CN116425193A - Gallium arsenide cluster and preparation method and application thereof - Google Patents
Gallium arsenide cluster and preparation method and application thereof Download PDFInfo
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- CN116425193A CN116425193A CN202310350439.6A CN202310350439A CN116425193A CN 116425193 A CN116425193 A CN 116425193A CN 202310350439 A CN202310350439 A CN 202310350439A CN 116425193 A CN116425193 A CN 116425193A
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- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910001218 Gallium arsenide Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 32
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 46
- 229910052785 arsenic Inorganic materials 0.000 claims description 23
- 238000004891 communication Methods 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 229910002804 graphite Inorganic materials 0.000 description 18
- 239000010439 graphite Substances 0.000 description 18
- 239000002699 waste material Substances 0.000 description 12
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000010431 corundum Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000441 X-ray spectroscopy Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a gallium arsenide cluster, a preparation method and application thereof, and belongs to the field of semiconductors. The preparation method of the gallium arsenide cluster provided by the invention comprises the following steps: and carrying out heating decomposition on the gallium arsenide particles to obtain the gallium arsenide cluster. During thermal decomposition of the gallium arsenide particles, a portion of the arsenic atoms and gallium atoms do not separate but cluster together to form clusters. Meanwhile, the preparation method has short operation flow and is environment-friendly. Example results show that gallium arsenide clusters are successfully prepared by the method.
Description
Technical Field
The invention relates to the field of semiconductors, in particular to a gallium arsenide cluster and a preparation method and application thereof.
Background
Gallium arsenide is a second-generation semiconductor material with high saturated electron velocity, high electron transmittance and semi-insulating property, and is widely applied in the fields of computers, light-emitting diodes, electronic communication, aerospace, military and the like. Gallium arsenide clusters, which are new systems of dimensions between macroscopic and microscopic, are composed of several to thousands of atoms, molecules or ions through physical or chemical bonding forces, with a number of unique properties. However, the current gallium arsenide cluster is researched through dynamic simulation, and the preparation method of the gallium arsenide cluster is not reported.
Disclosure of Invention
The invention aims to provide a gallium arsenide cluster, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a gallium arsenide cluster, which comprises the following steps:
carrying out heating decomposition on gallium arsenide particles under a vacuum condition to obtain gallium arsenide clusters;
the temperature of the thermal decomposition is 900-1100 ℃.
Preferably, the gallium element substance in the gallium arsenide particles is higher than the arsenic element substance.
Preferably, the particle size of the gallium arsenide particles is not higher than 10mm.
Preferably, the gallium-containing element in the gallium arsenide particles has a mass content of 47-52%, and the molar ratio of the gallium element to the arsenic element is more than or equal to 1.
Preferably, the raw materials of the gallium arsenide particles comprise gallium arsenide head and tail waste materials or gallium arsenide.
Preferably, the thermal insulation time of the thermal decomposition is 120-240 min, and the pressure of the vacuum condition is 1-5 Pa.
The invention also provides a gallium arsenide cluster prepared by the preparation method of the scheme, wherein the mass ratio of gallium element to arsenic element in the gallium arsenide cluster is 1.5-3: 1.
preferably, the gallium arsenide clusters are in a sheet structure.
Preferably, the size of the gallium arsenide cluster is 10-50 μm, and the thickness is 4-6 μm.
The invention also provides application of the gallium arsenide cluster in the fields of computers, light emitting diodes or electronic communication.
The invention provides a preparation method of a gallium arsenide cluster, which comprises the following steps: carrying out heating decomposition on gallium arsenide particles under a vacuum condition to obtain gallium arsenide clusters; the temperature of the thermal decomposition is 900-1100 ℃. During thermal decomposition of the gallium arsenide particles, a portion of the arsenic atoms and gallium atoms do not separate but cluster together to form clusters. Meanwhile, the preparation method has short operation flow and is environment-friendly. Example results show that gallium arsenide clusters are successfully prepared by the method.
