Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/51—Particles with a specific particle size distribution
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E30/00—Energy generation of nuclear origin
  • Y02E30/30—Nuclear fission reactors

Definitions

• the present invention relates to an amorphous silica powder suitable for a solid encapsulant and a resin composition containing the amorphous silica powder.
• a semiconductor device in which a semiconductor chip mounted on a substrate is sealed with a resin is well known.
• the flip-chip connection method is known as a technique for meeting the demands for further miniaturization, thinning, and high density of such semiconductor devices.
• Patent Document 1 discloses a technique relating to a flip chip connection method.
• this flip chip connection method two steps of underfilling the narrow gap and overmolding the entire chip are required, so the narrow gap under the chip can be filled and the entire chip can be sealed with only the non-liquid epoxy resin composition.
• the development of a technology (solid encapsulation technology) that collectively performs the above is underway. In this development, the fluidity of the resin composition is an issue (Patent Document 2).
• the present invention is to provide an amorphous silica powder having excellent fluidity and a resin composition containing the amorphous silica powder, which is suitable for solid encapsulation.
• the present inventors have the most frequent diameter in the range of 1 to 10 ⁇ m in the particle size frequency distribution, and the frequency of particles having a particle size of 0.50 to 1.83 ⁇ m in the particle size frequency distribution is less than 3.0%. By being there, we succeeded in solving the above problem.
• the most frequent diameter is in the range of 1 to 10 ⁇ m in the particle size frequency distribution, and the frequency of particles having a particle size of 0.50 to 1.83 ⁇ m is 3 in the particle size frequency distribution.
• an amorphous silica powder characterized by being less than 0.0%.
• the amorphous silica powder of the present invention has a specific surface area of 1 to 12 m 2 / g. The specific surface area is preferably 3 to 10.5 m 2 / g.
• the integrated distribution on the sieve of particles having a particle diameter of 13 ⁇ m or more is 1% by mass or less.
• the amorphous silica powder of the present invention has a melting rate of 95% or more, and the total concentration of the uranium element and the thorium element is 10 ppb or less.
• the present invention also provides a resin composition for solid encapsulation containing the amorphous silica powder of the present invention, an epoxy resin, a curing agent, and a curing accelerator.
• the resin composition of the present invention is characterized by containing 80 to 90% by mass of the amorphous silica powder.
• the resin composition containing the amorphous silica powder of the present invention is particularly useful as a semiconductor encapsulant because it has excellent flow characteristics such as spiral flow and narrow gap filling property.
• the amorphous silica powder of the present invention has a maximum frequency range of 1 to 10 ⁇ m in the particle size frequency distribution, and the frequency of particles having a particle size of 0.50 to 1.83 ⁇ m in the particle size frequency distribution is 3. When it is less than 0%, the fluidity can be improved.
• the mode is in the range of 1 to 10 ⁇ m. If the mode in the particle size frequency distribution of the amorphous silica powder exceeds 10 ⁇ m, the above problem occurs. On the other hand, in the case of powder having a small particle size such that the most frequent diameter in the particle size frequency distribution is less than 1 ⁇ m, the viscosity of the semiconductor encapsulant becomes too high, and the filling amount of the powder cannot be increased.
• the lower limit may be 1.5 ⁇ m or more, 2.0 ⁇ m or more, 2.5 ⁇ m or more, 3.0 ⁇ m or more, and 3.2 ⁇ m or more.
• the upper limit may be 8.0 ⁇ m or less, 7.0 ⁇ m or less, 6.0 ⁇ m or less, 5.0 ⁇ m or less, 4.2 ⁇ m or less, 4. It may be 0 ⁇ m or less.
• the mode is in the range of 3.0 to 4.2 ⁇ m.
• the most frequent diameter is a particle diameter showing the highest frequency in the particle diameter distribution obtained by the measuring method described later for powder. If the mode of the amorphous silica powder as a raw material exceeds 10 ⁇ m, classification is performed to adjust the particle size distribution.
• the frequency of particles having a particle diameter of 0.50 to 1.83 ⁇ m is less than 3.0% by volume at the peak having a maximum value in the range of 1 to 10 ⁇ m
• the fluidity of the amorphous silica powder can be improved.
