends to be within an appropriate range, and the ability to fill gaps and workability tend to improve. Adhesion, in particular, tends to be good when the content of inorganic filler (C) is 65% by mass or more.

[0052] The content of the inorganic filler (C1) relative to the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 45% by mass or more, and particularly preferably 50% by mass or more. Alternatively, it is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less.

[0053] The content of the inorganic filler (C2) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 9% by mass or more, even more preferably 12% by mass or more, and particularly preferably 15% by mass or more. Alternatively, it is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0054] The content of inorganic filler (C) relative to epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 100% by mass or more, more preferably 200% by mass or more, even more preferably 300% by mass or more, and particularly preferably 400% by mass or more. Alternatively, it is preferably 2000% by mass or less, more preferably 1600% by mass or less, even more preferably 1400% by mass or less, and particularly preferably 1200% by mass or less. When the content of inorganic filler (C) is within the above range, the coefficient of thermal expansion (CTE) of the cured product tends to be lower. In addition, the viscosity of the epoxy resin composition tends to be within an appropriate range, improving gap filling ability and workability.

[0055] • Curing accelerator (D) The curing accelerator (D) has the property of accelerating the curing of the epoxy resin. The curing accelerator is not particularly limited, but examples include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphorus-based curing accelerators, etc. Among these, imidazole-based curing accelerators are preferred from the viewpoint of suppressing wafer warping after molding and from the viewpoint of reliability. The curing accelerator (D) can be used alone or in combination of two or more types.

[0056] Examples of imidazole-based curing accelerators include imidazole compounds such as 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. Commercially available products include 2-ethyl-4-methylimidazole (product name "2E4MZ"), 2-phenyl-4-methylimidazole (product name "2P4MZ"), 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name "2P4MHZ-PW"), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine (product name "2MZA-PW"), "2MZ-OK", "2MA-OK", and "2PHZ", all manufactured by Shikoku Chemicals, Inc. In addition, encapsulated imidazoles, such as microencapsulated imidazoles and epoxy adduct imidazoles, may also be used. Commercially available products include "HX3941HP", "HXA3942HP", "HXA3922HP", "HXA3792", "HX3748", "HX3721", "HX3722", "HX3088", "HX3088F", "HX3741", "HX3742", and "HX3613" (all manufactured by Asahi Kasei Corporation), as well as "PN-23J", "PN-40J", and "PN-50" (manufactured by Ajinomoto Fine Techno Co., Ltd.), and "FXR-1121" (manufactured by Fuji Kasei Kogyo Co., Ltd.).

[0057] Examples of tertiary amine-based curing accelerators include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N'-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene, 1,5-diazabicyclo[4.3.0]nonene, and salts thereof. Examples of the salts include formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,8-diazabicyclo[5.4.0]undecene, and formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, or phenol novolac resin salt of 1,5-diazabicyclo[4.3.0]nonene.

[0058] Examples of phosphorus-based curing accelerators include phosphorus compounds such as triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium / tetraphenylborate, triphenylphosphine / triphenylborane, and 1,2-bis-(diphenylphosphine)ethane.

[0059] The content of the curing accelerator (D) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. Also, is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 4% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less. When the content of the curing accelerator (D) is within the above range, the curability tends to improve and the moldability tends to be good.

[0060] The content of the curing accelerator (D) relative to the epoxy resin (A) (100% by mass) in the above epoxy resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Also, is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. When the content of the curing accelerator (D) is within the above range, the curability tends to improve and the moldability tends to be good.

[0061] • Coupling agent (E) The coupling agent (E) has effects such as improving the adhesion between the epoxy resin (A) and the components of the semiconductor device. Examples of the coupling agent (E) include silane coupling agents such as vinyl, glycidoxy, (meth)acrylic, amino, mercapto, or imidazole; titanium coupling agents such as alkoxide, chelate, or acylate; and long-chain spacer type coupling agents such as glycidoxyoctyltrimethoxysilane or methacrylooctyltrimethoxysilane. The coupling agent (E) can be used alone or in combination of two or more types.

[0062] Examples of the silane coupling agents mentioned above include 3-isocyanatetopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

[0063] The content of the coupling agent (E) in the epoxy resin composition (100% by mass) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more. Also, is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.4% by mass or less, even more preferably 0.3% by mass or less, and particularly preferably 0.25% by mass or less. When the content of the coupling agent (E) is within the above range, the glass transition temperature tends to increase and the adhesive strength tends to improve.

[0064] Other Components (F) The epoxy resin composition described above may or may not contain components other than the epoxy resin (A), curing agent (B), inorganic filler (C), curing accelerator (D), and coupling agent (E) (hereinafter referred to as "other components (F)"). Examples of other components (F) include curable compounds other than epoxy resin (A), thermoplastic resins such as polyethylene resin, polyester resin, polyurethane resin, and polyamide resin, coupling agents, stress-reducing agents such as elastomers and acrylic block copolymers, surfactants, ion trapping agents, leveling agents, antioxidants, defoaming agents, flame retardants, colorants such as carbon black, reactive diluents, alcohol compounds having a polytetramethylene ether structure in the molecule, mercapto group-containing compounds, solvents, etc. Other components (F) may be used individually or in combination of two or more.

[0065] Examples of the above-mentioned elastomers include butadiene-based elastomers, silicone-based elastomers, acrylic copolymers, and styrene-butadiene-based elastomers. The above-mentioned elastomer may also be a core-shell rubber particle. That is, it may be a core-shell rubber type elastomer. A core-shell rubber particle means a rubber particle composed of a core portion and one or more shell layers covering the core portion.

