CN103508454A - Preparation method of highly pure silicon carbide raw material - Google Patents
Preparation method of highly pure silicon carbide raw material Download PDFInfo
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- CN103508454A CN103508454A CN201210202086.7A CN201210202086A CN103508454A CN 103508454 A CN103508454 A CN 103508454A CN 201210202086 A CN201210202086 A CN 201210202086A CN 103508454 A CN103508454 A CN 103508454A
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Abstract
The invention provides a preparation method of a highly pure silicon carbide raw material. The method comprises the following steps: providing highly pure silicon powder and highly pure carbon powder; mixing the highly pure silicon powder with the highly pure carbon powder to obtain a mixture, putting the mixture in a crucible, and forming a primary silicon carbide material in a high temperature furnace having a temperature of 1400-2200DEG C, crushing the primary silicon carbide material, and carrying out high temperature oxidation at 600-1400DEG C to form a secondary silicon carbide material; carrying out high temperature vacuum degassing in a high vacuum furnace at 800-1600DEG C to form a tertiary silicon carbide material; and carrying out wet chemical metallurgical treatment of the tertiary silicon carbide material to obtain the highly pure silicon carbide raw material.
Description
Technical field
The present invention relates to the preparation method of a kind of electronic industry, semiconductor material, relate more specifically to the preparation method of sic raw material.
Background technology
Since American's Archie inferior since within 1891, finding SiC material, SiC has the performance of many excellences because of it, as high in hardness, wear-resisting cutting, high temperature resistant, resistance to oxidation, corrosion-resistant, high heat conductance, high chemical stability, broad-band gap and high electron mobility etc., be used as abrasive material, refractory materials, electric-heating assembly, the raw material of the application such as black non-ferrous metal metallurgy, abrasive material wherein, metallurgical and high temperature bearing part is the main application fields of current silicon carbide, be applied to again now structural part in mechanical engineering and the sealing member in chemical engineering etc., and in corrosion, under the extreme condition such as abrasion and high temperature and space flight, there is very superior performance.Silicon carbide is through pyrotic smelting, to form in resistance furnace with raw materials such as quartz sands, refinery coke (or coal tar), wood chip (while producing green silicon carbide need to salt) traditionally, because being difficult to carry out precision, the techniques such as conventional carbon SiClx production process Raw, equipment, pulverizing control, the silicon carbide purity of producing is lower, between 95-99%, can meet general industry and production application.
The semi-conductor that the silicon of take is representative has promoted the development of microelectronics and photoelectron technology greatly, the silicon purification techniques that the improved Siemens Method of take is representative can be brought up to 9N(99.9999999% by the purity of silicon) more than, the HIGH-PURITY SILICON material of take has thoroughly changed our life looks and mode as basic microelectronics.But due to the restriction of the performance of material own, its device application is also tending towards the limit.The material that the increasing field of modern science and technology needs high frequency, high-power, high temperature resistant, chemical stability is good and can work in severe radiation border, the third generation semi-conductor that the silicon carbide of therefore take is representative has been a great deal of attention.SiC is owing to having the features such as broad-band gap, high critical electric field, high heat conductance, high carrier saturation drift velocity, at aspects such as high temperature, high frequency, high-power, photoelectron and radioprotectives, has huge potentiality.
But, need highly purified silicon materials the same with production Silicon Wafer, produce silicon carbide whisker fenestra and need highly purified sic raw material, traditional method is due to the intrinsic defect of its technique at present, the various foreign matter contents of silicon carbide of producing are higher, purity is lower, is very easy to produce as defects such as polycrystalline, microchannel, dislocation, parcels when as raw material grow silicon carbide crystals, is difficult to form high-quality carborundum crystals; And, due to the impact of various impurity especially transition metal impurity, crystal property degradation, wafer cannot be used as element manufacturing.
In sum, this area shortage makes purity reach the processing method of the requirement of growing silicon carbide crystal with high quality.Therefore, this area makes silicon carbide in the urgent need to developing a kind of raw material and process can accurately controlled, and makes its purity reach the new processing method of the requirement of growing silicon carbide crystal with high quality.
Summary of the invention
The object of the present invention is to provide a kind of method that obtains high-purity silicon carbide raw material, especially preparation is applicable to the method for high-purity silicon carbide raw material for high quality growing silicon carbice crystals.
