WO2022118749A1 - 封止用樹脂組成物および半導体装置 - Google Patents
封止用樹脂組成物および半導体装置 Download PDFInfo
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- WO2022118749A1 WO2022118749A1 PCT/JP2021/043352 JP2021043352W WO2022118749A1 WO 2022118749 A1 WO2022118749 A1 WO 2022118749A1 JP 2021043352 W JP2021043352 W JP 2021043352W WO 2022118749 A1 WO2022118749 A1 WO 2022118749A1
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Definitions
- the present invention relates to a sealing resin composition and a semiconductor device.
- An object of the present invention is to provide a sealing resin composition which prevents ion transfer of a metal and electrolytic corrosion due to an ionic halogen, has excellent moisture resistance, and retains the merits of a conventional composition.
- a sealing resin composition containing an epoxy resin, a novolak type phenol resin, a predetermined amount of 2-vinyl-4,6-diamino-s-triazine and a predetermined amount of an inorganic filler is described. The document describes that if a predetermined amount of 2-vinyl-4,6-diamino-s-triazine is blended, a resin composition for encapsulation that prevents electrolytic corrosion and has excellent moisture resistance can be obtained. ..
- the present inventors have found that the above problems can be solved by using a compound having a predetermined triazole skeleton, and have completed the present invention. That is, the present invention can be shown below.
- the sealing resin composition of the present invention is excellent in moldability, and the cured product obtained from the composition is excellent in adhesion to a metal member and product reliability.
- the sealing resin composition of the present embodiment is (A) 3,5-diamino-1,2,4-triazole and (B) Epoxy resin and including.
- A 3,5-diamino-1,2,4-triazole
- B Epoxy resin and including.
- Compound (A) is an aminotriazole compound, specifically 3,5-diamino-1,2,4-triazole. By using the compound, the adhesion to metal members such as silver, copper and nickel is excellent, and the moldability and product reliability are excellent.
- the content of the compound (A) in the sealing resin composition is adjusted with respect to the entire sealing resin composition from the viewpoint of stably improving the adhesion between the sealing material (cured product) and the metal member. It is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.04% by mass or more. Further, from the viewpoint of making the fluidity (moldability) and elastic modulus of the sealing resin composition preferable, the content of the compound (A) is preferably 1% by mass with respect to the entire sealing resin composition. It is more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less.
- 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.
- the epoxy resin (B) is a crystalline epoxy resin such as a biphenyl type epoxy resin, a bisphenol type epoxy resin, and a stillben type epoxy resin; a novolak type epoxy resin such as a phenol novolac type epoxy resin and a cresol novolak type epoxy resin.
- Polyfunctional epoxy resin such as trisphenylmethane type epoxy resin and alkyl-modified triphenol methane type epoxy resin; phenol aralkyl type epoxy resin such as phenylene skeleton-containing phenol aralkyl type epoxy resin and biphenylene skeleton-containing phenol aralkyl type epoxy resin; dihydroxynaphthalene Naftor type epoxy resin such as type epoxy resin and epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene dimer; triazine nucleus-containing epoxy resin such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene-modified phenol One or more selected from the group consisting of Aribashi cyclic hydrocarbon compound-modified phenol-type epoxy resins such as type epoxy resins.
- the epoxy resin (B) is preferably a trisphenylmethane type epoxy resin, a biphenyl aralkyl type polyfunctional epoxy resin, an orthocresol type bifunctional epoxy resin, or a biphenyl type bifunctional epoxy.
- the epoxy resin (B) is preferably a tris (hydroxyphenyl) methane type epoxy resin, a biphenylene skeleton-containing phenol aralkyl type epoxy resin, an orthocresol novolac type epoxy resin, 3,3', 5,5'.
- tetramethylbiphenylglycidyl ether type epoxy resin and dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin More preferably, it is selected from the group consisting of a phenol aralkyl type epoxy resin containing a biphenylene skeleton, a 3,3', 5,5'-tetramethylbiphenylglycidyl ether type epoxy resin, and a polyfunctional solid epoxy resin containing a dicyclopentadiene skeleton.
- phenol aralkyl type epoxy resin containing a biphenylene skeleton a 3,3', 5,5'-tetramethylbiphenylglycidyl ether type epoxy resin
- a polyfunctional solid epoxy resin containing a dicyclopentadiene skeleton One or more, More preferably, it is a phenol aralkyl type epoxy resin containing a biphenylene skeleton.
- the content of the epoxy resin (B) in the sealing resin composition is adjusted with respect to the entire sealing resin composition from the viewpoint of obtaining suitable fluidity at the time of molding and improving the filling property and the moldability. It is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more. Further, from the viewpoint of improving the reliability of the apparatus obtained by using the sealing resin composition, the content of the epoxy resin (B) in the sealing resin composition is based on the entire sealing resin composition. It is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 10% by mass or less.
- the sealing resin composition preferably does not contain a maleimide compound.
- the sealing resin composition contains the compound (A) and the epoxy resin (B) and not the maleimide compound, the sealing material and the metal member obtained by using the sealing resin composition can be used. While improving the adhesion, the curability of the sealing resin composition at a low temperature can be further improved.
- the maleimide compound is specifically a compound having two or more maleimide groups. Further, the maleimide compound is preferably not intentionally blended in the sealing resin composition, and the content of the maleimide compound in the sealing resin composition is preferably substantially 0% by mass. For example, it is below the detection limit.
- the sealing resin composition of the present embodiment can contain a silane coupling agent (C).
- a silane coupling agent (C) examples include aminosilanes such as epoxysilane, mercaptosilane, and phenylaminosilane.
- the silane coupling agent (C) is preferably epoxysilane or aminosilane, and more preferably secondary aminosilane.
- the silane coupling agent (C) is preferably one or more selected from the group consisting of phenylaminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. And More preferably, it is phenylaminopropyltrimethoxysilane.
- the content of the silane coupling agent (C) in the sealing resin composition is preferably the content of the sealing resin composition with respect to the entire sealing resin composition from the viewpoint of obtaining preferable fluidity at the time of molding the sealing resin composition. It is 0.01% by mass or more, more preferably 0.05% by mass or more. Further, from the viewpoint of suppressing the increase in the viscosity of the resin, the content of the silane coupling agent (C) in the sealing resin composition is preferably 2.0% by mass with respect to the entire sealing resin composition. It is more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less.
- the sealing resin composition of the present embodiment can contain an inorganic filler (D).
- an inorganic filler (D) one generally used in a resin composition for encapsulating a semiconductor can be used. Further, the inorganic filler (D) may be surface-treated.
