CN116515488B - Up-conversion luminescent material with double abrupt interfaces and preparation method thereof - Google Patents
Up-conversion luminescent material with double abrupt interfaces and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 96
- 229910004261 CaF 2 Inorganic materials 0.000 claims abstract description 66
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 28
- -1 rare earth ions Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 122
- 239000011259 mixed solution Substances 0.000 claims description 53
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 39
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 39
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 39
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000005642 Oleic acid Substances 0.000 claims description 39
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 39
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims description 24
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 23
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- RCPKXZJUDJSTTM-UHFFFAOYSA-L calcium;2,2,2-trifluoroacetate Chemical compound [Ca+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F RCPKXZJUDJSTTM-UHFFFAOYSA-L 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- VFRSADQPWYCXDG-LEUCUCNGSA-N ethyl (2s,5s)-5-methylpyrrolidine-2-carboxylate;2,2,2-trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.CCOC(=O)[C@@H]1CC[C@H](C)N1 VFRSADQPWYCXDG-LEUCUCNGSA-N 0.000 claims description 2
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- 239000013078 crystal Substances 0.000 abstract description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 34
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- 235000019441 ethanol Nutrition 0.000 description 21
- 238000010926 purge Methods 0.000 description 21
- 238000005406 washing Methods 0.000 description 21
- 229910052747 lanthanoid Inorganic materials 0.000 description 19
- 150000002602 lanthanoids Chemical class 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000011575 calcium Substances 0.000 description 13
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 9
- 230000035772 mutation Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
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- 238000010586 diagram Methods 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052691 Erbium Inorganic materials 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021266 NaErF4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- 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
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7732—Halogenides
- C09K11/7733—Halogenides with alkali or alkaline earth metals
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Abstract
The invention belongs to the technical field of luminescent materials, and discloses an up-conversion luminescent material with a double abrupt interface and a preparation method thereof. The structural formula of the material is CaF 2@NaReF4@CaF2, and the particle size of the material is 4 nm-100 nm. The invention also discloses a preparation method of the luminescent material, which comprises the following steps: s1, preparing precursor solutions of CaF 2 nano-particles and NaReF 4 shell layers respectively; s2, preparing CaF 2@NaReF4 nano-particles; s3, preparing a precursor solution of the CaF 2 shell, adding the CaF 2@NaReF4 nano particles prepared in the step S2 into the solution of the epitaxial growth CaF 2 shell, stirring and mixing uniformly, heating, preserving heat, cooling to room temperature, adding an organic solvent into the reaction solution, then centrifuging, and obtaining the required CaF 2@NaReF4@CaF2 luminescent material after centrifuging. According to the invention, surface quenching is inhibited, abrupt interfaces are formed between the active layer and the inner and outer inert layers to inhibit the migration of rare earth ions, and luminescence quenching caused by crystal defects and long-distance energy migration is reduced.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to an up-conversion luminescent material with a double-abrupt interface and a preparation method thereof.
Background
In recent years, rare earth doped up-conversion nanoparticles have been attracting attention due to their excellent spectral characteristics such as rich emission levels, long lifetime emission, and narrow bandwidth. It is because of these unique properties that make them potentially useful in many fields such as bioimaging, biosensing, information storage, security anti-counterfeiting, biomedical and super-resolution display technologies, but they are limited by their luminous intensity and luminous efficiency, which makes it difficult to obtain practical commercial applications. Therefore, the improvement of the up-conversion luminous efficiency is a key to the application of the up-conversion luminous efficiency and is always a hot spot for the study of the students in the field.
The core-shell structure (multi-layer structure) is one of the most widely applied and effective ways to improve the practical strategy of lanthanide nanoparticles, and with the significant progress made in the past few years, a number of new excitation and detection platforms can be used to characterize up-conversion nanoparticles, greatly enhancing our regulatory capability for photon up-conversion. Because of the importance of single-shell or multi-shell up-conversion architectures, a comprehensive understanding of their "structure-attribute" relationships is critical to their further successful development and deployment. In particular, the chemical and structural features of core-shell (multi-layer) nanoparticles are necessary to correctly interpret their upconverting properties and ultimately pave the way for rational design of more efficient upconverting architecture. It is therefore desirable to synthesize multilayered structured nanoparticles with sharp interfaces. The method has important guiding effect on the future synthesis of high-performance and high-quality lanthanide nanoparticles and the further development of the application value of the lanthanide nanoparticles with the multilayer structure in various fields.