Further, the gallium atoms and the arsenic atoms are combined into clusters with a larger number of gallium atoms under heating by making the amount of gallium element substances in the gallium arsenide particles higher than the amount of arsenic element substances. Gallium rich gallium arsenide clusters have lower resistivity than gallium rich arsenic arsenide clusters. Furthermore, the method adopts the gallium arsenide head and tail waste materials to prepare the gallium arsenide clusters, so that the recycling utilization of the gallium arsenide head and tail waste materials is realized while the manufacturing cost is reduced.
Drawings
FIG. 1 is a ground state structure diagram of a gallium-rich gallium arsenide cluster according to the present invention;
FIG. 2 is an electron micrograph of a gallium-rich gallium arsenide cluster of example 1 at 500 x;
FIG. 3 is a 5000 x electron micrograph of the gallium rich gallium arsenide cluster of example 1;
FIG. 4 is an XRD analysis pattern of the gallium-rich gallium arsenide cluster of example 1;
FIG. 5 is a graph showing the X-ray photoelectron spectrum of the gallium-rich gallium arsenide cluster of example 1;
FIG. 6 is an X-ray spectroscopy chart of the gallium element in the gallium-rich gallium arsenide cluster of example 1;
fig. 7 is an X-ray spectroscopy chart of the arsenic element in the gallium-rich gallium arsenide cluster of example 1.
Detailed Description
The invention provides a preparation method of a gallium arsenide cluster, which comprises the following steps:
carrying out heating decomposition on gallium arsenide particles under a vacuum condition to obtain gallium arsenide clusters;
the temperature of the thermal decomposition is 900-1100 ℃.
In the present invention, the particle diameter of the gallium arsenide particles is preferably not more than 10mm, more preferably 2 to 8mm, still more preferably 4 to 6mm. According to the invention, the gallium-rich gallium arsenide cluster is prepared by making the amount of gallium element substances in gallium arsenide particles higher than the amount of arsenic element substances, preferably, the mass content of gallium-containing elements in the gallium arsenide particles is 47-52%, and the molar ratio of the gallium elements to the arsenic elements is more than or equal to 1. The ground state structure of the gallium-rich gallium arsenide cluster is shown in figure 1.
In the invention, the raw materials of the gallium arsenide particles comprise gallium arsenide head and tail waste materials or gallium arsenide, and the purity of the gallium arsenide is preferably more than or equal to 99 percent. In the present invention, the preparation method of the gallium arsenide particles preferably comprises: the raw materials are cut and/or ground sequentially. The present invention is not particularly limited to the cutting and grinding, and gallium arsenide particles of a target particle diameter may be obtained by using a scheme well known to those skilled in the art. Specifically, in the embodiment of the invention, the gallium arsenide head and tail waste materials are cut by adopting a diamond wire; and grinding the gallium arsenide head and tail waste materials by adopting a corundum mortar. Small particle size favors cluster formation.
In the present invention, the temperature of the thermal decomposition is preferably 900 to 1100 ℃, more preferably 950 to 1050 ℃; the holding time is preferably 120 to 240 minutes, more preferably 150 to 200 minutes, and still more preferably 160 to 180 minutes; the pressure is preferably 1 to 5Pa, more preferably 3 to 4Pa.
In the present invention, the thermal decomposition is preferably performed in a quartz tube of a vacuum tube furnace. In the invention, before the thermal decomposition is carried out, the gallium arsenide particles are preferably loaded into a graphite crucible and then pushed into a heating zone of a quartz tube of the vacuum tube furnace.
In the invention, graphite paper is paved on the inner side of the quartz tube of the vacuum tube furnace. In the present invention, the graphite paper is preferably made of pure carbon, the carbon content of the graphite paper is preferably 99.9wt%, and the thickness is preferably 0.1 to 0.3mm. The graphite paper is used to collect gallium arsenide clusters.
After thermal decomposition, the present invention preferably cools the resulting thermal decomposition product to yield the gallium arsenide cluster. The cooling is not particularly limited in the present invention, and may be performed by cooling to room temperature using a scheme well known to those skilled in the art. During cooling, the gallium arsenide clusters formed are deposited on the graphite paper.
