CN110016713A - Be carbonized silicon preparation method - Google Patents
Be carbonized silicon preparation method Download PDFInfo
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- CN110016713A CN110016713A CN201910454359.9A CN201910454359A CN110016713A CN 110016713 A CN110016713 A CN 110016713A CN 201910454359 A CN201910454359 A CN 201910454359A CN 110016713 A CN110016713 A CN 110016713A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/36—Carbides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/10—Metal solvents
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Abstract
The invention discloses a kind of carbonization silicon preparation methods, are related to silicon carbide technology field.The method continuously grows carborundum crystals by flux method, then pass through the cooling stability to improve growing silicon carbice crystals of contact to crucible, pass through the cooling of multi-region liquid metal contacts and multi-portion heating simultaneously, wrappage is eliminated in different high-temperature gradient region multistage drop migrations to realize, as the decline of crucible is so that the wrappage in carborundum crystals is progressively reduced until disappearance, carborundum crystals of the preparation without wrappage and low stress.The method selects low melting point higher boiling liquid metal contacts coolant liquid that can be recycled and economical and practical, passes through multistage wrappage of eliminating and improves efficiency and quality that solvent method grows silicon carbide.
Description
Technical field
The present invention relates to silicon carbide technology field more particularly to a kind of carbonization silicon preparation methods.
Background technique
Silicon carbide is a kind of important functional material and structural material, due to its high-melting-point, high rigidity, high thermal conductivity system
Number, the features such as thermal expansion coefficient is small, forbidden bandwidth is big, make it be widely used in refractory ceramics, composite material, machining, light
It learns and the fields such as semiconductor.Mainly pass through as heat-resisting material, silicon carbide and is passed through with raw materials such as quartz sand, coke, sawdusts
It is heated at high temperature to 2500 DEG C or more high-temperature calcinations to form, is mainly prepared into silicon carbide powder.The preparation of bulky crystal mainly passes through
Sintering, physical vapour deposition (PVD) and the flux method of powder, wherein the bulky single crystal body of high quality or there are the more of bulky single crystal
Crystal mainly passes through physical vapour deposition (PVD) and flux method, but physical vapour deposition (PVD) temperature is high, inefficiency, carborundum crystals
In easily there is the defects of micro-pipe, this method is mainly used in semiconductor field, size at present also major limitation 6 inches with
Under.Although the crystal of flux method preparation is more perfect, the speed of growth is much higher relative to physical vapour deposition (PVD), is not easy
Prepare bulky crystal.Therefore, not yet mature for the bulk silicon carbide crystal of efficient, quick preparation good quality.
Summary of the invention
The technical problem to be solved by the present invention is to how provide a kind of economical and practical, high-efficient and high quality silicon carbide
Preparation method.
In order to solve the above technical problems, the technical solution used in the present invention is: a kind of carbonization silicon preparation method, uses carbon
SiClx preparation facilities, it is characterised in that include the following steps:
Carborundum crystals are put into as seed crystal in melting kettle bottom, then to melting aid alloy is put into inside melting kettle, in original
Silicon/carbon mixed powder, molar ratio 1:1 are put into material supplement crucible；Then melting kettle is put among primary heater,
The part that seed crystal is placed in melting kettle bottom is placed in the first cooling system, then to the first cooling system, the second cooling system
Recirculated cooling water is passed through in system and third cooling system；
Start primary heater, the secondary heater, third heater outside the internal heater and melting kettle in melting kettle
And the 4th heater；The power of internal heater and primary heater is adjusted first, until melting aid alloy is molten into melting aid alloy
Melt, so that the temperature gradient that melting aid alloy melt composition is high, then 10-30 minutes stable；
Slowly the lifting of starting melting kettle and device of rotation driving rotate melting kettle, and subsequent start-up contacts coolant liquid reflux pump
So that liquid metal contacts coolant liquid starts the cycle over, importing disk by contact coolant liquid makes it flow to the outer wall of the crucible of rotation
On, and controlling melting kettle lifting and device of rotation driving moves downward melting kettle slowly, moves downward speed control and exists
Between 0.1-5mm/h；After melting kettle moves downward, silicon/carbon mixed powder is constantly supplemented into crucible merging by raw material and is helped
In molten alloy melt；
Since melting kettle rotates and moves downward, liquid metal contacts coolant liquid is covered with melting kettle outer surface, melting kettle
It is moved in the first cooling system first, and forms liquid metal contacts coolant liquid between melting kettle and the first cooling system
Contact layer；With the movement of melting kettle, into after the first cooling system, pass through the contact layer of liquid metal contacts coolant liquid
Strong cooling effect is played to crucible；
Since melting kettle rotates and moves downward, crucible sequentially enters secondary heater and the second cooling system, third heating
After device and third cooling system, the 4th heater and contact coolant liquid backflash, when enter secondary heater, third heater with
And when four heaters, the region growing temperature is adjusted to 1500 K -2800K；
After primary heater, secondary heater, third heater, the 4th heater lower end are successively left in melting kettle top,
It is taken up in order of priority the heating for stopping primary heater, secondary heater, third heater, the 4th heater；Until in melting kettle
Melting aid alloy melt liquid level be lower than liquid metal contacts coolant liquid upper surface, be then shut off internal heater；
Silicon carbide whisker bulk single crystal growth is completed, and last crystalline portion is cut away, and by X-ray or ultrasonic examination, detection is brilliant
The wrappage in internal portion, if also continuing to reduce the decrease speed of melting kettle containing wrappage and repeating above step until packet
Object disappearance is wrapped up in, the silicon carbide whisker body portion finally crystallized is cut away, completes the growth of carborundum crystals.
