CN111808604A - Method for preparing orthogonal excitation-emission response three-primary-color up-conversion luminescent material - Google Patents
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Abstract
The invention provides a method for preparing an orthogonal excitation-emission response three-primary-color up-conversion luminescent material, belonging to the cross technical field of true three-dimensional color display, up-conversion luminescence and nano core-shell material preparation. The nanocrystal with the one-core five-shell structure is prepared by firstly preparing a blue light emitting core through a full-automatic nanometer synthesizer, and then sequentially inducing epitaxial growth by a layer-by-layer wrapping method to form a first inert isolation layer, a second red light emitting layer, a third inert isolation layer, a fourth green light emitting layer and a fifth 808nm excitation light energy absorption layer. Under the excitation of 1560nm, 808nm or 980nm near infrared light with different wavelengths, the five-shell core-shell structure nanocrystal can respond to the orthogonal up-conversion luminescence of red, green and blue three primary colors. The method provides technical support for full-color light-emitting adjustment, multicolor display, multicolor coding, anti-counterfeiting and the like.
Description
Technical Field
The invention belongs to the cross technical field of true three-dimensional color display, up-conversion luminescence and nano core-shell material preparation, and particularly relates to a method for preparing an orthogonal excitation-emission response three-primary-color up-conversion luminescent material.
Background
The core of true three-dimensional display technology based on up-conversion luminescence is up-conversion luminescent material with three primary colors of red, green and blue, which have orthogonal excitation-response. The technology requires that each point has the properties of vertical excitation and orthogonal emission in the three-dimensional space of the display. That is, excitation with a near infrared light can give fluorescence of red, green, or blue color; when two different near infrared lights are used for excitation, two colors of fluorescence in red, green and blue can be obtained; if the light with three different wavelengths is used for excitation at the same time, the up-conversion fluorescence with three colors of red, green and blue can be obtained at the same time. This upconversion fluorescence characteristic is known as orthogonal excitation-response three primary upconversion luminescence.
Lanthanide-doped upconversion luminescent nanocrystals (UCNPs) are of interest as one of the most promising nano-luminescent materials because of their unique anti-stokes shift photoluminescence capabilities. Due to the characteristics of a 4f electronic structure, near infrared excitation and the like, the up-conversion luminescence of the lanthanide-doped UCNPs shows excellent photophysical characteristics, such as narrow-band emission, long fluorescence lifetime, high optical stability and low biological background fluorescence interference. In addition, the processes of light absorption, quantum transition, luminescent color, surface effect, energy transfer and the like of the material can be accurately regulated and controlled under the nanoscale, so that the lanthanide-doped UCNPs have obvious advantages in the aspect of regulating and controlling multicolor luminescence compared with organic dyes and quantum dots. However, in lanthanide-doped mononuclear nanocrystals and core-shell nanomaterials with common structures, co-doping of multiple luminescent ions can cause photoexcitation crosstalk, harmful energy migration, cross relaxation between energy levels, fluorescence reabsorption, fluorescence quenching between different ions and other processes, so that UCNPs with simple structures are difficult to realize controllable three-primary-color luminescence. For example, for the above reasons, in true three-dimensional color display technology based on upconversion luminescence, researchers have not solved the problems of crosstalk of excitation light, harmful energy transfer and re-absorption of fluorescence for many years, and thus have not prepared a three-primary-color upconversion luminescent material with three-wavelength near-infrared excitation-orthogonal response.
Disclosure of Invention
Aiming at the luminescent materials and the technical problems, the invention provides a method for preparing an orthogonal excitation-emission response three-primary-color up-conversion luminescent material, which is respectively composed of a blue light emitting core, a first inert isolation layer, a second red light emitting layer, a third inert isolation layer, a fourth green light emitting layer and a fifth 808nm excitation light energy absorption layer. By setting the functions of each shell (emitting red, green and blue fluorescence, isolating between fluorescent layers and absorbing exciting light), the doping proportion and concentration of rare earth ions of the core and each shell, the preparation process, the flow and the method provided by the invention are adopted to realize the control preparation of the core and the multiple shells of the nano material, and the UCNPs with the complex structure and the specific doping concentration and the core-shell size are obtained. In the implementation process of the specific preparation process, the five-layer core-shell structure nano material which responds to the up-conversion luminescence of three primary colors of orthogonal red, green and blue under the excitation of three different near infrared wavelengths is prepared by a layer-by-layer wrapping method by using a full-automatic nano material synthesizer. The nanometer material with the structure not only reasonably utilizes exciting light with different wavelengths, but also effectively reduces mutual interference among three different light emitting processes, thereby achieving the purpose of realizing up-conversion light emission of three primary colors by utilizing a core-shell nanometer structure. In addition, the influence of surface defects on a luminescence center can be effectively reduced by wrapping the shell layer, and the luminescence intensity of the core-shell structure nano material is obviously improved.
