CN115478324A - Method for growing single crystal or polycrystalline SiC crystal by cosolvent method - Google Patents
Method for growing single crystal or polycrystalline SiC crystal by cosolvent method Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000006184 cosolvent Substances 0.000 title claims abstract description 47
- 239000011261 inert gas Substances 0.000 claims abstract description 45
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003723 Smelting Methods 0.000 claims abstract description 21
- 229910000691 Re alloy Inorganic materials 0.000 claims abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 238000005275 alloying Methods 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- 238000002109 crystal growth method Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 27
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 150000001247 metal acetylides Chemical class 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 229910008326 Si-Y Inorganic materials 0.000 description 14
- 229910006773 Si—Y Inorganic materials 0.000 description 14
- 229910001371 Er alloy Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical group [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- -1 rare earth carbides Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 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
- 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
-
- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
-
- 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
Abstract
The invention relates to a method for growing single crystal or polycrystalline SiC crystal by a cosolvent method, belonging to the technical field of semiconductor crystal materials. Mixing a cosolvent with high-purity silicon, and then carrying out alloying smelting under high-purity inert gas under negative pressure to obtain Si-RE alloy with uniform components; loading the obtained Si-RE alloy into a high-purity graphite crucible or a SiC crucible in a crystal growth furnace, raising the temperature under high-purity inert gas or mixed gas of hydrogen and inert gas to melt the Si-RE alloy, and preserving the heat for at least 1 hour at the set crystal growth temperature to fully dissolve C or SiC into the Si-RE alloy to obtain SiC saturated Si-RE-C melt; growing single crystal or polycrystal SiC crystal in the obtained SiC saturated Si-RE-C melt. The method can improve the solubility of C in the silicon melt, avoid the generation of other carbides, and is beneficial to the growth of high-quality SiC crystals.
Description
Technical Field
The invention relates to a method for growing single crystal or polycrystalline SiC crystal by a cosolvent method, belonging to the technical field of semiconductor crystal materials.
Background
SiC crystal has excellent properties as a third-generation wide bandgap semiconductor material, such as a wide bandgap (3 times that of Si), a high thermal conductivity (3 times that of Si or 10 times that of GaAs), a high electron saturation mobility (2.7 times that of Si or 2 times that of GaAs), and a high critical electric field (10 times that of Si or 5 times that of GaAs), compared to Si and GaAs. The SiC single crystal device can run at high speed, high frequency and high efficiency under extreme conditions due to the advantages of high temperature and high pressure resistance, radiation resistance, corrosion resistance, high heat conduction and the like, is suitable for the fields of rocket satellites, rail transit, ocean exploration, 5G base stations, smart grids, new energy automobiles/charging piles, new generation mobile communication power electronics, aerospace and the like, is a key core material for the autonomous innovation development and transformation upgrading of the energy Internet industry, and makes up the limitations and defects in the application process of the traditional semiconductor device.
At present, the method for industrially preparing bulk SiC single crystals is mainly a physical vapor transport method (PVT method), but the method has high temperature and energy consumption for growing SiC single crystals, and the yield of the grown SiC crystals is not high, and is usually accompanied with defects such as microcosmic defects and the like. The SiC crystal grown by the solution method has the advantage of low crystal defect density, can effectively avoid the microscopic defects existing in the SiC crystal grown by the PVT method, but the growth speed of the SiC crystal grown by the solution method is very slow due to the extremely low solubility of C in silicon melt and the limited mass transfer of C in the silicon melt.