A further technical solution lies in: the amount that the silicon/carbon mixed powder enters melting aid alloy melt meets formula:m=π
R2 vρ, in formula,M isThe quality put into silicon/carbon mixed powder unit time, R are the diameter of melting kettle,vFor melting kettle to
The rate of lower movement,ρFor the density of silicon carbide, with the addition of the silicon/carbon mixed powder, the internal heater and raw material are mended
Crucible is filled slowly to rise.
A further technical solution lies in: with the decline of melting kettle, melting kettle enters among the first cooling system,
It is provided with contact coolant liquid above first cooling system and imports disk, contact coolant liquid imports the export mouth of disk outside melting kettle
Wall；Liquid metal contacts coolant liquid is imported contact coolant liquid by contact coolant liquid reflux pump to import in disk, is made under stress
It obtains liquid metal contacts coolant liquid and flow to melting kettle outer wall, melting kettle is rotated and moved downward, so that liquid metal contacts
Coolant liquid enters in the gap of the first cooling system and melting kettle, due to the high thermally conductive system of liquid metal contacts coolant liquid
Number, so that part of the melting kettle near the first cooling system generates rapid cooling, so that the solid-liquid of carborundum crystals
Interface produces big temperature gradient and improves the growth stability at interface；
With the decline of melting kettle, level-one flux metal field trash is formed in carborundum crystals matrix, when melting kettle into
It when entering secondary heater, adjusts each adding thermal resistance and the temperature in secondary heater region is made to reach 1500-2800K, close to the
One cooling system and the second cooling system side generate ultra high temperature gradient, after entering secondary heater region in carborundum crystals
Level-one flux metal field trash be molten into level-one flux metal drop again, with melting kettle decline, the fluxing gold of level-one
Belonging to drop can migrate relatively upward up to opposing stationary at a certain temperature, while occur part one in region at this temperature
Grade flux metal drop collects, and forms level-one flux metal liquid phase enrichment region, reduces silicon carbide in melting kettle in this way
The quantity of level-one flux metal field trash in crystal；
With the decline of melting kettle, the liquid metal contacts coolant liquid for being attached to melting kettle outer surface can be with melting kettle
Into in the gap of the second cooling system and melting kettle；Carborundum crystals after melting kettle enters the second cooling system region
In level-one flux metal drop be solidified as second level flux metal field trash again；After melting kettle enters third heater,
Adjusting each adding thermal resistance makes the temperature of third heater area reach 1500-2800K, close to the second cooling system and third
Cooling system side generates ultra high temperature gradient, the second level flux metal folder after entering third heater area in carborundum crystals
Sundries is molten into second level flux metal drop again, and with the decline of melting kettle, second level flux metal drop can be relatively upward
There is part second level flux metal drop up to opposing stationary at a certain temperature in migration in region at this temperature
Collect, and form second level flux metal liquid phase enrichment region, reduces in melting kettle the fluxing gold of second level in carborundum crystals in this way
Belong to the quantity of field trash；
With the decline of melting kettle, the liquid metal contacts coolant liquid of melting kettle outer surface can enter the with melting kettle
In the gap of three cooling systems and melting kettle；After melting kettle enters third cooling system region in carborundum crystals two
Grade flux metal drop is solidified as three-level flux metal field trash again；After melting kettle enters four heaters, adjust each
Adding thermal resistance makes the temperature of the 4th heater area reach 1500-2800K, close to third cooling system and contact coolant liquid
Backflash side generates ultra high temperature gradient, and the three-level flux metal after entering the 4th heater area in carborundum crystals is mingled with
Object is molten into three-level flux metal drop again, and with the decline of melting kettle, three-level flux metal drop can move relatively upward
It moves up to opposing stationary at a certain temperature, while occurring the remittance of part three-level flux metal drop in region at this temperature
Collect and form three-level flux metal liquid phase enrichment region, thus essentially eliminates in melting kettle that three-level is fluxing in carborundum crystals
Metallic inclusion；
With the decline of melting kettle, the liquid metal contacts coolant liquid of melting kettle outer surface can be back to melting kettle
It contacts in coolant liquid backflash, then flow to contact coolant liquid importing disk recycling by contacting coolant liquid reflux pump again.
