CN113044843A - Recycling method of residual raw materials for growing silicon carbide by PVT (physical vapor transport) method - Google Patents
Recycling method of residual raw materials for growing silicon carbide by PVT (physical vapor transport) method Download PDFInfo
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Abstract
A method for recycling residual raw materials of silicon carbide grown by a PVT method belongs to the field of silicon carbide raw material recovery. The invention aims to solve the technical problem of low-efficiency recovery of residual raw materials of silicon carbide grown by a PVT method. After the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, crushing the raw material into 0.1-1cm particles, placing the particles into a ball mill, adding the particles into high-purity water after ball milling, stirring, standing, pouring out upper-layer suspended matters and water, keeping a lower-layer precipitated raw material, drying, placing the dried raw material in a muffle furnace, burning at 600-850 ℃ to obtain primary recovered SiC powder, washing the primary recovered SiC powder with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder doped or not doped with new silicon carbide raw material, heating to 1900-. The preparation method is simple.
Description
Technical Field
The invention belongs to the field of silicon carbide raw material recovery; in particular to a method for recycling residual raw materials of silicon carbide grown by a PVT method.
Background
The third generation semiconductor material represented by silicon carbide is considered to have very broad prospects in the emerging industries of rail transit, new energy automobiles, smart grids, 5G communication and the like, and a Physical Vapor Transport (PVT) method is a mainstream preparation process, and the principle of the method is that a silicon carbide raw material becomes a gas-phase component through high temperature and is gradually deposited on seed crystals to realize crystal growth.
However, the PVT process principle and the properties of silicon carbide at high temperatures determine that severe graphitization of the feedstock occurs during crystal growth, i.e. the feedstock in the higher temperature region gradually becomes graphitic and recrystallizes above the feedstock, i.e. polycrystalline silicon carbide is formed. Therefore, the raw materials after the crystal growth are not available, which causes waste of high-purity silicon carbide powder, increases the single crystal preparation cost, and is not beneficial to the industrial application of the substrate material.
Disclosure of Invention
The invention aims to provide a high-efficiency recycling method of residual raw materials for growing silicon carbide by a PVT method.
The invention is realized by the following technical scheme:
a method for recycling residual raw materials of silicon carbide grown by a PVT method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt at the temperature of 600-850 ℃ for 1-4 hours to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, doping or not doping a new silicon carbide raw material into the high-purity SiC powder obtained in the step 5, heating to 1900-2200 ℃ under the protection of atmosphere, preserving the heat for 5-40h, and cooling to obtain the 5N-grade high-purity SiC powder.
The invention relates to a method for recycling residual raw materials of silicon carbide grown by a PVT method, wherein an EP-100 type crusher is adopted for crushing in step 1, the production capacity is 0.2-1.0t/h, and the crushing time is 1-10 min.
The invention relates to a method for recycling residual raw materials of silicon carbide grown by a PVT method, wherein in the step 2, a ceramic ball mill is adopted for ball milling, silicon carbide balls are used for ball milling, the ball milling rotating speed is 30-300r/min, and the ball milling time is 20-60 min.
The method for recycling the residual raw materials of the silicon carbide grown by the PVT method, disclosed by the invention, has the advantages that the material-liquid ratio of the micro-powder raw material to the high-purity water in the step 3 is 1:3-5kg/L, the stirring speed is 50-200r/min, and the stirring time is 5-15 min.
The method for recycling the residual raw materials of the silicon carbide grown by the PVT method, disclosed by the invention, has the drying temperature of 100-120 ℃ and the drying time of 30-60min in the step 4.
The method for recycling the residual raw materials of the silicon carbide grown by the PVT method comprises the step 5, wherein the feed-liquid ratio of primary recovered powder to hydrofluoric acid is 1:5-10g/mL, and the concentration of the hydrofluoric acid is 10-15 wt%.
Fe3O2+HF→H2O+FeF3 (1)
Al2O3+HF→H2O+AlF3 (2)
The method for recycling the residual raw materials of the silicon carbide grown by the PVT method, disclosed by the invention, has the advantages that the material-liquid ratio of primary recovered powder to ultrapure water in the washing in the step 5 is 1:5-10g/mL, the washing times are 2-3 times, the drying temperature is 100-120 ℃, and the drying time is 30-60 min.
