CN117285016A - Method for preparing silicon nitride nanowire - Google Patents
Method for preparing silicon nitride nanowire Download PDFInfo
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- CN117285016A CN117285016A CN202311342710.8A CN202311342710A CN117285016A CN 117285016 A CN117285016 A CN 117285016A CN 202311342710 A CN202311342710 A CN 202311342710A CN 117285016 A CN117285016 A CN 117285016A
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 69
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002070 nanowire Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000002699 waste material Substances 0.000 claims abstract description 94
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 75
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 238000005121 nitriding Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 34
- 239000010703 silicon Substances 0.000 abstract description 34
- 238000002360 preparation method Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- 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
- C01B21/068—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 silicon
- C01B21/0682—Preparation by direct nitridation of silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to the technical field of secondary resource recycling, and provides a method for preparing a silicon nitride nanowire by utilizing photovoltaic silicon waste, wherein a silicon raw material of the preparation method is derived from waste silicon powder cut by the photovoltaic industry, a surface oxide layer is purified and removed through acid washing, then the silicon raw material is placed in a high-temperature atmosphere furnace, nitrogen is used as a nitrogen source, and the nitriding reaction temperature, the time, the atmosphere, the nitrogen source concentration and the flow rate of nitrogen source gas are controlled, so that the high-purity silicon nitride nanowire is directly nitrided. The preparation method can be used for preparing the ultra-long silicon nitride nanowire material with uniform growth and high purity; the preparation method realizes the high-value recycling of the cut waste silicon powder in a green and environment-friendly mode, has high silicon nitride conversion rate, low cost and no use and generation of toxic and harmful substances, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of silicon nitride nanowires, and particularly relates to a method for preparing silicon nitride nanowires by utilizing photovoltaic silicon waste.
Background
In recent years, the packaging amount of the photovoltaic solar cell is gradually increased year by year, the crystalline silicon solar cell accounts for over 96 percent, and the silicon wafer is used as a basic element of the crystalline silicon solar cell, so that the demand is huge. The silicon chip is manufactured by cutting high-purity silicon ingots by diamond wires, and in the process, 35% of silicon loss of the mass of the super-original silicon ingots enters silicon mud to form superfine waste silicon powder, and the annual production amount of the waste silicon powder is over 20 ten thousand tons. At present, the metallurgical recovery process through remelting refining can only realize the degradation and utilization of the metallurgical recovery process, and returns to the production process of the high-purity silicon ingot, which can cause serious problems of secondary energy consumption and environmental recontamination.
Si3N4 is a high-temperature resistant and oxidation resistant high-performance ceramic with high strength, high hardness, low density, excellent thermal shock resistance and mechanical shock resistance with high dielectric constant (epsilon=9.4), and is used as a structural material in high temperature, high radiation and other environments; meanwhile, si3N4 is also a wide-bandgap semiconductor material (5.3 eV), and has wide application in the fields of optoelectronic devices, microelectronic devices, dielectric ceramics, anti-reflection coatings and the like; in addition, the Si3N4 nanowire combines the characteristics of the Si3N4 ceramic body and the one-dimensional nanomaterial, has an elastic modulus of 570GPa which is twice that of a bulk material, and can be used as a one-dimensional wide band gap semiconductor material to regulate and control the electrical and optical properties through doping, so that important application is realized in the fields of nano electronic devices and photonic devices.
The current common methods for preparing the one-dimensional Si3N4 nanowire material include a template method, a direct nitriding method, a carbothermal reduction method, a precursor cracking method and the like. For example, CN115404457a discloses a method for oxidizing and vapor-phase depositing a silicon nitride layer on the surface of a carbon material, which uses silicon monoxide as a raw material, introduces nitrogen into a heat treatment furnace, and obtains silicon nitride nanowires by heat treatment under nitrogen atmosphere, wherein the silicon monoxide used is high in cost; CN114517091a discloses a method for preparing silicon nitride nanowires, which uses silicon powder and nitrogen as raw materials, and prepares silicon nanowires by a direct current arc method, and has large equipment energy consumption and poor controllability; CN110484998A and CN110436934a disclose a preparation method of ultralong silicon nitride nanowires, which uses waste silicon powder as raw material, synthesizes silicon nitride nanowires through ammonia nitridation reaction, uses ammonia gas as nitrogen source, is toxic and unsafe, and is difficult to apply in large scale; CN107161962a discloses a method for preparing silicon nitride nanowire, which uses iron, cobalt, nickel, copper and molybdenum as metal catalysts, and puts them into a reactor after mixing with silicon powder, and then pre-treating them with hydrogen at high temperature, and then introducing nitrogen-containing gas to make nitridation reaction to prepare silicon nitride nanowire.
