CN116623289A - Device and method for growing SiC monocrystal through directional solidification of bottom seed crystal - Google Patents
Device and method for growing SiC monocrystal through directional solidification of bottom seed crystal Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000007711 solidification Methods 0.000 title claims abstract description 35
- 230000008023 solidification Effects 0.000 title claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 63
- 239000000956 alloy Substances 0.000 claims abstract description 63
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 238000005086 pumping Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 108
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 229910002804 graphite Inorganic materials 0.000 claims description 39
- 239000010439 graphite Substances 0.000 claims description 39
- 238000004140 cleaning Methods 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910007933 Si-M Inorganic materials 0.000 description 28
- 229910008318 Si—M Inorganic materials 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 229910000676 Si alloy Inorganic materials 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000006184 cosolvent Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
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- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910017082 Fe-Si Inorganic materials 0.000 description 2
- 229910017133 Fe—Si Inorganic materials 0.000 description 2
- 229910020797 La-Si Inorganic materials 0.000 description 2
- 229910018643 Mn—Si Inorganic materials 0.000 description 2
- 229910018098 Ni-Si Inorganic materials 0.000 description 2
- 229910018529 Ni—Si Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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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
- C30B27/00—Single-crystal growth under a protective fluid
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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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Abstract
The invention provides a device and a method for directional solidification growth of SiC single crystals by bottom seed crystals. The method comprises the following steps: pre-smelting a silicon-based alloy body at a high temperature, crushing the obtained silicon-based alloy body, adding the crushed silicon-based alloy body into a reaction growth cavity, fixing the crushed silicon-based alloy body on a rotary tray at the bottom of a furnace body, pumping air in the furnace body, and heating the silicon-based alloy to a molten state under an inert atmosphere maintaining a certain pressure; immersing the immersed rotating body into a silicon-based alloy solution, and then regulating the temperature of a furnace body to perform SiC monocrystal growth; after the crystal growth is finished, the obtained crystal is treated to obtain the high-purity SiC single crystal. The method can effectively improve the flow field environment of SiC monocrystal growth, is beneficial to improving the growth rate and stability of the SiC monocrystal, and simultaneously adopts a directional solidification technology to control the grain orientation of SiC in the solidification process, eliminates the transverse grain boundary and is beneficial to growing high-purity SiC monocrystal.
Description
Technical Field
The invention belongs to the technical field of crystal growth, in particular to a technology for growing high-purity SiC single crystals, and particularly relates to a device and a method for growing SiC single crystals by directional solidification of bottom seed crystals.
Background
SiC belongs to a third generation semiconductor material, and compared with the first two generations of semiconductor materials, the SiC semiconductor material not only has a larger forbidden bandwidth, but also has the characteristics of radiation resistance, high thermal conductivity, high breakdown field, high chemical stability, high saturated electron mobility and the like, so that the SiC semiconductor material is often used for manufacturing high-temperature, high-frequency and high-power electronic power devices and radio frequency devices. The excellent performances enable the silicon carbide to play an important role in the fields of rail transit, new energy automobiles, high-voltage power grids, 5G communication, aerospace, national defense, military and the like, and have important strategic significance and wide application prospect.
The method for growing SiC single crystal is mainly three methods, namely a physical vapor transport method, a high-temperature chemical vapor deposition method and a liquid phase epitaxy method. The physical vapor transmission method is mature in production technology, is the mainstream method for growing SiC single crystals at present, has simple growth principle, mainly comprises the steps of filling SiC powder serving as a source material into a quasi-sealed crucible, sublimating the SiC powder at the high temperature of 2300-2400 ℃ and condensing the SiC powder on a top seed crystal for crystal growth. However, the method has higher energy consumption, and the grown SiC monocrystal has defects such as dislocation, micropipe and the like, which seriously affects the quality of the SiC monocrystal; in addition, the physical vapor transport method has the problems of slow growth rate (100-500 mu m/h), low yield, high production cost and the like. Therefore, improving the quality of SiC single crystals and reducing the production cost of SiC single crystals are a challenge to be solved by physical vapor transport growth methods. The high-temperature chemical vapor deposition method is to realize the growth of SiC monocrystal by utilizing the principle that Si source and C source gas react chemically in a high-temperature environment of about 2100 ℃ to generate SiC. The method not only has few defects and high purity of the grown SiC single crystal, but also can realize the rapid growth of the SiC single crystal by continuously supplying high-purity gas raw materials, and the growth rate can reach 2000-3000 mu m/h. However, the high-temperature chemical vapor deposition method not only requires higher growth temperature as the physical vapor transport method, but also requires high-purity gases such as SiH4, C3H8, H2 and the like as raw materials, and has higher production cost.