How to increase the solubility of C in the silicon melt is the key to increasing the growth rate of SiC crystals grown by the solution method. Therefore, in recent years, researchers at home and abroad have tried to solve the problem of low solubility of C in silicon melt by using a cosolvent method. The cosolvent method is to add one or more elements with affinity with C into the silicon melt, and to improve the solubility of C in the silicon melt by using the added cosolvent. On the other hand, since the cosolvent can form a low-melting-point melt with silicon, the cosolvent method can not only increase the solubility of C in the silicon melt, but also realize low-temperature growth of SiC crystals (the temperature is much lower than that of the PVT method). Typical Co-solvents reported so far are chromium (Cr), iron (Fe), titanium (Ti), aluminum (Al), cobalt (Co), nickel (Ni), and the like. However, with the above co-solvents, the solubility of C in the silicon melt is still limited. Researchers still need to continuously seek out new cosolvents to solve the key problem of how to greatly improve the solubility of C in Si melts.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for growing single crystal or polycrystalline SiC crystal by a cosolvent method, which can greatly improve the solubility of C in silicon melt and provides possibility for rapidly growing SiC single crystal. The difference between the invention and the patent CN106119951B is as follows: (1) The cosolvent used in the patent CN106119951B is praseodymium (Pr), cerium (Ce), lanthanum (La), dysprosium (Dy) and terbium (Tb), and one or two of yttrium (Y) and erbium (Er) are used as the cosolvent; (2) Before growing the SiC crystal, the cosolvent and the high-purity silicon are smelted into alloy, so that the process can avoid the cosolvent and a graphite crucible from generating rare earth carbide, the quality of the SiC crystal is improved, and the method has advancement; (3) Before the SiC crystal grows, the graphite crucible (SiC saturated melt can be obtained in the graphite crucible by controlling the addition amount of the cosolvent) or the SiC crucible is used as a container, and the SiC crystal grows after the SiC in the silicon melt is dissolved to be balanced, so that the SiC seed crystal is effectively prevented from being dissolved in the silicon melt; (4) The inert gas used as the protective gas in the patent CN106119951B is argon, and because the chemical property of the rare earth cosolvent is active, trace oxygen exists in the argon, and the trace oxygen can influence the effect of increasing the solubility of C or SiC in the cosolvent, therefore, the protective gas used in the invention is not only a high-purity inert gas, but also a mixed gas (containing 10% of hydrogen) of the high-purity inert gas and hydrogen, and the mixed gas is used for further removing oxygen in the silicon melt, so that the dissolution assisting effect of the cosolvent is ensured. The invention is realized by the following technical scheme.
A method for growing single crystal or polycrystalline SiC crystal by a cosolvent method comprises the following steps:
step 1, adopting one or two of rare earth elements (RE) yttrium (Y) or erbium (Er) as a cosolvent; the method specifically comprises the following steps:
mixing a cosolvent (more than or equal to 99.9 wt%) with high-purity silicon (more than or equal to 99.9999 wt%), and then carrying out alloying smelting under high-purity inert gas under negative pressure to obtain Si-RE alloy with uniform components; the smelting temperature is higher than the melting point of the Si-RE alloy, and the smelting time is not limited; the alloying smelting technology is a pollution-free water-cooled copper crucible technology;
step 2, filling the Si-RE alloy obtained in the step 1 into a high-purity graphite crucible or a SiC crucible in a crystal growth furnace, raising the temperature under high-purity inert gas or mixed gas of hydrogen and inert gas to melt the Si-RE alloy, and preserving the temperature for at least 1 hour at a temperature of not less than 1923K to fully dissolve C or SiC into the Si-RE alloy, thereby obtaining SiC saturated Si-RE-C melt;
step 3, growing single crystal or polycrystalline SiC crystal in the SiC saturated Si-RE-C melt obtained in the step 2 under the condition of high-purity inert gas or mixed gas of hydrogen and inert gas;
in the above step, the high-purity inert gas is high-purity argon or helium, the purity is more than 99.999%, and the negative pressure is lower than one atmosphere; h in the mixed gas of hydrogen and inert gas 2 The volume content is less than or equal to 10 percent.
In the step 1, the mol ratio of the cosolvent to the high-purity silicon is less than 2, namely the mol percentage content of the cosolvent RE in the Si-RE alloy is less than or equal to 40at.%, and the SiC saturated Si-RE-C melt can be obtained in a graphite crucible or a SiC crucible under the condition.
The SiC crystal growth method for growing the monocrystal or polycrystal SiC crystal in the step 3 is a conventional crystal growth method, and comprises but is not limited to a top seed crystal melt growth method and a crucible descending method, wherein the crystal growth temperature is not lower than 1923K; other conditions of crystal growth are not limited, namely, temperature gradient is not limited, siC seed crystal type is not limited, the rotation speed and rotation direction of a seed crystal rod or a crucible are not limited, and the heating mode (induction heating or resistance heating) of a crystal growth furnace is not limited.
The invention has the beneficial effects that:
(1) The invention provides a new method for growing SiC crystal by using one or two of rare earth elements of yttrium (Y) and erbium (Er) as a cosolvent.
(2) The cosolvent of the invention can improve the solubility of C in silicon melt at low temperature (low temperature compared with PVT method, and at least 400K lower than the temperature of PVT method), and provides possibility for rapidly growing SiC single crystal at low temperature.
(3) The invention can avoid the generation of other carbides and is beneficial to the growth of high-quality SiC crystals.