By utilizing the accurate preparation performance of the full-automatic nanometer material synthesizer, the invention synthesizes the one-core five-shell nanometer structure material. Experimental tests show that the prepared material has the performance of responding to up-conversion luminescence of orthogonal three primary colors under the excitation of near infrared light with three different wavelengths. The five-layer core-shell structure nanocrystalline is prepared by a layer-by-layer wrapping method, repeated comparison and selection of a comparison experiment are carried out, and in the embodiment, the five-layer core-shell structure NaYF is selected4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/Er@NaYF4The Nd nanocrystal realizes the characteristic of responding to orthogonal three primary colors to emit light under the excitation of near infrared light with three different wavelengths, and the size of the nanocrystal with the whole core-shell structure is about 71 nm. The chemical composition of each functional layer is as follows:
blue light emitting core, NaYF4:Yb/Tm
A first shell layer: inert barrier layer, NaYF4
A second shell layer: red light emitting layer, NaYF4:Er/Ho
A third shell layer: inert barrier layer, NaYF4
A fourth shell layer: green light emitting layer, NaYF4:Nd/Yb/Er
A fifth shell layer: 808nm excitation light energy absorbing layer, NaYF4:Nd。
The invention is realized by the following technical scheme:
a method for preparing an orthogonal excitation-emission response three-primary-color up-conversion luminescent material comprises the steps of firstly preparing NaYF4Yb/Tm luminous kernel, then using kernel as seed crystal to induce crystal epitaxial growth NaYF4Shell layer of NaYF with core-shell structure4:Yb/Tm@NaYF4The nano crystal is used as a seed crystal for further growing NaYF4A second Er/Ho shell layer; similarly, the prepared double-layer core-shell NaYF4:Yb/Tm@NaYF4@NaYF4Er/Ho nano-crystal as seed crystal for further growing NaYF4A third shell layer; similarly, the prepared three-layer core-shell NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4The nano crystal is used as a seed crystal for further growing NaYF4A fourth Nd/Yb/Er shell layer; similarly, the prepared four-layer core-shell NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4Further growing NaYF by taking Nd/Yb/Er nano-crystal as seed crystal4Nd as the fifth shell layer.
Preferably, the size of the light-emitting core is 22-30 nm, the thickness of the first shell is 4-6 nm, the thickness of the second shell is 3-6 nm, the thickness of the third shell is 5-7 nm, the thickness of the fourth shell is 4-6 nm, and the thickness of the fifth shell is 2-3 nm.
Preferably, the method for preparing the orthogonal excitation-emission response three-primary-color up-conversion luminescent material comprises the following specific steps:
(1) preparing a luminescent core: adding rare earth salt into a mixed high-temperature solvent of Oleic Acid (OA) and 1-Octadecene (ODE), reacting at high temperature under the protection of inert gas to obtain a rare earth oleic acid complex (Ln-OA), cooling, adding a methanol solution of a fluorine source and a sodium source, and reacting at the temperature of 280-320 ℃ under the protection of inert gas to obtain luminescent core nano-particles after methanol is volatilized;
(2) preparing a shell layer precursor: adding rare earth salt required by shell growth into a mixed high-temperature solvent of Oleic Acid (OA) and 1-Octadecene (ODE), and obtaining a rare earth oleic acid complex required by shell formation under the protection of high temperature and inert gas;
(3) preparing core-shell structure nanocrystals: adding the luminescent core nano-particles prepared in the step (1) into the shell layer precursor solution as seed crystals, introducing a fluorine source and a sodium source, and forming core-shell structure nanocrystals by inducing crystal epitaxial growth shell layers under the conditions of high temperature and inert gas protection;
(4) preparing the double-layer or multi-layer core-shell structure nanocrystal: core-shell or (n-1) layer core-shell structure nano particles prepared in the previous step are added into the shell layer precursor solution as seed crystals, a fluorine source and a sodium source are introduced, and double-layer or multi-layer core-shell structure nano crystals are formed in a mode of inducing crystal epitaxial growth shell layers under the conditions of high temperature and inert gas protection.
Preferably, the rare earth salt is a rare earth acetate salt, a rare earth chloride salt or a rare earth nitrate salt; the fluorine source is ammonium fluoride, potassium fluoride, lithium fluoride, sodium fluoride or sodium trifluoroacetate; the sodium source is sodium hydroxide, sodium fluoride, sodium acetate or sodium trifluoroacetate.