The synthesis method related to the patent CN106995701A is a hydrothermal method, and the synthesized nano-particle has a simple structure, is a co-doped structure and has lower luminous efficiency. The hydrothermal method for synthesizing the nano particles takes a long time, is unfavorable for rapid mass preparation, and has relatively uncontrollable size. The material of patent CN108384547B focuses on the spatial isolation between different rare earth ions, for example, er 3+ and Yb 3+ in NaErF 4@NaYbF4@NaYF4 are respectively located in two adjacent layers of the nanoparticle, the preparation process is uncontrollable due to the need of doping rare earth ions between different layers and the high doping amount of rare earth ions, and the preparation process is more complicated due to the complex composition of NaReF 4 nanoparticle, more raw materials and operation steps are needed for NaReF 4 nanoparticle with a multilayer structure.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides an up-conversion luminescent material with a double-abrupt interface and a preparation method thereof, and solves the technical problem of diffusion of rare earth ions at an interlayer interface in rare earth luminescent nano particles with a multilayer structure.
In order to achieve the above object, according to one aspect of the present invention, there is provided an up-conversion luminescent material having a double abrupt interface, wherein the material has a structural formula CaF 2@NaReF4@CaF2 and a particle size of 4nm to 100nm.
Further preferably, the Re is one or more of La, yb, er, ce, pr, nd, eu, gd, tb, dy, ho, tm, lu or Y atoms.
According to another aspect of the present invention, there is provided a method for producing the above-mentioned luminescent material, characterized in that the method comprises the steps of:
s1, preparing CaF 2 nano particles and NaReF 4 solution respectively;
S2, adding the CaF 2 nano particles into the NaReF 4 solution, uniformly stirring and mixing, heating, preserving heat, cooling to room temperature to obtain a reaction solution, adding an organic solvent into the reaction solution, then centrifuging, and obtaining a layer of NaReF 4 nano particles coated on the surface of CaF 2, namely CaF 2@NaReF4 nano particles;
S3, preparing CaF 2 solution, adding CaF 2@NaReF4 nano particles prepared in the step S3 into the CaF 2 solution, stirring and mixing uniformly, heating, preserving heat, cooling to room temperature to obtain reaction liquid, adding an organic solvent into the reaction liquid, centrifuging, and obtaining the required CaF 2@NaReF4@CaF2 luminescent material after centrifuging.
Further preferably, in step S1, the CaF 2 nanoparticles are performed according to the following steps:
S11, selecting calcium salt, adding the calcium salt into an organic solvent, and uniformly mixing and stirring;
S12, heating, preserving heat and cooling to room temperature to obtain a reaction solution;
And S13, adding an organic solvent into the reaction solution, centrifuging, and centrifuging to obtain the CaF 2 nano-particles.
Further preferably, in step S11, the calcium salt is one or more of calcium acetate, calcium trifluoroacetate, calcium chloride and calcium nitrate.
Further preferably, the heating temperature in the steps S12, S2 and S3 is 260-320 ℃, and the temperature is kept for 15-70 min.
Further preferably, after the steps S11, S2 and S3 are uniformly mixed and stirred, preheating the solution to remove residual low boiling point compounds in the solution, wherein the preheating temperature in the step S11 is 100-160 ℃, and the preheating temperature in the steps S2 and S3 is 90-100 ℃; in steps S13, S2 and S3, the centrifugation is performed at a rotational speed of 5000 rpm to 13500 rpm for 3 to 30 minutes.
Further preferably, in step S1, the precursor solution of NaReF 4 shells is prepared according to the following method: and selecting rare earth soluble salt, a sodium source, a fluorine source and an organic solvent, stirring and mixing, and heating to remove low-boiling-point compounds, thereby obtaining NaLnF 4 solution.
Further preferably, the rare earth-soluble salt includes one or more of a rare earth acetate salt, a rare earth trifluoroacetate salt, a rare earth chloride salt, and a rare earth nitrate salt; the sodium source is one or more of sodium hydroxide, sodium fluoride, sodium chloride, sodium acetate and sodium trifluoroacetate; the fluorine source is one or more of ammonium fluoride, lithium fluoride, potassium fluoride, sodium fluoride and sodium trifluoroacetate.
Further preferably, the precursor solution of the CaF 2 shell layer is performed according to the following steps: firstly, preparing a soluble salt solution of CaF 2, then adding the soluble salt solution into oleic acid and octadecene to be mixed to form a mixed solution, and finally continuously stirring the mixed solution under a protective atmosphere and heating the solution at 100-160 ℃ to form a transparent lanthanide oleic acid precursor solution, namely a precursor solution of a required CaF 2 shell layer.
