WO2012018684A1 - Encapsulating resin composition - Google Patents

Encapsulating resin composition Download PDF

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Publication number
WO2012018684A1
WO2012018684A1 PCT/US2011/045894 US2011045894W WO2012018684A1 WO 2012018684 A1 WO2012018684 A1 WO 2012018684A1 US 2011045894 W US2011045894 W US 2011045894W WO 2012018684 A1 WO2012018684 A1 WO 2012018684A1
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Prior art keywords
resin composition
encapsulating resin
percent
inorganic particles
mass
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PCT/US2011/045894
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French (fr)
Inventor
Kohichiro Kawate
Justina Sze Ying Lee
Kathy Rosalina
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3M Innovative Properties Company
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Publication of WO2012018684A1 publication Critical patent/WO2012018684A1/en

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    • 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
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01012—Magnesium [Mg]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0102—Calcium [Ca]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01025—Manganese [Mn]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01067—Holmium [Ho]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12044—OLED
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1301—Thyristor

Definitions

  • the present invention relates to an encapsulating resin composition and also to a semiconductor device encapsulated using the encapsulating resin composition.
  • U.S. Patent Application Publication No. 2005/0129956 describes an underfill composition comprising at least one epoxy resin in combination with at least one epoxy hardener, the at least one epoxy hardener comprising at least one difunctional siloxane anhydride.
  • Japanese Unexamined Patent Application Publication No. 2004-256646 describes a resin composition for underfilling, which contains an epoxy resin, a curing agent, a curing accelerator and an inorganic filler, wherein the content of a polyfunctional epoxy resin is from 5 to 20 percent by mass relative to the total quantity of epoxy resin, a phenolic compound and an acid anhydride are used as the curing agent, and the content of the phenolic compound relative to the total quantity of curing agent is from 3 to 20 percent by mass.
  • encapsulating resin compositions are generally highly filled with inorganic particles.
  • inorganic particles having a relatively large average particle diameter are used in encapsulating resin compositions in order to lower a viscosity of the composition.
  • the present invention is an encapsulating resin composition containing an epoxy resin, a curing agent, inorganic particles, an organic titanium compound and a phosphoric acid ester.
  • the average particle diameter of the inorganic particles is about 10 ⁇ or less.
  • the amount of inorganic particles relative to a total amount of the encapsulating resin composition is about 60 percent by mass or more.
  • the amount of organic titanium compound relative to the total quantity of the encapsulating resin composition is about 1 percent by mass or more and about 5 percent by mass or less.
  • the amount of phosphoric acid ester relative to the total quantity of the encapsulating resin composition is about 0.5 percent by mass or more and about 3 percent by mass or less.
  • an encapsulating resin composition is provided that is excellent in terms of thermal expansion coefficient and flowability and that can easily penetrate into a narrow gap.
  • Epoxy resins that can be used in the encapsulating resin composition of the present invention include aliphatic, alicyclic, aromatic or heterocyclic monomeric or oligomeric epoxy compounds. These materials generally have, on average, at least one polymerizable epoxy group per molecule, and may have at least 1.5 or at least 2 polymerizable epoxy groups per molecule. In certain modes, it is possible to use a polyfunctional epoxy compound having three or four polymerizable epoxy groups per molecule.
  • the epoxy compound may be a pure compound or may be a mixture of compounds containing one, two, or more epoxy groups per molecule.
  • the epoxy compounds mentioned above may have any type of main chain and may contain substituent groups.
  • allowable substituent groups include, but are not limited to: halogens, ester groups, ethers, sulfonate groups, siloxane groups, nitro groups, phosphate groups and the like.
  • the epoxy equivalent value of the epoxy compound can generally be altered within a range of from 50 to 2,000.
  • oligomeric epoxy compounds include, but are not limited to: linear oligomers having terminal epoxy groups (i.e., a diglycidyl ether of a polyoxyalkylene glycol), oligomers having skeletal epoxy units (i.e., polybutadiene polyepoxide), and oligomers having pendant epoxy groups (i.e., a glycidyl methacrylate oligomer or co-oligomer).
  • R is a radical having a valency of n, n being an integer between 1 and 6.
  • R can be an aromatic group, an alicyclic group, an aliphatic group or a combination thereof.
  • Typical epoxy compounds include glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of a chlorohydrin such as epichlorohydrin (for example, 2,2-bis-(2,3-epoxypropoxyphenol)-propane).
  • epichlorohydrin for example, 2,2-bis-(2,3-epoxypropoxyphenol)-propane.
  • aromatic epoxy compounds examples include, but are not limited to: a diglycidyl ether of bisphenol A (bisphenol A type epoxy resin), a diglycidyl ether of bisphenol F
  • bisphenol F type epoxy resin bisphenol F type epoxy resin
  • a diglycidyl ether of 4,4'-dihydroxybiphenyl oligomers of these diglycidyl ethers
  • polyglycidyl ethers of cresol novolac resins cresol novolac type epoxy resins
  • polyglycidyl ethers of phenol novolac resins phenol novolac type epoxy resins
  • Examples of the alicyclic epoxy compounds include, but are not limited to: compounds obtained by hydrogenating the aromatic epoxy compounds mentioned above, such as hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.
  • compounds containing a cyclohexene oxide group such as vinyl cyclohexene monoxide, l ,2-epoxy-4-vinyl cyclohexane, l ,2:8,9-diepoxylimonene, and epoxy cyclohexane carboxylates such as 3,4-epoxycyclohexenylmethyl-3',4'- epoxycyclohexene carboxylate, 3,4-epoxycyclohexenylmethyI-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane carboxylate and bis(3,4-epoxy-6-methylcyclohex
  • the aliphatic epoxy compounds include glycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Examples include, but are not limited to: ethylene glycol diglycidyl ether, di(ethylene glycol) diglycidyl ether, propylene glycol diglycidyl ether, tri(propylene glycol) diglycidyl ether, neopentyl glycol diglycidyl ether, 1 ,4-butane diol diglycidyl ether, 1,6-hexane diol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, poly(ethylene glycol) diglycidyl ether and the like.
  • Epoxy compounds having a glycidylamino group are epoxy compounds (epoxy resins) obtained by epoxidation by reacting amines and an epihalohydrin, and examples thereof include aminophenol type epoxy resins, triglycidyl isocyanurates, tetraglycidyl diaminodiphenylmethane, tetraglycidyl meta-xylenediamine and hexaglycidyl triaminobenzene.
  • aminophenol type epoxy resins are obtained by epoxidizing aminophenols using publicly known methods.
  • aminophenols include, but are not limited to:
  • aminophenols and aminocresols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol and 6-amino-m-cresol.
  • epoxy resins able to be used include, but are not limited to, copolymers of acrylic acid esters of glycidol (such as glycidyl acrylate and glycidyl methacrylate) with one or more copolymerizable vinyl compounds.
  • This type of copolymer includes styrene-glycidyl methacrylate and methyl methacrylate-glycidyl acrylate copolymers.
  • an epoxy-functional silicon which is a polydimethyl siloxane in which silicon atoms have been substituted with epoxyalkyl groups.
  • epoxy resins mentioned above it is particularly suitable to use a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or an aminophenol type epoxy resin from the perspective of characteristics after curing the encapsulating resin composition.
  • a bisphenol A type epoxy resin and a bisphenol F type epoxy resin or a three-component system obtained by further adding an aminophenol type epoxy resin to a bisphenol A type epoxy resin and a bisphenol F type epoxy resin it is preferable to use both a bisphenol A type epoxy resin and a bisphenol F type epoxy resin or a three-component system obtained by further adding an aminophenol type epoxy resin to a bisphenol A type epoxy resin and a bisphenol F type epoxy resin.
  • An amount of the epoxy resin is generally 20 percent by mass or less, and from 10 to 20 percent by mass in some embodiments, relative to a total amount of the encapsulating resin composition.
  • the curing agent contained in the encapsulating resin composition of the present invention can be a routine curing agent used to cure epoxy compounds. Specific examples thereof include, but are not limited to: amino compounds, acid anhydride compounds, amide compounds, phenolic compounds, trifluorinated boron complex compounds such as BF3- monoethanolamine, imidazoles such as 2-ethyl-4-methylimidazole, hydrazides such as aminodihydrazide, guanidines such as tetramethylguanidine, and dicyandiamide.
  • the curing agent can be a single curing agent or a mixture of different curing agents. From the perspective of viscosity, an acid anhydride compound is particularly suitable.
  • non-aromatic acid anhydride compound it is possible to use a non-aromatic acid anhydride compound.
  • 3-methylhexahydrophthalic acid anhydride 4-methylhexahydrophthalic acid anhydride, l-methylnorbornane-2,3-dicarboxylic acid anhydride, 5-methylnorbornane-2,3-dicarboxyiic acid anhydride or norbornane-2,3-dicarboxylic acid anhydride, which do not have a double bond in the compound.