[0066] Examples of alcohol compounds having a polytetramethylene ether structure within the above molecule include polycarbonate diol compounds having a tetramethylene glycol structure as an alkylene glycol structure, and polytetramethylene ether glycols. Commercially available alcohol compounds of this type include PEPCD NT2006 (a polycarbonate diol compound having a tetramethylene glycol structure as an alkylene glycol structure, liquid (transparent) at 25°C, number average molecular weight 2000, glass transition temperature -84°C, manufactured by Mitsubishi Chemical Corporation), PEPCD NT2002 (a polycarbonate diol compound having a tetramethylene glycol structure as an alkylene glycol structure, liquid (transparent) at 25°C, number average molecular weight 2000, glass transition temperature -71°C, manufactured by Mitsubishi Chemical Corporation), PTMG2000 (polytetramethylene ether glycol, number average molecular weight 2000, manufactured by Mitsubishi Chemical Corporation), and PTMG3000 (polytetramethylene ether glycol, number average molecular weight 3000, manufactured by Mitsubishi Chemical Corporation). The epoxy resin composition described above tends to be less prone to warping of the wafer after molding (after sealing) due to the inclusion of the alcohol compound.

[0067] Examples of the mercapto group-containing compounds include heterocyclic compounds having a mercapto group as a substituent (particularly compounds having a thiadiazole skeleton), specifically 2,5-dimercapto-1,3,4-thiadiazole and 5-amino-2-mercapto-1,3,4-thiadiazole. The epoxy resin composition tends to have improved adhesion due to the presence of the mercapto group-containing compound. However, on the other hand, the presence of the mercapto group-containing compound may increase the reactivity of the epoxy resin composition, leading to increased viscosity and reduced fillability and workability. Therefore, from the viewpoint of fillability and workability, the content of the mercapto group-containing compound in the epoxy resin composition (100% by mass) is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and even more preferably 0.001% by mass or less, and it is particularly preferable that it is substantially absent.

[0068] The content of other components (F) relative to the epoxy resin composition (100% by mass) is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.3% by mass or less. Also, for example, it may be 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more.

[0069] In particular, the solvent content relative to the epoxy resin composition (100% by mass) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, even more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, and especially preferably 0.01% by mass or less. Furthermore, by incorporating an alcohol compound in the epoxy resin composition (100% by mass) at a content of, for example, 0.1 to 5% by mass, warping after curing can be reduced.

[0070] (Physical properties and manufacturing method of epoxy resin composition) The epoxy resin composition may be solid (granular) or liquid at 25°C, but a liquid state is preferred from the viewpoint of workability.

[0071] The viscosity of the epoxy resin composition at 25°C is not particularly limited, but is preferably 5 to 1000 Pa·s, more preferably 10 to 800 Pa·s, even more preferably 30 to 800 Pa·s, even more preferably 50 to 600 Pa·s, and particularly preferably 100 to 500 Pa·s. When the viscosity is within the above range, the ability of the epoxy resin composition to fill gaps is improved, and the possibility of the epoxy resin composition leaking from the coated support is reduced, which tends to improve workability. The viscosity can be measured using a Brookfield viscometer (model number: HB-DV1, manufactured by Brookfield Corporation) at a liquid temperature of 25°C and rotated at 20 rpm for 1 minute, as shown in the examples described later.

[0072] In the epoxy resin composition described above, the glass transition temperature (Tg) of the cured product is not particularly limited, but is preferably 130°C or higher, more preferably 140°C or higher, even more preferably 145°C or higher, and particularly preferably 150°C or higher. Alternatively, it is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower. When the glass transition temperature is within the above range, adhesion tends to be improved and reliability is enhanced. The glass transition temperature can be measured using a dynamic viscoelastic device to measure the storage modulus (E') and loss modulus (E'') of the cured epoxy resin composition, as described in the examples below, and the peak value of tanδ, which is the ratio of these two values, is taken as the glass transition temperature (Tg). The above measurement may conform to the Japanese Industrial Standard JIS C6481. The cured product is obtained by curing at 180°C for 60 minutes. The glass transition temperature (Tg) can be measured using the method described in the examples below.

[0073] In the epoxy resin composition described above, the gel time at 150°C is not particularly limited, but is preferably 100 seconds or more, more preferably 120 seconds or more, even more preferably 140 seconds or more, and particularly preferably 160 seconds or more. Alternatively, it is preferably 500 seconds or less, more preferably 400 seconds or less, even more preferably 300 seconds or less, and particularly preferably 250 seconds or less. When the gel time at 150°C is within the above range, the filling properties and workability tend to improve. The gel time can be measured by the method described in the examples below.

[0074] The epoxy resin composition described above can be prepared by known and conventional methods. For example, the epoxy resin composition can be obtained by simultaneously or separately introducing at least one selected from the group consisting of epoxy resin (A), curing agent (B), inorganic filler (C), and optionally curing accelerator (D), coupling agent (E), and other components (F) into a suitable mixer, and stirring and mixing while melting by heating as needed. If the epoxy resin (A) is solid, it is preferable to liquefy or fluidize it by heating before mixing. If it is difficult to uniformly disperse the inorganic filler (C) in the epoxy resin composition, the epoxy resin (A) and inorganic filler (C) may be heated and mixed to uniformly disperse the inorganic filler (C) in the epoxy resin (A), then cooled as needed, and further mixing in components such as the curing agent (B) to prepare the epoxy resin composition.

[0075] The above-mentioned mixer is not particularly limited, but examples include a roll mill equipped with a stirring device and a heating device, a Leikai mill, a Henschel mixer, a tumbler, a self-rotating mill, a planetary mixer, etc. The mixing ratio of each component is appropriately set according to the content ratio of each component in the epoxy resin composition.