In general, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
1. The luminescent material provided by the invention has no ion diffusion between layers on the interface between two CaFs 2 and NaReF 4, has a clear interface and mainly comprises two reasons, namely, firstly, the valence of calcium ions is different from that of rare earth ions; secondly, the crystal structures of two adjacent layers are different, so that ion migration is difficult to occur between the layers in the growth process; taking CaF 2@NaYbF4:Er@CaF2 as an example, the specific expression is: the elemental distribution of Yb 3+ and Er 3+ of the Er layer in the nanoparticle has a tendency to suddenly decrease at the interface of NaYbF 4:er and CaF 2, that is, yb 3+ and Er 3+ do not diffuse into CaF 2 layer;
2. According to the invention, caF 2 with a crystal structure similar to that of a cubic phase NaReF 4 is used as an inner inert layer and an outer inert layer of the up-conversion nano-particle, so that on one hand, surface quenching is inhibited, and on the other hand, a mutation interface is formed between the active layer and the inner inert layer and the outer inert layer to inhibit rare earth ion migration, so that crystal defects and luminescence quenching caused by long-distance energy migration are reduced; under the near infrared excitation of 980nm, the emission color of the fluorescent lamp can be adjusted in the range from green light to red light;
3. Re of the present invention includes a total of 15 lanthanoids (La-Lu) and 2 group IIIB elements (Sc and Y). Because the crystal structures of the cubic phases NaReF 4 are almost consistent, abrupt interfaces can be formed between different NaReF 4 and CaF 2;
4. The luminescent material has stable luminescent property and chemical property, and the up-conversion luminous efficiency is improved by 10 times compared with NaYF 4@NaYbF4:Er@NaYF4 with the same structure under the near infrared excitation of 980nm, and the emission color of the luminescent material can be adjusted in the range from green light to red light. The synthesis method provided by the invention is simple, has strong anti-interference performance and universality, and is an efficient up-conversion luminescence strategy.
Drawings
FIG. 1 is a flow chart of a method for preparing an up-conversion luminescent material with a double abrupt interface constructed in accordance with a preferred embodiment of the present invention;
FIG. 2 is a high angle annular dark field image schematic of a prepared CaF 2@NaYbF4:Er@CaF2 constructed in accordance with preferred embodiment 1 of the present invention;
FIG. 3 is an XRD pattern for prepared CaF 2、CaF2@NaYbF4: er and CaF 2@NaYbF4:Er@CaF2 constructed in accordance with preferred embodiment 1 of the present invention;
FIG. 4 is an up-conversion emission spectrum of prepared CaF 2@NaYbF4:Er@CaF2 and reference NaYF 4@NaYbF4:Er@NaYF4 constructed in accordance with a preferred embodiment of the invention;
FIG. 5 is a chemical element profile of a prepared CaF 2@NaYbF4:Er@CaF2 constructed in accordance with alternative example 1 of the present invention, wherein (a) is a TEM image of nanoparticles under dark field image and (b) is an element profile on the white tip path in the TEM image;
FIG. 6 is an EDS-mapping of prepared CaF 2@NaYbF4:Er@CaF2 constructed in accordance with preferred embodiment 1 of the present invention, wherein (a) is a HAADF-STEM image; (b) The element distribution diagram of F, ca, er and Yb, (c) the element distribution diagram of F, (d) the element distribution diagram of Ca, (e) the element distribution diagram of Yb, and (F) the element distribution diagram of Er.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The rare earth up-conversion luminescent material provided by the invention is a photoluminescence sandwich structure (three layers) nanoparticle. The structural formula of the material is CaF 2@NaReF4@CaF2, and the up-conversion luminescent material with the double abrupt interface has an average particle size of 4-100 nm.
As shown in fig. 1, the present invention further provides a preparation method of the up-conversion luminescent material with the double abrupt interface, which specifically includes the following steps:
s1 preparation of CaF 2 nanoparticles and NaReF 4 solution respectively
Preparation of CaF 2 nanoparticles by S11
(1) Adding a soluble salt solution of CaF 2 into a 50ml three-necked flask containing a mixed solution of oleylamine, oleic acid and octadecene, continuously stirring the mixed solution under argon atmosphere, and heating the solution at 100-160 ℃ to remove water and oxygen in the water to form a transparent lanthanide oleic acid precursor solution;
(2) Heating the reaction solution obtained in the step (1) to 260-320 ℃ under the atmosphere of argon continuous purging, preserving heat for 15-70 min, and then cooling the reaction solution to room temperature; the temperature range of 260 c to 320 c is a suitable range for forming nanoparticles, where the higher the temperature, the smaller the nanoparticle size. Too high a temperature may not be controllable and too low a temperature may not be possible. The time required for the reaction to proceed is 15 to 70 minutes, and the use of the catalyst is widely known. The incubation time is in this range, so that the reaction can be fully carried out, the crystallinity of the nano-particles is reduced when the time is too short, and the nano-particles can be dissolved when the time is too long. (3) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (2), putting the mixed solution into a centrifuge tube for centrifugation, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol;
s12 preparation NaReF 4 solution
(4) Adding sodium source, fluorine source, oleic acid, oleylamine and octadecene into the corresponding rare earth soluble salt mixed solution required for preparing NaReF 4 layers, and continuously stirring and heating under argon atmosphere to remove low-boiling-point compounds; under argon atmosphere because the reaction needs to be in an oxygen-free environment.
