CN117987924A - Method for low-temperature growth of 3C-silicon carbide single crystal by liquid phase method - Google Patents
Method for low-temperature growth of 3C-silicon carbide single crystal by liquid phase method Download PDFInfo
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 162
- 239000013078 crystal Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000007791 liquid phase Substances 0.000 title claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 73
- 239000000956 alloy Substances 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 239000006184 cosolvent Substances 0.000 claims abstract description 17
- 229910018651 Mn—Ni Inorganic materials 0.000 claims abstract description 14
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 13
- 229910000599 Cr alloy Inorganic materials 0.000 claims abstract description 13
- 229910000583 Nd alloy Inorganic materials 0.000 claims abstract description 13
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims description 75
- 238000005530 etching Methods 0.000 claims description 32
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- 238000003723 Smelting Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 22
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910018619 Si-Fe Inorganic materials 0.000 description 5
- 229910008289 Si—Fe Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000542 Sc alloy Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910018645 Mn—Sn Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910008458 Si—Cr Inorganic materials 0.000 description 1
- 229910006638 Si—Mn—Al Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000024241 parasitism Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention relates to a method for growing 3C-silicon carbide single crystals at low temperature by a liquid phase method, belonging to the technical field of crystal growth. The alloy cosolvent used for growing the 3C-silicon carbide monocrystal at low temperature is one of Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy. The invention provides a novel alloy fluxing agent which can be used for growing 3C-silicon carbide single crystals, and the novel alloy fluxing agent is respectively Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy, has higher carbon solubility at the temperature of 1450-1700 ℃, is beneficial to the rapid growth of 3C-silicon carbide, and simultaneously, in a solid-liquid two-phase region, the silicon carbide is the only solid phase which can exist stably in a liquid phase, and is beneficial to the realization of the stable growth of 3C-silicon carbide.
Description
Technical Field
The invention relates to a method for growing 3C-silicon carbide single crystals at low temperature by a liquid phase method, belonging to the technical field of crystal growth.
Background
The silicon carbide semiconductor material has the excellent characteristics of larger forbidden bandwidth, high radiation resistance intensity and breakdown field intensity, good chemical stability and thermal stability and high saturated electron mobility, and has great application value in the fields of electric automobiles, rail transit, high-voltage power transmission and transformation, photovoltaics, 5G communication and the like.
Silicon carbide has a crystal structure known to date of more than 250, and the main types thereof are hexagonal type (e.g., 4H-silicon carbide, 6H-silicon carbide) and cubic type (e.g., 3C-silicon carbide) and the like. Although hexagonal type 4H-silicon carbide has been the main object of investigation, cubic type 3C-silicon carbide is superior to 4H-silicon carbide in both mobility and thermal conductivity from the viewpoint of material characteristics. These superior properties indicate that 3C-silicon carbide is more suitable for use in the preparation of high performance electronic and photonic devices. However, since the preparation of 3C-silicon carbide single crystals is extremely difficult, there is no 3C-silicon carbide bulk crystal available as a substrate at present, and this problem greatly limits the development and application of 3C-silicon carbide-based devices.
Physical Vapor Transport (PVT) is currently the most mature method for growing 4H/6H-SiC single crystals, and the high quality 4H/6H-silicon carbide produced by the method is already fully commercialized, but the technology for growing cubic 3C-silicon carbide single crystals is still lagging behind, mainly because 3C-silicon carbide is unstable at high temperature and can be converted into hexagonal silicon carbide at a temperature higher than 1850 ℃, while PVT method often needs to grow silicon carbide at an ultra-high temperature higher than 2000 ℃, which makes the method unsuitable for growing 3C-silicon carbide.
Compared with PVT method, the liquid phase method (LPE) can more easily adjust the interface energy between silicon carbide and melt, and ensure the stability and smooth growth of crystal interface. In addition, the LPE method can reduce the growth temperature, reduce dislocation caused by thermal stress in the process of cooling the crystal from a high temperature state, effectively inhibit the dislocation in the process of growing the crystal, and can also realize the conversion between different dislocation in the process of growing the silicon carbide crystal in a liquid phase, thereby effectively reducing the defects such as micropipes and the like in the process of growing the silicon carbide crystal by the PVT method, and further improving the crystal quality.
