CN115196670B - Gallium oxide quantum dot and preparation method thereof - Google Patents
Gallium oxide quantum dot and preparation method thereof Download PDFInfo
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- CN115196670B CN115196670B CN202110388339.3A CN202110388339A CN115196670B CN 115196670 B CN115196670 B CN 115196670B CN 202110388339 A CN202110388339 A CN 202110388339A CN 115196670 B CN115196670 B CN 115196670B
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- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 52
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002096 quantum dot Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 11
- 230000005669 field effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 31
- 238000000502 dialysis Methods 0.000 claims description 19
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000008092 positive effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010008 shearing Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000464 low-speed centrifugation Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- -1 hetero ions Chemical class 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000000927 vapour-phase epitaxy Methods 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a gallium oxide quantum dot, which is beta-gallium oxide with the diameter of 5-10 nm. The gallium oxide quantum dot has extremely small size and large specific surface area, and has positive effects on the development of field effect transistors, gas sensors and solar detectors. Meanwhile, the invention also provides a preparation method of the gallium oxide quantum dot, which has the advantages of simple process, mild reaction conditions and conventional equipment, and the gallium oxide quantum dot with high purity and uniform size can be obtained through mechanical shearing and chemical treatment.
Description
Technical Field
The invention relates to the technical field of nano materials. More particularly, to a gallium oxide quantum dot and a preparation method thereof.
Background
Gallium oxide (Ga) 2 O 3 ) As an excellent semiconductor material with a wide forbidden band, the material is widely applied to the fields of energy devices, solar blind ultraviolet detection, solar batteries, sensors and the like. Gallium oxide generally has five different crystalline states (α, β, γ, δ, ε), where β -Ga 2 O 3 The properties possessed by the composition are most stable under general conditions.
There are many methods of preparing nanostructured gallium oxides in the prior art, the most common being gas-liquid-solid (VLS) or gas-solid (VS) processes. In this process, a metal catalyst or metal alloy is used to form supersaturated droplets of alloy by dissolving the vapor component, the supersaturation of the droplets of alloy promoting the precipitation of the solid phase required for nanowire growth. Other Ga 2 O 3 The preparation method of the nano-structure comprises physical evaporation, thermal annealing of compacted gallium nitride powder, arc discharge, laser ablation, carbothermal reduction, chemical Vapor Deposition (CVD), metal Organic Chemical Vapor Deposition (MOCVD), microwave plasma reaction, vapor Phase Epitaxy (VPE) and the like, and the nano-structure prepared by the method is a film, a linear, a rod-shaped or other one-dimensional structure, so that the nano-structure type of gallium oxide in the prior art is mainly a nanowire, a nanorod or a nano-sheet.
However, reducing the size of gallium oxide materials has a positive effect on the development of gallium oxide-based nanowire field effect transistors, gas sensors, and solar detectors. Particularly, for a gas sensor, gallium oxide with a high surface ratio nano structure can effectively improve the detection sensitivity of the sensor and shorten the response time.
Accordingly, it is desirable to provide a gallium oxide quantum dot of extremely small size.
Disclosure of Invention
The invention aims to provide a gallium oxide quantum dot, which is beta-gallium oxide, has a diameter of 5-10 nm and has a larger specific surface area.
The invention further aims at providing a preparation method of the gallium oxide quantum dot.
It is yet another object of the present invention to provide a gallium oxide quantum dot for use.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the gallium oxide quantum dot is beta-gallium oxide, and the diameter of the gallium oxide quantum dot is 5-10 nm.
The gallium oxide nano structure is a quantum dot, has smaller size and large specific surface area, and has positive effects on the development of field effect transistors, gas sensors and solar detectors. Meanwhile, the gallium oxide quantum dot is beta-Ga 2 O 3 The performance is stable.
The preparation method of the gallium oxide quantum dot comprises the following steps:
adding liquid gallium metal into an acid solution, performing ultrasonic crushing, and centrifuging to remove macromolecular particles to obtain a precursor solution;
adding hydrogen peroxide aqueous solution into the precursor solution, uniformly mixing, dialyzing and drying to obtain the gallium oxide quantum dot.
It should be noted that, the gallium metal used in the preparation process is in a liquid state, and the solid gallium metal needs to be heated and melted and then added into the acid solution.
The preparation method provided by the invention is simple, the reaction condition is mild, the treatment equipment is conventional, and the gallium oxide quantum dots with high purity and uniformity can be prepared by means of mechanical shearing and chemical treatment.
Preferably, the volume ratio of the liquid gallium metal, the acid solution and the hydrogen peroxide aqueous solution used in the preparation process is (0.1-0.2): (20-50): (0.1 to 0.3); wherein the pH of the acid solution is 1.0-4.0, and the concentration of the aqueous hydrogen peroxide solution is 10-100 mM.
