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  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/90—Carbides
  • C01B32/914—Carbides of single elements
  • C01B32/956—Silicon carbide
  • C01B32/963—Preparation from compounds containing silicon
  • C01B32/984—Preparation from elemental silicon
• • 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
  • C01B32/90—Carbides
  • C01B32/914—Carbides of single elements
  • C01B32/956—Silicon carbide
• • 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
  • C01B32/90—Carbides
  • C01B32/914—Carbides of single elements
  • C01B32/956—Silicon carbide
  • C01B32/963—Preparation from compounds containing silicon
  • C01B32/97—Preparation from SiO or SiO2
• • 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
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area
• • 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
  • C01P2006/40—Electric properties
• • 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
  • C01P2006/80—Compositional purity

Definitions

• the present invention relates to silicon carbide powder and a method for producing silicon carbide powder.
• Silicon carbide has excellent properties such as high hardness, high strength, high heat resistance, and high thermal conductivity, so it has been used for abrasives, refractories, heating elements, etc.
• SiC Silicon carbide
• the demand is increasing as a raw material for SiC semiconductor wafers.
• Silicon carbide powders are manufactured according to these uses, and particularly high-purity silicon carbide powders are required for raw materials for SiC semiconductor wafers and raw materials for SiC sintered bodies for semiconductor manufacturing applications. It is known that unreacted silicon and carbon derived from the raw materials at the time of manufacture cause the purity of the silicon carbide powder to decrease, and that using silicon carbide powder containing these as a raw material adversely affects the product. .
• Patent Document 1 when unreacted carbon (free carbon) is contained in raw material silicon carbide powder for producing a SiC single crystal by sublimation recrystallization, carbon is incorporated into the SiC single crystal to generate defects. has been shown to cause Further, Patent Document 2 discloses that if free Si is contained in raw material silicon carbide powder for producing a silicon carbide sintered body, sintering is inhibited or defects are generated in the sintered body. ing.
• Silicon carbide is produced by (1) the Acheson method in which silica sand and coke are heated to a high temperature by electric heating (for example, Patent Documents 1 and 3), and (2) a mixture of silica and carbon powder is externally heated to cause a reduction and carbonization reaction. (e.g., Patent Document 4), (3) a method of externally heating and carbonizing a mixture of metallic silicon powder and carbon powder (e.g., Patent Document 5), (4) preheating a mixture of metallic silicon powder and carbon powder. A method of igniting and burning a portion of the sample later (for example, Patent Document 6) is known.
• Method (1) is the most common method for producing silicon carbide powder, and can be produced using large-scale equipment at relatively low cost. It is difficult to obtain a high-purity product.
• the production method (2) uses high-purity silica and carbon powder as raw materials to easily obtain relatively high-purity silicon carbide powder.
• the manufacturing method (3) uses high-purity metal silicon powder and carbon powder as raw materials to easily obtain relatively high-purity silicon carbide powder, but Si volatilizes during high-temperature firing, and free carbon is greatly reduced. I have not been able to.
• Patent Documents 1 and 4 for example, attempts have been made to improve the purity by removing impurities from the manufactured silicon carbide powder, but there is a limit to improving the purity.
• JP 2019-151533 Japanese Patent Laid-Open No. 63-17258 JP 2015-157737 JP 2012-246165 WO2012-157293 Japanese Patent Laid-Open No. 53-25300
• an object of the present invention is to provide a silicon carbide powder in which both Si-based impurities and free carbon are highly reduced.
• the present inventors used a mixed powder obtained by mixing metal silicon powder and carbon powder in a specific ratio as a raw material, preheated at a low temperature, and performed a combustion synthesis reaction. Later, it was found that by heating at a high temperature to react the unreacted portion, it was possible to obtain a high-purity silicon carbide powder in which both Si-based impurities and free carbon were suppressed to a level that could not be achieved by conventional methods. , have completed the present invention.
• the present invention is a silicon carbide powder having a free carbon content of 0.04% by mass or less and a ratio of silicon atoms to carbon atoms (Si/C molar ratio) of 1.00 to 1.02.
• the silicon carbide powder preferably has a metal impurity content of 200 ppm or less.
• a method for producing silicon carbide powder comprising:
• a mixed powder of metallic silicon powder and carbon powder having a Si/C molar ratio of 1.00 or more and 1.02 or less is heated at a temperature of 900 to 1300° C. under atmospheric pressure and in an inert atmosphere. and a combustion synthesis step of preheating at and then igniting a portion of the mixed powder to perform combustion synthesis to obtain silicon carbide powder.
• high-purity silicon carbide powder with less Si-based impurities and free carbon can be obtained.
• SiC single crystals produced by the sublimation recrystallization method single crystals with few defects can be produced.
• a sintered body with good sinterability and few defects can be produced.
• the silicon carbide powder of the present invention contains 0.04% by mass or less of free carbon.
• the free carbon content is 0.04% by mass or less, it can be used particularly preferably for semiconductor applications that require high purity.
• Free carbon is preferably 0.02% by mass or less, more preferably 0.01% by mass or less. Free carbon can be measured according to JISR1616:2007 850° C. combustion-weight correction method.
• the silicon carbide powder of the present invention has a Si/C molar ratio of 1.00 or more and 1.02 or less.
• the carbon atoms are present as silicon carbide or free carbon. If free carbon is 0.04% by mass or less, as in the silicon carbide powder of the present invention, most of the carbon atoms are present as silicon carbide. Therefore, the fact that Si/C is within the above range means that the amount of silicon atoms other than silicon carbide (that is, Si-based impurities) is small. More preferably, the Si/C molar ratio is 1.00 or more and 1.01 or less.
• the Si/C molar ratio is the total silicon content measured by dehydration gravimetric ICP emission spectroscopy (JISR1616:2007) and the ratio of the total carbon content measured by combustion (resistance heating)-infrared absorption method (JISR1616:2007). can be calculated.
• the silicon carbide powder of the present invention preferably has an average particle size of 0.5 ⁇ m to 50.0 ⁇ m, more preferably 1.0 to 35.0 ⁇ m.
• the particle size can be measured by a laser diffraction/scattering method.
• the specific surface area of the silicon carbide powder of the present invention is preferably 0.2 m 2 /g to 3.0 m 2 /g. A specific surface area can be measured by a gas adsorption method.
• the amount of metal impurities in the silicon carbide powder of the present invention is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
• the silicon carbide powder can be made particularly suitable for use in semiconductors that require high purity.
• the amount of metal impurities can be measured by glow discharge mass spectrometry.
• the amount of metal impurities is the total amount of alkali metals, alkaline earth metals, transition metals, zinc, cadmium, and mercury with atomic numbers of 3 to 92, and is measured by glow discharge mass spectrometry.
• the silicon carbide powder of the present invention is obtained by preheating a mixed powder of a mixed metal silicon powder and a carbon powder having a Si/C molar ratio of 1.00 to 1.02 at a temperature of 900 to 1300° C. in an inert atmosphere. After that, a combustion synthesis step of igniting a part of the mixed powder to perform combustion synthesis to obtain a crude silicon carbide powder, and a heating of heating the crude silicon carbide powder to a temperature of 2000° C. to 2500° C. in an inert atmosphere. It can be easily manufactured by a method for manufacturing silicon carbide powder, which includes the steps of This manufacturing method will be described below.
• a mixed powder of metallic silicon powder and carbon powder having a Si/C molar ratio of 1.00 or more and 1.02 or less is used.
• Si/C molar ratio of the manufactured silicon carbide powder can be in the range of 1.00 to 1.02.
• the metal silicon powder preferably has a particle size of 2.0 ⁇ m to 50.0 ⁇ m, more preferably 4.0 ⁇ m to 35.0 ⁇ m. If the particle size is smaller than this range, the ratio of the surface oxide film increases, so there is a risk that Si-based impurities and free carbon in the silicon carbide powder will increase. If the particle size is larger than this range, it becomes difficult to mix uniformly with the carbon powder, and there is a risk that the reaction rate will not be sufficiently high and Si-based impurities and free carbon will increase.
• the metal impurity concentration of the silicon carbide powder tends to increase, so the purity of the metal silicon powder is 99.9999999% or more, more preferably 99.99999999% or more, and still more preferably 99.9999999% or more. .999999999% or more is preferably used.
• the total content of these metal impurities is preferably 1 ppmwt or less, more preferably 0.1 ppm or less.
• the carbon powder preferably has a particle size of 10 nm or more and 1 ⁇ m or less. If the particle size is smaller than this range, air and moisture are likely to be adsorbed, and the purity of the silicon carbide powder may decrease. If the particle size is larger than this range, it becomes difficult to uniformly mix with the metallic silicon powder, and there is a risk that the reaction rate will not be sufficiently high and Si-based impurities and free carbon will increase. If the carbon powder contains metal impurities, the concentration of metal impurities in the silicon carbide powder tends to increase, so the concentration of metal impurities in the carbon powder is 50 ppm or less, preferably 10 ppm or less, and even more preferably 5 ppm or less.
• the type of carbon powder is not particularly limited, and carbon black, graphite, etc. can be used, for example.
• Carbon black produced by various methods such as the furnace method (furnace black), the channel method (channel black), the acetylene method (acetylene black), and the like can be used.
• the method of mixing the metal silicon powder and the carbon powder to obtain a mixed powder is not particularly limited as long as the mixture can be mixed to achieve the desired Si/C molar ratio.
• Metallic silicon powder and carbon powder may be weighed and mixed uniformly using a known mixing method.
• the method of mixing the metal silicon powder and the carbon powder is not particularly limited, and preferred methods include mixing with a blender, mixer, or ball mill.
• a method such as a ball mill that applies a load to the raw materials during mixing is more preferable because the homogeneity of the metallic silicon powder and the carbon powder is increased.
• the material of the container, balls, etc., in which the metal silicon powder and the carbon powder are filled should be one that is hard to be mixed with the raw material due to abrasion during mixing, and is more preferably high-purity silicon carbide.
• silicon carbide powder may be added as a diluent for the purpose of controlling the reaction temperature, etc., as long as the effects of the present invention are not impaired.
• silicon carbide powder is used as the diluent, the Si/C molar ratio of the mixed powder is adjusted including the silicon carbide powder as the diluent.
• the compounding amount of the silicon carbide powder is generally 50% by mass or less of the mixed powder.
• the amount of metal impurities contained in the silicon carbide powder is large, the amount of metal impurities in the silicon carbide powder to be produced is also large. is more preferably 50 ppm or less.
• the silicon carbide powder produced by the production method of the present invention may be used as a diluent.
• the inert atmosphere can use, for example, rare gases such as helium, neon, and argon.
• the pressure is not particularly limited, it is preferably 500 Pa or less, more preferably 100 Pa or less, and further preferably 20 Pa or less. By setting the pressure within the above range, it becomes easy to remove nitrogen, moisture, and low-boiling-point substances adsorbed on the raw material.
• the lower limit of the pressure is not particularly limited, and may be, for example, 0.5 Pa or more.
• the inside of the reaction vessel is made to be an inert atmosphere after the raw materials are placed in the reaction vessel, the pressure inside the reaction vessel is reduced to 0.5 Pa or more and 10 Pa or less, and then an inert gas is introduced to restore the pressure to a predetermined pressure. It is preferable to perform the step at least once.
• the pressure during preheating and/or combustion synthesis can also be carried out at normal pressure (atmospheric pressure).
• normal pressure atmospheric pressure
• the combustion synthesis step is performed under normal pressure, volatilization of Si content is suppressed, so that silicon carbide powder having a free carbon content of 0.04% by mass or less can be obtained after the combustion synthesis step.
• the later-described heating step may be omitted.
• the preheating temperature is 900°C to 1300°C, preferably 1000°C to 1200°C.
• the preheating temperature is 900°C to 1300°C, preferably 1000°C to 1200°C.
• the preheating method is not particularly limited, for example, the mixed powder filled in a heat-resistant reaction container made of ceramics, graphite, etc. is placed in the firing furnace, and after adjusting the atmosphere, the temperature in the firing furnace is preheated from room temperature.
• the temperature should be raised to the temperature.
• the heating time is not particularly limited, but it is preferable to raise the temperature over 1 hour or more because it is easy to raise the temperature uniformly.
• the upper limit of the heating time is not particularly limited, it is preferably 24 hours or less from the viewpoint of efficient production.
• the combustion synthesis reaction may be started immediately by igniting, or after holding at the preheating temperature for a while, ignition may be started to start the combustion synthesis reaction.
• the holding time at the preheating temperature is preferably within 24 hours from the viewpoint of efficient production.
• the conditions for the combustion synthesis reaction in the present invention are not particularly limited, and the ignition method and the like may be carried out by known methods.
• Heating process In the production method of the present invention, a heating step of heating the crude silicon carbide powder obtained in the combustion synthesis step to 2000° C. to 2500° C. under an inert atmosphere may be performed.
• the reaction between the metallic silicon powder and the carbon powder is accelerated, and almost the entire amount can be reacted. is greatly different from the blending ratio in the raw materials.
• most of the metallic silicon is converted to silicon carbide in advance in the combustion synthesis step, so that the mixture of metallic silicon and carbon powder is heated to a higher temperature than when heated at a high temperature. Since the amount of metal silicon that is used is reduced and volatilization of metal silicon is suppressed, it is possible to obtain silicon carbide powder with a Si/C molar ratio equivalent to that of the raw material while almost completely consuming the carbon powder through the reaction. becomes.
• the crude silicon carbide powder that has been heated in the combustion synthesis step may be continuously heated as it is, or it may be cooled once after the combustion synthesis step and heated again, but it is better to carry out continuously. This is preferable because the energy required for heating can be reduced.
• the inert atmosphere can use, for example, rare gases such as helium, neon, and argon.
• the pressure is not particularly limited, it is preferably 500 Pa or less, more preferably 100 Pa or less, and further preferably 20 Pa or less. By setting the pressure within the above range, it becomes easy to remove nitrogen, moisture, and low-boiling-point substances adsorbed on the raw material.
• the lower limit of the pressure is not particularly limited, and may be, for example, 0.5 Pa or more.
• at least one step of reducing the pressure in the reaction vessel to 0.5 Pa or more and 10 Pa or less and then introducing an inert gas and restoring the pressure to a predetermined pressure is performed. It is preferable to carry out at least once.
• the temperature in the heating step is 2000°C or higher and 2500°C or lower, preferably 2050°C or higher and 2400°C or lower, and more preferably 2100°C or higher and 2300°C or lower.
• the heating temperature is 2000°C or higher, preferably 2050°C or higher and 2400°C or lower, and more preferably 2100°C or higher and 2300°C or lower.
• the heating time is not particularly limited. can be time.
• pulverization may be performed after the heating step to adjust the particle size, if necessary.
• the pulverization method is not particularly limited, and preferred examples include pulverization using a vibrating ball mill, a rotary ball mill, and a jet mill.
• the material of the container, balls, etc. is preferably one that is hard to be mixed with the raw material due to abrasion, and is more preferably high-purity silicon carbide. Even if impurities are mixed in, they can be removed in the cleaning step described later.
• a cleaning treatment may be performed as necessary to reduce metal impurities.
• An acid aqueous solution or an alkaline aqueous solution can be used for washing, and it may be selected according to the element to be reduced.
• acid aqueous solutions such as hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid and phosphoric acid, and alkali aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution can be used.
• the wash solution may be heated to facilitate dissolution if necessary.
• the use of the silicon carbide powder of the present invention is not particularly limited, SiC single crystals produced by the sublimation recrystallization method, which are particularly required for high-purity silicon carbide powders, because they contain little Si-based impurities and free carbon. It can be particularly suitably used as a raw material for semiconductor manufacturing and as a raw material for SiC sintered bodies for semiconductor manufacturing applications.
• Si/C molar ratio Measurement of total silicon content by dehydration gravimetric ICP emission spectroscopy using ICP-OES (manufactured by Thermo Fisher Scientific, iCAP6500DUO) according to JISR1616:2007, and carbon/sulfur analyzer (manufactured by HORIBA, EMIA-Step), the total carbon content was measured by the combustion (resistance heating)-infrared absorption method, and the Si/C molar ratio was calculated from the obtained results.
• Metal Impurities The amount of metal impurities was determined by glow discharge mass spectrometry as the total amount of alkali metals, alkaline earth metals, transition metals, zinc, cadmium and mercury with atomic numbers of 3 to 92.
• the specific surface area was determined by the BET method based on nitrogen adsorption using a gas adsorption measurement device.
• Example 1 A metal silicon powder having an average particle size of 5.1 ⁇ m and a purity of 99.999999999% and acetylene black having an average particle size of 30 nm and a metal impurity concentration of 30 ppm as carbon powder were mixed at a molar ratio of 1.01:1.00 (Si /C molar ratio of 1.01) and mixed using a planetary ball mill to obtain a mixed powder.
• the atmosphere during mixing was argon, and after cooling, the atmosphere was replaced with air.
• the material of the ball and pot was silicon carbide.
• the mixed powder was filled in a graphite crucible and placed in a firing furnace. After reducing the pressure in the furnace to 0.5 Pa or more and 10 Pa or less, argon with a purity of 99.99% was introduced to restore the pressure to normal pressure, and the pressure was again reduced to 0.5 Pa or more and 20 Pa or less. Preheating was performed by raising the temperature from room temperature to 1200° C. over 3 hours while maintaining the degree of vacuum of 0.5 Pa or more and 20 Pa or less. As soon as the temperature reached 1200° C., a part of the mixed powder was electrically ignited to obtain crude silicon carbide powder through a combustion synthesis reaction. After confirming that the combustion synthesis reaction was completed, the mixture was heated at 2200° C. for 5 hours while maintaining 0.5 Pa or more and 20 Pa or less. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 2 The silicon carbide powder produced by the method of Example 1 was pulverized using a planetary ball mill. The material of the ball and pot was silicon carbide. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 3 A silicon carbide powder was synthesized in the same manner as in Example 1, except that the preheating temperature in the combustion synthesis step was set to 1000°C. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 4 A silicon carbide powder was synthesized in the same manner as in Example 1, except that metallic silicon powder having an average particle size of 30.2 ⁇ m and a purity of 99.999999999% was used as the raw material. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 5 As metal silicon powder and carbon powder having an average particle size of 5.0 ⁇ m and a total content of metal impurities of B, Al, Fe, Cu, Mg, Ni, and Ca of 0.51 ppm, an average particle size of 30 nm , B, Al, Fe, Cu, Mg, Ni, and Ca with acetylene black having a total metal impurity content of 1.5 ppm at a molar ratio of 1.01:1.00 (Si/C molar ratio of 1.00). 01) and mixed using a ball mill to obtain a mixed powder. The atmosphere during mixing was argon, and after cooling, the atmosphere was replaced with air. The material of the ball and pot was silicon carbide.
• the mixed powder was filled in a graphite crucible and placed in a firing furnace. After reducing the pressure in the furnace to 0.5 Pa or more and 10 Pa or less, the operation of introducing argon having a purity of 99.99% and restoring the pressure to normal pressure was repeated twice.
• the furnace was preheated from room temperature to 1200° C. over 3 hours while argon was passed through the electric furnace at a flow rate of 5 liters/minute while maintaining the atmospheric pressure. As soon as the temperature reached 1200° C., a portion of the mixed powder was electrically ignited to obtain silicon carbide powder through a combustion synthesis reaction. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 6 Combustion synthesis was performed in the same manner as in Example 5. After completion of combustion synthesis, the pressure inside the firing furnace was reduced to 0.5 Pa or more and 20 Pa or less, and the mixture was heated at 2200° C. for 5 hours while maintaining the pressure. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 1 A silicon carbide powder was synthesized in the same manner as in Example 1, except that the preheating temperature in the combustion synthesis step was set to 700°C. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 2 A silicon carbide powder was synthesized in the same manner as in Example 1, except that the preheating temperature in the combustion synthesis step was set to 1400°C. Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Silicon carbide powder was synthesized in the same manner as in Example 1, except that the ratio of metallic silicon powder and acetylene black in the mixed powder was 1.00:1.05 (Si/C ratio 0.95). Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Silicon carbide powder was synthesized in the same manner as in Example 1, except that the ratio of metallic silicon powder and acetylene black in the mixed powder was 1.05:1.00 (Si/C ratio 1.05). Table 1 shows the evaluation results of the obtained silicon carbide powder.
• Example 7 After obtaining a mixed powder using a ball mill in the same manner as in Example 5, the mixed powder was filled in a graphite crucible and placed in a firing furnace. After reducing the pressure in the furnace to 0.5 Pa or more and 10 Pa or less, argon with a purity of 99.99% was introduced to restore the pressure to normal pressure, and the pressure was again reduced to 0.5 Pa or more and 20 Pa or less. Preheating was performed by raising the temperature from room temperature to 1200° C. over 3 hours while maintaining the degree of vacuum of 0.5 Pa or more and 20 Pa or less. As soon as the temperature reached 1200° C., a portion of the mixed powder was electrically ignited to obtain silicon carbide powder through a combustion synthesis reaction. Table 1 shows the evaluation results of the obtained silicon carbide powder.

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