CN116023928A - Alloyed fluorescent quantum dot and preparation method and application thereof - Google Patents
Alloyed fluorescent quantum dot and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an alloyed fluorescent quantum dot and a preparation method and application thereof. The preparation method comprises the following steps: carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, an anion source and a weak polar solvent to obtain a silver quantum dot precursor; and (3) carrying out ion exchange reaction on a second uniform mixed reaction system containing a silver quantum dot precursor, an anion source and/or a metal cation source to obtain the alloyed fluorescent quantum dot, wherein the fluorescence emission peak wavelength is between 500 and 1700nm, and the absolute quantum efficiency is more than 85%. The method prepares the silver quantum dots by a simple high-temperature solvothermal method, and then obtains the alloyed quantum dots by an ion exchange method, so that the method has the advantages of simple and controllable synthesis process, higher yield, large-scale preparation, adjustable fluorescence emission from visible light to near infrared, excellent light stability, no toxic heavy metal elements, and wide application prospect in the fields of biological imaging, near infrared devices and the like.
Description
Technical Field
The invention relates to an alloyed fluorescent quantum dot, and a preparation method and application thereof, and belongs to the technical field of material science.
Background
The quantum dot is taken as an excellent fluorescent luminescent material and has the following characteristics: high biocompatibility, high quantum efficiency, adjustable excitation and emission wavelength, easy surface functionalization and the like, and has very wide application in the research of living body imaging, light emitting diodes, photodetectors, lasers, photovoltaic cells and the like. However, the absolute fluorescence quantum yield of the existing fluorescence quantum dots such as lead sulfide, cadmium telluride, lead selenide, mercury telluride, silver selenide and the like is not high, or the existing fluorescence quantum dots partially contain toxic heavy metal elements, so that the fluorescence intensity and the toxicity are difficult to be two-dimensional. Therefore, there is an urgent need to develop a novel fluorescent quantum dot material with continuously adjustable single emission, high fluorescence quantum efficiency and high biocompatibility in the visible-near infrared full window (500-1700 nm).
Disclosure of Invention
The invention mainly aims to provide an alloyed fluorescent quantum dot with high quantum efficiency, and a preparation method and application thereof, so as to overcome the defects in the properties of the existing quantum dot.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of an alloyed fluorescent quantum dot, which comprises the following steps:
carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, an anion source and a weak polar solvent to obtain a silver quantum dot precursor;
and (3) carrying out ion exchange reaction on a second uniform mixed reaction system containing a silver quantum dot precursor, an anion source and/or a metal cation source at 0-260 ℃ for 0.4-72 h to obtain the alloyed fluorescent quantum dot.
In some embodiments, the anion source comprises any one or a combination of two or more of a sulfur source, a selenium source, and a tellurium source.
In some embodiments, the metal element contained in the metal cation source comprises any one or a combination of two or more of Mn, fe, co, ni, cu, zn, au, pd, pt, in.
The embodiment of the invention also provides the alloyed fluorescent quantum dot prepared by the method, and the fluorescence emission peak wavelength of the alloyed fluorescent quantum dot is 500-1700 nm.
Further, the absolute quantum efficiency of the alloyed fluorescent quantum dot is greater than 85%.
Further, the alloyed fluorescent quantum dot comprises AgAuSe, cuAgS, agInTe 2 Any one or a combination of two or more of them.
Further, the alloyed fluorescent quantum dots include doped alloyed fluorescent quantum dots.
Further, the alloyed fluorescent quantum dot has a core-shell structure.