A further technical solution lies in: the silicon carbide preparation facilities includes contact coolant liquid backflash, the reflux
Melting kettle lifting and device of rotation driving and liquid metal contacts coolant liquid, the power of the driving device are provided in slot
Output end is connect with the lower end of crucible supporting bar, and the upper end of the crucible supporting bar is fixedly connected with the bottom of melting kettle, from
Top to bottm is disposed with annular primary heater, the first cooling system, secondary heater, the second cooling system, third and adds
Hot device, third cooling system and the 4th heater, it is the primary heater, the first cooling system, secondary heater, second cold
But the intermediate space of system, third heater, third cooling system and the 4th heater forms the movement of the melting kettle
Channel is provided with internal heater in the upper end opening of the melting kettle, and the lower end of raw material supplement crucible is provided with commissioning pipe, former
Silicon/carbon mixed powder is provided in material supplement crucible, the upper end opening of the commissioning pipe is connected with raw material supplement crucible, institute
The lower end for stating commissioning pipe enters the melting kettle after the internal heater；The primary heater and the first cooling system
Between be provided with contact coolant liquid import disk, it is described import disk on be provided with along the melting kettle radial direction extend contact
The liquid inlet of coolant liquid introduction channel, contact coolant liquid reflux pump is connected by pipeline with the backflash, and described time
The liquid outlet of stream pump is connected by pipeline with the exterior side port of the introduction channel, the driving device, the heating
Device, the cooling system and the reflux pump are controlled by control module, for working under the control of control module.
A further technical solution lies in: the primary heater, the first cooling system, secondary heater, the second cooling
System, third heater, third cooling system, the 4th heater and contact coolant liquid importing disk are outer with the melting kettle
It keeps having the gap between wall；The structure phase of the primary heater, secondary heater, third heater and the 4th heater
Together, including several adding thermal resistances.
A further technical solution lies in: first cooling system, the second cooling system and third cooling systems
Structure is identical, the cooling bath including ring-type setting, is provided with cooling system upper shielding layer, the cooling on the upside of the cooling bath
It is provided with shielded layer under cooling system on the downside of slot, liquid metal coolant liquid and cooling water pipe, institute are provided in the cooling bath
It states and is connected with cooling water in cooling water pipe.
Preferred: the liquid metal contacts coolant liquid is Ga-In-Sn, Ga-Sn or In-Sn.
A further technical solution lies in: the first cooling system, the second cooling system and third cooling system and melting earthenware
Gap between crucible is between 0.1-0.5mm.
A further technical solution lies in: it is provided in the melting kettle as the carborundum crystals of seed crystal and fluxing
Alloy, the melting aid alloy include Si-C-Cr, Si-C-Fe, Si-C-Al, Si-C-Mn or Si-C-Ni.
A further technical solution lies in: silicon/carbon mixed powder molar ratio is 1:1 in the raw material supplement crucible.
A further technical solution lies in: internal heater lifting device and raw material are provided on the outside of the melting kettle
Supplement crucible lift device, for respectively driving internal heater lifting and raw material supplement crucible lifting, and it is described in plus
Hot device lifting device and raw material supplement crucible lift device are controlled by the control module.
The beneficial effects of adopting the technical scheme are that device and method of the present invention pass through flux method
Continuous growth carborundum crystals, then by the cooling stability to improve growing silicon carbice crystals of contact to crucible, simultaneously
By the cooling of multi-region liquid metal contacts and multi-portion heating, Lai Shixian comes in different high-temperature gradient region multistage drop migrations
Wrappage is eliminated, as the decline of crucible is so that the wrappage in carborundum crystals is progressively reduced until disappearance, preparation is without package
The carborundum crystals of object and low stress.Described device and method selection low melting point higher boiling liquid metal contacts coolant liquid can be followed
Ring uses and economical and practical, passes through multistage wrappage of eliminating and improves efficiency and quality that solvent method grows silicon carbide.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the structural schematic diagram of device described in the embodiment of the present invention；
Fig. 2 is the operation schematic diagram of device early growth period described in the embodiment of the present invention；
Fig. 3 is the partial structure diagram of device described in the embodiment of the present invention；
Wherein: 1: raw material supplements crucible, and 2: silicon/carbon mixed powder, 3: commissioning pipe, 4: internal heater, 5: melting kettle, add at 6: the first
Hot device, 7: the first cooling systems, 8: secondary heater；9: the second cooling system, 10: third heater, 11: third cooling system
System；12: the four heaters, 13: melting aid alloy melt, 14: carborundum crystals, 15: level-one flux metal field trash, 16: level-one
Flux metal liquid phase enrichment region, 17: level-one flux metal drop；18: second level flux metal field trash, 19: second level flux metal
Liquid phase enrichment region, 20: second level flux metal drop；21: three-level flux metal field trash, 22: the enrichment of three-level flux metal liquid phase
Area, 23: three-level flux metal drop, 24: cooling system upper shielding layer；25: liquid metal coolant liquid；26: cooling bath；27: cold
But water pipe；28: shielded layer under cooling system；29: contact coolant liquid backflash；30: liquid metal contacts coolant liquid；31: crucible
Support rod；32: contact coolant liquid imports disk；33: contact coolant liquid reflux pump；34: infiltration liquid metal.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
As shown in Figure 1-Figure 3, the embodiment of the invention discloses a kind of silicon carbide preparation facilities, including contact coolant liquid reflux
Slot 29 is provided with melting kettle lifting and device of rotation driving and liquid metal contacts coolant liquid 30, institute in the backflash
Stating liquid metal contacts coolant liquid 30 can be the low-melting alloys such as Ga-In-Sn, Ga-Sn, In-Sn.The driving device is moved
Power output end is connect with the lower end of crucible supporting bar 31, and the upper end of the crucible supporting bar 31 and the bottom of melting kettle 5 are fixed
Connection, the melting kettle 5 can be gone up and down and be rotated under the action of melting kettle lifting and device of rotation driving
Movement.It is disposed with primary heater 6, the first cooling system 7, secondary heater 8, the second cooling system of annular from top to bottom
System 9, third heater 10, third cooling system 11 and the 4th heater 12, the primary heater 6, the first cooling system
7, the centre of secondary heater 8, the second cooling system 9, third heater 10, third cooling system 11 and the 4th heater 12
Space forms the moving conduit of the melting kettle 5.
