CN103508454B - A kind of preparation method of high-purity silicon carbide raw material - Google Patents
A kind of preparation method of high-purity silicon carbide raw material Download PDFInfo
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- CN103508454B CN103508454B CN201210202086.7A CN201210202086A CN103508454B CN 103508454 B CN103508454 B CN 103508454B CN 201210202086 A CN201210202086 A CN 201210202086A CN 103508454 B CN103508454 B CN 103508454B
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Abstract
The invention provides a kind of preparation method of high-purity silicon carbide raw material, described method comprises the steps: to provide high-purity silicon powder and high-purity carbon dust; Be positioned over crucible after described high-purity silicon powder and high-purity carbon dust fully mix, in the High Temperature Furnaces Heating Apparatus of 1400-2200 DEG C, form a silicon carbide material, after described silicon carbide material crushes in oxidized still through the high temperature oxidation of 600-1400 DEG C, form secondary silicon carbide material; Described secondary silicon carbide material is degassed through 800-1600 DEG C of high-temperature vacuum in high vacuum furnace, forms three silicon carbide material; Described three silicon carbide material, through wet chemistry Metallurgical processing, obtain high-purity 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 is inferior since discovery SiC material in 1891, SiC has the performance of many excellences because of it, as hardness is high, resistance to grinding, high temperature resistant, resistance to oxidation, corrosion-resistant, high heat conductance, high chemical stability, broad-band gap and high electron mobility etc., by as abrasive material, refractory materials, electric-heating assembly, the raw material of the application such as black non-ferrous metal metallurgy, wherein abrasive material, metallurgical and high temperature bearing part is the main application fields of current silicon carbide, be applied to again the structural part in mechanical engineering and the sealing member etc. in chemical engineering now, and in corrosion, under abrasion and the extreme condition such as high temperature and space flight, there is very superior performance.Silicon carbide forms through pyrotic smelting in resistance furnace with raw materials such as quartz sand, refinery coke (or coal tar), wood chips (needing with salt when producing green silicon carbide) traditionally, because the techniques such as Conventional silicon carbide production process Raw, equipment, pulverizing are difficult to carry out precise hard_drawn tuhes, the silicon carbide purity of producing is lower, between 95-99%, general industry and production application can be met.
Be that the semi-conductor of representative has promoted the development of microelectronics and photoelectron technology greatly with silicon, the purity of silicon can be brought up to 9N(99.9999999% with the silicon purification techniques that the Siemens Method improved is representative) more than, based on HIGH-PURITY SILICON material, microelectronics revolutionizes our life looks and mode.But due to the restriction of the performance of material own, its device application is also tending towards the limit.Therefore 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 is that the third generation semi-conductor of representative has been a great deal of attention with silicon carbide.SiC, owing to having the features such as broad-band gap, high critical electric field, high heat conductance, high carrier saturation drift velocity, has huge potentiality in high temperature, high frequency, high-power, photoelectron and radioprotective etc.
But, need highly purified silicon materials the same with production Silicon Wafer, produce silicon carbide whisker fenestra and need highly purified sic raw material, current traditional method is due to the intrinsic defect of its technique, the various foreign matter content of silicon carbide produced is higher, purity is lower, producing as defects such as polycrystalline, microchannel, dislocation, parcels as being very easy to during raw material grow silicon carbide crystals, is difficult to be formed high-quality carborundum crystals; And due to the impact of various impurity especially transition metal impurity, crystal property degradation, wafer cannot use 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 accurately can control raw material and process making silicon carbide in the urgent need to developing one, 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 obtaining high-purity silicon carbide raw material, especially preparation is applicable to the method for high quality growing silicon carbice crystals high-purity silicon carbide raw material.