The embodiment of the invention also provides application of any of the alloyed fluorescent quantum dots in the fields of biological imaging, biomedicine or near-infrared devices (such as near-infrared light emitting diodes) and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) The method comprises the steps of preparing silver quantum dots by a simple high-temperature solvothermal method, and then obtaining alloyed quantum dots by an ion exchange method, wherein the synthesis process is simple in steps, controllable in experimental conditions, simple and easily available in used reagents, high in yield of final products, and suitable for large-scale production;
2) The prepared final product alloying fluorescence quantum dot has uniform size distribution, fluorescence emission from visible light to near infrared is adjustable, has excellent light stability, does not contain any toxic heavy metal element, and has wide application prospect in the fields of biological imaging, near infrared devices and the like;
3) The preparation process of the invention can be further expanded to other preparation processes of fluorescent quantum dots, and has higher yield and easy amplification of reaction scale.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be given of the drawings used in the embodiments or the description of the prior art, it being obvious that the drawings described below are only examples of the invention herein, and that other drawings can be obtained from these drawings without the inventive effort of a person skilled in the art.
FIG. 1 is a transmission electron micrograph of an alloyed fluorescent quantum dot prepared in example 1 of the invention;
FIG. 2 is a graph of the visible-near infrared absorption spectrum of the alloyed fluorescent quantum dots prepared in example 1 of the invention;
FIG. 3 is a fluorescence emission spectrum of the alloyed fluorescent quantum dots prepared in example 1 of the invention;
fig. 4 is a graph of quantum efficiency measurements of the alloyed fluorescent quantum dots prepared in example 1 of the invention.
Detailed Description
As described above, in view of the existing fluorescent quantum dots, such as lead sulfide, cadmium telluride, lead selenide, mercury telluride, silver selenide, etc., the absolute fluorescent quantum yield is not high, and meanwhile, part of the fluorescent quantum dots contain toxic heavy metal elements, so that both the fluorescent intensity and the toxicity are difficult to be achieved. The inventor of the present application has found after long-term study and a great deal of practice that: the alloying quantum dot after ion exchange of some elements and silver-based quantum dots has good optical properties. The technical scheme of the invention will be explained in more detail as follows.
As an aspect of the present invention, it relates to a method for preparing an alloyed fluorescent quantum dot, comprising:
carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, an anion source and a weak polar solvent to obtain a silver quantum dot precursor;
and (3) carrying out ion exchange reaction on a second uniform mixed reaction system containing a silver quantum dot precursor, an anion source and/or a metal cation source at 0-260 ℃ for 0.4-72 h to obtain the alloyed fluorescent quantum dot.
In some embodiments, the silver source includes a silver salt including any one or a combination of two or more of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver acetate, silver sulfide, silver trifluoroacetate, silver diethyldithiocarbamate, and the like, but is not limited thereto.
In some embodiments, the anion source includes any one or a combination of two or more of a sulfur source, a selenium source, a tellurium source, and the like, but is not limited thereto.
Further, the sulfur source includes any one or a combination of two or more of sulfur, sodium thiosulfate, sodium sulfide, thiourea, and the like, but is not limited thereto.
Further, the selenium source includes any one or a combination of two or more of selenium dioxide, selenium, sodium selenate, sodium selenite, sodium selenide, diphenyl diselenide, etc., but is not limited thereto.
Further, the tellurium source includes any one or a combination of two or more of tellurium, sodium tellurate hydride, and the like, but is not limited thereto.
Further, the weak polar solvent includes any one or a combination of two or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecyl amine, octyl mercaptan, octadecyl mercaptan, etc., but is not limited thereto.
In some embodiments, the mass ratio of the silver source to the anion source is 1-10:1-10.
In some embodiments, the solvothermal reaction is at a temperature of 100 to 300 ℃ for a time of 0.5 to 24 hours.
In some preferred embodiments, the silver-based quantum dot precursor may be Ag 2 S、Ag 2 Se、Ag 2 Te, etc., but is not limited thereto.
Further, in a more typical embodiment, the method of preparation may include: firstly, silver nitrate is dissolved in oleylamine, a sulfur source is added, the reaction is carried out for 1 to 6 hours at 200 ℃, and then the silver quantum dot precursor of a target product is obtained after cleaning.
In some preferred embodiments, the method of making may comprise: and dissolving 0.1-1 g of silver salt in a weak polar solvent.
