WO2023210649A1 - PARTICULES COLONNAIRES DE NITRURE DE β-SILICIUM, PARTICULES COMPOSITES, SUBSTRAT FRITTÉ POUR RAYONNEMENT THERMIQUE, COMPOSITE DE RÉSINE, COMPOSITE INORGANIQUE, MÉTHODE DE PRODUCTION DE PARTICULES COLONNAIRES DE NITRURE DE β-SILICIUM, ET MÉTHODE DE PRODUCTION DE PARTICULES COMPOSITES - Google Patents

PARTICULES COLONNAIRES DE NITRURE DE β-SILICIUM, PARTICULES COMPOSITES, SUBSTRAT FRITTÉ POUR RAYONNEMENT THERMIQUE, COMPOSITE DE RÉSINE, COMPOSITE INORGANIQUE, MÉTHODE DE PRODUCTION DE PARTICULES COLONNAIRES DE NITRURE DE β-SILICIUM, ET MÉTHODE DE PRODUCTION DE PARTICULES COMPOSITES Download PDF

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WO2023210649A1
WO2023210649A1 PCT/JP2023/016330 JP2023016330W WO2023210649A1 WO 2023210649 A1 WO2023210649 A1 WO 2023210649A1 JP 2023016330 W JP2023016330 W JP 2023016330W WO 2023210649 A1 WO2023210649 A1 WO 2023210649A1
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silicon nitride
particles
composite
columnar particles
columnar
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Japanese (ja)
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和人 原田
好晴 鏡
博明 和泉
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株式会社燃焼合成
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/587—Fine ceramics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to ⁇ silicon nitride columnar particles, composite particles, a sintered substrate for heat dissipation, a resin composite, an inorganic composite, a method for producing ⁇ silicon nitride columnar particles, and a method for producing composite particles.
  • insulating inorganic fillers include alumina, boron nitride (BN), and aluminum nitride (AlN).
  • alumina is the cheapest and most used inorganic filler, but heat dissipation materials using alumina have not been able to sufficiently increase thermal conductivity.
  • Patent No. 6245602 Japanese Patent Application Publication No. 2004-352539 Patent No. 6845402
  • silicon nitride particles have very poor filling properties, and there is a problem in that the thermal conductivity of a heat dissipating material containing silicon nitride particles cannot be made sufficiently high.
  • alpha silicon nitride has been sold in large quantities as a sintering material
  • beta silicon nitride has insufficient sintering strength, so its sales volume has been small and its uses have been limited.
  • ⁇ silicon nitride has not been a material that has been fully expected to be used as a heat dissipation filler.
  • the present invention was made in view of the above problems, and includes ⁇ silicon nitride columnar particles, composite particles, a sintered substrate for heat dissipation, a resin composite, and an inorganic composite, which have excellent thermal conductivity and filling properties.
  • Another object of the present invention is to provide a method for producing ⁇ -silicon nitride columnar particles and a method for producing composite particles.
  • the ⁇ silicon nitride columnar particles in the present invention are columnar particles with an average particle diameter D50 of 10 ⁇ m or more and 200 ⁇ m or less, and have an aspect ratio of 0.05 or more and 0.6 or less as determined by SEM image analysis. .
  • the average particle diameter D50 is preferably 25 ⁇ m or more and 100 ⁇ m or less.
  • the composite particles in the present invention include the ⁇ silicon nitride columnar particles described above and the ⁇ silicon nitride pulverized particles, have an average particle diameter D50 of 5 ⁇ m or more and 150 ⁇ m or less, and have an aspect ratio determined by SEM image analysis. It is characterized by being 0.4 or more and 0.7 or less.
  • the sintered substrate for heat dissipation in the present invention is characterized by being formed by firing the ⁇ silicon nitride columnar particles described above or the composite particles described above.
  • the resin composite in the present invention is characterized by containing the ⁇ silicon nitride columnar particles described above or the composite particles described above.
  • the inorganic composite in the present invention is characterized by containing the ⁇ silicon nitride columnar particles described above or the composite particles described above.
