CN116145258A - Method for growing SiC crystal by low-temperature solution method - Google Patents
Method for growing SiC crystal by low-temperature solution method Download PDFInfo
- Publication number
- CN116145258A CN116145258A CN202211106371.9A CN202211106371A CN116145258A CN 116145258 A CN116145258 A CN 116145258A CN 202211106371 A CN202211106371 A CN 202211106371A CN 116145258 A CN116145258 A CN 116145258A
- Authority
- CN
- China
- Prior art keywords
- sic
- smelting
- temperature
- purity
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 86
- 239000013078 crystal Substances 0.000 title claims abstract description 81
- 238000003723 Smelting Methods 0.000 claims abstract description 58
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 16
- 238000005275 alloying Methods 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910000691 Re alloy Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 17
- 239000006184 cosolvent Substances 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 238000002109 crystal growth method Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000011651 chromium Substances 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 9
- 229910000858 La alloy Inorganic materials 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910000583 Nd alloy Inorganic materials 0.000 description 3
- 229910001154 Pr alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 102000029749 Microtubule Human genes 0.000 description 1
- 108091022875 Microtubule Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 210000004688 microtubule Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
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
- 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
- C30B27/00—Single-crystal growth under a protective fluid
-
- 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
- C30B27/02—Single-crystal growth under a protective fluid by pulling from a melt
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/10—Production of homogeneous polycrystalline material with defined structure from liquids by pulling from a melt
Landscapes
- 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 method for growing SiC crystals by a low-temperature solution method, and belongs to the technical field of crystal growth. Mixing high-purity silicon, metal Fe or Cr and rare earth metal, and carrying out alloying smelting for 5-30min to obtain Si-Me-RE alloy with uniform components; filling Si-Me-RE alloy into a high-purity compact graphite crucible or a SiC crucible in a crystal growth furnace, and preserving heat for at least 1 hour at a smelting temperature higher than 1823K to dissolve C or SiC into a high-temperature melt to obtain a SiC-saturated Si-Me-RE-C melt; and (3) growing SiC monocrystal or polycrystal SiC by a solution method in the Si-Me-RE-C melt saturated by SiC. The method for growing SiC crystals by the low-temperature solution method solves the problem of low C or SiC solubility when the SiC crystals are grown by the solution method, can greatly improve C or SiC solubility in Si melt at low temperature (which is at least 400K lower than the existing PVT method), and is a method for growing SiC crystals with low energy consumption, low cost, high efficiency and no pollution.
Description
Technical Field
The invention relates to a method for growing SiC crystals by a low-temperature solution method, and belongs to the technical field of crystal growth.
Background
SiC single crystal is a new generation of electronic core material, and is mainly used as a core substrate material of a third generation wide bandgap and high power semiconductor device. Compared with the first-generation and second-generation semiconductor materials, the SiC monocrystal has the characteristics of high temperature resistance, high pressure resistance, high power and radiation resistance, and can be used for manufacturing high-power devices which can operate at high speed and high frequency under severe environments such as high temperature, high pressure, strong radiation and the like.
At present, a physical vapor transmission method is a mainstream technology for industrially producing SiC single crystals at home and abroad, but the method has the advantages of low yield of the SiC single crystals, higher growth temperature and high energy consumption, high production cost, and the grown SiC single crystals have defects such as micropipes and the like, so that the material performance of the grown SiC single crystals is influenced. In addition, the physical vapor transport method decomposes SiC raw material into a complex mixed vapor at an ultra-high temperature, but the mixed vapor reaction obtained by such sublimation is relatively complex, and the crystal growth process is relatively difficult to control. Therefore, the SiC single crystal grown by the physical vapor transport method is relatively expensive, and the popularization and the use of the SiC single crystal on semiconductor devices are limited.
The solution method is another method of growing SiC single crystals, which is currently available under laboratory conditions to obtain SiC single crystals of low defect density and high quality. The solution method can realize the growth of high-quality SiC single crystal in a near-thermodynamic equilibrium state, and has the advantages of less grown crystal microtubules, stronger controllability of the growth process, easy realization of p-type doping and the like. When the solution method is adopted to grow SiC single crystal, the solubility of C in the silicon melt is a key factor for determining the growth speed of the SiC single crystal, and the solubility of C in the silicon melt below 2273K is very low, so that the mass transfer process of C in the silicon melt is limited, the quick growth of the SiC single crystal is difficult to realize by adopting the pure silicon melt, and the technical problem that how to improve the solubility of C in the silicon melt is needed to be solved for quickly growing the SiC single crystal at low temperature is solved.
