CN113005512B - Silicon carbide single crystal ingot growth equipment and method - Google Patents
Silicon carbide single crystal ingot growth equipment and method Download PDFInfo
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- CN113005512B CN113005512B CN202110416789.9A CN202110416789A CN113005512B CN 113005512 B CN113005512 B CN 113005512B CN 202110416789 A CN202110416789 A CN 202110416789A CN 113005512 B CN113005512 B CN 113005512B
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- 239000013078 crystal Substances 0.000 title claims abstract description 57
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 98
- 230000008022 sublimation Effects 0.000 claims abstract description 28
- 238000000859 sublimation Methods 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 94
- 229910002804 graphite Inorganic materials 0.000 claims description 93
- 239000010439 graphite Substances 0.000 claims description 93
- 239000007789 gas Substances 0.000 claims description 39
- 239000012159 carrier gas Substances 0.000 claims description 31
- 230000007246 mechanism Effects 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000005674 electromagnetic induction Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000005087 graphitization Methods 0.000 abstract description 4
- 230000002860 competitive effect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010288 cold spraying Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005092 sublimation method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
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Classifications
-
- 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
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
-
- 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
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/002—Controlling or regulating
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a silicon carbide single crystal ingot growth device and a method, wherein the device comprises a feeding device, a preheating device, a sublimation separation device and an ingot growth device; the feeding device, the preheating device and the sublimation separation device are sequentially communicated in the vertical direction, and the sublimation separation device and the ingot growth device are communicated in the horizontal direction. The invention can realize uninterrupted feeding in the ingot growing process and provide sufficient source material preparation for preparing large-size ingots. The granular powdery source material is heated in a movable mode, so that the graphitization of the source material can be avoided, the exhaustion of a growth source is avoided, and the preparation of a large-size ingot is facilitated. In addition, the system recovers the silicon carbide fixed substances and the gas phase substances in the ingot growing process, can be recycled through simple treatment, has low production source material cost, has no complicated mechanical design and low equipment cost, is particularly suitable for large-size ingot growth, and has more competitive products.
Description
Technical Field
The invention relates to the technical field of preparation of silicon carbide single crystal ingots, in particular to a silicon carbide single crystal ingot growth device and a silicon carbide single crystal ingot growth method.
Background
Currently, the main mass production technology of silicon carbide (SiC) single crystal ingots is the seeded sublimation method, also known as physical vapor transport growth PVT. The seed crystal sublimation method is to heat the solid source material of silicon carbide under vacuum environment to make the solid source material of silicon carbide produce sublimated gas phase substances, the main gas phase substances are Si, si 2 C、SC 2 . The single crystal ingot is grown by transporting the gas phase material to the seed crystal position for solidification by transporting the gas, as shown in fig. 1. In order to break through the limitation of PVT growth of silicon carbide, high temperature chemical vapor deposition method is proposed to grow silicon carbide single crystal ingot. Silicon carbide ingot growth is carried out in a vertically structured graphite crucible, wherein the ingot is pre-grownThe purge gas is transported upward and deposited after passing through a section of heating zone to the top seed crystal. The precursor gas adopts SiH diluted by carrier gas 4 And hydrocarbons such as alkanes, alkenes, etc., as shown in FIG. 2. Growing an ingot from a eutectic is one standard technique for preparing semiconductor ingots; a graphite crucible is filled with a silicon-based melt, and a seed crystal is placed in contact with the surface of the melt at a temperature slightly below the temperature of the melt to provide a growth drive. Aiming at the scheme of inhibiting the prior evaporation of silicon atoms from a melt, respectively providing a high-pressure growth method to improve the evaporation temperature of silicon; there is also a solution growth method of doping a solvent of metal to increase the solubility of carbon in silicon, and an ingot can be grown at a relatively low temperature, as shown in fig. 3.