(4) The cosolvent of the invention only plays a role in dissolving in growing a melt, is not consumed in the process of growing SiC single crystals and can be repeatedly used. In addition, the cosolvent of the invention has low solid solubility in SiC, and cannot pollute the grown SiC crystal.
Therefore, the cosolvent method of the invention is a method for growing SiC crystal with low energy consumption, low pollution, low cost and high efficiency, and is beneficial to promoting the popularization of SiC single crystal in the field of semiconductor materials.
Drawings
FIG. 1 is a schematic flow diagram of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
As shown in fig. 1, the method for growing single crystal or polycrystalline SiC crystal by the co-solvent method includes the steps of:
step 1, mixing yttrium cosolvent (Y, more than or equal to 99.9 wt%) with high-purity silicon (more than or equal to 99.9999 wt%), carrying out alloying smelting (the smelting temperature is higher than the melting point of Si-RE alloy) by adopting an electric arc furnace under negative pressure of high-purity inert gas (argon, 99.999%), wherein a reaction vessel is a water-cooled copper crucible, and obtaining Si-Y alloy with uniform components after smelting for 10 minutes; the mol ratio of the cosolvent to the high-purity silicon is 2;
step 2, the Si-Y alloy obtained in the step 1 is filled into a high-purity graphite crucible (with the purity of 99.999%) in a crystal growth furnaceMixed gas of hydrogen and inert gas (H in mixed gas of hydrogen and inert gas) 2 Volume content of 10%, argon as inert gas) to melt the Si-Y alloy, and maintaining the temperature at 1923K for 1 hour to fully dissolve C into the Si-Y alloy, to obtain SiC saturated Si-Y-C melt (content of C is 4.4 wt.%);
step 3, at 1923K, mixing gas of hydrogen and inert gas (H in the mixing gas of hydrogen and inert gas) 2 The volume content is 10 percent, and the inert gas is argon gas) to grow single crystal SiC crystals in the SiC saturated Si-Y-C melt obtained in the step 2; the crystal growth method is a top seed crystal solution growth method.
Example 2
As shown in fig. 1, the method for growing single crystal or polycrystalline SiC crystal by the co-solvent method includes the steps of:
step 1, mixing yttrium cosolvent (Y, more than or equal to 99.9 wt%) with high-purity silicon (more than or equal to 99.9999 wt%), then carrying out alloying smelting (the smelting temperature is higher than the melting point of Si-RE alloy) by adopting an electric arc furnace under the negative pressure of high-purity inert gas (argon, 99.999%) for 8 minutes, wherein a reaction vessel is a water-cooled copper crucible, and obtaining Si-Y alloy with uniform components after smelting; the mol ratio of the cosolvent to the high-purity silicon is 3;
step 2, the Si-Y alloy obtained in the step 1 is filled into a SiC crucible (purity 99.99%) in a crystal growth furnace, and the Si-Y alloy is placed under a mixed gas of hydrogen and an inert gas (H in the mixed gas of hydrogen and the inert gas) 2 10% by volume and argon as inert gas) to melt the Si-Y alloy, and keeping the temperature at 1923K for 1 hour to fully dissolve the SiC into the Si-Y alloy, to obtain SiC saturated Si-Y-C melt (0.93 wt.% of C);
step 3, mixing gas of hydrogen and inert gas (H in the mixing gas of hydrogen and inert gas) at the temperature of 1923K 2 The volume content is 10 percent, and the inert gas is argon gas) to grow single crystal SiC crystals in the SiC saturated Si-Y-C melt obtained in the step 2; the crystal growth method is a top seed crystal solution growth method.
Example 3
As shown in fig. 1, the method for growing single crystal or polycrystalline SiC crystal by the co-solvent method includes the steps of:
step 1, mixing yttrium and erbium cosolvent (Y and Er, more than or equal to 99.9 wt%) and high-purity silicon (more than or equal to 99.9999 wt%), carrying out alloying smelting (the smelting temperature is higher than the melting point of Si-RE alloy) by adopting an electric arc furnace under the negative pressure of high-purity inert gas (argon, 99.999%), wherein a reaction vessel is a water-cooled copper crucible, and smelting for 10 minutes to obtain Si-Y-Er alloy with uniform components; the mol ratio of the cosolvent to the high-purity silicon is 2;
step 2, the Si-Y-Er alloy obtained in the step 1 is filled into a high-purity graphite crucible (with the purity of 99.999%) in a crystal growth furnace, and the Si-Y-Er alloy is placed under the mixed gas of hydrogen and inert gas (H in the mixed gas of hydrogen and inert gas) 2 The volume content is 10 percent, and the inert gas is argon), the temperature is raised to melt the Si-Y-Er alloy, and the temperature is kept at 1923K for 1 hour to ensure that C is fully dissolved in the Si-Y-Er alloy, so as to obtain SiC saturated Si-Y-Er-C melt (the content of C is 3.85 wt.%);
step 3, mixing gas of hydrogen and inert gas (H in the mixing gas of hydrogen and inert gas) at the temperature of 1923K 2 The volume content is 10 percent, and the inert gas is argon) to grow polycrystalline SiC crystals in the SiC saturated Si-Y-Er-C melt obtained in the step 2; the crystal growth method is a Bridgman method.