Aiming at the difficult problem of low C solubility in the process of growing SiC single crystals by a solution method, researchers propose a method for improving the C solubility in a melt by adding a cosolvent into the silicon melt. This solution process with the addition of a cosolvent is known as a cosolvent process. In addition, the added cosolvent can form a low-melting-point melt with silicon, so that the cosolvent method is also a technology for growing SiC single crystals at a low temperature. The cosolvent which has been reported at present mainly comprises chromium, titanium, iron, cobalt and the like. When these are used as co-solvents, the solubility of C can be significantly improved compared to pure silicon melt, which is advantageous for growing SiC single crystals at low temperature, but the solubility of C in the melt is still limited. Therefore, there is a continuing need to develop new co-solvents to increase the C solubility in silicon melts to address the problem of limited SiC single crystal growth rates. On the other hand, high purity polycrystalline SiC is an important raw material for growing SiC single crystals. When purifying polycrystalline SiC by recrystallization, the problem of too low solubility of SiC in the melt is also faced, and purification of polycrystalline SiC by recrystallization cannot be achieved. In summary, both the solution method for growing SiC single crystals and the recrystallization method for preparing high purity polycrystalline SiC crystals are required to solve the problem of low solubility of SiC in the silicon melt, and the development of novel cosolvents is required to improve the solubility of C or SiC in the silicon melt.
Disclosure of Invention
The invention provides a method for growing SiC crystals by a low-temperature solution method aiming at the problems existing in the prior art. The invention can greatly improve the C solubility in the silicon melt under the low-temperature condition, and provides possibility for the low-temperature rapid growth of high-quality SiC single crystal and polycrystalline SiC by a solution method. The method solves the technical problem of low solubility of C in the silicon melt. The invention is realized by the following technical scheme.
A method for growing SiC crystals by a low temperature solution method, comprising the steps of:
and step 1, mixing high-purity silicon, metal Fe or Cr (Me) and rare earth metal (RE), and carrying out alloying smelting for 5-30min to obtain the Si-Me-RE alloy with uniform components, wherein the smelting atmosphere is high-purity inert gas (purity is more than 99.999%) under normal pressure or negative pressure, the smelting temperature is higher than the melting point of the Si-Me-RE alloy, and the alloying smelting method adopts a water-cooling copper crucible technology or an electromagnetic suspension smelting technology, preferably a water-cooling copper crucible technology.
Step 2, loading the Si-Me-RE alloy obtained in the step 1 into a high-purity compact graphite crucible or a SiC crucible in a crystal growth furnace, and preserving heat for at least 1 hour at a smelting temperature higher than 1823K to dissolve C or SiC into a high-temperature melt to obtain a SiC-saturated Si-Me-RE-C melt; the smelting atmosphere is high-purity inert gas or mixed gas of hydrogen and high-purity inert gas, and the volume content of hydrogen in the mixed gas is less than or equal to 10%;
step 3, carrying out solution method on the SiC saturated Si-Me-RE-C melt obtained in the step 2 to grow SiC monocrystal or polycrystal SiC; the crystal growth method is a conventional crystal growth method, including but not limited to a top seed crystal solution growth method or a crucible descending method, the crystal growth temperature is higher than 1823K, the SiC crystal growth atmosphere is high-purity inert gas (purity > 99.999%) or mixed gas of hydrogen and the high-purity inert gas, and the volume content of the hydrogen in the mixed gas is less than or equal to 10%.
In the step 1, the content of Me in the Si-Me-RE alloy is less than or equal to 45 at%, and Me represents one or two of Fe and Cr; RE represents one or more of rare earth metals, and the total content of RE is less than or equal to 35 at%; under the condition of ensuring the above conditions, the proportion of Me, RE and Si is adjusted to ensure that the total content of Me, RE and Si is 100 at percent.
The mixture of the metal Fe or Cr and the rare earth metal in the step 1 is taken as a cosolvent; the rare earth metal is one or more of rare earth elements, including scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu) in any proportion.