The basic principle of the growth is to dissolve Si and C elements by using cosolvent and then to separate out the Si and C elements on the SiC seed crystal substrate to realize the growth of SiC monocrystal. Theoretically, the method can grow micropipe-free and dislocation-free ultra-high quality SiC single crystal under the thermodynamic equilibrium condition. However, the solubility of the cosolvent to C is limited, the dissolution rate is low, and the addition of the cosolvent can influence the transmission and distribution of solutes, so that the growth rate of SiC single crystals is limited; when the solute is unevenly distributed and supersaturated, parasitic bodies such as polytype crystals and cosolvent packages can also grow.
Therefore, aiming at the problems of low growth rate and poor growth stability of the SiC single crystal caused by the key links of carbon dissolution, solute transmission and solute distribution in the current process of growing the SiC single crystal by using the top seed crystal solution, a new technology or method is needed to be explored to improve the growth environment of the SiC single crystal and improve the growth rate and stability of the SiC single crystal. .
Disclosure of Invention
The invention aims to provide a device and a method for directional solidification growth of SiC single crystal by bottom seed crystal, which are used for improving the dissolution rate and solute transmission rate of carbon, improving the flow field environment of SiC single crystal growth, avoiding parasitic growth such as polytype crystal and cosolvent package when the solute distribution is uneven and the supersaturation is too high, and improving the growth rate and stability of SiC single crystal; meanwhile, the directional solidification technology is adopted to control the grain orientation of SiC in the solidification process, and the transverse grain boundary is eliminated, so that the high-purity SiC monocrystal is obtained.
The technical scheme adopted by the invention comprises the following steps:
the device for directional solidification growth of SiC single crystal by using bottom seed crystal is characterized by comprising a reaction growth cavity, a rotary tray and an immersed rotating body. The reaction growth cavity is composed of a cavity area in the graphite crucible and SiC seed crystals arranged at the bottom of the inner side of the crucible, the bottom of the outer side of the graphite crucible is fixed on the rotary tray, the rotary tray is arranged at the bottom of the furnace body, can move up and down along an axis and rotates reversely relative to the immersed rotating body, and the immersed rotating body is arranged at the top of the furnace body, can move up and down along the axis and rotates reversely relative to the rotary tray.
Further, the material of the immersed rotating body is one of graphite, corundum, zirconia, sapphire and quartz.
Further, the shape of the submerged rotator is a cylinder, a cone or a prism.
Further, the ratio of the diameter of the submerged rotator to the inner diameter of the graphite crucible is 1/5 to 1/2.
The method for growing the SiC single crystal by directional solidification of the bottom seed crystal is applied to the device for growing the SiC single crystal by directional solidification of the bottom seed crystal, and comprises the following steps:
(1) Preparing a silicon-based alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained silicon-based alloy body and then adding the crushed silicon-based alloy body into a reaction growth cavity;
(3) Fixing a graphite crucible filled with a silicon-based alloy body on a rotary tray at the bottom of a furnace body;
(4) Pumping out air in the furnace body by using a vacuum pump, and continuously introducing protective gas and maintaining the pressure in the furnace body;
(5) Heating the graphite crucible to enable the silicon-based alloy to reach a molten state;
(6) Immersing the immersed rotating body into the silicon-based alloy solution, and then maintaining the temperature of the furnace body to enable SiC seed crystals to grow SiC single crystals under constant temperature and protective gas atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain the high-purity SiC monocrystal.
Further, the metal element used for preparing the silicon-based alloy is one or more of Fe, cr, ti, al, ni, co, mn, ce, sc, V, cu, rh, pd, tb, pr, nd, sn, ga, ge, la.
