Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/40—Carbon monoxide
• • 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
  • H01L23/295—Organic, e.g. plastic containing a filler
• • 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
  • H01L2924/0001—Technical content checked by a classifier
  • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0209—Inorganic, non-metallic particles

Definitions

• the present invention relates to a siliceous powder, a production method thereof and an application.
• semiconductors are rapidly becoming smaller, thinner, and higher in density.
• a semiconductor mounting method surface mounting suitable for high-density mounting on a wiring board or the like is mainly used.
• an ultra-thin semiconductor package has been used, and the thickness of the package has become very thin.
• a PoP (Package-on-Package) mounting method in which another semiconductor is mounted on a semiconductor has been put into practical use, and the semiconductor has been further reduced in thickness.
• Patent Document 1 a technique has been adopted in which bending strength is improved and stress is reduced by a technique of improving an epoxy resin, a phenol resin curing agent, or the like used for a semiconductor sealing material.
• Patent Document 2 a technique of improving an epoxy resin, a phenol resin curing agent, or the like used for a semiconductor sealing material.
• Patent Document 1 a technique of improving an epoxy resin, a phenol resin curing agent, or the like used for a semiconductor sealing material
• Patent Document 2 a technique of improving an epoxy resin, a phenol resin curing agent, or the like used for a semiconductor sealing material
• these methods do not provide sufficient bending strength improvement effects, and semiconductor encapsulants that can withstand mounting temperatures with lead-free solder and have significantly improved solder crack resistance are still available in thinner packages than before. Absent.
• An object of the present invention is to provide a siliceous powder suitable for the preparation of a semiconductor encapsulant having improved bending strength and further improved solder crack resistance.
• the present inventor conducted extensive research to achieve the above object, and found a siliceous powder that achieves this.
• the present invention is based on such knowledge and has the following gist.
• SiO 2, Al 2 O 3, and the content of B 2 O 3 (as oxide) is at total least 99.5 wt% of the total content of Al 2 O 3 and B 2 O 3
• the siliceous powder according to the above (1) in which is 0.1 to 20% by mass.
• the siliceous powder according to the above (1) or (2) which has a specific surface area of 0.5 to 5 m 2 / g and an average particle diameter of 1 to 60 ⁇ m.
• An inorganic powder comprising the siliceous powder according to any one of (1) to (3) above.
• At least two burners are arranged in the furnace body at an angle of 2 to 10 ° with respect to the central axis of the furnace body, and raw siliceous powder is supplied from one burner to at least one burner.
• a resin composition having improved bending strength and solder crack resistance particularly a resin composition as a semiconductor sealing material, and a siliceous powder suitable for preparing the resin composition are provided. Is done.
• the siliceous powder of the present invention is a siliceous powder having a Freundlich adsorption constant K of pyridine of 1.3 to 5.0. Since pyridine, which is a basic substance, adsorbs on the acid sites on the surface of the siliceous powder, the larger the value of the adsorption constant K of this material, the greater the number of acid sites on the surface of the siliceous powder. When the acid point of the siliceous powder is large, the bonding point with a basic silane coupling agent such as aminosilane or phenylaminosilane increases.
• a basic silane coupling agent such as aminosilane or phenylaminosilane
• the adhesion between the resin component such as epoxy resin and phenol resin in the semiconductor sealing material and the surface of the siliceous powder becomes stronger, the bending strength is improved, and moisture is present at the interface between the resin component and the siliceous powder. Since it becomes difficult to penetrate, solder crack resistance is also greatly improved.
• the Freundlich adsorption constant K of pyridine is less than 1.3, the bonding point between the silane coupling agent and the siliceous powder is reduced, so that the bending strength and solder crack resistance of the semiconductor encapsulant are remarkably improved. I can't.
• Freundlich adsorption constant K of pyridine exceeds 5.0, the number of acid sites on the surface of the siliceous powder becomes too large and the epoxy resin is cured. For this reason, since the viscosity of the sealing material at the time of packaging a semiconductor using a semiconductor sealing material rises, the malfunction that a moldability will be impaired will arise.