In a first aspect of the present invention, a kind of preparation method of high-purity silicon carbide raw material is provided, described method comprises the steps:
High-purity silicon powder and high pure carbon powder are provided;
Described high-purity silicon powder and high pure carbon powder are positioned over crucible after fully mixing, and form silicon carbide material in the High Temperature Furnaces Heating Apparatus of 1400-2200 ℃ one time,
After a described silicon carbide material crushes, in oxidized still, pass through the high temperature oxidation of 600-1400 ℃, form secondary silicon carbide material;
Described secondary silicon carbide material is degassed through 800-1600 ℃ of high-temperature vacuum in high vacuum furnace, forms silicon carbide material three times;
Described three silicon carbide material, through wet chemistry Metallurgical processing, obtain high-purity silicon carbide raw material.
In a preferred implementation, described high-purity silicon carbide raw material is high-purity silicon carbide raw material.
In a preferred implementation, the method of making high-purity silicon carbide of the present invention (SiC) raw material comprises: adopt high-purity silicon powder and high pure carbon powder, fully after mixing, be positioned over crucible synthesizing silicon carbide in High Temperature Furnaces Heating Apparatus, by controlling the synthetic loose shape silicon carbide such as synthesis temperature, furnace atmosphere, pressure, after pulverizing,, wet chemistry Metallurgical processing degassed through high temperature oxidation, high-temperature vacuum, obtain high-purity silicon carbide powder raw material.
In a preferred implementation, described high vacuum furnace is that low vacuum is in 5 * 10
-3the vacuum oven of Pa.
In a specific embodiment of the present invention, in the forming process of a described silicon carbide material, avoid the introducing of N element.
Preferably, in the forming process of a described silicon carbide material, mixed high-purity silicon powder and high pure carbon powder should be positioned in high purity aluminium oxide, zirconium white or plumbago crucible, preferably plumbago crucible.
Preferably, described high-purity silicon powder and high pure carbon powder are high purity reagent, and purity all should be not less than 99.999%.
Contriver's discovery, the present invention, by rational processing condition, has dropped to minimum by N to the pollution of crystal.
Concrete, introducing N element has been avoided in the selection of described container.
Concrete, introducing N element and other impurity have been avoided in the selection of described high purity reagent.
In a specific embodiment of the present invention, in the forming process of a described silicon carbide material, by control, comprise that the processing condition of synthesis temperature, furnace atmosphere, pressure form loose shape silicon carbide.The silicon carbide with loose shape form that the present invention synthesizes, need not pulverize especially, crushes gently, is not easy to introduce impurity.
Preferably, described synthesis temperature is 1400-2200 ° of C, and more preferably temperature of reaction is 1700-2000 ° of C, and the reaction times is 3-36 hour.
Preferably, furnace atmosphere is hydrogen, argon gas atmosphere or its mixed gas, preferably hydrogen atmosphere.
Preferably, the pressure of furnace atmosphere is 1-500Torr, preferably 10-200Torr.
In a specific embodiment of the present invention, the meta particle diameter D of the high-purity silicon powder providing (purity is not less than 99.999%)
50(meta particle diameter D
50: corresponding particle diameter when the cumulative particle sizes percentile of a sample reaches 50%.Its physical significance is that the particle that particle diameter is greater than it accounts for 50%, and the particle that is less than it also accounts for 50%, D
50also be meta particle diameter or median particle diameter.D50 is commonly used to represent the mean particle size of powder.) between 10-1000 μ m, representative value is between 100-500 μ m; The meta particle diameter D of high pure carbon powder (purity is not less than 99.999%)
50should be between 0.3-300 μ m, representative value should be between 10-100 μ m
In a specific embodiment of the present invention, described High Temperature Furnaces Heating Apparatus can be graphite resistor furnace or medium-frequency induction furnace, more preferably, adopts medium-frequency induction furnace.
Preferably, the vacuum tightness of described High Temperature Furnaces Heating Apparatus can reach 5 * 10
-3below Pa, preferred value is 1 * 10
-3below Pa.
In a specific embodiment of the present invention, while forming secondary silicon carbide material, during described high-temperature oxidation process, adopt high purity oxygen gas (purity is not less than 99.99%), in stove, temperature is 600-1500 ° of C, preferred 800-1200 ° of C, the time is 1-24 hour.In order to reduce impurity, contriver passes through high temperature oxidation process by a silicon carbide in oxidized still, gets rid of unnecessary carbon, and, by burning a small amount of in powder, obtain secondary silicon carbide.