  • a mixture of 4-methylhexahydrophthalic acid anhydride and hexahydrophthalic acid anhydride (such as Rikacid MH-700 produced by New Japan Chemical Co., Ltd.
  • Bisphenol A bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, l-(4- hydroxyphenyl)-2-[4- ⁇ l ,l-bis-(4-hydroxyphenyl)ethyl ⁇ phenyl]propane, 2,2'-methylene-bis(4- methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol),
  • Aliphatic amines such as diethylenetriamine, triethylenetetramine or
  • aromatic amines such as diaminodiphenylmethane
  • diaminodiphenylsulfone, meta-xylenediamine and condensation products of aromatic amines and aldehydes, polyamidoamines and the like can be used as amino-based curing agents.
  • an amount of the curing agent is particularly approximately equal to the quantity of the epoxy resin.
  • the quantity of the curing agent is from 5 to 15 percent by mass relative to total weight of the encapsulating resin composition.
  • Inorganic particles are dispersed substantially homogeneously in the encapsulating resin composition of the present invention.
  • the inorganic particles are used in order to impart the encapsulating resin composition with a high modulus of elasticity and a low thermal expansion coefficient, and it is possible to use a single type or a combination of two or more types of inorganic particles.
  • these inorganic particles can be a powder such as silica (molten silica, crystalline silica), alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite or titania, or beads, glass fibers and the like obtained by conglobating these powders. It is possible to use a single type or a combination of two or more types of these inorganic particles.
  • molten silica is particularly suitable from the perspective of thermal expansion properties and crystalline silica and alumina are particularly suitable from the perspective of having high thermal conductivity.
  • silica particles when producing silica particles as inorganic particles from an organic sol, because the particle size distribution thereof is narrow, it is possible to effectively distribute the particles in the resin composition.
  • the shape of the primary particles of the inorganic particles is not particularly important, but spherical particles are particularly suitable from the perspective of being able to flow and penetrate into fine gaps.
  • the inorganic particles are particularly suitable for the inorganic particles to have a small average particle diameter and a narrow particle size distribution. Because the inorganic particles are prone to stacking when the encapsulating resin composition is forced into a narrow gap, the inorganic particles used in the present invention have an average particle diameter of 10 um or less. In addition, the average particle diameter of the inorganic particles is particularly 5 um or less, more particularly 3 ⁇ or less, and even more particularly 2 ⁇ or less.
  • the lower limit of the average particle diameter of the inorganic particles is not particularly restricted, but from the perspective of flowability, 0.5 ⁇ or higher is preferred in the case of silica particles, and 0.1 ⁇ or higher is preferred in the case of alumina particles.
  • the particle diameter of the inorganic particles in the encapsulating resin composition is preferably within the range "average particle diameter ⁇ (average particle diameter x 0.3)" (for example, 1 ⁇ 0.3 ⁇ ).
  • the average particle diameter and particle size distribution of the inorganic particles can be measured with an electron microscope or a laser scattering device.
  • the inorganic particles may be surface treated to an extent that does not impair the dispersibility of the particles in the resin composition.
  • Silica particles prepared by the sol-gel method and having a narrow particle size distribution are preferred as the inorganic particles, and molten silica having an average particle diameter of from 0.8 to 1.8 ⁇ , prepared by the sol-gel method and having a narrow particle size distribution (average particle diameter ⁇ (average particle diameter x 0.3)) are more preferred.
  • Such inorganic particles are commercially available as, for example, Silica HPS- 1000 (produced by Toagosei Co., Ltd. by the sol-gel method) or Silica SS-07, SS-10 and SS-14 (produced by Tokuyama Corporation by the sol-gel method).
  • An amount of inorganic particles in the encapsulating resin composition is preferably 60 percent by mass or more relative to the total quantity of the encapsulating resin composition from the perspective of the thermal expansion coefficient of the cured product, and is particularly 90 percent by mass or less relative to the total quantity of the encapsulating resin composition from the perspective of the viscosity of the resin composition. If the amount of inorganic particles falls within this range, it is generally possible to obtain a cured product having a thermal expansion coefficient of 35 ppm or less and also possible for the encapsulating resin composition of the present invention to be used as an encapsulating resin composition for a semiconductor.
  • Organic titanium compounds able to be used in the encapsulating resin composition of the present invention include organic titanium compounds having a hydrolyzable group and a hydrophobic group in the compound. Such organic titanium compounds are generally known as titanium coupling agents.
  • the organic titanium compound reacts with -OH groups on the surface of the inorganic particles and, for example, forms covalent bonds with the titanium by eliminating an alcohol by hydrolysis. It is thought that this makes the surface of the inorganic particles organic, which results in good dispersibility of the inorganic particles in the epoxy resin.
  • R 1 can be a substituted or unsubstituted, straight chain or branched chain alkyl group, alkenyl group, aryl group or aralkyl group. Because R 1 is eliminated after the reaction with the inorganic particles (i.e., eliminated by forming an alcohol), it is particularly suitable for Rl to be a group having a somewhat lower boiling point following elimination. Therefore, R 1 is particularly a group having few carbon atoms, and preferably a substituted or unsubstituted, straight chain or branched chain alkyl group having 1 to 10 carbon atoms (and more particularly 1 to 8 carbon atoms).
  • hydrophobic group in the organic titanium compound can be any hydrophobic group in the organic titanium compound.
  • R 2 can be a substituted or unsubstituted, straight chain or branched chain alkyl group, alkenyl group, aryl group or aralkyl group.
  • R 2 is particularly a group having many carbon atoms, and particularly a substituted or unsubstituted, straight chain or branched chain alkyl group having from 8 to 30 carbon atoms.
  • R is a substituted or unsubstituted, straight chain or branched chain alkyl group having from 8 to 30 carbon atoms, and preferably 10 to 30 carbon atoms.
  • the titanium coupling agent can be a tetraalkoxy titanium (such as tetraethoxy titanium, tetraisopropoxy titanium or tetrabutoxy titanium), tetra(ethylene glycol) titanate, di-n-butylbis(triethanolamine) titanate, di-isopropoxy bis(acetyl acetonate)titanium, isopropoxy titanium octanoate, isopropyl titanium trimethacrylate, isopropyl titanium triacrylate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl (butyl, methylpyrophosphate) titanate, tetraisopropyl di(dilauryl phosphite) titanate,
  • pyrophosphate)oxyacetate titanate tris(dioctyl pyrophosphate)ethylene titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate and the like.
  • KRTTS isopropyltriisostearoyl titanate (CH 3 )2CHOTi[OCO(CH 2 )i4CH(CH 3 )2]3)
  • R 46B tetraoctylbis(di-tridecylphosphite) titanate
  • KR 55 tetra(2,2-diallyloxymethyl- l- butyl) bis(di-tridecyl) phosphite titanate
  • KR 41B tetraisopropylbis(dioctylphosphite) titanate
  • KR 38S isopropyltris(dioctylpyrophosphate) titanate
  • KR 138S isopropyltris(dioctylpyrophosphate) titanate
  • an amount of the organic titanium compound is 1 percent by mass or more, particularly 2 percent by mass or more, and more particularly 2.5 percent by mass or more, relative to the total quantity of the encapsulating resin composition.
  • the quantity of the organic titanium compound is 5 percent by mass or less, particularly 4 percent by mass or less, and more particularly 3 percent by mass or less, relative to the total quantity of the encapsulating resin composition.
  • phosphoric acid esters able to be used in the encapsulating resin composition of the present invention include esters obtained by subjecting phosphoric acid and an alcohol to dehydrocondensation.
  • the phosphoric acid ester forms weak bonds, such as coordinate bonds, with the titanium.
  • the organic layer on the surface of the inorganic particles, which is rendered organic by the organic titanium compound increases in depth.
  • the phosphoric acid ester has a structure in which all or some of the hydrogen atoms in the phosphoric acid (OP(OH)3) are replaced by organic groups.
  • Compounds in which 1 , 2 and 3 hydrogen atoms are replaced are known as a phosphoric acid monoester ((HO) 2 POZ) , a phosphoric acid diester (HOP(OZ) 2 ) and a phosphoric acid triester (P(OZ)3) respectively.
  • Z denotes a substituted or unsubstituted alkyl group, phenyl group, polyester or polycaprolactone having from 10 to 50 carbon atoms and the like.
  • Z From the perspective of increasing the thickness of the organic layer formed on the surface of the inorganic particles, it is preferable for Z to have a high molecular weight. Specifically, a weight average molecular weight of from 200 to 20,000 is suitable and a weight average molecular weight of from 300 to 10,000 is particularly suitable.