• it is 2.5% or less, 2.0% or less, 1.5% or less, 1.0% or less, 0.5% or less, and may be 0.0%.
• a conventionally known method can be adopted as a method of reducing the frequency of particles having a particle diameter of 0.50 to 1.83 ⁇ m to less than 3.0%.
• a precision wind classifier is used to cut the coarse powder side and the fine powder side. An example of how to do this.
• the frequency of particles having a particle size of 0.50 to 1.83 ⁇ m is a value obtained by the method for measuring the particle size distribution described later.
• the number of peaks showing the maximum frequency within the range of 1 to 10 ⁇ m in the particle size frequency distribution may be one or a plurality of peaks from the viewpoint of obtaining the effect of the present invention.
• the frequency at the maximum value of the peak with the most frequent diameter showing the maximum frequency within the range of 1 to 10 ⁇ m in the particle size frequency distribution may be 5% by volume or more.
• the lower limit of frequency may be 9% by volume or more.
• the upper limit of the frequency may be 20% by volume or less, 15% by volume or less, and 14.5% by volume or less.
• the specific surface area is preferably 1 to 12 m 2 / g.
• the frequency of particles having a particle diameter of 0.50 to 1.83 ⁇ m is less than 3.0%, the specific surface area tends to decrease. Therefore, it is preferable to add ultrafine powder of 0.5 ⁇ m or less to increase the specific surface area.
• the preferred ultrafine powder size is 0.1-0.5 ⁇ m with a median diameter.
• the upper limit may be 10.5 m 2 / g or less, 9 m 2 / g or less, and 8 m 2 / g or less.
• the specific surface area is less than 1 m 2 / g, it becomes difficult for the powder to form a close-packed structure, so that the fluidity of the semiconductor encapsulant decreases. 2 m 2 / g or more is more preferable, and 3 m 2 / g or more is further preferable.
• d10, d50 and d90 are not particularly limited.
• d10 may be 0.5 to 4.0 ⁇ m.
• d50 may be 3.5 to 7.0 ⁇ m.
• d90 may be 4.0 to 9.0 ⁇ m.
• d10 is preferably 1.5 to 3.5 ⁇ m.
• the d50 is preferably 3.0 to 5.0 ⁇ m.
• the d90 is preferably 4.0 to 7.0 ⁇ m.
• d10, d50, and d90 are particle diameters at which the cumulative values in the particle size cumulative distribution are 10%, 50%, and 90%, respectively.
• the particle size distribution is obtained by the method described later, is shown by the volume distribution, and the refractive index is set to 1.5.
• the amorphous silica powder of the present invention can have a cumulative distribution on the sieve of particles having a particle diameter of 13 ⁇ m or more of 1% by mass or less and 0% by mass.
• the small number of coarse particles makes it possible for the amorphous silica powder to more easily form a close-packed structure, and the fluidity of the semiconductor encapsulant is improved.
• the amorphous silica powder of the present invention may contain other components (additives, etc.) other than the amorphous silica powder as long as the effects of the present invention are not impaired.
• the other components may be 5% by mass or less, 3% by mass or less, 1% by mass or less, or 0% by mass.
• the amorphous silica powder of the present invention should not contain uranium element or thorium element as other components depending on the application.
• the total concentration of the uranium element and the thorium element is preferably 10 ppb or less from the viewpoint of suppressing the failure rate of memory rewriting.
• the amorphous silica powder of the present invention is optimally an amorphous silica powder produced by melting crystalline silica at a high temperature or a synthetic method in terms of bringing the thermal expansion rate between the semiconductor chip and the semiconductor encapsulant close to each other. be. Therefore, the melting rate of the amorphous silica powder of the present invention is preferably 95% or more.
• the shape of the amorphous silica powder may be spherical, crushed, needle-shaped, flake-shaped, etc., but it is spherical from the viewpoint of reducing the thermal expansion rate of the semiconductor encapsulant by filling as much as possible.
• Amorphous silica powder is suitable.
• the amorphous silica powder of the present invention may be mixed with other inorganic fillers and used.