As Figure 1-Figure 2, internal heater 4 is provided in the upper end opening of the melting kettle 5, raw material supplements crucible 1
Lower end be provided with commissioning pipe 3, silicon/carbon mixed powder 2 is provided in raw material supplement crucible 1, silicon in the raw material supplement crucible 1/
The molar ratio of carbon mixed powder 2 is 1:1.The upper end opening of the commissioning pipe 3 is connected with raw material supplement crucible 1, described
The lower end of commissioning pipe 3 enters the melting kettle 5 after passing through the internal heater 4, and supplementing crucible 1 by the raw material can be continuous
Put into raw material into the melting kettle；Contact coolant liquid is provided between the primary heater 6 and the first cooling system 7
Disk 32 is imported, it is described to import the contact coolant liquid introduction channel for being provided on disk and extending along the melting kettle radial direction, it connects
The liquid inlet of touching coolant liquid reflux pump 33 is connected by pipeline with the backflash, the liquid outlet of the reflux pump
Be connected by pipeline with the exterior side port of the introduction channel, the driving device, the heater, the cooling system with
And the reflux pump is controlled by control module, for working under the control of control module.
Further, the primary heater 6, the first cooling system 7, secondary heater 8, the second cooling system 9, third
Heater 10, third cooling system 11, the 4th heater 12 and contact coolant liquid importing disk 32 are outer with the melting kettle 5
It keeps having the gap between wall.The primary heater 6, secondary heater 8, third heater 10 and the 4th heater 12 knot
Structure is identical, including several adding thermal resistances.
The structure of first cooling system 7, the second cooling system 9 and third cooling system 11 is identical, including ring-type
The cooling bath 26 of setting, the upside of the cooling bath 26 are provided with cooling system upper shielding layer 24, the downside of the cooling bath 26
Shielded layer 28 under cooling system are provided with, liquid metal coolant liquid 25 and cooling water pipe 27, institute are provided in the cooling bath 26
It states in cooling water pipe 27 and is connected with cooling water.Further, the first cooling system 7, the second cooling system 9 and third cooling system 11
Gap between melting kettle 5 is between 0.1-0.5mm.
The carborundum crystals and melting aid alloy as seed crystal are provided in the melting kettle 5, the melting aid alloy can
Think one or more of Si-C-Cr, Si-C-Fe, Si-C-Al, Si-C-Mn, Si-C-Ni.The outside of the melting kettle 5
It is provided with internal heater lifting device and raw material supplement crucible lift device, is gone up and down for respectively driving the internal heater 4
And raw material supplement crucible 1 is gone up and down, and the internal heater lifting device and raw material supplement crucible lift device are controlled by institute
State control module.
The embodiment of the invention also discloses a kind of carbonization silicon preparation methods, using the silicon carbide preparation facilities, including such as
Lower step:
As shown in Fig. 2, be put into carborundum crystals as seed crystal in 5 bottom of melting kettle, then help to being put into inside melting kettle 5
Fusion gold is put into silicon/carbon mixed powder 2, molar ratio 1:1 in raw material supplement crucible 1；Then melting kettle 5 is put into
Among primary heater 6, the part that seed crystal is placed in melting kettle bottom is placed in the first cooling system 7, it is then cold to first
But recirculated cooling water is passed through in system 7, the second cooling system 9 and third cooling system 11；
Start primary heater 6, the secondary heater 8, third heating outside the internal heater 4 and melting kettle in melting kettle
Device 10 and the 4th heater 12；The power of internal heater 4 and primary heater 6 is adjusted first, until melting aid alloy is molten into
Melting aid alloy melt 13, so that melting aid alloy melt 13 forms high temperature gradient, it is then 10-30 minutes stable；
Slowly the lifting of starting melting kettle and device of rotation driving rotate melting kettle 5, and subsequent start-up contacts coolant liquid reflux
Pump 33 starts the cycle over liquid metal contacts coolant liquid 30, and importing disk 32 by contact coolant liquid makes it flow to the melting of rotation
On the outer wall of crucible 5, and controlling melting kettle lifting and device of rotation driving moves downward melting kettle 5 slowly, transports downwards
Dynamic speed control is between 0.1-5mm/h；After melting kettle moves downward, constantly silicon/carbon mixed powder 2 is mended by raw material
Crucible 1 is filled to be placed in melting aid alloy melt 13；
Since melting kettle 5 rotates and moves downward, liquid metal contacts coolant liquid 30 is covered with 5 outer surface of melting kettle, melting
Crucible 5 is moved to first in the first cooling system 7, and is formed liquid metal between melting kettle 5 and the first cooling system 7 and connect
Touch the contact layer of coolant liquid 30；It is cold by liquid metal contacts into after the first cooling system 7 with the movement of melting kettle 5
But the contact layer of liquid 30 plays strong cooling effect to melting kettle 5, as shown in Figure 3；
Since melting kettle 5 rotates and moves downward, melting kettle 5 sequentially enter secondary heater 8 and the second cooling system 9,
After third heater 10 and third cooling system 11, the 4th heater 12 and contact coolant liquid backflash 29, add when entering second
When hot device 8, third heater 10 and four heaters 12, the region growing temperature is adjusted to 1500 K -2800K；
When primary heater 6, secondary heater 8, third heater 10, the 4th heater 12 are successively left in 5 top of melting kettle
Behind lower end, it is taken up in order of priority the heating for stopping primary heater 6, secondary heater 8, third heater 10, the 4th heater 12；Directly
The liquid level of melting aid alloy melt 13 into melting kettle 5 is lower than the upper surface of liquid metal contacts coolant liquid 30, is then shut off
Internal heater 4；
14 crystal growth of carborundum crystals is completed, and cuts away last crystalline portion, and pass through X-ray or ultrasonic examination, detection
The wrappage of crystals, if also containing wrappage continue reduce melting kettle 5 decrease speed and repeat above step it is straight
It disappears to wrappage, cuts away 14 part of carborundum crystals finally crystallized, complete the growth of carborundum crystals.
Further, the amount that the silicon/carbon mixed powder 2 enters melting aid alloy melt 13 meets formula:m=πR2 vρ, in formula,M isThe quality put into silicon/2 unit time of carbon mixed powder, R are the diameter of melting kettle 5,vIt is moved downward for melting kettle 5
Rate,ρFor the density of silicon carbide, with the addition of the silicon/carbon mixed powder 2, the internal heater and raw material supplement crucible
Slowly rise.
Further, it during the melting kettle declines, implements work and principle is as follows:
With the decline of melting kettle 5, melting kettle 5 enters among the first cooling system 7, is arranged above the first cooling system 7
There is contact coolant liquid to import disk 32, contact coolant liquid imports the export mouth of disk 32 close to 5 outer wall of melting kettle；It is cooled down by contact
Liquid metal contacts coolant liquid 30 is imported contact coolant liquid and imported in disk 32 by liquid reflux pump 33, makes liquid metal under stress
Contact coolant liquid 30 flow to 5 outer wall of melting kettle, and melting kettle 5 is rotated and moved downward, so that liquid metal contacts coolant liquid
30 enter in the gap of the first cooling system 7 and melting kettle 5, due to the high thermally conductive system of liquid metal contacts coolant liquid 30
Number, so that part of the melting kettle 5 near the first cooling system 7 generates rapid cooling, so that carborundum crystals 14
Big temperature gradient is produced at solid liquid interface and improves the growth stability at interface；
With the decline of melting kettle 5, level-one flux metal field trash 15 is formed in carborundum crystals matrix, works as melting kettle
When 5 entrance secondary heater 8, adjusts each adding thermal resistance and the temperature in 8 region of secondary heater is made to reach 1500-2800K, leaning on
Nearly first cooling system 7 and 9 side of the second cooling system generate ultra high temperature gradient, are carbonized after entering 8 region of secondary heater
Level-one flux metal field trash 15 in silicon crystal is molten into level-one flux metal drop 17 again, under melting kettle 5
Drop, level-one flux metal drop 17 can migrate relatively upward up to opposing stationary at a certain temperature, while at this temperature
Occur collecting for part primary flux metal drop 17 in region, and form level-one flux metal liquid phase enrichment region 16, subtracts in this way
The quantity of level-one flux metal field trash 15 in carborundum crystals in melting kettle is lacked；
With the decline of melting kettle 5, the liquid metal contacts coolant liquid 30 for being attached to 5 outer surface of melting kettle can be with melting
Crucible 5 enters in the gap of the second cooling system 9 and melting kettle 5；After melting kettle 5 enters 9 region of the second cooling system
Level-one flux metal drop 17 in carborundum crystals is solidified as second level flux metal field trash 18 again；When melting kettle 5 into
After entering third heater 10, adjusts each adding thermal resistance and the temperature in 10 region of third heater is made to reach 1500-2800K, leaning on
Nearly the second cooling system 9 and 11 side of third cooling system generate ultra high temperature gradient, the carbon after entering 10 region of third heater
Second level flux metal field trash 18 in SiClx crystal is molten into second level flux metal drop 20 again, with melting kettle 5
Decline, second level flux metal drop 20 can migrate relatively upward up to opposing stationary at a certain temperature, while at this temperature
Region in there is collecting for part second level flux metal drop 20, and form second level flux metal liquid phase enrichment region 19, in this way
Reduce the quantity of second level flux metal field trash 18 in carborundum crystals in melting kettle；
With the decline of melting kettle 5, the liquid metal contacts coolant liquid 30 of 5 outer surface of melting kettle can be with melting kettle 5
Into in the gap of third cooling system 11 and melting kettle 5；It is carbonized after melting kettle 5 enters 11 region of third cooling system
Second level flux metal drop 20 in silicon crystal is solidified as three-level flux metal field trash 21 again；When melting kettle 5 enters the
It after four heaters 12, adjusts each adding thermal resistance and the temperature in 12 region of the 4th heater is made to reach 1500-2800K, close to the
Three cooling systems 11 and contact 29 side of coolant liquid backflash generate ultra high temperature gradient, the carbon after entering 12 region of the 4th heater
Three-level flux metal field trash 21 in SiClx crystal is molten into three-level flux metal drop 23 again, with melting kettle 5
Decline, three-level flux metal drop 23 can migrate relatively upward up to opposing stationary at a certain temperature, while at this temperature
Region in there is collecting and forming three-level flux metal liquid phase enrichment region 22 for part three-level flux metal drop 23, thus
Essentially eliminate in melting kettle three-level flux metal field trash 21 in carborundum crystals；
With the decline of melting kettle 5, the liquid metal contacts coolant liquid 30 of 5 outer surface of melting kettle can be with melting kettle 5
It is back in contact coolant liquid backflash 29, then flow to contact coolant liquid importing disk 32 by contacting coolant liquid reflux pump 33 again
It is recycled.
The quantity and size of field trash are constantly reduced during haveing suffered, and are pooled in flux metal liquid phase enrichment region,
22 ruler of level-one flux metal liquid phase enrichment region 16, second level flux metal liquid phase enrichment region 19 and three-level flux metal liquid phase enrichment region
Very little continuous reduction.Ultra high temperature gradient is formed between two neighboring cold-zone, the fusing migration of liquid phase field trash collects, and then solidification is equal
It is completed under high gradient.The quantity of field trash is reduced step by step in this way until disappearing.
To sum up, device and method of the present invention continuously grow carborundum crystals by flux method, then by earthenware
The cooling stability to improve growing silicon carbice crystals of the contact of crucible, while adding by the way that multi-region liquid metal contacts are cooling with multi-region
Heat, Lai Shixian migrates to eliminate wrappage in different high-temperature gradient region multistage drops, as the decline of crucible is so that carbon
Wrappage in SiClx crystal is progressively reduced until disappearance, prepares the carborundum crystals without wrappage and low stress.Described device
It can be recycled with method selection low melting point higher boiling liquid metal contacts coolant liquid and economical and practical, packet is eliminated by multistage
Wrap up in efficiency and quality that object improves solvent method growth silicon carbide.
Claims (10)
1. a kind of carbonization silicon preparation method, uses silicon carbide preparation facilities, it is characterised in that include the following steps:
Carborundum crystals are put into as seed crystal in melting kettle (5) bottom, are then put into fluxing conjunction to melting kettle (5) is internal
Gold is put into silicon/carbon mixed powder (2), molar ratio 1:1 in raw material supplement crucible (1)；Then melting kettle (5) is put
It is intermediate to enter primary heater (6), melting kettle bottom is placed in the part merging the first cooling system (7) of seed crystal, then to
Recirculated cooling water is passed through in first cooling system (7), the second cooling system (9) and third cooling system (11)；
Start primary heater (6), the secondary heater (8), the outside the internal heater (4) and melting kettle in melting kettle
Three heaters (10) and the 4th heater (12)；The power of internal heater (4) and primary heater (6) is adjusted first, until
Melting aid alloy is molten into melting aid alloy melt (13), so that melting aid alloy melt (13) forms high temperature gradient, it is then stable
10-30 minutes；
Slowly the lifting of starting melting kettle and device of rotation driving rotate melting kettle (5), and subsequent start-up contacts coolant liquid and returns
Stream pump (33) starts the cycle over liquid metal contacts coolant liquid (30), and importing disk (32) by contact coolant liquid makes it flow to rotation
On the outer wall of the melting kettle (5) turned, and controlling melting kettle lifting and device of rotation driving keeps melting kettle (5) slowly downward
Movement, moves downward speed control between 0.1-5mm/h；After melting kettle moves downward, constantly by silicon/carbon mixed powder
(2) by raw material supplement crucible (1) merging melting aid alloy melt (13)；
Since melting kettle (5) rotate and move downward, liquid metal contacts coolant liquid (30) is covered with melting kettle (5) appearance
Face, melting kettle (5) are moved to first in the first cooling system (7), and melting kettle (5) and the first cooling system (7) it
Between formed liquid metal contacts coolant liquid (30) contact layer；With the movement of melting kettle (5), into the first cooling system
(7) after, strong cooling effect is played to melting kettle (5) by the contact layer of liquid metal contacts coolant liquid (30)；
Since melting kettle (5) rotate and move downward, melting kettle (5) sequentially enters secondary heater (8) and the second cooling
System (9), third heater (10) and third cooling system (11), the 4th heater (12) and contact coolant liquid backflash (29)
Afterwards, when entering secondary heater (8), third heater (10) and the 4th heater (12), the region growing temperature is adjusted
To 1500 K -2800K；
When primary heater (6), secondary heater (8), third heater (10), the 4th are successively left in melting kettle (5) top
Behind heater (12) lower end, it is taken up in order of priority and stops primary heater (6), secondary heater (8), third heater (10), the 4th
The heating of heater (12)；Until the liquid level of the melting aid alloy melt (13) in melting kettle (5) is cold lower than liquid metal contacts
But the upper surface of liquid (30) is then shut off internal heater (4)；
Carborundum crystals (14) crystal growth is completed, and last crystalline portion is cut away, and by X-ray or ultrasonic examination, is visited
The wrappage of crystals is surveyed, if also continuing to reduce the decrease speed of melting kettle (5) containing wrappage and repeating the above step
Suddenly until wrappage disappears, carborundum crystals (14) part finally crystallized is cut away, the growth of carborundum crystals is completed.