Further, the preparation method specifically comprises the following steps: and mixing the silver sulfide precursor with a gold source, and reacting at 100 ℃ to obtain the silver-gold-sulfur fluorescent quantum dot.
Further, the preparation method further comprises the following steps: and after the reaction is completed, cleaning the obtained silver gold sulfur fluorescent quantum dots.
In some embodiments, the mass ratio of the silver-based quantum dot precursor to the metal cation source is 1-10:1-10.
In some preferred embodiments, the metal element contained in the metal cation source may include any one or a combination of two or more of Mn, fe, co, ni, cu, zn, au, pd, pt, in and the like, but is not limited thereto.
Further, the metal cation source may include any one or a combination of two or more of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, copper sulfate, copper acetate, copper nitrate, copper chloride, cuprous chloride, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, palladium acetate, palladium nitrate, palladium chloride, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, indium acetate, indium chloride, and the like, but is not limited thereto.
Among them, the foregoing silver salts, anion sources, weak polar solvents, metal cation sources, and the like may be selected from, but are not limited to, the above listed species.
In some embodiments, the preparation method specifically comprises:
uniformly mixing a silver source with a weak polar solvent, adding an anion source, and performing solvothermal reaction to obtain a silver-based quantum dot precursor (also called a silver-based quantum dot precursor);
and mixing the silver quantum dot precursor with a metal cation source at 0-260 ℃ for reaction to obtain the alloyed fluorescent quantum dot, wherein the fluorescence emission peak wavelength is 500-1700 nm.
Wherein, when the metal cation selects gold source and the anion selects sulfur source, the preparation method of the alloyed fluorescent quantum dot can comprise the following steps as one of more specific embodiments:
I. mixing silver salt with a weak polar solvent, and uniformly dispersing by ultrasonic waves;
II. Adding a sulfur source into the mixed solution obtained in the step I, uniformly mixing and dispersing, and reacting at 100-300 ℃ for 0.5-24 h;
III, separating a product obtained by the solvothermal reaction in the step II, and cleaning and drying;
and IV, reacting the product obtained in the step III with a gold source at 0-200 ℃ for 10-72 h to obtain the near infrared silver-gold-sulfur fluorescent quantum dot.
The final product prepared by the invention has the advantages of alloyed fluorescent quantum dots, uniform size distribution, fluorescence emission peak wavelength of 500-1700nm, preferably 800-1100 nm, ultrahigh absolute fluorescence quantum efficiency (more than 85%), and no toxic heavy metal elements. And the yield of the final product is high, and the preparation process is easy to enlarge the reaction scale.
As another aspect of the technical scheme of the invention, the invention also relates to the alloyed fluorescent quantum dot prepared by the method, which has uniform shape and size, high absolute quantum yield and no toxic heavy metal element, and has important application prospect in the fields of biological imaging, biomedicine or near infrared devices and the like.
Further, the alloyed fluorescent quantum dots may preferably include AgAuS, cuAgSe, agInTe 2 Any one or a combination of two or more of these, etc., but is not limited thereto.
Further, the alloyed fluorescent quantum dots include doped alloyed fluorescent quantum dots; for example, it may preferably include any one or a combination of two or more of manganese-doped silver selenide fluorescent quantum dots, nickel-doped silver telluride fluorescent quantum dots, indium-doped silver sulfide fluorescent quantum dots, cobalt-doped silver sulfide fluorescent quantum dots, and the like, but is not limited thereto.
Further, the alloyed fluorescent quantum dot has a core-shell structure; for example, the alloyed fluorescent quantum dots may preferably include Ag 2 S@ZnS、Ag 2 Te@Ag 2 S、Ag 2 Se@Ag 2 S、Ag 2 Se@ZnS、Ag 2 Se@ZnSe、Ag 2 Any one or a combination of two or more of s@mns and the like, but is not limited thereto.