• the other inorganic fillers include those having different types such as alumina powder and magnesia powder, as well as those having different particle size distributions even if they are the same amorphous silica powder.
• the particle size distribution of the amorphous silica powder of the present invention is measured using a Coulter particle size distribution measuring device LS13 320 type (Colter Beckman).
• a Coulter particle size distribution measuring device LS13 320 type Cold Beckman
• an aqueous silica solution dispersed in advance with an ultrasonic homogenizer is put into the device, and analysis is performed under the condition of a refractive index of 1.5.
• the amorphous silica powder of the present invention can be produced by mixing or classifying appropriate amounts of powders having different particle size configurations. Industrially, it is desirable to classify by a classifier, and the classifying operation may be performed by either a dry method or a wet method. From the viewpoint of productivity and removal of coarse particles, it is preferable to use a dry precision wind power classifier.
• the non-liquid resin composition used for solid encapsulation is a resin composition that is solid at room temperature, for example, powdery, granular, or tableted tablet.
• the resin composition for solid encapsulation contains a resin, a curing agent, an inorganic filler and a curing accelerator.
• each component will be described.
• Epoxy resin is preferably used as the resin for solid encapsulation.
• an epoxy resin conventionally used in the technical field of an epoxy resin composition for encapsulation can be used without particular limitation.
• examples of such epoxy resins include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, stilben type epoxy resin, triphenol methane type epoxy resin, phenol aralkyl type epoxy resin, and naphthol type epoxy resin.
• examples thereof include a naphthalene type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, a phenylene type epoxy resin, and a triphenylmethane type epoxy resin. These may be used alone or in combination of two or more.
• the content of the epoxy resin in the resin composition may be 2 to 15% by mass.
• a curing agent conventionally used in the technical field of the epoxy resin composition for encapsulation can be used without particular limitation.
• examples of such a curing agent include various polyhydric phenol compounds or naphthol compounds such as phenol novolac resin, cresol novolak resin, phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin and the like. These may be used alone or in combination of two or more.
• the mixing ratio of the epoxy resin and the curing agent is preferably 0.5 to 1.5, more preferably 0.8 to 1.2 in terms of equivalent ratio. If this blending ratio is excessively small, the amount of the curing agent is excessive, which is economically disadvantageous. If the blending ratio is excessively large, the amount of the curing agent is too small, resulting in insufficient curing.
• a curing accelerator conventionally used in the technical field of the epoxy resin composition for encapsulation can be used without particular limitation.
• examples of such a curing accelerator include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and 2-methyl-4-methylimidazole.
• Undecene-7 tertiary amines such as triethylenediamine and benzyldimethylamine, organic phosphines such as triphenylphosphine, tributylphosphine and tetraphenylphosphonium / tetraphenylborate. Etc., and those obtained by microencapsulating these are mentioned. These may be used alone or in combination of two or more.
• the content of the curing accelerator is preferably 1 to 10 parts by mass or less with respect to 100 parts by mass of the total content of the epoxy resin and the curing agent.
• the content of the curing accelerator is less than 1 part by mass, the curing promoting function is not exhibited well, and if the content of the curing accelerator is more than 10 parts by mass, there is a possibility that a defect in moldability may occur. It is preferably 2 to 4 parts by mass.
• the amorphous silica powder of the present invention is used as the inorganic filler.
• the content thereof is preferably 80 to 90% by mass, more preferably 83 to 90% by mass, still more preferably 86 to 90% by mass.
• the resin composition of the present invention may further contain other additives such as a coupling agent, a mold release agent, a colorant, a flame retardant, an ion trap agent, and a flexible agent as other components.
• a coupling agent such as ⁇ -aminopropyltriethoxysilane and N-phenyl- ⁇ -aminopropyltrimethoxysilane, mercaptosilanes such as mercaptopropyltrimethoxysilane, and ⁇ -.
• Examples thereof include glycidoxysilanes such as glycidoxypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxysilane, and these may be used alone or in combination of two or more.
• examples of the mold release agent that can be used in the present embodiment include waxes having a high melting point such as carnauba wax and montan wax, higher fatty acids such as stearic acid and salts and esters thereof, and carboxyl group-containing polyolefins. These may be used alone or in combination of two or more.
