CN113088288A - Rare earth fluorescent material with high quantum yield and preparation method thereof - Google Patents

Rare earth fluorescent material with high quantum yield and preparation method thereof Download PDF

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CN113088288A
CN113088288A CN202110375746.0A CN202110375746A CN113088288A CN 113088288 A CN113088288 A CN 113088288A CN 202110375746 A CN202110375746 A CN 202110375746A CN 113088288 A CN113088288 A CN 113088288A
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卢革宇
刘晓敏
潘嘉林
包浩强
张玲
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Jilin University
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Abstract

A rare earth fluorescent material with high quantum yield and a preparation method thereof belong to the technical field of fluorescent materials. It is doped Tm3+NaErF (g)4Nano luminous nuclear matrix externally coated with NaLuF4The structure of the inert shell is characterized in that the thickness of the shell layer is 4-5 nm, and the shell layer has a nanocrystalline microscopic form; the luminescent ion of the nano luminescent core is Er3+Ion, NaErF4Doped Tm in a Nanofluminescent core matrix3+Strengthening Er as energy capture center3+Luminescence level of, NaErF4Tm in a Nanofluminescent core matrix3+The doping molar concentration of (A) is 0.5-5.0%. The invention takes the nanometer luminescent core and the inert shell of the constituent materials as the entry points, and the optimum inert shell is selectedThe selection and the introduction of the energy capture central ions optimize the luminescence characteristics of the rare earth fluorescent nano material, solve the problems of low quantum yield and low luminescence efficiency of the current rare earth fluorescent nano material, and prepare the rare earth fluorescent nano material with high quantum yield.

Description

Rare earth fluorescent material with high quantum yield and preparation method thereof
Technical Field
The invention belongs to the technical field of fluorescent materials, and particularly relates to a rare earth fluorescent material with high quantum yield and a preparation method thereof.
Background
The rare earth element is composed of 15 elements of lanthanide series in the periodic table of chemical elements and two elements of 2, yttrium and scandium closely related to the lanthanide series. The rare earth element has a very unique electronic layer structure and abundant electronic energy levels, and can absorb or emit light waves from ultraviolet light to visible light and near infrared light regions, so that the rare earth element shows a plurality of unique physical and chemical properties and becomes a treasure house of new materials. Due to the advantages of wider fluorescence spectrum emission, good fluorescence stability, low biological toxicity and the like, the rare earth fluorescent material has great potential and wide application prospect in a plurality of research fields such as medical detection, biological imaging drug transportation, disease treatment and the like.
As an important medical imaging means, fluorescence imaging has the advantages of high imaging speed, high sensitivity and the like. However, the commonly used fluorescence imaging method is near-infrared one-zone imaging, the emission wavelength of which is maintained between 750 nm and 900nm, which is overlapped with the tissue self-fluorescence emission zone in the organism, so that the problems of high background interference, high scattering, small penetration depth, incapability of deep tissue imaging and the like exist. In contrast, the rare earth fluorescent material in the near-infrared two-region (1500nm to 1700nm) has longer emission wavelength, and because the scattering of light is reduced exponentially with the wavelength, the rare earth fluorescent material can penetrate deeper biological tissues such as skin and blood, and higher imaging resolution is obtained. The rare earth doped nano material can be generally used for near infrared two-region imaging due to larger Stokes shift and higher optical stability, but the emission wavelength of the rare earth doped nano material is generally 980 nm. Given that biological tissue has strong absorption of 980nm laser light, the resulting overheating effect easily causes thermal damage to the biological tissue. Compared with 980nm, the laser with the wavelength of 800nm has weaker absorption in the biological tissue, and the overheating effect can be effectively avoided. Therefore, the preparation of the high-efficiency near-outer two-region imaging probe under the excitation of 800nm can promote the acquisition of better and excellent biological probes, and has far-reaching significance for the development of nano biomedicine and the promotion of human health in the long run.
At present, Yb3+Ions are often used as co-dopants for Er-based applications3+In nanoparticles of (2), this is mainly due to Yb3+The ion has an excellent absorption cross section under 980nm laser. However, the wavelength of 980nm overlaps to a large extent with the absorption peak of water molecules. Overexposure of biological tissue to 980nm radiation can result in overheating, which can severely damage cells and tissues. And with Nd3+NaGdF as dopant ion4@Na(Gd,Yb)F4:Er3+@NaYF4:Yb3+@NaNdF4:Yb3+The structure is too complex and the quantum yield is low due to the presence of multiple energy transfer processes. At the same time, energy is from Er3+To Nd3+Or Yb3+There is a severe back-transfer making it difficult to obtain sufficient 1525nm emission, resulting in a large excitation energy loss.