At present, common cosolvent systems for growing silicon carbide single crystals by an LPE method mainly comprise Si-Cr, si-Fe, si-Ti, si-Co, si-Cr-Al, si-Cr-Ce, si-Cr-Al-Ce and the like, and the cosolvent systems have high carbon dissolving capacity in a high-temperature solution (1800-2300 ℃) and are used for growing 4H/6H-silicon carbide, however, at such high temperature, cube-type 3C-silicon carbide is unstable and can be converted into hexagonal 4H/6H-silicon carbide, so that silicon carbide polycrystal is generated, and 3C-silicon carbide single crystals cannot be obtained. There are researchers growing 3C-SiC at low temperatures of less than 1700 ℃ using solvent systems of Si, si-Fe, si-Sc, etc., however, at such low temperatures, solvents of Si, fe, sc, etc. have little solubility for carbon, resulting in extremely limited mass transfer of carbon in solution, resulting in very low growth rates of 3C-SiC single crystals.
Therefore, aiming at the problems that the growth rate is slow due to polycrystalline parasitism when the 3C-silicon carbide grows in a high-temperature solution and low carbon solubility when the 3C-silicon carbide grows in a low-temperature solution, a new cosolvent or a new method is needed to be explored to improve the stability and the growth rate of the 3C-silicon carbide single crystal.
Disclosure of Invention
In order to solve the problems and the defects of the prior art, the invention provides a method for growing 3C-silicon carbide single crystals at low temperature by a liquid phase method. The novel cosolvent provided by the invention can effectively improve the carbon solubility in the silicon-based melt at low temperature, and provides a novel growth scheme for stably and rapidly growing 3C-silicon carbide by a liquid phase method.
The invention is realized by the following technical scheme.
A method for growing 3C-silicon carbide single crystal at low temperature by liquid phase method, wherein the alloy cosolvent used for growing 3C-silicon carbide single crystal at low temperature is one of Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy.
A method for growing 3C-silicon carbide single crystals at low temperature by a liquid phase method, which comprises the following steps:
(1) Pre-smelting to prepare Si-Mn-M alloy with uniform components, wherein M is Ni, sn, nd, al or Cr;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), loading the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under an inert atmosphere, then preserving heat at a preset growth temperature, and finally regulating an axial temperature gradient to ensure that the bottom temperature of a melt is higher than the liquid level temperature;
(3) Immersing the seed rod filled with the silicon carbide seed crystal into the melt in the step (2) for etching;
(4) And after etching, the silicon carbide seed crystal is pulled to a position close to the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The mole fraction of each element of the Si-Mn-M alloy in the step (1) is expressed as Si x-Mny-Mz, wherein x is more than or equal to 30% and less than or equal to 65% by mole, y is more than or equal to 30% and less than or equal to 65% by mole, z is more than or equal to 5% and less than or equal to 35% by mole, and x+y+z=100% by mole.
The growth temperature in the step (2) is 1450-1700 ℃, and the temperature is kept for 30-120 min.
The axial temperature gradient in the step (2) is 1 ℃/cm-30 ℃/cm.
The silicon carbide seed crystal is a 3C-silicon carbide seed crystal.
The depth of the seed rod immersed into the melt in the step (3) is 1/2-9/10 of the height of the liquid level of the melt, and the etching time is 5-20 min.
And (3) in the step (4), the silicon carbide seed crystal is lifted to the liquid level of the melt, the immersion depth is 1/10-2/5 of the liquid level of the melt, and the growth time is 6-48 h.