- the inorganic filler (D) include fused silica and the like, crystalline silica, and silica such as amorphous silicon dioxide; alumina; talc; titanium oxide; silicon nitride; aluminum nitride. These inorganic fillers may be used alone or in combination of two or more.
- the inorganic filler (D) preferably contains silica from the viewpoint of excellent versatility.
- Examples of the shape of silica include spherical silica and crushed silica.
- the average diameter (D 50 ) of the inorganic filler (D) is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and preferably 80 ⁇ m or less from the viewpoint of improving moldability and adhesion. It is more preferably 50 ⁇ m or less, still more preferably 40 ⁇ m or less.
- the particle size distribution of the particles is measured on a volume basis using a commercially available laser diffraction type particle size distribution measuring device (for example, SALD-7000 manufactured by Shimadzu Corporation). Can be obtained by.
- the maximum particle size of the inorganic filler (D) is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and preferably 100 ⁇ m or less, from the viewpoint of improving moldability and adhesion. It is preferably 80 ⁇ m or less.
- the specific surface area of the inorganic filler (D) is preferably 1 m 2 / g or more, more preferably 3 m 2 / g or more, and preferably 20 m from the viewpoint of improving moldability and adhesion. It is 2 / g or less, more preferably 10 m 2 / g or less.
- the content of the inorganic filler (D) in the sealing resin composition is a semiconductor device obtained by improving the low hygroscopicity and low thermal expansion of the sealing material formed by using the sealing resin composition. From the viewpoint of more effectively improving the moisture resistance reliability and reflow resistance, the content is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65, based on the entire sealing resin composition. It is mass% or more. Further, from the viewpoint of more effectively improving the fluidity and filling property of the sealing resin composition at the time of molding, the content of the inorganic filler (D) in the sealing resin composition is the sealing resin.
- the sealing resin composition of the present embodiment contains 3,5-diamino-1,2,4-triazole (A), so that it is a cured product having excellent fluidity and adhesion to a metal member. (Encapsulant) can be obtained.
- the sealing resin composition containing the component (A) of the present embodiment has an excellent balance of these characteristics.
- the sealing resin composition of the present embodiment may further contain a curing agent.
- the curing agent can be roughly classified into three types, for example, a polyaddition type curing agent, a catalytic type curing agent, and a condensation type curing agent, and one or more of these can be used.
- heavy addition type curing agent examples include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metalxylerylene diamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA).
- Aromatic polyamines such as diaminodiphenylsulfone (DDS), as well as polyamine compounds containing dicyandiamide (DICY), organic acid dihydraradide, etc .; alicyclic acids such as hexahydrohydric anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA).
- Acid anhydrides including aromatic acid anhydrides such as anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); phenols such as novolak-type phenolic resins and polyvinylphenols. Resin curing agents; polypeptide compounds such as polysulfide, thioester and thioether; isocyanate compounds such as isocyanate prepolymer and blocked isocyanate; organic acids such as carboxylic acid-containing polyester resin and the like can be mentioned.
- aromatic acid anhydrides such as anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); phenols such as novolak-type phenolic resins and polyvinylphenols.
- Resin curing agents polypeptide compounds such as polysulfide, thioester and thioether
- Examples of the catalytic curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole and 2-ethyl-4-.
- Examples include imidazole compounds such as methylimidazole (EMI24); Lewis acids such as the BF 3 complex.
- condensation type curing agent examples include phenol resins; urea resins such as methylol group-containing urea resins; and melamine resins such as methylol group-containing melamine resins.
- a phenol resin curing agent is preferable from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like.
- a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not limited.
- Phenolic resin modified phenolic resin such as terpene-modified phenolic resin, dicyclopentadiene-modified phenolic resin; phenolaralkyl resin having at least one phenylene skeleton and biphenylene skeleton, naftor aralkyl resin having at least one phenylene and biphenylene skeleton, etc.
- Examples thereof include aralkyl-type phenolic resins; bisphenol compounds such as bisphenol A and bisphenol F, and these may be used alone or in combination of two or more.
- aralkyl-type phenolic resins bisphenol compounds such as bisphenol A and bisphenol F, and these may be used alone or in combination of two or more.
- trisphenol methane type phenol resin biphenyl aralkyl type phenol resin, novolak type phenol resin, biphenylene skeleton-containing phenol aralkyl type. It is more preferable to use one or more selected from the group consisting of a resin and a phenol aralkyl type / formaldehyde polycondensate containing a biphenylene skeleton.
- the content of the curing agent in the sealing resin composition is a sealing resin composition from the viewpoint of realizing excellent fluidity at the time of molding and improving fillability and moldability.
- it is 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more with respect to the whole.
- the content of the curing agent in the sealing resin composition is determined from the viewpoint of improving the moisture resistance reliability and the reflow resistance. It is preferably 25% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less with respect to the whole product.
- the sealing resin composition of the present embodiment may contain components other than the above-mentioned components, for example, a curing accelerator, a fluidity imparting agent, a mold release agent, an ion scavenger, a low stress component, a flame retardant, and a colorant. , One or more of various additives such as antioxidants can be appropriately blended.
- the encapsulating resin composition includes, for example, 2-hydroxy-N-1H-1,2,4-triazole-3-ylbenzamide and 3-amino-5-mercapto-1,2,4-triazole. It may further contain 1 or more.
- the curing accelerator is, for example, a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound; 8-diazabicyclo [5.4.0] Undecene-7, benzyldimethylamine, 2-methylimidazole and the like are exemplified by amidines and tertiary amines, and nitrogen atom-containing compounds such as the above-mentioned amidines and quaternary salts of amines; 2, It can contain one or more selected from polyhydroxynaphthalene compounds such as 3-dihydroxynaphthalene.
- a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound,
- a phosphorus atom-containing compound from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It is more preferable to include one.
- the content of the curing accelerator in the sealing resin composition is preferably 0.01% by mass or more with respect to the entire sealing resin composition from the viewpoint of improving the curing characteristics of the sealing resin composition. It is more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more. Further, from the viewpoint of obtaining preferable fluidity during molding of the sealing resin composition, the content of the curing accelerator in the sealing resin composition is preferably 2. It is 0% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less.
- the release agent is from 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; paraffins; and carboxylic acid amides such as erucic acid amide.
- Can include one or more selected from the group of
- the content of the mold release agent in the sealing resin composition is preferably 0. It is 01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass. Hereinafter, it is more preferably 0.5% by mass or less.
- the ion scavenger include hydrotalcite.
- the content of the ion scavenger in the sealing resin composition is preferably 0.01% by mass or more with respect to the entire sealing resin composition from the viewpoint of improving the reliability of the sealing material. It is more preferably 0.05% by mass or more, preferably 1.0% by mass or less, and more preferably 0.5% by mass or less.