  • dimethyl phosphate, diethyl phosphate, dipropyl phosphate, monobutyl phosphate, dibutyl phosphate, mono-2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, monophenyl phosphate, mono-2-ethylhexyl phosphite, dioctyl phosphate, diphenyl phosphate and the like can be used as the compound mentioned above.
  • commercially available products such as Disperbyk 1 1 1 produced by BYK Chemicals Japan can be obtained.
  • phosphoric acid diesters are particularly suitable, and phosphoric acid diesters in which Z is a polycaprolactone are more particularly suitable, from the perspective of dispersion of the inorganic particles.
  • an amount of the phosphoric acid ester is 0.5 percent by mass or more, particularly 1 percent by mass or more, and more particularly 1.2 percent by mass or more, relative to the total quantity of the encapsulating resin composition.
  • the quantity of the phosphoric acid ester is 3 percent by mass or less, particularly 2 percent by mass or less, and more particularly 1.8 percent by mass or less, relative to the total quantity of the encapsulating resin composition.
  • an organic titanium compound having a chemical structure represented by R 3 OTi(OCOR 4 H) 3 or (R 3 0) 4 Ti[HOP(OR 4 ) 2 ] (here, R 3 denotes a straight chain or branched chain alkyl group having from 3 to 8 carbon atoms and R 4 denotes a straight chain or branched chain alkyl group having from 10 to 20 carbon atoms.) and a phosphoric acid diester having a weight average molecular weight of from 200 to 20,000 and having a chemical structure represented by HOP(OZ) 2 (here, Z denotes a substituted or unsubstituted alkyl group, phenyl group, polyester or polycaprolactone having from 10 to 50 carbon atoms) is particularly
  • the encapsulating resin composition of the present invention may also contain a reaction accelerator.
  • the reaction accelerator used to accelerate the reaction between the epoxy resin and the curing agent can be a commonly used and publicly known reaction accelerator such as a cycloamidine compound, a tertiary amine, a quaternary ammonium salt, an imidazole, an organic metal compound that acts as a Lewis acid, a phosphorus-based compound such as an organic phosphine such as triphenyl phosphine, or a derivative or tetraphenyl boron salt thereof.
  • a single reaction accelerator or a combination of two or more types thereof can be used.
  • the quantity of the reaction accelerator is not particularly limited as long as a reaction acceleration effect is achieved.
  • an ion trapping agent in the encapsulating resin composition of the present invention in order to improve the moisture resistance and high temperature exposure characteristics of a semiconductor device.
  • the ion trapping agent is not particularly limited, and a publicly known ion trapping agent may be used. Specifically, it is possible to use hydrotalcite or a water-containing oxide of an element such as magnesium, aluminum, titanium, zirconium or bismuth.
  • stress relaxing agents such as silicone rubber powders, dyes, colorants such as carbon black, leveling agents, anti-foaming agents and other inorganic fillers (for example, inorganic fillers having a flame retardant effect, such as aluminum hydroxide, magnesium hydroxide, zinc silicate or zinc molybdate) may be blended in the encapsulating resin composition of the present invention at levels that do not impair the object of the present invention.
  • inorganic fillers having a flame retardant effect such as aluminum hydroxide, magnesium hydroxide, zinc silicate or zinc molybdate
  • nitrogen-containing compounds such as cyanuric acid derivatives or isocyanuric acid derivatives
  • phosphorus- and nitrogen-containing compounds such as cyclophosphazene
  • metal compounds such as zinc oxide, iron oxide, molybdenum oxide and ferrocene
  • antimony oxides such as antimony trioxide, antimony tetraoxide and antimony pentoxid
  • a cured product of the encapsulating resin composition of the present invention has a thermal expansion coefficient of from 10 to 35 ppm. Because silicon has a low thermal expansion coefficient, it is preferable for a material used to seal silicon to also have a low thermal expansion coefficient when encapsulating a semiconductor. If the thermal expansion coefficient exceeds 35 ppm, there are concerns over cracks occurring due to thermal stress. Moreover, it is possible to use a TMA (Thermal Mechanical Analyzer) to measure the thermal expansion coefficient. Specifically, it is possible to measure the thermal expansion coefficient with a TMA 8310 thermomechanical analysis apparatus manufactured by Rigaku Corporation. A sample (size: 4 x 5 > ⁇ 10 mm 3 ) is heated at a rate of 20°C/minute in a nitrogen stream, a load of 10 mN is applied and measurements are carried out in compression mode.
  • TMA Thermal Mechanical Analyzer
  • the encapsulating resin composition of the present invention has good flowability.
  • a viscosimeter can be used to measure the flowability, but it is sometimes not possible to determine whether or not the composition has actually penetrated into a narrow gap from viscosity values alone. Therefore, the most direct method is to measure the time taken for the resin composition to penetrate into a pair of plane parallel plates separated by a fixed gap. When measuring the penetration of this type of resin composition, two glass plates of different sizes are used.
  • a large glass plate measuring 40 ⁇ 40 ⁇ 1 mm 3 and a small glass plate measuring 30 30 ⁇ 1 mm 3 are prepared, adhesive tape having a thickness of 40 ⁇ and dimensions of 30 5 mm 2 is applied to two of the edges of the small glass plate, and the large glass plate is applied thereto so as to form a gap of 40 ⁇ between the glass plates.
  • the glass plates With the large glass plate on the bottom, the glass plates are placed on a hot plate adjusted to a temperature of 100°C, a resin is supplied to one edge of the small glass plate and the relationship between elapsed time and penetration distance of the resin is measured, thereby confirming the flowability of the encapsulating resin composition.
  • the present invention it is possible to adjust the measured time required for penetration of the encapsulating resin composition within the range of from 10 to 1 ,000 seconds by using this measurement method. If the penetration time is 10 seconds or shorter, the viscosity of the resin composition is too low, meaning that it is easy for air bubbles to enter, and if the penetration time is 1 ,000 seconds or longer, workability is poor when actually using the resin composition as an encapsulating material.
  • a cured product of the encapsulating resin composition of the present invention has a glass transition temperature (Tg) of from 60 to 120°C and modulus of elasticity (dynamic storage modulus; E') of from 5 to 40 GPa.
  • Tg glass transition temperature
  • E' modulus of elasticity
  • the glass transition temperature and modulus of elasticity can be measured using a DMA (dynamic mechanical analysis) apparatus.
  • the method of measurement involves the use of a solid analyzer (RSA-III) manufactured by Rheometric Scientific in a three point curve mode (strain: 0.05%, frequency: 1 Hz) and a sample (size: 2 10 ⁇ 35 mm 3 ) heated at a rate of 3°C/minute.
  • RSA-III solid analyzer manufactured by Rheometric Scientific in a three point curve mode (strain: 0.05%, frequency: 1 Hz) and a sample (size: 2 10 ⁇ 35 mm 3 ) heated at a rate of 3°C/minute.
  • the three point curve method to measure the modulus of elasticity (dynamic storage modulus) by placing the above-mentioned cuboid sample (size: 2 ⁇ 10 x 35 mm 3 ) on two knife edges (separated by 25 mm) and measuring the load used to push down on the central part of the sample, thereby deforming the sample.
  • the strain is applied as a sine wave having a maximum value of 0.05%, and the load is also measured as a sine wave (the frequency of the sine wave is 1 Hz).
  • the encapsulating resin composition of the present invention may be produced using any type of production method.
  • a common production method is to blend the specified amounts of the raw materials either together or separately, stir, dissolve, mix and disperse these components in a mixing roller, extruder, planetary mixer and the like while, if necessary, heating and cooling, and then to cool and, if necessary, defoam and crush the resulting mixture.
  • the encapsulating resin composition of the present invention can have a low viscosity even though inorganic particles having a low average particle diameter are filled at a high density. Therefore, the encapsulating resin composition of the present invention is excellent in terms of thermal expansion coefficient and flowability and can penetrate easily into a narrow gap.
  • the encapsulating resin composition of the present invention can be used in a variety of applications, and can be used in any type of common electronic component application.
  • the encapsulating resin composition of the present invention can be used in capacitors, resistors, semiconductor devices, integrated circuits, transistors, diodes, triodes, thyristers, coils, varistors, connectors, convenors, microswitches and composite parts obtained therefrom.
  • the encapsulating resin composition of the present _ invention can be preferably used to seal a semiconductor device.
  • the semiconductor device can be, for example, a flip chip mounted semiconductor device obtained by mounting an active element such as a semiconductor chip, a transistor, a diode or a thyristor or a passive element such as a capacitor, a resistor or a coil on a support member or a mounting board such as a wired tape carrier, a circuit board or a glass board and then encapsulating with an epoxy resin molding material for encapsulating.
  • the encapsulating resin composition of the present invention is particularly suitable as a resin composition for underfilling (an underfill encapsulation material).
  • a resin composition for underfilling an underfill encapsulation material
  • the viscosity at 25°C is preferably 5,000 centipoise or lower, and more preferably from 500 to 3,000 centipoise, from the perspectives of workability and the properties of the obtained cured product.