The conditions for crystal growth other than temperature in the above step 3 are not limited, that is, the temperature gradient, the type of SiC seed crystal, the rotation speed of the seed rod or crucible, and the heating mode (electromagnetic induction or resistance heating) of the crystal furnace.
The beneficial effects of the invention are as follows:
(1) The invention provides a novel method for improving the solubility of C or SiC in a silicon melt by using a cosolvent, namely, a mixed metal of Me+RE is used as the cosolvent, so that the problem of low C or SiC solubility when SiC crystals are grown by a low-temperature solution method is solved;
(2) The cosolvent for growing the SiC crystal by the low-temperature solution method provided by the invention can be used for growing SiC single crystal and can also be used as a material for preparing high-purity polycrystalline SiC;
(3) When rare earth is used as cosolvent, the molten rare earth is firstly reacted with the crucible to generate rare earth carbide, which affects the quality of the growing SiC crystal; the invention solves the problem by adopting a premelted alloy method;
(4) When rare earth is used as cosolvent, the rare earth is easy to react with trace oxygen in the furnace, so that the solubility of SiC in the melt is reduced; the invention adopts the method of mixing hydrogen and inert gas (the hydrogen content is less than or equal to 10 percent) to solve the problem;
(5) The invention is a technology for growing SiC crystal with low energy consumption, no pollution and low cost;
(6) The method for growing SiC crystals by the low-temperature solution method solves the problem of low C or SiC solubility when the SiC crystals are grown by the solution method, can greatly improve C or SiC solubility in Si melt at low temperature (which is at least 400K lower than the existing PVT method), and is a method for growing SiC crystals with low energy consumption, low cost, high efficiency and no pollution.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and detailed description.
Example 1
As shown in fig. 1, the method for growing SiC crystals by the low temperature solution method includes the steps of:
step 1, mixing high-purity silicon (purity 99.9999 wt%), metal Cr (purity 99.99 wt%) and rare earth Nd (purity 99.9 wt%) and then carrying out alloying smelting, wherein the smelting time is 5min, so as to obtain 50at.% Si-35at.% Cr-15at.% Nd alloy with uniform components, the smelting atmosphere is high-purity inert gas (argon, purity >99.999 wt%) under negative pressure, the smelting temperature is higher than the melting point of 50at.% Si-35at.% Cr-15at.% Nd alloy, and the alloying smelting method is an arc furnace smelting technology with a water-cooled copper crucible;
step 2, loading the 50at.% Si-35at.% Cr-15at.% Nd alloy obtained in the step 1 into a high-purity compact graphite crucible in a crystal growth furnace, and preserving heat for 1 hour at a smelting temperature of 1823K to dissolve C into a high-temperature melt to obtain a SiC saturated Si-Cr-Nd-C melt (the C content is 4.44 wt percent); the smelting atmosphere is high-purity argon (99.999 wt%) +10% H 2 Mixing the gases;
step 3, growing SiC monocrystal in the SiC saturated Si-Cr-Nd-C melt obtained in the step 2 by a solution method; the crystal growth method is a top seed crystal solution growth method, the crystal growth temperature is 1823K, the SiC crystal growth atmosphere is high-purity argon (99.999 wt%) +10% H 2 And (3) mixing the gases.
Example 2
As shown in fig. 1, the method for growing SiC crystals by the low temperature solution method includes the steps of:
step 1, mixing high-purity silicon (purity 99.9999 wt%), metal Fe (purity 99.99 wt%) and rare earth Pr (purity 99.9 wt%) and then carrying out alloying smelting, wherein the smelting time is 6min to obtain 50at.% Si-15at.% Fe-35at.% Pr alloy with uniform components, the smelting atmosphere is high-purity inert gas (argon, purity >99.999 wt%) under negative pressure, the smelting temperature is higher than the melting point of 50at.% Si-15at.% Fe-35at.% Pr alloy, and the alloying smelting method is an arc furnace smelting technology with a water-cooled copper crucible;
step 2, loading the 50at.% Si-15at.% Fe-35at.% Pr alloy obtained in the step 1 into a SiC crucible in a crystal growth furnace, and preserving heat for 1 hour at a smelting temperature of 1923K to dissolve SiC into a high-temperature melt to obtain a SiC saturated Si-Fe-Pr-C melt (the C content is 6.78 wt percent); the smelting atmosphere is high-purity argon (99.999 wt%);
step 3, growing SiC monocrystal in the SiC saturated Si-Fe-Pr-C melt obtained in the step 2 by a solution method; the crystal growth method is a top seed crystal solution growth method, the crystal growth temperature is 1923K, and the SiC crystal growth atmosphere is high-purity inert gas (argon, purity is more than 99.999%).