- the low stress component include silicones such as silicone oil, silicone rubber, silicone elastomer, and silicone resin; acrylonitrile butadiene rubber.
- the content of each low stress component in the sealing resin composition is preferably 0.01% by mass or more with respect to the entire sealing resin composition from the viewpoint of improving the reliability of the sealing material. , More preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less. be.
- the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.
- the content of the flame retardant in the sealing resin composition is preferably 1% by mass or more, more preferably 1% by mass or more, based on the entire sealing resin composition from the viewpoint of improving the flame retardancy of the sealing material. Is 5% by mass or more, preferably 20% by mass or less, and more preferably 10% by mass or less.
- the content of the colorant in the sealing resin composition is preferably 0.1% by mass or more with respect to the entire sealing resin composition from the viewpoint of making the color tone of the sealing material preferable. It is more preferably 0.2% by mass or more, preferably 2% by mass or less, and more preferably 1% by mass or less.
- antioxidants include hindered phenol compounds, hindered amine compounds, and thioether compounds.
- the encapsulating resin composition of the present embodiment is solid at room temperature (25 ° C.), and its shape can be selected according to the molding method of the encapsulating resin composition, for example, tablet-like; powder-like. , Granules and the like; Sheets and the like.
- the above-mentioned components are mixed by a known means, melt-kneaded by a kneader such as a roll, a kneader or an extruder, cooled, and then pulverized. It can be obtained by the method.
- the resin composition for encapsulation in the form of particles or a sheet may be obtained by molding.
- the resin composition for encapsulation in the form of particles may be obtained by tableting and molding into a tablet shape.
- a sheet-shaped sealing resin composition may be obtained by a vacuum extruder.
- the dispersity, fluidity and the like of the obtained sealing resin composition may be appropriately adjusted.
- the sealing resin composition obtained in the present embodiment contains the component (A) and the component (B), it has excellent adhesion to the metal member. More specifically, according to the present embodiment, it is also possible to improve the adhesion between the sealing material and a member made of Ag, Ni, Cu or an alloy containing one or more of these.
- the sealing resin composition of the present embodiment can be used for transfer molding, injection molding, or compression molding. Further, by using the sealing resin composition obtained in the present embodiment, a semiconductor device having excellent reliability can be obtained.
- the melt viscosity of the sealing resin composition of the present embodiment at 175 ° C. is 30 Pa ⁇ s or less, preferably 20 Pa ⁇ s or less. As a result, the moldability is excellent, and when the semiconductor element is sealed with the sealing resin composition, the processing stability is excellent.
- the rectangular pressure at 175 ° C. measured by the following method is 0.1 kgf / cm 2 to 20.0 kgf / cm 2 , preferably 0.5 kgf / cm 2 to 15. It is 0.0 kgf / cm 2 .
- the sealing resin composition of the present embodiment can further enhance the filling property in the gap between the substrate and the semiconductor element.
- the sealing resin composition is injected into a rectangular flow path having a width of 15 mm, a thickness of 1 mm, and a length of 175 mm under the conditions of a mold temperature of 175 ° C. and an injection speed of 177 mm 3 / sec. Then, the change over time of the pressure is measured by a pressure sensor embedded at a position 25 mm from the upstream tip of the flow path. Next, the minimum pressure at the time of flow of the sealing resin composition is calculated from the measurement result, and this minimum pressure is defined as the rectangular pressure.
- the cured product obtained from the sealing resin composition containing the component (A) of the present embodiment has high bending strength and a smaller increase in bending elastic modulus than the cured product containing a conventional adhesion-imparting agent. It is possible to provide a sealing material having excellent mechanical strength and product reliability.
- the flexural modulus of the cured product at room temperature (25 ° C.) is 15,000 MPa or more, preferably 16,000 MPa or more, more preferably. Is 17,000 MPa or more.
- the upper limit is not particularly limited, but can be 30,000 MPa or less.
- 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 may be 2000 MPa or less.
- the cured product obtained by curing the resin molding material of the present embodiment at 175 ° C. for 120 seconds has a bending strength at room temperature (25 ° C.) of 30 MPa or more, preferably 50 MPa or more, more preferably 100 MPa or more. ..
- the upper limit is not particularly limited, but may be 200 MPa or less.
- the bending 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.
- the cured product obtained from the sealing resin composition of the present embodiment has excellent adhesion to a metal member, and can provide a sealing material having excellent product reliability.
- the sealing resin composition of the present embodiment was cured on a copper plate at 175 ° C. for 180 seconds to obtain a cured product, and further heated at 175 ° C. for 3 hours, the die share strength between the copper plate and the cured product was obtained.
- room temperature 25 ° C., the same applies hereinafter
- it is preferably 10 MPa or more, more preferably 12 MPa or more.
- the die share strength between the copper plate and the cured product is preferably 0.95 MPa or more at 260 ° C. , More preferably 1.0 MPa or more, still more preferably 1.1 MPa or more.
- the upper limit of the die share strength is not limited, but is, for example, 30 MPa or less at room temperature or 260 ° C.
- the die share strength with and is preferably 5.0 MPa or more, more preferably 7.0 MPa or more, still more preferably 7.5 MPa or more, still more preferably 10 MPa or more at room temperature.
- the die share strength between the nickel plate and the cured product is preferably 0.5 MPa or more at 260 ° C. It is more preferably 0.7 MPa or more, still more preferably 1.0 MPa or more.
- the upper limit of the die share strength is not limited, but is, for example, 30 MPa or less at room temperature or 260 ° C.
- the sealing resin composition of the present embodiment was cured on a silver plate at 175 ° C. for 180 seconds to obtain a cured product, and further heated at 175 ° C. for 3 hours, the silver plate and the cured product were obtained.
- the die share strength with and is preferably 12 MPa or more, more preferably 15 MPa or more at room temperature.
- the die share strength between the silver plate and the cured product is preferably 0.95 MPa or more at 260 ° C. It is more preferably 1.0 MPa or more, still more preferably 1.1 MPa or more.
- the upper limit of the die share strength is not limited, but is, for example, 40 MPa or less at room temperature or 260 ° C.
- the semiconductor element is sealed by the cured product of the sealing resin composition according to the above-mentioned embodiment.
- semiconductor devices include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, solid-state image pickup devices, and the like.
- the semiconductor element is preferably a so-called element that does not involve light inflow and outflow, excluding optical semiconductor elements such as a light receiving element and a light emitting element (light emitting diode or the like).
- the base material of the semiconductor device is, for example, a wiring board such as an interposer or a lead frame. Further, the semiconductor element is electrically connected to the base material by wire bonding, flip chip connection, or the like.