  • the method for producing ⁇ -silicon nitride columnar particles in the present invention includes synthesizing ⁇ -silicon nitride composite crystals by a combustion synthesis method in a nitrogen atmosphere using a raw material containing Si; is crushed and classified to obtain columnar particles having an average particle diameter D50 of 10 ⁇ m or more and 200 ⁇ m or less, and an aspect ratio of 0.05 or more and 0.6 or less as determined by SEM image analysis.
  • the method for producing composite particles in the present invention includes crushing the agglomerated powder after extracting the ⁇ silicon nitride columnar particles described above to obtain crushed ⁇ silicon nitride particles, and then grinding the ⁇ silicon nitride columnar particles. and the ⁇ silicon nitride pulverized particles to obtain composite particles having an average particle diameter D50 of 5 ⁇ m or more and 150 ⁇ m or less, and an aspect ratio of 0.4 or more and 0.7 or less as determined by SEM image analysis. It is characterized by
  • the ⁇ silicon nitride columnar particles of the present invention have better water resistance and thermal conductivity than AlN. Furthermore, the filling rate can be increased, and it can be put to practical use in a variety of applications, such as as a heat dissipation filler or as a seed crystal for sintered substrates.
  • FIG. 1A is a scanning electron micrograph of a ⁇ -silicon nitride composite crystal.
  • FIG. 1B is a partial schematic diagram of FIG. 1A.
  • FIG. 2A is a scanning electron micrograph of beta silicon nitride columnar particles.
  • FIG. 2B is a partial schematic diagram of FIG. 2A.
  • FIG. 3B is a partial schematic diagram of FIG. 3A.
  • FIG. 4B is a partial schematic diagram of FIG. 4A.
  • the silicon nitride filler described in Patent Document 1 is agglomerated particles containing columnar silicon nitride particles. Although such a silicon nitride filler has a shape that can be easily obtained by combustion synthesis and has excellent productivity, since it has a shape in which columnar particles are aggregated, irregularities and holes are present on the filler surface. For this reason, the specific surface area becomes very large, and there is a problem with filling properties.
  • the rod-shaped silicon nitride filler described in Patent Document 2 is produced by heat-treating silicon nitride powder in flux and then repeating alkaline solution treatment and acid solution treatment to dissolve the flux component.
  • a method in which a mixture of a frac component and silicon nitride is heat-treated at a high temperature of 1,600 to 1,900 degrees Celsius in a nitrogen or argon atmosphere, and then washed with alkali and acid multiple times to obtain a rod-shaped silicon nitride filler. is proposed.
  • the manufacturing process is complicated and production costs are high.
  • Patent Document 2 is an unrealistic method in which a highly corrosion-resistant silicon nitride sintered body is formed and grain boundaries are melted to obtain columnar crystals. Further, although it is not described in Patent Document 2, the average particle diameter D50 is expected to be considerably small.
  • Patent Document 3 discloses an invention relating to crystal-oriented ceramics having composite particles (C) consisting of magnetically anisotropic particles (A) and seed particles (B), in which the seed particles (B) have ⁇ -nitrided Silicon is chosen.
  • C composite particles
  • the configuration described in Patent Document 3 has high production costs and is difficult to put into practical use. Further, there are also problems in that the average particle diameter D50 is very small and the orientation effect is also low.
  • Non-Patent Document 1 discloses a method of manufacturing silicon nitride nanowires by a reductive nitriding method. In this method, a method has been proposed in which a metal catalyst and carbon are added to SiO 2 and the mixture is maintained at 1850° C. for 10 hours in a nitrogen atmosphere of 0.95 MPa.
  • the crystal thickness is very small, 1 ⁇ m or less, has poor heat transfer efficiency, and contains impurities.
  • Non-Patent Document 2 ⁇ Si 3 N 4 is added as a seed crystal to form a sintered body.
  • a method has been proposed in which sintering is carried out in a nitrogen atmosphere of 0.9 MPa and maintained at 1850° C. for 6 hours.
  • sintering is carried out in a nitrogen atmosphere of 0.9 MPa and maintained at 1850° C. for 6 hours.