Example 3
As shown in fig. 1, the method for growing SiC crystals by the low temperature solution method includes the steps of:
step 1, mixing high-purity silicon (purity 99.9999 wt%), metal Fe (purity 99.99 wt%) and rare earth metal La (purity 99.9 wt%) and then carrying out alloying smelting, wherein the smelting time is 10min, so as to obtain 50at.% Si-45at.% Fe-5at.% La alloy with uniform components, the smelting atmosphere is high-purity inert gas (argon, purity >99.999 wt%) under negative pressure, the smelting temperature is higher than the melting point of 50at.% Si-45at.% Fe-5at.% La alloy, and the alloying smelting method is an arc furnace smelting technology with a water-cooled copper crucible;
step 2, loading the 50at.% Si-45at.% Fe-5at.% La alloy obtained in the step 1 into a SiC crucible in a crystal growth furnace, and preserving heat for 1.5 hours at a smelting temperature of 1923K to dissolve SiC into a high-temperature melt to obtain a SiC saturated Si-Fe-La-C melt (the C content is 0.4 wt.%); the smelting atmosphere is high-purity helium (99.999 wt%) +10% H 2 Mixing the gases;
step 3, growing SiC monocrystal in the SiC saturated Si-Fe-La-C melt obtained in the step 2 by a solution method; the crystal growth method is a top seed crystal solution growth method, the crystal growth temperature is 1923K, the SiC crystal growth atmosphere is smelting atmosphere which is high-purity helium (99.999 wt%) +10% H 2 And (3) mixing the gases.
Example 4
As shown in fig. 1, the method for growing SiC crystals by the low temperature solution method includes the steps of:
step 1, mixing high-purity silicon (purity 99.9999 wt%), metal Fe (purity 99.99 wt%), a mixture of rare earth metal Y and Pr (purity of Y and Pr is 99.9wt%, mass ratio of Y to Pr is 1:20), and then carrying out alloying smelting, wherein the smelting time is 10min to obtain 60at.% Si-10at.% Fe-30at.% alloy (Y+Pr) with uniform components, the smelting atmosphere is high-purity inert gas (argon, purity is >99.999 wt%) under negative pressure, the smelting temperature is higher than the melting point of 60at.% Si-10at.% Fe-30 at% (Y+Pr), and the alloying smelting method is an arc furnace smelting technology with a water-cooled copper crucible;
step 2, loading the 60at.% Si-10at.% Fe-30at.% (Y+Pr) alloy obtained in the step 1 into a high-purity compact graphite crucible in a crystal growth furnace, and preserving the temperature for 1.5 hours at a smelting temperature of 1923K to dissolve C into a high-temperature melt to obtain a SiC-saturated Si-Fe- (Y+Pr) -C melt (the C content is 3.23 wt percent); the smelting atmosphere is high-purity helium (99.999 wt%) +10% H 2 Mixing the gases;
step 3, growing SiC monocrystal in the SiC saturated Si-Fe- (Y+Pr) -C melt obtained in the step 2 by a solution method; the crystal growth method is a top seed crystal solution growth method, the crystal growth temperature is 1923K, the SiC crystal growth atmosphere is smelting atmosphere which is high-purity helium (99.999 wt%) +10% H 2 And (3) mixing the gases.