In the invention, the alloy cosolvent used for growing the 3C-silicon carbide single crystal at low temperature is one of Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy, and the alloy cosolvent used for growing the 3C-silicon carbide single crystal at low temperature has higher carbon solubility at 1450-1700 ℃, which is beneficial to the rapid growth of the 3C-silicon carbide; in addition, 3C-silicon carbide is stable at low temperature, and in a solid-liquid two-phase region, silicon carbide is the only solid phase which can exist stably, so that stable growth of 3C-silicon carbide is realized.
In the process of growing 3C-silicon carbide single crystals by the liquid phase method, when the Si-Mn-M alloy is heated to a molten state and then kept at a predetermined growth temperature for a while, the carbon source is sufficiently dissolved into the melt. The temperature of the bottom of the melt is controlled to be higher than the temperature of the liquid level, so that the melt can obtain a certain axial temperature gradient, the solute can be quickly transferred to the seed crystal, and the growth rate of the crystal is improved. Before growth, the seed rod filled with the silicon carbide seed crystal is immersed into a position with higher melt temperature for etching, and the etching can remove processing scratches, pits, surface stains on the surface of the seed crystal, dislocation defects existing in the seed crystal and the like, thereby being beneficial to the subsequent growth of the silicon carbide single crystal with higher quality.
The beneficial effects of the invention are as follows:
(1) The invention provides a novel alloy fluxing agent which can be used for growing 3C-silicon carbide single crystals, and the novel alloy fluxing agent is respectively Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy, has higher carbon solubility at the temperature of 1450-1700 ℃, is beneficial to the rapid growth of 3C-silicon carbide, and simultaneously, in a solid-liquid two-phase region, the silicon carbide is the only solid phase which can exist stably in a liquid phase, and is beneficial to the realization of the stable growth of 3C-silicon carbide.
(2) The method is used for growing 3C-silicon carbide at low temperature, can effectively avoid the transformation of cubic 3C-silicon carbide into hexagonal silicon carbide such as 4H/6H and the like at high temperature, and can further realize the stable growth of 3C-silicon carbide.
(3) Compared with PVT method, the method of the invention is simple, easy to operate, high in quality of crystal, high in yield, low in raw material cost and growth temperature, and has the characteristics of low energy consumption, low cost, high quality, pollution-free production and the like.
Drawings
FIG. 1 is a schematic flow chart of a method for growing 3C-silicon carbide single crystals at a low temperature by a liquid phase method according to the present invention;
FIG. 2 is an SEM image of 3C-silicon carbide prepared from Mn-M (M is Cr) alloy cosolvent according to example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and detailed description.
Example 1
Respectively adopting Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy as cosolvent, and combining with top seed crystal solution growth technology to prepare the 3C-silicon carbide.
The method for growing the 3C-silicon carbide monocrystal at low temperature by the liquid phase method comprises the following steps:
(1) The Si-Mn-M alloy with uniform components is prepared by pre-smelting, wherein M is Ni, sn, nd, al or Cr, and the mole fraction of each element of the Si-Mn-M alloy is Si:40mol%, mn:40mol%, M:20mol%;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), filling the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a preset growth temperature of 1600 ℃ to enable carbon in the graphite crucible to be fully dissolved into the melt to form a carbon-rich solution, and finally regulating the axial temperature gradient to be 20 ℃/cm to enable the bottom temperature of the melt to be higher than the liquid level temperature;
(3) Immersing a seed rod filled with silicon carbide seed crystals into the melt in the step (2) for etching, wherein the silicon carbide seed crystals are 3C-silicon carbide seed crystals, the depth of immersing the seed rod into the melt is 9/10 of the height of the liquid level of the melt, and the etching time is 10min;
(4) And after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
In this example, an SEM image of 3C-silicon carbide prepared by using Mn-M (M is Cr) alloy cosolvent is shown in FIG. 2, and it is further confirmed that 3C-silicon carbide is prepared in this example.
The growth rates of 3C-silicon carbide single crystals in the different Si-Mn-M (m= Ni, sn, nd, al, cr) melts of this example are shown in table 1.
Example 2
Respectively adopting Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy as cosolvent, and combining with top seed crystal solution growth technology to prepare the 3C-silicon carbide.