  • it is necessary to maintain a high-temperature, high-pressure atmosphere for a long time, and special equipment is required, leading to high costs.
  • columnar particles grow from seed crystals, the size of the columnar particles is very small, and there is also the problem that the orientation effect is low.
  • the ⁇ silicon nitride columnar particles in this embodiment are columnar particles with an average particle diameter D50 of 10 ⁇ m or more and 200 ⁇ m or less, and an aspect ratio determined by SEM image analysis of 0.05 or more and 0.6 or less. shall be.
  • FIG. 1A is a scanning electron microscope (SEM) photograph of a ⁇ -silicon nitride composite crystal.
  • FIG. 1B is a partial schematic diagram of FIG. 1A.
  • the ⁇ silicon nitride composite crystal (polycrystal) produced by the combustion synthesis method is a state in which many columnar particles (column filler) are aggregated, and this is crushed.
  • columnar particles having an average particle diameter D50 of 10 ⁇ m or more and 200 ⁇ m or less can be obtained (see FIGS. 2A and 2B).
  • columnar crystals consisting of many columnar particles with a size of 10 ⁇ m or more and 200 ⁇ m or less are crushed and produced, so as shown in FIGS. It is smooth and has excellent filling properties.
  • the average particle diameter can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-950 manufactured by HORIBA).
  • LA-950 manufactured by HORIBA
  • D50 refers to a particle size whose cumulative number is 50% of the total number of particles. Note that, although not limited to this, approximately 3 to 200 columnar particles are aggregated in the ⁇ silicon nitride composite crystal.
  • the average particle diameter D50 is preferably 50 ⁇ m or more and 200 ⁇ m or less.
  • the average particle diameter D50 is preferably 20 ⁇ m or more and 170 ⁇ m or less, more preferably 25 ⁇ m or more and 160 ⁇ m or less, even more preferably 25 ⁇ m or more and 150 ⁇ m or less, and even more preferably 25 ⁇ m or more and 100 ⁇ m or less. It is preferably 25 ⁇ m or more and 80 ⁇ m or less, even more preferably 30 ⁇ m or more and 70 ⁇ m or less.
  • the silicon nitride filler of columnar particles described in each patent document is smaller than that of this embodiment. This is especially clear from the SEM photograph shown in FIG. 1 of Patent Document 2.
  • the ⁇ silicon nitride columnar particles in this embodiment have an aspect ratio of 0.05 or more and 0.6 or less as determined by SEM image analysis.
  • the aspect ratio was determined by observing with SEM (Phenom Prox), measuring the aspect ratio (breadth axis/long axis) of 400 particles using analysis software (Particle Metric), and using the average value thereof.
  • the short axis and the long axis can be determined by the length ratio of two sides of a substantially rectangular shape (rectangular shape) when the ⁇ silicon nitride columnar particle is viewed from the front.
  • the aspect ratio is preferably 0.1 or more and 0.5 or less, more preferably 0.11 or more and 0.5 or less, and even more preferably 0.11 or more and 0.45 or less.
  • columnar particles grow into a columnar shape having the above-mentioned average particle diameter D50 and aspect ratio by the combustion synthesis method, so that substantially rectangular planes occupy a large area and the particles Contact between surfaces increases, not only between surfaces but also between surfaces and lines. Thereby, a large number of heat paths can be formed and excellent thermal conductivity can be obtained.
  • the area of the plane (which can also be referred to as a flat surface or smooth surface) occupying the surface of the columnar particles is preferably 50% or more, more preferably 60% or more, and 70% or more of the total area. is more preferable, and most preferably 80% or more. Thereby, the above effects can be appropriately achieved. Note that the area occupied by the planes of the columnar powders in the Examples described later was all 80% or more.
  • the ⁇ silicon nitride columnar particles in this embodiment preferably have a D10 (cumulative 10% particle size) in the particle size distribution of 0.1 ⁇ m or more and 50 ⁇ m or less, more preferably 0.5 ⁇ m or more and 30 ⁇ m or less. , more preferably 0.7 ⁇ m or more and 20 ⁇ m or less, and even more preferably 1 ⁇ m or more and 15 ⁇ m or less.