Another aspect of an embodiment of the present invention also provides the use of any of the aforementioned alloyed fluorescent quantum dots in the fields of bioimaging, biomedical or near infrared devices, etc.
Further, the near infrared device may be a near infrared light emitting diode, but is not limited thereto.
In summary, by adopting the technical scheme, the silver quantum dots are prepared by a simple high-temperature solvothermal method, and then the alloyed quantum dots are obtained by an ion exchange method, so that the method has the advantages of simple and controllable synthesis process, high yield, large-scale preparation, adjustable fluorescence emission from visible light to near infrared, excellent light stability, no toxic heavy metal elements, and wide application prospect in the fields of biological imaging, near infrared devices and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below with reference to several preferred embodiments, but the present invention is not limited to the following embodiments, and the technical solutions and modifications may be made by those skilled in the art under the core guiding ideas of the present invention without essential modifications and remain within the scope of the present invention. Unless otherwise indicated, the various reagents used in the following examples are well known to those skilled in the art and may be obtained by commercial means or the like. The experimental methods in the following examples, in which specific conditions are not specified, are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
Example 1
Dissolving 0.06g of silver nitrate in 20mL of oleylamine, uniformly dispersing by ultrasonic, then adding 0.06 sulfur powder, reacting for 5 hours at 200 ℃ to obtain a silver sulfide precursor, then adding 0.06g of chloroauric acid, and reacting for 48 hours at 100 ℃ to obtain the silver gold sulfur fluorescent quantum dot.
As can be seen from the graph I, the near-infrared silver-gold-sulfur fluorescent quantum dot product obtained in the embodiment has uniform morphology and size, and the size is about 4.5nm.
Dispersing the silver gold sulfur quantum dots in chloroform. The absorption spectrum is measured by using a visible-near infrared absorption spectrometer, and the quantum dots are known to have stronger absorption in the visible near infrared region, as shown in fig. 2. The luminescence spectrum and absolute fluorescence quantum yield were further tested using a near infrared fluorescence spectrometer. As can be seen from FIG. 3, the silver gold sulfur fluorescence quantum dot is located at 800-1100 nm, and the absolute quantum efficiency is 85.15% as can be seen from FIG. 4.
Example 2
Dissolving 0.06g of silver acetate in 20mL of oleic acid, uniformly dispersing by ultrasonic, then adding 0.6 sulfur powder, reacting for 0.5h at 250 ℃ to obtain a silver sulfide precursor, then adding 0.6g of cuprous chloride, and reacting for 10h at 200 ℃ to obtain the silver-copper-sulfur fluorescent quantum dot.
Example 3
Dissolving 0.6g of silver nitrate in 20mL of octadecanethiol, uniformly dispersing by ultrasonic, then adding 0.6g of tellurium powder, reacting for 5 hours at 150 ℃ to obtain a silver telluride precursor, then adding 0.6g of selenium powder, and reacting for 24 hours at 100 ℃ to obtain the silver-selenium-tellurium fluorescent quantum dot.
Example 4
Dissolving 0.06g of silver trifluoroacetate in 20mL of dodecyl amine, uniformly dispersing by ultrasonic, then adding 0.06 selenium powder, reacting for 10 hours at 180 ℃ to obtain a silver selenide precursor, then adding 0.06g of chloroplatinic acid, and reacting for 72 hours at 0 ℃ to obtain the silver-platinum-selenium fluorescent quantum dot.
Example 5
Dissolving 0.06g of silver chloride in 20mL of octanethiol, uniformly dispersing by ultrasonic, then adding 0.6 sulfur powder, reacting for 12 hours at 200 ℃ to obtain a silver sulfide precursor, then adding 0.06g of ferrous chloride, and reacting for 72 hours at 0 ℃ to obtain the silver-iron-selenium fluorescent quantum dot.
