CN113046834A - Method for recycling residual raw materials of PVT method aluminum nitride crystal growth - Google Patents
Method for recycling residual raw materials of PVT method aluminum nitride crystal growth Download PDFInfo
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- 239000002994 raw material Substances 0.000 title claims abstract description 160
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 126
- 239000013078 crystal Substances 0.000 title claims abstract description 93
- 238000004064 recycling Methods 0.000 title claims abstract description 57
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 13
- 239000012498 ultrapure water Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004065 semiconductor Substances 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
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
- C01B21/0728—After-treatment, e.g. grinding, purification
-
- 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
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for recycling residual raw materials of aluminum nitride crystal growth by a PVT method belongs to the technical field of recovery of residual raw materials of aluminum nitride crystal growth. The invention aims to solve the technical problem of efficiently recovering residual raw materials for growing the aluminum nitride crystal by the PVT method. After the growth of the aluminum nitride crystal is finished, crushing the raw material after the growth of the aluminum nitride crystal into 0.1-1cm of particle raw material, placing the particle raw material into a ball mill, drying the micro powder raw material with the particle size of 0.005-0.1mm after ball milling, washing the micro powder raw material with a mixed solution of hydrofluoric acid and nitric acid, cleaning the micro powder raw material with ultrapure water, ultrasonically cleaning the micro powder raw material with ethanol, drying the micro powder raw material to obtain high-purity aluminum nitride powder, carrying out cold isostatic pressing, heating the high-purity aluminum nitride powder to the temperature of 1500-1700 ℃ under the atmosphere protection, calcining the high-temperature aluminum nitride powder for 10-20h, and cooling the high-purity aluminum. The method is simple, utilizes the residual raw materials in the reaction, improves the total utilization rate of the raw materials and saves the cost.
Description
Technical Field
The invention belongs to the technical field of recovery of residual raw materials for aluminum nitride crystal growth; in particular to a method for recycling residual raw materials of the growth of aluminum nitride crystals by a PVT method.
Background
The third generation semiconductor material represented by aluminum nitride (AlN) has irreplaceable effect in industries such as power electronics, high-power devices, deep ultraviolet LEDs and the like, and is an important national defense industrial strategic material. The principle of the Physical vapor transport method (PVT) is that aluminum nitride raw material is formed into vapor phase components through high temperature and gradually deposited on seed crystals to realize crystal growth.
However, the PVT process principle determines that the feedstock undergoes severe local densification during crystal growth, i.e., the feedstock in the higher temperature region gradually rises, the feedstock is transported to the lower temperature region to form a dense ceramic-like feedstock, and recrystallization occurs above and in the feedstock to form polycrystalline aluminum nitride. Therefore, the excessive compactness of the residual raw materials after the crystal growth can cause the waste of high-purity aluminum nitride, thereby improving the preparation cost of the single crystal and being not beneficial to the industrial application of the substrate material.
Disclosure of Invention
The invention aims to provide a high-efficiency method for recycling residual raw materials of aluminum nitride crystal growth by a PVT method.
The invention is realized by the following technical scheme:
a method for recycling residual raw materials of PVT method aluminum nitride crystal growth comprises the following steps:
step 1, after the growth of the aluminum nitride crystal is finished, taking the raw material after the growth of the aluminum nitride crystal, crushing the raw material into 0.1-1cm of particle raw material 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, drying the micro powder raw material obtained in the step 2, washing with a mixed solution of hydrofluoric acid and nitric acid, then cleaning with ultrapure water, then ultrasonically cleaning with ethanol, and drying to obtain high-purity aluminum nitride powder;
step 4, carrying out cold isostatic pressing on the high-purity aluminum nitride powder obtained in the step 3 to obtain a high-purity aluminum nitride block raw material;
and 5, heating the high-purity aluminum nitride bulk raw material obtained in the step 4 to 1500-1700 ℃ under the atmosphere protection, calcining at high temperature for 10-20h, and cooling to obtain a 5N-grade high-purity aluminum nitride bulk raw material.
The invention relates to a method for recycling residual raw materials of PVT method aluminum nitride crystal growth, 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 invention relates to a method for recycling residual raw materials of aluminum nitride crystal growth by a PVT method, wherein in the step 2, a high-speed ball mill is adopted for ball milling by using aluminum nitride ceramic balls, the ball milling rotating speed is 1500-.