  • the ⁇ silicon nitride columnar particles in this embodiment preferably have a D90 (90% cumulative particle size) of 60 ⁇ m or more and 300 ⁇ m or less in the particle size distribution, more preferably 60 ⁇ m or more and 200 ⁇ m or less, and 70 ⁇ m or more.
  • the number of particles to obtain the particle size distribution and aspect ratio of ⁇ silicon nitride columnar particles is preferably from several tens to several hundreds, specifically about 100 to 500. be. In the experiment described later, the number was 400.
  • the ⁇ -silicon nitride columnar particles are synthesized by a combustion synthesis method, so that the crystals do not contain impurities or can contain very few impurities. Therefore, the thermal conductivity of the ⁇ silicon nitride columnar particles is not impaired compared to silicon nitride fillers such as those disclosed in Patent Document 2 that contain flux.
  • the composite particles in this embodiment include the ⁇ silicon nitride columnar particles described above and the ⁇ silicon nitride pulverized particles, have an average particle diameter D50 of 5 ⁇ m or more and 150 ⁇ m or less, and have an aspect ratio determined by SEM image analysis. It is characterized by being 0.4 or more and 0.7 or less.
  • the method for measuring the average particle diameter D50 and aspect ratio is as explained in the section ⁇ silicon nitride columnar particles in this embodiment> above.
  • the ⁇ silicon nitride composite crystals shown in FIGS. 1A and 1B are synthesized by a combustion synthesis method, and this is crushed. At this time, columnar particles having an average particle diameter D50 of 10 ⁇ m or more and 200 ⁇ m or less are classified and collected. On the other hand, the agglomerated powder that is not recovered as ⁇ -silicon nitride columnar particles can be pulverized using a ball mill to obtain pulverized ⁇ -silicon nitride particles.
  • the average particle diameter D50 of the ⁇ silicon nitride pulverized particles is 50 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 20 ⁇ m or less. , even more preferably 10 ⁇ m or less.
  • the average particle diameter D50 of the ⁇ silicon nitride pulverized particles is smaller than the average particle diameter D50 of the ⁇ silicon nitride columnar particles. In this way, by making the average particle diameter D50 of the ⁇ silicon nitride pulverized particles smaller than the average particle diameter D50 of the ⁇ silicon nitride columnar particles, the filling rate can be further increased.
  • FIG. 3A is a scanning electron micrograph of composite particles that are a mixture of columnar ⁇ silicon nitride particles and ground ⁇ silicon nitride particles.
  • the composite particles contain a mixture of ⁇ silicon nitride columnar particles and crushed ⁇ silicon nitride particles.
  • shape of the ⁇ silicon nitride pulverized particles is not limited, examples thereof include spherical, elliptical, polyhedral, and uneven shapes.
  • many of the ⁇ silicon nitride pulverized particles have a smaller particle size than the ⁇ silicon nitride columnar particles.
  • the D50 of the ⁇ silicon nitride columnar particles is smaller than the D50 of the ⁇ silicon nitride columnar particles.
  • it contains many single crystal particles (filler) (in other words, almost no agglomerated powder is found), and all of these particles have smooth particle surfaces and have poor filling properties. Excellent. That is, the surface of the ⁇ silicon nitride pulverized particles also has many flat portions, and the area ratio of flat surfaces is 30% or more, preferably 50% or more, and more preferably 70% or more.
  • the mixed particles of this embodiment include ⁇ silicon nitride columnar particles and ⁇ silicon nitride pulverized particles, so that the average particle diameter D50 and aspect ratio of the ⁇ silicon nitride columnar particles are smaller than the average particle diameter D50 and aspect ratio.
  • the ⁇ silicon nitride columnar particles or composite particles of this embodiment can be applied as a heat dissipation filler.