The growth temperature of the source material in PVT is 2300-2400 ℃, and the temperature cannot inhibit the preferential evaporation of silicon in the silicon carbide source material, so that the silicon carbide source material is ceramic in graphite in the growth process of the sublimation method, and the growth source material can enter a depleted state, which limits the growth size of the ingot. The high-temperature chemical vapor deposition method can continuously supply precursor gas in principle, source material exhaustion does not occur, typical growth temperature is very high, corrosion of seed crystal and graphite wall is easy to cause or reaction with the seed crystal and graphite wall is easy to cause, helium is adopted as carrier gas, the carrier gas can be immediately heated, cold injection is difficult to cause to the surface of the seed crystal, in addition, the cost of helium and high-purity precursor gas is high, so that the product has no competitiveness and is not suitable for large-scale mass production. Solution growth is still in experimental stage at present, and the variables in the solution growth system of high-pressure solution growth or metal solvent are difficult to master, and high-quality large-size ingots grown by using the system are not yet seen.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a silicon carbide single crystal ingot growth device and a silicon carbide single crystal ingot growth method, which can not cause the problems of growth source material exhaustion and the like caused by the graphitization of a silicon carbide source material, can be suitable for preparing a large-size silicon carbide single crystal ingot, and has low equipment cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a silicon carbide single crystal ingot growing device comprises a feeding device, a preheating device, a sublimation separation device and an ingot growing device; the feeding device, the preheating device and the sublimation separation device are sequentially communicated in the vertical direction, and the sublimation separation device is communicated with the ingot growing device in the horizontal direction;
the feeding device comprises a trough for storing source materials, a sealing cover for sealing an inlet of the trough, a discharging pipe arranged at an outlet at the bottom of the trough and a first air pipe for communicating the trough with an external vacuum pump air system; a discharge valve and a vacuum switch valve are sequentially arranged on the discharge pipe from top to bottom;
the preheating treatment device comprises a heating channel, a feeding valve arranged on the heating channel, and a second air pipe communicated with the heating channel and arranged at the lower end of the feeding valve; the second air pipe is used for introducing carrier gas;
the sublimation separation device comprises a cavity, wherein a laser module for heating and sublimating source materials discharged from a heating channel, a graphite crucible for promoting and maintaining the sublimation of the source materials, a recovery tank for recovering solid source materials, a plurality of third air pipes for introducing carrier gas and a first heating mechanism for heating the graphite crucible and the third air pipes are arranged in the cavity;
the ingot growing device comprises a graphite cavity, a second heating mechanism for heating the graphite cavity and a seed crystal support arranged in the graphite cavity; one end of the graphite cavity is communicated with the graphite crucible, and the other end of the graphite cavity is communicated with an external vacuum pump gas system.
Preferably, the feeding valve comprises a shell, a central column and a rotating shaft, wherein a cylindrical cavity is formed in the shell, and a through hole is formed in the shell; the central column is tightly matched with the inner cavity and rotates in the inner cavity, and the central column seals the through hole; a plurality of grooves are formed in the cylindrical surface of the central column in the vertical direction, the central column is rotated, and the grooves can be opposite to the through holes; the rotating shaft is connected with the center column and extends to the outside of the shell.
Preferably, the preheating treatment device further comprises a heating groove and a spiral heater, the feeding valve is arranged between the heating groove and the spiral heater, and the heating groove, the feeding valve and the spiral heater are matched to form the heating channel;
the heating tank is in a bucket shape, and a plurality of cooling fins are arranged in the heating tank; the heating groove is made of solid conductive materials, and the upper end and the lower end of the heating groove are respectively connected with two poles of a first alternating current power supply to form a first heating body;
the spiral heater comprises a circular tube and a spiral body arranged in the circular tube, wherein the spiral body is made of solid conductive materials, and the upper end and the lower end of the spiral body are respectively connected with two poles of a second alternating current power supply to form a second heating body.
Preferably, the device also comprises two groups of electromagnet mechanisms, wherein the electromagnet mechanisms comprise a magnetic iron core and coils coiled on the periphery of the magnetic iron core, and two ends of each coil are respectively connected with two poles of a direct current power supply; the two groups of electromagnet mechanisms respectively generate electromagnetic induction with the heating groove and the spiral body, so that the heating groove and the spiral body vibrate.
Preferably, the heating channel stretches into the cavity, a reflecting plate matched with the laser module is arranged at the outlet position of the heating channel, and an included angle of 45 degrees is formed between the reflecting plate and the horizontal plane.
