Sealing resin composition and semiconductor device

Abstract

To provide a sealing resin composition that can yield a cured product having excellent adhesion to metal member and product reliability, and has excellent moldability.SOLUTION: The sealing resin composition of the present invention includes (A) 3,5-diamino-1,2,4-triazole and (B) an epoxy resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a encapsulating resin composition and a semiconductor device. [Background technology]

[0002] Patent Document 1 describes a encapsulating resin composition for sealing electronic components. This document describes a technology aimed at providing an encapsulating resin composition that prevents ion migration of metals and galvanic corrosion caused by ionic halogens, has excellent moisture resistance, and retains the advantages of conventional compositions. The encapsulating resin composition comprises an epoxy resin, a novolac-type phenolic resin, a predetermined amount of 2-vinyl-4,6-diamino-s-triazine, and a predetermined amount of inorganic filler. The document states that by incorporating a predetermined amount of 2-vinyl-4,6-diamino-s-triazine, an encapsulating resin composition that prevents galvanic corrosion and has excellent moisture resistance can be obtained. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Unexamined Patent Publication No. 62-25118 [Patent Document 2] Japanese Patent Publication No. 2010-065160 [Patent Document 3] Japanese Patent Publication No. 2015-067618 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] When the present inventors examined the technology described in Patent Document 1, it became clear that the sealing resin composition described in the said document has poor moldability, and that the cured product obtained from the composition has room for improvement in terms of adhesion to metal members and product reliability. [Means for solving the problem]

[0005] The inventors of the present invention have found that the above problems can be solved by using a compound having a predetermined triazole skeleton, and have completed the present invention. In other words, the present invention can be described as follows.

[0006] According to the present invention, (A) 3,5-diamino-1,2,4-triazole and (B) A sealing resin composition comprising epoxy resin can be provided.

[0007] According to the present invention, Semiconductor elements and A semiconductor device can be provided that includes a cured product of the sealing resin composition for sealing the semiconductor element. [Effects of the Invention]

[0008] The sealing resin composition of the present invention exhibits excellent moldability, and the cured product obtained from this composition has excellent adhesion to metal components and product reliability. [Brief explanation of the drawing]

[0009] [Figure 1] This is a cross-sectional view showing the configuration of a semiconductor device in an embodiment. [Figure 2] This is a cross-sectional view showing the configuration of a semiconductor device in an embodiment. [Modes for carrying out the invention]

[0010] Embodiments of the present invention will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and descriptions are omitted as appropriate. Unless otherwise specified, "~" indicates a range from "greater than or equal to" to "less than or equal to".

[0011] [Sealing resin composition] The sealing resin composition of this embodiment is (A) 3,5-diamino-1,2,4-triazole and (B) Epoxy resin and It includes. The components included in the resin composition for sealing of the present embodiment will be described below.

[0012] (Compound (A)) Compound (A) is an aminotriazole compound, specifically 3,5-diamino-1,2,4-triazole. By using this compound, it has excellent adhesion to metal members such as silver, copper, and nickel, and furthermore has excellent moldability and product reliability.

[0013] From the viewpoint of stably improving the adhesion between the sealing resin composition (cured product) and the metal member, the content of compound (A) in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.04% by mass or more with respect to the entire sealing resin composition. Also, from the viewpoint of making the fluidity (moldability) and elastic modulus of the sealing resin composition favorable, the content of compound (A) is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.2% by mass or less with respect to the entire sealing resin composition.

[0014] [Epoxy resin (B)] Epoxy resin (B) is a compound having two or more epoxy groups in one molecule, and may be any of a monomer, an oligomer, and a polymer.

[0015] Specifically, epoxy resin (B) is one or more selected from the group consisting of crystalline epoxy resins such as biphenyl-type epoxy resins, bisphenol-type epoxy resins, and stilbene-type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; polyfunctional epoxy resins such as trisphenylmethane-type epoxy resins and alkyl-modified triphenolmethane-type epoxy resins; phenol aralkyl-type epoxy resins such as phenylene skeleton-containing phenol aralkyl-type epoxy resins and biphenylene skeleton-containing phenol aralkyl-type epoxy resins; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl etherification of a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and bridged cyclic hydrocarbon compound-modified phenol-type epoxy resins such as dicyclopentadiene-modified phenol-type epoxy resins.