Example 6
Dissolving 0.6g of silver sulfide in 20mL of hexadecylamine, uniformly dispersing by ultrasonic, then adding 0.06 selenium powder, reacting for 5 hours at 200 ℃ to obtain a silver selenide precursor, then adding 0.06g of palladium chloride, and reacting for 72 hours at 0 ℃ to obtain the palladium-silver-selenium fluorescent quantum dot.
Example 7
Dissolving 0.06g of silver iodide in 20mL of oleylamine, uniformly dispersing by ultrasonic, then adding 0.06 selenium powder, reacting for 5 hours at 200 ℃ to obtain a silver selenide precursor, then adding 0.06g of manganese chloride, and reacting for 72 hours at 0 ℃ to obtain the manganese doped silver selenide fluorescent quantum dot.
Example 8
Dissolving 0.06g of silver acetate in 20mL of oleylamine, uniformly dispersing by ultrasonic, then adding 0.06 selenium powder, reacting for 0.5h at 300 ℃ to obtain silver selenide precursor, then adding 0.06g of sulfur powder, reacting for 72h at 100 ℃ to obtain Ag 2 Se@Ag 2 S fluorescent quantum dots.
Example 9
Dissolving 0.6g of silver sulfate in 20mL of octadecanethiol, uniformly dispersing by ultrasonic, then adding 0.06g of tellurium powder, reacting for 1h at 150 ℃ to obtain a silver telluride precursor, then adding 0.6g of sulfur powder and 0.06g of zinc acetate, and reacting for 0.4h at 260 ℃ to obtain Ag 2 Te@ZnS fluorescent quantum dots.
Example 10
Dissolving 0.5g of silver diethyl dithiocarbamate in 20mL of octadecanethiol, uniformly dispersing by ultrasonic, then adding 0.06g of tellurium powder, reacting for 1h at 200 ℃ to obtain a silver telluride precursor, then adding 0.06g of nickel acetate, and reacting for 2h at 150 ℃ to obtain the nickel doped silver telluride fluorescent quantum dot.
Example 11
Dissolving 0.04g of silver acetate in 20mL of dodecyl mercaptan, uniformly dispersing by ultrasonic, then adding 0.06g of sulfur powder, reacting for 1h at 200 ℃ to obtain a silver sulfide precursor, then adding 0.06g of indium acetate, and reacting for 2h at 150 ℃ to obtain the indium-doped silver sulfide fluorescent quantum dot.
Example 12
Dissolving 0.06g of silver carbonate in 20mL of dodecyl mercaptan, uniformly dispersing by ultrasonic, then adding 0.06 sulfur powder, reacting for 24 hours at 100 ℃ to obtain a silver sulfide precursor, then adding 0.06g of cobalt chloride, and reacting for 48 hours at 100 ℃ to obtain the cobalt-doped silver sulfide fluorescent quantum dot.
In addition, the inventor also uses other raw materials listed above and other process conditions to replace various raw materials and corresponding process conditions in examples 1-12, and the obtained alloyed fluorescent quantum dots have ideal morphology, performance and the like, and are basically similar to the products in examples 1-12.
The method prepares the silver quantum dots by a simple high-temperature solvothermal method, and then obtains the alloyed quantum dots by an ion exchange method, so that the method has the advantages of simple and controllable synthesis process, higher yield, large-scale preparation, adjustable fluorescence emission from visible light to near infrared, excellent light stability, no toxic heavy metal elements, and wide application prospect in the fields of biological imaging, near infrared devices and the like.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the alloyed fluorescent quantum dot is characterized by comprising the following steps of:
carrying out solvothermal reaction on a first uniform mixed reaction system containing a silver source, an anion source and a weak polar solvent to obtain a silver quantum dot precursor;
and (3) carrying out ion exchange reaction on a second uniform mixed reaction system containing a silver quantum dot precursor, an anion source and/or a metal cation source at 0-260 ℃ for 0.4-72 h to obtain the alloyed fluorescent quantum dot.