The invention relates to a method for recycling residual raw materials of aluminum nitride crystal growth by a PVT method, wherein the material-liquid ratio of a micro-powder raw material to a mixed solution in step 3 is 1:2-3g/ml, and the washing time is 0.5-2 h.
The invention relates to a method for recycling residual raw materials of aluminum nitride crystal growth by a PVT method, wherein in step 3, the mass ratio of hydrofluoric acid to nitric acid in a mixed solution of hydrofluoric acid and nitric acid is 1:1-3, the concentration of the hydrofluoric acid is 10-20 wt%, and the concentration of the nitric acid is 30-50 wt%.
Fe3O2+HF→H2O+FeF3 (1)
Al2O3+HF→H2O+AlF3 (2)
The method for recycling the residual raw material for the growth of the aluminum nitride crystal by the PVT method comprises the following steps of cleaning ultrapure water for 2-3 times in the step 3, then carrying out ultrasonic cleaning on ethanol for 10-20min, wherein the ultrasonic cleaning frequency is 1000-2000Hz, the drying temperature is 100-120 ℃ and the drying time is 30-60 min.
The method for recycling the residual raw material of the aluminum nitride crystal growth by the PVT method has the advantage that the pressure of the cold isostatic pressing in the step 4 is 100-200 Mpa.
According to the method for recycling the residual raw materials of the growth of the aluminum nitride crystal by the PVT method, the protective atmosphere in the step 5 is nitrogen.
The method for recycling the residual raw materials for the growth of the aluminum nitride crystal by the PVT method is simple, utilizes the residual raw materials for reaction, improves the total raw material utilization rate, and greatly saves the cost; the prepared 5N-grade high-purity aluminum nitride bulk raw material is obtained by processing an aluminum nitride raw material after crystal growth, and the content of impurities in the bulk raw material is extremely low, so that the recovered new raw material has the characteristic of high purity and is beneficial to improving the crystal quality.
Drawings
FIG. 1 is a process flow diagram of a method for recycling residual raw materials in the growth of aluminum nitride crystal by PVT method according to the present invention;
FIG. 2 is a photograph of the raw material after the growth of the aluminum nitride crystal is finished in step 1 of the method for recycling the residual raw material for the growth of the aluminum nitride crystal by the PVT method according to the present invention.
Detailed Description
The first embodiment is as follows:
a method for recycling residual raw materials of PVT method aluminum nitride crystal growth comprises the following steps:
step 1, after the growth of the aluminum nitride crystal is finished, taking the raw material after the growth of the aluminum nitride crystal, crushing the raw material into 0.1-1cm of particle raw material 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, drying the micro powder raw material obtained in the step 2, washing with a mixed solution of hydrofluoric acid and nitric acid, then cleaning with ultrapure water, then ultrasonically cleaning with ethanol, and drying to obtain high-purity aluminum nitride powder;
step 4, carrying out cold isostatic pressing on the high-purity aluminum nitride powder obtained in the step 3 to obtain a high-purity aluminum nitride block raw material;
and 5, heating the high-purity aluminum nitride bulk raw material obtained in the step 4 to 1500 ℃ under the atmosphere protection, calcining at a high temperature for 20 hours, and cooling to obtain a 5N-grade high-purity aluminum nitride bulk raw material.
In the method for recycling the residual raw material of the PVT method aluminum nitride crystal growth, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.5t/h, and the crushing time is 5 min.
In the method for recycling the residual raw material for the growth of the aluminum nitride crystal by the PVT method, in the step 2, a high-speed ball mill is adopted for ball milling, aluminum nitride ceramic balls are used for ball milling, the ball milling rotating speed is 1700r/min, and the ball milling time is 12 hours.
In the method for recycling the residual raw material of the aluminum nitride crystal growth by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the mixed solution is 1:2g/ml, and the washing time is 1 h.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method according to the embodiment, in the step 3, the mass ratio of hydrofluoric acid to nitric acid in the mixed solution of hydrofluoric acid and nitric acid is 1:1, the concentration of the hydrofluoric acid is 10 wt%, and the concentration of the nitric acid is 30 wt%.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method, after the ultrapure water is cleaned for 3 times in the step 3, the ultrasonic cleaning time of the ethanol is 10min, the ultrasonic cleaning frequency is 2000Hz, the drying temperature is 100 ℃, and the drying time is 60 min.
In the method for recycling the residual raw material of the aluminum nitride crystal growth by the PVT method, the cold isostatic pressing pressure in the step 4 is 200 MPa.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method according to the embodiment, the protective atmosphere in step 5 is nitrogen.