[0076] The above epoxy resin composition can be preferably used as a material (epoxy resin composition for semiconductor encapsulation) for encapsulating materials mounted on a support such as semiconductor elements, wiring, and solder (solder bumps) in a semiconductor device. By using the above epoxy resin composition as an epoxy resin composition for semiconductor encapsulation, a highly reliable encapsulated body can be manufactured. Furthermore, the above epoxy resin composition can be preferably used as a material (epoxy resin composition for flip-chip semiconductor encapsulation) for encapsulating semiconductor elements mounted on a support in a flip-chip type semiconductor device. Specifically, by filling the gap between the semiconductor element and the support with the above epoxy resin composition and curing it, the bumps present in the gap can be encapsulated while fixing the semiconductor element and the support to each other as an encapsulated body.

[0077] The epoxy resin composition described above can be used, for example, as an underfill such as capillary underfill, liquid mold underfill, secondary underfill, and pre-filled underfill, as well as as a grab-top material and a liquid compression molding material. Among these uses, the epoxy resin composition is preferred when used as a liquid compression molding material because it fully exhibits the characteristic of suppressing delamination from copper pillars. Furthermore, the epoxy resin composition is not limited to its use as an epoxy resin composition for semiconductor encapsulation as described above, but can also be used, for example, as an adhesive for fixing, joining, or protecting components that constitute a semiconductor device.

[0078] The epoxy resin composition described above can also be used as an underfill material for multilayer semiconductors. The underfill material refers to an underfill material used in the manufacture of a semiconductor device having a structure in which multiple semiconductor elements (semiconductor chips) are stacked. By filling the entire stacked semiconductor device with the underfill material and subjecting it to compression molding, the sealing between multiple stacked semiconductor elements, the sealing between the semiconductor elements and the support (e.g., silicon wafer), and the molding of the semiconductor device can be performed simultaneously.

[0079] <Cured Product> A cured product is formed by curing the epoxy resin composition described above. The curing method is not particularly limited, but for example, it can be carried out by heat treatment of the epoxy resin composition. The temperature of the heat treatment is not particularly limited, but for example, 60 to 200°C is preferred, and 80 to 180°C is more preferred. The duration of the heat treatment is not particularly limited, but for example, 0.1 to 5 hours is preferred, and 0.5 to 3 hours is more preferred.

[0080] <Semiconductor device and method for manufacturing the same> The semiconductor device of the present invention comprises a support, a semiconductor element mounted on the support, and a cured product of the epoxy resin composition that encapsulates the semiconductor element. Preferably, the semiconductor device is a flip-chip type semiconductor device. The flip-chip type semiconductor device has a structure in which an electrode portion on the support and the semiconductor element are connected via bump electrodes. In addition, the gap between the semiconductor element and the support of the semiconductor device is sealed by the cured product (encapsulant) of the epoxy resin composition.

[0081] The present invention provides a method for manufacturing a semiconductor device, comprising: a step of supplying the epoxy resin composition onto a laminate comprising a support and a semiconductor element mounted on the support (hereinafter referred to as the "composition supply step"); and a step of filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to seal the semiconductor element, and obtaining a sealed body (hereinafter referred to as the "molding and sealing step").

[0082] The semiconductor device manufacturing method of the present invention may further include a step of polishing the above-mentioned encapsulant (hereinafter referred to as the "grinding step"). It may also include at least one selected from the group consisting of the laminate preparation step and the individualization step described later.

[0083] (Laminate Preparation Process) The laminate preparation process is a process of preparing a laminate comprising a support and semiconductor elements mounted on the support by mounting semiconductor elements on the support. In the laminate, the support and the semiconductor elements may be connected via solder, or they may be connected using adhesive films such as die attach films (DAF) or adhesive sheets. The support is not particularly limited, but examples include silicon wafers, silicon carbide wafers, sapphire wafers, compound semiconductor wafers (gallium phosphide, gallium arsenide, indium phosphide, gallium nitride), glass epoxy substrates, organic substrates (FR4 substrates), etc. The shape of the support in plan view is not particularly limited, but for example it may be circular or rectangular.

[0084] (Composition supply process) The composition supply process is a process of supplying the epoxy resin composition onto a laminate comprising a support and a semiconductor element mounted on the support.

[0085] This process may include a step of attaching a mold used to form a molded body in the molding and sealing process to the laminate. That is, the composition supply step may be a step of supplying an epoxy resin composition onto a laminate comprising a support and a semiconductor element mounted on the support, and then attaching a mold to the laminate.

[0086] Furthermore, this process may also involve supplying an epoxy resin composition to a mold used for forming a molded body in the molding and sealing process, and then mounting a laminate comprising a support and a semiconductor element mounted on the support into the mold. By performing such a process, the epoxy resin composition can be supplied onto the laminate comprising the support and the semiconductor element mounted on the support.

[0087] (Molding and Sealing Process) The molding and sealing process involves filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to seal the semiconductor element, and obtaining a sealed body. This process may include two steps: a step of filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body (molding process), and a step of curing the molded body obtained in the molding process to seal the semiconductor element and obtain a sealed body (sealing process).

[0088] The method for forming the molded body is not particularly limited, but for example, one method involves pushing a mold attached to the laminate in the direction of the laminate (support), and, if necessary, reducing the pressure inside the mold to fill the gap between the support and the semiconductor element with the epoxy resin composition, thereby forming a compression molded body containing the laminate and the epoxy resin composition. In this step, instead of pushing the mold in the direction of the laminate (support), the laminate (support) may be pushed in the direction of the mold, or a configuration in which the mold and the laminate (support) are squeezed together may be adopted.