- Examples of semiconductor devices obtained by sealing a semiconductor element by sealing molding using a sealing resin composition include MAP (Mold Array Package), QFP (Quad Flat Package), and 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 Felip Chip BGA
- Types such as MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In type eWLB, and Fan-Out type eWLB can be mentioned.
- the semiconductor device 100 shown in FIG. 1 includes a semiconductor element 20 mounted on a substrate 30, and a sealing material 50 for sealing the semiconductor element 20.
- the encapsulant 50 is composed of a cured product obtained by curing the encapsulating resin composition according to the present embodiment described above.
- FIG. 1 illustrates a case where the substrate 30 is a circuit board.
- a plurality of solder balls 60 are formed on the other surface of the substrate 30 on the side opposite to the one on which the semiconductor element 20 is mounted.
- the semiconductor element 20 is mounted on the substrate 30 and is electrically connected to the substrate 30 via the wire 40.
- the semiconductor element 20 may be flip-chip mounted on the substrate 30.
- the wire 40 is not limited, and examples thereof include Ag wire, Ni wire, Cu wire, Au wire, and Al wire, and preferably, the wire 40 is Ag, Ni, Cu, or one or more of them. Consists of an alloy containing.
- the sealing material 50 seals the semiconductor element 20 so as to cover the other surface of the semiconductor element 20 on the side opposite to the one facing the substrate 30.
- the sealing material 50 is formed so as to cover the other surface and the side surface of the semiconductor element 20.
- the sealing material 50 is composed of a cured product of the above-mentioned sealing resin composition. Therefore, in the semiconductor device 100, the adhesion between the sealing material 50 and the wire 40 is excellent, which makes the semiconductor device 100 excellent in reliability.
- the encapsulant 50 can be formed, for example, by encapsulating the encapsulating resin composition using a known method such as a transfer molding method or a compression molding method.
- FIG. 2 is a cross-sectional view showing the configuration of the semiconductor device 100 in the present embodiment, and shows an example different from FIG.
- the semiconductor device 100 shown in FIG. 2 uses a lead frame as the substrate 30.
- the semiconductor element 20 is mounted on the die pad 32 of the substrate 30, for example, and is electrically connected to the outer lead 34 via the wire 40.
- the sealing material 50 is composed of a cured product of the sealing resin composition in the present embodiment in the same manner as in the example shown in FIG.
- (Colorant) -Colorant 1 Carbon black, ERS-2001, manufactured by Tokai Carbon Co., Ltd.
- (Silane coupling agent) -Silane coupling agent 1 phenylaminopropyltrimethoxysilane, CF-4083, manufactured by Toray Dow Corning Co., Ltd.
- -Silane coupling agent 2 ⁇ -glycidoxypropyltrimethoxysilane, GPS-M, manufactured by JNC Corporation-Silane Coupling agent 3: 3-mercaptopropyltrimethoxysilane, manufactured by Chisso
- Epoxy resin (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, Mitsubishi Chemical Co., Ltd. ⁇
- Epoxy resin 3 Dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin, Epicron HP-7200L, manufactured by DIC ⁇
- Epoxy resin 4 Naftylene ether type epoxy resin, HP-6000L, manufactured by DIC,
- (Hardener) -Curing agent 1 Biphenylene skeleton-containing phenol aralkyl type resin, MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.
- -Curing agent 2 MFBA type phenol synthesized by the following method was used.
- a stirrer, a thermometer, a reflux cooler, and a nitrogen inlet are attached to the separable flask, and 1,3-dihydroxybenzene (manufactured by Tokyo Kasei Kogyo Co., Ltd., "resorcinol", melting point 111 ° C., molecular weight 110, purity 99.4% ) 291 parts by mass, phenol (special grade reagent manufactured by Kanto Chemical Co., Ltd., "phenol", melting point 41 ° C., molecular weight 94, purity 99.3%) 235 parts by mass, pre-ground granulated 4,4'-bischloromethylbiphenyl ( "4,4'-Bischloromethylbiphenyl” manufactured by Wako Pure Chemical Industries, Ltd., melting point 126 ° C., purity 95%, molecular weight 251) 125 parts by mass is weighed in a separable flask and heated while replacing with nitrogen to phenol.
- 1,3-dihydroxybenzene manufactured by
- the relative intensity ratio measured and analyzed by field desorption mass spectrometry is regarded as the mass ratio and calculated by arithmetic, and the repetition of the structural unit having one hydroxyl group.
- the ratio k0 / m0 of the average value k0 of several k and the average value m0 of the number of repetitions m of the structural unit having two hydroxyl groups was 0.98 / 1, and the number average molecular weight was 460.
- the number average molecular weight used was an alliance manufactured by Waters (2695 Separations Modul, 2414 Refractive Index Detector, TSK Gel GMHHR-Lx2 + TSK Guard Column HHR-Lx1, Mobile Phase: THF, 0.5 ml / min), and the column temperature was 40.
- the number average molecular weight was measured by gel permeation chromatography (GPC) under the conditions of 0.0 ° C., a differential refractometer temperature of 40.0 ° C., and a sample injection volume of 100 ⁇ l.
- GPC gel permeation chromatography
- two Ys each independently represent a hydroxyphenyl group represented by the following formula (1B) or the following formula (1C)
- X is the following formula (1D) or the following formula.
- (1E) represents a hydroxyphenylene group.
- Curing accelerator 1 Tetraphenylphosphonium ⁇ 4,4'-Sulfonyl diphenolate
- (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
- Ion scavenger 1 Magnesium, aluminum, hydroxide, carbonate, hydrate, DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd.
- (Low stress agent) -Low stress agent 1 Silicone oil, FZ-3730, manufactured by Toray Dow Corning Co., Ltd.-Low stress agent 2: A melt reaction product prepared by the following method was used.
- Epoxy resin represented by the following formula (2) bisphenol A type epoxy resin [manufactured by Javan Epoxy Resin Co., Ltd., jER® YL6810, softening point 45 ° C., epoxy equivalent 172] 66.1 parts by weight 140 It was heated and melted at ° C., 33.1 parts by weight of an organopolysiloxane represented by the following formula (3) and 0.8 parts by weight of triphenylphosphine were added, and the mixture was melt-mixed for 30 minutes to obtain a melt reaction product.
- Low stress agent 3 Acrylonitrile butadiene rubber, CTBN10008SP, manufactured by Ube Kosan Co., Ltd.
- Low stress agent 4 Silicone resin, KR-480, manufactured by Shin-Etsu Chemical Co., Ltd.
- Low stress agent 5 Epoxidized polybutadiene, JP200, manufactured by Nippon Soda Co., Ltd.
- Examples 1 and 2 Comparative Examples 1 and 2
- a sealing resin composition which is a powder or granular material.