Preferably, a slope is arranged at the bottom of the graphite crucible and is arranged below the heating channel, and the slope forms an included angle of 30-60 degrees with the horizontal plane; and a discharge hole communicated with the recovery groove is arranged at the bottom of the slope.
Preferably, the number of the third air pipes is two, and the two third air pipes are aligned up and down and are respectively arranged at the top of the slope and the middle position of the slope; the third air pipe is a graphite pipe integrally formed with the graphite crucible.
Preferably, the graphite cavity comprises a small graphite cavity and a large graphite cavity which are integrally formed, an air hole is formed in the graphite crucible, and the small graphite cavity is communicated with the air hole; the pipe diameter of the small graphite cavity is equal to the pore diameter of the air hole, and the pipe diameter of the large graphite cavity is more than one time larger than the pipe diameter of the small graphite cavity; the seed crystal support is arranged in the large graphite cavity.
Preferably, the first heating mechanism and the second heating mechanism each comprise a radio frequency coil and a radio frequency power supply.
Preferably, the heating channel, the graphite crucible, the third air pipe and the graphite cavity are wrapped by a heat insulation layer.
The invention also discloses a silicon carbide single crystal ingot growth method which is realized by adopting the silicon carbide single crystal ingot growth equipment, and the method comprises the following steps:
step one, feeding: closing a discharge valve and a vacuum switch valve, putting gravel-shaped or powder source materials into a feed chute, sealing, and vacuumizing an upper closed space and a lower closed space isolated by the vacuum switch valve respectively through an external vacuum pump gas system until the production requirements are met;
step two, introducing carrier gas: the second air pipe and the third air pipe preheat the carrier gas respectively;
step three, preheating: the heating channel forms two temperature fields by taking a feeding valve as a boundary, the temperature of the upper temperature field is 500-800 ℃, and the temperature of the lower temperature field is 1600-1800 ℃; the source material stays in the temperature field at the upper end for heating, the source material moves in the temperature field at the lower end for heating, and the source material can be heated to 1600-1800 ℃ when being discharged from the heating channel through the two temperature fields;
step four, sublimation separation: forming a temperature field with the temperature of 2300-2600 ℃ in the graphite crucible; irradiating the source materials discharged from the heating channel by laser beams, so that part of the source materials absorb a large amount of light energy to sublimate into gas-phase materials, part of the source materials which are not sublimated fall into the graphite crucible to be heated continuously, and further part of the source materials are sublimated into gas-phase materials, and finally, the source materials which are not sublimated fall into the recovery tank; the sublimated gas phase substance is carried by the carrier gas into the ingot growing device;
step five, ingot growing: forming a temperature field with decreasing temperature in the graphite cavity, wherein the decreasing direction is from the graphite crucible towards the graphite cavity, and the temperature of the seed crystal placement position is 100-200 ℃ lower than that of the graphite crucible; solidifying the gas phase substance on the seed crystal to form a silicon carbide single crystal ingot; and the unused carrier gas and gas phase material flow to the vacuum pump gas system for recycling.
Preferably, the source material fed into the feed chute has a particle radius of no more than 0.5mm.
Preferably, the carrier gas is an inert gas.
After the scheme is adopted, the feeding device can be isolated into an independent vacuum feeding space through the vacuum switch valve, so that uninterrupted feeding in the ingot growing process is realized, and sufficient source material preparation is provided for preparing large-size ingots. The granular powdery source material is firstly heated in a preheating treatment device in a movable way, so that the graphitization of the source material can be avoided, the exhaustion of a growth source is avoided, and the preparation of a large-size ingot is facilitated; meanwhile, the preheating treatment device preheats the source material, so that the heating time of the source material in the sublimation stage can be shortened, and the growth process is further accelerated. The preheating treatment device, the sublimation separation device and the ingot growing device are respectively provided with an independent heating mechanism, so that the heating mechanism becomes a production parameter of a direct control variable, the coupling between temperatures in different stages is reduced, the fineness and the accuracy of the temperature control of the whole system are improved, and the thermal budget of the system is effectively reduced. The carrier gas is heated before being mixed with the gas phase substance, so that the cold spraying effect of the carrier gas can be reduced; meanwhile, the silicon carbide fixing substances and gas phase substances in the ingot growing process are recovered by the system, the silicon carbide fixing substances and the gas phase substances can be recycled through simple treatment, the production source material cost is low, in addition, the invention has no complicated mechanical design, the equipment cost is low, and the invention is particularly suitable for large-size ingot growth and the product is more competitive.