[0089] One method for forming a molded body is to use a molding apparatus to reduce the viscosity of an epoxy resin composition by heating as needed, and then reduce the pressure of the epoxy resin composition to seal the laminate. A molded body can be obtained by this forming method.

[0090] When curing the above molded body to encapsulate the semiconductor element, the curing of the epoxy resin composition may be carried out by heating. The curing temperature is not particularly limited, but is preferably 110 to 200°C, more preferably 120 to 150°C. The curing time is not particularly limited, but is preferably 30 minutes to 7 hours, more preferably 1 to 6 hours, even more preferably 1 to 4 hours, and particularly preferably 1 to 2 hours.

[0091] (Grinding Process) The grinding process is a process of polishing the sealed body obtained by the molding and sealing process. More specifically, it is a process of grinding the surface of the sealed body on the semiconductor element side in order to flatten and thin the sealed body, and to expose a part of the semiconductor element as necessary. There are no particular limitations on the grinding method, and commercially available grinding wheels and grinding equipment can be used.

[0092] (Partitioning Process) The partitioning process is a process of dividing the sealed body obtained by the molding and sealing process, or the sealed body ground by the grinding process, into individual parts. The partitioning process may also be a process of dividing the sealed body into individual parts after removing it from the mold. In the partitioning process, the gaps between multiple semiconductor elements mounted on the support and sealed with a cured epoxy resin composition are cut using means such as a dicing blade or a laser to obtain a semiconductor device. The method of partitioning is not particularly limited, and commercially available partitioning devices can be used.

[0093] In this specification, the term "semiconductor device" refers not only to semiconductor elements, semiconductor elements mounted on a support (substrate), and semiconductor elements connected to each other, but also to all devices that can function by utilizing the properties of semiconductor elements. Such semiconductor devices may include electronic components other than semiconductor elements, such as resistors, coils, capacitors, and transformers.

[0094] The following describes embodiments of a method for manufacturing a semiconductor device using Figures 1 and 2, but the present invention is not limited thereto.

[0095] Figure 1 shows one embodiment of the method for manufacturing a semiconductor device according to the present invention. This embodiment will be described below with reference to Figure 1. A semiconductor element 1 having solder bumps 2 on one side is mounted on a support 3, and a laminate 4 is prepared including the semiconductor element 1, solder bumps 2, and support 3 in this order (laminated laminate preparation step, (a)). An epoxy resin composition 5 is supplied onto the semiconductor element 1 of the laminate 4 using a syringe 6, and then a mold 7 is attached (composition supply step, (b) and (c)). In this step, a release film may be provided on the surface of the mold 7 that is oriented toward the laminate 4. The release film is positioned so that the mold 7 and the epoxy resin composition 5 do not come into contact, and also to facilitate the removal of the sealant 9 from the mold 7 in step (f) described later. The release film is not shown. Next, the attached mold 7 is pushed toward the support 3, and the pressure inside the mold 7 is reduced as needed to form a compression molded body 8 including the laminate 4 and the epoxy resin composition 5 (molding step, (d)). In this step, instead of pushing the mold 7 in the direction of the support 3, the support 3 may be pushed in the direction of the mold 7, or a method may be adopted in which the mold 7 and the support 3 are narrowed relative to each other. In this step, the epoxy resin composition 5 is filled into the gap between the support 3 and the semiconductor element 1 to form a compression molded body 8. The compression molded body 8 is heat-cured to seal the semiconductor element 1 and form a sealant 9 (sealing step, (e)). After removing the mold 7, the sealant 9 containing the semiconductor element 1 is separated into individual pieces (separation steps, (f) and (g)).

[0096] Figure 2 shows another embodiment of the method for manufacturing a semiconductor device according to the present invention. This embodiment will be described below with reference to Figure 2. A semiconductor element 11 having solder bumps 12 on one side is mounted on a support 13, and a laminate 14 is prepared including the semiconductor element 11, solder bumps 12, and support 13 in this order (laminated laminate preparation step, (a)). After supplying an epoxy resin composition 15 to a mold 17 using a syringe 16, the laminate 14 is mounted in the mold (composition supply step, (b) and (c)). In this step, a release film may be provided on the supply surface of the epoxy resin composition 15 in the mold 17. That is, in this step, (1) the epoxy resin composition 15 may be supplied to the surface of the mold 17 that has a release film, or (2) the epoxy resin composition 15 may be supplied onto the release film, and then the release film may be placed in the mold 17. The release film described above is positioned so that the mold 17 and the epoxy resin composition 15 do not come into contact, and also serves to facilitate the removal of the sealant 19 from the mold 17 in step (f) described later. The release film is not shown in the figure. Next, the inside of the mold 17 is depressurized to form a compression molded body 18 containing the laminate 14 and the epoxy resin composition 15 (molding step, (d)). In this step, the epoxy resin composition 15 is filled into the gap between the support 13 and the semiconductor element 11, forming the compression molded body 18. The compression molded body 18 is heat-cured to seal the semiconductor element 11, thereby forming the sealant 19 (sealing step, (e)). After removing the mold 17, the sealant 19 containing the semiconductor element is separated into individual pieces (separation steps, (f) and (g)).

[0097] Although Figures 1 and 2 show the semiconductor element as a single-layer structure for illustrative purposes, it may also have a multilayer structure as shown in Figure 3.

[0098] Figure 3 shows one embodiment of the semiconductor device of the present invention. This embodiment will be described below with reference to Figure 3. The semiconductor device 20 comprises a semiconductor chip 21, solder bumps 22, a encapsulant 23, electrodes 24, a substrate 25, and a package substrate 26. The semiconductor device 20 is a semiconductor device in which the semiconductor chip 21 is three-dimensionally mounted and has a multilayer structure. The electrodes 24 consist of TSVs and connection portions between TSVs. TSV refers to electrodes that penetrate the semiconductor chip 21 in the thickness direction. The encapsulant 23 is a cured product of the epoxy resin composition of the present invention. The semiconductor device 20 can be manufactured, for example, by the semiconductor device manufacturing method described with reference to Figures 1 and 2.