  • the encapsulating method when using the encapsulating resin composition of the present invention is not particularly limited, and can be low pressure transfer molding, injection molding, compression molding and so on.
  • a dispensing method it is possible to use a casting method, a printing method and so on. From the perspective of filling properties, it is preferable to use a molding method that allows for molding under low pressure conditions.
  • the encapsulating resin composition of the present invention has a low viscosity, it is possible to use a method other than injecting from a narrow gap.
  • the encapsulating resin composition of the present invention has a low viscosity, and can therefore be effectively used in a method in which the resin composition is coated on a wafer using a variety of printing methods and this coated resin composition is then bonded while in a semi- cured state.
  • a semiconductor device obtained by encapsulating an element with the encapsulating resin composition obtained in the present invention can be, for example, a BGA or CSP (Chip Size Package) obtained by mounting an element on the surface of an organic or inorganic substrate having circuit board connection terminals formed on the rear surface thereof, connecting a circuit formed on an organic substrate to the element by bump joining or wire bonding, and then encapsulating the element with the encapsulating resin composition of the present invention.
  • BGA or CSP Chip Size Package
  • a flip chip mounted semiconductor device by aligning the surface of an element on which a circuit is formed face-to- face with the surface on which a circuit is formed of an organic or inorganic substrate to which the element is to be connected, electrically connecting the electrodes of the element to the circuit on the substrate via bumps, and then impregnating the gap between the element and the substrate with the encapsulating resin composition of the present invention.
  • This type of semiconductor device can be formed by connecting bump electrodes on a semiconductor chip to electrodes on the surface of a substrate, filling the above-mentioned encapsulating resin composition in the gap formed between the semiconductor chip and the substrate, and then curing the encapsulating resin composition so as to seal the above-mentioned gap.
  • the encapsulating resin composition of the present invention it is possible to use the encapsulating resin composition of the present invention on a wafer obtained by forming a bump on an electrode on a silicon wafer or on a wafer having bumps on both surfaces having through silicon vias.
  • the encapsulating resin composition of the present invention it is possible to form the encapsulating resin composition on the wafer using the various printing methods mentioned above and then leave the wafer to stand for from 5 to 120 minutes at from 10 to 120°C so as to obtain a B stage (semi-cured state).
  • SFP-30M Si0 2 filler (average particle diameter: 0.7 um, maximum particle diameter: 10 ⁇ , minimum particle diameter: 0.2 ⁇ , produced by Denki Kagaku Kogyo Kabushiki Kaisha)
  • HPS- 1000 Si0 2 filler (average particle diameter: 1 um, maximum particle diameter: 1.2 ⁇ , minimum particle diameter: 0.8 um, produced by Toagosei Co., Ltd.)
  • Tg measurements by the DMA method involved the use of a solid analyzer (RSA-III) manufactured by Rheometric Scientific in a three point curve mode (strain: 0.05%, frequency: 1 Hz). The size of the samples was 2 * 10 ⁇ 35 mm 3 , and the samples were heated at a rate of 3°C/minute.
  • Specific modulus of elasticity measurements used the three point curve method and involved placing the above-mentioned cuboid sample (size: 2 ⁇ 10 x 35 mm 3 ) on two knife edges (separated by 25 mm) and measuring the load used to push down on the central part of the sample, thereby deforming the sample.
  • the strain was applied as a sine wave having a maximum value of 0.05%, and the load was also measured as a sine wave (the frequency of the sine wave was 1 Hz).
  • thermal expansion coefficient was measured using a TMA 8310 thermomechanical analysis apparatus manufactured by Rigaku Corporation.
  • the sample was heated at a rate of 20°C/minute in a nitrogen stream.
  • the measurements were carried out in compression mode, and a load of 10 mN was applied during the measurements.
  • the sample size was 4 x 5 x 10 mm 3 .
  • the measurement results are shown in Table 4.

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Abstract

The present invention provides an encapsulating resin composition that is excellent in terms of thermal expansion coefficient and flowability and that can easily penetrate into a narrow gap. The encapsulating resin composition includes an epoxy resin, a curing agent, inorganic particles, an organic titanium compound and a phosphoric acid ester. The average particle diameter of the inorganic particles is about 10 μm or less. The amount of inorganic particles relative to a total amount of the composition is about 60 percent by mass or more. The amount of organic titanium compound relative to the total quantity of the composition is about 1 percent by mass or more and about 5 percent by mass or less. The amount of phosphoric acid ester relative to the total quantity of the composition is about 0.5 percent by mass or more and about 3 percent by mass or less.

Description

ENCAPSULATING RESIN COMPOSITION
Field of Invention
The present invention relates to an encapsulating resin composition and also to a semiconductor device encapsulated using the encapsulating resin composition.
Background
Heretofore encapsulation with resins such as epoxy resins has been carried out in the fields of encapsulation of semiconductor devices and the like. In recent years, smaller and thinner packages have been developed due to the densification of semiconductor devices.
Therefore, distances (gaps) between chips and substrates in semiconductors have been reduced and are expected to be further reduced in the future. As a result, encapsulation materials that can be used in narrower gaps are required.
U.S. Patent Application Publication No. 2005/0129956 describes an underfill composition comprising at least one epoxy resin in combination with at least one epoxy hardener, the at least one epoxy hardener comprising at least one difunctional siloxane anhydride.
PCT International Publication No. WO/2005/080502 describes a liquid epoxy resin composition for use in underfilling that contains an epoxy resin, a curing agent, a curing accelerator, an inorganic filler and a coupling agent, wherein the coupling agent has two or more structures represented by -Si(OR)„H3.n (n = 1 to 3) in the molecule, and the content of the coupling agent in the resin composition is 0.05 to 1.5 wt.%.
Japanese Unexamined Patent Application Publication No. 2004-256646 describes a resin composition for underfilling, which contains an epoxy resin, a curing agent, a curing accelerator and an inorganic filler, wherein the content of a polyfunctional epoxy resin is from 5 to 20 percent by mass relative to the total quantity of epoxy resin, a phenolic compound and an acid anhydride are used as the curing agent, and the content of the phenolic compound relative to the total quantity of curing agent is from 3 to 20 percent by mass. Summary of the Invention
For reasons of thermal expansion properties, encapsulating resin compositions are generally highly filled with inorganic particles. In addition to the high filling of these inorganic particles, from the perspective of the flowability of the obtained resin composition, inorganic particles having a relatively large average particle diameter (from 15 to 30 μηι) are used in encapsulating resin compositions in order to lower a viscosity of the composition. However, if a distance (gap) between a chip and a substrate in a semiconductor is reduced, in cases where the viscosity of an encapsulating resin composition is reduced through the use of inorganic particles having this sort of relatively large average particle diameter, a phenomenon can occur whereby the penetration of the encapsulating resin composition into the gap is inhibited due to the inorganic particles blocking the gap. Therefore, there is a need for an encapsulating resin composition that is excellent in terms of thermal expansion coefficient and flowability even if the average particle diameter of the inorganic particles is small and that can easily penetrate into a narrow gap.
In one embodiment, the present invention is an encapsulating resin composition containing an epoxy resin, a curing agent, inorganic particles, an organic titanium compound and a phosphoric acid ester. The average particle diameter of the inorganic particles is about 10 μπι or less. The amount of inorganic particles relative to a total amount of the encapsulating resin composition is about 60 percent by mass or more. The amount of organic titanium compound relative to the total quantity of the encapsulating resin composition is about 1 percent by mass or more and about 5 percent by mass or less. The amount of phosphoric acid ester relative to the total quantity of the encapsulating resin composition is about 0.5 percent by mass or more and about 3 percent by mass or less.
According to the present invention, an encapsulating resin composition is provided that is excellent in terms of thermal expansion coefficient and flowability and that can easily penetrate into a narrow gap.
Detailed Description of the Invention
Epoxy resins that can be used in the encapsulating resin composition of the present invention include aliphatic, alicyclic, aromatic or heterocyclic monomeric or oligomeric epoxy compounds. These materials generally have, on average, at least one polymerizable epoxy group per molecule, and may have at least 1.5 or at least 2 polymerizable epoxy groups per molecule. In certain modes, it is possible to use a polyfunctional epoxy compound having three or four polymerizable epoxy groups per molecule. The epoxy compound may be a pure compound or may be a mixture of compounds containing one, two, or more epoxy groups per molecule.
The epoxy compounds mentioned above may have any type of main chain and may contain substituent groups. Examples of allowable substituent groups include, but are not limited to: halogens, ester groups, ethers, sulfonate groups, siloxane groups, nitro groups, phosphate groups and the like. The epoxy equivalent value of the epoxy compound can generally be altered within a range of from 50 to 2,000.