  • the average particle diameter D50 of the ⁇ silicon nitride columnar particles in this embodiment is as large as several tens of ⁇ m or several hundred ⁇ m, external orientation treatment such as magnetic field orientation or pressurized orientation is facilitated. Therefore, the ⁇ silicon nitride columnar particles shown in FIGS. 2A and 2B, or the composite particles obtained by mixing the ⁇ silicon nitride columnar particles and the ⁇ silicon nitride pulverized particles shown in FIGS. 3A and 3B, are particles for heat dissipation sintered substrates. It is useful as a seed crystal for orientation.
  • the average particle diameter D50 of the ⁇ silicon nitride columnar particles in this embodiment is as large as several tens or hundreds of ⁇ m, they can be used as a reinforcing material for resins and the like. That is, the ⁇ silicon nitride columnar particles of this embodiment are mixed into the resin. Thereby, effects such as improvement in the abrasion resistance and bending strength of the resin can be obtained. Further, for example, the beta silicon nitride columnar particles of this embodiment can be added to glass to be used as a ceramic reinforcing material to increase the strength of the glass. In this way, a resin composite or an inorganic composite containing the ⁇ silicon nitride columnar particles or composite particles in this embodiment can be manufactured.
  • ⁇ silicon nitride columnar particles shown in FIGS. 2A and 2B, or composite particles obtained by mixing ⁇ silicon nitride columnar particles and crushed ⁇ silicon nitride particles shown in FIGS. 3A and 3B are provided.
  • the ⁇ silicon nitride columnar particles in this embodiment are (1) A step of synthesizing ⁇ -silicon nitride composite crystals by a combustion synthesis method in a nitrogen atmosphere using raw materials containing Si; (2) Crushing the ⁇ -silicon nitride composite crystal to obtain columnar particles having an average particle diameter D50 of 10 ⁇ m or more and 200 ⁇ m or less, and an aspect ratio of 0.05 or more and 0.6 or less as determined by SEM image analysis. It is characterized by having a process.
  • ⁇ -silicon nitride composite crystals are synthesized by a combustion synthesis method.
  • ⁇ -silicon nitride grows in a columnar shape, and as shown in FIGS. 1A and 1B, a plurality of columnar It is said to have a structure in which particles are aggregated.
  • the AlN crystal grows equiaxed by the combustion synthesis method and does not grow columnar.
  • the average particle diameter D50 of Si used as the raw material is, for example, within the range of 2 to 10 ⁇ m. This makes it possible to suppress the amount of oxygen impurities, increase the combustion rate, increase the synthesis temperature, and obtain good crystal growth.
  • the average particle diameter D50 of Si is 5 ⁇ m.
  • the silicon nitride powder may be either ⁇ type or ⁇ type. Further, the average particle diameter D50 of the silicon nitride powder is preferably in the range of 0.1 to 5 ⁇ m. As an example, the average particle diameter D50 of silicon nitride powder is 1 ⁇ m.
  • the diluent is used to adjust the amount of Si in the raw material. The amount of diluent added is preferably within the range of 10% by mass to 50% by mass in the raw material. Thereby, welding of Si can be suppressed and combustion can be appropriately caused, and excellent crystal growth can be obtained with a sufficient amount of heat. As an example, the diluent is added to the raw material in an amount of 20% by mass.
  • a diluent is mixed into the raw materials, and the mixture is filled into an insulating heat-resistant container.
  • This heat-insulating heat-resistant container has a thermal conductivity of 1 W/mK or less, and the material can be alumina or zirconia, but carbon is preferable in consideration of contamination with impurities.
  • cover the container with a material similar to that of the heat-insulating heat-resistant container.
  • the thickness of the mixed raw material is set to 50 mm or more, preferably 100 mm or more. Note that if it is 400 mm or more, it will take time to cool down and increase manufacturing cost, so it is preferably 400 mm or less.
  • combustion synthesis is performed under a nitrogen atmosphere in the range of 0.5 to 1 MPa (for example, 0.9 MPa). By adjusting the pressure range within the above range, efficient synthesis can be achieved and an increase in equipment costs can be suppressed.
  • a catalyst may be used to more effectively promote crystal growth.
  • Y 2 O 3 , Fe 2 O 3 , CaO, Ni, Co, C, etc. are added in an amount of about 0.01 to 0.1% by mass.