[0099] Figure 4 illustrates an example of a multilayer structure in the semiconductor device of the present invention. In the following description, the directions up, down, right, and left correspond to the directions up, down, right, and left in the figure. The semiconductor chip 31 has a wiring layer 32 on its lower surface. The copper pillar 33 is formed to extend downward from the surface of the semiconductor chip 31 (wiring layer 32). The pad 35 is mounted on the semiconductor chip 37 facing upward. The copper pillar 33 and the pad 35 are physically and electrically connected via solder 34. The TSV 36 is formed to penetrate the semiconductor chip 37 in the thickness direction. The TSV 36 is physically and electrically connected to the pad 35. In this configuration, the copper pillar 33, solder 34, pad 35, and TSV 36 are physically and electrically connected, functioning as a single electrode and electrically connecting the semiconductor chip 31 and the semiconductor chip 37. When the semiconductor device has the multilayer structure shown in this example, the epoxy resin composition of the present invention comes into contact with the copper pillars 33, solder 34, and pads 35 as a cured product (sealant). Since the cured product has good adhesion to the copper pillars 33, delamination from the copper pillars 33 is unlikely to occur. Furthermore, when the pads 35 are made of copper, the cured product has good adhesion to the pads 35, so delamination from the pads 35 is unlikely to occur.

[0100] Figure 5 illustrates another example of a multilayer structure in the semiconductor device of the present invention. In the following description, the directions up, down, right, and left correspond to the directions up, down, right, and left in the same figure. The semiconductor chip 41 has a wiring layer 42 on its lower surface. The copper pillar 43 is formed to extend downward from the surface of the semiconductor chip 41 (wiring layer 42). The TSV 45 is formed to penetrate the semiconductor chip 46 in the thickness direction. The copper pillar 43 and the TSV 45 are physically and electrically connected via solder 44. In this configuration, the copper pillar 43, solder 44, and TSV 45 are physically and electrically connected and function as a single electrode, electrically connecting the semiconductor chip 41 and the semiconductor chip 46. When the semiconductor device takes the multilayer structure shown in this example, the epoxy resin composition of the present invention comes into contact with the copper pillar 43 and the solder 44 as a cured product (sealant). Since the cured product has good adhesion to the copper pillar 43, delamination is unlikely to occur.

[0101] Figure 6 illustrates another example of a multilayer structure in the semiconductor device of the present invention. In the following description, the directions up, down, right, and left correspond to the directions up, down, right, and left in the same figure. The semiconductor chip 51 has a wiring layer 52 on its lower surface. The copper pillar 53 is formed to extend downward from the surface of the semiconductor chip 51 (wiring layer 52). The TSV 55 is formed to penetrate the semiconductor chip 56 in the thickness direction. The copper pillar 53 and the TSV 55 are physically and electrically connected via solder 54. In this configuration, the copper pillar 53, solder 54, and TSV 55 are physically and electrically connected and function as a single electrode, electrically connecting the semiconductor chip 51 and the semiconductor chip 56. When the semiconductor device has the multilayer structure shown in this example, the epoxy resin composition of the present invention comes into contact with the copper pillar 53, solder 54, and TSV 55 as a cured product (sealant). Since the cured product has good adhesion to the copper pillar 53 and TSV 55, delamination is unlikely to occur.

[0102] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0103] The epoxy resin compositions of the examples and comparative examples were prepared by mixing each component in the proportions shown in Table 1. Note that the values ​​for each component in Table 1 represent parts by mass.

[0104] The following describes each component in Table 1. (Epoxy resin (A)) HP-4032D (product name): Naphthalene-type epoxy resin, epoxy equivalent 140 g / eq, liquid at 25°C, manufactured by DIC Corporation YDF-870GS (product name): Bisphenol F-type epoxy resin, epoxy equivalent 163 g / eq, liquid at 25°C, manufactured by Nippon Steel Chemical & Material Co., Ltd. (Curing agent (B)) MH-700 (product name): Mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, acid anhydride-based curing agent, curing agent equivalent (acid anhydride equivalent) 163 g / eq, manufactured by Shin Nippon Rika Co., Ltd. HN-5500 (product name): Methylhexahydrophthalic anhydride, acid anhydride-based curing agent, curing agent equivalent (acid anhydride equivalent) 168 g / eq, manufactured by Resona Co., Ltd. MEH-8000H (Product Name): Liquid phenol novolac resin, phenol-based curing agent, curing agent equivalent (phenol equivalent) 141 g / eq, manufactured by UBE Corporation (Inorganic filler (C)) SE2200-SME (Product Name): Methacrylic surface-treated silicon dioxide, average particle size 0.6 μm, manufactured by Admatex Co., Ltd. YA050C-SM1 (Product Name): Surface-treated silicon dioxide with 3-methacryloxypropyltrimethoxysilane, average particle size 0.05 μm, manufactured by Admatex Co., Ltd. Curing accelerator (D) HX-3088F (Product Name): Microencapsulated latent curing accelerator, manufactured by Asahi Kasei Corporation, coupling agent (E) KBM-403 (Product Name): 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

[0105] (Evaluation 1: Measurement of viscosity at 25°C) The viscosity (Pa·s) of the epoxy resin compositions of Examples 1-5 and Comparative Examples 1 and 2 at 25°C was measured using a Brookfield HB-DV viscometer (model number: HB-DV1) when the epoxy resin compositions were rotated at 20 rpm for 1 minute at a liquid temperature of 25°C. For this measurement, the epoxy resin compositions were used immediately after preparation. The results are shown in Table 1 under "Viscosity at 25°C (Pa·s)".