Further, the rotation speed of the rotating tray is 1-500r/min, and the dropping speed is 300-3000 μm/h.
Further, the pressure in the furnace body is 5000-90000Pa.
Further, the immersion type rotating body is immersed in the silicon-based alloy solution to a depth of 1/10-9/10 of the height of the SiC seed crystal to the liquid level, and the rotating speed is 1-500r/min.
Further, the step of pickling the SiC crystal includes; ethanol cleaning, water cleaning, acid cleaning and water cleaning; the acid used for pickling is one or more of HCl, H2SO4, HNO3 and HF.
According to the invention, along with the continuous downward movement of the rotary tray, the SiC seed crystal in the graphite crucible also moves along with the continuous downward movement of the rotary tray, so that the supercooling degree of the SiC seed crystal is gradually increased, the equilibrium solid solubility of the SiC is gradually reduced, and the directional solidification on the SiC seed crystal is long. In addition, as the rotary tray keeps rotating in the opposite direction to the immersed rotating body in the downward moving process, convection in the silicon-based alloy solution keeps circulating and stable, and uniform transmission of solute is facilitated.
Compared with the prior art, the invention has the advantages that the invention changes the traditional top seed crystal solution growth mode, and invents the growth mode of combining the immersed rotating body and the bottom seed crystal directional solidification mechanism; the provided device for directional solidification growth of SiC single crystal by using the bottom seed crystal increases the mass transfer coefficient of the solution by using the stirring effect provided by the immersed rotating body, thereby effectively improving the solute transmission rate, improving the flow field environment of SiC single crystal growth, avoiding parasitic growth such as polytype crystal and cosolvent package when the solute is unevenly distributed and the supersaturation is too large, and improving the rate and stability of SiC single crystal growth; meanwhile, the directional solidification technology is adopted, so that the grain orientation of SiC in the solidification process can be effectively controlled, the transverse grain boundary is eliminated, and the high-purity SiC monocrystal is obtained.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, reference is made to the following drawings for a person skilled in the art, and it should be noted that the following drawings are used to illustrate and explain some embodiments of the present invention, and belong to the protection content of the present invention, but do not limit the scope of the present invention.
FIG. 1 is a schematic diagram of a device for directional solidification growth of SiC single crystals by using bottom seed crystals.
The icon represents: 1-a reaction growth chamber; 2-rotating a tray; 3-immersed rotator; 4-graphite crucible; 5-SiC seed crystal; 6, a furnace body; 7-heating means; 8-silicon-based alloy solution; 9-air inlet; 10-an air outlet; 11-drive control assembly.
Detailed Description
In connection with fig. 1 of the apparatus of the present invention, the present invention provides an apparatus for growth of SiC single crystal by bottom seed directional solidification, comprising a reaction growth chamber 1, a rotary tray 2 and an immersed rotary body 3. The reaction growth cavity 1 is composed of a cavity area in the graphite crucible 4 and SiC seed crystal 5 arranged at the bottom of the inner side of the crucible, the bottom of the outer side of the graphite crucible 4 is fixed on the rotary tray 2, the rotary tray 2 is arranged at the bottom of the furnace body 6, can move up and down along an axis under the control of the drive control assembly 11 and rotate reversely relative to the immersed rotating body 3, and the immersed rotating body 3 is arranged at the top of the furnace body 6, can move up and down along the axis under the control of the drive control assembly 11 and rotate reversely relative to the rotary tray 2.
The present invention will be described more fully with reference to the following examples. It should be noted that the following embodiments are only a part of the present invention and do not represent all embodiments of the present invention, and the described embodiments should not be construed as limiting the technical scope of the present invention by the following embodiments.
In the description of the present invention, it should be noted that, directions or positional relationships indicated by terms such as "inner", "outer", "upper", "lower", "bottom", etc., are directions or positional relationships based on those shown in the drawings, or those that are conventionally put in place when the inventive product is used, are merely for convenience of describing the present invention and simplifying the description, and are not indicative or implying that the apparatus or elements referred to must have a specific direction, be constructed and operated in a specific direction, and therefore should not be construed as limiting the present invention.