S2 preparation of CaF 2@NaReF4 nano-particles
(5) Adding the nano particles in the step (3) into the solution prepared in the step (4), and uniformly stirring; then heating to 90-100 ℃ to remove residual low boiling point compounds;
(6) Heating the solution obtained in the step (5) to 260-320 ℃ under the atmosphere of argon continuous purging, preserving heat for 15-70 min, and then cooling the reaction solution to room temperature;
(7) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (6), putting the mixed solution into a centrifuge tube for centrifugation, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol; dispersing the prepared nano particles in an organic solvent for standby.
S3 preparation of CaF 2@NaReF4@CaF2 luminescent material
(8) Adding the soluble salt solution for preparing CaF 2 into a 50ml three-necked flask containing oleic acid and octadecene mixed solution, continuously stirring the mixed solution under argon atmosphere, and heating the solution at 100-160 ℃ to form transparent lanthanide oleic acid precursor solution;
(9) Adding the nano particles in the step (7) into the solution prepared in the step (8), and uniformly stirring; then heating to 90-100 ℃ to remove residual low boiling point compounds;
(10) Heating the solution obtained in the step (9) to 260-320 ℃ under the atmosphere of argon continuous purging, preserving heat for 15-70 min, and then cooling the reaction solution to room temperature;
(11) And (3) adding absolute ethyl alcohol into the reaction liquid obtained in the step (10), putting the mixed solution into a centrifuge tube for centrifugation, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol to obtain the rare earth up-conversion nano material with the double mutation interface.
Further, in step (1) and step (8), the corresponding soluble salt of CaF 2 layer comprises one or more of calcium acetate, calcium trifluoroacetate, calcium chloride and calcium nitrate.
Further, in the step (1), the step (4) and the step (8), the organic solvent is one or more of oleic acid, oleylamine and octadecene.
Further, in the step (1), the step (4), the step (5), the step (9) and the step (10), the heating time is 20-70 min.
Sufficient heating time is required to complete the reaction.
Further, in the step (3), the step (7) and the step (11), the centrifugation is carried out for 3 to 30 minutes at a rotational speed of 5000 to 13500 rpm. The rotational speed and the centrifugation time are both for the purpose of collecting the sample as completely as possible. Since the nanoparticles have different sizes, the rotational speed required to separate the nanoparticles is also different, and the smaller the nanoparticle size, the higher the rotational speed required, and the longer the time required for centrifugation.
Further, the sodium source in step (4) is one or more of sodium hydroxide, sodium fluoride, sodium chloride, sodium acetate and sodium trifluoroacetate.
Further, in the step (4), the fluorine source is one or more of ammonium fluoride, lithium fluoride, potassium fluoride, sodium fluoride and sodium trifluoroacetate.
Further, in the step (4), the NaReF 4 layers of the corresponding rare earth soluble salt include one or more of rare earth acetate, rare earth trifluoroacetate, rare earth greening salt and rare earth nitrate.
The low boiling point compound is removed because water and cyclohexane in the precursor solution need to be removed in advance before the high temperature reaction in order to stabilize the reaction. (these low boiling compounds would otherwise explode at high temperatures). The temperature range of 100 deg.c to 160 deg.c is chosen because the low boiling compounds contain water, while too high a temperature may react the precursor.
The invention will be further illustrated with reference to specific examples.
Example 1
Synthesis of CaF 2@NaYbF4:Er@CaF2 with particle size of 10 nm:
(1) An aqueous solution containing 1mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing a mixed solution of 6ml oleylamine, 4ml oleic acid and 10ml octadecene, then the mixed solution was stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(2) Heating the reaction solution obtained in the step (1) to 280 ℃ under the atmosphere of argon continuous purging, preserving heat for 60min, and then cooling the reaction solution to room temperature;
(3) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (2), putting the mixed solution into a centrifuge tube, centrifuging for 3 minutes at the rotating speed of 11000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times;
(4) An aqueous solution containing 0.98mmol Yb (CF 3COO)3 and 0.02mmol Er (CF 3COO)3), 1mmol sodium hydroxide, 8ml oleic acid, 8ml octadecene was taken, stirred continuously and heated to 150 ℃ under argon atmosphere to remove low boiling compounds;
(5) Adding the nano particles in the step (3) into the solution prepared in the step (4), and uniformly stirring; and then heated to 90 ℃ to remove residual low boiling compounds;
(6) Heating the solution obtained in the step (5) to 280 ℃ under the atmosphere of argon continuous purging, preserving heat for 15min, and then cooling the reaction solution to room temperature;
(7) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (6), putting the mixed solution into a centrifuge tube, centrifuging for 3 minutes at the rotating speed of 11000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol; the prepared nano particles are dispersed in cyclohexane for the next growth.