The invention also provides the gallium arsenide cluster prepared by the scheme, and the mass ratio of gallium element to arsenic element in the gallium arsenide cluster is 1.5-3: 1, preferably 2 to 2.5:1. In the present invention, the gallium arsenide clusters are preferably in a plate-like structure, and the size of the gallium arsenide clusters is preferably 10 to 50 μm, more preferably 20 to 40 μm, and even more preferably 25 to 35 μm; the thickness is preferably 4 to 6. Mu.m, more preferably 4.5 to 5. Mu.m. In the present invention, the gallium arsenide clusters are preferably uncharged. The gallium arsenide clusters of the present invention exhibit semiconducting and semi-insulating properties and possess lower resistivity than arsenic-rich gallium arsenide clusters.
The invention also provides application of the gallium arsenide cluster in computer, light-emitting diode or electronic communication.
The gallium arsenide clusters, the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Cutting 9.42g of gallium arsenide head and tail scraps (the content of gallium and arsenic is 51.01wt% and 48.04 wt%) into square crystals with the size of 10mm by adopting a diamond wire, paving a layer of graphite paper with the thickness of 0.3mm and the carbon content of 99.9wt% in a quartz tube of a vacuum tube furnace, and pushing a graphite boat crucible filled with the gallium arsenide scraps into a heating zone of the vacuum tube furnace; the furnace pressure is pumped to 1Pa, the furnace is heated for 3 hours at 1050 ℃, the vacuum pump is closed after the furnace is cooled to room temperature, and 1.84g gallium-rich gallium arsenide clusters are collected on graphite paper.
Electron microscope scanning analysis of different magnifications was performed on gallium-rich gallium arsenide clusters prepared in example 1, and the results are shown in fig. 2 to 3. As can be seen from FIGS. 2 to 3, the gallium-rich gallium arsenide cluster prepared in example 1 has a particle size in the range of 10 to 40 μm and a thickness of 5. Mu.m.
XRD analysis was performed on gallium-rich gallium arsenide clusters prepared in example 1, and the results are shown in fig. 4. As can be seen from fig. 4, the gallium-rich gallium arsenide cluster prepared in example 1 exhibits the phase of gallium arsenide semiconductor.
The gallium-rich gallium arsenide cluster prepared in example 1 was subjected to X-ray photoelectron spectroscopy, and the results are shown in fig. 5. As can be seen from fig. 5, the gallium-rich gallium arsenide cluster prepared in example 1 has a mass ratio of gallium to arsenic of 66.51% to 33.49%, respectively, and a mass ratio of gallium to arsenic of 1.98.
The gallium and arsenic elements in the gallium-rich gallium arsenide cluster prepared in example 1 were subjected to X-ray energy spectrum analysis, and the results are shown in fig. 6 to 7. As can be seen from fig. 6 to 7, the gallium arsenide cluster prepared in example 1 exists in the form of molecular compound, is a neutral gallium arsenide cluster, and has a significantly changed valence state of gallium and arsenic elements compared with gallium arsenide crystal.
Example 2
Grinding 8.30g of gallium arsenide head and tail waste materials (the content of gallium and arsenic is 51.01wt% and 48.04 wt%) to a particle size smaller than 1mm by adopting a corundum mortar, paving a layer of graphite paper with a thickness of 0.3mm and a carbon content of 99.9wt% in a quartz tube of a vacuum tube furnace, and pushing a graphite boat crucible filled with the gallium arsenide waste materials into a heating zone of the vacuum tube furnace; the furnace pressure is pumped to 1Pa, the furnace is heated for 3 hours at 1050 ℃, the vacuum pump is closed after the furnace is cooled to room temperature, and 1.87g gallium-rich gallium arsenide clusters are collected on graphite paper.
In example 2, the gallium and arsenic element mass ratio in the gallium-rich gallium arsenide cluster is 64.10% and 35.90%, respectively, and the gallium and arsenic mass ratio is 1.79.