Drawings
Fig. 1 is a schematic diagram of PVT process.
FIG. 2 is a schematic diagram of a high temperature chemical vapor deposition process.
FIG. 3 is a schematic diagram of a solution growth method.
Fig. 4 is a schematic diagram of the apparatus of the present invention.
Fig. 5 is a schematic view of a feeding device according to the present invention.
FIG. 6 is a schematic diagram of a preheating treatment apparatus according to the present invention.
FIG. 7 is a schematic view of a feed valve in a preheating treatment apparatus according to the present invention.
FIG. 8 is a schematic view of a sublimation separation apparatus of the present invention.
Fig. 9 is a schematic view of an ingot growing apparatus of the present invention.
Description of the reference numerals:
the device comprises a feeding device 10, a trough 11, a sealing cover 12, a discharging pipe 13, a first air pipe 14, a discharging valve 15 and a vacuum switch valve 16;
the preheating treatment device 20, the heating tank 21, the cooling fins 211, the feeding valve 22, the shell 221, the central column 222, the rotating shaft 223, the through hole 224, the groove 225, the round tube 231, the spiral body 232, the second air tube 24 and the electromagnet mechanism 25;
sublimation separation apparatus 30, chamber 31, laser module 32, reflecting plate 33, graphite crucible 34, slope 341, recovery tank 35, third gas pipe (graphite pipe) 36, first heating mechanism 37;
ingot growing apparatus 40, small graphite chamber 411, large graphite chamber 412, second heating mechanism 42, seed crystal holder 43;
a seed crystal 50;
and an insulating layer 60.
Detailed Description
As shown in fig. 4 to 9, the present invention discloses a silicon carbide single crystal ingot growing apparatus comprising a feeding device 10, a preheating treatment device 20, a sublimation separation device 30, and an ingot growing device 40. The feeding device 10, the preheating treatment device 20 and the sublimation separation device 30 are sequentially communicated in the vertical direction, and the sublimation separation device 30 and the ingot growing device 40 are communicated in the horizontal direction.
The feeding device 10 comprises a trough 11 for storing source materials, a sealing cover 12 for sealing an inlet of the trough 11, a discharging pipe 13 arranged at an outlet at the bottom of the trough 11 and a first air pipe 14 for communicating the trough 11 with an external vacuum pump air system. The discharging valve 15 and the vacuum switch valve 16 are sequentially arranged on the discharging pipe 13 from top to bottom, and the drift diameter of the vacuum switch valve 16 is larger than that of the discharging valve 15, so that source materials cannot fall on the vacuum switch valve 16, the problem of difficult source material cleaning is avoided, and meanwhile, the vacuum isolation effect of the vacuum switch valve 16 is ensured.
The preheating treatment device 20 comprises a heating channel, a feeding valve 22 arranged on the heating channel, and a second air pipe 24 communicated with the heating channel and arranged at the lower end of the feeding valve 22. The second air pipe 24 is used for passing a carrier gas. Specifically, the heating channel is bounded by a feeding valve 22, the upper end of the heating channel is a heating groove 21, the lower end of the heating channel is a spiral heater, the feeding valve 22 is arranged between the heating groove 21 and the spiral heater, and the heating groove 21, the feeding valve 22 and the spiral heater are matched to form the heating channel.
The heating tank 21 is bucket-shaped, a plurality of radiating fins 211 are arranged in the heating tank 21, the heating tank 21 and the radiating fins 211 are made of solid conductive materials, and the upper end and the lower end of the heating tank 21 are respectively connected with two poles of a first alternating current power supply to form a first heating body. The spiral heater comprises a circular tube 231 and a spiral body 232 arranged in the circular tube 231, wherein the spiral body 232 is made of solid conductive materials, and the upper end and the lower end of the spiral body are respectively connected with two poles of a second alternating current power supply to form a second heating body. The second air pipe 24 is connected to the upper end of the circular pipe 231.