(8) An aqueous solution containing 1.5mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing 8ml oleic acid and 8ml octadecene mixed solution, the mixed solution was then stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(9) Adding the nano particles in the step (7) into the solution prepared in the step (8), and uniformly stirring; and then heated to 90 ℃ to remove residual low boiling compounds;
(10) Heating the solution obtained in the step (9) to 280 ℃ under the atmosphere of argon continuous purging, preserving heat for 60min, and then cooling the reaction solution to room temperature;
(11) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (10), putting the mixed solution into a centrifuge tube, centrifuging for 3 minutes at the rotating speed of 11000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times; dispersing the prepared nano particles in cyclohexane to obtain the rare earth up-conversion nano material with a mutation interface.
Example 2
Synthesis of CaF 2@NaYbF4:Tm@CaF2 with particle size of 20 nm:
(1) An aqueous solution containing 1mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing 2ml of oleylamine, 8ml of oleic acid and 10ml of octadecene mixed solution, and then the mixed solution was stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(2) Heating the reaction solution obtained in the step (1) to 290 ℃ under the atmosphere of argon continuous purging, preserving heat for 45min, and then cooling the reaction solution to room temperature;
(3) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (2), putting the mixed solution into a centrifuge tube, centrifuging for 30 minutes at a rotating speed of 13500 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times;
(4) Taking an aqueous solution containing 2mmol Yb (CF 3COO)3 and 0.5mmol Tm (CF 3COO)3), adding 3mmol sodium hydroxide, 8ml oleic acid, 8ml octadecene, stirring continuously and heating to 100 ℃ under argon atmosphere to remove low boiling compounds;
(5) Adding the nano particles in the step (3) into the solution prepared in the step (4), and uniformly stirring; and then heated to 95 ℃ to remove residual low boiling compounds;
(6) Heating the solution obtained in the step (5) to 290 ℃ under the atmosphere of argon continuous purging, preserving heat for 60min, and then cooling the reaction solution to room temperature;
(7) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (6), putting the mixed solution into a centrifuge tube, centrifuging for 25 minutes at a rotating speed of 13500 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol; the prepared nano particles are dispersed in cyclohexane for the next growth.
(8) An aqueous solution containing 5mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing 8ml oleic acid and 8ml octadecene mixed solution, the mixed solution was then stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(9) Adding the nano particles in the step (7) into the solution prepared in the step (8), and uniformly stirring; and then heated to 95 ℃ to remove residual low boiling compounds;
(10) Heating the solution obtained in the step (9) to 290 ℃ under the atmosphere of argon continuous purging, preserving heat for 30min, and then cooling the reaction solution to room temperature;
(11) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (10), putting the mixed solution into a centrifuge tube, centrifuging for 30 minutes at the rotating speed of 13000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times; dispersing the prepared nano particles in cyclohexane to obtain the rare earth up-conversion nano material with a mutation interface.
Example 3
Synthesis of CaF 2@NaYbF4:Nd@CaF2 with particle size of 100 nm:
(1) A 50ml three-necked flask containing 5ml of oleylamine, 8ml of oleic acid and 10ml of octadecene was charged with an aqueous solution containing 1mmol of Ca (CH 3COO)2 and 1mmolNH 4 F), and then the mixed solution was continuously stirred under argon atmosphere for 30min and the solution was heated at 160 ℃ to form a transparent lanthanide oleic acid precursor solution;
(2) Heating the reaction solution obtained in the step (1) to 320 ℃ under the atmosphere of argon continuous purging, preserving heat for 15min, and then cooling the reaction solution to room temperature;
(3) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (2), putting the mixed solution into a centrifuge tube, centrifuging for 25 minutes at the rotating speed of 12000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times;
(4) An aqueous solution containing 8mmol of Yb (CF 3COO)3 and 1mmol of Nd (CF 3COO)3), 6mmol of sodium hydroxide, 8ml of oleic acid, 8ml of octadecene were added, and stirring was continued with an open mouth under argon atmosphere and heated to 120 ℃ to remove low boiling compounds;
(5) Adding the nano particles in the step (3) into the solution prepared in the step (4), and uniformly stirring; and then heated to 100 ℃ to remove residual low boiling compounds;
(6) Heating the solution obtained in the step (5) to 320 ℃ under the atmosphere of argon continuous purging, preserving heat for 50min, and then cooling the reaction solution to room temperature;
(7) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (6), putting the mixed solution into a centrifuge tube, centrifuging for 30 minutes at the rotating speed of 12000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol; the prepared nano particles are dispersed in cyclohexane for the next growth.
(8) An aqueous solution containing 15mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing 8ml oleic acid and 8ml octadecene mixed solution, the mixed solution was then stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(9) Adding the nano particles in the step (7) into the solution prepared in the step (8), and uniformly stirring; and then heated to 100 ℃ to remove residual low boiling compounds;
(10) Heating the solution obtained in the step (9) to 320 ℃ under the atmosphere of argon continuous purging, preserving heat for 20min, and then cooling the reaction solution to room temperature;
(11) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (10), putting the mixed solution into a centrifuge tube, centrifuging for 20 minutes at the rotating speed of 12000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times; dispersing the prepared nano particles in cyclohexane to obtain the rare earth up-conversion nano material with a mutation interface.