Example 1:
the Si-M (M= Fe, mn, ni, la) alloy is prepared by adopting a metal element M (M= Fe, mn, ni, la), the material of the immersed rotating body is graphite, the shape of the immersed rotating body is a cylinder, and the ratio of the diameter to the inner diameter of the graphite crucible is 1/2. The specific steps of directional solidification growth of SiC single crystal by the bottom seed crystal in the embodiment are as follows:
(1) Preparing an Si-M alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained Si-M alloy body and then adding the crushed Si-M alloy body into a reaction growth cavity 1;
(3) A graphite crucible 4 filled with Si-M gold body is fixed on a rotary tray 2 at the bottom of a furnace body 6;
(4) Pumping out the air of the furnace body 6 by using a vacuum pump, continuously introducing argon into the air inlet 9 and discharging the argon from the air outlet 10, and maintaining the pressure in the furnace body 6 at 10000Pa;
(5) Heating the graphite crucible 4 to 1600 ℃, and preserving heat for 5min to enable the Si-M alloy to reach a molten state;
(6) Under the control of the drive control assembly 11, immersing the immersed rotating body 3 into the Si-M alloy solution 8 to a depth of 9/10 of the SiC seed crystal 5 to the liquid level, and then starting to rotate at a speed of 50r/min, at the same time, controlling the rotating tray 2 to reversely rotate relative to the immersed rotating body 3 at a rotating speed of 100r/min and move downwards along the axis at a speed of 300 mu M/h by the drive control assembly 11, wherein the temperature and the pressure in the furnace body 6 are kept unchanged in the process, so that the SiC seed crystal 5 grows SiC single crystal for 24 hours under constant temperature and argon atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain a high-purity SiC monocrystal, wherein the acid washing steps are as follows: ethanol cleaning, water cleaning, acid cleaning and water cleaning.
The growth rate and purity of SiC single crystals in the different si—m (m= Fe, mn, ni, la) alloys of this example are shown in tables 1 and 2, respectively.
Example 2:
the Si-M (M= Fe, mn, ni, la) alloy is prepared by adopting a metal element M (M= Fe, mn, ni, la), the material of the immersed rotating body is graphite, the shape of the immersed rotating body is a cylinder, and the ratio of the diameter to the inner diameter of the graphite crucible is 1/5. The specific steps of directional solidification growth of SiC single crystal by the bottom seed crystal in the embodiment are as follows:
(1) Preparing an Si-M alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained Si-M alloy body and then adding the crushed Si-M alloy body into a reaction growth cavity 1;
(3) A graphite crucible 4 filled with Si-M gold body is fixed on a rotary tray 2 at the bottom of a furnace body 6;
(4) Pumping out the air of the furnace body 6 by using a vacuum pump, continuously introducing argon into the air inlet 9 and discharging the argon from the air outlet 10, and maintaining the pressure in the furnace body 6 at 10000Pa;
(5) Heating the graphite crucible 4 to 1600 ℃, and preserving heat for 5min to enable the Si-M alloy to reach a molten state;
(6) Under the control of the drive control assembly 11, immersing the immersed rotating body 3 into the Si-M alloy solution 8 to a depth of 9/10 of the SiC seed crystal 5 to the liquid level, and then starting to rotate at a speed of 500r/min, at the same time, controlling the rotating tray 2 to reversely rotate relative to the immersed rotating body 3 at a rotating speed of 100r/min and move downwards along the axis at a speed of 300 mu M/h by the drive control assembly 11, wherein the temperature and the pressure in the furnace body 6 are kept unchanged in the process, so that the SiC seed crystal 5 grows SiC single crystal for 24 hours under constant temperature and argon atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain a high-purity SiC monocrystal, wherein the acid washing steps are as follows: ethanol cleaning, water cleaning, acid cleaning and water cleaning.
The growth rate and purity of SiC single crystals in the different si—m (m= Fe, mn, ni, la) alloys of this example are shown in tables 1 and 2, respectively.
