Liquid resin composition and semiconductor device

Abstract

The present disclosure provides a liquid resin composition that makes it possible to achieve good fluidity and obtain both high curability and excellent storage stability. The liquid resin composition contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and a stabilizer (D). The stabilizer (D) has at least one anion selected from the group consisting of an anion represented by formula (1), an anion represented by formula (2), and an anion represented by formula (3).

Description

Liquid resin composition and semiconductor device

[0001] The present disclosure generally relates to a liquid resin composition and a semiconductor device, and more particularly to a liquid resin composition containing an epoxy compound and a semiconductor device.

[0002] Patent Document 1 discloses a liquid encapsulant comprising (A) a liquid epoxy resin, (B) a curing agent, (C) a silica filler having an average particle size of 7 to 50 nm and surface-treated with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (D) a silica filler having an average particle size of 0.2 to 5 μm, and (E) a Lewis base or a salt thereof, wherein the curing agent (B) is an aromatic polyamine, and the component (E) is triphenylphosphine. The combined content of the silica filler (C) and the silica filler (D) is 45 to 77 parts by mass per 100 parts by mass of all components of the liquid encapsulant, and the blending ratio (mass ratio) of the silica filler (C) to the silica filler (D) is 1:17.7 to 1:76. The liquid encapsulant is also disclosed to have good injectability into the gap between a semiconductor element and a substrate.

[0003] Patent No. 6415104

[0004] It is difficult to achieve a liquid encapsulant that has both high curability and excellent storage stability while also achieving good injectability into the gap between the semiconductor element and the substrate.

[0005] An object of the present disclosure is to provide a liquid resin composition and a semiconductor device that can achieve both high curability and excellent storage stability, and also achieve good fluidity.

[0006] A liquid resin composition according to one embodiment of the present disclosure contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and a stabilizer (D), wherein the stabilizer (D) has at least one anion selected from the group consisting of an anion represented by formula (1), an anion represented by formula (2), and an anion represented by formula (3).

[0007]

[0008] A semiconductor device according to one aspect of the present disclosure includes a substrate, a semiconductor element mounted on the substrate, and a sealing portion interposed in a gap between the substrate and the semiconductor element, the sealing portion including a cured product of the liquid resin composition.

[0009] FIG. 1 is a cross-sectional view of a semiconductor device according to an embodiment of the present disclosure.

[0010] 1. Overview An embodiment of the present disclosure will be described. Note that the following embodiments are merely a portion of various embodiments of the present disclosure. Furthermore, the following embodiments can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. The figures referred to below are schematic diagrams, and the dimensional ratios of the components in the figures do not necessarily reflect the actual dimensional ratios. Although the mechanism of action in the embodiments may be described below, the description of the mechanism of action includes an explanation based on speculation, and the present disclosure is not bound by the description of the mechanism of action.

[0011] A liquid resin composition (hereinafter also referred to as composition (X)) according to an embodiment contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and a stabilizer (D). The stabilizer (D) has at least one anion selected from the group consisting of an anion represented by formula (1), an anion represented by formula (2), and an anion represented by formula (3).

[0012]

[0013] According to an embodiment, the composition (X) can achieve both high curability and excellent storage stability. Furthermore, the composition (X) can achieve good fluidity. In particular, the viscosity of the composition (X) can be reduced by heating the composition (X), and the composition (X) can achieve good fluidity when molding the composition (X) while flowing in this state.

[0014] The composition (X) can be used to produce a semiconductor device. More specifically, the composition (X) can be used to produce a sealing portion included in the semiconductor device. In particular, the composition (X) can be suitably used to produce a sealing portion interposed between a semiconductor element and a substrate when the semiconductor element is flip-chip mounted. That is, the composition (X) can be suitably used as an underfill material. In this case, the composition (X) easily flows between the semiconductor element and the substrate during production of the sealing portion, thereby improving the manufacturing efficiency of the semiconductor device and suppressing unfilled sealing portions.

[0015] The use of composition (X) is not limited to the production of semiconductor devices, but composition (X) can be used for various purposes other than the production of semiconductor devices.

[0016] 2. Composition 2.1 Composition of the Composition As described above, the composition (X) contains the liquid epoxy compound (A), the liquid aromatic amine compound (B), the inorganic filler (C), and the stabilizer (D).

[0017] (Epoxy Compound) As described above, the epoxy compound (A) is liquid. Liquid means that it has the property of flowing at 25°C. All components contained in the epoxy compound (A) may be liquid. However, for example, the epoxy compound (A) may contain a liquid component and a solid component, and by mixing the components, the epoxy compound (A) as a whole may be liquid. The liquid epoxy compound (A) can impart fluidity to the composition (X).