Example 4
As shown in fig. 1, the method for growing single crystal or polycrystalline SiC crystal by the co-solvent method includes the steps of:
step 1, mixing yttrium cosolvent (Y, more than or equal to 99.9 wt%) with high-purity silicon (more than or equal to 99.9999 wt%), carrying out alloying smelting (the smelting temperature is higher than the melting point of Si-RE alloy) by adopting an electric arc furnace under negative pressure of high-purity inert gas (argon, 99.999%), wherein a reaction vessel is a water-cooled copper crucible, and obtaining Si-Y alloy with uniform components after smelting for 8 minutes; the mol ratio of the cosolvent to the high-purity silicon is 27;
step 2, the Si-Y alloy obtained in the step 1 is filled into a SiC crucible (purity 99.99%) in a crystal growth furnace, and the Si-Y alloy is placed under a mixed gas of hydrogen and an inert gas (H in the mixed gas of hydrogen and the inert gas) 2 The volume content is 10 percent, the inert gas is argon), the temperature is raised to melt the Si-Y alloy, and the temperature is kept for 1 hour at the temperature of 1923K, so that the SiC is fully dissolved in the Si-Y alloy; however, the Si-Y-C melt (C content 7.64 wt.%) obtained under these conditions is a Si-Y-C melt saturated with rare earth carbides, not a Si-Y-C melt saturated with SiC, and therefore it is not possible to grow single-crystal or polycrystalline SiC crystals using this Si-Y-C melt.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (3)
1. A method for growing single crystal or polycrystalline SiC crystal by a cosolvent method is characterized by comprising the following steps:
step 1, adopting one or two of rare earth elements of yttrium and erbium as a cosolvent; the method specifically comprises the following steps:
mixing a cosolvent with high-purity silicon, and then carrying out alloying smelting under high-purity inert gas under negative pressure to obtain Si-RE alloy with uniform components; the smelting temperature is higher than the melting point of the Si-RE alloy, and the smelting time is not limited; the alloying smelting technology is a pollution-free water-cooled copper crucible technology;
step 2, the Si-RE alloy obtained in the step 1 is filled into a high-purity graphite crucible or a SiC crucible in a crystal growth furnace, the temperature is raised under high-purity inert gas or mixed gas of hydrogen and inert gas to melt the Si-RE alloy, and the temperature is kept for at least 1 hour at the temperature of not less than 1923K to fully dissolve C or SiC into the Si-RE alloy, so that SiC saturated Si-RE-C melt is obtained;
step 3, growing single crystal or polycrystalline SiC crystal in the SiC saturated Si-RE-C melt obtained in the step 2 under the condition of high-purity inert gas or mixed gas of hydrogen and inert gas;
in the above step, the high-purity inert gas is high-purity argon or helium, the purity is more than 99.999%, and the negative pressure is lower than one atmosphere; h in the mixed gas of hydrogen and inert gas 2 The volume content is less than or equal to 10 percent.
2. The method for growing single crystal or polycrystalline SiC crystal according to claim 1, characterized in that: in the step 1, the mol ratio of the cosolvent to the high-purity silicon is less than 2, namely the mol percent content of the cosolvent RE in the Si-RE alloy is less than or equal to 40at.%, and the SiC saturated Si-RE-C melt can be obtained in a graphite crucible or an SiC crucible under the condition.
3. The method for growing single crystal or polycrystalline SiC crystal according to claim 1, characterized in that: the SiC crystal growth method for growing the single crystal or polycrystalline SiC crystal in the step 3 is a conventional crystal growth method, including but not limited to a top seed crystal melt growth method and a Bridgman method, and the crystal growth temperature is not lower than 1923K.
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