Fig. 2 shows a raw material photograph after the aluminum nitride crystal growth is finished in step 1 of the method for recycling the residual raw material for the aluminum nitride crystal growth by the PVT method according to the present embodiment, and it can be seen from fig. 2 that after the crystal growth is finished, the middle edge portion of the residual aluminum nitride raw material is sublimated, the densification of the bottom of the raw material is increased, and polycrystalline grains are generated at the top. The bottom is more and more compact, so that the sublimation rate is changed, the stable state of the air pressure in the crystal growth chamber is influenced, and the later-stage crystal growth rate is influenced. Crystal quality can also be affected.
The method for recycling the residual raw materials for the growth of the aluminum nitride crystal by the PVT method is simple and easy, utilizes the residual raw materials for reaction, improves the total utilization rate of the raw materials, and greatly saves the cost; the prepared 5N-grade high-purity aluminum nitride bulk raw material is obtained by processing an aluminum nitride raw material after crystal growth, and the content of impurities in the bulk raw material is extremely low, so that the recovered new raw material has the characteristic of high purity and is beneficial to improving the crystal quality.
According to the method for recycling the residual raw material of the PVT method aluminum nitride crystal growth, the recycled high-purity aluminum nitride reaches 5N grade, and the recovery rate is 98%.
The second embodiment is as follows:
a method for recycling residual raw materials of PVT method aluminum nitride crystal growth comprises the following steps:
step 1, after the growth of the aluminum nitride crystal is finished, taking the raw material after the growth of the aluminum nitride crystal, crushing the raw material into 0.1-1cm of particle raw material 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, drying the micro powder raw material obtained in the step 2, washing with a mixed solution of hydrofluoric acid and nitric acid, then cleaning with ultrapure water, then ultrasonically cleaning with ethanol, and drying to obtain high-purity aluminum nitride powder;
step 4, carrying out cold isostatic pressing on the high-purity aluminum nitride powder obtained in the step 3 to obtain a high-purity aluminum nitride block raw material;
and 5, heating the high-purity aluminum nitride bulk raw material obtained in the step 4 to 1700 ℃ under the atmosphere protection, calcining at a high temperature for 15 hours, and cooling to obtain a 5N-grade high-purity aluminum nitride bulk raw material.
In the method for recycling the residual raw material of the PVT method aluminum nitride crystal growth, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.5t/h, and the crushing time is 6 min.
In the method for recycling the residual raw material for the growth of the aluminum nitride crystal by the PVT method, in the step 2, a high-speed ball mill is adopted for ball milling, aluminum nitride ceramic balls are used for ball milling, the ball milling rotating speed is 1500r/min, and the ball milling time is 15 hours.
In the method for recycling the residual raw material of the aluminum nitride crystal growth by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the mixed solution is 1:3g/ml, and the washing time is 0.5 h.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method according to the embodiment, the mass ratio of the hydrofluoric acid to the nitric acid in the mixed solution of the hydrofluoric acid and the nitric acid in step 3 is 1: 3.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method, after the ultrapure water is cleaned for 3 times in the step 3, the ultrasonic cleaning time of the ethanol is 10min, the ultrasonic cleaning frequency is 2000Hz, the drying temperature is 120 ℃, and the drying time is 30 min.
In the method for recycling the residual raw material of the aluminum nitride crystal growth by the PVT method, the cold isostatic pressing pressure in the step 4 is 100 MPa.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method according to the embodiment, the protective atmosphere in step 5 is nitrogen.
The method for recycling the residual raw materials for the growth of the aluminum nitride crystal by the PVT method is simple and easy, utilizes the residual raw materials for reaction, improves the total utilization rate of the raw materials, and greatly saves the cost; the prepared 5N-grade high-purity aluminum nitride bulk raw material is obtained by processing an aluminum nitride raw material after crystal growth, and the content of impurities in the bulk raw material is extremely low, so that the recovered new raw material has the characteristic of high purity and is beneficial to improving the crystal quality.
According to the method for recycling the residual raw material of the PVT method aluminum nitride crystal growth, the recycled high-purity aluminum nitride reaches 5N grade, and the recovery rate is 97%.
