CN111187624A - Up-conversion micron particle, preparation method thereof and fluorescence lifetime regulation method - Google Patents
Up-conversion micron particle, preparation method thereof and fluorescence lifetime regulation method Download PDFInfo
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- CN111187624A CN111187624A CN202010084445.8A CN202010084445A CN111187624A CN 111187624 A CN111187624 A CN 111187624A CN 202010084445 A CN202010084445 A CN 202010084445A CN 111187624 A CN111187624 A CN 111187624A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Abstract
The invention belongs to the technical field of inorganic nano materials, and relates to up-conversion micro-particles, a preparation method thereof and a fluorescence lifetime regulating method. The micron particle has a chemical formula of NaLuF8:Yb3+/A3+(A3+Is Er3+,Tm3+,Ho3+One of them) in hexagonal prism shape and uniform in size distribution. The preparation method comprises the following steps: adding a certain proportion of rare earth acetate aqueous solution into trisodium citrate aqueous solution, and stirring for a certain time; adding an aqueous solution of ammonium fluoride into the solution, stirring for a certain time, and transferring the mixed solution into a reaction kettle for hydrothermal reaction; and after the reaction is finished, cooling to room temperature, washing and centrifuging to obtain the target product. The fluorescence lifetime of the micron particles can be regulated and controlled by changing the peak power density of the pump laser, and the micron particles have wide application prospects in the field of fluorescence anti-counterfeiting.
Description
Technical Field
The invention belongs to the technical field of up-conversion materials, and particularly relates to up-conversion micro-particles, a preparation method thereof and a fluorescence lifetime regulating method.
Background
The rare earth ion doped up-conversion luminescent material has unique optical advantages, and the luminescence has the characteristics of high emission spectrum purity, narrow bandwidth, long fluorescence life, small influence of matrix environment and temperature and the like. The upconversion material developed based on the optical properties has wide application prospects in the fields of fluorescence anti-counterfeiting, optical coding, display, three-dimensional imaging and the like. The upconversion material suitable for specific applications can be obtained by controlling the fluorescence spectrum or fluorescence lifetime of the upconversion.
In recent years, researchers at home and abroad have carried out a plurality of studies on up-conversion regulation. For example, in 2013, Jinda Yong et al proposedControl of Yb3+Ion and Tm3+The method for regulating and controlling the blue light emission peak life by the ion doping concentration realizes the regulation and control of the fluorescence life from 25.6 mus to 662.4 mus and proves the fluorescence anti-counterfeiting (Tunable life timeexemplified using fluorescent nanoparticles [ J ] based on the life regulation and control]Nature Photonics,2014,8(1): 32). In 2014, Liu Xiao just et al reported a single NaYF4A process for epitaxially growing nanoparticles with composite structure on the both end surfaces of the seed crystal of micrometer rod includes doping Er to the seed and end surfaces3+Ion or Tm3+Ion, special micron rod (multi-color barcode in a single upper conversion crystal) with different luminescence of seed and end face crystal can be obtained]Journal of the American Chemical Society,2014,136(13): 4893). Zhang et al in 2016 designed a multilayer core-shell structure rare earth doped nanoparticle, using NaGdF4The filtering effect of the Yb/Tm intermediate layer on 980nm pump light realizes different colors of luminescence under 808nm or 980nm excitation light (filtered light doped power condensation emission luminescence)].Angewandte Chemie International Edition,2016,55:2464-2469.)。
Nevertheless, we have found that the fluorescence spectrum or fluorescence lifetime of most of the upconversion materials with fixed components is fixed, and no research on the regulation of the fluorescence lifetime of the fixed materials and no patent related thereto are published. The invention provides up-conversion micron particles with adjustable fluorescence lifetime, which are prepared by aiming at NaLuF with fixed components4Yb/Er micron rod, and its fluorescent life can be changed by changing the power of exciting light. The up-conversion nano particles with adjustable service life can become a novel fluorescent anti-counterfeiting material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides up-conversion micron particles, a preparation method thereof and a fluorescence lifetime regulating method.
The first object of the present invention is to provide a process for the preparation of upconversion microparticles, NaLuF4:Yb3+/A3+Up conversionThe micron-changed crystal synthesis steps are as follows:
(1) adding aqueous solution of acetate of lutetium acetate, ytterbium acetate and activator ions into aqueous solution of trisodium citrate, and stirring uniformly;
(2) adding an aqueous solution of ammonium fluoride into the solution, and stirring the solution uniformly;
(3) transferring the mixed solution obtained in the step (2) to a reaction kettle for hydrothermal reaction;
(4) and naturally cooling to room temperature after the reaction is finished, washing the reaction solution with ethanol and water, and centrifuging to obtain a white product.