Preferably, the method for preparing the orthogonal excitation-emission response three-primary-color up-conversion luminescent material comprises the following specific steps:
the method comprises the following steps: preparation of blue light emitting nuclear NaYF by full-automatic nano material synthesizer430 mol% Yb,0.5 mol% Tm, for emitting blue fluorescence of 474nm under the excitation of 980nm near infrared light; 0.278mmol of Y (CH)3COO)30.120mmol of Yb (CH)3COO)3And a Tm (CH) of 0.002mmol3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene at room temperature, stirring and heating to 150 ℃, and reacting for 60 minutes to form an oleic acid complex Y, Yb, Tm-OA nuclear precursor; the resulting mixed solution was naturally cooled to room temperature, and 4mL of NH was added4F (0.4moL/L) and 2mL of methanol solution of NaOH (0.5moL/L) are heated to 50 ℃ and continuously stirred for 30 minutes, then stirred and heated to 100 ℃ and reacted for 10 minutes under vacuum condition to remove methanol, and finally heated to 290 ℃ under argon atmosphere and reacted for 90 minutes; cooling to room temperature after the reaction is finished, centrifuging the reaction solution for 5 minutes at 9000r/min, collecting the precipitate, repeatedly washing the precipitate for three times by using cyclohexane and ethanol, and finally dispersing the obtained product in the cyclohexane for preparing the nanocrystalline with the characteristic and core-shell structure;
step two: 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ for reacting for 60 minutes to form an oleic acid complex Y-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and addingAdding the cyclohexane solution (0.4mmol) of the core nanocrystal prepared in the step one and 4mLNH4Continuously stirring a methanol solution of F (0.4moL/L) and 2mLNaOH (0.5moL/L) for 30 minutes under the reaction condition of 50 ℃, then stirring and heating to 100 ℃, reacting for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under the argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution for 5 minutes at 9000r/min, collecting precipitates, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and preparation of the nanocrystal with the next double-layer core-shell structure;
step three: taking the formed core-shell structure nanocrystal as seed crystal again, and inducing epitaxial growth of a second red light emitting layer NaYF4:5mol％Er,5mol％Ho；
Preparing the double-layer core-shell structure nanocrystal by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.36mmol of Y (CH)3COO)30.02mmol of Er (CH)3COO)3And 0.02mmol of Ho (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Er, Ho-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (0.4mmol) of the core-shell structure nanocrystal prepared in the second step and 4mL of NH4Continuously stirring the solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol at 50 ℃ for 30 minutes, then stirring and heating to 100 ℃, reacting for 20 minutes under a vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under an argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution at 9000r/min for 5 minutes, collecting precipitates, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and next preparation of three-layer core-shell structure nanocrystals;
step four: will be coated with NaYF4Taking Er/Ho double-layer core-shell nano-crystal as seed crystal again, and inducing epitaxial growth of third layer of inert isolating layer NaYF4；
Preparing three-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃, reacting for 60 minutes to form an oleic acid complex Y-OA shell layer precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (about 0.4mmol) of the double-layer core-shell structure nanocrystal prepared in the step three and 4mL of NH4Continuously stirring the solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol at 50 ℃ for 30 minutes, then stirring and heating to 100 ℃, reacting for 20 minutes under a vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under an argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution at 9000r/min for 5 minutes, collecting precipitates, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and preparation of four-layer core-shell structure nanocrystals in the next step;
step five: coating a third inert isolating layer NaYF4The three layers of core-shell nanocrystals are used as seed crystals again to induce epitaxial growth of a fourth layer of green light emitting layer NaYF4:0.5mol％Nd,20mol％Yb,2mol％Er；
Preparing four-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.31mmol of Y (CH)3COO)30.002mmol of Nd (CH)3COO)30.08mmol of Yb (CH)3COO)3And 0.008mmol of Er (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Nd, Yb, Er-OA shell layer precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (0.4mmol) of the three-layer core-shell structure nanocrystalline prepared in the step four and 4mL of NH4F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol, stirring was continued for 30 minutes at 50 ℃ and then heated to 100 ℃ with stirring under vacuumReacting for 20 minutes under an empty condition to remove cyclohexane and methanol, finally heating to 290 ℃ under an argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction liquid for 5 minutes at 9000r/min, collecting precipitate, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and preparation of five-layer core-shell structure nanocrystals in the next step;
step six: will be coated with NaYF4Taking Nd/Yb/Er four-layer core-shell nano-crystal as seed crystal again, inducing epitaxial growth of fifth 808nm excitation light energy absorption layer NaYF4:20mol％Nd；
Preparing five-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.32mmol of Y (CH)3COO)3And 0.08mmol of Nd (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Nd-OA shell layer precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (about 0.4mmol) of the four-layer core-shell structure nanocrystal prepared in the fifth step and 4mL of NH4And F (0.4moL/L) and 2mL of methanol solution of NaOH (0.5moL/L) are stirred for 30 minutes under the reaction condition of 50 ℃, then stirred and heated to 100 ℃, and reacted for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally the temperature is raised to 290 ℃ under the argon atmosphere for 90 minutes of reaction, the reaction solution is cooled to room temperature after the reaction is finished, the reaction solution is centrifuged for 5 minutes at 9000r/min, the precipitate is collected and repeatedly washed with cyclohexane and ethanol for three times, and finally the obtained product is dispersed in cyclohexane for characterization.
Compared with the prior art, the invention has the following advantages:
(1) in the aspect of preparation process, the full-automatic nanometer material synthesizer can achieve high-precision control of the synthesis conditions of the core-shell structure nanometer crystals, further can achieve accurate regulation and control of the size, the shape, the thickness of a shell layer and the number of the shell layers of the nanometer crystals, and solves the problems that the traditional artificial synthesis method is complicated in experimental operation steps, uncontrollable human errors, poor in experimental repeatability and the like.
(2) In terms of material design, a luminescent layer (core) based on three primary colors is integrated on a single nanocrystal through a layer-by-layer packaging method, and inert NaYF is used4The introduction of the isolation layer effectively avoids the interference among three different luminescence processes, and realizes independent three-primary-color up-conversion luminescence in the core-shell structure nanocrystal with one core and five shell layers.
(3) In terms of material preparation, so far, in the preparation of a core-shell structure based on orthogonal three-primary-color up-conversion luminescence, the one-core five-shell structure is the core-shell structure with the least number of wrapping shells. Therefore, the preparation method of the five-layer core-shell structure nanocrystal is the simplest method for realizing up-conversion luminescence of the orthogonal three primary colors.