The feeding valve 22 comprises a housing 221, a central column 222 and a rotary shaft 223, wherein a cylindrical cavity is arranged in the housing 221, and a through hole 224 penetrating the housing 221 is arranged on the housing 221. The central post 222 is tightly fitted with the inner cavity and freely rotates in the inner cavity, and the central post 222 seals the through hole 224. The cylindrical surface of the central column 222 is vertically provided with a groove 225, and the central column 222 is rotated, and the groove 225 can be opposite to the through hole 224. The rotation shaft 223 is connected to the center post 222 and the rotation shaft 223 extends to the outside of the case 221. The bottom opening of the heating tank 21 is opposite to the through hole 224 at the upper end of the housing 221, and the top opening of the circular tube 231 is opposite to the through hole 224 at the lower end of the housing 221.
In addition, the preheating device 20 further includes two groups of electromagnet mechanisms 25, the electromagnet mechanisms 25 include a magnetic core and a coil wound around the periphery thereof, and both ends of the coil are respectively connected with two poles of the dc power supply. The two groups of electromagnet mechanisms 25 respectively generate electromagnetic induction with alternating current passing through the heating tank 11 and the spiral body 232, so that the heating tank 11 and the spiral body 232 vibrate. Through producing vibration for the source material can supplement kinetic energy in the removal in-process, and then overcomes the kinetic energy loss such as friction etc. causes, guarantees that the source material can move continually.
The sublimation separation apparatus 30 includes a chamber 31, and a laser module 32 for heating and sublimating a source material discharged from a heating passage, a graphite crucible 34 for promoting and maintaining sublimation of the source material, a recovery tank 35 for recovering a solid source material, two sets of third air pipes 36 for passing a carrier gas, and a first heating mechanism 37 for heating the graphite crucible 34 and the third air pipes 36 are provided in the chamber 31. The heating channel stretches into the cavity 31, the outlet position of the spiral heater is provided with a reflecting plate 33 matched with the laser module 32, the reflecting plate 33 forms an included angle of 45 degrees with the horizontal plane, the pulse laser beam is emitted from the laser module 32 and is absorbed by source materials falling from the spiral heater, so that the source materials begin to sublimate, laser energy which is not absorbed by the source materials enters the spiral heater through the reflecting plate 33, and the preheating effect of the source materials is further enhanced.
A slope 341 is arranged at the bottom of the graphite crucible 34, the slope 341 forms an included angle of 30-60 degrees with the horizontal plane, and the slope 341 is arranged below the heating channel. Two third air pipes 36 are aligned up and down and are respectively arranged at the top of the slope 341 and the middle position of the slope 341; preferably, the third gas tube 36 is a graphite tube integrally formed with the graphite crucible 34. The graphite crucible 34 is provided with an air hole communicating with the ingot growing apparatus at a position opposite to the side where the third air pipe 36 is provided. The slope bottom of the slope 341 is provided with a discharge port communicated with the recovery tank 35. The solid raw material which has absorbed the laser energy and has not been sublimated is dropped onto the slope 341, and is heated by the graphite crucible 34 until sublimated in the course of moving downward on the slope 341, and finally the solid raw material which has not been sublimated is dropped into the recovery tank 35.
The ingot growing apparatus includes a graphite chamber, a second heating mechanism 42 for heating the graphite chamber, and a seed crystal holder 43 disposed inside the graphite chamber. Specifically, the graphite chambers include an integrally formed small graphite chamber 411 and a large graphite chamber 412, the small graphite chamber 411 being in communication with the air holes. The pipe diameter of the small graphite cavity 411 is equal to the pore diameter of the air hole, and the pipe diameter of the large graphite cavity 412 is more than one time larger than the pipe diameter of the small graphite cavity 411. The seed crystal 50 is disposed within the large graphite chamber 412. The gap between the seed crystal 50 torr and the large graphite chamber 412 forms an exhaust vent that is vented to an external vacuum pump gas system.