NaLuF for different rare earth ion doping concentrations4The synthesis of the micron rod only needs to adjust the corresponding feeding proportion of the rare earth acetate according to the doping concentration, and the synthesis steps and conditions are kept unchanged.
In the invention, the rare earth source is acetate, the fluorine source is ammonium fluoride, and trisodium citrate is used as a complexing agent in the synthesis process.
A second object of the present invention is to provide upconversion microparticles prepared by the above method, wherein the upconversion microparticles have the chemical formula: NaLuF4:Yb3+/A3+(A3+Is Er3+,Tm3+,Ho3+One of them).
The NaLuF of the invention4:Yb3+/A3+Up-conversion of micro-crystals: NaLuF4Denotes the substrate Yb3+Ions and A3+The ions being dopant ions which displace Lu in the matrix3+Position of ion in which Yb3+The ion doping concentration is more than 20 mol%.
The NaLuF of the invention4:Yb3+/A3+The size of the up-conversion micro-crystals is in the micron scale, the length of at least one direction is more than 2 μm, and the typical morphology is hexagonal prism with the length of about 20 μm.
The NaLuF of the invention4:Yb3+/A3+The up-conversion micro crystal can perform up-conversion luminescence, and under the excitation of near infrared light near 980nm, the characteristic emission peak of an activator ion is contained in the emission spectrum of the up-conversion micro crystal. For exampleNaLuF4:Yb3+/Er3+Upconversion nanocrystals can emit at central wavelengths around 410nm,520nm,540nm and 654 nm.
The third purpose of the invention is to provide the method for regulating and controlling the fluorescence lifetime of the upconversion microparticles, which is to fix the pulse width and the repetition frequency of the exciting light and only regulate the peak power density of the exciting light.
The laser with pulse width more than 1ms and repetition frequency lower than 100Hz and wavelength of 980nm is adopted to excite the sample, and the changed fluorescence lifetime can be obtained by changing the peak power density of the laser.
The invention has the following beneficial effects:
1. the invention provides a rare earth ion doped NaLuF4The micrometer rod can perform high-efficiency up-conversion luminescence, and the fluorescence lifetime of the micrometer rod can be regulated and controlled by adjusting the peak power density of exciting light.
2. The method for regulating and controlling the fluorescence lifetime is simple and feasible, and can realize the regulation and control of the fluorescence lifetime of the fixed material in a larger range.
3. In addition, the preparation method provided by the invention has the advantages of simple process, high yield, high product purity, uniform phase and the like.
4. Rare earth ion doped NaLuF obtained based on preparation method and fluorescence life regulation method provided by the invention4The micron rod is expected to realize high-level fluorescence anti-counterfeiting.
Drawings
FIG. 1 shows NaLuF of example 1 of the present invention4:Yb3+/Er3+(90/2 mol%) X-ray diffraction pattern of the micron rod;
FIG. 2 shows NaLuF of example 1 of the present invention4:Yb3+/Er3+(90/2 mol%) low power scanning electron microscope image of micrometer rod;
FIG. 3 shows NaLuF of example 1 of the present invention4:Yb3+/Er3+(90/2 mol%) fluorescence emission spectrum of the micron rod;
FIG. 4 shows NaLuF of example 1 of the present invention4:Yb3+/Er3+(90/2 mol%) fluorescence lifetime of the micrometer rodsHit the regulation and control results.
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples. These examples are to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. After reading the disclosure of the present invention, various changes or modifications made based on the principle of the present invention also fall within the scope of the present invention as defined in the appended claims. Meanwhile, the technical scheme of the invention is not limited to the specific embodiments listed below, and also comprises any combination of the reaction conditions of the specific embodiments; and is not limited to the specific reactants listed below, but also includes any combination of the same types of reagents of the same family.
Example 1
NaLuF synthesized in this embodiment4:Yb3+/Er3+(90/2 mol%) the method of preparing the micron rod is realized by the following steps:
(1) adding 0.16mL of 0.2mol/L lutetium acetate, 1.8mL of 0.2mol/L ytterbium acetate and 0.04mL of 0.2mol/L erbium acetate into 2mL of rare earth acetate aqueous solution, adding the aqueous solution into 8mL of aqueous solution containing 0.2mmol of trisodium citrate, and stirring for 15 min;
(2) 1mL of an aqueous solution containing 2.5mmol of ammonium fluoride was added to the above solution and stirred for 1 hour.
(3) Transferring the mixed solution into a 20mL polytetrafluoroethylene reaction kettle, reacting for 12h at 200 ℃,
(4) and naturally cooling to room temperature after the reaction is finished, washing the reaction solution with ethanol and water, centrifuging for 3 times, and drying the obtained white centrifugal product in a vacuum drying oven at 50 ℃ for 12 hours for later use.
This embodiment tests NaLuF as follows4:Yb3+/Er3+(90/2 mol%) fluorescence spectrum of the micron bar:
taking a proper amount of NaLuF4:Yb3+/Er3+(90/2 mol%) the micron rod solid powder is placed in a powder sample groove and fixed in a sample chamber of a fluorescence spectrometer;
setting the working mode of the 980nm laser to be continuous output and the power density to be 280W/cm2Setting the spectrumThe integration time of the instrument is 0.1ms, and the fluorescence emission spectrum is obtained through testing.
The NaLuF is regulated and controlled according to the following method4:Yb3+/Er3+(90/2 mol%) fluorescence lifetime of the nanorods:
taking a proper amount of NaLuF4:Yb3+/Er3+(90/2 mol%) the micron rod solid powder is placed in a powder sample groove and fixed in a sample chamber of a fluorescence spectrometer;
setting the pulse width of 980nm laser at 8ms, repetition frequency at 20Hz, and peak power density at 280W/cm2The test wavelength is 540nm, and a first fluorescence lifetime curve is obtained through testing;
setting the pulse width of 980nm laser at 8ms, repetition frequency at 20Hz, and peak power density at 2450W/cm2The test wavelength was 540nm, and a second fluorescence lifetime curve was obtained.
Example 2
NaLuF synthesized in this embodiment4:Yb3+/Ho3+(90/2 mol%) the method of preparing the micron rod is realized by the following steps:
(1) adding 0.16mL of 0.2mol/L lutetium acetate, 1.8mL of 0.2mol/L ytterbium acetate and 0.04mL of 0.2mol/L holmium acetate into 2mL of rare earth acetate aqueous solution, wherein the rare earth acetate aqueous solution is 8mL of aqueous solution containing 0.2mmol of trisodium citrate, and stirring for 15 min;
(2) 1mL of an aqueous solution containing 2.5mmol of ammonium fluoride was added to the above solution and stirred for 1 hour.
(3) Transferring the mixed solution into a 20mL polytetrafluoroethylene reaction kettle, reacting for 12h at 200 ℃,
(4) and naturally cooling to room temperature after the reaction is finished, washing the reaction solution with ethanol and water, centrifuging for 3 times, and drying the obtained white centrifugal product in a vacuum drying oven at 50 ℃ for 12 hours for later use.
This embodiment tests NaLuF as follows4:Yb3+/Ho3+(90/2 mol%) fluorescence spectrum of the micron bar:
taking a proper amount of NaLuF4:Yb3+/Ho3+(90/2 mol%) the micron rod solid powder is placed in a powder sample groove and fixed in a sample chamber of a fluorescence spectrometer;
setting the working mode of the 980nm laser to be continuous output and the power density to be 280W/cm2And setting the integration time of the spectrometer to be 0.1ms, and testing to obtain the fluorescence emission spectrum.
The NaLuF is regulated and controlled according to the following method4:Yb3+/Ho3+(90/2 mol%) fluorescence lifetime of the nanorods:
taking a proper amount of NaLuF4:Yb3+/Ho3+(90/2 mol%) the micron rod solid powder is placed in a powder sample groove and fixed in a sample chamber of a fluorescence spectrometer;
setting the pulse width of 980nm laser at 8ms, repetition frequency at 20Hz, and peak power density at 280W/cm2Testing to obtain a first fluorescence lifetime curve, wherein the testing wavelength is 545 nm;
setting the pulse width of 980nm laser at 8ms, repetition frequency at 20Hz, and peak power density at 2450W/cm2And the test wavelength is 545nm, and a second fluorescence lifetime curve is obtained through testing.
Example 3
NaLuF synthesized in this embodiment4:Yb3+/Tm3+(90/1 mol%) the method of preparing the micron rod is realized by the following steps:
(1) adding 0.18mL of 0.2mol/L lutetium acetate, 1.8mL of 0.2mol/L ytterbium acetate and 0.02mL of 0.2mol/L thulium acetate into 8mL of aqueous solution of rare earth acetate with 0.2mmol of trisodium citrate, and stirring for 15 min;
(2) 1mL of an aqueous solution containing 2.5mmol of ammonium fluoride was added to the above solution and stirred for 1 hour.