Preferably, the purity of the liquid gallium metal is greater than 99.9%.
Preferably, the ultrasonic intensity in the ultrasonic crushing process is 70-100% of amplitude, and the ultrasonic time is 20-40 min. The ultrasonic crushing process makes liquid gallium fully dissolved in acid solution and the solution temperature is less than 200 deg.c during ultrasonic treatment to prepare for the subsequent reaction of gallium and hydrogen peroxide.
Preferably, the centrifugal speed in the process of removing the macromolecular particles by centrifugation is 1000-4000 rpm, and the centrifugal time is 5 minutes.
Preferably, the dialysis process uses a bag dialysis molecular weight of 3000-5000D and a dialysis time of 8-12 hours. The dialysis process can make the hetero ions and hetero atoms in the solution dialyze into water, so as to avoid affecting the purity of gallium oxide ions.
Preferably, the drying process is to dry the dialyzed solution at 50 to 100 ℃ for 2 to 6 hours.
The application of the gallium oxide quantum dot in preparing a field effect transistor, a gas sensor and a solar detector. The gallium oxide quantum dot provided by the invention has extremely small size and larger specific surface area, and particularly for a gas sensor, the detection sensitivity of the sensor can be improved, and the response time is shortened.
The beneficial effects of the invention are as follows:
the invention provides a gallium oxide quantum dot which is beta-gallium oxide, has the diameter of 5-10 nm, is extremely small in size and has larger specific surface area. The gallium oxide quantum dot has positive effects on the development of field effect transistors, gas sensors and solar detectors.
Meanwhile, the invention also provides a preparation method of the gallium oxide quantum dot, which has the advantages of simple process, mild reaction conditions and conventional equipment, and the gallium oxide quantum dot with high purity and uniform size can be obtained through mechanical shearing and chemical treatment.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 shows a transmission electron microscope image of the gallium oxide quantum dot prepared in example 1 of the present invention.
Fig. 2 shows a photoelectron spectrum of the gallium oxide quantum dot prepared in example 1 of the present invention.
Fig. 3 shows the uv-vis absorption spectrum of the gallium oxide quantum dot prepared in example 1 of the present invention.
Fig. 4 shows the PL spectrum of the gallium oxide quantum dot prepared in example 1 of the present invention.
Fig. 5 is a transmission electron microscope image of the gallium oxide quantum dot prepared in example 2 of the present invention.
Fig. 6 shows a transmission electron micrograph of larger size nanoparticles prepared according to the comparative example of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
(1) Heating and melting solid gallium in a water bath with constant temperature of 60 ℃, adding 100 mu L of gallium into 1moL/L of 20mL of hydrochloric acid, performing ultrasonic crushing on the mixed solution, and continuously performing ultrasonic treatment for 30min by using 70% amplitude, wherein the temperature of the mixed solution is controlled below 150 ℃;
then centrifuging at a low speed to remove large molecular weight particles, wherein the rotation speed of the low speed centrifugation is 1000rpm, and centrifuging for 5 minutes to obtain a precursor solution;
(2) Adding 100 mu L of hydrogen peroxide water solution with the concentration of 100mM into the precursor solution of the gallium oxide quantum dot, and uniformly mixing;
then transferring the solution into a dialysis bag with a dialysis molecular weight of 3000D, and placing the dialysis bag into a beaker filled with deionized water for dialysis for 8 hours; and (3) placing the dialyzed solution in a vacuum drying oven to be dried for 2 hours at 50 ℃ to obtain the gallium oxide quantum dot.
The projection electron microscope diagram of the obtained gallium oxide quantum dot is shown in figure 1, and the visible quantity isThe size of the sub-dots is not more than 10nm and the size is uniform. FIG. 2 shows the photoelectron spectrum of the gallium oxide quantum dot, illustrating that the main component of the prepared material is Ga 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the FIG. 3 shows the ultraviolet-visible absorption spectrum of gallium oxide quantum dots, the dominant absorbance of which is 254nm; fig. 4 shows a PL spectrum of a gallium oxide quantum dot, which illustrates that when the excitation wavelength is 254nm, the prepared quantum dot has the characteristics of 352nm emission wavelength, purple emission and photoluminescence according with the quantum dot.
Example 2
(1) Placing solid gallium metal in a 60 ℃ constant-temperature water bath kettle, heating and melting, adding 100 mu L of gallium metal into 1moL/L of 20mL of hydrochloric acid, performing ultrasonic crushing on the mixed solution, and continuously performing ultrasonic treatment for 20min by using 70% amplitude;
then centrifuging at a low speed to remove large molecular weight particles, wherein the rotation speed of the low speed centrifugation is 1000rpm, and centrifuging for 5 minutes to obtain a precursor solution;
(2) Adding 100 mu L of hydrogen peroxide water solution with the concentration of 100mM into the precursor solution of the gallium oxide quantum dot, and uniformly mixing;
then transferring the solution into a dialysis bag with a dialysis molecular weight of 3000D, and placing the dialysis bag into a beaker filled with deionized water for dialysis for 6 hours; and (3) placing the dialyzed solution in a vacuum drying oven to be dried for 2 hours at 50 ℃ to obtain the gallium oxide quantum dot.