Example 3
Grinding 12.37g of gallium arsenide head and tail waste materials (the content of gallium and arsenic is 51.01wt% and 48.04 wt%) to a particle size smaller than 1mm by adopting a corundum mortar, paving a layer of graphite paper with a thickness of 0.3mm and a carbon content of 99.9wt% in a quartz tube of a vacuum tube furnace, and pushing a graphite boat crucible filled with the gallium arsenide waste materials into a heating zone of the vacuum tube furnace; pumping the pressure in the furnace to 1Pa, heating for 3 hours at 900 ℃, cooling to room temperature, closing a vacuum pump, and collecting 0.705g gallium-rich gallium arsenide clusters on graphite paper.
Comparative example 1
Grinding 13.09g of gallium arsenide head and tail waste materials (the content of gallium and arsenic is 51.01wt% and 48.04 wt%) to a particle size smaller than 1mm by adopting a corundum mortar, paving a layer of graphite paper with a thickness of 0.3mm and a carbon content of 99.9wt% in a quartz tube of a vacuum tube furnace, and pushing a graphite boat crucible filled with the gallium arsenide waste materials into a heating zone of the vacuum tube furnace; pumping the pressure in the furnace to 1Pa, heating for 3 hours at 850 ℃, cooling to room temperature, and closing a vacuum pump, wherein gallium arsenide clusters are not collected on the graphite paper.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the gallium arsenide cluster is characterized by comprising the following steps:
carrying out heating decomposition on gallium arsenide particles under a vacuum condition to obtain gallium arsenide clusters;
the temperature of the thermal decomposition is 900-1100 ℃.
2. The method of claim 1, wherein the gallium arsenide particles have a higher amount of elemental gallium species than arsenic species.
3. The method of claim 1, wherein the gallium arsenide particles have a particle size of no more than 10mm.
4. The preparation method according to claim 1 or 2, wherein the gallium-containing element in the gallium arsenide particles has a mass content of 47-52%, and the molar ratio of the gallium element to the arsenic element is not less than 1.
5. The method of claim 1, wherein the feedstock of gallium arsenide particles comprises gallium arsenide head-to-tail scrap or gallium arsenide.
6. The method according to claim 1, wherein the thermal decomposition is carried out for a period of 120 to 240 minutes, and the vacuum condition is carried out at a pressure of 1 to 5Pa.
7. The gallium arsenide cluster prepared by the preparation method of any one of claims 1 to 6, wherein the mass ratio of gallium element to arsenic element in the gallium arsenide cluster is 1.5 to 3:1.
8. the gallium arsenide cluster according to claim 7, wherein said gallium arsenide cluster is a platelet-like structure.
9. Gallium arsenide cluster according to claim 7 or 8, characterized in that the size of said gallium arsenide cluster is 10-50 μm and the thickness is 4-6 μm.
10. Use of the gallium arsenide cluster according to any of claims 7-9 in the field of computers, light emitting diodes or electronic communication.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1598016A (en) * | 2004-07-19 | 2005-03-23 | 昆明理工大学 | Process for comprehensive recovering gallium and arsenic from industrial waste material of gallium arsenide |
CN201358292Y (en) * | 2009-03-02 | 2009-12-09 | 南京金美镓业有限公司 | Vacuum decomposer capable of decomposing gallium arsenicde into metallic gallium and metallic arsenic |
CN115451700A (en) * | 2022-09-05 | 2022-12-09 | 昆明理工大学 | Device and method for recovering arsenic and gallium |
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- 2023-04-03 CN CN202310350439.6A patent/CN116425193A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1598016A (en) * | 2004-07-19 | 2005-03-23 | 昆明理工大学 | Process for comprehensive recovering gallium and arsenic from industrial waste material of gallium arsenide |
CN201358292Y (en) * | 2009-03-02 | 2009-12-09 | 南京金美镓业有限公司 | Vacuum decomposer capable of decomposing gallium arsenicde into metallic gallium and metallic arsenic |
CN115451700A (en) * | 2022-09-05 | 2022-12-09 | 昆明理工大学 | Device and method for recovering arsenic and gallium |
Non-Patent Citations (1)
Title |
---|
曲胜利: "《高纯半导体基础原料及化合物制备技术》", 30 April 2022, 北京:冶金工业出版社, pages: 170 * |
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