The first heating mechanism 37 and the second heating mechanism 42 each include a radio frequency coil and a radio frequency power source. In addition, an insulating layer 60 is provided for encasing the heating tunnel, graphite crucible 34, third gas tube 36 and graphite chamber.
The invention also discloses a silicon carbide single crystal ingot growth method which is realized by adopting the silicon carbide single crystal ingot growth equipment, and the method comprises the following steps:
step one, feeding: the discharge valve 15 and the vacuum switch valve 16 are closed, and a gravel-shaped or powder source material is adopted, wherein the particle radius of the source material is not more than 0.5mm. And (3) putting the source materials into the feed tank 11, sealing, and vacuumizing an upper closed space and a lower closed space which are isolated by the vacuum switch valve 16 respectively through an external vacuum pump gas system until the production requirements are met. After the source material enters the next stage from the feeding device 10, the vacuum switch valve 16 is closed again, so that the feeding device 10 can be isolated, the feeding step can be repeated under the condition that the working of the next stage is not affected, the source material is replenished, the source material can be continuously supplied to the production without interruption, and the problem of source material exhaustion can not occur.
Step two, introducing carrier gas: the second gas pipe 24 and the third gas pipe 36 preheat the carrier gas, respectively.
Step three, preheating: the heating channel is bounded by a feed valve 22 to form two temperature fields, the upper temperature field is a heating tank 21, the temperature is 500-800 ℃, the lower temperature field is a spiral heater, and the temperature is 1600-1800 ℃. The source material is heated in the heating tank 21, and then a fixed amount of source material is fed into the screw heater by controlling the rotation frequency of the feed valve 22. The source material is heated in a moving manner in the spiral heater and is heated by two temperature fields, so that the source material can be heated to 1600-1800 ℃ when the source material is discharged from the heating channel. When the source material is in the spiral heater, the moving speed of the source material is controlled by controlling the current passing through the electromagnet mechanism 25 and further controlling the vibration frequency of the spiral body 232. In addition, the vibration also increases the rolling of the granular source material in the screw 232, making the source material more uniformly heated.
Step four, sublimation separation: a temperature field of 2300-2600 c is formed in the graphite crucible 34. The source material discharged from the heating passage and falling onto the reflecting plate 33 is irradiated with the laser beam, so that a part of the source material absorbs a large amount of light energy to sublimate into a gas phase material, and a part of the source material which is not sublimated falls into the graphite crucible 34 to continue heating, so that a part of the source material is sublimated into a gas phase material, and finally the source material which is not sublimated falls into the recovery tank 35. The sublimated vapor phase material is mixed with a carrier gas and flows into the ingot growing apparatus 40.
Step five, ingot growing: a temperature field is formed in the graphite chamber in a decreasing direction from the graphite crucible 34 toward the graphite chamber, the seed crystal 50 being placed at a temperature 100-200 c lower than the temperature at the graphite crucible 34. The vapor phase material solidifies on the seed crystal 50 into a single crystal ingot of silicon carbide, while the unused carrier gas and vapor phase material flow to the vacuum pump gas system for recycling.
In the above steps, the carrier gas is one or two inert gases, preferably argon, which has relatively low cost because the carrier gas has long heating time, and the argon can meet the use requirement. Alternatively, the carrier gas may be other inert gases than argon, or a mixture of argon and other inert gases; the carrier gas may be a mixture of a small amount of an auxiliary gas and/or an organometallic gas, and the auxiliary gas may be one or two or all of nitrogen, hydrogen and hydrogen chloride.