Example 4
Synthesis of CaF 2@NaErF4@CaF2 with particle size of 4 nm:
(1) An aqueous solution containing 1mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing a mixed solution of 6ml oleylamine, 4ml oleic acid and 10ml octadecene, then the mixed solution was stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(2) Heating the reaction solution obtained in the step (1) to 260 ℃ under the atmosphere of argon continuous purging, preserving heat for 70min, and then cooling the reaction solution to room temperature;
(3) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (2), putting the mixed solution into a centrifuge tube, centrifuging for 5 minutes at a rotation speed of 5000 rpm, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times;
(4) An aqueous solution containing 0.2mmol Er (CF 3COO)3, 1mmol sodium hydroxide, 8ml oleic acid, 8ml octadecene was taken, stirred continuously and heated to 150℃under argon atmosphere to remove low boilers;
(5) Adding the nano particles in the step (3) into the solution prepared in the step (4), and uniformly stirring; and then heated to 95 ℃ to remove residual low boiling compounds;
(6) Heating the solution obtained in the step (5) to 260 ℃ under the atmosphere of argon continuous purging, preserving heat for 30min, and then cooling the reaction solution to room temperature;
(7) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (6), putting the mixed solution into a centrifuge tube, centrifuging for 20 minutes at a rotation speed of 5000 rpm, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol; the prepared nano particles are dispersed in cyclohexane for the next growth.
(8) An aqueous solution containing 0.5mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing 8ml oleic acid and 8ml octadecene mixed solution, the mixed solution was then stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(9) Adding the nano particles in the step (7) into the solution prepared in the step (8), and uniformly stirring; and then heated to 95 ℃ to remove residual low boiling compounds;
(10) Heating the solution obtained in the step (9) to 260 ℃ under the atmosphere of argon continuous purging, preserving heat for 15min, and then cooling the reaction solution to room temperature;
(11) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (10), putting the mixed solution into a centrifuge tube, centrifuging for 10 minutes at a rotation speed of 5000 rpm, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times; dispersing the prepared nano particles in cyclohexane to obtain the rare earth up-conversion nano material with a mutation interface.
Example 5
Synthesis of CaF 2@NaEuF4@CaF2 with particle size of 30 nm:
(1) An aqueous solution containing 1mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing a mixed solution of 6ml oleylamine, 4ml oleic acid and 10ml octadecene, then the mixed solution was stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(2) Heating the reaction solution obtained in the step (1) to 300 ℃ under the atmosphere of argon continuous purging, preserving heat for 30min, and then cooling the reaction solution to room temperature;
(3) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (2), putting the mixed solution into a centrifuge tube, centrifuging for 10 minutes at the rotating speed of 9000 rpm, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times;
(4) Taking an aqueous solution containing 2mmol Eu (CF 3COO)3, adding 2mmol sodium hydroxide, 8ml oleic acid, 8ml octadecene, stirring continuously and heating to 140℃under argon atmosphere to remove low boiling compounds;
(5) Adding the nano particles in the step (3) into the solution prepared in the step (4), and uniformly stirring; and then heated to 90 ℃ to remove residual low boiling compounds;
(6) Heating the solution obtained in the step (5) to 300 ℃ under the atmosphere of argon continuous purging, preserving heat for 40min, and then cooling the reaction solution to room temperature;
(7) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (6), putting the mixed solution into a centrifuge tube, centrifuging for 10 minutes at the rotating speed of 9000 rpm, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol; the prepared nano particles are dispersed in cyclohexane for the next growth.
(8) An aqueous solution containing 5mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing 8ml oleic acid and 8ml octadecene mixed solution, the mixed solution was then stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(9) Adding the nano particles in the step (7) into the solution prepared in the step (8), and uniformly stirring; and then heated to 90 ℃ to remove residual low boiling compounds;
(10) Heating the solution obtained in the step (9) to 300 ℃ under the atmosphere of argon continuous purging, preserving heat for 40min, and then cooling the reaction solution to room temperature;
(11) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (10), putting the mixed solution into a centrifuge tube, centrifuging for 5 minutes at the rotating speed of 9000 rpm, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times; dispersing the prepared nano particles in cyclohexane to obtain the rare earth up-conversion nano material with a mutation interface.