  • similar columnar crystals can be obtained by a combustion synthesis method using self-ignition by performing external auxiliary heating in the range of 500° C. to 1700° C. (for example, 1500° C.) because the combustion temperature becomes higher.
  • the ⁇ -silicon nitride composite crystal is in the form of agglomerated columnar particles, so in the step (2) above, the ⁇ -silicon nitride composite crystal is crushed and classified. .
  • the crushing step for example, the composite is crushed using a general coarse crushing device such as a hammer mill or a disc mill until it passes through a sieve with an opening of 150 ⁇ m.
  • the columnar crystals are collected through a wedge wire with a 25 ⁇ m slit.
  • the collected columnar particles are passed through a sieve with an opening of 25 ⁇ m to remove any agglomerated powder with a diameter of 25 ⁇ m or less.
  • ⁇ silicon nitride columnar particles having an average particle diameter D50 of 10 ⁇ m or more and 200 ⁇ m or less and an aspect ratio of 0.05 or more and 0.6 or less as determined by SEM image analysis are obtained. Obtainable.
  • the method for producing ⁇ -silicon nitride columnar particles of the present embodiment involves simple steps such as synthesizing ⁇ -silicon nitride composite crystals using the heat of formation in the combustion synthesis method, and crushing and classifying the crystals. Through this process, ⁇ silicon nitride columnar particles having a larger average particle diameter D50 than conventional ones can be obtained. Therefore, ⁇ -silicon nitride columnar particles with high thermal conductivity and excellent filling properties can be manufactured with high productivity.
  • the combustion synthesis method enables energy-saving production and reduces production costs.
  • step (2) After extracting the ⁇ -silicon nitride columnar particles in step (2), pulverizing the unrecovered agglomerated powder to obtain pulverized ⁇ -silicon nitride particles; (4) By mixing ⁇ -silicon nitride columnar particles and ⁇ -silicon nitride pulverized particles (mixing ratio: 1:9 to 9:1), the average particle diameter D50 is 5 ⁇ m or more and 150 ⁇ m or less, and the result is determined by SEM image analysis. A step of obtaining composite particles having an aspect ratio of 0.4 or more and 0.7 or less.
  • the agglomerated powder removed in step (2) above is pulverized in step (3) above, for example, until the average particle diameter D50 becomes 10 ⁇ m or less.
  • the pulverization method is not limited, and a general rolling ball mill, planetary ball mill, vibrating ball mill, jet mill, etc. can be used. Note that the average particle diameter D50 to be pulverized can be variously selected depending on the purpose and the like.
  • the ⁇ silicon nitride pulverized particles obtained here have a shape other than columnar crystals, such as spherical or polyhedral, and have very smooth particle surfaces.
  • step (4) above in this embodiment, the ⁇ silicon nitride columnar particles obtained in step (2) above and the ground ⁇ silicon nitride particles obtained in step (3) above are mixed.
  • the ⁇ silicon nitride pulverized particles are smaller than the ⁇ silicon nitride columnar particles, and can be inserted between the ⁇ silicon nitride columnar particles and the ⁇ silicon nitride columnar particles to increase the filling rate.
  • particles have more surface-to-line contact than surface contact or point contact, which increases the number of heat paths and provides excellent thermal conductivity.
  • the ⁇ silicon nitride columnar particles obtained in step (2) above and the crushed ⁇ silicon nitride particles obtained in step (3) above are heated at 500° C. to 800° C. (for example, It is preferable to perform the heat treatment at a temperature of 600° C. in an air atmosphere. This is because an oxide film is attached to the particle surface to stabilize it and make it hydrophilic.
  • Two types of heat-treated powders are placed in water, stirred and mixed, and then subjected to wet classification. Wet classification includes sieve classification and specific gravity classification, and cyclone classification was used. Through this mixing process, it is possible to control the amount of columnar powder mixed in and create characteristics that suit the application. For example, if orientation is required for heat dissipation properties, the amount of columnar powder mixed is increased.
  • the ⁇ silicon nitride columnar particles of this embodiment have excellent thermal conductivity by adjusting the average particle diameter D50 and aspect ratio.