The invention relates to a method for recycling residual raw materials of silicon carbide grown by a PVT method, wherein in step 6, the protective atmosphere is argon.
According to the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, the 5N-grade high-purity SiC powder obtained in the step 6 is used as a raw material for preparing the silicon carbide crystal on the seed crystal.
The method for recycling the residual raw materials for growing the silicon carbide by the PVT method has the advantages of simple process method, simple and convenient technical operation, short period for recycling the raw materials and less pollution.
According to the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, the purity of the recycled raw materials can reach 5N grade, and the recovery rate is over 85%.
Drawings
FIG. 1 is a photograph of the starting material after the completion of the growth of a silicon carbide crystal according to the present invention;
FIG. 2 is a view showing SiC particles recovered by a method for recycling residual raw materials for growing SiC by the PVT method according to a first embodiment;
FIG. 3 is a process flow diagram of the method for recycling residual raw materials of silicon carbide grown by PVT method according to the present invention.
Detailed Description
The first embodiment is as follows:
a method for recycling residual raw materials of silicon carbide grown by a PVT method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt at 850 ℃ for 1 hour to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, adding or not adding new silicon carbide raw materials into the high-purity SiC powder obtained in the step 5, heating to 2200 ℃ under the protection of atmosphere, preserving the temperature for 10 hours, and cooling to obtain the 5N-grade high-purity SiC powder.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.2t/h, and the crushing time is 5 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method in the embodiment, in the step 2, a ceramic ball mill is adopted for ball milling, silicon carbide balls are used for ball milling, the ball milling rotating speed is 30r/min, and the ball milling time is 60 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the high-purity water is 1:3kg/L, the stirring speed is 100r/min, and the stirring time is 10 min.
In the method for recycling the residual raw material for growing the silicon carbide by the PVT method in the embodiment, the drying temperature in the step 4 is 100 ℃, and the drying time is 60 min.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method according to this embodiment, the feed-to-liquid ratio of the primary recovered powder to the hydrofluoric acid in step 5 is 1:5g/mL, and the concentration of the hydrofluoric acid is 10 wt%.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method in the embodiment, the material-liquid ratio of the primary recovered powder and the ultrapure water in the washing in the step 5 is 1:5g/mL, the washing times are 3 times, the drying temperature is 100 ℃, and the drying time is 60 min.
In the method for recycling excess raw material for growing silicon carbide by the PVT method according to this embodiment, the protective atmosphere in step 6 is argon gas.
In the method for recycling residual raw materials for growing silicon carbide by the PVT method according to the embodiment, the 5N-grade high-purity SiC powder obtained in step 6 is used as a raw material for preparing silicon carbide crystals on seed crystals.
In the method for recycling excess raw material for silicon carbide growth by the PVT method according to the present embodiment, a photograph of the raw material after the silicon carbide crystal growth is completed is shown in fig. 1, and as can be seen from fig. 1, the amount of the raw material remaining after the silicon carbide crystal growth is large, and the raw material is not recycled, which causes a large waste.
In the method for recycling excess raw material for growing silicon carbide by the PVT method according to the present embodiment, as shown in fig. 2, the SiC grains after being recovered have a uniform grain size, as can be seen from fig. 2.
According to the method for recycling the residual raw material for growing the silicon carbide by the PVT method, the purity of the recovered raw material can reach 5N grade, and the recovery rate is 87%.
The second embodiment is as follows:
a method for recycling residual raw materials of silicon carbide grown by a PVT method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt at 700 ℃ for 2 hours to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, adding or not adding new silicon carbide raw materials into the high-purity SiC powder obtained in the step 5, heating to 1900 ℃ under the protection of atmosphere, preserving the temperature for 36 hours, and cooling to obtain the 5N-grade high-purity SiC powder.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.2t/h, and the crushing time is 10 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method in the embodiment, in the step 2, a ceramic ball mill is adopted for ball milling, silicon carbide balls are used for ball milling, the ball milling rotating speed is 100r/min, and the ball milling time is 30 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the high-purity water is 1:5kg/L, the stirring speed is 200r/min, and the stirring time is 15 min.