Example 5
Step 1, mixing high-purity silicon (purity 99.9999 wt%), metal Fe and Cr (purity 99.99wt%, mass ratio of Fe to Cr is 4:3) and rare earth metal La (both 99.9 wt%) and then carrying out alloying smelting for 10min to obtain 50at.% Si-35at.% Fe+Cr) -15at.% La alloy with uniform components, wherein the smelting atmosphere is high-purity inert gas (argon gas, purity >99.999 wt%) under negative pressure, the smelting temperature is higher than the melting point of 50at.% Si-35at.% Fe+Cr) -15at.% La alloy, and the alloying smelting method is an arc furnace smelting technology with a water-cooled copper crucible;
step 2, loading 50at.% Si-35at.% (Fe+Cr) -15at.% La alloy obtained in the step 1 into a high-purity compact graphite crucible in a crystal growth furnace, and preserving heat for 1.5 hours at a smelting temperature of 1823K to dissolve C into a high-temperature melt to obtain a Si- (Fe+Cr) -La-C melt saturated with SiC (the C content is 2.4 wt percent); the smelting atmosphere is high-purity helium (99.999 wt%) +10%H 2 Mixing the gases;
step 3, growing SiC polycrystal in the SiC saturated Si- (Fe+Cr) -La-C melt obtained in the step 2 by a solution method; the crystal growth method is a crucible descending method, the crystal growth temperature is 1823K, the SiC crystal growth atmosphere is smelting atmosphere which is high-purity helium (99.999 wt%) +10% H 2 And (3) mixing the gases.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (3)
1. A method for growing SiC crystals by a low-temperature solution method, which is characterized by comprising the following steps:
step 1, mixing high-purity silicon, metal Fe or Cr and rare earth metal, and then carrying out alloying smelting for 5-30min to obtain Si-Me-RE alloy with uniform components, wherein the smelting atmosphere is high-purity inert gas under normal pressure or negative pressure, the smelting temperature is higher than the melting point of the Si-Me-RE alloy, and the alloying smelting method adopts a water-cooling copper crucible technology or an electromagnetic suspension smelting technology;
step 2, loading the Si-Me-RE alloy obtained in the step 1 into a high-purity compact graphite crucible or a SiC crucible in a crystal growth furnace, and preserving heat for at least 1 hour at a smelting temperature higher than 1823K to dissolve C or SiC into a high-temperature melt to obtain a SiC-saturated Si-Me-RE-C melt; the smelting atmosphere is high-purity inert gas or mixed gas of hydrogen and high-purity inert gas, and the volume content of hydrogen in the mixed gas is less than or equal to 10%;
step 3, growing SiC monocrystal or polycrystal SiC by a solution method in the SiC saturated Si-Me-RE-C melt obtained in the step 2; the crystal growth method is a conventional crystal growth method, including but not limited to a top seed crystal solution growth method or a crucible descending method, the crystal growth temperature is higher than 1823K, the SiC crystal growth atmosphere is high-purity inert gas or mixed gas of hydrogen and high-purity inert gas, and the volume content of hydrogen in the mixed gas is less than or equal to 10 percent.
2. The method for growing SiC crystals by the low temperature solution method according to claim 1, characterized in that: in the step 1, the content of Me in the Si-Me-RE alloy is less than or equal to 45 at%, and Me represents one or two of Fe and Cr; RE represents one or more of rare earth metals, and the total content of RE is less than or equal to 35 at%; under the condition of ensuring the above conditions, the proportion of Me, RE and Si is adjusted to ensure that the total content of Me, RE and Si is 100 at percent.
3. The method for growing SiC crystals by the low temperature solution method according to claim 1, characterized in that: the mixture of the metal Fe or Cr and the rare earth metal in the step 1 is taken as a cosolvent; the rare earth metal is one or more of rare earth elements including scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211106371.9A CN116145258A (en) | 2022-09-11 | 2022-09-11 | Method for growing SiC crystal by low-temperature solution method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211106371.9A CN116145258A (en) | 2022-09-11 | 2022-09-11 | Method for growing SiC crystal by low-temperature solution method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116145258A true CN116145258A (en) | 2023-05-23 |
Family