Recently, an Er3+Ion self-sensitive NaErF4@NaYF4The system is discovered. This simple structure can result in an emission of 800nm excitation to 1525nm compared to conventional sensitizer/activator co-dopant systems. Most importantly, the excitation energy can completely contribute to Er3+Ions, which can remarkably improve Er at 1525nm3+Luminous efficiency of the ions. However, most of the current research is focused on NaErF4Little attention has been paid to the up-conversion emission characteristics of the system. The optimization of the luminescent property of the rare earth fluorescent material can lead the rare earth fluorescent material to be better applied to in-vivo deep tissue microscopic imaging. The method will also generate great push to China in the brain science imaging field and clinical diagnosis and other aspectsAnd (5) performing dynamic operation.
Disclosure of Invention
The invention aims to solve the problems of low quantum yield and low luminous efficiency of a rare earth fluorescent material, and provides a rare earth up-conversion fluorescent material with high quantum yield and a preparation method thereof.
The rare earth fluorescent nano material with high quantum yield is doped with Tm3+NaErF (g)4The diameter of the nanometer luminescent core is 24-26 nm. Coating NaLuF outside the substrate4The structure of the inert shell is characterized in that the thickness of the shell layer is 4-5 nm, and the shell layer has a nanocrystalline microscopic form; the luminescent ion of the nano luminescent core is Er3+Ion, NaErF4Doped Tm in a Nanofluminescent core matrix3+Strengthening Er as energy capture center3+Luminescence level of, NaErF4Tm in a Nanofluminescent core matrix3+The doping molar concentration of (A) is 0.5-5.0%.
The invention relates to a preparation method of a rare earth fluorescent nano material with high quantum yield, which comprises the following steps:
(1) 6mL of oleic acid and 15mL of octadecene were added to the reaction vessel, and 0.382 g of ErCl was added3With 0.00191-0.0192 g of TmCl3Adding to dissolve; deoxidizing for 20-40 minutes under the protection of argon, gradually heating to 150-170 ℃, and stirring for 20-40 minutes until ErCl3Completely dissolving to obtain Tm with the molar doping concentration of 0.5-5.0%3+Doped NaErF4A nano luminescent core precursor solution;
(2) tm obtained in the step (1)3+Doped NaErF4After the nano luminescent nuclear precursor solution is completely clarified, cooling the mixture to room temperature; 5mL of a solution containing 0.1 g NaOH and 0.148 g NH was added4Gradually heating the methanol solution of F to 60-80 ℃ and keeping for 20-30 minutes to remove the methanol solution; heating to 280-320 ℃ under the protection of argon, and then keeping for 60-120 minutes to obtain Tm with the molar doping concentration of 0.5-5.0%3+NaErF (g)4A nano luminescent core solution;
(3) tm obtained in the step (2)3+Doped NaErF4Nano luminous core solutionCooling the solution to room temperature, then centrifugally washing the solution for 1-2 times by using acetone, and then centrifugally washing the solution for 2-3 times by using ethanol; then dispersed with 8mL cyclohexane to obtain Tm3+Doped NaErF4A cyclohexane solution of fluorescent nanoparticles;
(4) inert shell NaLuF4The preparation of (1):
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3Refluxing the COOH mixed solution at 85-95 ℃ for 20-30 hours, and evaporating at 50-70 ℃ to obtain (CF)3COO)3Lu; 0.272 g of CF3COONa and 1.064 g (CF)3COO)3Dissolving Lu in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirring for 20-40 minutes at 150-170 ℃ to dissolve the mixture; then heating to 280-300 ℃ for 0.5-2.0 hours, finally cooling the solution to room temperature, centrifuging with ethanol, dissolving the centrifuged product in 8mL of octadecene to obtain NaLuF4Octadecene solution of inert shell;
(5) adding 2mL of Tm obtained in step (3)3+Doped NaErF4Mixing the cyclohexane solution of the fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 85-95 ℃, and keeping for 10-20 minutes to remove cyclohexane; then gradually heating to 280-320 ℃, and adding 0.329g of NaLuF obtained in the step (4)4Adding the octadecylene solution of the inert shell into the solution twice at intervals of 40-50 minutes, continuing to react for 0.5-2.0 hours after the injection for the second time, and then cooling to room temperature;
(6) and (3) centrifugally washing the solution obtained in the step (5) with acetone for 1-2 times, centrifugally washing with ethanol for 2-3 times, and dissolving the centrifugal product in cyclohexane to obtain the rare earth fluorescent nano material with the core-shell structure, wherein the core diameter is about 25nm, and the shell thickness is 4-5 nm.