In summary, a preparation method of the silicon nitride nanowire using the waste silicon powder as a raw material without using a metal catalyst and a toxic nitrogen source is developed, so that high-value recycling of the waste silicon powder can be realized, the preparation cost of the silicon nitride nanowire can be reduced, and the conversion rate of silicon nitride can be improved.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a method for preparing a silicon nitride nanowire by utilizing photovoltaic silicon waste, wherein the preparation method takes waste silicon powder cut by the photovoltaic industry as a raw material, and utilizes the characteristics of fine granularity and high purity of the waste silicon powder and takes nitrogen as a nitrogen source to prepare the silicon nitride nanowire in a high-temperature atmosphere furnace. The preparation method can be used for preparing the silicon nitride nanowire material which is uniform in growth, high in purity and ultra-long; the preparation method can realize high-value recycling of the waste silicon powder in an environment-friendly mode, has short flow, high silicon nitride conversion rate and low cost, and is suitable for large-scale industrial production.
To achieve the purpose, the invention adopts the following technical scheme:
s1, carrying out acid cleaning purification and surface oxide layer removal on silicon powder to obtain high-purity low-oxidation waste silicon powder;
s2, loosening the high-purity low-oxidation waste silicon powder and placing the high-purity low-oxidation waste silicon powder into an inert high-temperature crucible;
s3, placing the crucible containing the waste silicon powder into a high-temperature atmosphere furnace, and then introducing a gas nitrogen source, and continuously heating to obtain the high-purity ultra-long silicon nitride nanowire.
Further, S1, the silicon waste is derived from the waste silicon mud of the photovoltaic industry cutting;
further, the particle size of the silicon waste material is 0.2-0.9 mu m;
further, S1, the silicon waste is flake powder;
further, the high-purity waste silicon powder is obtained by pickling any one or a combination of at least two of hydrochloric acid, nitric acid, hydrofluoric acid and sulfuric acid;
further, the pickling time is 5-120 min in S1;
further, the purity of the high-purity waste silicon powder is more than 99.9wt percent in S1;
further, S1, the oxygen content of the waste silicon powder after the oxide layer is removed is less than 1%;
further, the inert high temperature crucible in S2 comprises an alumina crucible, a graphite crucible, a magnesia crucible, a metal crucible and a ceramic crucible;
further, S3, the nitriding reaction is carried out in a high-temperature atmosphere furnace;
further, the nitriding reaction atmosphere in S3 is hydrogen-nitrogen mixed gas, and the hydrogen accounts for 1% -10%;
further, the temperature rising rate of the nitriding reaction is 2-10 ℃/min;
further, the nitriding reaction temperature of S3 is 1300-1500 ℃;
further, the nitriding reaction time is 30-600 min in S3;
further, the nitrogen source gas of the nitriding reaction is nitrogen;
further, the purity of the nitrogen source gas in S3 is more than 99.9%;
further, the concentration of the nitrogen source gas is 90% -99%;
further, the flow rate of the nitrogen source gas is 100-500 ml/min;
further, S3 is to obtain the high-purity ultra-long silicon nitride nanowire;
further, the purity of the silicon nitride nanowire in S3 is more than 99%;
further, the length of the silicon nitride nanowire in the step S3 is more than 100 μm.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
s1, carrying out acid cleaning purification and surface oxide layer removal on the recovered silicon waste to obtain waste silicon powder with the particle size of 0.3-0.9 mu m, the purity of more than 99.9% and the oxygen content of less than 1%, and loosely placing the waste silicon powder into an inert crucible for standby;
s2, placing the inert high-temperature crucible containing the waste silicon powder obtained in the S1 into a high-temperature atmosphere furnace, controlling the temperature rising rate to be 2-10 ℃/min, raising the temperature to 1300-1500 ℃, and preserving the temperature for 30-600 min; the concentration of the nitrogen source is regulated to be 90-99%, and the gas flow rate of the nitrogen source is regulated to be 100-500 ml/min, so that the high-purity ultra-long silicon nitride nanowire is prepared.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The preparation method of the invention uses the photovoltaic silicon waste as the raw material, which can reduce the production cost of the silicon nitride nanowire; the silicon waste has fine granularity and high purity, can obviously improve the conversion efficiency and purity of the silicon nitride nanowire, fully expands the source range of available silicon raw materials, realizes high-value secondary utilization of waste silicon powder in a green and environment-friendly mode, and saves huge energy and resource consumption;
(2) According to the preparation method, the silicon nitride nanowire is prepared by directly using the silicon nitride waste, on one hand, the preparation method is high in silicon nitride conversion efficiency, uniform in growth and high in purity of the silicon nitride nanowire, and on the other hand, a catalyst and a toxic and harmful nitrogen source are not required in the nitriding process, and the preparation method is simple to operate, green, low in cost and high in efficiency, and is suitable for large-scale industrial production;
the preparation method of the invention uses the waste silicon powder cut by the photovoltaic industry as a raw material, and uses the characteristics of fine granularity and high purity of the waste silicon powder and uses nitrogen as a nitrogen source to prepare the silicon nitride nanowire in a high-temperature atmosphere furnace; the surface oxide layer is removed from the silicon powder before the reaction, and a deoxidizer and a metal catalyst are not needed in the subsequent process. The preparation method can also prepare the silicon nitride nanowire material with uniform growth, high purity and overlength.