Example 3:
the Si-M (M= Fe, mn, ni, la) alloy is prepared by adopting a metal element M (M= Fe, mn, ni, la), the material of the immersed rotating body is graphite, the shape of the immersed rotating body is a cylinder, and the ratio of the diameter to the inner diameter of the graphite crucible is 1/2. The specific steps of directional solidification growth of SiC single crystal by the bottom seed crystal in the embodiment are as follows:
(1) Preparing an Si-M alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained Si-M alloy body and then adding the crushed Si-M alloy body into a reaction growth cavity 1;
(3) A graphite crucible 4 filled with Si-M gold body is fixed on a rotary tray 2 at the bottom of a furnace body 6;
(4) Pumping out the air of the furnace body 6 by using a vacuum pump, continuously introducing argon into the air inlet 9 and discharging the argon from the air outlet 10, and maintaining the pressure in the furnace body 6 at 10000Pa;
(5) Heating the graphite crucible 4 to 1600 ℃, and preserving heat for 5min to enable the Si-M alloy to reach a molten state;
(6) Under the control of the drive control assembly 11, immersing the immersed rotating body 3 into the Si-M alloy solution 8 to a depth of 9/10 of the SiC seed crystal 5 to the liquid level, and then starting to rotate at a speed of 50r/min, at the same time, controlling the rotating tray 2 to reversely rotate relative to the immersed rotating body 3 at a rotating speed of 100r/min and move downwards along the axis at a speed of 500 mu M/h by the drive control assembly 11, wherein the temperature and the pressure in the furnace body 6 are kept unchanged in the process, so that the SiC seed crystal 5 grows SiC single crystal for 24 hours under constant temperature and argon atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain a high-purity SiC monocrystal, wherein the acid washing steps are as follows: ethanol cleaning, water cleaning, acid cleaning and water cleaning.
The growth rate and purity of SiC single crystals in the different si—m (m= Fe, mn, ni, la) alloys of this example are shown in tables 1 and 2, respectively.
Example 4:
the Si-M (M= Fe, mn, ni, la) alloy is prepared by adopting a metal element M (M= Fe, mn, ni, la), the material of the immersed rotating body is graphite, the shape of the immersed rotating body is a conical body, and the ratio of the bottom diameter to the inner diameter of the graphite crucible is 1/2. The specific steps of directional solidification growth of SiC single crystal by the bottom seed crystal in the embodiment are as follows:
(1) Preparing an Si-M alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained Si-M alloy body and then adding the crushed Si-M alloy body into a reaction growth cavity 1;
(3) A graphite crucible 4 filled with Si-M gold body is fixed on a rotary tray 2 at the bottom of a furnace body 6;
(4) Pumping out the air of the furnace body 6 by using a vacuum pump, continuously introducing argon into the air inlet 9 and discharging the argon from the air outlet 10, and maintaining the pressure in the furnace body 6 at 90000Pa;
(5) Heating the graphite crucible 4 to 1600 ℃, and preserving heat for 5min to enable the Si-M alloy to reach a molten state;
(6) Under the control of the drive control assembly 11, immersing the immersed rotating body 3 into the Si-M alloy solution 8 to a depth of 9/10 of the SiC seed crystal 5 to the liquid level, and then starting to rotate at a speed of 500r/min, at the same time, controlling the rotating tray 2 to reversely rotate relative to the immersed rotating body 3 at a rotating speed of 100r/min and move downwards along the axis at a speed of 500 mu M/h by the drive control assembly 11, wherein the temperature and the pressure in the furnace body 6 are kept unchanged in the process, so that the SiC seed crystal 5 grows SiC single crystal for 24 hours under constant temperature and argon atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain a high-purity SiC monocrystal, wherein the acid washing steps are as follows: ethanol cleaning, water cleaning, acid cleaning and water cleaning.
The growth rate and purity of SiC single crystals in the different si—m (m= Fe, mn, ni, la) alloys of this example are shown in tables 1 and 2, respectively.