The principle of the invention is as follows: original Er3+The essence of the emission of the nano material with ions as the luminescent centers at 1525nm is Er3+Is/are as follows4I13/2Returning energy of energy level to ground state4I15/2Energy level is generated. In the case where other particles are not doped,4I13/2energy level of energyThe energy obtained from both the cross relaxation and the multiphoton nonradiative relaxation is very limited, resulting in low luminous efficiency. Meanwhile, the inert shell is wrapped outside the luminescent material, the closer the lattice constant of the inert shell is to the nano luminescent core, the closer the nano luminescent core is to uniform epitaxial growth, the fewer surface defects are generated, and the better luminescent performance can be obtained.
The invention takes the nanometer luminescent core and the inert shell as the entry points, optimizes the luminescent property of the rare earth fluorescent nanometer material by selecting the optimal inert shell and introducing the energy capture central ions, and solves the problems of low quantum yield and low luminescent efficiency of the current rare earth fluorescent nanometer material. The rare earth fluorescent nano material with high quantum yield is prepared.
The invention has the beneficial effects that:
(1) the rare earth fluorescent nano material is coated by adopting an inert shell, and the surface defects are minimized by selecting a proper inert shell, so that the optimal emission at 1525nm is obtained.
(2) Compared with the prior art, the rare earth fluorescent nano material introduces Tm3+The ions serve as energy trapping centers to provide transition energy levels, so that energy can be more effectively transferred to Er3+The luminous energy level of the ions is higher, and the luminous efficiency is improved.
(3) The inert shell of the outer layer is optimally selected to be NaLuF4The thickness of the film is 4-5 nm. The inert shell can passivate surface defects to the maximum extent, so that the surface is quenched in the filling4I13/2Plays an active role in the process of energy level, and obtains stronger 1525nm Er under the excitation of 800nm3+Emitting light and achieving a high quantum yield of 13.92% in the region of 1500-1700 nm.
(4) When the rare earth fluorescent nano material is applied to in vivo imaging (such as skull micro cerebrovascular imaging and large-area gastrointestinal tract imaging), the excitation power density of an imaging plane of the rare earth fluorescent nano material can be as low as 35mW/cm2The value is much smaller than that reported in previous work, and the probe serving as a novel imaging probe is better in brain science research, clinical diagnosis and the likeGood application prospect.
(5) The invention effectively enhances the luminous efficiency of the rare earth fluorescent nano material in the near infrared region II.
(6) The material granularity of the rare earth fluorescent nano material can reach nano level, the average grain diameter can reach 29nm, the grain diameter is small, and the distribution is uniform.
(7) The preparation method of the rare earth fluorescent nano material has high reaction repetition rate, and the particle size change rate of the nano particles obtained by repeating three times of experiments is not more than 5%.
Drawings
FIG. 1 is a scanning electron microscope image of the rare earth fluorescent material nanoparticles prepared in example 1; FIG. 1 shows that the average particle diameter of the prepared rare earth fluorescent material nanoparticles is 29 nm.
FIG. 2 is a scanning electron microscope image of the rare earth fluorescent nanoparticles prepared in example 2; FIG. 2 shows that the average particle diameter of the prepared rare earth fluorescent material nanoparticles is 29 nm.
FIG. 3 is a scanning electron microscope image of the rare earth fluorescent material nanoparticles prepared in example 3; FIG. 3 shows that the average particle diameter of the prepared rare earth fluorescent material nanoparticles is 29 nm.
FIG. 4 is a scanning electron microscope image of the rare earth fluorescent material nanoparticles prepared in example 4; FIG. 4 shows that the average particle diameter of the prepared rare earth fluorescent material nanoparticles is 29 nm.
FIG. 5 is a scanning electron microscope image of the rare earth fluorescent material nanoparticles prepared in example 5; FIG. 5 shows that the average particle diameter of the prepared rare earth fluorescent material nanoparticles is 29 nm.