(4) In the aspect of luminous performance, the invention expands a binary orthogonal excitation emission system which generates double-color orthogonal up-conversion luminescence (blue-green or red-green) based on double-wavelength excitation into an emission system which realizes three-primary-color orthogonal up-conversion luminescence based on three-wavelength excitation and is excited by near infrared light with three different wavelengths, so that a new method is provided in the aspects of full-color luminescence adjustment and the like.
Drawings
FIG. 1: and (3) a full-automatic nanometer material synthesizer diagram. The whole process of the experiment is automatically controlled by a program, and the instrument can automatically complete the synthesis of the nano material under the unattended condition.
FIG. 2: the synthetic schematic diagram of the five-layer core-shell structure nanocrystal which is prepared by a layer-by-layer wrapping method and responds to the up-conversion luminescence of orthogonal three primary colors under the excitation of near infrared light with three different wavelengths.
FIG. 3: NaYF-based synthesized by layer-by-layer wrapping method by utilizing full-automatic nano material synthesizer4Transmission Electron Microscope (TEM) images of multilayer core-shell structured nanocrystals. As shown, (a) is NaYF4Yb/Tm nucleus up-conversion luminescence nanocrystals; (b) is NaYF4:Yb/Tm@NaYF4Converting luminescent nanocrystals on the core-shell structure; (c) is NaYF4:Yb/Tm@NaYF4@NaYF4Er/Ho double-layer core-shell structure up-conversion luminescence nanocrystalline; (d) is composed ofNaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4Converting luminescent nanocrystals on the three-layer core-shell structure; (e) is NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4Nd/Yb/Er four-layer core-shell structure up-conversion luminescence nanocrystalline; (f) is NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/Er@NaYF4Nd five-layer core-shell structure up-conversion nanocrystalline. The core, the core-shell, the double-layer, the three-layer, the four-layer and the five-layer core-shell structure nanocrystals all have good monodispersity, and the appearance of the nanocrystals gradually changes from the spherical shape of the core nanocrystals to the hexagonal shape of the five-layer core-shell structure nanocrystals.
FIG. 4: NaYF-based synthesized by layer-by-layer wrapping method by utilizing full-automatic nano material synthesizer4The grain size distribution diagram of the multilayer core-shell structure nanocrystalline. As shown in fig. (a-f), the prepared core nanocrystals were gradually grown from the first 25nm to 34nm, 43nm, 55nm, 65nm and 71nm in average particle size after the first, second, third, fourth and fifth shell layers were grown by successive epitaxial growth, respectively.
FIG. 5: the five-layer core-shell structure nanocrystalline responds to the up-conversion luminescence of the orthogonal three primary colors under the excitation of near infrared light with three different wavelengths and has an emission spectrum under the excitation of 1560nm near infrared light. The nanocrystals produced red emission under 1560nm excitation.
FIG. 6: the emission spectrum of the five-layer core-shell structure nanocrystalline under the excitation of near infrared light with 808nm responds to the up-conversion luminescence of three orthogonal primary colors under the excitation of near infrared light with three different wavelengths. The nanocrystals produced green emission under 808nm excitation.
FIG. 7: the five-layer core-shell structure nanocrystalline responds to the up-conversion luminescence of the orthogonal three primary colors under the excitation of near infrared light with three different wavelengths and has an emission spectrum under the excitation of the 980nm near infrared light. The nanocrystals produced blue light emission under 980nm excitation.
Detailed Description
The following embodiments are only used for illustrating the technical solutions of the present invention more clearly, and therefore, the following embodiments are only used as examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
By utilizing the accurate preparation performance of the full-automatic nanometer material synthesizer, the invention synthesizes the one-core five-shell nanometer structure material. Experimental tests show that the prepared material has the performance of responding to up-conversion luminescence of orthogonal three primary colors under the excitation of near infrared light with three different wavelengths. The five-layer core-shell structure nanocrystalline is prepared by a layer-by-layer wrapping method, repeated comparison and selection of a comparison experiment are carried out, and in the embodiment, the five-layer core-shell structure NaYF is selected4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/Er@NaYF4The Nd nanocrystal realizes the characteristic of responding to orthogonal three primary colors to emit light under the excitation of near infrared light with three different wavelengths, and the size of the nanocrystal with the whole core-shell structure is about 71 nm. The chemical composition of each functional layer is as follows:
blue light emitting core, NaYF4:Yb/Tm
A first shell layer: inert barrier layer, NaYF4
A second shell layer: red light emitting layer, NaYF4:Er/Ho
A third shell layer: inert barrier layer, NaYF4
A fourth shell layer: green light emitting layer, NaYF4:Nd/Yb/Er
A fifth shell layer: 808nm excitation light energy absorbing layer, NaYF4:Nd。
Example 1: NaYF4Preparation of a core nanocrystal of Yb/Tm (30/0.5 mol%).
Firstly preparing NaYF by utilizing a full-automatic nano material synthesizer4Yb/Tm (30/0.5 mol%) core nanocrystal.