[0106] (Evaluation 2: Measurement of Gel Time) The gel time of the epoxy resin compositions of Examples 1-5 and Comparative Examples 1 and 2 at 150°C was measured using the "Madoka" automatic curing time measuring device manufactured by Matsuo Sangyo Co., Ltd. The measurement conditions were a rotation speed of 120 rpm, a test temperature of 150°C, a sample volume of 0.3 ml, and a torque judgment value of 30%. The gel time (in seconds) for each resin composition is shown in "Gel Time (sec)" in Table 1.

[0107] (Evaluation 3: Measurement of Glass Transition Temperature (Tg)) The epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were cured at 180°C for 60 minutes to produce cured products, and the glass transition temperature (Tg) of the cured products was measured by DMA (Dynamic Mechanical Analysis). The glass transition temperature (Tg) is the temperature at which the loss tangent (tanδ) changes with temperature, as measured by the DMA method, reaches its peak value (maximum value). The tanδ is obtained by measuring the storage modulus (E') and loss modulus (E'') of the cured product at an arbitrary temperature, and dividing the loss modulus (E'') by the storage modulus (E').

[0108] First, spacers (made of overlapping heat-resistant tape) were placed in two locations on a glass plate coated with a release agent so that the thickness of the cured material would be 2 mm. Next, the epoxy resin composition was applied between the spacers, and the mixture was sandwiched between another glass plate coated with a release agent to prevent air bubbles from being trapped. The mixture was then cured at 180°C for 60 minutes to obtain a cured material. After peeling the cured material from the glass plate coated with the release agent, it was cut to a predetermined size (10 mm x 50 mm) using a cutting machine to obtain test specimens. The glass transition temperature (Tg) of these test specimens was measured using a dynamic viscoelasticity measuring device (product name: DMS6100, manufactured by Seiko Instruments Inc.) with a frequency of 1 Hz, strain amplitude of 10 μm, heating rate of 3 °C / min, measurement temperature range of -30 °C to 300 °C, and the double cantilever beam (DCB) method. The results are listed in "Glass Transition Temperature (°C)" in Table 1.

[0109] (Evaluation 4: Measurement of Thermal Expansion Coefficient CTE) The epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were cured at 180°C for 60 minutes to produce cured products, and test specimens were prepared by molding them into cylindrical shapes with a diameter of 8 mm and a height of 20 mm. The thermal expansion coefficient (CTE) of these test specimens was measured by thermomechanical analysis (TMA) using a TMA4000SA (Bruker). The length of the test specimen at 30°C and the length of the test specimen at 50°C were measured, and the slope in the range of 30 to 50°C was determined and defined as CTE1. Similarly, the length of the test specimen at 180°C and the length of the test specimen at 200°C were measured, and the slope in the range of 180 to 200°C was determined and defined as CTE2. The results are listed in Table 1 as "CTE1 (ppm / °C)" and "CTE2 (ppm / °C)".

[0110] (Evaluation 5: Peel evaluation / Measurement of adhesive strength) Test specimens were prepared by placing the epoxy resin compositions of Examples 1-5 and Comparative Examples 1 and 2 on a copper plate using a mold to create a truncated cone shape with a base diameter of 5 mm, a top diameter of 3 mm, and a height of 7 mm, and then heating and curing them at 150°C for 60 minutes. The shear adhesive strength (MPa) was measured by applying a load from the side of the test specimen using a bond tester (Dage 4000, manufactured by Nordson Advanced Technologies, Inc.). The results are listed in "Adhesive Strength (MPa)" in Table 1.

[0111] Since the CTE1 is 20 ppm / °C or less and the CTE2 is 75 ppm / °C or less, and the shear adhesive strength (MPa) is 14 MPa or more, the cured product of the epoxy resin composition of the example exhibits high adhesion to copper materials, and therefore peeling from TSVs and connection parts between TSVs (for example, pads made of copper pillars or copper members) is unlikely to occur.

[0112]