Example 6
Synthesis of CaF 2@NaGdF4@CaF2 with particle size of 50 nm:
(1) An aqueous solution containing 1mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing a mixed solution of 6ml oleylamine, 4ml oleic acid and 10ml octadecene, then the mixed solution was stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(2) Heating the reaction solution obtained in the step (1) to 310 ℃ under the atmosphere of argon continuous purging, preserving heat for 70min, and then cooling the reaction solution to room temperature;
(3) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (2), putting the mixed solution into a centrifuge tube, centrifuging for 20 minutes at the speed of 13000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times;
(4) Taking an aqueous solution containing 5mmol Gd (CF 3COO)3, adding 2mmol sodium hydroxide, 8ml oleic acid, 8ml octadecene, stirring continuously and heating to 160 ℃ under argon atmosphere to remove low boiling compounds;
(5) Adding the nano particles in the step (3) into the solution prepared in the step (4), and uniformly stirring; and then heated to 95 ℃ to remove residual low boiling compounds;
(6) Heating the solution obtained in the step (5) to 310 ℃ under the atmosphere of argon continuous purging, preserving heat for 20min, and then cooling the reaction solution to room temperature;
(7) Adding absolute ethyl alcohol into the reaction liquid obtained in the step (6), putting the mixed solution into a centrifuge tube, centrifuging for 5 minutes at the speed of 13000 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol; the prepared nano particles are dispersed in cyclohexane for the next growth.
(8) An aqueous solution containing 10mmol Ca (CF 3COO)2) was added to a 50ml three-necked flask containing 8ml oleic acid and 8ml octadecene mixed solution, the mixed solution was then stirred continuously under argon atmosphere for 30min and the solution was heated at 160℃to form a transparent lanthanide oleic acid precursor solution;
(9) Adding the nano particles in the step (7) into the solution prepared in the step (8), and uniformly stirring; and then heated to 95 ℃ to remove residual low boiling compounds;
(10) Heating the solution obtained in the step (9) to 310 ℃ under the atmosphere of argon continuous purging, preserving heat for 70min, and then cooling the reaction solution to room temperature;
(11) Adding excessive absolute ethyl alcohol into the reaction liquid obtained in the step (10), putting the mixed solution into a centrifuge tube, centrifuging for 3 minutes at a rotating speed of 13500 r/min, and finally washing the obtained nano particles with cyclohexane and ethyl alcohol for three times; dispersing the prepared nano particles in cyclohexane to obtain the rare earth up-conversion nano material with a mutation interface.
Fig. 2 is a high angle annular dark field photograph of CaF 2@NaYbF4:Er@CaF2 prepared in example 1. It can be seen that the nanoparticles are uniform in size and monodisperse, showing a distinct sandwich structure.
XRD measurements were performed on CaF 2、CaF2@NaYbF4:Er、CaF2@NaYbF4:Er@CaF2 prepared in example 1, respectively, and as shown in FIG. 3, it was seen that the half-widths of XRD diffraction peaks of the corresponding nanoparticles gradually decreased as different shell layers were grown.
As shown in fig. 4, the up-converted emission spectrum of CaF 2@NaYbF4:Er@CaF2 prepared in example 1 was tested under 980nm laser excitation, and compared with the up-converted emission of the reference NaYF 4@NaYbF4:Er@NaYF4, the up-converted emission intensity of CaF 2@NaYbF4:Er@CaF2 was found to be 10 times that of NaYF 4@NaYbF4:Er@NaYF4;
FIG. 5 is an EDXS/STEM line profile chemical concentration profile analysis of CaF 2@NaYbF4:2％Er@CaF2 core-shell nanoparticles of example 1, with white arrows indicating the EDXS scanning direction.
FIG. 6 is a core-shell nanoparticle elemental distribution of CaF 2@NaYbF4:2％Er@CaF2 prepared in example 1, showing that the CaF 2 layer is significantly bounded by a NaYbF 4:2% Er layer.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. An up-conversion luminescent material with a double abrupt interface is characterized in that the structural formula of the material is CaF 2@NaReF4@CaF2, and the particle size of the material is 4 nm-100 nm; the Re is one or more of Yb, er, nd, eu, gd and Tm.
2. A method of producing a luminescent material as claimed in claim 1, characterized in that the method comprises the steps of:
S1, preparing precursor solutions of CaF 2 nano-particles and NaReF 4 shell layers respectively;
S2, adding the CaF 2 nano particles into the precursor solution of the NaReF 4 shell layer, uniformly stirring and mixing, heating, preserving heat, cooling to room temperature to obtain a reaction solution, adding an organic solvent into the reaction solution, and then centrifuging to obtain a layer of NaReF 4 nano particles, namely CaF 2@NaReF4 nano particles, coated on the surface of CaF 2;
S3, preparing a precursor solution of the CaF 2 shell, adding the CaF 2@NaReF4 nano particles prepared in the step S2 into the precursor solution of the CaF 2 shell, stirring and mixing uniformly, heating, preserving heat, cooling to room temperature to obtain a reaction solution, adding an organic solvent into the reaction solution, centrifuging, and obtaining the required CaF 2@NaReF4@CaF2 luminescent material after centrifuging.