The preparation method comprises the following specific steps: at a predetermined ratio of Y (CH)3COO)3(0.278mmol)、Yb(CH3COO)3(0.120mmol) and Tm (CH)3COO)3(0.002mmol) in waterAdding the mixture into a mixed solvent of 3mL of oleic acid and 7mL of octadecene at room temperature, stirring and heating to 150 ℃, and reacting for 60 minutes to form an oleic acid complex Y, Yb, Tm-OA nuclear precursor. After the obtained mixed solution is naturally cooled to room temperature, 4mL of NH is added4F (0.4moL/L) and 2mL of a methanol solution of NaOH (0.5moL/L) are heated to 50 ℃ and stirred continuously for 30 minutes, then stirred and heated to 100 ℃ and reacted under vacuum for 10 minutes to remove methanol, and finally heated to 290 ℃ under an argon atmosphere and reacted for 90 minutes. And after the reaction is finished, cooling to room temperature, centrifugally separating the reaction liquid, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for preparing the nano-crystal with the characteristic and core-shell structure.
Example 2: NaYF4:Yb/Tm@NaYF4And (3) preparing core-shell structure nanocrystals.
The nucleus prepared in the example 1 is used as a seed crystal and added into a reaction system of a precursor of a Y-OA shell layer to induce the epitaxial growth of NaYF4And (4) shell layer.
The preparation method comprises mixing Y (CH)3COO)3Adding (0.4mmol) aqueous solution into a mixed solvent of 3mL oleic acid and 7mL octadecene, stirring and heating the obtained mixture to 150 ℃ for reaction for 60 minutes to form an oleic acid complex Y-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and adding the prepared cyclohexane solution (0.4mmol) of the core nanocrystal and 4mL NH4And F (0.4moL/L) and 2mL of methanol solution of NaOH (0.5moL/L) are continuously stirred for 30 minutes under the reaction condition of 50 ℃, then stirred and heated to 100 ℃, reacted for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally heated to 290 ℃ under the argon atmosphere for 90 minutes of reaction, cooled to room temperature after the reaction is finished, the reaction liquid is centrifugally separated, and repeatedly washed with cyclohexane and ethanol for three times, and finally the obtained product is dispersed in cyclohexane for characterization and preparation of the nanocrystal with the next double-layer core-shell structure.
Example 3: NaYF4:Yb/Tm@NaYF4@NaYF4Preparation of Er/Ho (5/5 mol%) double-layer core-shell structure nanocrystalline.
And preparing the double-layer core-shell structure nanocrystal by using a full-automatic nanomaterial synthesizer through a layer-by-layer wrapping method.
The specific preparation process is that the preparation of the double-layer core-shell structure nanocrystalline is similar to the preparation method of the core-shell structure nanocrystalline. Only the prepared precursor of the Y-OA shell layer is replaced by the precursor of the Y, Er, Ho-OA shell layer, the obtained core-shell structure nanocrystal prepared in the embodiment 2 is used as seed crystal, and NaYF is induced and epitaxially grown4Er/Ho shell layer. And dispersing the prepared product into cyclohexane for characterization and next preparation of the three-layer core-shell structure nanocrystal.
Example 4: NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4And (3) preparing the three-layer core-shell structure nanocrystal.
And preparing the three-layer core-shell structure nanocrystal by using a full-automatic nanomaterial synthesizer through a layer-by-layer wrapping method.
The specific preparation process is that the preparation of the nanocrystal with the three-layer core-shell structure is similar to the preparation method of the nanocrystal with the two-layer core-shell structure. Only the precursor of the Y, Er, Ho-OA shell prepared above is replaced by the precursor of the Y-OA shell, the double-layer core-shell structure nanocrystal prepared in the above example 3 is used as a seed crystal, and NaYF is induced and epitaxially grown4And (4) shell layer. And dispersing the prepared product into cyclohexane for characterization and next preparation of the four-layer core-shell structure nanocrystal.
Example 5: NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4Nd/Yb/Er (0.5/20/2 mol%) four-layer core-shell structure nanocrystalline.
And preparing the four-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer.
The specific preparation process is that the preparation of the four-layer core-shell structure nanocrystalline is similar to the preparation method of the three-layer core-shell structure nanocrystalline. Only the precursor of the Y-OA shell layer prepared above needs to be replaced by the precursor of the Y, Nd, Yb, Er-OA shell layer, the three-layer core-shell structure nanocrystal prepared above in example 4 is used as seed crystal, and NaYF is induced and epitaxially grown4Nd/Yb/Er shell layer. Dispersing the prepared product into cyclohexane for characterization and next five layersAnd (3) preparing core-shell structure nanocrystals.
Example 6:
NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4:Nd/Yb/Er@NaYF4nd (20 mol%) is used for preparing the five-layer core-shell structure nanocrystalline.
And preparing the five-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer.
The specific preparation process is that the preparation of the five-layer core-shell structure nanocrystalline is similar to the preparation method of the four-layer core-shell structure nanocrystalline. Only the precursor of the Y, Nd, Yb, Er-OA shell layer prepared above needs to be replaced by the precursor of the Y, Nd-OA shell layer, the four-layer core-shell structure nanocrystalline prepared in the above example 5 is used as seed crystal, and NaYF is induced and epitaxially grown4Nd shell layer. And dispersing the prepared five-layer core-shell structure nanocrystalline into cyclohexane for characterization.