  • ⁇ silicon nitride columnar particles or composite particles are superior to AlN in terms of water resistance and thermal conductivity.
  • ⁇ silicon nitride columnar particles can be obtained by crushing ⁇ silicon nitride composite crystals as large crystals, ⁇ silicon nitride columnar particles having smooth planes, and ⁇ silicon nitride columnar particles obtained by crushing aggregated powder.
  • the crushed silicon nitride particles also have a smooth particle shape, and composite particles made by mixing these particles have excellent filling properties.
  • the composite particles also contain columnar crystals, they have an advantageous effect on the heat path and can improve thermal conductivity.
  • ⁇ silicon nitride columnar particles or composite particles in this embodiment can be used not only as a filler but also as a seed crystal or a resin reinforcing material for a sintered substrate.
  • the D50 of the columnar particles was found to be within the range of 10 ⁇ m to 200 ⁇ m, preferably within the range of 20 ⁇ m to 100 ⁇ m. Further, it has been found that the aspect ratio is within the range of 0.05 to 0.6, preferably within the range of 0.1 to 0.5.
  • Example 1 had an average particle diameter D50 of 5 ⁇ m
  • Example 2 had an average particle diameter D50 of 10 ⁇ m
  • Example 3 had an average particle diameter D50 of 20 ⁇ m.
  • FIGS. 3A and 3B are a SEM photograph and a partial schematic diagram of Example 3. Then, the aspect ratio and thermal conductivity of each example were measured. "Thermal conductivity" was measured by temperature wave measurement method (ai-Phase).
  • Comparative Examples 1 to 6 were prepared. Comparative Examples 1 to 3 are coarsely classified ⁇ silicon nitride particles obtained by conventional synthesis, Comparative Example 1 has an average particle diameter D50 of 5 ⁇ m, Comparative Example 2 has an average particle diameter D50 of 10 ⁇ m, and In No. 3, the average particle diameter D50 was 20 ⁇ m.
  • 4A and 4B are a SEM photograph and a partial schematic diagram of Comparative Example 3. Note that "normal synthesis” is a synthesis method that does not intend crystal growth, and uses a non-insulated crucible made of carbon, the dilution rate is 50 wt%, the gas pressure is 700 KPa, and the raw material size is the same as in the example. , the raw material layer thickness was 40 mm.
  • Comparative Examples 4 to 6 are AlN particles
  • Comparative Example 4 is an AlN filler with an average particle diameter D50 of 5 ⁇ m (AN-HF05LG-HTZ manufactured by Kabuki Gosei Co., Ltd.)
  • Comparative Example 5 is an AlN filler with an average particle diameter D50 of 5 ⁇ m.
  • Comparative Example 6 was an AlN filler with a particle diameter D50 of 10 ⁇ m (AN-HF10LG-HTZ, manufactured by Yasushi Gosei Co., Ltd.)
  • Comparative Example 6 was an AlN filler (AN-HF20LG-HTZ, manufactured by Yasushi Gosei Co., Ltd.) with an average particle diameter D50 of 20 ⁇ m. there were.
  • the experimental results are shown in Table 2 below.
  • Examples 1 to 3 were all able to obtain high thermal conductivity when compared with the same D50 as Comparative Examples 1 to 6. In addition, Examples 1 to 3 have smaller aspect ratios than Comparative Examples 1 to 6, confirming the characteristics of Examples 1 to 3 as composite particles of ⁇ silicon nitride columnar particles and ⁇ silicon nitride pulverized particles. did it.
  • the filling rate of the particles was varied from 46% by volume to 58% by volume, and the viscosity (25°C) at each filling rate was measured. Further, the viscosity was measured at 25° C. using a B-type viscometer. Note that when the tap density was measured, it was about 1.00 to 1.40 (g/cc) in the examples.