- the sealing resin composition is injected into a rectangular flow path having a width of 15 mm, a thickness of 1 mm, and a length of 175 mm under the conditions of a mold temperature of 175 ° C. and an injection speed of 177 mm 3 / sec. Then, the change over time of the pressure is measured by a pressure sensor embedded at a position 25 mm from the upstream tip of the flow path. Next, the minimum pressure at the time of flow of the sealing resin composition was calculated from the measurement results, and this minimum pressure was taken as the rectangular pressure.
- the sealing resin composition is molded 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., an injection pressure of 10.0 MPa, and a curing time of 120 seconds. Injection molded. As a result, a molded product having a width of 10 mm, a thickness of 4 mm, and a length of 80 mm was obtained. Then, the obtained molded product was post-cured at 175 ° C. for 4 hours. As a result, a test piece for evaluation of mechanical strength was prepared. Then, the bending strength (MPa) and the bending elastic modulus (MPa) of the test piece at 260 ° C. or room temperature (25 ° C.) were measured according to JIS K 6911.
- the die shear strength in post-mold cure was measured by the following method as an index of adhesion.
- a low-pressure transfer molding machine manufactured by Yamashiro Seiki Co., Ltd., "AV-600-50-TF" was used to mold temperature 175 ° C., injection pressure 10 MPa, curing time.
- 10 pieces of 3.6 mm ⁇ ⁇ 3 mm adhesion strength test pieces were formed on a 9 ⁇ 29 mm strip-shaped test copper lead frame, a silver-plated lead frame, or a nickel plate.
- the die shear strength was measured at room temperature (RT) or 260 ° C. using an automatic die shear measuring device (DAGE4000 type manufactured by Nordson Advanced Technology). , Die share strength (MPa) was determined.
- Example 1 and Comparative Example 1 and Example 2 and Comparative Example 2 are compared, the encapsulating resin composition obtained in each Example is 3,5-diamino-1,2,4-.
- the fluidity was excellent, and the obtained cured product had excellent adhesion to the metal member and excellent mechanical strength.
- the sealing resin composition obtained in each example a semiconductor device having excellent reliability was obtained.
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Abstract
Description
すなわち、本発明は、以下に示すことができる。
(A)3,5-ジアミノ-1,2,4-トリアゾールと、
(B)エポキシ樹脂と、を含む封止用樹脂組成物を提供することができる。
半導体素子と、
前記半導体素子を封止する、前記封止用樹脂組成物の硬化物と、を含む半導体装置を提供することができる。
本実施形態の封止用樹脂組成物は、
(A)3,5-ジアミノ-1,2,4-トリアゾールと、
(B)エポキシ樹脂と、
を含む。
以下に、本実施形態の封止用樹脂組成物に含まれる各成分を説明する。
化合物(A)は、アミノトリアゾール化合物であり、具体的には、3,5-ジアミノ-1,2,4-トリアゾールである。
当該化合物を用いることにより、銀、銅、ニッケル等の金属部材との密着性に優れ、さらに成形性および製品信頼性に優れる。
エポキシ樹脂(B)は、1分子内に2個以上のエポキシ基を有する化合物であり、モノマー、オリゴマーおよびポリマーのいずれであってもよい。
同様の観点から、エポキシ樹脂(B)は、好ましくは、トリス(ヒドロキシフェニル)メタン型エポキシ樹脂、ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、3,3',5,5'-テトラメチルビフェニルグリシジルエーテル型エポキシ樹脂、およびジシクロペンタジエン骨格含有多官能固形エポキシ樹脂からなる群から選択される1種または2種以上であり、
より好ましくは、ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂、3,3',5,5'-テトラメチルビフェニルグリシジルエーテル型エポキシ樹脂、およびジシクロペンタジエン骨格含有多官能固形エポキシ樹脂からなる群から選択される1種または2種以上であり、
さらに好ましくはビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂である。