Example 7:
a method for preparing an orthogonal excitation-emission response three-primary-color up-conversion luminescent material comprises the following specific steps:
the method comprises the following steps: preparation of blue light emitting nuclear NaYF by full-automatic nano material synthesizer430 mol% Yb,0.5 mol% Tm, for emitting blue fluorescence of 474nm under the excitation of 980nm near infrared light; 0.278mmol of Y (CH)3COO)30.120mmol of Yb (CH)3COO)3And a Tm (CH) of 0.002mmol3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene at room temperature, stirring and heating to 150 ℃, and reacting for 60 minutes to form an oleic acid complex Y, Yb, Tm-OA nuclear precursor; the resulting mixed solution was naturally cooled to room temperature, and 4mL of NH was added4F (0.4moL/L) and 2mL of methanol solution of NaOH (0.5moL/L) are heated to 50 ℃ and continuously stirred for 30 minutes, then stirred and heated to 100 ℃ and reacted for 10 minutes under vacuum condition to remove methanol, and finally heated to 290 ℃ under argon atmosphere and reacted for 90 minutes; cooling to room temperature after the reaction is finished, centrifuging the reaction solution for 5 minutes at 9000r/min, collecting the precipitate, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in the cyclohexanePreparing the nanocrystalline with the characteristic and core-shell structure in the alkane;
step two: 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (0.4mmol) of the nuclear nanocrystal prepared in the step one and 4mL of NH4Continuously stirring the solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol at 50 ℃ for 30 minutes, then stirring and heating to 100 ℃, reacting for 20 minutes under a vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under an argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution at 9000r/min for 5 minutes, collecting precipitates, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and preparation of the nanocrystal with the double-layer core-shell structure in the next step;
step three: taking the formed core-shell structure nanocrystal as seed crystal again, and inducing epitaxial growth of a second red light emitting layer NaYF4:5mol％Er,5mol％Ho；
Preparing the double-layer core-shell structure nanocrystal by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.36mmol of Y (CH)3COO)30.02mmol of Er (CH)3COO)3And 0.02mmol of Ho (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Er, Ho-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (0.4mmol) of the core-shell structure nanocrystal prepared in the second step and 4mL of NH4Stirring the solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol for 30 minutes under the reaction condition of 50 ℃, then stirring and heating to 100 ℃, reacting for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under the argon atmosphere for reacting for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution for 5 minutes at 9000r/min, collectingPrecipitating, repeatedly washing with cyclohexane and ethanol for three times, and dispersing the finally obtained product in cyclohexane for characterization and next preparation of three-layer core-shell structure nanocrystals;
step four: will be coated with NaYF4Taking Er/Ho double-layer core-shell nano-crystal as seed crystal again, and inducing epitaxial growth of third layer of inert isolating layer NaYF4；
Preparing three-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃, reacting for 60 minutes to form an oleic acid complex Y-OA shell layer precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (about 0.4mmol) of the double-layer core-shell structure nanocrystal prepared in the step three and 4mL of NH4Continuously stirring the solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol at 50 ℃ for 30 minutes, then stirring and heating to 100 ℃, reacting for 20 minutes under a vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under an argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution at 9000r/min for 5 minutes, collecting precipitates, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and preparation of four-layer core-shell structure nanocrystals in the next step;
step five: coating a third inert isolating layer NaYF4The three layers of core-shell nanocrystals are used as seed crystals again to induce epitaxial growth of a fourth layer of green light emitting layer NaYF4:0.5mol％Nd,20mol％Yb,2mol％Er；
Preparing four-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.31mmol of Y (CH)3COO)30.002mmol of Nd (CH)3COO)30.08mmol of Yb (CH)3COO)3And 0.008mmol of Er (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃, and reacting for 60 DEG CForming a precursor of an oleic acid complex Y, Nd, Yb, Er-OA shell layer in minutes, naturally cooling the obtained mixed solution to room temperature, and adding cyclohexane solution (0.4mmol) of the three-layer core-shell structure nanocrystalline prepared in the fourth step and 4mL of NH4Continuously stirring the solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol at 50 ℃ for 30 minutes, then stirring and heating to 100 ℃, reacting for 20 minutes under a vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under an argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution at 9000r/min for 5 minutes, collecting precipitates, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and next preparation of five-layer core-shell structure nanocrystals;
step six: will be coated with NaYF4Taking Nd/Yb/Er four-layer core-shell nano-crystal as seed crystal again, inducing epitaxial growth of fifth 808nm excitation light energy absorption layer NaYF4:20mol％Nd；
Preparing five-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.32mmol of Y (CH)3COO)3And 0.08mmol of Nd (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Nd-OA shell layer precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution (about 0.4mmol) of the four-layer core-shell structure nanocrystal prepared in the fifth step and 4mL of NH4And F (0.4moL/L) and 2mL of methanol solution of NaOH (0.5moL/L) are stirred for 30 minutes under the reaction condition of 50 ℃, then stirred and heated to 100 ℃, and reacted for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally the temperature is raised to 290 ℃ under the argon atmosphere for 90 minutes of reaction, the reaction solution is cooled to room temperature after the reaction is finished, the reaction solution is centrifuged for 5 minutes at 9000r/min, the precipitate is collected and repeatedly washed with cyclohexane and ethanol for three times, and finally the obtained product is dispersed in cyclohexane for characterization.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (5)
1. A method for preparing an orthogonal excitation-emission response three-primary-color up-conversion luminescent material is characterized by comprising the following steps of: firstly preparing NaYF4Yb/Tm (30/0.5 mol%) luminous core, and then using the core as seed crystal to induce crystal epitaxial growth of NaYF4Shell layer of NaYF with core-shell structure4:Yb/Tm@NaYF4The nano crystal is used as a seed crystal for further growing NaYF4A second shell layer of Er/Ho (5/5 mol%); similarly, the prepared double-layer core-shell NaYF4:Yb/Tm@NaYF4@NaYF4Er/Ho nano-crystal as seed crystal for further growing NaYF4A third shell layer; similarly, the prepared three-layer core-shell NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4The nano crystal is used as a seed crystal for further growing NaYF4A fourth shell layer of Nd/Yb/Er (0.5/20/2 mol%); similarly, the prepared four-layer core-shell NaYF4:Yb/Tm@NaYF4@NaYF4:Er/Ho@NaYF4@NaYF4Further growing NaYF by taking Nd/Yb/Er nano-crystal as seed crystal4Nd fifth shell (20 mol%).