Examples of oligomeric epoxy compounds include, but are not limited to: linear oligomers having terminal epoxy groups (i.e., a diglycidyl ether of a polyoxyalkylene glycol), oligomers having skeletal epoxy units (i.e., polybutadiene polyepoxide), and oligomers having pendant epoxy groups (i.e., a glycidyl methacrylate oligomer or co-oligomer).
In certain modes, it is possible to use a glycidyl ether monomer represented by the following formula.
Formula I
r OCH2 CH-CH2
In the formula, R is a radical having a valency of n, n being an integer between 1 and 6. R can be an aromatic group, an alicyclic group, an aliphatic group or a combination thereof. Typical epoxy compounds include glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of a chlorohydrin such as epichlorohydrin (for example, 2,2-bis-(2,3-epoxypropoxyphenol)-propane). Specifically, it is possible to use an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound and the like.
Examples of the aromatic epoxy compounds include, but are not limited to: a diglycidyl ether of bisphenol A (bisphenol A type epoxy resin), a diglycidyl ether of bisphenol F
(bisphenol F type epoxy resin), a diglycidyl ether of 4,4'-dihydroxybiphenyl, oligomers of these diglycidyl ethers, polyglycidyl ethers of cresol novolac resins (cresol novolac type epoxy resins) and polyglycidyl ethers of phenol novolac resins (phenol novolac type epoxy resins).
Examples of the alicyclic epoxy compounds include, but are not limited to: compounds obtained by hydrogenating the aromatic epoxy compounds mentioned above, such as hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds. In addition, it is possible to use compounds containing a cyclohexene oxide group, such as vinyl cyclohexene monoxide, l ,2-epoxy-4-vinyl cyclohexane, l ,2:8,9-diepoxylimonene, and epoxy cyclohexane carboxylates such as 3,4-epoxycyclohexenylmethyl-3',4'- epoxycyclohexene carboxylate, 3,4-epoxycyclohexenylmethyI-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane carboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate.
The aliphatic epoxy compounds include glycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Examples include, but are not limited to: ethylene glycol diglycidyl ether, di(ethylene glycol) diglycidyl ether, propylene glycol diglycidyl ether, tri(propylene glycol) diglycidyl ether, neopentyl glycol diglycidyl ether, 1 ,4-butane diol diglycidyl ether, 1,6-hexane diol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, poly(ethylene glycol) diglycidyl ether and the like.
In addition to the epoxy resins mentioned above, it is possible to use a halogenated epoxy resin (such as a brominated bisphenol type epoxy resin) or an epoxy compound having a glycidylamino group. Epoxy compounds having a glycidylamino group are epoxy compounds (epoxy resins) obtained by epoxidation by reacting amines and an epihalohydrin, and examples thereof include aminophenol type epoxy resins, triglycidyl isocyanurates, tetraglycidyl diaminodiphenylmethane, tetraglycidyl meta-xylenediamine and hexaglycidyl triaminobenzene.
The aminophenol type epoxy resins are obtained by epoxidizing aminophenols using publicly known methods. Examples of the aminophenols include, but are not limited to:
aminophenols and aminocresols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- amino-m-cresol, 2-amino-p-cresol, 3-amino-o-cresol, 4-amino-m-cresol and 6-amino-m-cresol.
Other epoxy resins able to be used include, but are not limited to, copolymers of acrylic acid esters of glycidol (such as glycidyl acrylate and glycidyl methacrylate) with one or more copolymerizable vinyl compounds. This type of copolymer includes styrene-glycidyl methacrylate and methyl methacrylate-glycidyl acrylate copolymers. In addition, it is also possible to use an epoxy-functional silicon, which is a polydimethyl siloxane in which silicon atoms have been substituted with epoxyalkyl groups.
Of the epoxy resins mentioned above, it is particularly suitable to use a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or an aminophenol type epoxy resin from the perspective of characteristics after curing the encapsulating resin composition. In addition, from the perspective of obtaining a balance between the viscosity of the encapsulating resin composition and the characteristics after curing, it is preferable to use both a bisphenol A type epoxy resin and a bisphenol F type epoxy resin or a three-component system obtained by further adding an aminophenol type epoxy resin to a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. Specifically, it is possible to use the product ZX1059 (produced by Tohto Kasei Co., Ltd., a mixture of bisphenol A and bisphenol F) or the aminophenol type epoxy jER (registered trademark) 630 (produced by Mitsubishi Chemical Corporation), both of which are commercially available.
An amount of the epoxy resin is generally 20 percent by mass or less, and from 10 to 20 percent by mass in some embodiments, relative to a total amount of the encapsulating resin composition. The curing agent contained in the encapsulating resin composition of the present invention can be a routine curing agent used to cure epoxy compounds. Specific examples thereof include, but are not limited to: amino compounds, acid anhydride compounds, amide compounds, phenolic compounds, trifluorinated boron complex compounds such as BF3- monoethanolamine, imidazoles such as 2-ethyl-4-methylimidazole, hydrazides such as aminodihydrazide, guanidines such as tetramethylguanidine, and dicyandiamide. The curing agent can be a single curing agent or a mixture of different curing agents. From the perspective of viscosity, an acid anhydride compound is particularly suitable.
It is possible to use a non-aromatic acid anhydride compound. For example, it is possible to use hexahydrophthalic acid anhydride, 3-methylhexahydrophthalic acid anhydride, 4-methylhexahydrophthalic acid anhydride, l-methylnorbornane-2,3-dicarboxylic acid anhydride, 5-methylnorbornane-2,3-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, 1-methylnadic acid anhydride, 5-methylnadic acid anhydride, nadic acid anhydride, tetrahydrophthalic acid anhydride, 3-methyltetraahydrophthalic acid anhydride, 4-methyltetrahydiophthalic acid anhydride, dodecenylsuccinic acid anhydride and the like.
Of these, it is particularly suitable to use hexahydrophthalic acid anhydride,
3-methylhexahydrophthalic acid anhydride, 4-methylhexahydrophthalic acid anhydride, l-methylnorbornane-2,3-dicarboxylic acid anhydride, 5-methylnorbornane-2,3-dicarboxyiic acid anhydride or norbornane-2,3-dicarboxylic acid anhydride, which do not have a double bond in the compound. A mixture of 4-methylhexahydrophthalic acid anhydride and hexahydrophthalic acid anhydride (such as Rikacid MH-700 produced by New Japan Chemical Co., Ltd.
(4-methylhexahydrophthalic acid anhydride/hexahydrophthalic acid anhydride ratio = 70/30) is particularly suitable due to an encapsulating resin composition that contains this mixture having a low viscosity and not being prone to crystallization.
Bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, l-(4- hydroxyphenyl)-2-[4-{ l ,l-bis-(4-hydroxyphenyl)ethyl}phenyl]propane, 2,2'-methylene-bis(4- methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol),
trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, diisopropylidene, phenols having a terpene skeleton, phenols having a fluorene skeleton such as l,l-di-4- hydroxyphenylfluorene, phenolated polybutadienes, phenol, cresols, ethylphenols, butylphenols, octylphenoJs, and novolac resins such as novolac resins obtained using phenols such as bisphenol A, bisphenol F, bisphenol S, naphthols, terpene diphenols and the like as raw materials, phenol novolac resins having a xylylene skeleton, phenol novolac resins having a dicyclopentadiene skeleton, phenol novolac resins having a biphenyl skeleton, phenol novolac resins having a fluorene skeleton and phenol novolac resins having a furan skeleton can be used as phenol-based curing agents.
Aliphatic amines such as diethylenetriamine, triethylenetetramine or
tetraethylenepentamine, aromatic amines such as diaminodiphenylmethane,
diaminodiphenylsulfone, meta-xylenediamine and condensation products of aromatic amines and aldehydes, polyamidoamines and the like can be used as amino-based curing agents.
From the perspective of the characteristics of the obtained cured product, an amount of the curing agent is particularly approximately equal to the quantity of the epoxy resin. In general, the quantity of the curing agent is from 5 to 15 percent by mass relative to total weight of the encapsulating resin composition.
Inorganic particles are dispersed substantially homogeneously in the encapsulating resin composition of the present invention. The inorganic particles are used in order to impart the encapsulating resin composition with a high modulus of elasticity and a low thermal expansion coefficient, and it is possible to use a single type or a combination of two or more types of inorganic particles. In general, these inorganic particles can be a powder such as silica (molten silica, crystalline silica), alumina, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite or titania, or beads, glass fibers and the like obtained by conglobating these powders. It is possible to use a single type or a combination of two or more types of these inorganic particles.
Of the inorganic particles mentioned above, molten silica is particularly suitable from the perspective of thermal expansion properties and crystalline silica and alumina are particularly suitable from the perspective of having high thermal conductivity. In addition, when producing silica particles as inorganic particles from an organic sol, because the particle size distribution thereof is narrow, it is possible to effectively distribute the particles in the resin composition. Moreover, the shape of the primary particles of the inorganic particles is not particularly important, but spherical particles are particularly suitable from the perspective of being able to flow and penetrate into fine gaps.