また、封止用樹脂組成物を用いて得られる装置の信頼性を向上する観点から、封止用樹脂組成物中のエポキシ樹脂(B)の含有量は、封止用樹脂組成物全体に対して、好ましくは40質量%以下であり、より好ましくは30質量%以下、さらに好ましくは20質量%以下、さらにより好ましくは10質量%以下である。
ここで、マレイミド化合物は、具体的には、マレイミド基を2つ以上有する化合物である。また、封止用樹脂組成物には、好ましくはマレイミド化合物が意図的に配合されておらず、封止用樹脂組成物中のマレイミド化合物の含有量は、好ましくは実質的に0質量%であり、たとえば検出限界以下である。
本実施形態の封止用樹脂組成物は、シランカップリング剤(C)を含むことができる。
シランカップリング剤(C)として、たとえば、エポキシシラン、メルカプトシラン、フェニルアミノシラン等のアミノシランが挙げられる。封止材と金属部材との密着性を向上する観点から、シランカップリング剤(C)は、好ましくはエポキシシランまたはアミノシランであり、より好ましくは2級アミノシランである。
同様の観点から、シランカップリング剤(C)は、好ましくはフェニルアミノプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシランおよび3-メルカプトプロピルトリメトキシシランからなる群から選択される1つ以上であり、
より好ましくはフェニルアミノプロピルトリメトキシシランである。
また、樹脂粘度の増粘抑制の観点から、封止用樹脂組成物中のシランカップリング剤(C)の含有量は、封止用樹脂組成物全体に対して、好ましくは2.0質量%以下であり、より好ましくは1.0質量%以下、さらに好ましくは0.5質量%以下である。
本実施形態の封止用樹脂組成物は、無機充填材(D)を含むことができる。
無機充填材(D)として、一般的に半導体封止用樹脂組成物に使用されているものを用いることができる。また、無機充填材(D)は表面処理がなされているものであってもよい。
ここで、無機充填材(D)の粒径分布は、市販のレーザー回折式粒度分布測定装置(たとえば、島津製作所社製、SALD-7000)を用いて粒子の粒度分布を体積基準で測定することにより取得することができる。
また、封止用樹脂組成物の成形時における流動性や充填性をより効果的に向上させる観点から、封止用樹脂組成物中の無機充填材(D)の含有量は、封止用樹脂組成物全体に対してたとえば97質量%以下であってもよく、好ましくは95質量%以下であり、より好ましくは90質量%以下である。
従来の封止用樹脂組成物は、得られる封止材の絶縁性等の観点から無機充填材を上記の量で含む場合、流動性が低下したり、金属部材との密着性が低下することがあった。本実施形態の封止用樹脂組成物は、3,5-ジアミノ-1,2,4-トリアゾール(A)を含むことにより、流動性に優れ、さらに金属部材との密着性に優れた硬化物(封止材)を得ることができる。言い換えれば、本実施形態の成分(A)を含む封止用樹脂組成物は、これらの特性のバランスに優れる。
本実施形態の封止用樹脂組成物は、硬化剤をさらに含んでもよい。硬化剤は、たとえば重付加型の硬化剤、触媒型の硬化剤、および縮合型の硬化剤の3タイプに大別することができ、これらの1種または2種以上を用いることができる。
また、封止用樹脂組成物を用いて得られる半導体装置について、耐湿信頼性や耐リフロー性を向上させる観点から、封止用樹脂組成物中の硬化剤の含有量は、封止用樹脂組成物全体に対して好ましくは25質量%以下であり、より好ましくは15質量%以下、さらに好ましくは10質量%以下である。
本実施形態の封止用樹脂組成物は、上述した成分以外の成分を含んでもよく、たとえば硬化促進剤、流動性付与剤、離型剤、イオン捕捉剤、低応力成分、難燃剤、着色剤、酸化防止剤等の各種添加剤のうち1種以上を適宜配合することができる。また、封止用樹脂組成物は、たとえば、2-ヒドロキシ-N-1H-1,2,4-トリアゾール-3-イルベンズアミドおよび3-アミノ-5-メルカプト-1,2,4-トリアゾールのうち1以上をさらに含んでもよい。
また、封止用樹脂組成物の成形時に好ましい流動性を得る観点から、封止用樹脂組成物中の硬化促進剤の含有量は、封止用樹脂組成物全体に対して、好ましくは2.0質量%以下であり、より好ましくは1.0質量%以下、さらに好ましくは0.5質量%以下である。
封止用樹脂組成物中の離型剤の含有量は、封止用樹脂組成物の硬化物の離型性を向上する観点から、封止用樹脂組成物全体に対して、好ましくは0.01質量%以上であり、より好ましくは0.05質量%以上、さらに好ましくは0.1質量%以上であり、また、好ましくは2.0質量%以下であり、より好ましくは1.0質量%以下、さらに好ましくは0.5質量%以下である。
封止用樹脂組成物中のイオン捕捉剤の含有量は、封止材の信頼性を向上する観点から、封止用樹脂組成物全体に対して、好ましくは0.01質量%以上であり、より好ましくは0.05質量%以上であり、また、好ましくは1.0質量%以下であり、より好ましくは0.5質量%以下である。
封止用樹脂組成物中の各低応力成分の含有量は、封止材の信頼性を向上する観点から、封止用樹脂組成物全体に対して、好ましくは0.01質量%以上であり、より好ましくは0.05質量%以上、さらに好ましくは0.1質量%以上であり、また、好ましくは5質量%以下であり、より好ましくは3質量%以下、さらに好ましくは1質量%以下である。
封止用樹脂組成物中の難燃剤の含有量は、封止材の難燃性を向上する観点から、封止用樹脂組成物全体に対して、好ましくは1質量%以上であり、より好ましくは5質量%以上であり、また、好ましくは20質量%以下であり、より好ましくは10質量%以下である。
封止用樹脂組成物中の着色剤の含有量は、封止材の色調の好ましいものとする観点から、封止用樹脂組成物全体に対して、好ましくは0.1質量%以上であり、より好ましくは0.2質量%以上であり、また、好ましくは2質量%以下であり、より好ましくは1質量%以下である。
本実施形態の封止用樹脂組成物は、常温(25℃)で固体であり、その形状は封止用樹脂組成物の成形方法等に応じて選択することができ、たとえばタブレット状;粉末状、顆粒状等の粒子状;シート状が挙げられる。
本実施形態の封止用樹脂組成物は、トランスファー成型、射出成型、または圧縮成型に用いることができる。
また、本実施形態において得られる封止用樹脂組成物を用いることにより、信頼性に優れる半導体装置を得ることができる。
これにより、本実施形態の封止樹脂組成物は、基板と半導体素子との間隙中への充填性をより高めることができる。
低圧トランスファー成形機を用いて、金型温度175℃、注入速度177mm3/秒の条件にて、幅15mm、厚さ1mm、長さ175mmの矩形状の流路に封止用樹脂組成物を注入し、流路の上流先端から25mmの位置に埋設した圧力センサーにて圧力の経時変化を測定する。次いで、測定結果から、封止用樹脂組成物の流動時における最低圧力を算出して、この最低圧力を矩形圧とする。
本実施形態の(A)成分を含む封止用樹脂組成物から得られる硬化物は、曲げ強度が高く、従来の密着付与剤を含む硬化物に比べて曲げ弾性率の上り幅が小さいため、機械強度および製品信頼性に優れた封止材を提供することができる。
本実施形態の樹脂成形材料を175℃、120秒の条件で硬化させたときの硬化物の、常温(25℃)における曲げ弾性率が、15,000MPa以上、好ましくは16,000MPa以上、より好ましくは17,000MPa以上である。上限値は特に限定されないが30,000MPa以下とすることができる。