• the value of Freundlich adsorption constant K of pyridine is preferably 1.5 to 4.5, particularly preferably 2.0 to 4.3. These values are specific when compared with the values of Freundlich adsorption constant K of conventional siliceous powders of 0.07 to 0.8.
• the Freundlich adsorption constant K of pyridine can be measured by the following procedure.
• log K is obtained from the Y axis intercept, and K can be calculated.
• A is the amount of pyridine adsorbed on 1 g of siliceous powder ( ⁇ mol / g)
• C is the residual pyridine concentration ( ⁇ mol / ml) in the supernatant
• K and n are constants.
• An example of an ultraviolet-visible spectrophotometer used for measurement is “Ultraviolet-visible spectrophotometer model UV-1800” manufactured by Shimadzu Corporation.
• Examples of the reagent used to prepare the pyridine standard solution are pyridine (grade for spectroscopic analysis) and n-heptane (grade for spectroscopic analysis) manufactured by Wako Pure Chemical Industries, Ltd.
• the absorbance measurement wavelength was 251 nm, and only n-heptane was measured to correct the background.
• 0.00 mmol / l, 0.25 mmol / l, 0.50 mmol / l, and 1.00 mmol / l pyridine standard solutions were used.
• the siliceous powder of the present invention is characterized in that the total content of SiO 2 , Al 2 O 3 , and B 2 O 3 (as oxide) is 99.5% by mass or more, and Al 2 O 3 and The total content of B 2 O 3 is 0.1 to 20% by mass.
• the total content of SiO 2 , Al 2 O 3 , and B 2 O 3 is less than 99.5% by mass, that is, the content other than SiO 2 , Al 2 O 3 , and B 2 O 3 is 0.5% by mass. If it exceeds 50%, a substance that becomes an unnecessary impurity increases when the semiconductor sealing material is used, which is not preferable.
• the total content of SiO 2 , Al 2 O 3 , and B 2 O 3 is preferably 99.6% by mass or more, and more preferably 99.7% by mass or more.
• the total content of Al 2 O 3 and B 2 O 3 in the siliceous powder is preferably 0.1 to 20% by mass.
• This acid point increases the bonding point between the basic silane coupling agent and the surface of the siliceous powder, thereby improving the bending strength and solder crack resistance.
• the acid point is not sufficiently increased.
• the thermal expansion coefficient of the siliceous powder Becomes too large and adversely affects solder crack resistance.
• the total content of Al 2 O 3 and B 2 O 3 is more preferably 0.2 to 18% by mass, still more preferably 0.3 to 15% by mass.
• the SiO 2 content (oxide conversion) of the siliceous powder of the present invention is the mass reduction method
• the Al 2 O 3 content (oxide conversion) is the atomic absorption analysis method
• the B 2 O 3 content (oxide conversion) is The measurement can be performed by the following procedure using ICP emission analysis.
• (1) Measurement of SiO 2 content 2.5 g of siliceous powder is precisely weighed in a platinum dish, and 20 ml, 1 ml and 1 ml of reagent-grade hydrofluoric acid, reagent-grade sulfuric acid and pure water are added to the platinum dish. The platinum dish is allowed to stand on a sand bath heated to 300 ° C. for 15 minutes to dissolve and dry the powder.
• a platinum dish is put in a muffle furnace heated to 1000 ° and heated for 10 minutes to evaporate fluorinated silicic acid. After cooling to room temperature in a desiccator, the mass of the platinum dish is precisely weighed, and the content of SiO 2 in the siliceous powder is calculated from the mass reduction rate.
• An example of an atomic absorption photometer is the product name “Atomic Absorption Photometer Model AA-969” manufactured by Nippon Jarrel Ash.
• An example of a standard solution used for preparing a calibration curve is an Al standard solution for atomic absorption (concentration 1000 ppm) manufactured by Kanto Chemical. Note that an acetylene-nitrous oxide flame was used as a flame for measurement, and the absorbance at a wavelength of 309.3 nm was measured and quantified.
• the amount of B in this solution is quantified by a calibration curve method using an ICP emission spectroscopic analyzer.