In the method for recycling the residual raw material for growing the silicon carbide by the PVT method in the embodiment, the drying temperature in the step 4 is 120 ℃, and the drying time is 30 min.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method according to this embodiment, the feed-to-liquid ratio of the primary recovered powder to the hydrofluoric acid in step 5 is 1:10g/mL, and the concentration of the hydrofluoric acid is 10 wt%.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method in the embodiment, the material-liquid ratio of the primary recovered powder to the ultrapure water in the washing in the step 5 is 1:10g/mL, the washing times are 2 times, the drying temperature is 120 ℃, and the drying time is 30 min.
In the method for recycling excess raw material for growing silicon carbide by the PVT method according to this embodiment, the protective atmosphere in step 6 is argon gas.
In the method for recycling residual raw materials for growing silicon carbide by the PVT method according to the embodiment, the 5N-grade high-purity SiC powder obtained in step 6 is used as a raw material for preparing silicon carbide crystals on seed crystals.
According to the method for recycling the residual raw material for growing the silicon carbide by the PVT method, the purity of the recovered raw material can reach 5N grade, and the recovery rate is 90%.
The third concrete implementation mode:
a method for recycling residual raw materials of silicon carbide grown by a PVT method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt at 650 ℃ for 3 hours to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, adding or not adding new silicon carbide raw materials into the high-purity SiC powder obtained in the step 5, heating to 2200 ℃ under the protection of atmosphere, preserving the temperature for 15h, and cooling to obtain the 5N-grade high-purity SiC powder.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.2t/h, and the crushing time is 10 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method in the embodiment, in the step 2, a ceramic ball mill is adopted for ball milling, silicon carbide balls are used for ball milling, the ball milling rotating speed is 300r/min, and the ball milling time is 20 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the high-purity water is 1:4kg/L, the stirring speed is 100r/min, and the stirring time is 10 min.
In the method for recycling the residual raw material for growing the silicon carbide by the PVT method in the embodiment, the drying temperature in the step 4 is 110 ℃, and the drying time is 40 min.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method according to this embodiment, the feed-to-liquid ratio of the primary recovered powder to the hydrofluoric acid in step 5 is 1:7g/mL, and the concentration of the hydrofluoric acid is 15 wt%.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method in the embodiment, the material-liquid ratio of the primary recovered powder and the ultrapure water in the washing in the step 5 is 1:7g/mL, the washing times are 3 times, the drying temperature is 120 ℃, and the drying time is 40 min.
In the method for recycling excess raw material for growing silicon carbide by the PVT method according to this embodiment, the protective atmosphere in step 6 is argon gas.
In the method for recycling residual raw materials for growing silicon carbide by the PVT method according to the embodiment, the 5N-grade high-purity SiC powder obtained in step 6 is used as a raw material for preparing silicon carbide crystals on seed crystals.
According to the method for recycling the residual raw material for growing the silicon carbide by the PVT method, the purity of the recovered raw material can reach 5N grade, and the recovery rate is 88%.
The fourth concrete implementation mode:
a method for recycling residual raw materials of silicon carbide grown by a PVT method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt for 4 hours at 750 ℃ to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, adding or not adding new silicon carbide raw materials into the high-purity SiC powder obtained in the step 5, heating to 2000 ℃ under the protection of atmosphere, preserving the heat for 24 hours, and cooling to obtain the 5N-grade high-purity SiC powder.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.2t/h, and the crushing time is 5 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method in the embodiment, in the step 2, a ceramic ball mill is adopted for ball milling, silicon carbide balls are used for ball milling, the ball milling rotating speed is 50r/min, and the ball milling time is 40 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the high-purity water is 1:3kg/L, the stirring speed is 50r/min, and the stirring time is 15 min.
In the method for recycling the residual raw material for growing the silicon carbide by the PVT method in the embodiment, the drying temperature in the step 4 is 100 ℃, and the drying time is 60 min.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method according to this embodiment, the feed-to-liquid ratio of the primary recovered powder to the hydrofluoric acid in step 5 is 1:5g/mL, and the concentration of the hydrofluoric acid is 15 wt%.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method in the embodiment, the material-liquid ratio of the primary recovered powder and the ultrapure water in the washing in the step 5 is 1:10g/mL, the washing times are 3 times, the drying temperature is 120 ℃, and the drying time is 40 min.