[0018] The viscosity of the epoxy compound (A) at 25°C is preferably 100 Pa s or less. This viscosity is more preferably 50 Pa s or less, and even more preferably 20 Pa s or less. Furthermore, the viscosity of the epoxy compound (A) at 25°C is, for example, 0.01 Pa s or more. This viscosity is more preferably 0.02 Pa s or more.

[0019] The epoxy compound (A) preferably contains a compound having two or more epoxy groups in one molecule, which can enhance the reactivity of the epoxy compound (A) with the aromatic amine compound (B).

[0020] The epoxy compound (A) contains at least one selected from the group consisting of diglycidyl ether epoxy compounds such as p-aminophenol-type epoxy compounds, naphthalene-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol AD-type epoxy compounds, bisphenol S-type epoxy compounds, and hydrogenated bisphenol A-type epoxy compounds; epoxy compounds obtained by epoxidizing novolac compounds obtained by the reaction of phenols with aldehydes, such as orthocresol novolac-type epoxy compounds; glycidyl ester-type epoxy compounds obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; aminodiphenylmethane and isocyanuric acid-type epoxy compounds; and silicone-modified epoxy compounds (A1). Among these, it is preferable that the epoxy compound (A) contains the silicone-modified epoxy compound (A1). In this case, the fluidity of the composition (X) can be further enhanced. Furthermore, the silicone-modified epoxy compound (A1) is less likely to lower the glass transition temperature of the cured product of the composition (X) and is less likely to cause weight loss of the cured product under heating. This is thought to be because the silicone skeleton of the silicone-modified epoxy compound (A1) has high heat resistance, and the bond between silicon and oxygen in the silicone skeleton flexibly modifies the molecular chain of the silicone-modified epoxy compound (A1), thereby lowering the viscosity of the composition (X).

[0021] When the epoxy compound (A) contains a silicone-modified epoxy compound (A1), the content of the silicone-modified epoxy compound (A1) is preferably 1% by mass or more and 30% by mass or less relative to the epoxy compound (A). If this content is 1% by mass or more, the fluidity of the composition (X) can be further increased. If this content is 30% by mass or less, weight loss during curing of the composition (X) can be further suppressed. This content is more preferably 5% by mass or more, and even more preferably 7% by mass or more. This content is more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0022] 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 compound (B) can be increased. The epoxy equivalent of this epoxy compound (A) is preferably 50 g / eq. or more. The epoxy equivalent of this epoxy compound (A) is preferably 300 g / eq. or less.

[0023] (Aromatic Amine Compound) As described above, the aromatic amine compound (B) is liquid. All components contained in the aromatic amine compound (B) may be liquid. However, for example, the aromatic amine compound (B) may contain a liquid component and a solid component, and the aromatic amine compound (B) may be liquid as a whole by mixing the components. The liquid aromatic amine compound (B) can impart fluidity to the composition (X).

[0024] The aromatic amine compound (B) preferably contains an aromatic amine compound having two or more amino groups in one molecule. In this case, the reactivity of the epoxy compound (A) with the aromatic amine compound (B) can be further enhanced. As a result, the curability of the composition (X) and the heat resistance of the cured product can be further enhanced.

[0025] Examples of the aromatic amine compound (B) include aliphatic aromatic amine compounds such as m-xylenediamine; aromatic amine compounds having one aromatic ring such as metaphenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole, and dimethylthiotoluenediamine; and aromatic amine compounds having one aromatic ring such as 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline). ), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, and polytetramethylene oxide diparaaminobenzoate; condensation products of aromatic diamines and epichlorohydrin; and reaction products of aromatic diamines and styrene.

[0026] The amine active hydrogen equivalent of the aromatic amine compound (B) is, for example, 20 g / eq. or more and 500 g / eq. or less. In this case, the reactivity of the epoxy compound (A) and the aromatic amine compound (B) can be increased. The amine active hydrogen equivalent means the mass (g) of the aromatic amine compound (B) containing 1 mole of amine active hydrogen. The amine active hydrogen equivalent of the aromatic amine compound (B) is, for example, preferably 30 g / eq. or more. The amine active hydrogen equivalent of the aromatic amine compound (B) is, for example, preferably 100 g / eq. or less.

[0027] The equivalent ratio of the amine active hydrogen of the aromatic amine compound (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 compound (B) can react efficiently. Therefore, the glass transition temperature of the cured product can be appropriately increased. This equivalent ratio is more preferably 0.7 or more, and even more preferably 0.8 or more. It is also more preferable that this equivalent ratio is 1.3 or less.

[0028] (Inorganic Filler) The inorganic filler (C) can reduce the linear expansion coefficient of the cured product. This reduces warping of the semiconductor device and suppresses breakage. The inorganic filler (C) can also contribute to improving the thermal conductivity of the cured product. In other words, the inorganic filler (C) can improve the heat dissipation properties of the semiconductor device.