ID=86349623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211106371.9A Pending CN116145258A (en) | 2022-09-11 | 2022-09-11 | Method for growing SiC crystal by low-temperature solution method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116145258A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117585679A (en) * | 2024-01-19 | 2024-02-23 | 昆明理工大学 | Method for preparing high-purity semi-insulating SiC powder by high-temperature solution method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013056806A (en) * | 2011-09-08 | 2013-03-28 | National Institute Of Advanced Industrial Science & Technology | METHOD FOR PRODUCING SiC SINGLE CRYSTAL, AND SiC SINGLE CRYSTAL OBTAINED THEREBY |
| CN108286075A (en) * | 2010-11-26 | 2018-07-17 | 信越化学工业株式会社 | The manufacturing method of SiC single crystal |
| JP2019104661A (en) * | 2017-12-14 | 2019-06-27 | トヨタ自動車株式会社 | METHOD FOR MANUFACTURING SiC SINGLE CRYSTAL |
| CN115478324A (en) * | 2022-08-31 | 2022-12-16 | 昆明理工大学 | Method for growing single crystal or polycrystalline SiC crystal by cosolvent method |
-
2022
- 2022-09-11 CN CN202211106371.9A patent/CN116145258A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108286075A (en) * | 2010-11-26 | 2018-07-17 | 信越化学工业株式会社 | The manufacturing method of SiC single crystal |
| JP2013056806A (en) * | 2011-09-08 | 2013-03-28 | National Institute Of Advanced Industrial Science & Technology | METHOD FOR PRODUCING SiC SINGLE CRYSTAL, AND SiC SINGLE CRYSTAL OBTAINED THEREBY |
| JP2019104661A (en) * | 2017-12-14 | 2019-06-27 | トヨタ自動車株式会社 | METHOD FOR MANUFACTURING SiC SINGLE CRYSTAL |
| CN115478324A (en) * | 2022-08-31 | 2022-12-16 | 昆明理工大学 | Method for growing single crystal or polycrystalline SiC crystal by cosolvent method |
Non-Patent Citations (1)
| Title |
|---|
| LI, PENG: "Promising Approach for Rapid Growth of High-Quality SiC Crystals Using Si-Nd-C Solutions", CRYSTAL GROWTH & DESIGN, vol. 23, no. 7, 20 June 2023 (2023-06-20), pages 5173 - 5180 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117585679A (en) * | 2024-01-19 | 2024-02-23 | 昆明理工大学 | Method for preparing high-purity semi-insulating SiC powder by high-temperature solution method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101235772B1 (en) | Method for growing silicon carbide single crystal | |
| KR101310546B1 (en) | Manufacturing method for silicon carbide monocrystals | |
| WO2017022536A1 (en) | SiC CRUCIBLE, SiC SINTERED BODY, AND METHOD OF PRODUCING SiC SINGLE CRYSTAL | |
| CN113120909B (en) | Preparation method of high-purity semi-insulating silicon carbide powder | |
| CN115478324A (en) | Method for growing single crystal or polycrystalline SiC crystal by cosolvent method | |
| KR101152857B1 (en) | Method for growing silicon carbide single crystal | |
| JP2009126770A (en) | Method for growing silicon carbide single crystal | |
| CN110016718A (en) | A kind of processing method for growing silicon carbide crystal with high quality feedstock purification | |
| US20120171848A1 (en) | Method and System for Manufacturing Silicon and Silicon Carbide | |
| CN116145258A (en) | Method for growing SiC crystal by low-temperature solution method | |
| JP2023024315A (en) | METHOD FOR MANUFACTURING SiC SINGLE CRYSTAL | |
| CN116121870A (en) | Method for growing SiC monocrystal by solution method | |
| CN115124040A (en) | Solid-phase synthesis method for improving material ratio of large-particle-size silicon carbide powder | |
| CN108560053A (en) | The yttrium luetcium silicate scintillation material and its growing method that a kind of lanthanum, dysprosium, cerium are co-doped with | |
| CN111908472B (en) | Rare earth element doped silicon carbide powder as well as preparation method and application thereof | |
| CN110092411B (en) | Polycrystalline material synthesis device and method for gallium-containing garnet structure scintillation crystal | |
| WO2024045470A1 (en) | Growth method for rare earth-ferrite-boron permanent magnet single crystal using fluxing agent | |
| Mason | Growth and characterization of transition metal silicides | |
| JP2005112718A5 (en) | ||
| CN113788480B (en) | Preparation method of high-purity silicon carbide and corresponding high-purity silicon carbide | |
| CN106119951B (en) | Fluxing agent for low-temperature high-speed growth of SiC single crystal | |
| CN114496441A (en) | High-saturation-magnetic-induction-intensity iron-based alloy strip and preparation method thereof | |
| CN117585679A (en) | Method for preparing high-purity semi-insulating SiC powder by high-temperature solution method | |
| CN114182350B (en) | Method for preparing FePbSeTe monocrystal superconducting material by suspension smelting method | |
| CN117926387A (en) | Method for inducing monocrystallization of metal surface by hexagonal boron nitride monocrystal growth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |