CN115448262B - Long-life boron nitride phosphorescent material with wide temperature range and preparation method and application thereof - Google Patents
Long-life boron nitride phosphorescent material with wide temperature range and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a wide-temperature-range long-life boron nitride phosphorescent material, and a preparation method and application thereof. The preparation method comprises the following steps: dissolving boric acid and a fluorine source in deionized water, adding a nitrogen-carbon source, stirring and uniformly mixing, and reacting; after the reaction is completed, cooling, washing and drying are carried out to obtain the long-service-life boron nitride phosphorescent material with wide temperature range. The preparation method disclosed by the invention is simple in preparation process, low in cost, green and environment-friendly, does not need complex post-treatment, can be used for rapidly realizing mass preparation, and has the advantages of low toxicity and good light stability. The wide-temperature-range long-life boron nitride phosphorescent material powder has blue fluorescence and green phosphorescence, and the phosphorescence emission can be covered to a high-temperature environment of 150 ℃, thereby having wide application prospect.
Description
Technical Field
The invention relates to a wide-temperature-range long-life boron nitride phosphorescent material, and a preparation method and application thereof, and belongs to the technical field of functional materials.
Background
The Room Temperature Phosphorescence (RTP) material can emit fluorescence under the excitation of a light source, and can emit phosphorescence for eliminating background interference after the excitation light is removed, and the excellent optical property enables the material to be widely applied to the aspects of information encryption, photoelectricity, photodynamic therapy, biological imaging and the like. The traditional room temperature phosphorescent material such as an organometallic complex has the defects of high manufacturing cost and high toxicity; although the pure organic compound solves the problems, the spin orbit coupling is weak and the non-radiative transition rate constant is large, so that the triplet exciton is easily influenced by the environment such as temperature, humidity and the like, and the non-radiative transition is deactivated. Currently, methods for achieving efficient phosphorescence include facilitating intersystem crossing of singlet to triplet states, such as introducing heavy atom substituents, increasing spin-orbit coupling; inhibiting non-radiative deactivation rates, such as creating a rigid environment, reduces vibration of the molecule.
There are several patent literature reports on room temperature phosphorescent materials. For example: chinese patent document CN108440603A reports a preparation method of an organic metal complex phosphorescent material, and a ligand containing pyridine units is introduced into an organic metal complex of cyclometalated iridium to obtain the iridium heteroleptic complex phosphorescent material, but the material contains toxic metal elements, so that the environment is polluted and the application range of the iridium heteroleptic complex phosphorescent material is limited. Chinese patent document CN113717151A reports a preparation method of a pure organic room temperature phosphorescent compound, which is prepared by taking potassium tert-butoxide, carbazole and 2-cyano-6-fluoropyridine as raw materials and N, N-Dimethylformamide (DMF) as solvents and reacting in a stirring and heating mode. Chinese patent document CN113817460a provides a full-color tunable long-life room temperature phosphorescent material, which is a composite composed of boron oxide polycrystal and carbon dots, wherein the carbon dots are generated in situ and uniformly dispersed and embedded in the boron oxide polycrystal, and the boron oxide polycrystal is a block polycrystal generated by in situ dehydration of boric acid molecules. Although the method realizes the adjustable phosphorescence wavelength, the longest phosphorescence service life is only 581ms under the room temperature condition, and the method involves embedding the phosphorescence material into a specific matrix, which limits the application range. At present, the room temperature phosphorescent material tends to have serious non-radiative transition under the high temperature condition, the phosphorescence efficiency is greatly reduced, and the research value is higher when the material which still keeps phosphorescence emission under the high temperature condition is explored.
Many phosphorescent materials currently require loading into a matrix, blocking contact with oxygen and water, and reducing vibration of molecules to exhibit their properties. The room temperature phosphorescent material without matrix has good thermal stability and chemical stability and has greater application potential. Therefore, the preparation of wide-temperature-range phosphorescent materials with long service life, low toxicity and low cost and easy mass production is particularly urgent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a wide-temperature-range long-life boron nitride phosphorescent material, and a preparation method and application thereof. The invention takes boric acid, fluorine source and nitrogen-carbon source as raw materials, and prepares the fluorine-carbon-oxygen doped boron nitride phosphorescent material without matrix after dissolving in water and calcining. The phosphorescence material obtained by the invention has long phosphorescence service life, low toxicity, good thermal stability and chemical stability, and phosphorescence at 150 ℃ and realizes phosphorescence emission in a wide temperature range. The preparation method has the advantages of simple steps, low cost and easy mass production.
The technical scheme of the invention is as follows:
a preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
dissolving boric acid and a fluorine source in deionized water, adding a nitrogen-carbon source, stirring and uniformly mixing, and reacting; after the reaction is completed, cooling, washing and drying are carried out to obtain the long-service-life boron nitride phosphorescent material with wide temperature range.
According to the present invention, the ratio of the mole number of boric acid to the volume of deionized water is preferably 0.0001 to 0.001mol:1mL, more preferably 0.0003 to 0.0005mol:1mL.
Preferably according to the invention, the fluorine source is ammonium fluoride and/or ammonium fluoroborate; the molar ratio of the fluorine source to boric acid is 0.02 to 0.3:1, and more preferably 0.1 to 0.2:1.
According to the invention, the nitrogen-carbon source is one or more than two of ethylenediamine, diethylamine, propylenediamine, butylenediamine, oleylamine and ethanolamine, and more preferably ethylenediamine; the molar ratio of the nitrogen-carbon source to boric acid is 0.3-3:1, and more preferably 0.5-1.5:1.
According to the invention, the temperature of the reaction is preferably 200-400 ℃, more preferably 250-300 ℃; the reaction time is 10 to 90 minutes, more preferably 20 to 30 minutes, and the reaction is performed under an open heating condition, for example, the reaction may be performed in a muffle furnace with open heating.
Preferably, according to the invention, the cooling is naturally cooled to room temperature, which is 25+/-5 ℃.
According to the invention, preferably, the washing is carried out by dispersing the solid obtained by the reaction in ethanol and centrifuging at a rotational speed of 5000 to 10000rmp, more preferably 7000 to 8000rmp; the centrifugation time is 5 to 15min, more preferably 10min, and the supernatant is removed and repeated 5 to 8 times.
According to the present invention, the drying is preferably performed at 40 to 90℃for 8 to 15 hours, more preferably at 50 to 60℃for 10 to 12 hours.
The long-life boron nitride phosphorescent material with wide temperature range is prepared by adopting the preparation method.
According to the invention, the wide-temperature-range long-life boron nitride phosphorescent material is applied to information encryption or cell imaging.
The invention has the technical characteristics and beneficial effects that:
1. according to the invention, the fluorine-carbon-oxygen defect is introduced into the boron nitride, so that the optical band gap of the boron nitride can be effectively reduced due to the existence of the carbon-oxygen defect, and blue fluorescence emission and green phosphorescence emission of the boron nitride are realized; the surface of a sample obtained by the reaction in the form of aqueous solution contains rich functional groups, the water solubility is good, the existence of hydroxyl, amino and fluorine substituents on the surface of the obtained material can enhance the interaction of intermolecular hydrogen bonds, inhibit the vibration and rotation of molecules, reduce the quenching of water and oxygen on phosphorescence, realize the phosphorescence service life as long as 1.17s, and can observe phosphorescence lasting for 10s under the eyes; meanwhile, after fluorine doping, the material has the property of high Wen Linguang, phosphorescence can be still observed at the high temperature of 150 ℃, and the boron nitride phosphorescence material has the phosphorescence property in a wider temperature range.
2. The preparation method is simple in preparation process, low in cost, environment-friendly, free of complex post-treatment and capable of rapidly realizing mass preparation. The obtained product has low toxicity, good light stability and huge application prospect.
Drawings
FIG. 1 is an optical photograph of the wide temperature range long-life boron nitride phosphor powder prepared in example 1 under sunlight (a), 405nm ultraviolet lamp (b) and 405nm ultraviolet lamp (c) after being turned off.
Fig. 2 is an atomic force micrograph and a profile height profile (inset) of a wide temperature range long life boron nitride phosphorescent material prepared in example 1.
Fig. 3 is a fluorescence emission spectrum of the wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
Fig. 4 is a phosphorescence emission spectrum of a wide temperature range long life boron nitride phosphorescent material prepared in example 1.
Fig. 5 is a time resolved spectrum of a wide temperature range long life boron nitride phosphorescent material prepared in example 1.
FIG. 6 is an X-ray diffraction pattern of a wide temperature range long life boron nitride phosphorescent material prepared in example 1.
Fig. 7 is a fourier transform infrared spectrum of a wide temperature range long life boron nitride phosphorescent material prepared in example 1.
FIG. 8 is an X-ray photoelectron spectroscopy analysis of the wide temperature range long life boron nitride phosphorescent material prepared in example 1.
Fig. 9 is a graph showing phosphorescence effect of the wide temperature range long-life boron nitride phosphorescent material prepared in example 1 under different temperature conditions and the carbon-oxygen doped boron nitride room temperature phosphorescent material prepared in comparative example 1 after being irradiated and turned off by a 405nm ultraviolet lamp at 150 ℃.
Fig. 10 is a temperature-swing phosphorescence emission spectrum of a wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 11 is a graph showing the effect of the anti-counterfeit ink of the wide temperature range long-life boron nitride phosphorescent material prepared in example 1 after the pen is irradiated with 405nm ultraviolet light (a) and the ultraviolet light (b) is turned off.
Fig. 12 is a phosphorescent image of kanji drawn by the wide-temperature-range long-life boron nitride phosphorescent material prepared in example 1 and the carbon-oxygen-doped boron nitride room-temperature phosphorescent material prepared in comparative example 1 after the ultraviolet lamp of room temperature (a) and 150 ℃ high temperature (b) is irradiated and turned off.
Detailed Description
The invention is further illustrated by the following specific examples which are provided for the understanding of the invention and are not intended to limit the invention.
The methods described in the examples are conventional, unless otherwise specified; the reagents used are commercially available unless otherwise specified.
Example 1
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 50mg of ammonium fluoborate are dissolved in 10mL of deionized water, 202mg of ethylenediamine is added after magnetic stirring for 30min, and magnetic stirring is continued for 20min, so as to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace for heating at 300℃for 25min, and then taken out and naturally cooled to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) placing the centrifuged sample in an oven to be dried for 12 hours at 60 ℃, and grinding to obtain the long-service-life boron nitride phosphorescent material with a wide temperature range.
The optical photographs of the wide temperature range long-life boron nitride phosphor powder prepared in this example under sunlight (a), 405nm ultraviolet lamp (b) and 405nm ultraviolet lamp (c) after being turned off are shown in fig. 1. As can be seen from fig. 1, the obtained product is yellowish in sunlight, emits blue fluorescence under irradiation of an ultraviolet lamp, and emits green phosphorescence after the ultraviolet light source is turned off.
Atomic force microscopic images and profile height distribution diagrams of the wide-temperature-range long-life boron nitride phosphorescent material prepared in the embodiment are shown in fig. 2. As can be seen from FIG. 2, the prepared boron nitride phosphorescent material is uniformly distributed nano particles, and the contour height is 2-3 nm.
The fluorescence emission spectrum of the wide temperature range long-life boron nitride phosphorescent material prepared in this example is shown in fig. 3. As can be seen from fig. 3, the optimal excitation wavelength is 340nm and the optimal emission wavelength is 410nm.
The phosphorescence emission spectrum of the wide temperature range long life boron nitride phosphorescent material prepared in this example is shown in fig. 4. As can be seen from fig. 4, the optimal excitation wavelength is 360nm and the optimal emission wavelength is 525nm.
The time-resolved spectrum of the wide-temperature-range long-life boron nitride phosphorescent material prepared in this example is shown in fig. 5, and the data fitting result shows that the phosphorescent decay lifetime is 1.17 seconds.
The X-ray diffraction pattern of the wide temperature range long life boron nitride phosphorescent material prepared in this example is shown in fig. 6. As can be seen from fig. 6, a broad diffraction peak around 23 degrees corresponds to the (002) crystal plane of hexagonal boron nitride, and a diffraction peak around 43 degrees corresponds to the (100) crystal plane. The diffraction peaks are shifted to a small angle compared to pure hexagonal boron nitride due to the expansion of interplanar spacing caused by the incorporation of heteroatoms.
The wide temperature range long life boron nitride phosphorescence prepared in this exampleThe fourier transform infrared spectrum of the material is shown in fig. 7. From FIG. 7, it can be seen that the position is 1337cm -1 And 761cm -1 The absorption peaks at the positions correspond to the stretching vibration and the bending vibration of the B-N respectively; located at 1043cm -1 And 708cm -1 The absorption peaks at the positions correspond to the stretching vibration and the bending vibration of the B-O respectively; located at 3210cm -1 And 3120cm -1 The absorption peaks at the positions correspond to-OH and-NH respectively 2 Is a vibration of (2); at 1606cm -1 The absorption peak at corresponds to the vibration of c=n.
An X-ray photoelectron spectrum analysis chart of the wide-temperature-range long-life boron nitride phosphorescent material prepared in the embodiment is shown in fig. 8. As can be seen in fig. 8, in addition to boron and nitrogen, carbon, oxygen, fluorine elements are also present, indicating successful incorporation of carbon, oxygen, fluorine elements.
The effect graph of the wide temperature range long-life boron nitride phosphor powder prepared in this example after irradiation and shutdown with 405nm uv lamp at 150 ℃ and the carbon-oxygen doped boron nitride room temperature phosphor prepared in comparative example 1 at different temperatures is shown in fig. 9. From the graph, the phosphorescence time of the material of the embodiment is gradually shortened along with the rise of the temperature, but the material still has phosphorescence emission at 150 ℃, which shows that the boron nitride phosphorescence material prepared by the invention has phosphorescence property in a wider temperature range, and the material of the comparison example 1 of the comparison group has no phosphorescence at 150 ℃.
The temperature-variable phosphorescence emission spectrum of the wide temperature range long-life boron nitride phosphorescent material prepared in this example is shown in fig. 10. It can be seen from the figure that the phosphorescence intensity gradually decreases with increasing temperature, but still has a stronger phosphorescence emission at 150 ℃.
The wide-temperature-range long-life boron nitride phosphorescent material prepared by the embodiment is dissolved in deionized water, and the concentration is 50mg/mL, so that the anti-counterfeiting ink is obtained. As shown in fig. 11, "101010" is written with a pen on cellulose paper using the prepared anti-counterfeit ink, and the effect patterns thereof upon irradiation and after turning off of a 405nm ultraviolet lamp are shown in fig. 11 (a) and 11 (b), respectively.
The long-life boron nitride phosphorescent material with wide temperature range prepared in the embodiment and the carbon-oxygen doped boron nitride room temperature phosphorescent material prepared in the comparative example 1 are dissolved in deionized water, the concentration is 50mg/mL, the ink is obtained, chinese character's' is drawn together, namely the 'sub' character part is drawn by the ink prepared by the phosphorescent material in the embodiment 1, and the rest part is drawn by the ink prepared by the phosphorescent material in the comparative example 1. As shown in fig. 12, a phosphorescent image after being irradiated with a 405nm ultraviolet lamp and turned off at room temperature is shown in fig. 12 (a), and a phosphorescent image after being irradiated with a 405nm ultraviolet lamp and turned off after being heated at 150 ℃ for 5 minutes on a hot stage is shown in fig. 12 (b). It can be seen from fig. 12 that the whole "learning" character is displayed at room temperature, and only the "sub" character portion drawn by the material of example 1 can be displayed after heating at high temperature, which indicates that the material has high Wen Linguang property after fluorine doping, can resist high temperature, and can be applied to higher-level anti-counterfeiting.
Example 2
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 50mg of ammonium fluoborate are dissolved in 10mL of deionized water, after magnetic stirring for 30min, 249mg of propylene diamine is added, and magnetic stirring is continued for 20min, so as to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace for heating at 300℃for 25min, and then taken out and naturally cooled to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) placing the centrifuged sample in an oven to be dried for 12 hours at 60 ℃, and grinding to obtain the long-service-life boron nitride phosphorescent material with a wide temperature range.
Example 3
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 20mg of ammonium fluoride are dissolved in 10mL of deionized water, 202mg of ethylenediamine is added after magnetic stirring for 30min, and magnetic stirring is continued for 20min, so that a uniformly mixed solution is obtained. The solution was transferred to a muffle furnace for heating at 300℃for 25min, and then taken out and naturally cooled to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) placing the centrifuged sample in an oven to be dried for 12 hours at 60 ℃, and grinding to obtain the long-service-life boron nitride phosphorescent material with a wide temperature range.
Example 4
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 10mg of ammonium fluoborate are dissolved in 10mL of deionized water, 202mg of ethylenediamine is added after magnetic stirring for 30min, and magnetic stirring is continued for 20min, so as to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace for heating at 300℃for 25min, and then taken out and naturally cooled to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) placing the centrifuged sample in an oven to be dried for 12 hours at 60 ℃, and grinding to obtain the long-service-life boron nitride phosphorescent material with a wide temperature range.
Example 5
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 50mg of ammonium fluoborate are dissolved in 10mL of deionized water, 303mg of ethylenediamine is added after magnetic stirring for 30min, and magnetic stirring is continued for 20min, so as to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace for heating at 300℃for 25min, and then taken out and naturally cooled to room temperature. The resulting product was dispersed in 30ml of ethanol and centrifuged at 8000rmp for 10min, the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) placing the centrifuged sample in an oven to be dried for 12 hours at 60 ℃, and grinding to obtain the long-service-life boron nitride phosphorescent material with a wide temperature range.
Example 6
A method for preparing a wide temperature range long life boron nitride phosphorescent material is described in example 1, except that: the reaction time was 50min.
Example 7
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material is as described in example 1, except that the reaction temperature is 350 ℃.