[0113] The following describes variations of the invention relating to this disclosure. [Note 1] An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and an inorganic filler (C), wherein the epoxy resin (A) includes a naphthalene-type epoxy resin, the content of the naphthalene-type epoxy resin relative to the epoxy resin (A) (100% by mass) is 51% by mass or more, and the content of the inorganic filler (C) is 40% to 90% by mass. [Note 2] The epoxy resin composition according to [Note 1], wherein the epoxy resin (A) may or may not include an alicyclic epoxy resin. [Note 3] The epoxy resin composition according to [Note 1] or [Note 2], wherein the content of epoxy resin (A) is 1% by mass or more, 3% by mass or more, 5% by mass or more, or 6% by mass or more, and / or 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, or 16% by mass or less, or 1 to 40% by mass, 3 to 30% by mass, 5 to 25% by mass, 6 to 20% by mass, or 6 to 16% by mass. [Note 4] The epoxy resin composition according to any one of [Note 1] to [Note 3], wherein the content of naphthalene-type epoxy resin relative to epoxy resin (A) (100% by mass) is 55% by mass or more, 60% by mass or more, 62% by mass or more, 65% by mass or more, 70% by mass or more, or 80% by mass or more. [Note 5] The epoxy resin composition according to any one of [Note 1] to [Note 4], comprising at least one selected from the group consisting of acid anhydride-based curing agents and phenol-based curing agents as the curing agent (B). [Note 6] The epoxy resin composition according to [Note 5], comprising at least one selected from the group consisting of alkylated tetrahydrophthalic anhydride such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, phthalic anhydride, dodecenyl succinic anhydride, and methylnadoic anhydride as the acid anhydride-based curing agent.[Note 7] The epoxy resin composition according to [Note 5], wherein the phenolic curing agent comprises at least one selected from the group consisting of phenol novolac resin, cresol novolac resin, naphthol-modified phenolic resin, dicyclopentadiene-modified phenolic resin, and p-xylene-modified phenolic resin. [Note 8] The epoxy resin composition according to any one of [Note 1] to [Note 7], wherein the content of the phenolic curing agent relative to curing agent (B) (100% by mass) is 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 6% by mass or less. [Note 9] The epoxy resin composition according to any one of [Note 1] to [Note 8], wherein the curing agent (B) comprises an acid anhydride-based curing agent, and the content of the acid anhydride-based curing agent relative to curing agent (B) (100% by mass) is 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more. [Note 10] The epoxy resin composition according to any one of [Note 1] to [Note 9], wherein the content of the curing agent (B) is 1% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, or 6% by mass or more, and / or 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less, or 1 to 30% by mass, 3 to 25% by mass, 4 to 20% by mass, 5 to 15% by mass, or 6 to 15% by mass. [Note 11] The epoxy resin composition according to any one of [Note 1] to [Note 10], wherein the content of the curing agent (B) relative to the epoxy resin (A) (100% by mass) is 40% by mass or more, 60% by mass or more, 80% by mass or more, or 90% by mass or more, and / or 200% by mass or less, 180% by mass or less, 160% by mass or less, 140% by mass or less, or 120% by mass or less, or 40 to 200% by mass, 60 to 180% by mass, 80 to 160% by mass, 90 to 140% by mass, or 90 to 120% by mass. [Note 12] The epoxy resin composition according to any one of [Note 1] to [Note 11], wherein the inorganic filler (C) is surface-treated with a coupling agent having a functional group such as an epoxy group, a (meth)acryloyl group, or an amino group (especially a phenylamino group).[Note 13] The epoxy resin composition according to any one of [Note 1] to [Note 12], wherein the average particle size of the inorganic filler (C) is 1 nm to 10 μm, 5 nm to 7 μm, 10 nm to 5 μm, 10 nm to 3 μm, or 30 nm to 1 μm. [Note 14] The epoxy resin composition according to any one of [Note 1] to [Note 13], comprising, as the inorganic filler (C), an inorganic filler (C1) having an average particle size of 0.2 to 10 μm (particularly 0.25 to 7 μm, 0.3 to 5 μm, 0.35 to 3 μm, or 0.4 to 1 μm) and an inorganic filler (C2) having an average particle size of 1 nm or more and less than 200 nm (particularly 5 to 150 nm, 10 to 120 nm, 20 to 100 nm, or 30 to 80 nm). [Note 15] The epoxy resin composition according to any one of [Note 1] to [Note 14], wherein the inorganic filler (C) comprises an inorganic filler (CX) having an average particle size of 3 μm or less (particularly 2 μm or less, 1.5 μm or less, or 1 μm or less), and the content of the inorganic filler (CX) relative to the inorganic filler (C) (100% by mass) in the epoxy resin composition is 30% by mass or more, 60% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. [Note 16] The epoxy resin composition according to any one of [Note 1] to [Note 15], wherein the content of the inorganic filler (C) is 40 to 90% by mass, 50 to 88% by mass, 60 to 86% by mass, 65 to 85% by mass, 70 to 83% by mass, or 70 to 80% by mass. [Note 17] The epoxy resin composition according to any one of [Notes 14] to [Note 16], wherein the content of inorganic filler (C1) is 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, and / or 80% by mass or less, 75% by mass or less, 70% by mass or less, or 65% by mass or less, or 20 to 80% by mass, 30 to 75% by mass, 40 to 70% by mass, 45 to 65% by mass, or 50 to 65% by mass.[Note 18] An epoxy resin composition according to any one of [Notes 14] to [Note 17], wherein the content of inorganic filler (C2) is 3% by mass or more, 6% by mass or more, 9% by mass or more, 12% by mass or more, or 15% by mass or more, and / or 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less, or 3 to 40% by mass, 6 to 35% by mass, 9 to 30% by mass, 12 to 25% by mass, or 15 to 25% by mass. [Note 19] The epoxy resin composition according to any one of [Note 1] to [Note 18], wherein the content of inorganic filler (C) relative to epoxy resin (A) (100% by mass) in the epoxy resin composition is 100% by mass or more, 200% by mass or more, 300% by mass or more, or 400% by mass or more, and / or 2000% by mass or less, 1600% by mass or less, 1400% by mass or less, or 1200% by mass or less, or 100 to 2000% by mass, 200 to 1600% by mass, 300 to 1400% by mass, or 400 to 1200% by mass. [Note 20] The epoxy resin composition according to any one of [Note 1] to [Note 19], further comprising at least one selected from the group consisting of imidazole-based curing accelerators, tertiary amine-based curing accelerators, and phosphorus-based curing accelerators as a curing accelerator (D). [Note 21] The epoxy resin composition according to [Note 20], wherein the content of the curing accelerator (D) is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.4% by mass or more, and / or 10% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less, or 0.01 to 10% by mass, 0.05 to 5% by mass, 0.1 to 4% by mass, 0.2 to 3% by mass, or 0.4 to 2% by mass. [Note 22] The epoxy resin composition according to [Note 20] or [Note 21], wherein the content of the curing accelerator (D) relative to the epoxy resin (A) (100% by mass) is 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 3% by mass or more, or 5% by mass or more, and / or 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less, or 0.1 to 40% by mass, 0.5 to 30% by mass, 1 to 25% by mass, 3 to 20% by mass, or 5 to 15% by mass.[Note 23] The epoxy resin composition according to any one of [Note 1] to [Note 22], further comprising a silane coupling agent such as 3-isocyanatetopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 3-methacryloxypropyltrimethoxysilane as a coupling agent (E). [Note 24] The epoxy resin composition according to any one of [Note 1] to [Note 23], wherein the viscosity at 25°C is 5 to 1000 Pa·s, 10 to 800 Pa·s, 30 to 800 Pa·s, 50 to 600 Pa·s, or 100 to 500 Pa·s. [Note 25] The epoxy resin composition according to any one of [Note 1] to [Note 24], wherein the glass transition temperature (Tg) of the cured product is 130°C or higher, 140°C or higher, 145°C or higher, or 150°C or higher, and / or 200°C or lower, 180°C or lower, or 160°C or lower, or 130 to 200°C, 140 to 180°C, 145 to 160°C, or 150 to 160°C. [Note 26] An epoxy resin composition according to any one of [Note 1] to [Note 25], wherein the gel time at 150°C is 100 seconds or more, 120 seconds or more, 140 seconds or more, or 160 seconds or more, and / or 500 seconds or less, 400 seconds or less, 300 seconds or less, or 250 seconds or less, or 100 to 500 seconds, 120 to 400 seconds, 140 to 300 seconds, or 160 to 250 seconds. [Note 27] An epoxy resin composition according to any one of [Note 1] to [Note 26] that is a liquid compression molding material. [Note 28] An epoxy resin composition according to any one of [Note 1] to [Note 27] that is an underfill material for multilayer semiconductors. [Note 29] A cured product of an epoxy resin composition according to any one of [Note 1] to [Note 28]. [Note 30] A semiconductor device comprising the cured product described in [Note 29]. [Note 31] A semiconductor device comprising: a support; a semiconductor element mounted on the support; and the cured product described in [Note 29] that seals the semiconductor element.[Note 32] A method for manufacturing a semiconductor device, comprising the steps of: supplying an epoxy resin composition described in any one of [Note 1] to [Note 28] onto a laminate comprising a support and a semiconductor element mounted on the support; and filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body, curing the molded body to seal the semiconductor element, and obtaining a sealed body.