3. The method of claim 2, wherein in step S1, the CaF 2 nanoparticles are prepared according to the following steps:
s11, selecting calcium salt, adding the calcium salt into an organic solvent, and uniformly mixing and stirring;
S12, heating, preserving heat and cooling to room temperature to obtain a reaction solution;
S13, adding an organic solvent into the reaction liquid, centrifuging, and centrifuging to obtain CaF 2 nano particles.
4. The method of claim 3, wherein in step S11, the calcium salt is one or more of calcium acetate, calcium trifluoroacetate, calcium chloride, and calcium nitrate.
5. The method according to claim 3, wherein the heating temperature in steps S12, S2 and S3 is 260℃to 320℃and the temperature is kept for 15min to 70min.
6. The preparation method according to claim 3, wherein after the steps S11, S2 and S3 are uniformly mixed and stirred, preheating the solution to remove residual low boiling point compounds in the solution, wherein the preheating temperature in the step S11 is 100-160 ℃, and the preheating temperature in the steps S2 and S3 is 90-100 ℃; in steps S13, S2 and S3, the centrifugation is performed at a rotational speed of 5000 rpm to 13500 rpm for 3 to 30 minutes.
7. The method according to claim 2, wherein in step S1, the precursor solution of NaReF 4 shell is prepared according to the following method: and selecting rare earth soluble salt, a sodium source, a fluorine source and an organic solvent, stirring and mixing, and heating to remove low-boiling-point compounds, thereby obtaining NaReF 4 solution.
8. The method of preparing of claim 7, wherein the rare earth soluble salt comprises one or more of a rare earth acetate salt, a rare earth trifluoroacetate salt, a rare earth chloride salt, and a rare earth nitrate salt; the sodium source is one or more of sodium hydroxide, sodium fluoride, sodium chloride, sodium acetate and sodium trifluoroacetate; the fluorine source is one or more of ammonium fluoride, lithium fluoride, potassium fluoride, sodium fluoride and sodium trifluoroacetate.
9. The method of claim 2, wherein the precursor solution of CaF 2 shell is prepared by the steps of: firstly, preparing a soluble salt solution of CaF 2, then adding the soluble salt solution into oleic acid and octadecene to be mixed to form a mixed solution, and finally continuously stirring the mixed solution under a protective atmosphere and heating the solution at 100-160 ℃ to form a transparent precursor solution, namely a precursor solution of a required CaF 2 shell layer.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107815302A (en) * | 2016-09-14 | 2018-03-20 | 首都师范大学 | A kind of rare earth up-conversion luminescence nanomaterial of controlledly synthesis core shell structure and preparation method and application |
| CN107828408A (en) * | 2017-10-12 | 2018-03-23 | 复旦大学 | The lower conversion nano fluorescence probe of the window of near-infrared second transmitting and its synthetic method |
| CN108956556A (en) * | 2018-05-18 | 2018-12-07 | 复旦大学 | A kind of luminescence probe and time-resolved fluorescence detection system |
| CN111808604A (en) * | 2020-07-16 | 2020-10-23 | 吉林大学 | Method for preparing orthogonal excitation-emission response three-primary-color up-conversion luminescent material |
| CN112300801A (en) * | 2020-11-16 | 2021-02-02 | 哈尔滨工业大学 | Non-contact ultralow-temperature sensing up-conversion nano probe and preparation method and application thereof |
| CN113817469A (en) * | 2021-10-19 | 2021-12-21 | 南京林业大学 | Ultra-bright monochromatic up-conversion nano probe for excitation/emission in biological window and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107815302A (en) * | 2016-09-14 | 2018-03-20 | 首都师范大学 | A kind of rare earth up-conversion luminescence nanomaterial of controlledly synthesis core shell structure and preparation method and application |
| CN107828408A (en) * | 2017-10-12 | 2018-03-23 | 复旦大学 | The lower conversion nano fluorescence probe of the window of near-infrared second transmitting and its synthetic method |
| CN108956556A (en) * | 2018-05-18 | 2018-12-07 | 复旦大学 | A kind of luminescence probe and time-resolved fluorescence detection system |
| CN111808604A (en) * | 2020-07-16 | 2020-10-23 | 吉林大学 | Method for preparing orthogonal excitation-emission response three-primary-color up-conversion luminescent material |
| CN112300801A (en) * | 2020-11-16 | 2021-02-02 | 哈尔滨工业大学 | Non-contact ultralow-temperature sensing up-conversion nano probe and preparation method and application thereof |
| CN113817469A (en) * | 2021-10-19 | 2021-12-21 | 南京林业大学 | Ultra-bright monochromatic up-conversion nano probe for excitation/emission in biological window and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Dual-Mode Upconversion Nanoprobe Enables Broad-Range Thermometry from Cryogenic to Room Temperature;Yunfei Shang等;《ACS Applied Materials & Interfaces》;第11卷;第42455-42461页 * |
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