It can be seen that the same production effect can be obtained by the method of the present invention after omitting part of the elements.
Drawings
FIG. 1 is a scanning electron microscope image of the cut waste silicon powder of examples 1-13 of the present invention;
FIG. 2 is a scanning electron microscope image of the synthesis of ultra-long high purity silicon nitride nanowires according to example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of the ultra-long high purity silicon nitride nanowire synthesized in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The closest prior art to the present invention, such as patent (CN 106477538B) discloses a method for preparing silicon nitride nanowires, which can obtain high purity silicon nitride nanowires and silicon nitride powder products without using a catalyst; but its implementation differs from the present invention which includes removal of the oxide layer without the need to apply a catalyst. Specifically, the waste cutting silicon powder in the embodiment of the invention is dried and crushed in advance to obtain waste silicon powder with the granularity of 0.2-0.9 mu m, the waste silicon powder is characterized by adopting a scanning electron microscope (JSM-7800), the obtained scanning electron microscope image is shown in figure 1, and the waste cutting silicon powder is flaky powder.
Example 1
The embodiment provides a method for preparing a silicon nitride nanowire by utilizing photovoltaic silicon waste, which comprises the following steps:
s1, drying and crushing the cut waste silicon powder to obtain waste silicon powder A with the particle size of 0.3-0.9 mu m;
s2, carrying out pickling purification and surface oxide layer removal on the waste silicon powder A obtained in the step S1 to obtain waste silicon powder B with the purity of more than 99.9% and the oxygen content of less than 1%;
s3, loosening the waste silicon powder B obtained in the S2 and placing the waste silicon powder B into an alumina crucible for standby;
s4, placing the crucible containing the waste silicon powder B obtained in the S3 into a high-temperature atmosphere furnace, heating to 1350 ℃ at a heating rate of 5 ℃/min, and preserving heat for 300min; the nitrogen source concentration is (5%H) 2 +95％N 2 ) The gas flow rate was 200ml/min, and high-purity ultra-long silicon nitride nanowires were prepared as shown in fig. 2 and 3.
Example 2
The embodiment provides a method for preparing a silicon nitride nanowire by utilizing photovoltaic silicon waste, which comprises the following steps:
s1, drying and crushing the cut waste silicon powder to obtain waste silicon powder A with the particle size of 0.3-0.9 mu m;
s2, carrying out pickling purification and surface oxide layer removal on the waste silicon powder A obtained in the step S1 to obtain waste silicon powder B with the purity of more than 99.9% and the oxygen content of less than 1%;
s3, loosening the waste silicon powder B obtained in the S2 and placing the waste silicon powder B into an alumina crucible for standby;
s4, placing the crucible containing the waste silicon powder B obtained in the S3 into a high-temperature atmosphere furnace, heating to 1300 ℃ at a heating rate of 3 ℃/min, and preserving heat for 600min; the nitrogen source concentration was (10% H 2 +90％N 2 ) The gas flow rate is 300ml/min, and the high-purity silicon nitride nanowire is prepared.
Example 3
The embodiment provides a method for preparing a silicon nitride nanowire by utilizing photovoltaic silicon waste, which comprises the following steps:
s1, drying and crushing the cut waste silicon powder to obtain waste silicon powder A with the particle size of 0.3-0.9 mu m;
s2, carrying out pickling purification and surface oxide layer removal on the waste silicon powder A obtained in the step S1 to obtain waste silicon powder B with the purity of more than 99.9% and the oxygen content of less than 1%;
s3, loosening the waste silicon powder B obtained in the S2 and placing the waste silicon powder B into an alumina crucible for standby;
s4, placing the crucible containing the waste silicon powder B obtained in the S3 into a high-temperature atmosphere furnace, heating to 1400 ℃ at a heating rate of 4 ℃/min, and preserving heat for 400min; the nitrogen source concentration is (1%H) 2 +99％N 2 ) The gas flow rate is 100ml/min, and the high-purity silicon nitride nanowire is prepared.