The third concrete implementation mode:
a method for recycling residual raw materials of PVT method aluminum nitride crystal growth comprises the following steps:
step 1, after the growth of the aluminum nitride crystal is finished, taking the raw material after the growth of the aluminum nitride crystal, crushing the raw material into 0.1-1cm of particle raw material 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, drying the micro powder raw material obtained in the step 2, washing with a mixed solution of hydrofluoric acid and nitric acid, then cleaning with ultrapure water, then ultrasonically cleaning with ethanol, and drying to obtain high-purity aluminum nitride powder;
step 4, carrying out cold isostatic pressing on the high-purity aluminum nitride powder obtained in the step 3 to obtain a high-purity aluminum nitride block raw material;
and 5, heating the high-purity aluminum nitride bulk raw material obtained in the step 4 to 1600 ℃ under the atmosphere protection, calcining at a high temperature for 20 hours, and cooling to obtain a 5N-grade high-purity aluminum nitride bulk raw material.
In the method for recycling the residual raw material of the PVT method aluminum nitride crystal growth, an EP-100 type crusher is used for crushing in the step 1, the production capacity is 0.5t/h, and the crushing time is 10 min.
In the method for recycling the residual raw material of the growth of the aluminum nitride crystal by the PVT method, in the step 2, a high-speed ball mill is adopted for ball milling, aluminum nitride ceramic balls are used for ball milling, the ball milling rotating speed is 2000r/min, and the ball milling time is 10 hours.
In the method for recycling the residual raw material of the aluminum nitride crystal growth by the PVT method, in the step 3, the material-liquid ratio of the micro-powder raw material to the mixed solution is 1:3g/ml, and the washing time is 2 hours.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method according to the embodiment, in the step 3, the mass ratio of hydrofluoric acid to nitric acid in the mixed solution of hydrofluoric acid and nitric acid is 1:2, the concentration of the hydrofluoric acid is 15 wt%, and the concentration of the nitric acid is 40 wt%.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method, after the ultrapure water is cleaned for 3 times in the step 3, the ultrasonic cleaning time of the ethanol is 15min, the ultrasonic cleaning frequency is 2000Hz, the drying temperature is 100 ℃, and the drying time is 50 min.
In the method for recycling the residual raw material of the aluminum nitride crystal growth by the PVT method, the cold isostatic pressing pressure in the step 4 is 200 MPa.
In the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method according to the embodiment, the protective atmosphere in step 5 is nitrogen.
The method for recycling the residual raw materials for the growth of the aluminum nitride crystal by the PVT method is simple and easy, utilizes the residual raw materials for reaction, improves the total utilization rate of the raw materials, and greatly saves the cost; the prepared 5N-grade high-purity aluminum nitride bulk raw material is obtained by processing an aluminum nitride raw material after crystal growth, and the content of impurities in the bulk raw material is extremely low, so that the recovered new raw material has the characteristic of high purity and is beneficial to improving the crystal quality.
According to the method for recycling the residual raw material of the PVT method aluminum nitride crystal growth, the recycled high-purity aluminum nitride reaches 5N grade, and the recovery rate is 98%.
The fourth concrete implementation mode:
a method for recycling residual raw materials of PVT method aluminum nitride crystal growth comprises the following steps:
step 1, after the growth of the aluminum nitride crystal is finished, taking the raw material after the growth of the aluminum nitride crystal, crushing the raw material into 0.1-1cm of particle raw material 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, drying the micro powder raw material obtained in the step 2, washing with a mixed solution of hydrofluoric acid and nitric acid, then cleaning with ultrapure water, then ultrasonically cleaning with ethanol, and drying to obtain high-purity aluminum nitride powder;
step 4, carrying out cold isostatic pressing on the high-purity aluminum nitride powder obtained in the step 3 to obtain a high-purity aluminum nitride block raw material;
and 5, heating the high-purity aluminum nitride bulk raw material obtained in the step 4 to 1500-1700 ℃ under the atmosphere protection, calcining at high temperature for 10-20h, and cooling to obtain a 5N-grade high-purity aluminum nitride bulk raw material.
The fifth concrete implementation mode:
according to the fourth 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 sixth specific implementation mode:
according to the fourth specific embodiment, in the step 2, the ball milling is performed by using a high-speed ball mill with aluminum nitride ceramic balls at the ball milling rotation speed of 1500-.
The seventh embodiment:
according to the fourth specific embodiment, the material-liquid ratio of the micro-powder raw material to the mixed solution in the step 3 is 1:2-3g/ml, and the washing time is 0.5-2 h.