[0029] The inorganic filler (C) contains at least one selected from the group consisting of silica particles such as fused silica, synthetic silica, and crystalline silica; metal oxide particles such as alumina and titanium oxide; sulfate or sulfite particles such as barium sulfate, calcium sulfate, and calcium sulfite; borate particles such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitride particles such as aluminum nitride, boron nitride, and silicon nitride.The inorganic filler (C) more preferably contains silica particles.In this case, the silica particles can particularly contribute to reducing the linear expansion coefficient of the cured product.

[0030] The particle shape of the inorganic filler (C) is not particularly limited and may be crushed, needle-like, scale-like, spherical, etc. In order to improve the dispersibility of the inorganic filler (C) in the composition (X) and to control the viscosity of the composition (X), the particle shape of the inorganic filler (C) is preferably spherical.

[0031] The particles of the inorganic filler (C) are preferably surface-treated with a surface treatment agent. In this case, the dispersibility of the inorganic filler (C) in the composition (X) can be improved. This can suppress a decrease in the fluidity of the composition (X) due to the inorganic filler (C). The surface treatment agent contains at least one selected from the group consisting of, for example, silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. The silane compound contains at least one selected from the group consisting of, for example, silane compounds having an amino group, silane compounds having an acrylic group, silane compounds having a methacryl group, silane compounds having an epoxy group, mercaptosilane, alkylsilane, ureidosilane, and vinylsilane. Among these, the silane compound preferably contains at least one selected from the group consisting of silane compounds having an amino group, silane compounds having a methacryl group, and silane compounds having an epoxy group. Furthermore, the silane compound having an amino group preferably contains a silane compound having a phenylamino group. Therefore, it is particularly preferred that the inorganic filler (C) contains silica particles surface-treated with a silane compound having at least one group selected from the group consisting of a phenylamino group, a methacryl group, and an epoxy group, which can particularly enhance the dispersibility of the inorganic filler (C) in the composition (X).

[0032] The inorganic filler (C) preferably contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and 15 μm or less and a second inorganic filler (C2) having an average particle size of 0.1 μm or less. In this case, an increase in viscosity of the composition (X) due to the inorganic filler (C) can be suppressed. This allows the fluidity of the composition (X) to be maintained at a good level. The average particle size of the first inorganic filler (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 (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 (C2) is more preferably 80 nm or less, and even more preferably 60 nm or less.

[0033] When the inorganic filler (C) contains a first inorganic filler (C1) and a second inorganic filler (C2), the total content of the first inorganic filler (C1) and the second inorganic filler (C2) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the inorganic filler (C).

[0034] The content of the second inorganic filler (C2) is preferably 1% by mass or more and 10% by mass or less relative to the inorganic filler (C). In this case, the increase in viscosity of the composition (X) can be further suppressed. This content is preferably 2% by mass or more. This content is more preferably 8% by mass or less.

[0035] The inorganic filler (C) may contain only the first inorganic filler (C1) and the second inorganic filler (C2). The content of the inorganic filler (C) is preferably 40% by mass or more and 80% by mass or less relative to the total amount of the composition (X). When the content of the inorganic filler (C) is 40% by mass or more, the linear expansion coefficient of the composition (X) can be further reduced. When the content of the inorganic filler (C) is 80% by mass or less, the fluidity of the composition (X) can be well maintained. This content is more preferably 42% by mass or more, and even more preferably 45% by mass or more. This content is more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0036] (Stabilizer) The stabilizer (D) can contribute to the storage stability of the composition (X). The stabilizer (D) has at least one anion selected from the group consisting of an anion represented by formula (1), an anion represented by formula (2), and an anion represented by formula (3). That is, the stabilizer is at least one of compound (D1) which is a salt of the anion represented by formula (1), compound (D2) which is a salt of the anion represented by formula (2), and compound (D3) which is a salt of the anion represented by formula (3).

[0037]

[0038] When the stabilizer (D) contains at least one anion selected from the group consisting of these anions, the storage stability of the composition (X) can be improved without impairing the curability of the composition (X).

[0039] The stabilizer (D) has a cation that pairs with the anion listed above. The cation contained in the stabilizer (D) is not particularly limited, but for example, the stabilizer (D) has at least one cation selected from the group consisting of imidazolium cations and phosphonium cations. Among the cations listed above, the stabilizer (D) preferably has at least one cation selected from the group consisting of imidazolium cations and phosphonium cations. In this case, the viscosity of the composition (X) when heated can be reduced, and the flowability can be improved.

[0040] The imidazolium cation has, for example, a structure represented by formula (4).