Example 5:
the Cr-Al-Ce-Si alloy is prepared by adopting metallic elements Cr, al and Ce, the immersed rotating body is made of corundum, the immersed rotating body is cylindrical, and the ratio of the diameter to the inner diameter of the graphite crucible is 1/5. The specific steps of directional solidification growth of SiC single crystal by the bottom seed crystal in the embodiment are as follows:
(1) Preparing Cr-Al-Ce-Si alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained Cr-Al-Ce-Si alloy body and adding the crushed Cr-Al-Ce-Si alloy body into a reaction growth cavity 1;
(3) A graphite crucible 4 filled with Cr-Al-Ce-Si gold body is fixed on a rotary tray 2 at the bottom of a furnace body 6;
(4) Pumping out air of the furnace body 6 by using a vacuum pump, continuously introducing argon into the air inlet 9 and discharging the argon from the air outlet 10, and maintaining the pressure in the furnace body 6 at 60000Pa;
(5) Heating the graphite crucible 4 to 1900 ℃, and preserving heat for 5min to enable the Cr-Al-Ce-Si alloy to reach a molten state;
(6) Under the control of the drive control assembly 11, immersing the immersed rotary body 3 into the Cr-Al-Ce-Si alloy solution 8 to a depth of 1/10 of the height of the SiC seed crystal 5, and then starting to rotate at a speed of 50r/min, and simultaneously, reversely rotating the rotary tray 2 relative to the immersed rotary body 3 at a rotating speed of 100r/min and moving downwards along the axis at a speed of 1000 mu m/h under the control of the drive control assembly 11, wherein the temperature and the pressure in the furnace body 6 are kept unchanged during the process, so that the SiC seed crystal 5 grows SiC single crystals for 24 hours under constant temperature and argon atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain a high-purity SiC monocrystal, wherein the acid washing steps are as follows: ethanol cleaning, water cleaning, acid cleaning and water cleaning.
Example 6:
the Cr-Al-Ce-Si alloy is prepared by adopting metal elements Cr, al and Ce, the immersed rotating body is made of graphite, the shape of the immersed rotating body is a cone, and the ratio of the bottom diameter to the inner diameter of the graphite crucible is 1/2. The specific steps of directional solidification growth of SiC single crystal by the bottom seed crystal in the embodiment are as follows:
(1) Preparing Cr-Al-Ce-Si alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained Cr-Al-Ce-Si alloy body and adding the crushed Cr-Al-Ce-Si alloy body into a reaction growth cavity 1;
(3) A graphite crucible 4 filled with Cr-Al-Ce-Si gold body is fixed on a rotary tray 2 at the bottom of a furnace body 6;
(4) Pumping out air of the furnace body 6 by using a vacuum pump, continuously introducing argon into the air inlet 9 and discharging the argon from the air outlet 10, and maintaining the pressure in the furnace body 6 at 60000Pa;
(5) Heating the graphite crucible 4 to 1900 ℃, and preserving heat for 5min to enable the Cr-Al-Ce-Si alloy to reach a molten state;
(6) Under the control of the drive control assembly 11, immersing the immersed rotary body 3 into the Cr-Al-Ce-Si alloy solution 8 to a depth of 9/10 of the height of the SiC seed crystal 5, and then starting to rotate at a speed of 500r/min, and simultaneously, reversely rotating the rotary tray 2 relative to the immersed rotary body 3 at a rotating speed of 100r/min and moving downwards along the axis at a speed of 1000 mu m/h under the control of the drive control assembly 11, wherein the temperature and the pressure in the furnace body 6 are kept unchanged during the process, so that the SiC seed crystal 5 grows SiC single crystals for 24 hours under constant temperature and argon atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain a high-purity SiC monocrystal, wherein the acid washing steps are as follows: ethanol cleaning, water cleaning, acid cleaning and water cleaning.
The growth rate and purity of SiC single crystals in the different si—m (m= Fe, mn, ni, la) alloys of this example are shown in tables 1 and 2, respectively.