In addition, from the perspective of the flowability of the encapsulating resin composition, it is particularly suitable for the inorganic particles to have a small average particle diameter and a narrow particle size distribution. Because the inorganic particles are prone to stacking when the encapsulating resin composition is forced into a narrow gap, the inorganic particles used in the present invention have an average particle diameter of 10 um or less. In addition, the average particle diameter of the inorganic particles is particularly 5 um or less, more particularly 3 μπι or less, and even more particularly 2 μπι or less. However, the lower limit of the average particle diameter of the inorganic particles is not particularly restricted, but from the perspective of flowability, 0.5 μπι or higher is preferred in the case of silica particles, and 0.1 μπι or higher is preferred in the case of alumina particles. In addition, the particle diameter of the inorganic particles in the encapsulating resin composition is preferably within the range "average particle diameter ± (average particle diameter x 0.3)" (for example, 1 ± 0.3 μπι). The average particle diameter and particle size distribution of the inorganic particles can be measured with an electron microscope or a laser scattering device. Moreover, the inorganic particles may be surface treated to an extent that does not impair the dispersibility of the particles in the resin composition.
Silica particles prepared by the sol-gel method and having a narrow particle size distribution are preferred as the inorganic particles, and molten silica having an average particle diameter of from 0.8 to 1.8 μπι, prepared by the sol-gel method and having a narrow particle size distribution (average particle diameter ± (average particle diameter x 0.3)) are more preferred. Such inorganic particles are commercially available as, for example, Silica HPS- 1000 (produced by Toagosei Co., Ltd. by the sol-gel method) or Silica SS-07, SS-10 and SS-14 (produced by Tokuyama Corporation by the sol-gel method).
An amount of inorganic particles in the encapsulating resin composition is preferably 60 percent by mass or more relative to the total quantity of the encapsulating resin composition from the perspective of the thermal expansion coefficient of the cured product, and is particularly 90 percent by mass or less relative to the total quantity of the encapsulating resin composition from the perspective of the viscosity of the resin composition. If the amount of inorganic particles falls within this range, it is generally possible to obtain a cured product having a thermal expansion coefficient of 35 ppm or less and also possible for the encapsulating resin composition of the present invention to be used as an encapsulating resin composition for a semiconductor.
Organic titanium compounds able to be used in the encapsulating resin composition of the present invention include organic titanium compounds having a hydrolyzable group and a hydrophobic group in the compound. Such organic titanium compounds are generally known as titanium coupling agents. The organic titanium compound reacts with -OH groups on the surface of the inorganic particles and, for example, forms covalent bonds with the titanium by eliminating an alcohol by hydrolysis. It is thought that this makes the surface of the inorganic particles organic, which results in good dispersibility of the inorganic particles in the epoxy resin.
The hydrolyzable group in the organic compound can be R'O-, -O-CH2-CH2-O- or -0-CH2-C(=0)-0- and the like. Here, R1 can be a substituted or unsubstituted, straight chain or branched chain alkyl group, alkenyl group, aryl group or aralkyl group. Because R1 is eliminated after the reaction with the inorganic particles (i.e., eliminated by forming an alcohol), it is particularly suitable for Rl to be a group having a somewhat lower boiling point following elimination. Therefore, R1 is particularly a group having few carbon atoms, and preferably a substituted or unsubstituted, straight chain or branched chain alkyl group having 1 to 10 carbon atoms (and more particularly 1 to 8 carbon atoms).
[0037]
In addition, the hydrophobic group in the organic titanium compound can be
-0-C(=0)-R2, -0-S(=0)2-Ph-R2, -0-P(=0)(-OH)-0-P(=0)-(OR2)2, -0-P(=0)-(OR2)2,
HO-P-(OR2)2, -0-(CH2)m-NH-(CH2)n-NH2 and the like. Here, Ph denotes a phenyl group, m and n are each an integer from 1 to 10, and R2 can be a substituted or unsubstituted, straight chain or branched chain alkyl group, alkenyl group, aryl group or aralkyl group. In order to improve the efficiency with which the surface of the inorganic particles is covered, R2 is particularly a group having many carbon atoms, and particularly a substituted or unsubstituted, straight chain or branched chain alkyl group having from 8 to 30 carbon atoms.
Of these, -0-C(=0)-R2, HO-P-(OR )2 and -0-(CH2)m-NH-(CH2)n-NH2 are particularly suitable hydrophobic groups from the perspectives of reactivity with the inorganic particles in the encapsulating resin composition and reduced viscosity of the encapsulating resin
composition. From the perspective of flowability, -0-C(=0)-R2 or HO-P-(OR2)2 is particularly suitable, and from the perspective of the stability of the titanium coupling agent, -0-C(=0)-R2 is particularly suitable. Here, R is a substituted or unsubstituted, straight chain or branched chain alkyl group having from 8 to 30 carbon atoms, and preferably 10 to 30 carbon atoms.
Specifically, the titanium coupling agent can be a tetraalkoxy titanium (such as tetraethoxy titanium, tetraisopropoxy titanium or tetrabutoxy titanium), tetra(ethylene glycol) titanate, di-n-butylbis(triethanolamine) titanate, di-isopropoxy bis(acetyl acetonate)titanium, isopropoxy titanium octanoate, isopropyl titanium trimethacrylate, isopropyl titanium triacrylate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl (butyl, methylpyrophosphate) titanate, tetraisopropyl di(dilauryl phosphite) titanate,
dimethacryloxyacetate titanate, diacryloxyacetate titanate, di(dioctyl phosphite)ethylene titanate, isopropoxy titanium tri(dioctyl phosphate), isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-l -butyl) bis(di-tridecyl)phosphite titanate, bis(dioctyl
pyrophosphate)oxyacetate titanate, tris(dioctyl pyrophosphate)ethylene titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate and the like.
KRTTS (isopropyltriisostearoyl titanate (CH3)2CHOTi[OCO(CH2)i4CH(CH3)2]3),
R 46B (tetraoctylbis(di-tridecylphosphite) titanate), KR 55 (tetra(2,2-diallyloxymethyl- l- butyl) bis(di-tridecyl) phosphite titanate), KR 41B (tetraisopropylbis(dioctylphosphite) titanate), KR 38S (isopropyltris(dioctylpyrophosphate) titanate), KR 138S
(bis(dioctylpyrophosphate)oxyacetate titanate), KR 238S (tris(dioctylpyrophosphate)ethylene titanate), 338X (isopropyldioctylpyrophosphate titanate), KR 44 (isopropyltri(N- aminoethylaminoethyl) titanate) and KR 9SA (isopropyltris(dodecylbenzylphenyl) titanate and the like of the Plenact (registered trademark) series, which is sold by Ajinomoto Fine-Techno Co., Inc., can be used. Plenact KR TTS, KR 46B and KR 9SA are preferred, and Plenact KR TTS and KR 46B are particularly suitable.
From the perspective of reducing the viscosity of the encapsulating resin composition, an amount of the organic titanium compound is 1 percent by mass or more, particularly 2 percent by mass or more, and more particularly 2.5 percent by mass or more, relative to the total quantity of the encapsulating resin composition. However, from the perspectives of reduced glass transition temperature and modulus of elasticity of the obtained cured product, the quantity of the organic titanium compound is 5 percent by mass or less, particularly 4 percent by mass or less, and more particularly 3 percent by mass or less, relative to the total quantity of the encapsulating resin composition.
Among organic phosphoric acid compounds, phosphoric acid esters able to be used in the encapsulating resin composition of the present invention include esters obtained by subjecting phosphoric acid and an alcohol to dehydrocondensation. By further adding a phosphoric acid ester to the above-mentioned organic titanium compound, the phosphoric acid ester forms weak bonds, such as coordinate bonds, with the titanium. As a result, the organic layer on the surface of the inorganic particles, which is rendered organic by the organic titanium compound, increases in depth.
Specifically, the phosphoric acid ester has a structure in which all or some of the hydrogen atoms in the phosphoric acid (OP(OH)3) are replaced by organic groups. Compounds in which 1 , 2 and 3 hydrogen atoms are replaced are known as a phosphoric acid monoester ((HO)2POZ) , a phosphoric acid diester (HOP(OZ)2) and a phosphoric acid triester (P(OZ)3) respectively. Here, Z denotes a substituted or unsubstituted alkyl group, phenyl group, polyester or polycaprolactone having from 10 to 50 carbon atoms and the like. From the perspective of increasing the thickness of the organic layer formed on the surface of the inorganic particles, it is preferable for Z to have a high molecular weight. Specifically, a weight average molecular weight of from 200 to 20,000 is suitable and a weight average molecular weight of from 300 to 10,000 is particularly suitable.