(3) Transferring the mixed solution into a 20mL polytetrafluoroethylene reaction kettle, reacting for 12h at 200 ℃,
(4) and naturally cooling to room temperature after the reaction is finished, washing the reaction solution with ethanol and water, centrifuging for 3 times, and drying the obtained white centrifugal product in a vacuum drying oven at 50 ℃ for 12 hours for later use.
This embodiment tests NaLuF as follows4:Yb3+/Tm3+(90/1 mol%) fluorescence spectrum of the micron bar:
taking a proper amount of NaLuF4:Yb3+/Tm3+(90/1 mol%) the micron rod solid powder is placed in a powder sample groove and fixed in a sample chamber of a fluorescence spectrometer;
the working mode of the 980nm laser is set as continuous output, and the power density is 400W/cm2And setting the integration time of the spectrometer to be 0.1ms, and testing to obtain the fluorescence emission spectrum.
The NaLuF is regulated and controlled according to the following method4:Yb3+/Tm3+(90/1 mol%) fluorescence lifetime of the nanorods:
taking a proper amount of NaLuF4:Yb3+/Tm3+(90/1 mol%) the micron rod solid powder is placed in a powder sample groove and fixed in a sample chamber of a fluorescence spectrometer;
setting the pulse width of 980nm laser at 8ms, repetition frequency at 20Hz, and peak power density at 400W/cm2The test wavelength is 475nm, and a first fluorescence lifetime curve is obtained through testing;
setting the pulse width of 980nm laser at 8ms, repetition frequency at 20Hz, and peak power density at 3000W/cm2And the test wavelength is 475nm, and a second fluorescence lifetime curve is obtained through testing.
Claims (7)
1. A method for preparing up-conversion microparticles is characterized in that: the method comprises the following steps:
(1) adding aqueous solution of acetate of lutetium acetate, ytterbium acetate and activator ions into aqueous solution of trisodium citrate, and stirring uniformly;
(2) adding an aqueous solution of ammonium fluoride into the solution, and stirring the solution uniformly;
(3) transferring the mixed solution obtained in the step (2) to a reaction kettle for hydrothermal reaction;
(4) and naturally cooling to room temperature after the reaction is finished, washing the reaction solution with ethanol and water, and centrifuging to obtain a white product.
2. The method of claim 1, wherein the upconversion microparticles are prepared by: the rare earth source is acetate, the fluorine source is ammonium fluoride, and trisodium citrate is used as a complexing agent in the synthesis process.
3. The method of claim 1 or 2 for making upconverting microparticles, wherein: the chemical formula of the upconversion microparticles is NaLuF4:Yb3+/A3+Wherein A is3+Is Er3+,Tm3+,Ho3+One kind of (1).
4. The upconverting microparticle according to claim 3, wherein: yb of3+The ion doping concentration is more than 20 mol%.
5. The upconverting microparticle according to claim 3, wherein: the length of at least one direction is more than 2 μm, and the typical appearance is hexagonal prism shape.
6. The method for controlling fluorescence lifetime of upconverting microparticles according to claim 3, wherein: the pulse width and repetition frequency of the excitation light are fixed and only the peak power density of the excitation light is adjusted.
7. The method for controlling fluorescence lifetime of upconverting microparticles according to claim 3, wherein: the pulse width of the exciting light is more than 1ms, and the repetition frequency is less than 100 Hz.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276809A (en) * | 2021-11-23 | 2022-04-05 | 盐城工学院 | Hexagonal phase NaREF with high yield and high up-conversion luminous intensity4Method for preparing micron crystal |
| CN114569741A (en) * | 2022-03-14 | 2022-06-03 | 中国人民解放军空军军医大学 | X-ray excitation type chemotherapy drug delivery system based on rare earth nanoparticles and application |
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| CN105713612A (en) * | 2016-01-19 | 2016-06-29 | 中山大学 | Up-conversion fluorescent powder with substantially increased red-green ratio and preparation method of up-conversion fluorescent powder with substantially increased red-green ratio |
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| CN105713612A (en) * | 2016-01-19 | 2016-06-29 | 中山大学 | Up-conversion fluorescent powder with substantially increased red-green ratio and preparation method of up-conversion fluorescent powder with substantially increased red-green ratio |
Non-Patent Citations (1)
| Title |
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| 邵华: "NaLuF4微米晶的合成及发光性能调变研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276809A (en) * | 2021-11-23 | 2022-04-05 | 盐城工学院 | Hexagonal phase NaREF with high yield and high up-conversion luminous intensity4Method for preparing micron crystal |
| CN114569741A (en) * | 2022-03-14 | 2022-06-03 | 中国人民解放军空军军医大学 | X-ray excitation type chemotherapy drug delivery system based on rare earth nanoparticles and application |
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Application publication date: 20200522 |