• Examples of the colorant that can be used in this embodiment include carbon black and various pigments.
• a halogen-free or antimony-free flame retardant is preferable, and for example, a metal hydroxide (metal hydrate) such as magnesium hydroxide, aluminum hydroxide, or calcium hydroxide is used.
• metal hydroxide metal hydrate
• the content of these other additives in the epoxy resin composition may be appropriately determined within a range in which the functions of each additive are satisfactorily exhibited. For example, 0.01 to 0.01 to the total amount of the epoxy resin composition. It is in the range of 5% by mass. Further, the total of these other components and impurities may be 10% by mass or less, 8% by mass or less, 5% by mass or less, and 3% by mass or less.
• the non-liquid epoxy resin composition is prepared, for example, as follows. That is, an epoxy resin, a curing agent, an inorganic filler, a curing accelerator, and other components are mixed in predetermined amounts, uniformly mixed with a mixer, a blender, or the like, and then heated and kneaded with a kneader, a roll, or the like. After kneading, it is cooled and solidified, and pulverized to a predetermined particle size to obtain a powdery or granular epoxy resin composition in the form of a solid at room temperature. If necessary, it may be further tableted to form a tablet.
• the semiconductor device (not the flip chip connection method) is manufactured, for example, as follows. That is, a semiconductor chip is mounted on a semiconductor chip mounting substrate, the substrate and the semiconductor chip are electrically connected (wire bonded) with a gold wire, and then the semiconductor chip on the substrate is sealed with the resin composition of the present invention. Transfer molding using a mold can be adopted to perform this sealing.
• the flip-chip connection type semiconductor device is manufactured, for example, as follows. That is, a protruding electrode (bump) is formed on the circuit surface of the semiconductor chip, directly connected to the electrode terminal of the semiconductor chip mounting substrate by face-down, and then the semiconductor chip on the substrate is collectively sealed with the resin composition of the present invention. do. That is, mold underfilling is performed in which the narrow gap under the chip is filled and the entire chip is sealed. Transfer molding using a mold can be adopted to perform this batch sealing.
• a protruding electrode bump
• amorphous silica powder of the preparation example of the present invention was prepared by the following procedure.
• Commercially available amorphous silica was used as a raw material. This raw material has one peak with the most frequent diameter in the range of 1 to 10 ⁇ m.
• the amorphous silica powder having a small particle diameter (medium diameter of 0.19, 0.28 or 0.37 ⁇ m is ultrafine powder). ) was blended at the internal addition ratio shown in Table 2.
• Epoxy resin, curing agent, inorganic filler, curing accelerator and other materials are mixed in the formulation (% by mass) shown in Table 1, homogenized, and then heated and kneaded with a twin-screw roll heated to 80 ° C. Then, it was extruded, cooled and solidified, and then pulverized to a predetermined particle size with a pulverizer to prepare a powdery epoxy resin composition in the form of a solid at room temperature.
• the particle size frequency distribution and the particle size cumulative distribution of the fine powder were measured using the Coulter method, which is not affected by the sample density.
• the medium diameter d ( ⁇ m) of the ultrafine powder is the following formula for silica particles (density 2.2 g / cm 3 ) from the BET value measured using the BET method:
• Table 2 shows the preparation conditions (powder classification conditions, compounding) of each amorphous silica powder, powder characteristics, and flow characteristics (spiral flow, narrow gap filling property) of the resin composition using each amorphous silica powder. Indicates the physical property value.
• the most frequent diameter is in the range of 1 to 10 ⁇ m, and in the particle size frequency distribution, the frequency of particles having a particle size of 0.50 to 1.83 ⁇ m is less than 3.0%, according to the present invention.
• the resin composition filled with the crystalline silica powder has excellent fluidity and filling property, and is therefore suitable as a sealing agent for semiconductor devices.

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• Polymers & Plastics (AREA)
• Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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• Epoxy Resins (AREA)

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• 2020
  • 2020-08-25 JP JP2020141931A patent/JP6867539B1/ja active Active
• 2021
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  • 2021-08-17 EP EP21861305.7A patent/EP4206131A4/en not_active Withdrawn
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