The key point of the invention is that the feeding device 10 can be isolated into an independent vacuum feeding space through the vacuum switch valve 16, so that uninterrupted feeding in the ingot growing process is realized, and sufficient source material preparation is provided for preparing large-size ingots. The granular powdery source material is firstly and movably heated in the preheating treatment device 20, and is also in a movable heating state in the sublimation separation device 30, so that the graphitization of the source material can be avoided, the exhaustion of a growth source is avoided, and the preparation of a large-size ingot is facilitated; meanwhile, the preheating treatment device 20 preheats the source material, so that the heating time of the source material in the sublimation stage can be shortened, and the growth process can be further accelerated. The preheating treatment device 20, the sublimation separation device 30 and the ingot growing device 40 are respectively provided with independent heating mechanisms, become production parameters of a direct control variable, reduce the coupling between temperatures in different stages, improve the fineness and the accuracy of the temperature control of the whole system and effectively reduce the thermal budget of the system. The carrier gas is heated before being mixed with the gas phase substance, so that the cold spraying effect of the carrier gas can be reduced; meanwhile, the silicon carbide fixing substances and gas phase substances in the ingot growing process are recovered by the system, the silicon carbide fixing substances and the gas phase substances can be recycled through simple treatment, the production source material cost is low, in addition, the invention has no complicated mechanical design, the equipment cost is low, and the invention is particularly suitable for large-size ingot growth and the product is more competitive.
The foregoing embodiments of the present invention are not intended to limit the technical scope of the present invention, and therefore, any minor modifications, equivalent variations and modifications made to the above embodiments according to the technical principles of the present invention still fall within the scope of the technical proposal of the present invention.
Claims (13)
1. A silicon carbide single crystal ingot growing apparatus, characterized in that: comprises a feeding device, a preheating device, a sublimation separation device and an ingot growing device; the feeding device, the preheating device and the sublimation separation device are sequentially communicated in the vertical direction, and the sublimation separation device is communicated with the ingot growing device in the horizontal direction;
the feeding device comprises a trough for storing source materials, a sealing cover for sealing an inlet of the trough, a discharging pipe arranged at an outlet at the bottom of the trough and a first air pipe for communicating the trough with an external vacuum pump air system; a discharge valve and a vacuum switch valve are sequentially arranged on the discharge pipe from top to bottom;
the preheating treatment device comprises a heating channel, a feeding valve arranged on the heating channel, and a second air pipe communicated with the heating channel and arranged at the lower end of the feeding valve; the second air pipe is used for introducing carrier gas;
the sublimation separation device comprises a cavity, wherein a laser module for heating and sublimating source materials discharged from a heating channel, a graphite crucible for promoting and maintaining the sublimation of the source materials, a recovery tank for recovering solid source materials, a plurality of third air pipes for introducing carrier gas and a first heating mechanism for heating the graphite crucible and the third air pipes are arranged in the cavity; the heating channel extends into the cavity, and a reflecting plate matched with the laser module is arranged at the outlet position of the heating channel; the bottom of the graphite crucible is provided with a slope which is arranged below the heating channel, and the slope bottom of the slope is provided with a discharge hole communicated with the recovery groove;
the ingot growing device comprises a graphite cavity, a second heating mechanism for heating the graphite cavity and a seed crystal support arranged in the graphite cavity; one end of the graphite cavity is communicated with the graphite crucible, and the other end of the graphite cavity is communicated with an external vacuum pump gas system.
2. A silicon carbide single crystal ingot growth apparatus as claimed in claim 1, wherein: the feeding valve comprises a shell, a central column and a rotating shaft, wherein a cylindrical cavity is formed in the shell, and a through hole is formed in the shell; the central column is tightly matched with the inner cavity and rotates in the inner cavity, and the central column seals the through hole; a plurality of grooves are formed in the cylindrical surface of the central column in the vertical direction, the central column is rotated, and the grooves can be opposite to the through holes; the rotating shaft is connected with the center column and extends to the outside of the shell.
3. A silicon carbide single crystal ingot growth apparatus as claimed in claim 1 or 2, wherein: the preheating treatment device further comprises a heating groove and a spiral heater, the feeding valve is arranged between the heating groove and the spiral heater, and the heating groove, the feeding valve and the spiral heater are matched to form the heating channel;
the heating tank is in a bucket shape, and a plurality of cooling fins are arranged in the heating tank; the heating groove is made of solid conductive materials, and the upper end and the lower end of the heating groove are respectively connected with two poles of a first alternating current power supply to form a first heating body;
the spiral heater comprises a circular tube and a spiral body arranged in the circular tube, wherein the spiral body is made of solid conductive materials, and the upper end and the lower end of the spiral body are respectively connected with two poles of a second alternating current power supply to form a second heating body.