[0041]

[0042] In formula (4), R1 and R2 are the same or different and represent hydrogen or a substituted or unsubstituted hydrocarbon group having from 1 to 5 carbon atoms. From the viewpoints of curability, storage stability, and flowability, each of R1 and R2 preferably has from 1 to 3 carbon atoms, and more preferably has from 1 to 2 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a pentyl group. Of these, a methyl group or an ethyl group is preferred.

[0043] The phosphonium cation has, for example, a structure represented by formula (5).

[0044]

[0045] In formula (5), R3 to R6 are the same or different and represent a substituted or unsubstituted hydrocarbon group having from 1 to 12 carbon atoms. From the viewpoints of curability, storage stability, and flowability, each of R3 to R6 preferably has from 4 to 6 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a cyclohexyl group, a phenyl group, a methoxymethyl group, and a benzyl group. Of these, an n-butyl group or a phenyl group is preferred.

[0046] As described above, the stabilizer (D) contains a compound (D1) having an anion represented by formula (1). In this case, the viscosity of the composition (X) can be further reduced when heated, and the flowability can be further improved. The cation contained in the compound (D1) is not particularly limited, but the compound (D1) preferably contains at least one cation selected from the group consisting of imidazolium cations and phosphonium cations. In this case, the imidazolium cation is particularly preferably a compound represented by formula (4) in which R1 is an ethyl group and R2 is a methyl group. The phosphonium cation is particularly preferably a compound represented by formula (5) in which all of R3 to R6 are phenyl groups. In other words, the compound (D1) preferably contains at least one selected from the group consisting of a compound represented by formula (6) and a compound represented by formula (7).

[0047]

[0048] The compounds represented by formula (6) and formula (7) have the advantage of being able to particularly increase the glass transition temperature of the cured product.

[0049] As described above, the stabilizer (D) contains a compound (D2) having an anion represented by formula (2). In this case, the viscosity of the composition (X) can be further reduced when heated, and the flowability can be further improved. The cation contained in the compound (D2) is not particularly limited, but it is preferable that the compound (D2) has a phosphonium cation. In this case, it is particularly preferable that the phosphonium cation is one in which all of R3 to R6 in formula (5) are phenyl groups. In other words, it is particularly preferable that the compound (D2) contains a compound represented by formula (8). The compound represented by formula (8) has the advantage of being able to particularly increase the glass transition temperature of the cured product.

[0050]

[0051] As described above, the stabilizer (D) contains a compound (D3) having an anion represented by formula (3). In this case, the viscosity of the composition (X) can be further reduced when heated, and the flowability can be further improved. The cation contained in the compound (D3) is not particularly limited, but it is preferable that the compound (D3) has a phosphonium cation. In this case, it is particularly preferable that the phosphonium cation is one in which all of R3 to R6 in formula (5) are n-butyl groups. In other words, it is particularly preferable that the compound (D3) contains a compound represented by formula (9). The compound represented by formula (9) has the advantage of being able to particularly increase the glass transition temperature of the cured product.

[0052]

[0053] The content of the stabilizer (D) is preferably 0.03% by mass or more and 1.0% by mass or less relative to the composition (X). When this content is 0.03% by mass or more, the viscosity of the composition (X) at high temperatures can be reduced. When this content is 1.0% by mass or less, the storage stability of the composition (X) is further improved and high curability can be sufficiently maintained. The content of the stabilizer (D) is more preferably 0.05% by mass or more. The content of the stabilizer (D) is more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less.

[0054] (Rubber particles) The composition (X) may further contain rubber particles (E). When the composition (X) contains rubber particles (E), the crack resistance of the cured product can be improved. The rubber particles (E) preferably contain at least one selected from the group consisting of silicone rubber particles and butadiene rubber particles. In this case, the crack resistance of the cured product can be further improved.

[0055] The silicone rubber particles may include, but are not limited to, silicone-based core-shell particles, specifically, commercially available products such as Kane Ace (registered trademark) MX-965 manufactured by Kaneka Corporation. The butadiene rubber particles may include, but are not limited to, butadiene-based core-shell particles, specifically, commercially available products such as Kane Ace (registered trademark) MX-136 and MX-139 manufactured by Kaneka Corporation.

[0056] The content of the rubber particles (E) is preferably 0.1% by mass or more and 3.0% by mass or less relative to the composition (X). If this content is 0.1% by mass or more, the crack resistance of the cured product can be particularly improved. If this content is 3.0% by mass or less, an increase in the viscosity of the composition (X) can be suppressed. This content is more preferably 2.5% by mass or less, and even more preferably 2.0% by mass or less.