In a specific embodiment of the present invention, while forming three silicon carbide material in high vacuum furnace, in the process of the degassed processing of high-temperature vacuum, in stove, vacuum tightness is 5 * 10
-2below Pa, preferred value is 1 * 10
-3below Pa, temperature is 1200-1700 ° of C, time 2-24 hour.In order to reduce impurity, contriver processes secondary silicon carbide by high temperature high vacuum degassing, will at high temperature hold volatile metal oxide volatilization, obtains silicon carbide three times.
In a specific embodiment of the present invention, the acid solution that wet chemistry Metallurgical processing adopts is HCl, HF, H
2sO
4, HNO
3one or more mixing acid soak, temperature is 20-85 ° of C, the time is not less than 6 hours.
A second aspect of the present invention provides a kind of high-purity silicon carbide raw material making as any one method of the present invention.
Preferred, the meta particle diameter D of described high-purity silicon carbide raw material
50between 50-800 μ m, purity is greater than 99.999%.
A third aspect of the present invention provides the growth of a kind of high-purity silicon carbide raw material of the present invention for crystal formation crystal.
Preferably, described crystalline form crystal is one or more in 3C-SiC, 4H-SiC, 6H-SiC and 15R-SiC crystal.
Accompanying drawing explanation
Fig. 1 is process flow sheet.
Embodiment
The inventor, through extensive and deep research, by improving preparation technology, has obtained a kind of typical meta particle diameter D
50in 50-800 μ m, purity, be greater than the preparation method of 99.999% high-purity silicon carbide raw material.Completed on this basis the present invention.
Technical conceive of the present invention is as follows:
Present method is by the high-purity silicon powder and the high pure carbon powder synthesizing silicon carbide in high temperature that mix, by controlling synthesis temperature, furnace atmosphere, the synthetic loose shape silicon carbide of pressure and other parameters, after crushing gently, through high temperature oxidation, high temperature high vacuum degassing, wet chemistry Metallurgical processing process wet chemistry Metallurgical processing, obtain typical meta particle diameter D
50the high-purity silicon carbide raw material that is greater than 99.999% in 50-800 μ m, purity.
Below describe in detail to various aspects of the present invention:
Raw material: high-purity silicon powder and high pure carbon powder
Preferably, described high-purity silicon powder and high pure carbon powder are high purity reagent, and purity all should be not less than 99.999%.
In a preferred implementation, described high-purity silicon carbide raw material is high-purity silicon carbide powder raw material.
In a preferred implementation, the meta particle diameter of high-purity (purity the is not less than 99.999%) silica flour providing between 10-1000 μ m, representative value should be between 100-500 μ m; The meta particle diameter D of high-purity (purity is not less than 99.999%) carbon dust
50should be between 0.3-300 μ m, representative value should be between 10-100 μ m
The formation of a silicon carbide material
In a specific embodiment of the present invention, in the forming process of a described silicon carbide material, avoid the introducing of N element;
Preferably, in the forming process of a described silicon carbide material, mixed high-purity silicon powder and high pure carbon powder should be positioned in high purity aluminium oxide, zirconium white or plumbago crucible, preferably plumbago crucible.
Contriver's discovery, the present invention, by rational processing condition, has dropped to minimum by N to the pollution of crystal.
Concrete, introducing N element has been avoided in the selection of described container.
Concrete, introducing N element and other impurity have been avoided in the selection of described high purity reagent.
In order more to reduce and to pollute, in the forming process of a described silicon carbide material, by control, comprise that the processing condition of synthesis temperature, furnace atmosphere, pressure form loose shape silicon carbide.
Preferably, described synthesis temperature is 1500-2200 ° of C, and more preferably temperature of reaction is 1700-2000 ° of C, and the reaction times is 3-36 hour.
Preferably, furnace atmosphere is hydrogen, argon gas atmosphere or its mixed gas, preferably hydrogen atmosphere.
Preferably, the pressure of furnace atmosphere is 1-500Torr, preferably 10-200Torr.
The silicon carbide with loose shape form that the present invention synthesizes, need not crush gently through pulverizing, and is not easy to introduce impurity.