[0016] From the viewpoint of improving adhesion with metal members, the epoxy resin (B) is preferably one or more selected from the group consisting of trisphenylmethane type epoxy resin, biphenyl aralkyl type polyfunctional epoxy resin, orthocresol type difunctional epoxy resin, biphenyl type difunctional epoxy resin, and bisphenol type difunctional epoxy resin. From a similar viewpoint, epoxy resin (B) is preferably one or more selected from the group consisting of tris(hydroxyphenyl)methane type epoxy resin, biphenylene skeleton-containing phenol aralkyl type epoxy resin, orthocresol novolac type epoxy resin, 3,3',5,5'-tetramethylbiphenylglycidyl ether type epoxy resin, and dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin. More preferably, one or more selected from the group consisting of biphenylene skeleton-containing phenol aralkyl type epoxy resins, 3,3',5,5'-tetramethylbiphenylglycidyl ether type epoxy resins, and dicyclopentadiene skeleton-containing polyfunctional solid epoxy resins. More preferably, it is a biphenylene skeleton-containing phenol aralkyl type epoxy resin.

[0017] The content of epoxy resin (B) in the sealing resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, relative to the total sealing resin composition, from the viewpoint of obtaining suitable fluidity during molding and improving filling properties and moldability. Furthermore, from the viewpoint of improving the reliability of the device obtained using the sealing resin composition, the content of epoxy resin (B) in the sealing resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to the entire sealing resin composition.

[0018] Furthermore, the sealing resin composition preferably does not contain a maleimide compound. By having a sealing resin composition that contains compound (A) and epoxy resin (B) but does not contain a maleimide compound, it is possible to improve the adhesion between the sealing material obtained using the sealing resin composition and the metal member, while further improving the low-temperature curability of the sealing resin composition. Here, the maleimide compound is specifically a compound having two or more maleimide groups. Furthermore, the sealing resin composition preferably does not intentionally contain the maleimide compound, and the content of the maleimide compound in the sealing resin composition is preferably substantially 0% by mass, for example, below the detection limit.

[0019] [Silane coupling agent (C)] The sealing resin composition of this embodiment may contain a silane coupling agent (C). Examples of silane coupling agents (C) include aminosilanes such as epoxysilane, mercaptosilane, and phenylaminosilane. From the viewpoint of improving the adhesion between the sealing material and the metal member, the silane coupling agent (C) is preferably epoxysilane or aminosilane, and more preferably secondary aminosilane. From a similar viewpoint, the silane coupling agent (C) is preferably one or more selected from the group consisting of phenylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. More preferably, phenylaminopropyltrimethoxysilane.

[0020] The content of the silane coupling agent (C) in the sealing resin composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total sealing resin composition, from the viewpoint of obtaining favorable fluidity when molding the sealing resin composition. Furthermore, from the viewpoint of suppressing the thickening of the resin viscosity, the content of the silane coupling agent (C) in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the total sealing resin composition.

[0021] (Inorganic filler (D)) The sealing resin composition of this embodiment may contain an inorganic filler (D). As the inorganic filler (D), one commonly used in semiconductor encapsulation resin compositions can be used. Furthermore, the inorganic filler (D) may be surface-treated.

[0022] Specific examples of inorganic fillers (D) include silica such as fused silica, crystalline silica, and amorphous silicon dioxide; alumina; talc; titanium oxide; silicon nitride; and aluminum nitride. These inorganic fillers may be used individually or in combination of two or more types.

[0023] The inorganic filler (D) preferably contains silica from the viewpoint of excellent versatility. Examples of silica shapes include spherical silica and crushed silica.

[0024] Average diameter of inorganic filler (D) 50The thickness of the slab is preferably 5 μm or more, more preferably 10 μm or more, preferably 80 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less, from the viewpoint of improving moldability and adhesion. Here, the particle size distribution of the inorganic filler (D) can be obtained by measuring the particle size distribution on a volume basis using a commercially available laser diffraction particle size distribution analyzer (for example, Shimadzu Corporation's SALD-7000).

[0025] Furthermore, the maximum particle size of the inorganic filler (D) is preferably 10 μm or more, more preferably 20 μm or more, more preferably 100 μm or less, and more preferably 80 μm or less, from the viewpoint of improving moldability and adhesion.

[0026] Furthermore, the specific surface area of ​​the inorganic filler (D) is preferably 1 m² from the viewpoint of improving moldability and adhesion. 2 / g or more, more preferably 3m 2 It is 1 / g or more, and preferably 20m 2 / g or less, more preferably 10m 2 It is less than / g.