2. The method of manufacturing according to claim 1, characterized in that: the silver source comprises silver salt, and the silver salt comprises any one or more than two of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver acetate, silver sulfide, silver trifluoroacetate and silver diethyl dithiocarbamate.
3. The method of manufacturing according to claim 1, characterized in that: the anion source comprises any one or more than two of a sulfur source, a selenium source and a tellurium source; preferably, the sulfur source comprises any one or more than two of sulfur, sodium thiosulfate, sodium sulfide and thiourea, preferably, the selenium source comprises any one or more than two of selenium dioxide, selenium, sodium selenate, sodium selenite, sodium selenide and diphenyl diselenide, preferably, the tellurium source comprises any one or more than two of tellurium, sodium tellurate and sodium tellurate hydride.
4. The method of manufacturing according to claim 1, characterized in that: the weak polar solvent comprises one or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecyl amine, dodecyl mercaptan, octyl mercaptan and octadecyl mercaptan.
5. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the silver source to the anion source is 1-10:1-10.
6. The method of manufacturing according to claim 1, characterized in that: the temperature of the solvothermal reaction is 100-300 ℃ and the time is 0.5-24 h.
7. The method of manufacturing according to claim 1, characterized in that: the silver quantum dot precursor comprises Ag 2 S、Ag 2 Se、Ag 2 Any one or a combination of two or more of Te; and/or the mass ratio of the silver quantum dot precursor to the metal cation source is 1-10:1-10.
8. The method of manufacturing according to claim 1, characterized in that: the metal element contained in the metal cation source comprises any one or more than two of Mn, fe, co, ni, cu, zn, au, pd, pt, in, preferably, the metal cation source comprises any one or more than two of ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, ferric nitrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, copper sulfate, copper acetate, copper nitrate, copper chloride, cuprous chloride, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, palladium acetate, palladium nitrate, palladium chloride, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, indium acetate and indium chloride.
9. An alloyed fluorescent quantum dot having a fluorescence emission peak wavelength of 500-1700nm, preferably 800-1100 nm, produced by the method of any one of claims 1-8, the absolute quantum efficiency of the alloyed fluorescent quantum dot being greater than 85%, preferably the alloyed fluorescent quantum dot comprising AgAuS, cuAgSe, agInTe 2 Any one or a combination of two or more of them;
preferably, the alloyed fluorescent quantum dots comprise doped alloyed fluorescent quantum dots; preferably comprises any one or more than two of manganese doped silver selenide fluorescent quantum dots, nickel doped silver telluride fluorescent quantum dots, indium doped silver sulfide fluorescent quantum dots and cobalt doped silver sulfide fluorescent quantum dots;
preferably, the alloyed fluorescent quantum dot has a core-shell structure; particularly preferably, the alloyed fluorescent quantum dot comprises Ag 2 S@ZnS、Ag 2 Te@Ag 2 S、Ag 2 Se@Ag 2 S、Ag 2 Se@ZnS、Ag 2 Se@ZnSe、Ag 2 Any one or more than two of S@MnS.
10. Use of the alloyed fluorescent quantum dot of claim 9 in the field of bioimaging, biomedical or near infrared devices, preferably comprising near infrared light emitting diodes.
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| CN202111243959.4A CN116023928A (en) | 2021-10-25 | 2021-10-25 | Alloyed fluorescent quantum dot and preparation method and application thereof |
| US17/785,420 US20230247846A1 (en) | 2021-01-20 | 2021-12-21 | Fluorescent quantum dots as well as preparation method and use thereof |
| EP21920841.0A EP4092095B1 (en) | 2021-01-20 | 2021-12-21 | Fluorescent quantum dots and preparation method therefor and use thereof |
| PCT/CN2021/140056 WO2022156467A1 (en) | 2021-01-20 | 2021-12-21 | Fluorescent quantum dots and preparation method therefor and use thereof |
| JP2022536547A JP7378857B2 (en) | 2021-01-20 | 2021-12-21 | Preparation method of near-infrared silver gold selenium fluorescent quantum dots |
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