In a specific embodiment of the present invention, described High Temperature Furnaces Heating Apparatus can be graphite resistor furnace or medium-frequency induction furnace, more preferably, adopts medium-frequency induction furnace;
Preferably, the vacuum tightness of described High Temperature Furnaces Heating Apparatus can reach 5 * 10
-3below Pa, preferred value is 1 * 10
-3below Pa.
Form secondary silicon carbide material
While forming secondary silicon carbide material in oxidized still, adopt high purity oxygen gas (purity is not less than 99.99%) during described high-temperature oxidation process, in stove, temperature is 600-1500 ° of C, preferred 800-1200 ° of C, and the time is 1-24 hour.
In order to reduce impurity, contriver by high temperature oxidation process, gets rid of unnecessary carbon by a silicon carbide, and, by burning a small amount of in powder, obtain secondary silicon carbide.
Form three times silicon carbide material
In a specific embodiment of the present invention, while forming three silicon carbide material in high vacuum furnace, in the process of the degassed processing of high-temperature vacuum, in stove, vacuum tightness is 5 * 10
-2below Pa, preferred value is 1 * 10
-3below Pa, temperature is 1200-1700 ° of C, time 2-24 hour.
In order to reduce impurity, contriver processes secondary silicon carbide by high temperature high vacuum degassing, will at high temperature hold volatile metal oxide volatilization, obtains silicon carbide three times.
Wet chemistry Metallurgical processing
In a specific embodiment of the present invention, the acid solution that wet chemistry Metallurgical processing adopts is HCl, HF, H
2sO
4, HNO
3one or more mixing acid soak, temperature is 20-85 ° of C, the time is not less than 6 hours.
High-purity silicon carbide raw material and its production and use
The meta particle diameter D of described high-purity silicon carbide raw material of the present invention
50between 50-800 μ m, purity is greater than 99.999%.
The preparation method of described high-purity silicon carbide raw material comprises the steps:
High-purity silicon powder and high pure carbon powder are provided;
Described high-purity silicon powder and high pure carbon powder are positioned over crucible after fully mixing, and form silicon carbide material in High Temperature Furnaces Heating Apparatus one time,
A described silicon carbide material passes through high temperature oxidation after pulverizing in oxidized still, forms secondary silicon carbide material;
Degassed through high-temperature vacuum in the high vacuum furnace of described secondary silicon carbide material, form silicon carbide material three times;
Described three silicon carbide material, through wet chemistry Metallurgical processing, obtain high-purity silicon carbide raw material.
In a preferred implementation, the method of making high-purity silicon carbide of the present invention (SiC) raw material comprises: adopt high-purity silicon powder and high pure carbon powder, fully after mixing, be positioned over crucible synthesizing silicon carbide in High Temperature Furnaces Heating Apparatus, by controlling synthesis temperature, furnace atmosphere, the synthetic loose shape silicon carbide of pressure and other parameters, after pulverizing,, wet chemistry Metallurgical processing degassed through high temperature oxidation, high-temperature vacuum, obtain high-purity silicon carbide powder raw material.
High-purity silicon carbide raw material of the present invention is for the growth of crystal formation crystal; Preferably, described crystalline form crystal is one or more in 3C-SiC, 4H-SiC, 6H-SiC and 15R-SiC crystal.
Advantage
The present invention adopts following measures, guarantees the silicon carbide of synthesis of high purity:
Raw material adopts 99.999% above silica flour and carbon dust, and high purity graphite crucible can reach the Reaktionsofen of condition of high vacuum degree, and the possibility of the pollution that raw material, crucible and environment are brought has dropped to bottom line;
By rational processing condition, N has been dropped to minimum, and synthetic and there is a silicon carbide of loose shape form to the pollution of crystal, without pulverizing, crush gently, be not easy to introduce impurity;
A silicon carbide is passed through to high temperature oxidation process in oxidized still, get rid of unnecessary carbon, and, by burning a small amount of in powder, obtain secondary silicon carbide;
To in the high vacuum furnace of secondary silicon carbide, by high temperature high vacuum degassing, process, will at high temperature hold volatile metal oxide volatilization, obtain silicon carbide three times;
By three silicon carbide that obtain, by hydrometallurgical process, deionized water filters, and dries, and obtains highly purified sic raw material.