[0027] The content of the inorganic filler (D) in the sealing resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, relative to the entire sealing resin composition, from the viewpoint of improving the low hygroscopicity and low thermal expansion of the sealing material formed using the sealing resin composition, and more effectively improving the moisture resistance reliability and reflow resistance of the resulting semiconductor device. Furthermore, from the viewpoint of more effectively improving the fluidity and fillability of the sealing resin composition during molding, the content of the inorganic filler (D) in the sealing resin composition may be, for example, 97% by mass or less of the total sealing resin composition, preferably 95% by mass or less, and more preferably 90% by mass or less. Conventional encapsulating resin compositions, when containing inorganic fillers in the above-mentioned amounts, sometimes suffered from reduced fluidity or poor adhesion to metal components, from the viewpoint of the insulating properties of the resulting encapsulant. The encapsulating resin composition of this embodiment, by containing 3,5-diamino-1,2,4-triazole (A), can produce a cured product (encapsulant) with excellent fluidity and superior adhesion to metal components. In other words, the encapsulating resin composition containing component (A) of this embodiment offers an excellent balance of these properties.

[0028] [Hardening agent] The sealing resin composition of this embodiment may further contain a curing agent. Curing agents can be broadly classified into three types, for example, polyaddition curing agents, catalytic curing agents, and condensation curing agents, and one or more of these types can be used.

[0029] Examples of polyaddition-type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), aromatic polyamines such as diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS), as well as polyamine compounds including dicyandiamide (DICY) and organic acid dihydrazides; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), and acid anhydrides including aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenonetetracarboxylic acid (BTDA); phenolic resin curing agents such as novolac-type phenolic resins and polyvinylphenol; polymercaptan compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins.

[0030] Examples of catalytic curing agents include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24); and Lewis acids such as BF3 complexes.

[0031] Examples of condensation-type curing agents include phenolic resins, urea resins such as methylol group-containing urea resins, and melamine resins such as methylol group-containing melamine resins.

[0032] Among these, phenolic resin curing agents are preferred from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical properties, curability, and storage stability. As phenolic resin curing agents, monomers, oligomers, and polymers in general that have two or more phenolic hydroxyl groups in one molecule can be used, and their molecular weight and molecular structure are not limited.

[0033] Examples of phenolic resin curing agents used as curing agents include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and bisphenol novolac; polyvinylphenol; polyfunctional phenolic resins such as phenol-hydroxybenzaldehyde resin and triphenolmethane-type phenolic resin; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl-type phenolic resins such as phenol aralkyl resin having at least one of a phenylene skeleton and a biphenylene skeleton, and naphthol aralkyl resin having at least one of a phenylene and biphenylene skeleton; and bisphenol compounds such as bisphenol A and bisphenol F. These may be used individually or in combination of two or more types. Among these, from the viewpoint of improving the insulating properties of semiconductor devices obtained using the sealing resin composition, it is more preferable to use one or more selected from the group consisting of trisphenolmethane-type phenolic resin, biphenylaralkyl-type phenolic resin, novolac-type phenolic resin, biphenylene skeleton-containing phenolaralkyl-type resin, and biphenylene skeleton-containing phenolaralkyl-type formaldehyde polycondensate.

[0034] In this embodiment, the content of the curing agent in the sealing resin composition is, from the viewpoint of achieving excellent fluidity during molding and improving filling and moldability, for example, 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the total sealing resin composition. Furthermore, with respect to semiconductor devices obtained using the sealing resin composition, from the viewpoint of improving moisture resistance reliability and reflow resistance, the content of the curing agent in the sealing resin composition is preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total sealing resin composition.

[0035] [Other ingredients] The encapsulating resin composition of this embodiment may contain components other than those described above, and may appropriately include one or more additives such as curing accelerators, fluidity imparters, mold release agents, ion scavenging agents, low-stress components, flame retardants, colorants, and antioxidants. Furthermore, the encapsulating resin composition may further contain, for example, one or more of 2-hydroxy-N-1H-1,2,4-triazole-3-ylbenzamide and 3-amino-5-mercapto-1,2,4-triazole.

[0036] Of these, the curing accelerator may include one or more selected from the following: phosphorus-containing compounds such as organophosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; nitrogen-containing compounds such as amidines and tertiary amines, exemplified by 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine, and 2-methylimidazole, and quaternary salts of the above amidines and amines; and polyhydroxynaphthalene compounds such as 2,3-dihydroxynaphthalene. Among these, it is more preferable to include phosphorus-containing compounds from the viewpoint of improving curability. Furthermore, from the viewpoint of improving the balance between moldability and curability, it is more preferable to include latent compounds such as tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds.

[0037] From the viewpoint of improving the curing characteristics of the encapsulating resin composition, the content of the curing accelerator in the encapsulating resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total encapsulating resin composition. Furthermore, from the viewpoint of obtaining favorable fluidity during molding of the sealing resin composition, the content of the curing accelerator in the sealing resin composition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the total sealing resin composition.