The method for growing the 3C-silicon carbide monocrystal at low temperature by the liquid phase method comprises the following steps:
(1) The Si-Mn-M alloy with uniform components is prepared by pre-smelting, wherein M is Ni, sn, nd, al or Cr, and the mole fraction of each element of the Si-Mn-M alloy is Si:40mol%, mn:40mol%, M:20mol%;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), filling the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a preset growth temperature of 1600 ℃ to enable carbon in the graphite crucible to be fully dissolved into the melt to form a carbon-rich solution, and finally regulating the axial temperature gradient to be 15 ℃/cm to enable the bottom temperature of the melt to be higher than the liquid level temperature;
(3) Immersing a seed rod filled with silicon carbide seed crystals into the melt in the step (2) for etching, wherein the silicon carbide seed crystals are 3C-silicon carbide seed crystals, the depth of immersing the seed rod into the melt is 9/10 of the height of the liquid level of the melt, and the etching time is 10min;
(4) And after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The growth rates of 3C-silicon carbide single crystals in the different Si-Mn-M (m= Ni, sn, nd, al, cr) melts of this example are shown in table 1.
Example 3
Respectively adopting Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy as cosolvent, and combining with top seed crystal solution growth technology to prepare the 3C-silicon carbide.
The method for growing the 3C-silicon carbide monocrystal at low temperature by the liquid phase method comprises the following steps:
(1) The Si-Mn-M alloy with uniform components is prepared by pre-smelting, wherein M is Ni, sn, nd, al or Cr, and the mole fraction of each element of the Si-Mn-M alloy is Si:30mol%, mn:65mol%, M:5mol%;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), filling the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a preset growth temperature of 1600 ℃ to enable carbon in the graphite crucible to be fully dissolved into the melt to form a carbon-rich solution, and finally regulating the axial temperature gradient to be 5 ℃/cm to enable the bottom temperature of the melt to be higher than the liquid level temperature;
(3) Immersing a seed rod filled with silicon carbide seed crystals into the melt in the step (2) for etching, wherein the silicon carbide seed crystals are 3C-silicon carbide seed crystals, the depth of immersing the seed rod into the melt is 9/10 of the height of the liquid level of the melt, and the etching time is 10min;
(4) And after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The growth rates of 3C-silicon carbide single crystals in the different Si-Mn-M (m= Ni, sn, nd, al, cr) melts of this example are shown in table 1.
Example 4
Respectively adopting Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy as cosolvent, and combining with top seed crystal solution growth technology to prepare the 3C-silicon carbide.
The method for growing the 3C-silicon carbide monocrystal at low temperature by the liquid phase method comprises the following steps:
(1) The Si-Mn-M alloy with uniform components is prepared by pre-smelting, wherein M is Ni, sn, nd, al or Cr, and the mole fraction of each element of the Si-Mn-M alloy is Si:30mol%, mn:65mol%, M:5mol%;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), filling the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a predetermined 1450 ℃ growth temperature, fully dissolving carbon in the graphite crucible into the melt to form a carbon-rich solution, and finally regulating an axial temperature gradient to be 5 ℃/cm to ensure that the bottom temperature of the melt is higher than the liquid level temperature;
(3) Immersing a seed rod filled with silicon carbide seed crystals into the melt in the step (2) for etching, wherein the silicon carbide seed crystals are 3C-silicon carbide seed crystals, the depth of immersing the seed rod into the melt is 9/10 of the height of the liquid level of the melt, and the etching time is 10min;
(4) And after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The growth rates of 3C-silicon carbide single crystals in the different Si-Mn-M (m= Ni, sn, nd, al, cr) melts of this example are shown in table 1.
Example 5
Respectively adopting Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy as cosolvent, and combining with top seed crystal solution growth technology to prepare the 3C-silicon carbide.