The sic raw material of preparing according to these processing condition, for the growth of carborundum crystals, under the condition of vanadium that undopes, has grown and has had good profile, and resistivity is 1 * 10
7crystal more than Ω cm.
As no specific instructions, various raw material of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer is carried out.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
Weigh respectively purity and be not less than 99.999%, D
50footpath is not less than 99.999%, D in 250 grams of silica flours and the purity of 200 μ m
50footpath, 100 grams of the carbon dusts of 30 μ m, is positioned over full and uniform mixing in clean plastic containers or polytetrafluoroethylcontainer container, and mixed powder is transferred in high purity graphite crucible, is positioned in medium-frequency induction furnace, is evacuated to 5 * 10
-4pa, then passes into argon gas and hydrogen, and flow is respectively 6L/min and 1L/min, and controls furnace pressure and remain on about 50Torr.Speed heating crucible to 1800 ° C with 800 ° of C/h, is incubated 12 hours, stops heating.In stove, temperature drops to 500 ° of C when following, stops argon gas and hydrogen flowing quantity supply, during cool to room temperature, plumbago crucible is taken out, and tentatively synthetic loose shape silicon carbide is crushed gently, obtains silicon carbide material one time.
A silicon carbide material is positioned in a high purity aluminium oxide crucible, is positioned in oxidized still, under high purity oxygen gas atmosphere, be heated to 900 ° of C, be incubated 8 hours, fully synthetic material is carried out to oxide treatment, obtain secondary oxidation silicon carbide material.
Then the secondary silicon carbide material after oxidation is transferred in plumbago crucible, is positioned in high vacuum furnace, be evacuated to and be less than 1 * 10
-3below Pa, and be heated to 1450 ° of C, be incubated 10 hours, cooling, obtains three silicon carbide material of vacuum outgas.
Three silicon carbide material are positioned in clean polytetrafluoroethylcontainer container, and adding 800mL concentration is 36.5%MOS level HCl, and 200mL concentration is 40%MOS level HF, 600mL deionized water, by container sealing, be positioned over water-bath in 80 ° of C water-baths and filter after 36 hours, obtain approximately 410 grams of carborundum powders.Through GDMS(glow discharge mass spectrometry) to measure, metallic impurity total content is below 10ppmw, and SIMS (second ion mass spectroscopy) detects N content below 8ppmw, laser particle analyzer test silicon carbide powder meta particle diameter D
50be 120 μ m.
Embodiment 2
Weigh respectively purity and be not less than 99.999%, D
50footpath is not less than 99.999%, D in 210 grams of silica flours and the purity of 200 μ m
50footpath, 100 grams of the carbon dusts of 90 μ m, is positioned over full and uniform mixing in clean plastic containers or polytetrafluoroethylcontainer container, and mixed powder is transferred in high purity graphite crucible, is positioned in medium-frequency induction furnace, is evacuated to 5 * 10
-4pa, then passes into argon gas and hydrogen, and flow is respectively 10L/min and 2L/min, and controls furnace pressure and remain on about 100Torr.Speed heating crucible to 1900 ° C with 800 ° of C/h, is incubated 12 hours, stops heating.In stove, temperature drops to 500 ° of C when following, stops argon gas and hydrogen flowing quantity supply, during cool to room temperature, plumbago crucible is taken out, and tentatively synthetic loose shape silicon carbide is crushed gently, obtains silicon carbide material one time.
A silicon carbide material is positioned in a high purity aluminium oxide crucible, is positioned in oxidized still, under high purity oxygen gas atmosphere, be heated to 800 ° of C, be incubated 10 hours, fully synthetic material is carried out to oxide treatment, obtain secondary oxidation silicon carbide material.
Then the secondary silicon carbide material after oxidation is transferred in plumbago crucible, is positioned in high vacuum furnace, be evacuated to and be less than 1 * 10
-3below Pa, and be heated to 1600 ° of C, be incubated 10 hours, cooling, obtains three silicon carbide material of vacuum outgas.