FIG. 6 is a scanning electron microscope image of the rare earth fluorescent material nanoparticles prepared in example 6; FIG. 6 shows that the average particle diameter of the prepared rare earth fluorescent material nanoparticles is 29 nm.
FIG. 7 is the 0.5% Tm obtained after coating with different inert shells3+The contrast curve of the luminescence intensity of the doped up-conversion nano material at 1535nm under the irradiation of 800nm laser shows that the optimal shell material is NaLuF4, the luminescence is optimal at the moment, and the quantum yield of the formed nano composite material is 13.92%.
FIG. 8 is Tm values of different molar ratios under 800nm laser excitation3+The contrast curve of the luminescence intensity of the doped core-shell material at 1525nm shows that the optimal luminescence can be obtained under the doping of 0.5% Tm, and the luminescence quantum yield of the upconversion core-shell material under the concentration is 13.92%.
FIG. 9 is 0.5% Tm3+Schematic structure of upconversion nanoparticles prepared under doping.
Detailed Description
Example 1: NaErF4@NaLuF4Preparation of rare-earth fluorescent material
(1) In a three-necked flask, 6mL of oleic acid and 15mL of octadecene were charged, and 0.382 g of ErCl was added3Adding to dissolve; then deoxygenated under argon protection for 30 minutes, gradually warmed to 160 ℃ and stirred for 30 minutes to ErCl3Completely dissolving to obtain NaErF4 nanometer luminescent core precursor solution;
(2) NaErF to be subjected to step (1)4After the nano luminescent nuclear precursor solution is completely clarified, the solution is cooled to room temperature, and 5mL of the solution containing 0.1 g of NaOH and 0.148 g of NH is added4F, heating to 70 ℃ and keeping for 25 minutes to remove the methanol; heating to 300 ℃ under the protection of argon and keeping for 90 minutes to obtain NaErF4A nano luminescent core solution;
(3) NaErF obtained in the step (2)4Cooling the nano luminescent nuclear solution to room temperature, then centrifugally washing the nano luminescent nuclear solution with acetone once, and centrifugally washing the nano luminescent nuclear solution with ethanol twice; then dispersed with 8mL cyclohexane to obtain NaErF4A cyclohexane solution of fluorescent nanoparticles;
(4)NaLuF4preparation of inert shell:
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3COOH and refluxing at 90 deg.C for 24 hr, and then evaporating at 60 deg.C to obtain (CF)3COO)3Lu. In a 50mL beaker, 0.272 g CF3COONa and 1.064 g (CF)3COO)3Lu was dissolved in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirred at 160 ℃ for 30 minutes to dissolve the mixture. Then the temperature was raised to 290 ℃ for 1 hour,finally, after the solution is cooled to room temperature, the solution is centrifuged by ethanol, and the centrifuged product is dissolved in 8mL of octadecene to obtain NaLuF4Octadecene solution of inert shell;
(5) in a three-necked flask, 2mL of NaErF obtained in step (3) was placed4Mixing the cyclohexane solution of the fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 90 ℃ and keeping for 15 minutes to remove cyclohexane; then gradually heating to 300 ℃, and adding 0.329g of NaLuF obtained in the step (4)4The octadecene solution of inert shell was added in two portions with an interval of 45 minutes, and the reaction was continued for one hour after the second injection, after which it was cooled to room temperature.
(6) And (4) after the solution finally obtained in the step (5) is cooled to room temperature, centrifugally washing the solution once by using acetone, centrifugally washing the solution twice by using ethanol, and dissolving the final product in cyclohexane. The final product is an up-conversion nanoparticle oil phase solution with a core-shell structure, the core diameter is about 25nm, and the shell thickness is 4-5 nm.