  • Example 3 As shown in Table 3, in Comparative Example 3, the filling rate reached the filling limit at 52% by volume, but in Example 3, the filling limit reached 58% by volume, and Example 3 was better than Comparative Example 3. It was found that the filling properties were excellent. In Example 3, both the ⁇ -silicon nitride columnar particles and the ⁇ -silicon nitride crushed particles had smooth flat surfaces (it was confirmed that they occupied more than 80% of the surface), and as a result, the filling properties were excellent, and the columnar particles also From Table 2, it was confirmed that the inclusion of the compound had an advantageous effect on the heat path and improved thermal conductivity.
  • the ⁇ silicon nitride columnar particles of the present invention have excellent water resistance and thermal conductivity, can be manufactured at low cost, and are effective not only as heat dissipation fillers but also as seed crystals for sintered substrates. It can be used for.

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Abstract

Le but de la présente invention est de fournir des particules colonnaires de nitrure de β-silicium excellentes en termes de conductivité thermique et de propriété de remplissage, des particules composites, un substrat fritté pour rayonnement thermique, une méthode de production des particules colonnaires de nitrure de β-silicium, et une méthode de production des particules composites. Les particules colonnaires de nitrure de β-silicium selon la présente invention sont caractérisées en ce qu'elles ont un diamètre de particule moyen D50 de 10 à 200 µm et un rapport d'aspect, tel que déterminé par analyse d'image MEB, de 0,05 à 0,6. Les particules composites selon la présente invention sont caractérisées en ce qu'elles comprennent les particules colonnaires de nitrure de β-silicium et des particules pulvérisées de nitrure de β-silicium et en ce qu'elles ont un diamètre de particule moyen D50 de 5 à 150 µm et un rapport d'aspect, tel que déterminé par analyse d'image MEB, de 0,4 à 0,7.
PCT/JP2023/016330 2022-04-27 2023-04-25 PARTICULES COLONNAIRES DE NITRURE DE β-SILICIUM, PARTICULES COMPOSITES, SUBSTRAT FRITTÉ POUR RAYONNEMENT THERMIQUE, COMPOSITE DE RÉSINE, COMPOSITE INORGANIQUE, MÉTHODE DE PRODUCTION DE PARTICULES COLONNAIRES DE NITRURE DE β-SILICIUM, ET MÉTHODE DE PRODUCTION DE PARTICULES COMPOSITES WO2023210649A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01182331A (ja) * 1988-01-14 1989-07-20 Denki Kagaku Kogyo Kk 充填剤
JPH0664906A (ja) * 1992-08-21 1994-03-08 Denki Kagaku Kogyo Kk 窒化珪素粉末
JPH11268903A (ja) * 1998-03-24 1999-10-05 Denki Kagaku Kogyo Kk 窒化珪素質充填材及び半導体封止用樹脂組成物
CN101857441A (zh) * 2010-06-25 2010-10-13 清华大学 一种制备β-氮化硅粉体的方法
WO2018110560A1 (fr) * 2016-12-12 2018-06-21 宇部興産株式会社 Poudre de nitrure de silicium, agent de démoulage pour lingot de silicium polycristallin, et méthode de production de lingot de silicium polycristallin
WO2018110565A1 (fr) * 2016-12-12 2018-06-21 宇部興産株式会社 Méthode de production de poudre de nitrure de silicium de haute pureté

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01182331A (ja) * 1988-01-14 1989-07-20 Denki Kagaku Kogyo Kk 充填剤
JPH0664906A (ja) * 1992-08-21 1994-03-08 Denki Kagaku Kogyo Kk 窒化珪素粉末
JPH11268903A (ja) * 1998-03-24 1999-10-05 Denki Kagaku Kogyo Kk 窒化珪素質充填材及び半導体封止用樹脂組成物
CN101857441A (zh) * 2010-06-25 2010-10-13 清华大学 一种制备β-氮化硅粉体的方法
WO2018110560A1 (fr) * 2016-12-12 2018-06-21 宇部興産株式会社 Poudre de nitrure de silicium, agent de démoulage pour lingot de silicium polycristallin, et méthode de production de lingot de silicium polycristallin
WO2018110565A1 (fr) * 2016-12-12 2018-06-21 宇部興産株式会社 Méthode de production de poudre de nitrure de silicium de haute pureté

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