In a first aspect of the present invention, provide a kind of preparation method of high-purity silicon carbide raw material, described method comprises the steps:
High-purity silicon powder and high-purity carbon dust are provided;
Be positioned over crucible after described high-purity silicon powder and high-purity carbon dust fully mix, in the High Temperature Furnaces Heating Apparatus of 1400-2200 DEG C, form a silicon carbide material,
After described silicon carbide material crushes in oxidized still through the high temperature oxidation of 600-1400 DEG C, form secondary silicon carbide material;
Described secondary silicon carbide material is degassed through 800-1600 DEG C of high-temperature vacuum in high vacuum furnace, forms three silicon carbide material;
Described three silicon carbide material, through wet chemistry Metallurgical processing, obtain high-purity silicon carbide raw material.
In a preferred embodiment, described high-purity silicon carbide raw material is high-purity silicon carbide raw material.
In a preferred embodiment, the method of making high-purity silicon carbide (SiC) raw material of the present invention comprises: be positioned over crucible synthesizing silicon carbide in High Temperature Furnaces Heating Apparatus after adopting high-purity silicon powder and high-purity carbon dust, fully mixing, by controlling the loose shape silicon carbide of the synthesis such as synthesis temperature, furnace atmosphere, pressure, after pulverizing, wet chemistry Metallurgical processing degassed through high temperature oxidation, high-temperature vacuum, obtains high-purity silicon carbide powder raw material.
In a preferred embodiment, 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-purity carbon dust should be positioned in high purity aluminium oxide, zirconium white or plumbago crucible, preferred plumbago crucible.
Preferably, described high-purity silicon powder and high-purity carbon dust are high purity reagent, and purity all should be not less than 99.999%.
Contriver finds, the pollution of N to crystal, by rational processing condition, to drop to minimum by the present invention.
Concrete, the selection of described container avoids introducing N element.
Concrete, the selection of described high purity reagent avoids introduces N element and other impurity.
In a specific embodiment of the present invention, in the forming process of a described silicon carbide material, by control comprise synthesis temperature, furnace atmosphere, pressure processing condition and form loose shape silicon carbide.A silicon carbide with loose shape form of the present invention's synthesis, need not pulverize especially, crush 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, preferred hydrogen atmosphere.
Preferably, the pressure of furnace atmosphere is 1-500Torr, preferred 10-200Torr.
In a specific embodiment of the present invention, the median D of the high-purity silicon powder (purity is not less than 99.999%) provided
50(median D
50: particle diameter corresponding 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 being less than it also accounts for 50%, D
50also median or median particle diameter is.D50 is commonly used to the mean particle size representing powder.) between 10-1000 μm, representative value is between 100-500 μm; The median D of high-purity carbon dust (purity is not less than 99.999%)
50should between 0.3-300 μm, representative value should between 10-100 μm
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, when forming secondary silicon carbide material, adopt high purity oxygen gas (purity is not less than 99.99%) during described high-temperature oxidation process, in-furnace temperature is 600-1500 ° of C, preferred 800-1200 ° C, and the time is 1-24 hour.In order to reduce impurity, a silicon carbide is passed through high temperature oxidation process by contriver 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, when forming three silicon carbide material in high vacuum furnace, in the process of the degassed process 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, secondary silicon carbide by the process of high temperature high vacuum degassing, at high temperature will be held the volatilization of volatile metal oxide, obtain three silicon carbide by contriver.
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, and 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 as obtained in any one method of the present invention.
Preferred, the median D of described high-purity silicon carbide raw material
50between 50-800 μm, purity is greater than 99.999%.
A third aspect of the present invention provides a kind of high-purity silicon carbide raw material of the present invention 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.
Accompanying drawing explanation
Fig. 1 is process flow sheet.
Embodiment
The present inventor, through extensive and deep research, by improving preparation technology, obtains a kind of typical median D
5050-800 μm, purity is greater than the preparation method of the high-purity silicon carbide raw material of 99.999%.Complete the present invention on this basis.
Technical conceive of the present invention is as follows:
Present method passes through high-purity silicon powder and high-purity carbon dust synthesizing silicon carbide in high temperature of mixing, by controlling synthesis temperature, furnace atmosphere, the loose shape silicon carbide of pressure and other parameters synthesis, gently crush after through high temperature oxidation, high temperature high vacuum degassing, wet chemistry Metallurgical processing through wet chemistry Metallurgical processing, obtain typical median D
50at 50-800 μm, the purity high-purity silicon carbide raw material that is greater than 99.999%.