[0038] The release agent may include one or more types selected from the group consisting of, for example, natural waxes such as carnauba wax; synthetic waxes such as montanic acid ester wax and polyethylene oxide wax; higher fatty acids such as zinc stearate and their metal salts; paraffin; and carboxylic acid amides such as erucic acid amide. The content of the release agent in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.5% by mass or less, relative to the entire sealing resin composition, from the viewpoint of improving the release properties of the cured product of the sealing resin composition.

[0039] Hydrotalcite is a specific example of an ion scavenger. From the viewpoint of improving the reliability of the sealing material, the content of the ion scavenger in the sealing resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1.0% by mass or less, and more preferably 0.5% by mass or less, relative to the total sealing resin composition.

[0040] Specific examples of low-stress components include silicones such as silicone oil, silicone rubber, silicone elastomer, and silicone resin; and acrylonitrile butadiene rubber. From the viewpoint of improving the reliability of the sealing material, the content of each low-stress component in the sealing resin composition 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, and also preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, relative to the total sealing resin composition.

[0041] Specific examples of flame retardants include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. From the viewpoint of improving the flame retardancy of the sealing material, the content of the flame retardant in the sealing resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the total sealing resin composition.

[0042] Specific examples of colorants include carbon black and red iron oxide. From the viewpoint of obtaining a desirable color tone for the sealing material, the content of the coloring agent in the sealing resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, preferably 2% by mass or less, and more preferably 1% by mass or less, relative to the total sealing resin composition.

[0043] Specific examples of antioxidants include hindered phenol compounds, hindered amine compounds, and thioether compounds.

[0044] <Sealing resin composition> The sealing resin composition of this embodiment is solid at room temperature (25°C), and its shape can be selected according to the molding method of the sealing resin composition, for example, it can be in tablet form; powder form, granular form or other particulate form; or sheet form.

[0045] Furthermore, the sealing resin composition can be obtained, for example, by mixing the above-mentioned components by known means, then melt-kneading them in a kneader such as a roll, kneader, or extruder, cooling, and then pulverizing. Alternatively, after pulverization, the mixture may be molded to obtain a granular or sheet-like sealing resin composition. For example, a granular sealing resin composition may be obtained by tablet molding. Alternatively, a sheet-like sealing resin composition may be obtained, for example, by a vacuum extruder. The degree of dispersion and fluidity of the obtained sealing resin composition may also be adjusted as appropriate.

[0046] Since the resin composition for sealing obtained in this embodiment contains component (A) and component (B), it has excellent adhesion to a metal member. More specifically, according to this embodiment, it is also possible to improve the adhesion between the sealing material and a member composed of Ag, Ni, Cu, or an alloy containing one or more of these. The resin composition for sealing of this embodiment can be used for transfer molding, injection molding, or compression molding. Moreover, by using the resin composition for sealing obtained in this embodiment, a semiconductor device with excellent reliability can be obtained.

[0047] The melt viscosity of the resin composition for sealing of this embodiment at 175 °C is 30 Pa·s or less, preferably 20 Pa·s or less. Thereby, it has excellent moldability, and when sealing a semiconductor element with the resin composition for sealing, it has excellent processing stability.

[0048] The resin composition for sealing of this embodiment has a rectangular pressure at 175 °C measured by the following method of 0.1 kgf / cm 2 ~20.0 kgf / cm 2 , preferably 0.5 kgf / cm 2 ~15.0 kgf / cm 2 is. Thereby, the resin composition for sealing of this embodiment can further enhance the filling property into the gap between the substrate and the semiconductor element.

[0049] (Measurement method) Using a low-pressure transfer molding machine, at a mold temperature of 175 °C and an injection speed of 177 mm 3 / second, inject the resin composition for sealing into a rectangular flow path with a width of 15 mm, a thickness of 1 mm, and a length of 175 mm, and measure the change in pressure over time with a pressure sensor embedded at a position 25 mm from the upstream tip of the flow path. Then, from the measurement results, calculate the minimum pressure during the flow of the resin composition for sealing, and use this minimum pressure as the rectangular pressure.

[0050] Next, the physical properties of the resin composition for sealing or its cured product will be described. The cured product obtained from the sealing resin composition containing component (A) of this embodiment has high flexural strength and a smaller increase in flexural modulus compared to conventional cured products containing adhesion promoters, thus providing a sealing material with excellent mechanical strength and product reliability. The flexural modulus of the cured product of the resin molding material of this embodiment, when cured at 175°C for 120 seconds, is 15,000 MPa or higher, preferably 16,000 MPa or higher, and more preferably 17,000 MPa or higher at room temperature (25°C). The upper limit is not particularly limited, but can be 30,000 MPa or lower. The flexural modulus of the cured product at 260°C is 200 MPa or more, preferably 250 MPa or more, and more preferably 300 MPa or more. The upper limit is not particularly limited, but can be 2000 MPa or less.