[0057] Composition (X) may contain additives other than the components listed above, as needed, such as at least one selected from the group consisting of a resin modifier, a curing aid, a coupling agent, a colorant, a thixotropic agent, an ion trapping agent, an antifoaming agent, a leveling agent, and an antioxidant.

[0058] It is preferred that the composition (X) contains no solvent or only a trace amount of solvent that is unavoidably mixed in.

[0059] 2.2 Properties of the composition (viscosity at 25°C) For example, the viscosity of composition (X) at 25°C is 400 Pa s or less. Therefore, composition (X) can have good fluidity at room temperature. By appropriately setting the composition of composition (X), the viscosity of composition (X) at 25°C can be set to 200 Pa s or less, and can also be set to 100 Pa s or less. The method for measuring viscosity will be explained in the Examples section.

[0060] (Viscosity at 110°C) For example, the viscosity of composition (X) at 110°C is 0.4 Pa s or less. Therefore, composition (X) can have good fluidity when heated. Note that by appropriately setting the composition of composition (X), the viscosity of composition (X) at 110°C can be set to 0.3 Pa s or less, and can also be set to 0.2 Pa s or less. Note that the method for measuring viscosity will be explained in the Examples section.

[0061] (Gel Time) For example, the gel time of composition (X) at 165°C is 600 seconds or more. Therefore, composition (X) can have good fluidity when heated. By appropriately setting the composition of composition (X), the gel time of composition (X) at 165°C can be made 1000 seconds or more. Furthermore, if the gel time is 1800 seconds or less, good curability can be maintained. The method for measuring the gel time will be explained in the Examples section.

[0062] (Glass transition temperature) For example, the glass transition temperature of the cured product of composition (X) is 80°C or higher. Therefore, the cured product can have good heat resistance. By appropriately setting the composition of composition (X), the glass transition temperature of the cured product can be set to 100°C or higher, and can also be set to 130°C or higher. The method for measuring the glass transition temperature of the cured product will be explained in the Examples section.

[0063] 3. Application Examples Application examples of composition (X) will be described.

[0064] (Semiconductor Device) In the embodiment, the composition (X) is used for semiconductor encapsulation. For example, the composition (X) can be used to produce an encapsulation portion 5 in a semiconductor device 1 (see FIG. 1 ). The encapsulation portion 5 is a member that protects the semiconductor element 3 by covering a part or all of the semiconductor element 3 in the semiconductor device 1.

[0065] Among the compositions (X) for semiconductor encapsulation, it is particularly suitable for use as an underfill. An underfill material is a material for producing a sealing portion 5 interposed in the gap between a substrate 2 and a semiconductor element 3 surface-mounted on the substrate 2. That is, in this case, the semiconductor device 1 includes the substrate 2, the semiconductor element 3 mounted on the substrate 2, and the sealing portion 5 interposed in the gap between the substrate 2 and the semiconductor element 3, and the sealing portion 5 includes a cured product of the composition (X).

[0066] The substrate 2 includes an insulating substrate such as a glass epoxy substrate, a polyimide substrate, a polyester substrate, or a ceramic substrate, and conductive wiring 21 overlaid on the insulating substrate. The conductive wiring 21 includes, for example, electrode pads. The substrate 2 is, for example, a motherboard, a package substrate, or an interposer substrate.

[0067] The semiconductor element 3 may be any suitable surface-mount type element. The semiconductor element 3 has bump electrodes 31 on the surface facing the substrate 2. The semiconductor element 3 may be a bare chip, a packaged component, or a wafer-level package. The semiconductor element 3 may be a flip-chip type chip such as a BGA (ball grid array), an LGA (land grid array), or a CSP (chip-size package). The semiconductor element 3 may also be a PoP (package-on-package) type chip.

[0068] A semiconductor element 3 is surface-mounted on the substrate 2. More specifically, the surface of the semiconductor element 3 having bump electrodes 31 faces the substrate 2, the bump electrodes 31 on the semiconductor element 3 are joined to the electrode pads of the conductor wiring 21 on the substrate 2 by solder bumps 4, and the bump electrodes 31 are electrically connected to the electrode pads by the solder bumps 4. Note that the manner of connection between the semiconductor element 3 and the substrate 2 is not limited to the above, as long as the semiconductor element 3 is mounted on the substrate 2 so that a gap is left between the semiconductor element 3 and the substrate 2.

[0069] The sealing portion 5 is interposed in the gap between the semiconductor element 3 and the substrate 2. Therefore, the bump electrodes 31, the solder bumps 4, and the electrode pads of the conductor wiring 21 are buried in the sealing portion 5.

[0070] (Method for Manufacturing Semiconductor Device) An example of a method for manufacturing the semiconductor device 1 will be described.

[0071] First, the substrate 2, the semiconductor element 3, and the composition (X) are prepared.

[0072] Next, the semiconductor element 3 is surface-mounted on the substrate 2. Specifically, the surface of the semiconductor element 3 having the bump electrodes 31 is placed opposite the substrate 2, and solder bumps 4 are interposed between the bump electrodes 31 on the semiconductor element 3 and the electrode pads of the conductor wiring 21 on the substrate 2. The solder contained in the solder bumps 4 is a lead-free solder with a melting point of 210°C or higher, such as Sn-3.5Ag (melting point 221°C), Sn-2.5Ag-0.5Cu-1Bi (melting point 214°C), Sn-0.7Cu (melting point 227°C), or Sn-3Ag-0.5Cu (melting point 217°C). In this state, the solder bumps 4 are heated and melted by an appropriate heating method such as reflow heating, and then solidified. The heating temperature is set appropriately depending on the solder bumps 4 so that the solder bumps 4 melt, but for example, the maximum heating temperature is 180°C or higher and 300°C or lower. As a result, the conductor wiring 21 and the electrode pads are joined by the solder bumps 4, and the conductor wiring 21 and the electrode pads are electrically connected by the solder bumps 4.

[0073] Next, composition (X) is injected into the gap between the semiconductor element 3 and the substrate 2 using a dispenser or the like. The composition (X) flows through the gap between the semiconductor element 3 and the substrate 2 due to capillary action. When causing the composition (X) to flow, the viscosity of the composition (X) may be reduced by heating the composition (X), if necessary. In this case, the heating temperature of the composition (X) is, for example, 80°C or higher and 130°C or lower. This allows the composition (X) to fill the gap between the semiconductor element 3 and the substrate 2. In the embodiment, the fluidity of the composition (X) can be increased when the composition (X) is heated as described above. Therefore, the composition (X) can be successfully filled into the gap between the semiconductor element 3 and the substrate 2. The composition (X) is cured by heating it in this state. The heating conditions in this case are appropriately set depending on the composition of the composition (X), but are, for example, a heating temperature of 80°C or higher and 180°C or lower, and a heating time of 60 minutes or higher and 300 minutes or lower. As a result, a sealing portion 5 containing the cured product of the composition (X) is produced in the gap between the semiconductor element 3 and the substrate 2 .

[0074] In the embodiment, the composition (X) may have high fluidity, which can prevent the composition (X) and the sealing portion 5 from being left unfilled between the semiconductor element 3 and the substrate 2.

[0075] The method for manufacturing the semiconductor device 1 is not limited to the above.

[0076] A liquid resin composition according to a first aspect of the present disclosure contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and a stabilizer (D). The stabilizer (D) has at least one anion selected from the group consisting of an anion represented by formula (1), an anion represented by formula (2), and an anion represented by formula (3).

[0077]

[0078] According to this embodiment, it is possible to achieve both high curability and excellent storage stability, and also to realize good fluidity.

[0079] In the liquid resin composition according to the second aspect of the present disclosure, in the first aspect, the stabilizer (D) contains a compound (D1) having an anion represented by formula (1). The compound (D1) includes at least one selected from the group consisting of a compound represented by formula (6) and a compound represented by formula (7).

[0080]

[0081] In the liquid resin composition according to the third aspect of the present disclosure, in the first or second aspect, the stabilizer (D) contains a compound (D2) having an anion represented by formula (2). The compound (D2) includes a compound represented by formula (8).

[0082]

[0083] In the liquid resin composition according to the fourth aspect of the present disclosure, in any one of the first to third aspects, the stabilizer (D) contains a compound (D3) having an anion represented by formula (3). The compound (D3) includes a compound represented by formula (9).

[0084]

[0085] In the liquid resin composition according to a fifth aspect of the present disclosure, in any one of the first to fourth aspects, the inorganic filler (C) contains a first inorganic filler (C1) having an average particle size of more than 0.1 μm and not more than 15 μm and a second inorganic filler (C2) having an average particle size of 0.1 μm or less, and the content of the second inorganic filler (C2) is 1% by mass or more and 10% by mass or less relative to the inorganic filler (C).

[0086] In the liquid resin composition according to a sixth aspect of the present disclosure, in any one of the first to fifth aspects, the epoxy compound (A) contains a silicone-modified epoxy compound (A1).

[0087] A liquid resin composition according to a seventh aspect of the present disclosure is the sixth aspect, wherein the content of the silicone-modified epoxy compound (A1) is 1% by mass or more and 30% by mass or less relative to the epoxy compound (A).

[0088] The liquid resin composition according to the eighth aspect of the present disclosure is any of the first to seventh aspects, further containing rubber particles (E).

[0089] In the liquid resin composition according to the ninth aspect of the present disclosure, in the eighth aspect, the rubber particles (E) contain at least one selected from the group consisting of butadiene rubber particles and silicone rubber particles.

[0090] The liquid resin composition according to the tenth aspect of the present disclosure is any one of the first to ninth aspects, in which the inorganic filler (C) contains silica particles surface-treated with a silane compound having at least one group selected from the group consisting of a phenylamino group, a methacryl group, and an epoxy group.

[0091] The liquid resin composition according to an eleventh aspect of the present disclosure, in any one of the first to tenth aspects, is for semiconductor encapsulation.

[0092] The liquid resin composition according to a twelfth aspect of the present disclosure is for underfilling in any one of the first to eleventh aspects.

[0093] A semiconductor device (1) according to a thirteenth aspect of the present disclosure includes a substrate (2), a semiconductor element (3) mounted on the substrate (2), and a sealing portion (5) interposed in a gap between the substrate (2) and the semiconductor element (3). The sealing portion (5) includes a cured product of the liquid resin composition according to any one of the first to twelfth aspects.

[0094] Specific examples of the embodiments will be described below, but the present disclosure is not limited to these examples.

[0095] 1. Preparation of Compositions Compositions were prepared by mixing the components shown in the table. Details of the components in the table are as follows: - Epoxy compound #1: Manufactured by Nippon Steel Chemical & Material Co., Ltd. Product name: YDF8170. Liquid bisphenol F type epoxy resin. Epoxy equivalent: 160 g / eq. - Epoxy compound #2: Manufactured by Momentive Performance Materials Japan LLC. Product name: TSL9906. Liquid silicone-modified epoxy compound (siloxane oligomer with glycidoxypropyl groups at both ends). Epoxy equivalent: 181 g / eq. - Epoxy compound #3: Manufactured by Nippon Steel Chemical & Material Co., Ltd. Product name: YD8125. Liquid bisphenol A type epoxy resin. Epoxy equivalent: 175 g / eq. - Epoxy compound #4: Manufactured by DIC Corporation. Product name: HP-4032D. Liquid naphthalene type epoxy resin. Epoxy equivalent: 140 g / eq. - Epoxy compound #5: Manufactured by ADEKA Corporation. Product name: EP-3950S. Liquid aminophenol-type epoxy resin. Epoxy equivalent: 94 g / eq. - Aromatic amine compound #1: Manufactured by Mitsubishi Chemical Corporation. Product name: JER Cure WA. Liquid aromatic amine compound. Amine equivalent: 45 g / eq. - Aromatic amine compound #2: Manufactured by ADEKA Corporation. Product name: EH-105L. Amine equivalent: 61 eq / g. - Aromatic amine compound #3: Manufactured by Nippon Kayaku Co., Ltd. Product name: KAYAHARD AA. Liquid aromatic amine resin. Amine active hydrogen equivalent: 63.5 g / eq. - Inorganic filler #1: Silica with an average particle size of 0.4 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Inorganic filler #2: Silica having an average particle size of 50 nm, which has been surface-treated with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. - Inorganic filler #3: Silica having an average particle size of 1.5 μm. - Inorganic filler #4: Silica having an average particle size of 1.5 μm, which has been surface-treated with 3-glycidoxypropyltrimethoxysilane. - Inorganic filler #5: Silica having an average particle size of 1.5 μm, which has been surface-treated with 3-methacryloxypropyltrimethoxysilane. - Inorganic filler #6: Silica having an average particle size of 0.7 μm, which has been surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. - Stabilizer #1: A compound represented by formula (6).

[0096]

[0097] - Stabilizer #2: Compound of formula (7).

[0098]

[0099] - Stabilizer #3: Compound of formula (8).

[0100]

[0101] - Stabilizer #4: Compound of formula (9).

[0102]

[0103] Organophosphorus compound #1: triphenylphosphine. Organophosphorus compound #2: a mixture containing about 85 mol % of the compound represented by formula (10) and about 15 mol % of the compound represented by formula (11).

[0104]

[0105] - Rubber Particles #1: Manufactured by Kaneka Corporation. Product name: Kane Ace (registered trademark) MX-965. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 and core-shell rubber particles with a silicone rubber core. Concentration of rubber particles: 25% by mass. - Rubber Particles #2: Manufactured by Kaneka Corporation. Product name: Kane Ace (registered trademark) MX-139. A mixture of bisphenol F epoxy resin with an epoxy equivalent of 160 and core-shell rubber particles with a polybutadiene rubber core. Concentration of rubber particles: 33% by mass. - Additive #1: Manufactured by Momentive Performance Materials Japan, LLC. Product name: SILQUEST A-187 SILANE. 3-glycidoxypropyltrimethoxysilane.

[0106] 2. Evaluation The compositions were evaluated as follows, and the results are shown in the table below.

[0107] (1) Viscosity at 25° C. The viscosity of the composition at 25° C. was measured using a B-type rotational viscometer (TVB-10, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm.

[0108] (2) 110°C Viscosity The temperature dependence of the composition was measured using a rheometer (MCR-102, manufactured by Anton Paar) under conditions of a rotation speed of 1 rpm, a gap of 300 μm, and a heating rate of 5°C / min, and the viscosity of the composition at 110°C was read from the results. If this result was 0.4 Pa s or less, the fluidity could be evaluated as good, and if it was 0.2 Pa s or less, the fluidity could be evaluated as particularly good.

[0109] (3) Fluidity Two glass slides were placed facing each other with a gap of 50 μm between them, and the temperature of the glass slides was kept at 110° C. The composition was poured between the glass slides to allow the composition to flow between the glass slides. The time from the start of pouring until the maximum movement distance of the composition between the glass slides reached 30 mm was measured.

[0110] If the result is 800 seconds or less, the fluidity can be evaluated as good, if it is 500 seconds or less, the fluidity can be evaluated as better, if it is 400 seconds or less, the fluidity can be evaluated as even better, and if it is 300 seconds or less, the fluidity can be evaluated as particularly good. In the table, "Not reached" indicates that the movement distance of the composition between the glass slides did not reach 30 mm.

[0111] (4) Gel Time Using a Curastometer testing device (Curastometer 7P, manufactured by JSR Corporation), the upper and lower mold temperatures were set to 165°C, and time measurement was started when 1.67 ml of a composition sample was poured. The torque value was measured, and the time (gel time) until the torque value reached 0.1 kgf cm (0.0098 N m) was measured. The values ​​obtained by the measurement are shown in Table 1.

[0112] (5) Storage Stability The composition was subjected to a treatment of being exposed to a temperature of 40°C for 8 hours. The viscosity of the composition before this treatment (η0) and the viscosity of the composition after this treatment (η1) were measured using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., TVB-10H) at a temperature of 40°C and a rotation speed of 20 rpm. From these results, the viscosity increase rate ((η1-η0) × 100 / η0) was calculated.

[0113] When this result is 100% or less, the storage stability can be evaluated as good, and when it is 50% or less, the storage stability can be evaluated as particularly good.

[0114] (6) Glass Transition Temperature

[0049] A sample for evaluation measuring 5 mm x 50 mm x 2 mm was prepared by molding and curing the composition under conditions of 100°C / 2 hours and 165°C / 2 hours. The sample was measured using a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Corporation, model number: DMA7100) under conditions of a double-support bending mode, a frequency of 10 Hz, and a heating rate of 10°C / min.

[0115]

[0116]

[0117]

[0118] REFERENCE SIGNS LIST 1 semiconductor device 2 substrate 3 semiconductor element 5 sealing portion

Claims

1. A composition comprising a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), and a stabilizer (D), wherein the stabilizer (D) has at least one anion selected from the group consisting of an anion represented by formula (1), an anion represented by formula (2), and an anion represented by formula (3). Liquid resin composition.

2. The stabilizer (D) contains a compound (D1) having an anion represented by formula (1), and the compound (D1) includes at least one selected from the group consisting of a compound represented by formula (6) and a compound represented by formula (7). The liquid resin composition according to claim 1.

3. The stabilizer (D) contains a compound (D2) having an anion represented by formula (2), and the compound (D2) includes a compound represented by formula (8). The liquid resin composition according to claim 1.

4. The stabilizer (D) contains a compound (D3) having an anion represented by formula (3), and the compound (D3) includes a compound represented by formula (9). The liquid resin composition according to claim 1.

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

6. The liquid resin composition according to claim 1, wherein the epoxy compound (A) contains a silicone-modified epoxy compound (A1).

7. The liquid resin composition according to claim 6, wherein the content of the silicone-modified epoxy compound (A1) is 1% by mass or more and 30% by mass or less relative to the epoxy compound (A).

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

9. The liquid resin composition according to claim 8, wherein the rubber particles (E) contain at least one selected from the group consisting of butadiene rubber particles and silicone rubber particles.

10. The liquid resin composition according to claim 1, wherein the inorganic filler (C) contains silica particles that have been surface-treated with a silane compound having at least one group selected from the group consisting of a phenylamino group, a methacryl group, and an epoxy group.

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

12. The liquid resin composition according to claim 11, which is used for underfill.

13. A semiconductor device comprising: a substrate; a semiconductor element mounted on the substrate; and a sealing portion interposed in a gap between the substrate and the semiconductor element, wherein the sealing portion comprises a cured product of the liquid resin composition according to any one of claims 1 to 12.

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