2. The method for preparing the orthorhombic excitation-emission response three-primary-color up-conversion luminescent material according to claim 1, wherein the size of the luminescent core is 22-30 nm, the thickness of the first shell is 4-6 nm, the thickness of the second shell is 3-6 nm, the thickness of the third shell is 5-7 nm, the thickness of the fourth shell is 4-6 nm, and the thickness of the fifth shell is 2-3 nm.
3. The method for preparing an orthogonal excitation-emission responsive three-primary-color up-conversion luminescent material according to claim 1, comprising the following steps:
(1) preparing a luminescent core: adding rare earth salt into a mixed high-temperature solvent of Oleic Acid (OA) and 1-Octadecene (ODE), reacting at high temperature under the protection of inert gas to obtain a rare earth oleic acid complex (Ln-OA), cooling, adding a methanol solution of a fluorine source and a sodium source, and reacting at the temperature of 280-320 ℃ under the protection of inert gas to obtain luminescent core nano-particles after methanol is volatilized;
(2) preparing a shell layer precursor: adding rare earth salt required by shell growth into a mixed high-temperature solvent of Oleic Acid (OA) and 1-Octadecene (ODE), and obtaining a rare earth oleic acid complex required by shell formation under the protection of high temperature and inert gas;
(3) preparing core-shell structure nanocrystals: adding the luminescent core nano-particles prepared in the step (1) into the shell layer precursor solution as seed crystals, introducing a fluorine source and a sodium source, and forming core-shell structure nanocrystals by inducing crystal epitaxial growth shell layers under the conditions of high temperature and inert gas protection;
(4) preparing the double-layer or multi-layer core-shell structure nanocrystal: core-shell or (n-1) layer core-shell structure nano particles prepared in the previous step are added into the shell layer precursor solution as seed crystals, a fluorine source and a sodium source are introduced, and double-layer or multi-layer core-shell structure nano crystals are formed in a mode of inducing crystal epitaxial growth shell layers under the conditions of high temperature and inert gas protection.
4. The method of claim 2, wherein the rare earth salt is a rare earth acetate salt, a rare earth chloride salt, or a rare earth nitrate salt; the fluorine source is ammonium fluoride, potassium fluoride, lithium fluoride, sodium fluoride or sodium trifluoroacetate; the sodium source is sodium hydroxide, sodium fluoride, sodium acetate or sodium trifluoroacetate.
5. The method for preparing an orthogonal excitation-emission responsive three-primary-color up-conversion luminescent material according to claim 1, comprising the following steps:
the method comprises the following steps: preparation of blue light emitting nuclear NaYF by full-automatic nano material synthesizer430 mol% Yb,0.5 mol% Tm, for emitting blue fluorescence of 474nm under the excitation of 980nm near infrared light; 0.278mmol of Y (CH)3COO)30.120mmol of Yb (CH)3COO)3And a Tm (CH) of 0.002mmol3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene at room temperature, stirring and heating to 150 ℃, and reacting for 60 minutes to form an oleic acid complex Y, Yb, Tm-OA nuclear precursor; naturally cooling the obtained mixed solution to room temperature, and adding NH4F and NaOH methanol solution are heated to 50 ℃ and continuously stirred for 30 minutes, then stirred and heated to 100 ℃ and reacted for 10 minutes under a vacuum condition to remove methanol, and finally heated to 290 ℃ under an argon atmosphere and reacted for 90 minutes; cooling to room temperature after the reaction is finished, centrifuging the reaction solution for 5 minutes at 9000r/min, collecting the precipitate, repeatedly washing the precipitate for three times by using cyclohexane and ethanol, and finally dispersing the obtained product in the cyclohexane for preparing the nanocrystalline with the characteristic and core-shell structure;
step two: preparing core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution of the nuclear nanocrystal prepared in the step one and NH4Continuously stirring the solution of F and NaOH for 30 minutes under the reaction condition of 50 ℃, then stirring and heating to 100 ℃, reacting for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under the argon atmosphere for reacting for 90 minutes, cooling to room temperature after the reaction is finishedCentrifuging the reaction solution for 5 minutes at 9000r/min, collecting precipitates, repeatedly washing the precipitates with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and preparation of a double-layer core-shell structure nanocrystal in the next step;
step three: taking the formed core-shell structure nanocrystal as seed crystal again, and inducing epitaxial growth of a second red light emitting layer NaYF4:5mol％Er,5mol％Ho；