Example 2: NaErF4：0.5％Tm@NaLuF4Preparation of rare-earth fluorescent material
(1) In a three-necked flask, 6mL of oleic acid and 15mL of octadecene were charged, and 0.382 g of ErCl was added3With 0.00191 g of TmCl3Added to dissolve it. Under the protection of argon, deoxidizing for 30 minutes, gradually heating to 160 ℃ and stirring for 30 minutes to ErCl3Completely dissolving to obtain NaErF4 nanometer luminescent core precursor solution;
(2) NaErF of step (1)4: after the 0.5% Tm nano luminescent core precursor solution was completely clear, the mixture was cooled to room temperature. 5mL of a solution containing 0.1 g NaOH and 0.148 g NH was added4F, gradually heating to 70 ℃ and keeping for 25 minutes to remove the methanol solution. Followed by heating to 300 ℃ under argon. Keeping the temperature at 300 ℃ for 90 minutes to obtain NaErF4: 0.5% Tm nano luminescent core solution;
(3) NaErF obtained in the step (2)4: after cooling to room temperature, the 0.5% Tm nano luminescent core solution is firstly washed by acetone in a centrifugal way, and then washed by ethanol in a centrifugal way twice. Finally, disperse with 8mL cyclohexaneObtaining NaErF4: 0.5% Tm in cyclohexane solution of fluorescent nanoparticles;
(4) inert shell NaLuF4The preparation of (1):
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3COOH and refluxing at 90 deg.C for 24 hr, evaporating at 60 deg.C to obtain (CF)3COO)3Lu. 0.272 g CF in a 50mL beaker3COONa and 1.064 g (CF)3COO)3Lu was dissolved in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirred at 160 ℃ for 30 minutes to dissolve the mixture. The temperature was then raised to 290 ℃ for one hour. Finally, after the solution is cooled to room temperature, the solution is centrifuged by ethanol, and the centrifuged product is dissolved in 8mL of octadecene to obtain NaLuF4Octadecene solution of inert shell;
(5) in a three-necked flask, 2mL of NaErF obtained in step (3) was placed4: mixing cyclohexane solution of 0.5% Tm fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 90 ℃ and keeping for 15 minutes to remove cyclohexane; then gradually heating to 300 ℃, and adding 0.329g of NaLuF obtained in the step (4)4The octadecene solution of inert shell was added in two portions with an interval of 45 minutes, and the reaction was continued for one hour after the second injection, after which it was cooled to room temperature.
(6) And (4) after the solution finally obtained in the step (5) is cooled to room temperature, centrifugally washing the solution once by using acetone, centrifugally washing the solution twice by using ethanol, and dissolving the final product in cyclohexane. The final product is up-conversion nano particles with a core-shell structure, the core diameter is about 25nm, and the shell thickness is 4-5 nm.
Example 3: NaErF4：1.0％Tm@NaLuF4Rare earth fluorescent material
(1) In a three-necked flask, 6mL of oleic acid and 15mL of octadecene were charged, and 0.382 g of ErCl was added3With 0.00383 g of TmCl3Added to dissolve it. Under the protection of argon, deoxidizing for 30 minutes, gradually heating to 160 ℃ and stirring for 30 minutes to ErCl3Completely dissolving to obtain NaErF4: 1.0% Tm nano luminescent core precursor solution;
(2) step (1)) NaErF (g)4: after the 1.0% Tm nanophosphor precursor solution was completely clear, the mixture was cooled to room temperature. 5mL of a solution containing 0.1 g NaOH and 0.148 g NH was added4F in methanol, gradually warmed to 70 ℃ and kept for 25 minutes to remove the formaldehyde solution. Followed by heating to 300 ℃ under argon. Keeping the temperature at 300 ℃ for 90 minutes to obtain NaErF4: 1.0% Tm nano luminescent core solution;
(3) NaErF obtained in the step (2)4: after cooling to room temperature, the 1.0% Tm nano luminescent core solution is firstly washed by acetone in a centrifugal mode, and then washed by ethanol in a centrifugal mode twice. Finally, disperse with 8mL cyclohexane to obtain NaErF4: 1.0% Tm in cyclohexane solution of fluorescent nanoparticles;
(4) inert shell NaLuF4The preparation of (1):
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3COOH and refluxing at 90 deg.C for 24 hr, evaporating at 60 deg.C to obtain (CF)3COO)3Lu. 0.272 g CF in a 50mL beaker3COONa and 1.064 g (CF)3COO)3Lu was dissolved in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirred at 160 ℃ for 30 minutes to dissolve the mixture. The temperature was then raised to 290 ℃ for one hour. Finally, after the solution is cooled to room temperature, the solution is centrifuged by ethanol, and the centrifuged product is dissolved in 8mL of octadecene to obtain NaLuF4Octadecene solution of inert shell;
(5) in a three-necked flask, 2mL of NaErF obtained in step (3) was placed4: mixing cyclohexane solution of 1.0% Tm fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 90 ℃ and keeping for 15 minutes to remove cyclohexane; then gradually heating to 300 ℃, and adding 0.329g of NaLuF obtained in the step (4)4The octadecene solution of inert shell was added in two portions with an interval of 45 minutes, and the reaction was continued for one hour after the second injection, after which it was cooled to room temperature.