The method for growing the 3C-silicon carbide monocrystal at low temperature by the liquid phase method comprises the following steps:
(1) The Si-Mn-M alloy with uniform components is prepared by pre-smelting, wherein M is Ni, sn, nd, al or Cr, and the mole fraction of each element of the Si-Mn-M alloy is Si:65mol%, mn:30mol%, M:5mol%;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), filling the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a preset growth temperature of 1600 ℃ to enable carbon in the graphite crucible to be fully dissolved into the melt to form a carbon-rich solution, and finally regulating the axial temperature gradient to be 20 ℃/cm to enable the bottom temperature of the melt to be higher than the liquid level temperature;
(3) Immersing a seed rod filled with silicon carbide seed crystals into the melt in the step (2) for etching, wherein the silicon carbide seed crystals are 3C-silicon carbide seed crystals, the depth of immersing the seed rod into the melt is 9/10 of the height of the liquid level of the melt, and the etching time is 10min;
(4) And after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The growth rates of 3C-silicon carbide single crystals in the different Si-Mn-M (m= Ni, sn, nd, al, cr) melts of this example are shown in table 1.
Example 6
Respectively adopting Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy as cosolvent, and combining with top seed crystal solution growth technology to prepare the 3C-silicon carbide.
The method for growing the 3C-silicon carbide monocrystal at low temperature by the liquid phase method comprises the following steps:
(1) The Si-Mn-M alloy with uniform components is prepared by pre-smelting, wherein M is Ni, sn, nd, al or Cr, and the mole fraction of each element of the Si-Mn-M alloy is Si:65mol%, mn:30mol%, M:5mol%;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), filling the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a predetermined 1450 ℃ growth temperature, fully dissolving carbon in the graphite crucible into the melt to form a carbon-rich solution, and finally regulating an axial temperature gradient to be 5 ℃/cm to ensure that the bottom temperature of the melt is higher than the liquid level temperature;
(3) Immersing a seed rod filled with silicon carbide seed crystals into the melt in the step (2) for etching, wherein the silicon carbide seed crystals are 3C-silicon carbide seed crystals, the depth of immersing the seed rod into the melt is 9/10 of the height of the liquid level of the melt, and the etching time is 10min;
(4) And after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The growth rates of 3C-silicon carbide single crystals in the different Si-Mn-M (m= Ni, sn, nd, al, cr) melts of this example are shown in table 1.
TABLE 1 growth rate (. Mu.m/h) of 3C-silicon carbide single crystals obtained in the examples
| Alloy | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Si-Mn-Ni | 356 | 342 | 275 | 230 | 188 | 178 |
| Si-Mn-Sn | 345 | 338 | 263 | 228 | 175 | 160 |
| Si-Mn-Nd | 365 | 360 | 285 | 247 | 205 | 195 |
| Si-Mn-Al | 324 | 316 | 242 | 215 | 170 | 160 |
| Si-Mn-Cr | 381 | 370 | 298 | 285 | 213 | 227 |
Comparative example 1
Pre-smelting to prepare Si-Fe alloy with uniform components (the mole fraction of each element of the alloy is Si:40mol percent and Fe:60mol percent), crushing the Si-Fe alloy obtained in the step (1), loading the crushed Si-Fe alloy into a graphite crucible, heating the Si-Fe alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a preset growth temperature of 1600 ℃, regulating the axial temperature gradient to be 20 ℃/cm, immersing a seed rod filled with silicon carbide seed crystal into the melt for etching, wherein the silicon carbide seed crystal is 3C-silicon carbide seed crystal, the depth of immersing into the melt is 9/10 of the liquid level of the melt, and the etching time is 10min; and after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The growth rate of the 3C-silicon carbide single crystal in this comparative example 1 was 125 μm/h.