4. A silicon carbide single crystal ingot growth apparatus according to claim 3, wherein: the electromagnetic mechanism comprises a magnetic iron core and a coil coiled around the periphery of the magnetic iron core, and two ends of the coil are respectively connected with two poles of a direct current power supply; the two groups of electromagnet mechanisms respectively generate electromagnetic induction with the heating groove and the spiral body, so that the heating groove and the spiral body vibrate.
5. A silicon carbide single crystal ingot growth apparatus as claimed in claim 1, wherein: the reflecting plate forms an included angle of 45 degrees with the horizontal plane.
6. A silicon carbide single crystal ingot growth apparatus as claimed in claim 1, wherein: the inclined plane forms an included angle of 30-60 degrees with the horizontal plane.
7. A silicon carbide single crystal ingot growth apparatus as claimed in claim 6, wherein: the two third air pipes are aligned up and down and are respectively arranged at the top of the slope and the middle position of the slope; the third air pipe is a graphite pipe integrally formed with the graphite crucible.
8. A silicon carbide single crystal ingot growth apparatus as claimed in claim 1, wherein: the graphite cavity comprises a small graphite cavity and a large graphite cavity which are integrally formed, an air hole is formed in the graphite crucible, and the small graphite cavity is communicated with the air hole; the pipe diameter of the small graphite cavity is equal to the pore diameter of the air hole, and the pipe diameter of the large graphite cavity is more than one time larger than the pipe diameter of the small graphite cavity; the seed crystal support is arranged in the large graphite cavity.
9. A silicon carbide single crystal ingot growth apparatus as claimed in claim 1, wherein: the first heating mechanism and the second heating mechanism comprise a radio frequency coil and a radio frequency power supply.
10. A silicon carbide single crystal ingot growth apparatus as claimed in claim 1, wherein: the graphite crucible further comprises an insulating layer used for wrapping the heating channel, the graphite crucible, the third air pipe and the graphite cavity.
11. A method for growing a silicon carbide single crystal ingot, characterized by being implemented using the silicon carbide single crystal ingot growth apparatus according to any one of claims 1 to 10, comprising:
step one, feeding: closing a discharge valve and a vacuum switch valve, putting gravel-shaped or powder source materials into a feed chute, sealing, and vacuumizing an upper closed space and a lower closed space isolated by the vacuum switch valve respectively through an external vacuum pump gas system until the production requirements are met;
step two, introducing carrier gas: the second air pipe and the third air pipe preheat the carrier gas respectively;
step three, preheating: the heating channel forms two temperature fields by taking a feeding valve as a boundary, the temperature of the upper temperature field is 500-800 ℃, and the temperature of the lower temperature field is 1600-1800 ℃; the source material stays in the temperature field at the upper end for heating, the source material moves in the temperature field at the lower end for heating, and the source material can be heated to 1600-1800 ℃ when being discharged from the heating channel through the two temperature fields;
step four, sublimation separation: forming a temperature field with the temperature of 2300-2600 ℃ in the graphite crucible; irradiating the source materials discharged from the heating channel by laser beams, so that part of the source materials absorb a large amount of light energy to sublimate into gas-phase materials, part of the source materials which are not sublimated fall into the graphite crucible to be heated continuously, and further part of the source materials are sublimated into gas-phase materials, and finally, the source materials which are not sublimated fall into the recovery tank; the sublimated gas phase substance is carried by the carrier gas into the ingot growing device;
step five, ingot growing: forming a temperature field with decreasing temperature in the graphite cavity, wherein the decreasing direction is from the graphite crucible towards the graphite cavity, and the temperature of the seed crystal placement position is 100-200 ℃ lower than that of the graphite crucible; solidifying the gas phase substance on the seed crystal to form a silicon carbide single crystal ingot; and the unused carrier gas and gas phase material flow to the vacuum pump gas system for recycling.
12. A method for growing a silicon carbide single crystal according to claim 11, wherein: the radius of the particles of the source materials put into the feeding groove is not more than 0.5mm.
13. A method for growing a silicon carbide single crystal according to claim 11, wherein: the carrier gas is an inert gas.
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