And carrying out transmission electron microscope observation on the nanoparticle sample preparation to obtain the nanoparticle shown in fig. 5.
Comparative example
To demonstrate the necessity of a chemical treatment of hydrogen peroxide therein, the following comparative examples are exemplified:
(1) Heating and melting solid gallium in a water bath with constant temperature of 60 ℃, adding 100 mu L of gallium into 1moL/L of 20mL of hydrochloric acid, performing ultrasonic crushing on the mixed solution, and continuously performing ultrasonic treatment for 30min by using 70% amplitude, wherein the temperature of the mixed solution is controlled below 150 ℃;
then centrifuging at a low speed to remove large molecular weight particles, wherein the rotation speed of the low speed centrifugation is 1000rpm, and centrifuging for 5 minutes to obtain a precursor solution;
(2) Transferring the solution into a dialysis bag with a dialysis molecular weight of 3000D, and placing the dialysis bag into a beaker filled with deionized water for dialysis for 8 hours; and (3) placing the dialyzed solution in a vacuum drying oven at 50 ℃ for drying for 2 hours to obtain the prepared nano particles.
The nanoparticle preparation was observed by transmission electron microscopy to obtain larger size nanoparticles as shown in fig. 6.
In the comparative example, the aqueous hydrogen peroxide solution is not added in the step (2), so that the prepared nano particles have larger size, and the gallium oxide quantum dots in the invention cannot be prepared.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (9)
1. The preparation method of the gallium oxide quantum dot is characterized in that the gallium oxide quantum dot is beta-gallium oxide, and the diameter of the beta-gallium oxide quantum dot is 5-10 nm; the preparation method comprises the following steps:
adding liquid gallium metal into an acid solution, performing ultrasonic crushing, and centrifuging to remove macromolecular particles to obtain a precursor solution;
adding hydrogen peroxide aqueous solution into the precursor solution, uniformly mixing, dialyzing and drying to obtain the gallium oxide quantum dot.
2. The preparation method according to claim 1, wherein the volume ratio of the liquid gallium metal, the acid solution and the aqueous hydrogen peroxide solution used in the preparation process is (0.1-0.2): (20-50): (0.1 to 0.3); wherein the pH of the acid solution is 1.0-4.0, and the concentration of the aqueous hydrogen peroxide solution is 10-100 mM.
3. The method of claim 1, wherein the liquid gallium metal has a purity of greater than 99.9%.
4. The method according to claim 1, wherein the acid solution is one selected from the group consisting of hydrochloric acid, sulfuric acid solution, and acetic acid solution.
5. The method according to claim 1, wherein the ultrasonic intensity in the ultrasonic crushing process is 70% -100% of the amplitude, and the ultrasonic time is 20-40 min.
6. The method according to claim 1, wherein the centrifugation speed during the centrifugation to remove the macromolecular particles is 1000 to 4000rpm and the centrifugation time is 5 minutes.
7. The method according to claim 1, wherein the dialysis process uses a bag with a dialysis molecular weight of 3000 to 5000D and a dialysis time of 8 to 12 hours.
8. The preparation method according to claim 1, wherein the drying temperature is 50 to 100 ℃ and the drying time is 2 to 6 hours.
9. Use of gallium oxide quantum dots prepared by the preparation method of any one of claims 1-8 in the preparation of field effect transistors, gas sensors and solar detectors.
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| CN202110388339.3A CN115196670B (en) | 2021-04-12 | 2021-04-12 | Gallium oxide quantum dot and preparation method thereof |
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| CN202110388339.3A CN115196670B (en) | 2021-04-12 | 2021-04-12 | Gallium oxide quantum dot and preparation method thereof |
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| CN115196670B true CN115196670B (en) | 2023-11-28 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2354611C1 (en) * | 2007-08-03 | 2009-05-10 | Георгий Георгиевич Кознов | Method of gallium oxide production |
| CN108821329A (en) * | 2018-07-10 | 2018-11-16 | 成都中建材光电材料有限公司 | A kind of preparation method of high-purity gallium oxide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2354611C1 (en) * | 2007-08-03 | 2009-05-10 | Георгий Георгиевич Кознов | Method of gallium oxide production |
| CN108821329A (en) * | 2018-07-10 | 2018-11-16 | 成都中建材光电材料有限公司 | A kind of preparation method of high-purity gallium oxide |
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