(6) And (4) after the solution finally obtained in the step (5) is cooled to room temperature, centrifugally washing the solution once by using acetone, centrifugally washing the solution twice by using ethanol, and dissolving the final product in cyclohexane. The final product is up-conversion nano particles with a core-shell structure, the core diameter is about 25nm, and the shell thickness is 4-5 nm.
Example 4: NaErF4：2.0％Tm@NaLuF4Rare earth fluorescent material
(1) In a three-necked flask, 6mL of oleic acid and 15mL of octadecene were charged, and 0.382 g of ErCl was added3With 0.0077 g of TmCl3Added to dissolve it. Under the protection of argon, deoxidizing for 30 minutes, gradually heating to 160 ℃ and stirring for 30 minutes to ErCl3Completely dissolving to obtain NaErF4: 1.0% Tm nano luminescent core precursor solution;
(2) NaErF of step (1)4: after the 2.0% Tm nanophase luminescent core precursor solution was completely clear, the mixture was cooled to room temperature. 5mL of a solution containing 0.1 g NaOH and 0.148 g NH was added4F in methanol, gradually warmed to 70 ℃ and kept for 25 minutes to remove the formaldehyde solution. Followed by heating to 300 ℃ under argon. Keeping the temperature at 300 ℃ for 90 minutes to obtain NaErF4: 1.0% Tm nano luminescent core solution;
(3) NaErF obtained in the step (2)4: after cooling to room temperature, the 1.0% Tm nano luminescent core solution is firstly washed by acetone in a centrifugal mode, and then washed by ethanol in a centrifugal mode twice. Finally, disperse with 8mL cyclohexane to obtain NaErF4: 1.0% Tm in cyclohexane solution of fluorescent nanoparticles;
(4) inert shell NaLuF4The preparation of (1):
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3COOH and refluxing at 90 deg.C for 24 hr, evaporating at 60 deg.C to obtain (CF)3COO)3Lu. 0.272 g CF in a 50mL beaker3COONa and 1.064 g (CF)3COO)3Lu was dissolved in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirred at 160 ℃ for 30 minutes to dissolve the mixture. The temperature was then raised to 290 ℃ for one hour. Finally, after the solution is cooled to room temperature, the solution is centrifuged by ethanol, and the centrifuged product is dissolved in 8mL of octadecene to obtain NaLuF4Octadecene solution of inert shell;
(5) in a three-necked flask, 2mL of NaErF obtained in step (3) was placed4: mixing cyclohexane solution of 2.0% Tm fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 90 ℃ and keeping for 15 minutes to remove cyclohexane; then gradually heating to 300 ℃, and adding 0.329g of NaLuF obtained in the step (4)4The octadecene solution of inert shell was added in two portions with an interval of 45 minutes, and the reaction was continued for one hour after the second injection, after which it was cooled to room temperature.
(6) And (4) after the solution finally obtained in the step (5) is cooled to room temperature, centrifugally washing the solution once by using acetone, centrifugally washing the solution twice by using ethanol, and dissolving the final product in cyclohexane. The final product is up-conversion nano particles with a core-shell structure, the core diameter is about 25nm, and the shell thickness is 4-5 nm.