Comparative example 1
A preparation method of a carbon-oxygen doped boron nitride room temperature phosphorescent material comprises the following steps:
206mg of boric acid is dissolved in 10mL of deionized water, after magnetic stirring for 30min, 202mg of ethylenediamine is added, and magnetic stirring is continued for 20min, so as to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace for heating at 300℃for 25min, and then taken out and naturally cooled to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) placing the centrifuged sample in an oven to be dried for 12 hours at 60 ℃, and grinding to obtain the carbon-oxygen doped boron nitride room-temperature phosphorescent material.
The phosphorescent decay lifetime of the carbon-oxygen doped boron nitride room temperature phosphorescent material prepared in this comparative example was 0.89 seconds, which is lower than that of inventive example 1, and it can be seen from fig. 9 and 12 that it does not have the property of high Wen Linguang.
Claims (12)
1. A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
dissolving boric acid and a fluorine source in deionized water, adding a nitrogen-carbon source, stirring and uniformly mixing, and reacting; after the reaction is finished, cooling, washing and drying are carried out to obtain the long-life boron nitride phosphorescent material with wide temperature range;
the fluorine source is ammonium fluoride and/or ammonium fluoroborate; the molar ratio of the fluorine source to the boric acid is 0.02-0.3:1;
the nitrogen-carbon source is one or the combination of more than two of ethylenediamine, diethylamine, propylenediamine, butylenediamine, oleylamine and ethanolamine; the molar ratio of the nitrogen-carbon source to the boric acid is 0.3-3:1;
the temperature of the reaction is 200-400 ℃, the time of the reaction is 10-90 min, and the reaction is carried out under the open heating condition.
2. The method for preparing a wide temperature range long-life boron nitride phosphorescent material according to claim 1, wherein the ratio of the number of moles of boric acid to the volume of deionized water is 0.0001-0.001 mol/1 ml.
3. The method for preparing a wide temperature range long-life boron nitride phosphor material according to claim 1, wherein the ratio of the number of moles of boric acid to the volume of deionized water is 0.0003 to 0.0005 mol/1 ml.
4. The method for preparing a wide-temperature-range long-life boron nitride phosphorescent material according to claim 1, wherein the molar ratio of the fluorine source to boric acid is 0.1-0.2:1.
5. The method for preparing a wide temperature range long life boron nitride phosphor material of claim 1, wherein said nitrogen carbon source is ethylenediamine.
6. The method for preparing a wide-temperature-range long-life boron nitride phosphorescent material according to claim 1, wherein the molar ratio of the nitrogen-carbon source to boric acid is 0.5-1.5:1.
7. The method for preparing a wide-temperature-range long-life boron nitride phosphorescent material according to claim 1, wherein the reaction temperature is 250-300 ℃; the reaction time is 20-30 min.
8. The method for preparing a wide temperature range long life boron nitride phosphorescent material according to claim 1, wherein said cooling is natural cooling to room temperature; the washing is to disperse the solid obtained by the reaction in ethanol for centrifugation, and the centrifugation speed is 5000-10000 rpm; centrifuging for 5-15min, removing supernatant, and repeating for 5-8 times.
9. The method for preparing a wide-temperature-range long-life boron nitride phosphorescent material according to claim 1, wherein the drying is performed at 40-90 ℃ for 8-15 h.
10. The method for preparing the wide-temperature-range long-life boron nitride phosphorescent material according to claim 1, wherein the drying is performed at 50-60 ℃ for 10-12 hours.
11. A long-life boron nitride phosphorescent material with wide temperature range is characterized in that the material is prepared by the preparation method of claim 1.
12. Use of the broad temperature range long life boron nitride phosphor material of claim 11 in information encryption or cell imaging.
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| JP2017510540A (en) * | 2014-01-06 | 2017-04-13 | モーメンティブ・パフォーマンス・マテリアルズ・インク | High aspect boron nitride, methods, and compositions containing the same |
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| DE102011123066B3 (en) * | 2010-10-28 | 2023-04-06 | Lg Display Co., Ltd. | Phosphorescent compound and organic electroluminescent device using the same |
| JP5955566B2 (en) * | 2012-01-18 | 2016-07-20 | 住友化学株式会社 | Composition containing phosphorescent light emitting compound and polymer compound, and light emitting device using the same |
| CN110734764B (en) * | 2019-10-31 | 2020-12-04 | 山东大学 | Method for rapidly preparing carbon-oxygen co-doped boron nitride room temperature phosphorescent material by microwave heating |
| CN112342017B (en) * | 2020-11-06 | 2021-08-10 | 山东大学 | Ultra-long-life room temperature phosphorescent material and preparation method and application thereof |
| CN113845902B (en) * | 2021-09-18 | 2023-04-21 | 山东大学 | Carbon-oxygen co-doped boron nitride quantum dot with green fluorescence and preparation method and application thereof |
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