For example, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, monobutyl phosphate, dibutyl phosphate, mono-2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, monophenyl phosphate, mono-2-ethylhexyl phosphite, dioctyl phosphate, diphenyl phosphate and the like can be used as the compound mentioned above. Specifically, commercially available products such as Disperbyk 1 1 1 produced by BYK Chemicals Japan can be obtained.
Of the phosphoric acid esters mentioned above, phosphoric acid diesters are particularly suitable, and phosphoric acid diesters in which Z is a polycaprolactone are more particularly suitable, from the perspective of dispersion of the inorganic particles.
From the perspective of reducing the viscosity of the encapsulating resin composition, an amount of the phosphoric acid ester is 0.5 percent by mass or more, particularly 1 percent by mass or more, and more particularly 1.2 percent by mass or more, relative to the total quantity of the encapsulating resin composition. However, from the perspective of the possibility of causing a reduction in the electrical properties (insulating properties) of the obtained cured product, the quantity of the phosphoric acid ester is 3 percent by mass or less, particularly 2 percent by mass or less, and more particularly 1.8 percent by mass or less, relative to the total quantity of the encapsulating resin composition.
As mentioned above, by combining an organic titanium compound with a phosphoric acid ester, it is possible to improve the dispersibility of the inorganic particles in the epoxy resin and to improve the flowability of the obtained encapsulating resin composition. In particular, a combination of an organic titanium compound having a chemical structure represented by R3OTi(OCOR4H)3 or (R30)4Ti[HOP(OR4)2] (here, R3 denotes a straight chain or branched chain alkyl group having from 3 to 8 carbon atoms and R4 denotes a straight chain or branched chain alkyl group having from 10 to 20 carbon atoms.) and a phosphoric acid diester having a weight average molecular weight of from 200 to 20,000 and having a chemical structure represented by HOP(OZ)2 (here, Z denotes a substituted or unsubstituted alkyl group, phenyl group, polyester or polycaprolactone having from 10 to 50 carbon atoms) is particularly suitable. In addition to the components mentioned above, the encapsulating resin composition of the present invention may also contain a reaction accelerator. Here, the reaction accelerator used to accelerate the reaction between the epoxy resin and the curing agent can be a commonly used and publicly known reaction accelerator such as a cycloamidine compound, a tertiary amine, a quaternary ammonium salt, an imidazole, an organic metal compound that acts as a Lewis acid, a phosphorus-based compound such as an organic phosphine such as triphenyl phosphine, or a derivative or tetraphenyl boron salt thereof. A single reaction accelerator or a combination of two or more types thereof can be used. Moreover, the quantity of the reaction accelerator is not particularly limited as long as a reaction acceleration effect is achieved.
In addition, it is possible to blend an ion trapping agent in the encapsulating resin composition of the present invention in order to improve the moisture resistance and high temperature exposure characteristics of a semiconductor device. The ion trapping agent is not particularly limited, and a publicly known ion trapping agent may be used. Specifically, it is possible to use hydrotalcite or a water-containing oxide of an element such as magnesium, aluminum, titanium, zirconium or bismuth.
Furthermore, stress relaxing agents such as silicone rubber powders, dyes, colorants such as carbon black, leveling agents, anti-foaming agents and other inorganic fillers (for example, inorganic fillers having a flame retardant effect, such as aluminum hydroxide, magnesium hydroxide, zinc silicate or zinc molybdate) may be blended in the encapsulating resin composition of the present invention at levels that do not impair the object of the present invention. In addition, red phosphorus, phosphoric acid esters, melamine, melamine derivatiyes, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives or isocyanuric acid derivatives, phosphorus- and nitrogen-containing compounds such as cyclophosphazene, metal compounds such as zinc oxide, iron oxide, molybdenum oxide and ferrocene, antimony oxides such as antimony trioxide, antimony tetraoxide and antimony pentoxide, and flame retardants such as brominated epoxy resins may also be blended in the encapsulating resin composition of the present invention.
A cured product of the encapsulating resin composition of the present invention has a thermal expansion coefficient of from 10 to 35 ppm. Because silicon has a low thermal expansion coefficient, it is preferable for a material used to seal silicon to also have a low thermal expansion coefficient when encapsulating a semiconductor. If the thermal expansion coefficient exceeds 35 ppm, there are concerns over cracks occurring due to thermal stress. Moreover, it is possible to use a TMA (Thermal Mechanical Analyzer) to measure the thermal expansion coefficient. Specifically, it is possible to measure the thermal expansion coefficient with a TMA 8310 thermomechanical analysis apparatus manufactured by Rigaku Corporation. A sample (size: 4 x 5 >< 10 mm3) is heated at a rate of 20°C/minute in a nitrogen stream, a load of 10 mN is applied and measurements are carried out in compression mode.
In addition, the encapsulating resin composition of the present invention has good flowability. Here, a viscosimeter can be used to measure the flowability, but it is sometimes not possible to determine whether or not the composition has actually penetrated into a narrow gap from viscosity values alone. Therefore, the most direct method is to measure the time taken for the resin composition to penetrate into a pair of plane parallel plates separated by a fixed gap. When measuring the penetration of this type of resin composition, two glass plates of different sizes are used. For example, a large glass plate measuring 40 χ 40 χ 1 mm3 and a small glass plate measuring 30 30 χ 1 mm3 are prepared, adhesive tape having a thickness of 40 μπι and dimensions of 30 5 mm2 is applied to two of the edges of the small glass plate, and the large glass plate is applied thereto so as to form a gap of 40 μηι between the glass plates. With the large glass plate on the bottom, the glass plates are placed on a hot plate adjusted to a temperature of 100°C, a resin is supplied to one edge of the small glass plate and the relationship between elapsed time and penetration distance of the resin is measured, thereby confirming the flowability of the encapsulating resin composition. In the present invention, it is possible to adjust the measured time required for penetration of the encapsulating resin composition within the range of from 10 to 1 ,000 seconds by using this measurement method. If the penetration time is 10 seconds or shorter, the viscosity of the resin composition is too low, meaning that it is easy for air bubbles to enter, and if the penetration time is 1 ,000 seconds or longer, workability is poor when actually using the resin composition as an encapsulating material.
In addition, a cured product of the encapsulating resin composition of the present invention has a glass transition temperature (Tg) of from 60 to 120°C and modulus of elasticity (dynamic storage modulus; E') of from 5 to 40 GPa. Moreover, the glass transition temperature and modulus of elasticity can be measured using a DMA (dynamic mechanical analysis) apparatus. The method of measurement involves the use of a solid analyzer (RSA-III) manufactured by Rheometric Scientific in a three point curve mode (strain: 0.05%, frequency: 1 Hz) and a sample (size: 2 10 χ 35 mm3) heated at a rate of 3°C/minute.
Specifically, it is possible to use the three point curve method to measure the modulus of elasticity (dynamic storage modulus) by placing the above-mentioned cuboid sample (size: 2 χ 10 x 35 mm3) on two knife edges (separated by 25 mm) and measuring the load used to push down on the central part of the sample, thereby deforming the sample. In this case, the strain is applied as a sine wave having a maximum value of 0.05%, and the load is also measured as a sine wave (the frequency of the sine wave is 1 Hz).
As long as the components mentioned above can be blended and dispersed uniformly, the encapsulating resin composition of the present invention may be produced using any type of production method. A common production method is to blend the specified amounts of the raw materials either together or separately, stir, dissolve, mix and disperse these components in a mixing roller, extruder, planetary mixer and the like while, if necessary, heating and cooling, and then to cool and, if necessary, defoam and crush the resulting mixture. Moreover, it is also possible firstly to prepare a mixture of all the components except the inorganic particles and then to add the inorganic particles to this mixture to obtain the encapsulating resin composition. In addition, it is also possible to form the encapsulating resin composition into tablets having dimensions and weights appropriate to the molding conditions if required.
As mentioned above, it is possible for the encapsulating resin composition of the present invention to have a low viscosity even though inorganic particles having a low average particle diameter are filled at a high density. Therefore, the encapsulating resin composition of the present invention is excellent in terms of thermal expansion coefficient and flowability and can penetrate easily into a narrow gap. The encapsulating resin composition of the present invention can be used in a variety of applications, and can be used in any type of common electronic component application. For example, the encapsulating resin composition of the present invention can be used in capacitors, resistors, semiconductor devices, integrated circuits, transistors, diodes, triodes, thyristers, coils, varistors, connectors, convenors, microswitches and composite parts obtained therefrom. The encapsulating resin composition of the present _ invention can be preferably used to seal a semiconductor device. The semiconductor device can be, for example, a flip chip mounted semiconductor device obtained by mounting an active element such as a semiconductor chip, a transistor, a diode or a thyristor or a passive element such as a capacitor, a resistor or a coil on a support member or a mounting board such as a wired tape carrier, a circuit board or a glass board and then encapsulating with an epoxy resin molding material for encapsulating.