前記硬化物の260℃における曲げ弾性率が、200MPa以上、好ましくは250MPa以上、より好ましくは300MPa以上である。上限値は特に限定されないが2000MPa以下とすることができる。
前記硬化物の260℃における曲げ強度が、3MPa以上、好ましくは5MPa以上、より好ましくは7MPa以上である。上限値は特に限定されないが50MPa以下とすることができる。
本実施形態の封止用樹脂組成物を、銅板上で175℃、180秒の条件で硬化させた硬化物を得、さらに、175℃で3時間加熱した際、銅板と硬化物とのダイシェア強度が、室温(25℃、以下同じ。)において、好ましくは10MPa以上であり、より好ましくは12MPa以上である。このように設定することで、たとえば、半導体装置として発熱の大きい素子を用いた場合や、より高温条件に曝される装置を作製する場合であっても、一段と高い信頼性を確保することができる。
同様の観点から、銅板上で上記の条件で硬化させて硬化物を得、さらに上記条件で加熱した際、銅板と硬化物とのダイシェア強度は、260℃において、好ましくは0.95MPa以上であり、より好ましくは1.0MPa以上、さらに好ましくは1.1MPa以上である。
このダイシェア強度の上限値は限定されないが、室温または260℃において、たとえば、30MPa以下である。
同様の観点から、ニッケル板上で上記の条件で硬化させて硬化物を得、さらに上記条件で加熱した際、ニッケル板と硬化物とのダイシェア強度は、260℃において、好ましくは0.5MPa以上であり、より好ましくは0.7MPa以上、さらに好ましくは1.0MPa以上である。
このダイシェア強度の上限値は限定されないが、室温または260℃において、たとえば、30MPa以下である。
同様の観点から、銀板上で上記の条件で硬化させて硬化物を得、さらに上記条件で加熱した際、銀板と硬化物とのダイシェア強度は、260℃において、好ましくは0.95MPa以上であり、より好ましくは1.0MPa以上、さらに好ましくは1.1MPa以上である。
このダイシェア強度の上限値は限定されないが、室温または260℃において、たとえば、40MPa以下である。
本実施形態における半導体装置は、上述した本実施形態における封止用樹脂組成物の硬化物により半導体素子が封止されているものである。半導体素子の具体例としては、集積回路、大規模集積回路、トランジスタ、サイリスタ、ダイオード、固体撮像素子等が挙げられる。半導体素子は、好ましくは、受光素子および発光素子(発光ダイオード等)等の光半導体素子を除く、いわゆる、光の入出を伴わない素子である。
以下、図面を参照してさらに具体的に説明する。
まず、図1に示した半導体装置100は、基板30上に搭載された半導体素子20と、半導体素子20を封止してなる封止材50と、を備えている。
封止材50は、上述した本実施形態における封止用樹脂組成物を硬化して得られる硬化物により構成されている。
本実施形態において、封止材50は、上述の封止用樹脂組成物の硬化物により構成される。このため、半導体装置100においては、封止材50とワイヤ40との密着性に優れており、これにより、半導体装置100は信頼性に優れるものである。
封止材50は、たとえば封止用樹脂組成物をトランスファー成形法または圧縮成形法等の公知の方法を用いて封止成形することにより形成することができる。
(無機充填材)
・無機充填材1:溶融球状シリカ、TS13-006、マイクロン社製(平均径28μm、比表面積2.5m2/g、上限カット75μm)
・無機充填材2:溶融球状シリカ、FB-105、デンカ社製(平均径10.6μm、比表面積5.1m2/g、上限カット71μm)
・無機充填材3:溶融球状シリカ、SC-2500-SQ、アドマテックス社製
・無機充填材4:シリカ、マイクロン社製(平均径2μm)
・無機充填材5:溶融球状シリカ(体積平均粒径23μm)、FB-950、デンカ社製
・着色剤1:カーボンブラック、ERS-2001、東海カーボン社製
・シランカップリング剤1:フェニルアミノプロピルトリメトキシシラン、CF-4083、東レ・ダウコーニング社製
・シランカップリング剤2:γ-グリシドキシプロピルトリメトキシシラン、GPS-M、JNC社製
・シランカップリング剤3:3-メルカプトプロピルトリメトキシシラン、チッソ社製
・エポキシ樹脂1:ビフェニレン骨格含有フェノールアラルキル型エポキシ樹脂、NC3000、日本化薬社製
・エポキシ樹脂2:3,3',5,5'-テトラメチルビフェニルグリシジルエーテル型エポキシ樹脂、YX4000K、三菱ケミカル社製
・エポキシ樹脂3:ジシクロペンタジエン骨格含有多官能固形エポキシ樹脂、エピクロンHP-7200L、DIC社製
・エポキシ樹脂4:ナフチレンエーテル型エポキシ樹脂、HP-6000L、DIC社製、
・硬化剤1:ビフェニレン骨格含有フェノールアラルキル型樹脂、MEH-7851SS、明和化成社製
・硬化剤2:以下の方法により合成されたMFBA型フェノールを用いた。
セパラブルフラスコに撹拌装置、温度計、還流冷却器、窒素導入口を装着し、1,3-ジヒドロキシベンゼン(東京化成工業社製、「レゾルシノール」、融点111℃、分子量110、純度99.4%)291質量部、フェノール(関東化学社製特級試薬、「フェノール」、融点41℃、分子量94、純度99.3%)235質量部、あらかじめ粒状に砕いた4,4’-ビスクロロメチルビフェニル(和光純薬工業社製、「4,4’-ビスクロロメチルビフェニル」、融点126℃、純度95%、分子量251)125質量部を、セパラブルフラスコに秤量し、窒素置換しながら加熱し、フェノールの溶融の開始に併せて攪拌を開始した。
その後、系内温度を110~130℃の範囲に維持しながら3時間反応させた後、加熱し、140~160℃の範囲に維持しながら3時間反応させた。なお、上記の反応によって系内に発生した塩酸ガスは、窒素気流によって系外へ排出した。
反応終了後、150℃、2mmHgの減圧条件で未反応成分を留去した。次いで、トルエン400質量部を添加し、均一溶解させた後、分液漏斗に移し、蒸留水150質量部を加えて振とうした後に、水層を棄却する操作(水洗)を洗浄水が中性になるまで繰り返し行った後、油層を125℃減圧処理することによってトルエン、残留未反応成分等の揮発成分を留去し、下記式(1A)で表されるフェノール樹脂硬化剤(重合体)を得た。
なお、このフェノール樹脂硬化剤における水酸基当量は135であった。
また、電界脱離質量分析(Field Desorption Mass Spectrometry;FD-MS)により測定・分析された相対強度比を質量比とみなして算術計算することにより得られた、水酸基が1個の構造単位の繰り返し数kの平均値k0、水酸基が2個の構造単位の繰り返し数mの平均値m0の比k0/m0は、0.98/1であり、数平均分子量は460であった。
なお、前記数平均分子量はWaters社製アライアンス(2695セパレーションズモデュール、2414リフラクティブインデックスディテクター、TSKゲルGMHHR-Lx2+TSKガードカラムHHR-Lx1、移動相:THF、0.5ml/分)を用い、カラム温度40.0℃、示差屈折率計温度40.0℃、サンプル注入量100μlの条件にてゲルパーミエーションクロマトグラフィー(GPC)により数平均分子量を測定した。
・硬化促進剤1:テトラフェニルホスホニウム・4,4’-スルフォニルジフェノラート
・離型剤1:カルナバワックス、TOWAX-132、東亜合成社製