In the method for recycling excess raw material for growing silicon carbide by the PVT method according to this embodiment, the protective atmosphere in step 6 is argon gas.
In the method for recycling residual raw materials for growing silicon carbide by the PVT method according to the embodiment, the 5N-grade high-purity SiC powder obtained in step 6 is used as a raw material for preparing silicon carbide crystals on seed crystals.
According to the method for recycling the residual raw material for growing the silicon carbide by the PVT method, the purity of the recovered raw material can reach 5N grade, and the recovery rate is 89%.
The fifth concrete implementation mode:
a method for recycling residual raw materials of silicon carbide grown by a PVT method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt for 4 hours at the temperature of 600 ℃ to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, adding or not adding new silicon carbide raw materials into the high-purity SiC powder obtained in the step 5, heating to 2100 ℃ under the protection of atmosphere, preserving the temperature for 30 hours, and cooling to obtain 5N-grade high-purity SiC powder.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.2t/h, and the crushing time is 10 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method in the embodiment, in the step 2, a ceramic ball mill is adopted for ball milling, silicon carbide balls are used for ball milling, the ball milling rotation speed is 150r/min, and the ball milling time is 40 min.
In the method for recycling the residual raw materials for growing the silicon carbide by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the high-purity water is 1:4kg/L, the stirring speed is 100r/min, and the stirring time is 10 min.
In the method for recycling the residual raw material for growing the silicon carbide by the PVT method in the embodiment, the drying temperature in the step 4 is 100 ℃, and the drying time is 60 min.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method according to this embodiment, the feed-to-liquid ratio of the primary recovered powder to the hydrofluoric acid in step 5 is 1:6g/mL, and the concentration of the hydrofluoric acid is 12 wt%.
In the method for recycling the residual raw material for growing silicon carbide by the PVT method in the embodiment, the material-liquid ratio of the primary recovered powder and the ultrapure water in the washing in the step 5 is 1:5g/mL, the washing times are 3 times, the drying temperature is 100 ℃, and the drying time is 60 min.
In the method for recycling excess raw material for growing silicon carbide by the PVT method according to this embodiment, the protective atmosphere in step 6 is argon gas.
In the method for recycling residual raw materials for growing silicon carbide by the PVT method according to the embodiment, the 5N-grade high-purity SiC powder obtained in step 6 is used as a raw material for preparing silicon carbide crystals on seed crystals.
According to the method for recycling the residual raw material for growing the silicon carbide by the PVT method, the purity of the recovered raw material can reach 5N grade, and the recovery rate is 86%.
The sixth specific implementation mode:
a method for recycling residual raw materials of silicon carbide grown by a PVT method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt at the temperature of 600-850 ℃ for 1-4 hours to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, doping or not doping a new silicon carbide raw material into the high-purity SiC powder obtained in the step 5, heating to 1900-2200 ℃ under the protection of atmosphere, preserving the heat for 5-40h, and cooling to obtain the 5N-grade high-purity SiC powder.
The seventh embodiment:
according to the sixth specific embodiment, in the step 1, an EP-100 type crusher is adopted for crushing, the production capacity is 0.2-1.0t/h, and the crushing time is 1-10 min.
The specific implementation mode is eight:
according to the sixth specific embodiment, in the step 2, a ceramic ball mill is used for ball milling, silicon carbide balls are used for ball milling, the ball milling rotation speed is 30-300r/min, and the ball milling time is 20-60 min.
The specific implementation method nine:
according to the sixth specific embodiment, in the step 3, the material-liquid ratio of the micro-powder raw material to the high-purity water is 1:3-5kg/L, the stirring speed is 50-200r/min, and the stirring time is 5-15 min.
The detailed implementation mode is ten:
according to the method for recycling the residual raw material of the silicon carbide grown by the PVT method in the sixth specific embodiment, the drying temperature in the step 4 is 100-120 ℃, and the drying time is 30-60 min.
The concrete implementation mode eleven:
according to the sixth specific embodiment, in the method for recycling the residual raw material for growing the silicon carbide by the PVT method, the feed-liquid ratio of the primary recovered powder to the hydrofluoric acid in the step 5 is 1:5-10g/mL, and the concentration of the hydrofluoric acid is 10-15 wt%.