Below describe in detail to various aspects of the present invention:
Raw material: high-purity silicon powder and high-purity carbon dust
Preferably, described high-purity silicon powder and high-purity carbon dust are high purity reagent, and purity all should be not less than 99.999%.
In a preferred embodiment, described high-purity silicon carbide raw material is high-purity silicon carbide powder raw material.
In a preferred embodiment, the median of high-purity (purity the is not less than 99.999%) silica flour provided between 10-1000 μm, representative value should between 100-500 μm; The median D of high-purity (purity is not less than 99.999%) carbon dust
50should between 0.3-300 μm, representative value should between 10-100 μm
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-purity carbon dust should be positioned in high purity aluminium oxide, zirconium white or plumbago crucible, preferred plumbago crucible.
Contriver finds, the pollution of N to crystal, by rational processing condition, to drop to minimum by the present invention.
Concrete, the selection of described container avoids introducing N element.
Concrete, the selection of described high purity reagent avoids introduces N element and other impurity.
In order to decreasing pollution more, in the forming process of a described silicon carbide material, by control to comprise synthesis temperature, furnace atmosphere, pressure processing condition and 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, preferred hydrogen atmosphere.
Preferably, the pressure of furnace atmosphere is 1-500Torr, preferred 10-200Torr.
A silicon carbide with loose shape form of the present invention's synthesis, requires no pulverizing, crushes gently, 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
When 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-furnace temperature is 600-1500 ° of C, preferred 800-1200 ° C, and the time is 1-24 hour.
In order to reduce impurity, a silicon carbide by high temperature oxidation process, is got rid of unnecessary carbon by contriver, and, by burning a small amount of in powder, obtain secondary silicon carbide.
Form three silicon carbide material
In a specific embodiment of the present invention, when forming three silicon carbide material in high vacuum furnace, in the process of the degassed process 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, secondary silicon carbide by the process of high temperature high vacuum degassing, at high temperature will be held the volatilization of volatile metal oxide, obtain three silicon carbide by contriver.
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, and the time is not less than 6 hours.
High-purity silicon carbide raw material and its production and use
The median D of described high-purity silicon carbide raw material of the present invention
50between 50-800 μm, 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-purity carbon dust are provided;
Be positioned over crucible after described high-purity silicon powder and high-purity carbon dust fully mix, in High Temperature Furnaces Heating Apparatus, form a silicon carbide material,
Described silicon carbide material pulverize after in oxidized still through high temperature oxidation, form secondary silicon carbide material;
Degassed through high-temperature vacuum in the most high vacuum furnace of described secondary silicon carbide material, form three silicon carbide material;
Described three silicon carbide material, through wet chemistry Metallurgical processing, obtain high-purity silicon carbide raw material.
In a preferred embodiment, the method of making high-purity silicon carbide (SiC) raw material of the present invention comprises: be positioned over crucible synthesizing silicon carbide in High Temperature Furnaces Heating Apparatus after adopting high-purity silicon powder and high-purity carbon dust, fully mixing, by controlling synthesis temperature, furnace atmosphere, the loose shape silicon carbide of pressure and other parameters synthesis, after pulverizing, wet chemistry Metallurgical processing degassed through high temperature oxidation, high-temperature vacuum, obtains high-purity silicon carbide powder raw material.