・離型剤2:酸化ポリエチレンワックス、リコワックス PED191、クラリアント・ジャパン社製
イオン捕捉剤1:マグネシウム・アルミニウム・ハイドロオキサイド・カーボネート・ハイドレート、DHT-4H、協和化学工業社製
・添加剤1:3,5-ジアミノ-1,2,4-トリアゾール、四国化成社製
・低応力剤1:シリコーンオイル、FZ-3730、東レダウコーニング社製
・低応力剤2:以下の方法により調製された溶融反応物を用いた。
下記式(2)で表されるエポキシ樹脂(ビスフェノールA型エポキシ樹脂)[ジャバンエポキシレジン(株)製、jER(登録商標)YL6810、軟化点45℃、エポキシ当量172]66.1重量部を140℃で加温溶融し、下記式(3)で示されるオルガノポリシロキサン33.1重量部及びトリフェニルホスフィン0.8重量部を添加して、30分間溶融混合して溶融反応物を得た。
・低応力剤3:アクリロニトリルブタジエンゴム、CTBN1008SP、宇部興産社製
・低応力剤4:シリコーンレジン、KR-480、信越化学工業社製
・低応力剤5:エポキシ化ポリブタジエン、JP200、日本曹達社製
表1に示す各成分をミキサーにより混合した。次いで、得られた混合物を、ロール混練した後、冷却、粉砕して粉粒体である封止用樹脂組成物を得た。
各例で得られた樹脂組成物または当該組成物を用いて以下の方法で評価用試料を作製し、得られた試料の密着性および信頼性を以下の方法で評価した。
[スパイラルフロー(SF)]
実施例および比較例の封止用樹脂組成物を用いてスパイラルフロー試験を行った。
試験は、低圧トランスファー成形機(コータキ精機(株)製「KTS-15」)を用いて、EMMI-1-66に準じたスパイラルフロー測定用の金型に、金型温度175℃、注入圧力6.9MPa、硬化時間120秒の条件で封止用樹脂組成物を注入し、流動長を測定することにより行った。数値が大きいほど、流動性が良好であることを示す。
175℃に加熱した熱板上で実施例および比較例の封止用樹脂組成物をそれぞれ溶融後、へらで練りながら硬化するまでの時間(単位:秒)を測定した。
実施例および比較例のそれぞれの封止用樹脂組成物について、高化式フローテスター(島津製作所(株)製、CFT-500C)を用いて、温度175℃、荷重40kgf(ピストン面積1cm2)、ダイ穴直径0.50mm、ダイ長さ1.00mmの試験条件で溶解した封止用エポキシ樹脂組成物のみかけの粘度ηを測定した。ηは、以下の計算式より算出し、流動時における最低粘度を溶融粘度とした。計算式中、Qは単位時間あたりに流れる封止用エポキシ樹脂組成物の流量である。
η=(πD4 P×103/128LQ)(Pa・秒)
η:みかけの粘度
D:ダイ穴直径(mm)
P:試験圧力(Pa)
L:ダイ長さ(mm)
Q:フローレート(cm3/秒)
低圧トランスファー成形機を用いて、金型温度175℃、注入速度177mm3/秒の条件にて、幅15mm、厚さ1mm、長さ175mmの矩形状の流路に封止用樹脂組成物を注入し、流路の上流先端から25mmの位置に埋設した圧力センサーにて圧力の経時変化を測定する。次いで、測定結果から、封止用樹脂組成物の流動時における最低圧力を算出して、この最低圧力を矩形圧とした。
封止用樹脂組成物を、低圧トランスファー成形機(コータキ精機株式会社製「KTS-30」)を用いて、金型温度175℃、注入圧力10.0MPa、硬化時間120秒の条件で金型に注入成形した。これにより、幅10mm、厚み4mm、長さ80mmの成形品を得た。次いで、得られた成形品を175℃、4時間の条件で後硬化させた。これにより、機械的強度の評価用の試験片を作製した。そして、試験片の260℃または常温(25℃)における曲げ強度(MPa)および曲げ弾性率(MPa)を、JIS K 6911に準拠して測定した。
各例で得られた封止用樹脂組成物について、密着性の指標として、以下の方法でポストモールドキュア(PMC)におけるダイシェア強度を測定した。
各例で得られた封止用樹脂組成物について、低圧トランスファー成形機(山城精機社製、「AV-600-50-TF」)を用いて、金型温度175℃、注入圧力10MPa、硬化時間180秒の条件で、9×29mmの短冊状の試験用銅リードフレーム上、銀メッキリードフレーム上若しくはニッケル板上に3.6mmφ×3mmの密着強度試験片を10個成形した。
その後、175℃3時間の条件で硬化したサンプルについて、自動ダイシェア測定装置(ノードソン・アドバンスド・テクノロジー社製、DAGE4000型)を用いて、室温(RT)若しくは260℃にてダイシェア強度を測定することで、ダイシェア強度(MPa)を求めた。
30 基板
32 ダイパッド
34 アウターリード
40 ワイヤ
50 封止材
60 半田ボール
100 半導体装置
Claims (10)
- (A)3,5-ジアミノ-1,2,4-トリアゾールと、
(B)エポキシ樹脂と、
を含む封止用樹脂組成物。 - さらにシランカップリング剤(C)を含む、請求項1に記載の封止用樹脂組成物。
- さらに無機充填剤(D)を含む、請求項1または2に記載の封止用樹脂組成物。
- 前記封止用樹脂組成物の硬化物の常温(25℃)における曲げ弾性率が15,000MPa以上である、請求項1~3のいずれかに記載の封止用樹脂組成物。
- 175℃における溶融粘度が30Pa・s以下である、請求項1~4のいずれかに記載の封止用樹脂組成物。
- 以下の方法で測定された175℃での矩形圧が0.1kgf/cm2~20.0kgf/cm2である、請求項1~5のいずれかに記載の封止用樹脂組成物。
(測定方法)
低圧トランスファー成形機を用いて、金型温度175℃、注入速度177mm3/秒の条件にて、幅15mm、厚さ1mm、長さ175mmの矩形状の流路に封止用樹脂組成物を注入し、流路の上流先端から25mmの位置に埋設した圧力センサーにて圧力の経時変化を測定する。次いで、測定結果から、封止用樹脂組成物の流動時における最低圧力を算出して、この最低圧力を矩形圧とする。 - 常温(25℃)で固体である、請求項1~6のいずれかに記載の封止用樹脂組成物。
- タブレット状、粒子状又はシート状である、請求項1~7のいずれかに記載の封止用樹脂組成物。
- トランスファー成型、射出成型、または圧縮成型に用いられる、請求項1~8のいずれかに記載の封止用樹脂組成物。
- 半導体素子と、
前記半導体素子を封止する、請求項1~9のいずれかに記載の封止用樹脂組成物の硬化物と、
を含む、半導体装置。
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JP2015067618A (ja) * | 2013-09-26 | 2015-04-13 | 株式会社日本触媒 | 硬化性樹脂組成物及びその用途 |
JP2017110051A (ja) * | 2015-12-14 | 2017-06-22 | 住友ベークライト株式会社 | 封止用樹脂組成物、半導体装置および車載用電子制御ユニット |
WO2019131379A1 (ja) * | 2017-12-25 | 2019-07-04 | 住友ベークライト株式会社 | 電子装置の製造方法 |
CN110437764A (zh) * | 2019-08-16 | 2019-11-12 | 严佳飞 | 一种树脂改性淀粉粘合剂及其制备方法 |
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