The encapsulating resin composition of the present invention is particularly suitable as a resin composition for underfilling (an underfill encapsulation material). For example, it is possible to fill the encapsulating resin composition of the present invention in the gap between a polyimide substrate on which a copper circuit is formed and a semiconductor chip mounted on this substrate, and then cure by heating and drying to form a cured film of the encapsulating resin composition of the present invention in this gap. After forming this cured film of the encapsulating resin composition, the surface of the copper circuit is protected by applying a coverlay. When using the encapsulating resin composition of the present invention as a underfill encapsulation material, the viscosity at 25°C is preferably 5,000 centipoise or lower, and more preferably from 500 to 3,000 centipoise, from the perspectives of workability and the properties of the obtained cured product.
The encapsulating method when using the encapsulating resin composition of the present invention is not particularly limited, and can be low pressure transfer molding, injection molding, compression molding and so on. In addition, it is possible to use a dispensing method, a casting method, a printing method and so on. From the perspective of filling properties, it is preferable to use a molding method that allows for molding under low pressure conditions. Moreover, because the encapsulating resin composition of the present invention has a low viscosity, it is possible to use a method other than injecting from a narrow gap. Specifically, it is possible to apply the resin composition to a substrate using a variety of methods, such as spin coating, stencil coating, jet dispensing, screen printing and pad coating. By crimping an adherend on a printed resin, it is possible to obtain a structure embedded between a substrate and the adherend.
As the pitch and height of semiconductor bumps has decreased in recent years, there has been a tendency for the gap between the semiconductor and the substrate following bump joining to become smaller, and an encapsulating resin composition which is able to penetrate into narrow gaps, such as that of the present invention, is therefore suitable. In addition, the encapsulating resin composition of the present invention has a low viscosity, and can therefore be effectively used in a method in which the resin composition is coated on a wafer using a variety of printing methods and this coated resin composition is then bonded while in a semi- cured state.
A semiconductor device obtained by encapsulating an element with the encapsulating resin composition obtained in the present invention can be, for example, a BGA or CSP (Chip Size Package) obtained by mounting an element on the surface of an organic or inorganic substrate having circuit board connection terminals formed on the rear surface thereof, connecting a circuit formed on an organic substrate to the element by bump joining or wire bonding, and then encapsulating the element with the encapsulating resin composition of the present invention. More specifically, it is possible to obtain, for example, a flip chip mounted semiconductor device by aligning the surface of an element on which a circuit is formed face-to- face with the surface on which a circuit is formed of an organic or inorganic substrate to which the element is to be connected, electrically connecting the electrodes of the element to the circuit on the substrate via bumps, and then impregnating the gap between the element and the substrate with the encapsulating resin composition of the present invention. This type of semiconductor device can be formed by connecting bump electrodes on a semiconductor chip to electrodes on the surface of a substrate, filling the above-mentioned encapsulating resin composition in the gap formed between the semiconductor chip and the substrate, and then curing the encapsulating resin composition so as to seal the above-mentioned gap. In addition, it is possible to use the encapsulating resin composition of the present invention on a wafer obtained by forming a bump on an electrode on a silicon wafer or on a wafer having bumps on both surfaces having through silicon vias. When using the encapsulating resin composition of the present invention on a wafer, it is possible to form the encapsulating resin composition on the wafer using the various printing methods mentioned above and then leave the wafer to stand for from 5 to 120 minutes at from 10 to 120°C so as to obtain a B stage (semi-cured state).
Examples
Preparation of encapsulating resin compositions
Component used
The components used to prepare the encapsulating resin compositions are shown in
Table 1.
Table 1
Figure imgf000016_0001
Compound name
DisperByk-1 1 1 Phosphoric acid ester (Mw=940) (product name DisperByk-1 1 1 , produced by BYK Chemicals Japan)
HOPOrO{(CH2)4COO}m{(CH2)s COO}„{(CH2)20}aCH3l2
DisperByk-145 Phosphoric acid ester (Mw=1700) (product name DisperByk- 145, produced by BYK Chemicals Japan) HOPO(OR)(OR)' (R and R' are both polyester chains)
TXP Trixylylene phosphate (Mw=410) (product name TXP, phosphoric acid ester, produced by Daihachi Chemical Industry Co., Ltd.)
SFP-30M Si02 filler (average particle diameter: 0.7 um, maximum particle diameter: 10 μπι, minimum particle diameter: 0.2 μπι, produced by Denki Kagaku Kogyo Kabushiki Kaisha)
HPS- 1000 Si02 filler (average particle diameter: 1 um, maximum particle diameter: 1.2 μπι, minimum particle diameter: 0.8 um, produced by Toagosei Co., Ltd.)
SS-10 Si02 filler (average particle diameter: 1 um, maximum particle diameter: 2 μπι, minimum particle diameter: 0.5 μηι, produced by Tokuyama Coφόration)
AA-3 A12C>3 filler (average particle diameter: 3 μπι, minimum particle diameter: 2.7 μπι, produced by Sumitomo Chemical Co., Ltd.)
Working examples 1-1 1 and comparative examples 1-4
(Preparation of encapsulating resin compositions)
In accordance with the compositions shown in Table 2, the components were added to a planetary mixer (Thinky Model AR250) and blended by stirring at 3000 rpm at room temperature so as to produce the encapsulating resin compositions of Working Examples 1-1 1 and Comparative Examples 1 -4.
Table 2
Figure imgf000018_0001
(Units: percent by mass)
Evaluation of the encapsulating resin compositions
Flowabiiitv (penetration time")
The time required for the encapsulating resin compositions obtained above to penetrate between glass plates (upper plate 30 mm χ 30 mm, lower plate 40 mm χ 40 mm) separated by a gap of 40 μπι was measured. The glass plates were placed on a hot plate at a temperature of 100°C and the encapsulating resin composition was applied to the edge of the upper plate. The time required for the encapsulating resin composition to penetrate 10 mm from the edge of the upper plate was measured, and the measurement results are shown in Table 3.
Table 3
Figure imgf000020_0001
Measurement of Tg, modulus of elasticity and thermal expansion coefficient
A sample obtained by curing the encapsulating resin composition of Working Example 1 for 2 hours at 150°C and samples obtained by curing the encapsulating resin compositions of working examples 2 and 10 for 2 hours at 165°C were prepared and measured for glass transition temperature. (Tg), modulus of elasticity (dynamic storage modulus; E') (DMA method) and thermal expansion coefficient (CTE). The Tg measurements by the DMA method involved the use of a solid analyzer (RSA-III) manufactured by Rheometric Scientific in a three point curve mode (strain: 0.05%, frequency: 1 Hz). The size of the samples was 2 * 10 χ 35 mm3, and the samples were heated at a rate of 3°C/minute. Specific modulus of elasticity measurements used the three point curve method and involved placing the above-mentioned cuboid sample (size: 2 χ 10 x 35 mm3) on two knife edges (separated by 25 mm) and measuring the load used to push down on the central part of the sample, thereby deforming the sample. In this case, the strain was applied as a sine wave having a maximum value of 0.05%, and the load was also measured as a sine wave (the frequency of the sine wave was 1 Hz).
In addition, the thermal expansion coefficient was measured using a TMA 8310 thermomechanical analysis apparatus manufactured by Rigaku Corporation. The sample was heated at a rate of 20°C/minute in a nitrogen stream. The measurements were carried out in compression mode, and a load of 10 mN was applied during the measurements. The sample size was 4 x 5 x 10 mm3. The measurement results are shown in Table 4.
Table 4
Figure imgf000021_0001

Claims

1. An encapsulating resin composition comprising:
an epoxy resin;
a curing agent;
inorganic particles;
an organic titanium compound; and
a phosphoric acid ester;
wherein an average particle diameter of the inorganic particles is about 10 μιη or less, wherein an amount of the inorganic particles relative to a total amount of the
encapsulating resin composition is about 60 percent by mass or more, wherein an amount of the organic titanium compound relative to the total quantity of the encapsulating resin composition is about 1 percent by mass or more and about 5 percent by mass or less, and
wherein an amount of the phosphoric acid ester relative to the total quantity of the
encapsulating resin composition is about 0.5 percent by mass or more and about 3 percent by mass or less.
2. The encapsulating resin composition according to claim 1, wherein the average particle diameter of the inorganic particles is about 5 um or less.
3. The encapsulating resin composition according to claim 1 or claim 2, wherein the encapsulating resin composition is an underfill encapsulation material.
4. A semiconductor device encapsulated with the encapsulating resin composition according to any one of claims 1 to 3.
PCT/US2011/045894 2010-08-04 2011-07-29 Encapsulating resin composition WO2012018684A1 (en)

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