High-purity silicon carbide raw material of the present invention is used 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, ensures the silicon carbide of synthesis of high purity:
Raw material adopts more than 99.999% silica flour and carbon dust, and high purity graphite crucible, can reach the Reaktionsofen of condition of high vacuum degree, and the possibility of pollution raw material, crucible and environment brought has dropped to bottom line;
By rational processing condition, the pollution of N to crystal dropped to minimum, and synthesis and there is a silicon carbide of loose shape form, without pulverizing, crush gently, be not easy introducing impurity;
A silicon carbide is passed through high temperature oxidation process in oxidized still, gets rid of unnecessary carbon, and, by burning a small amount of in powder, obtain secondary silicon carbide;
By in most for secondary silicon carbide high vacuum furnace by the process of high temperature high vacuum degassing, at high temperature will hold the volatilization of volatile metal oxide, obtain three silicon carbide;
By three silicon carbide obtained, by hydrometallurgical process, deionized water filters, and dries, obtains highly purified sic raw material.
The sic raw material prepared according to these processing condition is for the growth of carborundum crystals, and under the condition of vanadium that undopes, grown and had good profile, resistivity is 1 × 10
7the crystal of more than Ω cm.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.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, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
Weigh purity respectively and be not less than 99.999%, D
50footpath is not less than 99.999%, D at the silica flour 250 grams of 200 μm with purity
50footpath, at the carbon dust 100 grams of 30 μm, is positioned over full and uniform mixing in clean plastic containers or polytetrafluoroethylcontainer container, is transferred in high purity graphite crucible by mixed powder, be positioned in medium-frequency induction furnace, be evacuated to 5 × 10
-4pa, then pass into argon gas and hydrogen, flow is respectively 6L/min and 1L/min, and controls furnace pressure and remain on about 50Torr.With speed heating crucible to the 1800 ° C of 800 ° of C/h, be incubated 12 hours, stop heating.When in-furnace temperature drops to 500 ° of below C, stop argon gas and hydrogen flowing quantity supply, during cool to room temperature, plumbago crucible is taken out, the loose shape silicon carbide tentatively synthesized is crushed gently, obtains a silicon carbide material.
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 oxide treatment carried out to synthetic material, 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, is evacuated to and is less than 1 × 10
-3below Pa, and be heated to 1450 ° of C, be incubated 10 hours, cooling, obtains vacuum outgas three silicon carbide material.
Three silicon carbide material be positioned in clean polytetrafluoroethylcontainer container, to add 800mL concentration be 36.5%MOS level HCl, 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 about 410 grams of carborundum powders.Through GDMS(glow discharge mass spectrometry) to measure, metallic impurity total content detects N content at below 8ppmw at below 10ppmw, SIMS (second ion mass spectroscopy), laser particle analyzer test silicon carbide powder median D
50it is 120 μm.
Embodiment 2
Weigh purity respectively and be not less than 99.999%, D
50footpath is not less than 99.999%, D at the silica flour 210 grams of 200 μm with purity
50footpath, at the carbon dust 100 grams of 90 μm, is positioned over full and uniform mixing in clean plastic containers or polytetrafluoroethylcontainer container, is transferred in high purity graphite crucible by mixed powder, be positioned in medium-frequency induction furnace, be evacuated to 5 × 10
-4pa, then pass into argon gas and hydrogen, flow is respectively 10L/min and 2L/min, and controls furnace pressure and remain on about 100Torr.With speed heating crucible to the 1900 ° C of 800 ° of C/h, be incubated 12 hours, stop heating.When in-furnace temperature drops to 500 ° of below C, stop argon gas and hydrogen flowing quantity supply, during cool to room temperature, plumbago crucible is taken out, the loose shape silicon carbide tentatively synthesized is crushed gently, obtains a silicon carbide material.
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 oxide treatment carried out to synthetic material, 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, is evacuated to and is less than 1 × 10
-3below Pa, and be heated to 1600 ° of C, be incubated 10 hours, cooling, obtains vacuum outgas three silicon carbide material.
Three silicon carbide material be positioned in clean polytetrafluoroethylcontainer container, to add 800mL concentration be 36.5%MOS level HCl, 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 about 270 grams of carborundum powders.Through GDMS(glow discharge mass spectrometry) to measure, metallic impurity total content detects N content at below 5ppmw at below 5ppmw, SIMS (second ion mass spectroscopy), laser particle analyzer test silicon carbide powder median D
50it is 200 μm.