• the amount of B is converted into B 2 O 3 to calculate the content in the siliceous powder.
• an ICP emission spectroscopic analyzer is a trade name “Model SPS-1700R” manufactured by Seiko Instruments Inc., which measures emission intensity at a wavelength of 249.8 nm.
• An example of a standard solution used for preparing a calibration curve is an atomic absorption B standard solution (concentration 1000 ppm) manufactured by Kanto Chemical Co., Inc.
• the effect of improving the bending strength and solder crack resistance in the resin composition of the present invention is that when the specific surface area of the siliceous powder is in the range of 0.5 to 5 m 2 / g and the average particle diameter is in the range of 1 to 60 ⁇ m. Is further encouraged. When the specific surface area is less than 0.5 m 2 / g, the bonding area between the silane coupling agent and the siliceous powder surface is too small, and it is difficult to improve the bending strength and solder crack resistance.
• the specific surface area exceeds 5 m 2 / g, it means that the siliceous powder contains a large amount of small particles or there are irregularities on part or all of the particle surface, and the semiconductor is encapsulated using a semiconductor encapsulant. Since the viscosity of the sealing material at the time of packaging rises, moldability will be impaired.
• the range of the specific surface area is preferably 0.6 to 4.8 m 2 / g, more preferably 0.7 to 4.7 m 2 / g.
• the average particle size of the siliceous powder is less than 1 ⁇ m, so that the viscosity of the sealing material when packaging the semiconductor using the semiconductor sealing material is increased, so that the moldability is impaired. Absent. Conversely, when the average particle diameter exceeds 60 ⁇ m, the thickness of the semiconductor package is so thin that the semiconductor chip is damaged or a uniform package without unevenness cannot be obtained. Will occur.
• a preferred average particle size range is 2 to 55 ⁇ m, and a more preferred range is 3 to 50 ⁇ m.
• the maximum particle size is preferably 196 ⁇ m or less, more preferably 128 ⁇ m or less.
• the average particle size of the siliceous powder of the present invention is measured based on particle size measurement by a laser diffraction scattering method.
• a measuring instrument to be used for example, a product name “Cirrus Granurometer Model 920” manufactured by Cirrus Co., Ltd. is used, and siliceous powder is dispersed in water. Measure from The particle size distribution was measured when the particle diameter channel was 0.3, 1, 1.5, 2, 3, 4, 6, 8, 12, 16, 24, 32, 48, 64, 96, 128, 196 ⁇ m. Do. In the measured particle size distribution, the particle size at which the cumulative mass is 50% is the average particle size, and the particle size at which the cumulative mass is 100% is the maximum particle size.
• the content of the siliceous powder of the present invention in the inorganic powder is preferably 0.5% by mass or more, and more preferably 2% by mass or more.
• the inorganic powder is preferably a siliceous powder and / or an alumina powder. These powders may be used alone or in combination. Silica powder is selected when the thermal expansion coefficient of the semiconductor encapsulant is lowered or when the wear of the mold is reduced, and alumina powder is selected when thermal conductivity is imparted. In addition, it is preferable that siliceous powder is 95% or more by the value of the amorphous ratio measured by the postscript method.
• the siliceous powder of the present invention preferably has an amorphous ratio measured by the following method of 95% or more, particularly 98% or more.
• Amorphous ratio is specified by X-ray diffraction analysis using a powder X-ray diffractometer (for example, “Model Mini Flex” manufactured by RIGAKU) in the range of 2 ⁇ of CuK ⁇ ray of 26 ° to 27.5 °. Measured from the intensity ratio of diffraction peaks.
• crystalline silica has a main peak at 26.7 °, but amorphous silica has no peak.
• the average sphericity of the siliceous powder, the inorganic powder, and the alumina powder of the present invention is preferably 0.80 or more, and particularly preferably 0.85 or more. Thereby, the viscosity of a resin composition falls and a moldability can also be improved.
• the average sphericity is obtained by taking a particle image taken with a stereomicroscope (for example, trade name “Model SMZ-10” manufactured by Nikon Corporation) into an image analysis apparatus (for example, trade name “MacView” manufactured by Mountec Co., Ltd.). Measured from the projected area (A) and the perimeter (PM).