The specific implementation mode is eight:
according to a fourth specific embodiment, in the step 3, the mass ratio of the hydrofluoric acid to the nitric acid in the mixed solution of the hydrofluoric acid and the nitric acid is 1:1-3, the concentration of the hydrofluoric acid is 10-20 wt%, and the concentration of the nitric acid is 30-50 wt%.
The specific implementation method nine:
according to the fourth specific embodiment, after the step 3 of cleaning with ultrapure water for 2-3 times, the ultrasonic cleaning time of ethanol is 10-20min, the ultrasonic cleaning frequency is 1000-2000Hz, the drying temperature is 100-120 ℃, and the drying time is 30-60 min.
The detailed implementation mode is ten:
according to the method for recycling the residual raw material in the growth of the aluminum nitride crystal by the PVT method in the fourth embodiment, the pressure of the cold isostatic pressing in the step 4 is 100-200 MPa.
The concrete implementation mode eleven:
according to the fourth specific embodiment, in the step 5, the protective atmosphere is nitrogen.
Claims (8)
1. A method for recycling residual raw materials of PVT method aluminum nitride crystal growth is characterized in that: the method comprises the following steps:
step 1, after the growth of the aluminum nitride crystal is finished, taking the raw material after the growth of the aluminum nitride crystal, crushing the raw material into 0.1-1cm of particle raw material 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, drying the micro powder raw material obtained in the step 2, washing with a mixed solution of hydrofluoric acid and nitric acid, then cleaning with ultrapure water, then ultrasonically cleaning with ethanol, and drying to obtain high-purity aluminum nitride powder;
step 4, carrying out cold isostatic pressing on the high-purity aluminum nitride powder obtained in the step 3 to obtain a high-purity aluminum nitride block raw material;
and 5, heating the high-purity aluminum nitride bulk raw material obtained in the step 4 to 1500-1700 ℃ under the atmosphere protection, calcining at high temperature for 10-20h, and cooling to obtain a 5N-grade high-purity aluminum nitride bulk raw material.
2. The method for recycling the residual raw material of the PVT method aluminum nitride crystal growth according to claim 1, which is characterized in that: 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 the residual raw material of the PVT method aluminum nitride crystal growth according to claim 2, which is characterized in that: and 2, ball milling in the step 2 is carried out by adopting a high-speed ball mill with aluminum nitride ceramic balls, the ball milling rotating speed is 1500-2000r/min, and the ball milling time is 10-15 h.
4. The method for recycling the residual raw material of the PVT method aluminum nitride crystal growth 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 mixed solution is 1:2-3g/ml, and the washing time is 0.5-2 h.
5. The method for recycling the residual raw material of the PVT method aluminum nitride crystal growth according to claim 4, wherein the method comprises the following steps: in the step 3, the mass ratio of hydrofluoric acid to nitric acid in the mixed solution of hydrofluoric acid and nitric acid is 1:1-3, the concentration of the hydrofluoric acid is 10-20 wt%, and the concentration of the nitric acid is 30-50 wt%.
6. The method for recycling the residual raw material of the PVT method aluminum nitride crystal growth according to claim 5, wherein the method comprises the following steps: and (3) after the ultrapure water is cleaned for 2-3 times in the step 3, the ultrasonic cleaning time of the ethanol is 10-20min, the frequency of the ultrasonic cleaning is 1000-.
7. The method for recycling the residual raw material of the PVT method aluminum nitride crystal growth according to claim 6, wherein the method comprises the following steps: the pressure of the cold isostatic pressing in the step 4 is 100-200 MPa.
8. The method for recycling the residual raw material of the PVT method aluminum nitride crystal growth according to claim 7, wherein the method comprises the following steps: the protective atmosphere in step 5 was nitrogen.
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| CN105314984A (en) * | 2014-12-03 | 2016-02-10 | 南京工业大学东海先进硅基材料研究院 | Method for preparing beta-silicon nitride toughened particles by recycling waste silicon nitride |
| CN111364104A (en) * | 2020-04-23 | 2020-07-03 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Preparation method of high-purity raw material for aluminum nitride single crystal growth |
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| CN105314984A (en) * | 2014-12-03 | 2016-02-10 | 南京工业大学东海先进硅基材料研究院 | Method for preparing beta-silicon nitride toughened particles by recycling waste silicon nitride |
| CN111364104A (en) * | 2020-04-23 | 2020-07-03 | 哈尔滨科友半导体产业装备与技术研究院有限公司 | Preparation method of high-purity raw material for aluminum nitride single crystal growth |
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