Table 1 growth rate (μm/h) of SiC single crystal obtained in examples
| Alloy | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Fe-Si | 326 | 334 | 587 | 580 | ||
| Mn-Si | 348 | 362 | 604 | 598 | ||
| Ni-Si | 209 | 214 | 398 | 412 | ||
| La-Si | 440 | 455 | 645 | 627 | ||
| Cr-Al-Ce-Si | 1150 | 1215 |
TABLE 2 purity (wt%) of SiC single crystals obtained in examples
| Alloy | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Fe-Si | 98.87 | 99.92 | 98.80 | 99.96 | ||
| Mn-Si | 99.05 | 99.98 | 98.86 | 99.95 | ||
| Ni-Si | 98.68 | 99.45 | 98.73 | 99.60 | ||
| La-Si | 99.91 | 99.98 | 99.87 | 99.98 | ||
| Cr-Al-Ce-Si | 98.45 | 99.94 |
Claims (10)
1. The device for directional solidification growth of SiC single crystal by using bottom seed crystal is characterized by comprising a reaction growth cavity, a rotary tray and an immersed rotating body. The reaction growth cavity is composed of a cavity area in the graphite crucible and SiC seed crystals arranged at the bottom of the inner side of the crucible, the bottom of the outer side of the graphite crucible is fixed on the rotary tray, the rotary tray is arranged at the bottom of the furnace body, can move up and down along an axis and rotates reversely relative to the immersed rotating body, and the immersed rotating body is arranged at the top of the furnace body, can move up and down along the axis and rotates reversely relative to the rotary tray.
2. The apparatus for directional solidification of SiC single crystal as claimed in claim 1, wherein the material of the immersed rotating body is one of graphite, corundum, zirconia, sapphire and quartz.
3. A device for the growth of SiC single crystals by bottom-seeded directional solidification according to claims 1 and 2, characterized in that the immersed rotating body is in the shape of a cylinder, cone or prism.
4. A device for growth of SiC single crystal by bottom seed directional solidification according to claims 1, 2 and 3, characterized in that the ratio of the diameter of the immersed rotating body to the inner diameter of the graphite crucible is 1/5-1/2.
5. A method for growing a SiC single crystal by bottom seed directional solidification, characterized by being applied to the apparatus according to any one of claims 1 to 5, comprising the steps of:
(1) Preparing a silicon-based alloy body in advance in a high-temperature smelting furnace;
(2) Crushing the obtained silicon-based alloy body and then adding the crushed silicon-based alloy body into a reaction growth cavity;
(3) Fixing a graphite crucible filled with a silicon-based alloy body on a rotary tray at the bottom of a furnace body;
(4) Pumping out air in the furnace body by using a vacuum pump, and continuously introducing protective gas and maintaining the pressure in the furnace body;
(5) Heating the graphite crucible to enable the silicon-based alloy to reach a molten state;
(6) Immersing the immersed rotating body into the silicon-based alloy solution, and then maintaining the temperature of the furnace body to enable SiC seed crystals to grow SiC single crystals under constant temperature and protective gas atmosphere;
(7) After the crystal growth is finished, cutting and acid washing are carried out on the obtained crystal, and alloy solvent components are removed to obtain the high-purity SiC monocrystal.
6. The method for growing a SiC single crystal by bottom seed directional solidification according to claim 6, wherein the metal element used for preparing the silicon-based alloy in step (1) is one or more of Fe, cr, ti, al, ni, co, mn, ce, sc, V, cu, rh, pd, tb, pr, nd, sn, ga, ge, la.
7. The method for directional solidification of a single crystal of SiC as claimed in claim 6, wherein the rotation speed of the rotary tray in the step (3) is 1-500r/min and the descent speed is 300-3000 μm/h.
8. The method for directional solidification of a silicon carbide single crystal as claimed in claim 6, wherein the pressure in the furnace in the step (4) is 5000 to 90000Pa.
9. The method for directional solidification of a bottom seed crystal for growing a single crystal of SiC according to claim 6, wherein the depth of immersion of the immersed rotary body in the silicon-based alloy solution in step (6) is 1/10 to 9/10 of the height of the liquid surface of the SiC seed crystal, and the rotation speed is 1 to 500r/min.
10. A method for growing a SiC single crystal by bottom seed directional solidification according to claim 6, wherein the step of pickling the SiC crystal in step (7) comprises: ethanol cleaning, water cleaning, acid cleaning and water cleaning.
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