Example 5: NaErF4：3.0％Tm@NaLuF4Rare earth fluorescent material
(1) In a three-necked flask, 6mL of oleic acid and 15mL of octadecene were charged, and 0.382 g of ErCl was added3With 0.0115 g of TmCl3Added to dissolve it. Under the protection of argon, deoxidizing for 30 minutes, gradually heating to 160 ℃ and stirring for 30 minutes to ErCl3Completely dissolving to obtain NaErF4: a 3.0% Tm nano luminescent core precursor solution;
(2) NaErF of step (1)4: after the 3.0% Tm nanophase luminescent core precursor solution was completely clear, the mixture was cooled to room temperature. 5mL of a solution containing 0.1 g NaOH and 0.148 g NH was added4F in methanol, gradually warmed to 70 ℃ and kept for 25 minutes to remove the formaldehyde solution. Followed by heating to 300 ℃ under argon. Keeping the temperature at 300 ℃ for 90 minutes to obtain NaErF4: a 3.0% Tm nano luminescent core solution;
(3) NaErF obtained in the step (2)4: after cooling to room temperature, the 3.0% Tm nano luminescent core solution is firstly washed by acetone in a centrifugal mode, and then washed by ethanol in a centrifugal mode twice. Finally, disperse with 8mL cyclohexane to obtain NaErF4: a cyclohexane solution of 3.0% Tm fluorescent nanoparticles;
(4) inert shell NaLuF4The preparation of (1):
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3COOH and refluxing at 90 deg.C for 24 hr, evaporating at 60 deg.C to obtain (CF)3COO)3Lu. 0.272 g CF in a 50mL beaker3COONa and 1.064 g (CF)3COO)3Lu was dissolved in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirred at 160 ℃ for 30 minutes to dissolve the mixture. The temperature was then raised to 290 ℃ for one hour. Finally, after the solution is cooled to room temperature, the solution is centrifuged by ethanol, and the centrifuged product is dissolved in 8mL of octadecene to obtain NaLuF4Octadecene solution of inert shell;
(5) in a three-necked flask, 2mL of NaErF obtained in step (3) was placed4: mixing cyclohexane solution of 3.0% Tm fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 90 ℃ and keeping for 15 minutes to remove cyclohexane; then gradually heating to 300 ℃, and adding 0.329g of NaLuF obtained in the step (4)4The octadecene solution of inert shell was added in two portions with an interval of 45 minutes, and the reaction was continued for one hour after the second injection, after which it was cooled to room temperature.
(6) And (4) after the solution finally obtained in the step (5) is cooled to room temperature, centrifugally washing the solution once by using acetone, centrifugally washing the solution twice by using ethanol, and dissolving the final product in cyclohexane. The final product is up-conversion nano particles with a core-shell structure, the core diameter is about 25nm, and the shell thickness is 4-5 nm.
Example 6: NaErF4：5.0％Tm@NaLuF4Rare earth fluorescent material
(1) In a three-necked flask, 6mL of oleic acid and 15mL of octadecene were charged, and 0.382 g of ErCl was added3With 0.0192 g of TmCl3Added to dissolve it. Under the protection of argon, deoxidizing for 30 minutes, gradually heating to 160 ℃ and stirring for 30 minutes to ErCl3Completely dissolving to obtain NaErF4: 5.0% Tm nano luminescent core precursor solution;
(2) NaErF of step (1)4: after the 5.0% Tm nanophase luminescent core precursor solution was completely clear, the mixture was cooled to room temperature. 5mL of a solution containing 0.1 g NaOH and 0.148 g NH was added4F in methanol, gradually warmed to 70 ℃ and kept for 25 minutes to remove the formaldehyde solution. Followed by heating to 300 ℃ under argon. Keeping the temperature at 300 ℃ for 90 minutes to obtain NaErF4: a 5.0% Tm nano luminescent core solution;
(3) NaErF obtained in the step (2)4: the 5.0% Tm nano luminescent core solution is cooled to room temperature, then is centrifugally washed once by acetone and twice by ethanol. Finally, disperse with 8mL cyclohexane to obtain NaErF4: a cyclohexane solution of 5.0% Tm fluorescent nanoparticles;
(4) inert shell NaLuF4The preparation of (1):
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3COOH and refluxing at 90 deg.C for 24 hr, evaporating at 60 deg.C to obtain (CF)3COO)3Lu. 0.272 g CF in a 50mL beaker3COONa and 1.064 g (CF)3COO)3Lu was dissolved in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirred at 160 ℃ for 30 minutes to dissolve the mixture. The temperature was then raised to 290 ℃ for one hour. Finally, after the solution is cooled to room temperature, the solution is centrifuged by ethanol, and the centrifuged product is dissolved in 8mL of octadecene to obtain NaLuF4Octadecene solution of inert shell;
(5) in a three-necked flask, 2mL of NaErF obtained in step (3) was placed4: mixing a cyclohexane solution of 5.0% Tm fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 90 ℃ and keeping for 15 minutes to remove cyclohexane; then gradually heating to 300 ℃, and adding 0.329g of NaLuF obtained in the step (4)4The octadecene solution of inert shell was added in two portions with an interval of 45 minutes, and the reaction was continued for one hour after the second injection, after which it was cooled to room temperature.
(6) And (4) after the solution finally obtained in the step (5) is cooled to room temperature, centrifugally washing the solution once by using acetone, centrifugally washing the solution twice by using ethanol, and dissolving the final product in cyclohexane. The final product is up-conversion nano particles with a core-shell structure, the core diameter is about 25nm, and the shell thickness is 4-5 nm.