2. carbonization silicon preparation method as described in claim 1, it is characterised in that: the silicon/carbon mixed powder (2) enters fluxing conjunction
The amount of golden melt (13) meets formula:m=πR2 vρ, in formula,mFor the quality put into silicon/carbon mixed powder (2) unit time, R is
The diameter of melting kettle (5),vFor the rate that melting kettle (5) moves downward,ρFor the density of silicon carbide, with the silicon/carbon
The addition of mixed powder (2), the internal heater and raw material supplement crucible slowly rise.
3. carbonization silicon preparation method as described in claim 1, it is characterised in that:
With the decline of melting kettle (5), melting kettle (5) enters among the first cooling system (7), the first cooling system (7)
Top be provided with contact coolant liquid import disk (32), contact coolant liquid import disk (32) export mouth close to melting kettle (5) outside
Wall；Liquid metal contacts coolant liquid (30) are imported into contact coolant liquid by contact coolant liquid reflux pump (33) and import disk (32)
In, make liquid metal contacts coolant liquid (30) flow to melting kettle (5) outer wall under stress, melting kettle (5) rotation and to
Lower movement, so that liquid metal contacts coolant liquid (30) enters in the gap of the first cooling system (7) and melting kettle (5), by
In the high thermal coefficient of liquid metal contacts coolant liquid (30) so that melting kettle (5) in the first cooling system (7) nearby
Part generates rapid cooling, so that producing big temperature gradient at the solid liquid interface of carborundum crystals (14) and improving interface
Growth stability；
With the decline of melting kettle (5), level-one flux metal field trash (15) are formed in carborundum crystals matrix, work as melting
When crucible (5) enters secondary heater (8), adjusts each adding thermal resistance and the temperature in secondary heater (8) region is made to reach 1500-
2800K is generating ultra high temperature gradient close to the first cooling system (7) and the second cooling system (9) side, is entering the second heating
Level-one flux metal field trash (15) behind device (8) region in carborundum crystals is molten into level-one flux metal drop again
(17), with the decline of melting kettle (5), level-one flux metal drop (17) can be migrated relatively upward up to phase at a certain temperature
To static, while occurring collecting for part primary flux metal drop (17) in region at this temperature, and forms level-one
Flux metal liquid phase enrichment region (16) reduces in melting kettle level-one flux metal field trash (15) in carborundum crystals in this way
Quantity；
With the decline of melting kettle (5), the liquid metal contacts coolant liquid (30) for being attached to melting kettle (5) outer surface can be with
Melting kettle (5) enter in the gap of the second cooling system (9) and melting kettle (5)；When melting kettle (5) are cold into second
But the level-one flux metal drop (17) behind system (9) region in carborundum crystals is solidified as second level flux metal field trash again
(18)；After melting kettle (5) enter third heater (10), adjusts each adding thermal resistance and make third heater (10) region
Temperature reaches 1500-2800K, is generating ultra high temperature gradient close to the second cooling system (9) and third cooling system (11) side,
Second level flux metal field trash (18) after entering third heater (10) region in carborundum crystals is molten into second level again
Flux metal drop (20), with melting kettle (5) decline, second level flux metal drop (20) can relatively upward migration until
It is opposing stationary at a certain temperature, while occurring the remittance of part second level flux metal drop (20) in region at this temperature
Collection, and forms second level flux metal liquid phase enrichment region (19), reduces in melting kettle that second level is fluxing in carborundum crystals in this way
The quantity of metallic inclusion (18)；
With the decline of melting kettle (5), the liquid metal contacts coolant liquid (30) of melting kettle (5) outer surface can be with melting
Crucible (5) enters in the gap of third cooling system (11) and melting kettle (5)；When melting kettle (5) enter third cooling system
Second level flux metal drop (20) behind system (11) region in carborundum crystals is solidified as three-level flux metal field trash again
(21)；After melting kettle (5) enter the 4th heater (12), adjusts each adding thermal resistance and make the 4th heater (12) region
Temperature reaches 1500-2800K, is generating ultra-high temperature close to third cooling system (11) and contact coolant liquid backflash (29) side
Gradient, the three-level flux metal field trash (21) after entering the 4th heater (12) region in carborundum crystals are molten into again
Three-level flux metal drop (23), with the decline of melting kettle (5), three-level flux metal drop (23) can migrate relatively upward
Until it is opposing stationary at a certain temperature, while occurring part three-level flux metal drop (23) in region at this temperature
Collect and form three-level flux metal liquid phase enrichment region (22), thus essentially eliminates in melting kettle three in carborundum crystals
Grade flux metal field trash (21)；
With the decline of melting kettle (5), the liquid metal contacts coolant liquid (30) of melting kettle (5) outer surface can be with melting
Crucible (5) be back to contact coolant liquid backflash (29) in, then again by contact coolant liquid reflux pump (33) flow to contact it is cold
But liquid imports disk (32) and is recycled.