Comparative example 2
Pre-smelting to prepare Si-Sc alloy with uniform components (the mole fraction of each element of the alloy is Si:40 mole percent, -Sc:60 mole percent), crushing the Si-Sc alloy obtained in the step (1), loading the crushed Si-Sc alloy into a graphite crucible, heating the Si-Fe alloy in the graphite crucible to a molten state under inert atmosphere (argon), then preserving heat for 120min at a preset growth temperature of 1600 ℃, regulating an axial temperature gradient to be 15 ℃/cm, immersing a seed rod filled with silicon carbide seed crystal into the melt for etching, wherein the silicon carbide seed crystal is 3C-silicon carbide seed crystal, the depth of immersing into the melt is 9/10 of the liquid level of the melt, and the etching time is 10min; and after etching, the silicon carbide seed crystal is lifted to a position close to the liquid level of the melt, the immersion depth is 1/10 of the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out for 12 hours, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
The growth rate of the 3C-silicon carbide single crystal in this comparative example 2 was 156. Mu.m/h.
As can be seen from Table 1 and comparative examples 1 and 2, the growth rate of the 3C-silicon carbide single crystal of the present invention is significantly improved, and Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy, mn-Cr alloy, has high carbon solubility at a temperature of 1450℃to 1700℃and is advantageous for rapid growth of 3C-silicon carbide.
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 (8)
1. A method for growing 3C-silicon carbide single crystal at low temperature by liquid phase method is characterized in that: the alloy cosolvent used for growing the 3C-silicon carbide monocrystal at low temperature is one of Mn-Ni alloy, mn-Sn alloy, mn-Nd alloy, mn-Al alloy and Mn-Cr alloy.
2. The method for low-temperature growth of 3C-silicon carbide single crystals by liquid phase method according to claim 1, characterized by comprising the steps of:
(1) Pre-smelting to prepare Si-Mn-M alloy with uniform components, wherein M is Ni, sn, nd, al or Cr;
(2) Crushing the Si-Mn-M alloy obtained in the step (1), loading the crushed Si-Mn-M alloy into a graphite crucible, heating the Si-Mn-M alloy in the graphite crucible to a molten state under an inert atmosphere, then preserving heat at a preset growth temperature, and finally regulating an axial temperature gradient to ensure that the bottom temperature of a melt is higher than the liquid level temperature;
(3) Immersing the seed rod filled with the silicon carbide seed crystal into the melt in the step (2) for etching;
(4) And after etching, the silicon carbide seed crystal is pulled to a position close to the liquid level of the melt, 3C-silicon carbide single crystal growth is carried out, and finally the 3C-silicon carbide single crystal is obtained in the seed crystal.
3. The method for low-temperature growth of 3C-silicon carbide single crystals by liquid phase method according to claim 1, wherein: the mole fraction of each element of the Si-Mn-M alloy in the step (1) is expressed as Si x-Mny-Mz, wherein x is more than or equal to 30% and less than or equal to 65% by mole, y is more than or equal to 30% and less than or equal to 65% by mole, z is more than or equal to 5% and less than or equal to 35% by mole, and x+y+z=100% by mole.
4. The method for low-temperature growth of 3C-silicon carbide single crystals by liquid phase method according to claim 1, wherein: the growth temperature in the step (2) is 1450-1700 ℃, and the temperature is kept for 30-120 min.
5. The method for low-temperature growth of 3C-silicon carbide single crystals by liquid phase method according to claim 1, wherein: the axial temperature gradient in the step (2) is 1 ℃/cm-30 ℃/cm.
6. The method for low-temperature growth of 3C-silicon carbide single crystals by liquid phase method according to claim 1, wherein: the silicon carbide seed crystal is a 3C-silicon carbide seed crystal.
7. The method for low-temperature growth of 3C-silicon carbide single crystals by liquid phase method according to claim 1, wherein: the depth of the seed rod immersed into the melt in the step (3) is 1/2-9/10 of the height of the liquid level of the melt, and the etching time is 5-20 min.
8. The method for low-temperature growth of 3C-silicon carbide single crystals by liquid phase method according to claim 1, wherein: and (3) in the step (4), the silicon carbide seed crystal is lifted to the liquid level of the melt, the immersion depth is 1/10-2/5 of the liquid level of the melt, and the growth time is 6-48 h.
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