Three silicon carbide material are positioned in clean polytetrafluoroethylcontainer container, and adding 800mL concentration is 36.5%MOS level HCl, and 200mL concentration is 40%MOS level HF, 600mL deionized water, by container sealing, be positioned over water-bath in 70 ° of C water-baths and filter after 24 hours, obtain approximately 270 grams of carborundum powders.Through GDMS(glow discharge mass spectrometry) to measure, metallic impurity total content is below 5ppmw, and SIMS (second ion mass spectroscopy) detects N content below 5ppmw, laser particle analyzer test silicon carbide powder meta particle diameter D
50be 200 μ m.
Embodiment 3
Weigh respectively purity and be not less than 99.999%, D
50footpath is not less than 99.999%, D in 700 grams of silica flours and the purity of 200 μ m
50footpath, 300 grams of the carbon dusts of 30 μ m, is positioned over full and uniform mixing in clean plastic containers or polytetrafluoroethylcontainer container, and mixed powder is transferred in high purity graphite crucible, is positioned in medium-frequency induction furnace, is evacuated to 5 * 10
-4pa, then passes into argon gas and hydrogen, and flow is respectively 10L/min and 3L/min, and controls furnace pressure and remain on about 80Torr.Speed heating crucible to 2000 ° C with 800 ° of C/h, is incubated 12 hours, stops heating.In stove, temperature drops to 500 ° of C when following, stops argon gas and hydrogen flowing quantity supply, during cool to room temperature, plumbago crucible is taken out, and tentatively synthetic loose shape silicon carbide is crushed gently, obtains silicon carbide material one time.
A silicon carbide material is positioned in a high purity aluminium oxide crucible, is positioned in oxidized still, under high purity oxygen gas atmosphere, be heated to 900 ° of C, be incubated 10 hours, fully synthetic material is carried out to oxide treatment, obtain secondary oxidation silicon carbide material.
Then the secondary silicon carbide material after oxidation is transferred in plumbago crucible, is positioned in high vacuum furnace, be evacuated to and be less than 1 * 10
-3below Pa, and be heated to 1600 ° of C, be incubated 12 hours, cooling, obtains three silicon carbide material of vacuum outgas.
Three silicon carbide material are positioned in clean polytetrafluoroethylcontainer container, and adding 1000mL concentration is 36.5%MOS level HCl, and 300mL concentration is 40%MOS level HF, 600mL deionized water, by container sealing, be positioned over water-bath in 80 ° of C water-baths and filter after 36 hours, obtain approximately 950 grams of carborundum powders.Through GDMS(glow discharge mass spectrometry) to measure, metallic impurity total content is below 1ppmw, and SIMS (second ion mass spectroscopy) detects N content below 2ppmw, laser particle analyzer test silicon carbide powder meta particle diameter D
50be 500 μ m.
The foregoing is only preferred embodiment of the present invention, not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is to be broadly defined in the claim scope of application, any technology entity or method that other people complete, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that, after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a preparation method for high-purity silicon carbide raw material, is characterized in that, described method comprises the steps:
High-purity silicon powder and high pure carbon powder are provided;
Described high-purity silicon powder and high pure carbon powder are positioned over crucible after fully mixing, and form silicon carbide material in the High Temperature Furnaces Heating Apparatus of 1400-2200 ℃ one time,
After a described silicon carbide material crushes, in oxidized still, pass through the high temperature oxidation of 600-1400 ℃, form secondary silicon carbide material;
Described secondary silicon carbide material is degassed through 800-1600 ℃ of high-temperature vacuum in high vacuum furnace, forms silicon carbide material three times;
Described three silicon carbide material, through wet chemistry Metallurgical processing, obtain high-purity silicon carbide raw material.
2. the method for claim 1, is characterized in that, in the forming process of a described silicon carbide material, avoids the introducing of N element;
Preferably, in the forming process of a described silicon carbide material, mixed high-purity silicon powder and high pure carbon powder should be positioned in high purity aluminium oxide, zirconium white or plumbago crucible, preferably plumbago crucible.
Preferably, described high-purity silicon powder and high pure carbon powder are high purity reagent, and purity all should be not less than 99.999%.
3. the method for claim 1, is characterized in that,
In the forming process of a described silicon carbide material, by control, comprise that the processing condition of synthesis temperature, furnace atmosphere, pressure form loose shape silicon carbide;
Preferably, described synthesis temperature is 1400-2200 ° of C, and more preferably temperature of reaction is 1700-2000 ° of C, and the reaction times is 3-36 hour;
Preferably, furnace atmosphere is hydrogen atmosphere, argon gas atmosphere or its mixed gas, preferably hydrogen atmosphere;
Preferably, the pressure of furnace atmosphere is 1-500Torr, preferably 10-200Torr.