Embodiment 3
Weigh purity respectively and be not less than 99.999%, D
50footpath is not less than 99.999%, D at the silica flour 700 grams of 200 μm with purity
50footpath, at the carbon dust 300 grams of 30 μm, is positioned over full and uniform mixing in clean plastic containers or polytetrafluoroethylcontainer container, is transferred in high purity graphite crucible by mixed powder, be positioned in medium-frequency induction furnace, be evacuated to 5 × 10
-4pa, then pass into argon gas and hydrogen, flow is respectively 10L/min and 3L/min, and controls furnace pressure and remain on about 80Torr.With speed heating crucible to the 2000 ° C of 800 ° of C/h, be incubated 12 hours, stop heating.When in-furnace temperature drops to 500 ° of below C, stop argon gas and hydrogen flowing quantity supply, during cool to room temperature, plumbago crucible is taken out, the loose shape silicon carbide tentatively synthesized is crushed gently, obtains a silicon carbide material.
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 oxide treatment carried out to synthetic material, 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, is evacuated to and is less than 1 × 10
-3below Pa, and be heated to 1600 ° of C, be incubated 12 hours, cooling, obtains vacuum outgas three silicon carbide material.
Three silicon carbide material be positioned in clean polytetrafluoroethylcontainer container, to add 1000mL concentration be 36.5%MOS level HCl, 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 about 950 grams of carborundum powders.Through GDMS(glow discharge mass spectrometry) to measure, metallic impurity total content detects N content at below 2ppmw at below 1ppmw, SIMS (second ion mass spectroscopy), laser particle analyzer test silicon carbide powder median D
50it is 500 μm.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (22)
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-purity carbon dust are provided;
Crucible is positioned over after described high-purity silicon powder and high-purity carbon dust fully mix, react in the High Temperature Furnaces Heating Apparatus of 1400-2200 DEG C and within 3-36 hour, form loose shape silicon carbide material, furnace atmosphere is hydrogen atmosphere, argon gas atmosphere or its mixed gas, and the pressure of furnace atmosphere is 1-500Torr
After described silicon carbide material crushes in oxidized still through the high temperature oxidation of 800-1200 DEG C, the time is 1-24 hour, forms secondary silicon carbide material; Purity is adopted to be not less than the high purity oxygen gas of 99.99% during described high-temperature oxidation process;
Described secondary silicon carbide material is degassed through 800-1600 DEG C of high-temperature vacuum in high vacuum furnace, forms three silicon carbide material;
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.
3. method as claimed in claim 2, it is characterized in that, in the forming process of a described silicon carbide material, mixed high-purity silicon powder and high-purity carbon dust should be positioned in high purity aluminium oxide, zirconium white or plumbago crucible.
4. the method for claim 1, is characterized in that, described high-purity silicon powder and high-purity carbon dust are high purity reagent, and purity all should be not less than 99.999%.
5. method as claimed in claim 3, it is characterized in that, in the forming process of a described silicon carbide material, mixed high-purity silicon powder and high-purity carbon dust should be positioned in plumbago crucible.
6. the method for claim 1, is characterized in that,
In the forming process of a described silicon carbide material
Temperature of reaction is 1700-2000 DEG C.
7. the method for claim 1, is characterized in that, the furnace atmosphere in the forming process of a described silicon carbide material is hydrogen atmosphere.
8. the method for claim 1, is characterized in that, in the forming process of a described silicon carbide material, the pressure of furnace atmosphere is 10-200Torr.
9. the method for claim 1, is characterized in that, the median D of the high-purity silicon powder provided
50between 10-1000 μm; The median D of high-purity carbon dust
50should between 0.3-300 μm.
10. method as claimed in claim 9, is characterized in that, the median D of the high-purity silicon powder provided
50representative value is between 100-500 μm; The median D of high-purity carbon dust
50representative value is between 10-100 μm.
11. the method for claim 1, is characterized in that, described High Temperature Furnaces Heating Apparatus is graphite resistor furnace or medium-frequency induction furnace.