Example 4
The embodiment provides a method for preparing a silicon nitride nanowire by utilizing photovoltaic silicon waste, which comprises the following steps:
s1, drying and crushing the cut waste silicon powder to obtain waste silicon powder A with the particle size of 0.3-0.9 mu m;
s2, carrying out pickling purification and surface oxide layer removal on the waste silicon powder A obtained in the step S1 to obtain waste silicon powder B with the purity of more than 99.9% and the oxygen content of less than 1%;
s3, loosening the waste silicon powder B obtained in the S2 and placing the waste silicon powder B into an alumina crucible for standby;
s4, placing the crucible containing the waste silicon powder B obtained in the S3 into a high-temperature atmosphere furnace, heating to 1500 ℃ at a heating rate of 10 ℃/min, and preserving heat for 300min; the nitrogen source concentration is (5%H) 2 +95％N 2 ) The gas flow rate is 200ml/min, and the high-purity ultra-long silicon nitride nanowire is prepared.
Example 5
The embodiment provides a method for preparing a silicon nitride nanowire by utilizing photovoltaic silicon waste, which comprises the following steps:
s1, drying and crushing the cut waste silicon powder to obtain waste silicon powder A with the particle size of 0.3-0.9 mu m;
s2, carrying out pickling purification and surface oxide layer removal on the waste silicon powder A obtained in the step S1 to obtain waste silicon powder B with the purity of more than 99.9% and the oxygen content of less than 1%;
s3, loosening the waste silicon powder B obtained in the S2 and placing the waste silicon powder B into an alumina crucible for standby;
s4, placing the crucible containing the waste silicon powder B obtained in the S3 into a high-temperature atmosphere furnace, heating to 1300 ℃ at a heating rate of 8 ℃/min, and preserving heat for 400min; the nitrogen source concentration is (1%H) 2 +99％N 2 ) The gas flow rate is 500ml/min, and the high-purity ultra-long silicon nitride nanowire is prepared.
Example 6
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is exactly the same as example 1 except that the temperature rising rate is 2 ℃/min in S4.
Example 7
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is exactly the same as example 1 except that the temperature rising rate is 10 ℃/min in S4.
Example 8
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is identical to example 1 except that the nitriding temperature is 1300 ℃ in S4.
Example 9
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is identical to example 1 except that the nitriding temperature is 1400 ℃ in S4.
Example 10
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is identical to example 1 except that the nitriding temperature is 1500 ℃ in S4.
Example 11
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is identical to example 1 except that the nitriding time is 600min in S4.
Example 12
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is identical to example 1 except that the concentration of nitrogen source in S4 is 99%.
Example 13
This example provides a method for preparing silicon nitride nanowires using photovoltaic silicon waste, which is identical to example 1 except that the flow rate of nitrogen source in S4 is 500 ml.
The foregoing is a further detailed description of the invention in connection with specific embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several simple deductions or substitutions can be made without departing from the spirit of the invention.
Claims (10)
1. A method of preparing silicon nitride nanowires, comprising the steps of:
s1, carrying out acid cleaning purification and surface oxide layer removal on silicon powder to obtain high-purity low-oxidation waste silicon powder;
s2, loosening the high-purity low-oxidation waste silicon powder and placing the high-purity low-oxidation waste silicon powder into an inert high-temperature crucible;
s3, placing the crucible containing the waste silicon powder into a high-temperature atmosphere furnace, and then introducing a gas nitrogen source, and continuously heating to obtain the high-purity ultra-long silicon nitride nanowire.
2. The method for preparing silicon nitride nanowires according to claim 1, wherein the high-purity waste silicon powder in S1 is obtained by pickling with any one or a combination of at least two of hydrochloric acid, nitric acid, hydrofluoric acid and sulfuric acid.
3. The method of preparing silicon nitride nanowires according to claim 2, wherein the pickling time is 5min to 120min;
4. a method of preparing silicon nitride nanowires as claimed in claim 2 wherein the purity of the highly pure waste silicon powder is greater than 99.9wt%; the oxygen content of the waste silicon powder after the oxide layer is removed is less than 1%.
5. The method of claim 1, wherein the nitriding atmosphere is a hydrogen-nitrogen mixture, and the hydrogen accounts for 1% -10%;
6. the method of claim 1, wherein the rate of temperature rise of the nitridation reaction is 2-10 ℃/min; the reaction temperature is 1300-1500 ℃; the reaction time is 30-600 min.
7. The method of claim 1, wherein the nitrogen source gas of the nitridation reaction is nitrogen with a purity of greater than 99.9%;
8. the method of claim 1, wherein the concentration of the nitrogen source gas is 90% to 99%.
9. The method of silicon nitride nanowires according to claim 8 or 7, characterized in that the flow rate of the nitrogen source gas is 100-500 ml/min.
10. The method of any one of claims 1-9, wherein the high purity ultralong silicon nitride nanowires have a purity of greater than 99%; the length is greater than 100 μm.
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