4. the method for claim 1, is characterized in that, the meta particle diameter D of the high-purity silicon powder providing
50between 10-1000 μ m, representative value is between 100-500 μ m; The meta particle diameter D of high pure carbon powder
50should be between 0.3-300 μ m, representative value is between 10-100 μ m.
5. the method for claim 1, is characterized in that, described High Temperature Furnaces Heating Apparatus is graphite resistor furnace or medium-frequency induction furnace, more preferably, adopts medium-frequency induction furnace;
Preferably, the vacuum tightness of described High Temperature Furnaces Heating Apparatus can reach 5 * 10
-3below Pa, preferred value is 1 * 10
-3below Pa.
6. the method for claim 1, is characterized in that,
While forming secondary silicon carbide material, adopt purity to be not less than 99.99% high purity oxygen gas during described high-temperature oxidation process, in stove, temperature is 600-1500 ° of C, preferred 800-1200 ° of C, and the time is 1-24 hour.
7. the method for claim 1, is characterized in that, while forming three silicon carbide material in high vacuum furnace, in the process of the degassed processing of high-temperature vacuum, in stove, vacuum tightness is 5 * 10
-2below Pa, the preferred value of described vacuum tightness is 1 * 10
-3below Pa, temperature is 1200-1700 ° of C, time 2-24 hour.
8. the method for claim 1, is characterized in that, in described wet chemistry Metallurgical processing, the acid solution of employing is HCl, HF, H
2sO
4, HNO
3one or more mixing acid soak, temperature is 20-85 ° of C, the time is not less than 6 hours.
9. the high-purity silicon carbide raw material making as claim 1～8 any one method;
Preferred, the meta particle diameter D of prepared high-purity silicon carbide raw material
50between 50-800 μ m, purity is greater than 99.999%.
10. a high-purity silicon carbide raw material as claimed in claim 9 is for the growth of crystal formation crystal;
Preferably, for one or more of growth 3C-SiC, 4H-SiC, 6H-SiC and the 15R-SiC crystal of crystal formation crystal.
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| CN104445202A (en) * | 2014-11-25 | 2015-03-25 | 德清州晶新材料科技有限公司 | High-purity aluminum-doped silicon carbide powder and synthetic method thereof |
| CN105417541A (en) * | 2015-12-22 | 2016-03-23 | 中国电子科技集团公司第二研究所 | Method for preparing high-purity silicon carbide powder |
| CN105600785A (en) * | 2015-12-24 | 2016-05-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method for silicon carbide aerogel |
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| CN104445202A (en) * | 2014-11-25 | 2015-03-25 | 德清州晶新材料科技有限公司 | High-purity aluminum-doped silicon carbide powder and synthetic method thereof |
| CN105417541A (en) * | 2015-12-22 | 2016-03-23 | 中国电子科技集团公司第二研究所 | Method for preparing high-purity silicon carbide powder |
| CN105600785A (en) * | 2015-12-24 | 2016-05-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method for silicon carbide aerogel |
| CN105603530A (en) * | 2016-01-12 | 2016-05-25 | 台州市一能科技有限公司 | Raw material for high-speed growth of silicon carbide crystals and silicon carbide crystal growing method |
| CN105603530B (en) * | 2016-01-12 | 2018-02-27 | 台州市一能科技有限公司 | For the raw material of carborundum crystals high-speed rapid growth and the growing method of carborundum crystals |
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| WO2019095634A1 (en) * | 2017-11-14 | 2019-05-23 | 山东天岳先进材料科技有限公司 | Method for synthesizing high-purity silicon carbide raw material and application thereof |
| CN108892513A (en) * | 2018-09-20 | 2018-11-27 | 东北大学 | A method of silicon carbide powder is prepared using induction furnace |
| WO2020098094A1 (en) * | 2018-11-12 | 2020-05-22 | 山东天岳先进材料科技有限公司 | Method for preparing high-purity silicon carbide powder |
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| CN112142052A (en) * | 2020-10-13 | 2020-12-29 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Method for recovering silicon carbide powder from silicon carbide crystal diamond wire multi-wire cutting waste liquid |
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