12. methods as claimed in claim 11, it is characterized in that, described High Temperature Furnaces Heating Apparatus is medium-frequency induction furnace.
13. the method for claim 1, is characterized in that, the vacuum tightness of described High Temperature Furnaces Heating Apparatus can reach 5 × 10
-3below Pa.
14. methods as claimed in claim 13, it is characterized in that, the vacuum tightness of described High Temperature Furnaces Heating Apparatus can reach 1 × 10
-3below Pa.
15. the method for claim 1, is characterized in that,
When forming secondary silicon carbide material, during described high-temperature oxidation process, in-furnace temperature is 800-1200 DEG C.
16. the method for claim 1, is characterized in that, when forming three silicon carbide material in high vacuum furnace, in the process of the degassed process of high-temperature vacuum, in stove, vacuum tightness is 5 × 10
-2below Pa, temperature is 1200-1600 DEG C, time 2-24 hour.
17. methods as claimed in claim 16, is characterized in that, when forming three silicon carbide material in high vacuum furnace, in the process of the degassed process of high-temperature vacuum, in stove, vacuum tightness is 1 × 10
-3below Pa.
18. 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 DEG C, and the time is not less than 6 hours.
19. 1 kinds of high-purity silicon carbide raw materials obtained as claim 1 ~ 18 any one method.
20. high-purity silicon carbide raw materials as claimed in claim 19, is characterized in that, the median D of obtained high-purity silicon carbide raw material
50between 50-800 μm, purity is greater than 99.999%.
21. 1 kinds of high-purity silicon carbide raw materials as described in claim 19 or 20 are used for the growth of crystal formation crystal.
The purposes of 22. high-purity silicon carbide raw materials as claimed in claim 21, is characterized in that, for one or more in growth 3C-SiC, 4H-SiC, 6H-SiC and 15R-SiC crystal of crystal formation crystal.
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| CN104445202B (en) * | 2014-11-25 | 2017-04-12 | 德清州晶新材料科技有限公司 | High-purity aluminum-doped silicon carbide powder and synthetic method thereof |
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| 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 |
| CN108193282B (en) * | 2017-11-14 | 2019-06-25 | 山东天岳先进材料科技有限公司 | A kind of synthetic method and its application of high-purity silicon carbide raw material |
| CN108892513A (en) * | 2018-09-20 | 2018-11-27 | 东北大学 | A method of silicon carbide powder is prepared using induction furnace |
| CN109502589A (en) * | 2018-11-12 | 2019-03-22 | 山东天岳先进材料科技有限公司 | A method of preparing high-purity silicon carbide powder |
| CN110950341B (en) * | 2019-12-24 | 2021-11-02 | 山东天岳先进科技股份有限公司 | Silicon carbide powder and preparation method and device thereof |
| 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 |
| CN112960673B (en) * | 2021-03-19 | 2023-07-04 | 河南醒狮供应链管理有限公司 | Process for preparing 4H silicon carbide electronic material by in-situ synthesis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281910A (en) * | 1999-07-21 | 2001-01-31 | 中国科学院山西煤炭化学研究所 | Preparation method of nanometer silicon carbide whiskers |
| CN101302011A (en) * | 2008-06-04 | 2008-11-12 | 山东大学 | Artificial synthetic method of high-pure SiC power for semiconductor single-crystal growth |
-
2012
- 2012-06-19 CN CN201210202086.7A patent/CN103508454B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1281910A (en) * | 1999-07-21 | 2001-01-31 | 中国科学院山西煤炭化学研究所 | Preparation method of nanometer silicon carbide whiskers |
| CN101302011A (en) * | 2008-06-04 | 2008-11-12 | 山东大学 | Artificial synthetic method of high-pure SiC power for semiconductor single-crystal growth |
Non-Patent Citations (1)
| Title |
|---|
| 刘劲松.第九章非金属材料.《工程材料与热加工实践》.2011,第245页. * |
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