Claims (5)

1. A preparation method of rare earth fluorescent nano material with high quantum yield comprises the following steps:
(1) 6mL of oleic acid and 15mL of octadecene were added to the reaction vessel, and 0.382 g of ErCl was added3With 0.00191-0.0192 g of TmCl3Adding to dissolve; deoxidizing for 20-40 minutes under the protection of argon, gradually heating to 150-170 ℃, and stirring for 20-40 minutes until ErCl3Completely dissolving to obtain Tm with the molar doping concentration of 0.5-5.0%3+Doped NaErF4A nano luminescent core precursor solution;
(2) tm obtained in the step (1)3+Doped NaErF4After the nano luminescent nuclear precursor solution is completely clarified, cooling the mixture to room temperature; 5mL of a solution containing 0.1 g NaOH and 0.148 g NH was added4Gradually heating the methanol solution of F to 60-80 ℃ and keeping for 20-30 minutes to remove the methanol solution; heating to 280-320 ℃ under the protection of argon, and then keeping for 60-120 minutes to obtain Tm with the molar doping concentration of 0.5-5.0%3+NaErF (g)4A nano luminescent core solution;
(3) tm obtained in the step (2)3+Doped NaErF4Cooling the nano luminescent core solution to room temperature, then centrifugally washing the nano luminescent core solution for 1 to 2 times by using acetone, and then centrifugally washing the nano luminescent core solution for 2 to 3 times by using ethanol; then dispersed with 8mL cyclohexane to obtain Tm3+Doped NaErF4A cyclohexane solution of fluorescent nanoparticles;
(4) inert shell NaLuF4The preparation of (1):
mixing 1.99 g Lu3O2Dissolved in 20mL deionized water and 20mL CF3Refluxing the COOH mixed solution at 85-95 ℃ for 20-30 hours, and evaporating at 50-70 ℃ to obtain (CF)3COO)3Lu; 0.272 g of CF3COONa and 1.064 g (CF)3COO)3Dissolving Lu in 6mL of oleic acid, 10mL of octadecene and 6mL of oleylamine, and stirring for 20-40 minutes at 150-170 ℃ to dissolve the mixture; then heating to 280-300 ℃ for 0.5-2.0 hours, finally cooling the solution to room temperature, centrifuging with ethanol, and dissolving the centrifuged product in 8mL of tenIn octaene to obtain NaLuF4Octadecene solution of inert shell;
(5) adding 2mL of Tm obtained in step (3)3+Doped NaErF4Mixing the cyclohexane solution of the fluorescent nanoparticles with 6mL of oleic acid and 15mL of octadecene, gradually heating to 85-95 ℃, and keeping for 10-20 minutes to remove cyclohexane; then gradually heating to 280-320 ℃, and adding 0.329g of NaLuF obtained in the step (4)4Adding the octadecylene solution of the inert shell into the solution twice at intervals of 40-50 minutes, continuing to react for 0.5-2.0 hours after the injection for the second time, and then cooling to room temperature;
(6) and (3) centrifugally washing the solution obtained in the step (5) with acetone for 1-2 times, centrifugally washing with ethanol for 2-3 times, and dissolving the centrifugal product in cyclohexane to obtain the rare earth fluorescent nano material with the core-shell structure.
2. A rare earth fluorescent nano material with high quantum yield is characterized in that: is prepared by the method of claim 1.
3. The rare earth fluorescent nanomaterial of high quantum yield of claim 2, wherein: it is doped Tm3 +NaErF (g)4Nano luminous nuclear matrix externally coated with NaLuF4The inert shell has a structure, the diameter of a core is about 25nm, the thickness of a shell layer is 4-5 nm, and the inert shell has a nanocrystalline microscopic form.
4. The rare earth fluorescent nanomaterial of high quantum yield of claim 3, wherein: the luminescent ion is Er3+Ion, NaErF4Doped Tm in a Nanofluminescent core matrix3+Strengthening Er as energy capture center3+The light emission level of (1).
5. The rare earth fluorescent nanomaterial of high quantum yield of claim 3 or 4, wherein: NaErF4Tm in a Nanofluminescent core matrix3+The doping molar concentration of (A) is 0.5-5.0%.
CN202110375746.0A 2021-04-08 2021-04-08 Rare earth fluorescent material with high quantum yield and preparation method thereof Pending CN113088288A (en)

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