4. carbonization silicon preparation method as described in claim 1, it is characterised in that: the silicon carbide preparation facilities includes that contact is cold
But liquid backflash (29), melting kettle lifting and device of rotation driving are provided in the backflash and liquid metal contacts are cold
But the power output end of liquid (30), the driving device is connect with the lower end of crucible supporting bar (31), the crucible supporting bar
(31) upper end is fixedly connected with the bottom of melting kettle (5), be disposed with from top to bottom annular primary heater (6),
First cooling system (7), secondary heater (8), the second cooling system (9), third heater (10), third cooling system (11)
And the 4th heater (12), the primary heater (6), the first cooling system (7), secondary heater (8), the second cooling system
System (9), third heater (10), third cooling system (11) and the 4th heater (12) intermediate space form the melting
The moving conduit of crucible (5) is provided with internal heater (4) in the upper end opening of the melting kettle (5), and raw material supplements crucible
(1) lower end is provided with commissioning pipe (3), is provided with silicon/carbon mixed powder (2), the commissioning pipe (3) in raw material supplement crucible (1)
Upper end opening and the raw material supplement crucible (1) be connected, the lower end of the commissioning pipe (3) passes through the internal heater (4)
Enter the melting kettle (5) afterwards；Contact coolant liquid is provided between the primary heater (6) and the first cooling system (7)
It imports disk (32), it is described to import the contact coolant liquid introduction channel for being provided on disk and extending along the melting kettle radial direction,
The liquid inlet of contact coolant liquid reflux pump (33) is connected by pipeline with the backflash, the liquid row of the reflux pump
Outlet is connected by pipeline with the exterior side port of the introduction channel, the driving device, the heater, the cooling system
System and the reflux pump are controlled by control module, for working under the control of control module.
5. carbonization silicon preparation method as claimed in claim 4, it is characterised in that: the primary heater (6), the first cooling system
It unites (7), secondary heater (8), the second cooling system (9), third heater (10), third cooling system (11), the 4th heating
Device (12) and contact coolant liquid import between disk (32) and the outer wall of the melting kettle (5) and keep having the gap；Described first
Heater (6), secondary heater (8), the structure of third heater (10) and the 4th heater (12) are identical, including several
Adding thermal resistance.
6. carbonization silicon preparation method as claimed in claim 4, it is characterised in that: first cooling system (7), the second cooling
System (9) and the structure of third cooling system (11) are identical, the cooling bath (26) including ring-type setting, the cooling bath (26)
Upside be provided with cooling system upper shielding layer (24), be provided with shielded layer under cooling system on the downside of the cooling bath (26)
(28), liquid metal coolant liquid (25) and cooling water pipe (27), the cooling water pipe (27) are provided in the cooling bath (26)
Inside it is connected with cooling water.
7. carbonization silicon preparation method as claimed in claim 4, it is characterised in that: the liquid metal contacts coolant liquid (30) is
Ga-In-Sn, Ga-Sn or In-Sn.
8. carbonization silicon preparation method as claimed in claim 4, it is characterised in that: the first cooling system (7), the second cooling system
(9) and the gap between third cooling system (11) and melting kettle (5) is between 0.1-0.5mm.
9. carbonization silicon preparation method as claimed in claim 4, it is characterised in that: be provided in the melting kettle 5 as seed
Brilliant carborundum crystals and melting aid alloy, the melting aid alloy include Si-C-Cr, Si-C-Fe, Si-C-Al, Si-C-Mn or
Si-C-Ni。
10. carbonization silicon preparation method as claimed in claim 4, it is characterised in that: silicon/carbon in raw material supplement crucible (1)
The molar ratio of mixed powder (2) is 1:1, is provided with internal heater lifting device and raw material on the outside of the melting kettle (5)
Crucible lift device is supplemented, for respectively driving the internal heater (4) lifting and raw material supplement crucible (1) lifting, and institute
It states internal heater lifting device and raw material supplement crucible lift device is controlled by the control module.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108615A (en) * | 2020-09-16 | 2020-12-22 | 王德忠 | Aluminum product casting solution conveying system |
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| JP2008303125A (en) * | 2007-06-11 | 2008-12-18 | Toyota Motor Corp | METHOD FOR PRODUCING SiC SINGLE CRYSTAL |
| CN102534797A (en) * | 2010-11-26 | 2012-07-04 | 信越化学工业株式会社 | Method of producing sic single crystal |
| CN108546987A (en) * | 2018-07-26 | 2018-09-18 | 孟静 | The method of purifying solar energy level polysilicon |
| CN109112615A (en) * | 2018-11-12 | 2019-01-01 | 孟静 | The preparation method of large size silicon-carbide monocrystalline plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008303125A (en) * | 2007-06-11 | 2008-12-18 | Toyota Motor Corp | METHOD FOR PRODUCING SiC SINGLE CRYSTAL |
| CN102534797A (en) * | 2010-11-26 | 2012-07-04 | 信越化学工业株式会社 | Method of producing sic single crystal |
| CN108546987A (en) * | 2018-07-26 | 2018-09-18 | 孟静 | The method of purifying solar energy level polysilicon |
| CN109112615A (en) * | 2018-11-12 | 2019-01-01 | 孟静 | The preparation method of large size silicon-carbide monocrystalline plate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112108615A (en) * | 2020-09-16 | 2020-12-22 | 王德忠 | Aluminum product casting solution conveying system |
| CN112108615B (en) * | 2020-09-16 | 2021-11-23 | 江西晶科铝业有限公司 | Aluminum product casting solution conveying system |
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