[0114] The epoxy resin composition of the present invention exhibits excellent adhesion. Therefore, semiconductor devices equipped with a cured product of the epoxy resin composition exhibit high reliability. The factors contributing to this "adhesion" are thought to be the interplay between (1) high adhesion between the cured product of the epoxy resin composition and the copper material, and (2) a small coefficient of thermal expansion of the cured product, i.e., a small rate of expansion due to temperature. In other words, the epoxy resin composition of the present invention exhibits high adhesion to copper materials when cured, and its low coefficient of thermal expansion results in high adhesion to copper materials.

[0115] 1 Semiconductor element 2 Solder bump 3 Support 4 Laminate 5 Epoxy resin composition 6 Syringe 7 Mold 8 Compression molded body 9 Encapsulation body 11 Semiconductor element 12 Solder bump 13 Support 14 Laminate 15 Epoxy resin composition 16 Syringe 17 Mold 18 Compression molded body 19 Encapsulation body 20 Semiconductor device 21 Semiconductor chip 22 Solder bump 23 Encapsulation body 24 Electrode 25 Substrate 26 Package substrate 31 Semiconductor chip 32 Wiring layer 33 Copper pillar 34 Solder 35 Pad 36 TSV 37 Semiconductor chip 41 Semiconductor chip 42 Wiring layer 43 Copper pillar 44 Solder 45 TSV 46 Semiconductor chip 51 Semiconductor chip 52 Wiring layer 53 Copper pillar 54 Solder 55 TSV 56 Semiconductor chip

Claims

1. An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and an inorganic filler (C), wherein the epoxy resin (A) includes a naphthalene-type epoxy resin, the content of the naphthalene-type epoxy resin relative to the epoxy resin (A) (100% by mass) is 51% by mass or more, and the content of the inorganic filler (C) is 40% to 90% by mass.

2. The epoxy resin composition according to claim 1, wherein the content of the phenolic curing agent relative to the curing agent (B) (100% by mass) is 10% by mass or less.

3. The epoxy resin composition according to claim 1 or 2, wherein the curing agent (B) contains an acid anhydride-based curing agent, and the content of the acid anhydride-based curing agent relative to curing agent (B) (100% by mass) is 50% by mass or more.

4. The epoxy resin composition according to claim 1 or 2, wherein the viscosity at 25°C is 5 to 1000 Pa·s.

5. The epoxy resin composition according to claim 1 or 2, wherein the glass transition temperature (Tg) of the cured product is 130 to 200°C.

6. The epoxy resin composition according to claim 1 or 2, wherein the gel time at 150°C is 100 to 500 seconds.

7. The epoxy resin composition according to claim 1 or 2, which is a liquid compression molding material.

8. The epoxy resin composition according to claim 1 or 2, which is an underfill material for multilayer semiconductors.

9. A cured product of the epoxy resin composition according to claim 1 or 2.

10. A semiconductor device comprising the cured product described in claim 9.

11. A semiconductor device comprising: a support; a semiconductor element mounted on the support; and a cured product according to claim 9 for sealing the semiconductor element.

12. A method for manufacturing a semiconductor device, comprising the steps of: supplying the epoxy resin composition according to claim 1 or 2 onto a laminate comprising a support and a semiconductor element mounted on the support; filling the gap between the support and the semiconductor element with the epoxy resin composition to form a molded body; curing the molded body to seal the semiconductor element and obtain a sealed body.

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