The specific implementation mode twelve:
according to the method for recycling the residual raw material of the silicon carbide grown by the PVT method in the specific embodiment, the material-liquid ratio of the primary recovered powder and the ultrapure water in the washing in the step 5 is 1:5-10g/mL, the washing frequency is 2-3 times, the drying temperature is 100-120 ℃, and the drying time is 30-60 min.
The specific implementation mode is thirteen:
according to the sixth specific embodiment, in the recycling method of the residual raw material for growing silicon carbide by the PVT method, the protective atmosphere in the step 6 is argon.
The specific implementation mode is fourteen:
according to the method for recycling the residual raw materials of the silicon carbide grown by the PVT method in the sixth specific embodiment, the 5N-grade high-purity SiC powder obtained in the step 6 is used as a raw material for preparing the silicon carbide crystals on the seed crystals.
Claims (9)
1. A method for recycling residual raw materials of silicon carbide grown by a PVT method is characterized by comprising the following steps: the method comprises the following steps:
step 1, after the growth of the silicon carbide crystal is finished, taking a raw material after the growth of the silicon carbide crystal, and crushing the raw material into a particle raw material of 0.1-1cm for later use;
step 2, placing the particle raw material obtained in the step 1 into a ball mill, and obtaining a micro powder raw material with the particle size of 0.005-0.1mm after ball milling for later use;
step 3, adding the micro-powder raw material obtained in the step 2 into high-purity water, stirring, standing, pouring out upper-layer suspended matters and water, and keeping the lower-layer precipitated raw material for later use;
step 4, drying the precipitation raw material obtained in the step 3, and then placing the dried precipitation raw material in a muffle furnace to be burnt at the temperature of 600-850 ℃ for 1-4 hours to obtain primary recovered SiC powder for later use;
step 5, washing the primary recovered powder obtained in the step 4 with hydrofluoric acid, washing with ultrapure water, filtering and drying to obtain high-purity SiC powder;
and 6, doping or not doping a new silicon carbide raw material into the high-purity SiC powder obtained in the step 5, heating to 1900-2200 ℃ under the protection of atmosphere, preserving the heat for 5-40h, and cooling to obtain the 5N-grade high-purity SiC powder.
2. The method for recycling residual raw materials of silicon carbide grown by PVT method according to claim 1, wherein the method comprises the following steps: in the step 1, an EP-100 type crusher is adopted for crushing, the production capacity is 0.2-1.0t/h, and the crushing time is 1-10 min.
3. The method for recycling residual raw materials of silicon carbide grown by PVT method according to claim 2, wherein the method comprises the following steps: and 2, ball milling is carried out by adopting a ceramic ball mill and silicon carbide balls, wherein the ball milling rotation speed is 30-300r/min, and the ball milling time is 20-60 min.
4. The method for recycling residual raw materials of PVT method-grown silicon carbide according to claim 3, wherein the method comprises the following steps: in the step 3, the material-liquid ratio of the micro-powder raw material to the high-purity water is 1:3-5kg/L, the stirring speed is 50-200r/min, and the stirring time is 5-15 min.
5. The method for recycling residual raw materials of PVT method-grown silicon carbide according to claim 4, wherein the method comprises the following steps: in the step 4, the drying temperature is 100-120 ℃, and the drying time is 30-60 min.
6. The method for recycling residual raw materials of PVT method-grown silicon carbide according to claim 5, wherein the method comprises the following steps: in the step 5, the ratio of the primary recovered powder to hydrofluoric acid is 1:5-10g/mL, and the concentration of hydrofluoric acid is 10-15 wt%.
7. The method for recycling residual raw materials of PVT method-grown silicon carbide according to claim 5, wherein the method comprises the following steps: and 5, during washing, the material-liquid ratio of the primary recovered powder to the ultrapure water is 1:5-10g/mL, the washing times are 2-3 times, the drying temperature is 100-.
8. The method for recycling residual raw materials of PVT method-grown silicon carbide according to claim 7, wherein the method comprises the following steps: in step 6, the protective atmosphere is argon.
9. The method for recycling residual raw materials of PVT method-grown silicon carbide according to claim 8, wherein the method comprises the following steps: and (4) using the 5N-grade high-purity SiC powder obtained in the step (6) as a raw material for preparing the silicon carbide crystal on the seed crystal.
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