[0051] When the resin molding material of this embodiment is cured at 175°C for 120 seconds, the cured product has a bending strength of 30 MPa or more, preferably 50 MPa or more, and more preferably 100 MPa or more at room temperature (25°C). The upper limit is not particularly limited, but it can be 200 MPa or less. The flexural strength of the cured product at 260°C is 3 MPa or more, preferably 5 MPa or more, and more preferably 7 MPa or more. The upper limit is not particularly limited, but can be 50 MPa or less.

[0052] The cured product obtained from the sealing resin composition of this embodiment exhibits excellent adhesion to metal components, and can provide a sealing material with excellent product reliability. In this embodiment, when the sealing resin composition is cured on a copper plate at 175°C for 180 seconds to obtain a cured product, and then heated at 175°C for 3 hours, the die shear strength between the copper plate and the cured product is preferably 10 MPa or more, and more preferably 12 MPa or more, at room temperature (25°C, the same applies hereafter). By setting it in this way, for example, when using elements that generate a lot of heat as semiconductor devices, or when manufacturing equipment that is exposed to higher temperature conditions, an even higher level of reliability can be ensured. From a similar viewpoint, when a hardened product is obtained by curing on a copper plate under the above conditions and then heated under the above conditions, the die shear strength between the copper plate and the hardened product is preferably 0.95 MPa or higher, more preferably 1.0 MPa or higher, and even more preferably 1.1 MPa or higher at 260°C. There is no upper limit to this die shear strength, but at room temperature or 260°C, it is, for example, 30 MPa or less.

[0053] Furthermore, when the sealing resin composition of this embodiment is cured on a nickel plate at 175°C for 180 seconds to obtain a cured product, and then heated at 175°C for 3 hours, the die shear strength between the nickel plate and the cured product is preferably 5.0 MPa or higher, more preferably 7.0 MPa or higher, even more preferably 7.5 MPa or higher, and even more preferably 10 MPa or higher at room temperature. By setting it in this way, for example, when using elements that generate a lot of heat as semiconductor devices, or when manufacturing equipment that is exposed to higher temperature conditions, an even higher level of reliability can be ensured. From a similar viewpoint, when a hardened product is obtained by curing on a nickel plate under the above conditions and then heated under the above conditions, the die shear strength between the nickel plate and the hardened product is preferably 0.5 MPa or more, more preferably 0.7 MPa or more, and even more preferably 1.0 MPa or more at 260°C. There is no upper limit to this die shear strength, but at room temperature or 260°C, it is, for example, 30 MPa or less.

[0054] Furthermore, when the sealing resin composition of this embodiment is cured on a silver plate at 175°C for 180 seconds to obtain a cured product, and then heated at 175°C for 3 hours, the die shear strength between the silver plate and the cured product is preferably 12 MPa or more, and more preferably 15 MPa or more, at room temperature. By setting it in this way, for example, when using elements that generate a lot of heat as semiconductor devices, or when manufacturing equipment that is exposed to higher temperature conditions, an even higher level of reliability can be ensured. From a similar viewpoint, when a hardened product is obtained by hardening on a silver plate under the above conditions and then heated under the above conditions, the die shear strength between the silver plate and the hardened product is preferably 0.95 MPa or higher, more preferably 1.0 MPa or higher, and even more preferably 1.1 MPa or higher at 260°C. There is no upper limit to this die shear strength, but at room temperature or 260°C, it is, for example, 40 MPa or less.

[0055] <Semiconductor device> The semiconductor device in this embodiment is characterized by the encapsulation of semiconductor elements by a cured product of the encapsulation resin composition described above. Specific examples of semiconductor elements include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and solid-state image sensors. The semiconductor elements are preferably so-called elements that do not involve the input or output of light, excluding photosensitive elements and light-emitting elements (such as light-emitting diodes).

[0056] The substrate for semiconductor devices is, for example, a wiring board such as an interposer, or a lead frame. Semiconductor elements are electrically connected to the substrate by methods such as wire bonding or flip-chip connections.

[0057] Examples of semiconductor devices obtained by encapsulating semiconductor elements using encapsulation molding with a encapsulation resin composition include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Flame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In type eWLB, and Fan-Out type eWLB. Further details will be explained below with reference to the diagrams.

[0058] Figures 1 and 2 are cross-sectional views showing the configuration of a semiconductor device. Note that in this embodiment, the configuration of the semiconductor device is not limited to those shown in Figures 1 and 2. First, the semiconductor device 100 shown in Figure 1 comprises a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 that encloses the semiconductor element 20. The sealing material 50 is composed of a cured product obtained by curing the sealing resin composition in this embodiment described above.

[0059] Furthermore, Figure 1 illustrates a case where the substrate 30 is a circuit board. In this case, as shown in Figure 1, for example, a plurality of solder balls 60 are formed on the other side of the substrate 30 opposite to the side on which the semiconductor element 20 is mounted. The semiconductor element 20 is mounted on the substrate 30 and electrically connected to the substrate 30 via wires 40. On the other hand, the semiconductor element 20 may also be flip-chip mounted on the substrate 30. Here, the wires 40 are not limited to, but examples include Ag wires, Ni wires, Cu wires, Au wires, and Al wires, and preferably the wires 40 are composed of Ag, Ni, or Cu or an alloy containing one or more of these.

[0060] The sealing material 50 seals the semiconductor element 20, for example, by covering the other side of the semiconductor element 20 that is opposite to the side facing the substrate 30. In the example shown in Figure 1, the sealing material 50 is formed to cover the other side and the side of the semiconductor element 20. In this embodiment, the sealing material 50 is made of a cured product of the sealing resin composition described above. Therefore, in the semiconductor device 100, the sealing material 50 and the wire 40 have excellent adhesion, and as a result, the semiconductor device 100 has excellent reliability. The sealing material 50 can be formed, for example, by sealing a sealing resin composition using a known method such as transfer molding or compression molding.

[0061] Figure 2 is a cross-sectional view showing the configuration of the semiconductor device 100 in this embodiment, and shows an example different from Figure 1. The semiconductor device 100 shown in Figure 2 uses a lead frame as the substrate 30. In this case, the semiconductor element 20 is mounted, for example, on a die pad 32 on the substrate 30 and is electrically connected to the outer lead 34 via a wire 40. The encapsulating material 50 is made of a cured product of the encapsulating resin composition in this embodiment, similar to the example shown in Figure 1.

[0062] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. [Examples]

[0063] This embodiment will be described in detail below with reference to examples and comparative examples. However, this embodiment is not limited in any way to the descriptions of these examples.

[0064] The following components were used in the examples. (Inorganic filler) • Inorganic filler 1: Fused spherical silica, TS13-006, manufactured by Micron Corporation (average diameter 28 μm, specific surface area 2.5 m²) 2 ( / g, upper limit cutoff 75μm) • Inorganic filler 2: Molten spherical silica, FB-105, manufactured by Denka Co., Ltd. (average diameter 10.6 μm, specific surface area 5.1 m²) 2 ( / g, upper limit cutoff 71μm) • Inorganic filler 3: Fused spherical silica, SC-2500-SQ, manufactured by Admatex Corporation. • Inorganic filler 4: Silica, manufactured by Micron (average diameter 2 μm) • Inorganic filler 5: Molten spherical silica (volume average particle size 23 μm), FB-950, manufactured by Denka Co., Ltd.

[0065] (Coloring agent) • Coloring agent 1: Carbon black, ERS-2001, manufactured by Tokai Carbon Co., Ltd.

[0066] (Silane coupling agent) • Silane coupling agent 1: Phenylaminopropyltrimethoxysilane, CF-4083, manufactured by Toray Dow Corning. • Silane coupling agent 2: γ-glycidoxypropyltrimethoxysilane, GPS-M, manufactured by JNC Corporation • Silane coupling agent 3:3-mercaptopropyltrimethoxysilane, manufactured by Chisso Corporation

[0067] (Epoxy resin) • Epoxy resin 1: Biphenylene skeleton-containing phenol aralkyl type epoxy resin, NC3000, manufactured by Nippon Kayaku Co., Ltd. • Epoxy resin 2:3,3',5,5'-tetramethylbiphenylglycidyl ether type epoxy resin, YX4000K, manufactured by Mitsubishi Chemical Corporation. • Epoxy resin 3: Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin, Epiclon HP-7200L, manufactured by DIC Corporation. • Epoxy resin 4: Naphthylene ether type epoxy resin, HP-6000L, manufactured by DIC Corporation.

[0068] (Hardening agent) • Hardener 1: Biphenylene skeleton-containing phenol aralkyl type resin, MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd. • Curing agent 2: An MFBA-type phenol synthesized by the following method was used. A stirrer, thermometer, reflux condenser, and nitrogen inlet were fitted to a separable flask. 291 parts by mass of 1,3-dihydroxybenzene (Tokyo Chemical Industries, Ltd., "Resorcinol", melting point 111°C, molecular weight 110, purity 99.4%), 235 parts by mass of phenol (Kanto Chemical Co., Ltd., special grade reagent, "Phenol", melting point 41°C, molecular weight 94, purity 99.3%), and 125 parts by mass of 4,4'-bischloromethylbiphenyl (Wako Pure Chemical Industries, Ltd., "4,4'-bischloromethylbiphenyl", melting point 126°C, purity 95%, molecular weight 251), which had been pre-crushed into granules, were weighed into the separable flask, and the flask was heated while purging with nitrogen. Stirring was started when the phenol began to melt. Subsequently, the reaction was carried out for 3 hours while maintaining the system temperature in the range of 110-130°C, then heated and carried out for 3 hours while maintaining the temperature in the range of 140-160°C. The hydrochloric acid gas generated in the system by the above reaction was removed from the system using a nitrogen stream. After the reaction was complete, unreacted components were removed by distillation under reduced pressure conditions of 150°C and 2 mmHg. Next, 400 parts by mass of toluene were added and uniformly dissolved. The mixture was then transferred to a separatory funnel, 150 parts by mass of distilled water was added and shaken, and the aqueous layer was discarded (washing) repeatedly until the washing water became neutral. Finally, the oil layer was treated under reduced pressure at 125°C to remove volatile components such as toluene and residual unreacted components, yielding a phenolic resin curing agent (polymer) represented by the following formula (1A). The hydroxyl group equivalent in this phenolic resin curing agent was 135. Furthermore, the ratio k0 / m0, obtained by arithmetic calculation using the relative intensity ratio measured and analyzed by field desorption mass spectrometry (FD-MS) as the mass ratio, was 0.98 / 1, and the number-average molecular weight was 460. This ratio was obtained by the average value k0 of the number of repeats k for structural units with one hydroxyl group and the average value m0 of the number of repeats m for structural units with two hydroxyl groups. The number-average molecular weight was measured by gel permeation chromatography (GPC) using a Waters Alliance (2695 separation module, 2414 refractive index detector, TSK gel GMHHR-Lx2 + TSK guard column HHR-Lx1, mobile phase: THF, 0.5 ml / min) under the conditions of column temperature 40.0°C, differential refractometer temperature 40.0°C, and sample injection volume 100 μl. [ka] (In formula (1A), the two Ys each independently represent a hydroxyphenyl group represented by formula (1B) or formula (1C) below, and X represents a hydroxyphenylene group represented by formula (1D) or formula (1E) below.) [ka]

[0069] (Curing accelerator) • Curing accelerator 1: Tetraphenylphosphonium·4,4'-sulfonyldiphenolate

[0070] (Release agent) • Release agent 1: Carnauba wax, TOWAX-132, manufactured by Toagosei Co., Ltd. • Release agent 2: Polyethylene oxide wax, Ricowax PED191, manufactured by Clariant Japan Co., Ltd.

[0071] (Ion scavenger) Ion scavenger 1: Magnesium aluminum hydroxide carbonate hydrate, DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd.

[0072] (Additives) • Additive 1: 3,5-diamino-1,2,4-triazole, manufactured by Shikoku Chemicals Co., Ltd.

[0073] (Stress-reducing agent) • Low-stress agent 1: Silicone oil, FZ-3730, manufactured by Toray Dow Corning Co., Ltd. • Low-stress agent 2: A molten reactant prepared by the following method was used. 66.1 parts by weight of epoxy resin represented by the following formula (2) (bisphenol A type epoxy resin) [manufactured by Japan Epoxy Resin Co., Ltd., jER(registered trademark) YL6810, softening point 45°C, epoxy equivalent 172] was heated and melted at 140°C, and 33.1 parts by weight of organopolysiloxane represented by the following formula (3) and 0.8 parts by weight of triphenylphosphine were added and the mixture was melted and mixed for 30 minutes to obtain a molten reaction product. [ka] [ka] (In equation (3), the mean value of n is 7.5.) • Low-stress agent 3: Acrylonitrile butadiene rubber, CTBN1008SP, manufactured by Ube Industries, Ltd. • Low-stress agent 4: Silicone resin, KR-480, manufactured by Shin-Etsu Chemical Co., Ltd. • Low-stress agent 5: Epoxy-modified polybutadiene, JP200, manufactured by Nippon Soda Co., Ltd.

[0074] (Examples 1-2, Comparative Examples 1-2) The components shown in Table 1 were mixed using a mixer. The resulting mixture was then roll-kneaded, cooled, and pulverized to obtain a granular sealing resin composition.

[0075] <Rating> The resin compositions obtained in each example, or evaluation samples using the compositions, were prepared by the following method, and the adhesion and reliability of the obtained samples were evaluated by the following method. [Spiral Flow (SF)] A spiral flow test was performed using the encapsulating resin compositions of the examples and comparative examples. The test was conducted using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.) by injecting the sealing resin composition into a mold for spiral flow measurement in accordance with EMMI-1-66 under conditions of mold temperature 175°C, injection pressure 6.9 MPa, and curing time 120 seconds, and then measuring the flow length. A higher value indicates better fluidity.

[0076] [Geltime (GT)] The sealing resin compositions of the examples and comparative examples were melted on a hot plate heated to 175°C, and the time (in seconds) until they hardened while being kneaded with a spatula was measured.

[0077] [Melting viscosity] For each of the sealing resin compositions in the examples and comparative examples, a high-efficiency flow tester (Shimadzu Corporation, CFT-500C) was used to measure the temperature at 175°C and load at 40 kgf (piston area 1 cm²). 2The apparent viscosity η of the encapsulating epoxy resin composition dissolved under test conditions of a die bore diameter of 0.50 mm and a die length of 1.00 mm was measured. η was calculated using the following formula, and the minimum viscosity during flow was defined as the melt viscosity. In the formula, Q is the flow rate of the encapsulating epoxy resin composition per unit time. η = (πD) 4 P x 10 3 / 128LQ)(Pa·sec) η: Apparent viscosity D: Die hole diameter (mm) P: Test pressure (Pa) L: Die length (mm) Q: Flow rate (cm 3 / sec)

[0078] [Rectangular pressure] Using a low-pressure transfer molding machine, with a mold temperature of 175°C and an injection speed of 177 mm, 3 Under the condition of flow rate per second, a sealing resin composition was injected into a rectangular channel measuring 15 mm in width, 1 mm in thickness, and 175 mm in length. The change in pressure over time was measured using a pressure sensor embedded 25 mm from the upstream end of the channel. Subsequently, the minimum pressure during the flow of the sealing resin composition was calculated from the measurement results, and this minimum pressure was defined as the rectangular pressure.

[0079] [Evaluation of mechanical strength (flexural strength and flexural modulus)] The sealing resin composition was injected into a mold using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under the conditions of a mold temperature of 175°C, injection pressure of 10.0 MPa, and curing time of 120 seconds. This yielded a molded product with a width of 10 mm, a thickness of 4 mm, and a length of 80 mm. The obtained molded product was then post-cured at 175°C for 4 hours. This prepared a test specimen for evaluating mechanical strength. The bending strength (MPa) and flexural modulus (MPa) of the test specimen at 260°C or room temperature (25°C) were measured in accordance with JIS K 6911.

[0080] [Adhesion] For the sealing resin compositions obtained in each example, the die shear strength in post-mold curing (PMC) was measured as an indicator of adhesion using the following method. For each example, ten 3.6mmφ×3mm adhesion strength test pieces were molded using a low-pressure transfer molding machine (Yamashiro Seiki Co., Ltd., "AV-600-50-TF") under the following conditions: mold temperature 175°C, injection pressure 10MPa, and curing time 180 seconds, onto a 9×29mm strip-shaped copper lead frame, a silver-plated lead frame, or a nickel plate. Subsequently, the die shear strength (MPa) was determined by measuring the die shear strength of the samples cured at 175°C for 3 hours using an automated die shear measuring device (Nordson Advanced Technologies, DAGE4000 model) at room temperature (RT) or 260°C.

[0081] [Table 1]

[0082] As shown in Table 1, when comparing Example 1 with Comparative Example 1 and Example 2 with Comparative Example 2, the encapsulating resin compositions obtained in each example exhibited excellent fluidity due to the inclusion of 3,5-diamino-1,2,4-triazole, and the resulting cured products showed excellent adhesion to metal components as well as superior mechanical strength. Furthermore, semiconductor devices with excellent reliability were obtained by using the encapsulating resin compositions obtained in each example. [Explanation of Symbols]

[0083] 20 Semiconductor elements 30 circuit boards 32 die pads 34 Outer lead 40 wires 50 Sealing material 60 Solder Balls 100 Semiconductor Equipment

Claims

[Claim 1] (A) 3,5-diamino-1,2,4-triazole, (B) an epoxy resin; and An encapsulating resin composition comprising:

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