• At least two burners are disposed in the furnace body at an angle of 2 to 10 ° with respect to the central axis of the furnace body, and at least raw silica material powder is contained from one burner.
• a siliceous powder manufacturing method is characterized in that an Al source material and / or a B source material are injected into a flame from one burner.
• the raw material siliceous powder and the Al source material and / or B source material are injected into the flame from the same burner, the injected raw material always spreads in a conical shape, so the Al source material is formed on the surface of the raw material siliceous powder.
• the arrangement angle of the burner is less than 2 °, the focal point is located outside the flame, and the proportion of the Al source material and / or B source material fused to the surface of the raw siliceous powder decreases.
• the burner arrangement angle exceeds 10 °, it is not preferable because the Al source material and / or the B source material are focused on the surface of the raw siliceous powder before fusing.
• a more preferable burner arrangement angle is in the range of 3 to 8 °.
• the resin composition of the present invention is a resin composition containing the siliceous powder or inorganic powder of the present invention.
• the content of the siliceous powder or inorganic powder in the resin composition is 10 to 95% by mass, more preferably 30 to 90% by mass.
• the resin examples include epoxy resin, silicone resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyamide such as polyimide, polyamideimide and polyetherimide, polyester such as polybutylene terephthalate and polyethylene terephthalate, polyphenylene sulfide , Aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, ABS resin, AAS (acrylonitrile / acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / diene rubber / styrene) resin, etc. can do.
• epoxy resins, silicone resins, phenol resins and the like are preferable.
• an epoxy resin having two or more epoxy groups in one molecule is preferable.
• phenol novolac type epoxy resin orthocresol novolak type epoxy resin
• epoxidized phenol and aldehyde novolak resin epoxidized phenol and aldehyde novolak resin
• glycidyl ether such as bisphenol A, bisphenol F and bisphenol S
• phthalic acid dimer acid, etc.
• Novolak-type resin obtained by reacting with para-xylene under an oxidation catalyst; polyparahydroxystyrene resin; bisphenol compounds such as bisphenol A and bisphenol S; trifunctional phenols such as pyrogallol and phloroglucinol; maleic anhydride and phthalic anhydride Acid anhydrides such as acid and pyromellitic anhydride; aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; That.
• a curing accelerator such as triphenylphosphine, benzyldimethylamine, 2-methylimidazole can be used.
• the following components can be further blended as necessary.
• rubbery substances such as silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, styrene block copolymer, and saturated elastomer; resinous substances such as various thermoplastic resins and silicone resins; and epoxy And a resin obtained by modifying a part or all of a resin or phenol resin with amino silicone, epoxy silicone, alkoxy silicone, or the like.
• the amorphous ratio of the siliceous powder was 99.5% or more. These siliceous powders were measured for Freundlich adsorption constant K of pyridine, SiO 2 content, Al 2 O 3 content, B 2 O 3 content, specific surface area, average particle diameter, average sphericity, etc. It was shown to.
• siliceous powder and inorganic powder as a filler for a semiconductor encapsulant, 86.5 parts (parts by mass, the same applies hereinafter) of 4,4′-bis (2 , 3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl type epoxy resin 6.7 parts, phenol resin 5.5 parts, triphenylphosphine 0.3 part, phenylaminosilane 0.6 part, Carbon black (0.1 part) and carnauba wax (0.3 part) were added and dry blended with a Henschel mixer.
• a resin composition particularly a semiconductor sealing material, which is superior in bending strength and solder crack resistance than the Comparative Examples is prepared. Can do.

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• Engineering & Computer Science (AREA)
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• Organic Chemistry (AREA)
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• Condensed Matter Physics & Semiconductors (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
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• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

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• 2009
  • 2009-01-23 WO PCT/JP2009/051125 patent/WO2009096343A1/ja active Application Filing
  • 2009-01-23 KR KR1020107013421A patent/KR101442034B1/ko active IP Right Grant
  • 2009-01-23 SG SG2013007372A patent/SG188093A1/en unknown
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