Preparing the double-layer core-shell structure nanocrystal by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.36mmol of Y (CH)3COO)30.02mmol of Er (CH)3COO)3And 0.02mmol of Ho (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Er, Ho-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution of the core-shell structure nanocrystal prepared in the second step and 4mL of NH4Continuously stirring the solution of F (0.4moL/L) and 2mL of NaOH (0.5moL/L) in methanol at 50 ℃ for 30 minutes, then stirring and heating to 100 ℃, reacting for 20 minutes under a vacuum condition to remove cyclohexane and methanol, finally heating to 290 ℃ under an argon atmosphere to react for 90 minutes, cooling to room temperature after the reaction is finished, centrifuging the reaction solution at 9000r/min for 5 minutes, collecting precipitates, repeatedly washing with cyclohexane and ethanol for three times, and finally dispersing the obtained product in cyclohexane for characterization and next preparation of three-layer core-shell structure nanocrystals;
step four: will be coated with NaYF4Taking Er/Ho double-layer core-shell nano-crystal as seed crystal again, and inducing epitaxial growth of third layer of inert isolating layer NaYF4；
Preparing three-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.4mmol of Y (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃, reacting for 60 minutes to form an oleic acid complex Y-OA shell precursor, and obtaining a mixed solutionThen cooling to room temperature, adding the cyclohexane solution of the double-layer core-shell structure nanocrystal prepared in the third step and 4mL of NH4F and 2mL of NaOH methanol solution are continuously stirred for 30 minutes under the reaction condition of 50 ℃, then stirred and heated to 100 ℃, and reacted for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally the temperature is raised to 290 ℃ under the argon atmosphere for reaction for 90 minutes, the reaction solution is cooled to room temperature after the reaction is finished, the reaction solution is centrifuged for 5 minutes at 9000r/min, the precipitate is collected and repeatedly washed for three times by cyclohexane and ethanol, and finally the obtained product is dispersed in cyclohexane for characterization and preparation of four-layer core-shell structure nanocrystalline in the next step;
step five: coating a third inert isolating layer NaYF4The three layers of core-shell nano-crystals are used as seed crystals again to induce epitaxial growth of a green light emitting layer NaYF4:0.5mol％Nd,20mol％Yb,2mol％Er；
Preparing four-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.31mmol of Y (CH)3COO)30.002mmol of Nd (CH)3COO)30.08mmol of Yb (CH)3COO)3And 0.008mmol of Er (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Nd, Yb, Er-OA shell precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution of the three-layer core-shell structure nanocrystalline prepared in the step four and 4mL of NH4F and 2mL of NaOH methanol solution are continuously stirred for 30 minutes under the reaction condition of 50 ℃, then stirred and heated to 100 ℃, and reacted for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally the temperature is raised to 290 ℃ under the argon atmosphere for reaction for 90 minutes, the reaction solution is cooled to room temperature after the reaction is finished, the reaction solution is centrifuged for 5 minutes at 9000r/min, the precipitate is collected and repeatedly washed for three times by cyclohexane and ethanol, and finally the obtained product is dispersed in cyclohexane for characterization and preparation of five-layer core-shell structure nanocrystalline in the next step;
step six: will be coated with NaYF4Four-layer core-shells of Nd/Yb/ErThe nanocrystalline is used as seed crystal again to induce the epitaxial growth of the NaYF4:20mol％Nd；
Preparing five-layer core-shell structure nanocrystalline by a layer-by-layer wrapping method by using a full-automatic nanomaterial synthesizer, wherein the specific preparation process is to use 0.32mmol of Y (CH)3COO)3And 0.08mmol of Nd (CH)3COO)3Adding the aqueous solution into a mixed solvent of 3mL of oleic acid and 7mL of octadecene, stirring and heating the obtained mixture to 150 ℃ to react for 60 minutes to form an oleic acid complex Y, Nd-OA shell layer precursor, naturally cooling the obtained mixed solution to room temperature, and adding the cyclohexane solution of the four-layer core-shell structure nanocrystal prepared in the fifth step and 4mL of NH4And F and 2mL of a methanol solution of NaOH are continuously stirred for 30 minutes under the reaction condition of 50 ℃, then stirred and heated to 100 ℃, and the mixture is reacted for 20 minutes under the vacuum condition to remove cyclohexane and methanol, finally the temperature is raised to 290 ℃ under the argon atmosphere for reaction for 90 minutes, the reaction solution is cooled to room temperature after the reaction is finished, the reaction solution is centrifuged for 5 minutes at 9000r/min, the precipitate is collected and repeatedly washed with cyclohexane and ethanol for three times, and finally the obtained product is dispersed in cyclohexane for characterization.
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| 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 |
| CN112300801B (en) * | 2020-11-16 | 2023-01-03 | 哈尔滨工业大学 | Non-contact ultralow-temperature sensing up-conversion nano probe and preparation method and application thereof |
| CN112903649A (en) * | 2021-01-26 | 2021-06-04 | 上海大学 | Double-excitation orthogonal emission up-conversion luminescence nanoparticle, multi-flux detection immunochromatography test paper and application thereof |
| CN112903649B (en) * | 2021-01-26 | 2022-07-15 | 上海大学 | Double-excitation orthogonal emission up-conversion luminescence nanoparticle, multi-flux detection immunochromatography test paper and application thereof |
| CN113980682A (en) * | 2021-11-16 | 2022-01-28 | 广州医科大学附属第二医院 | Preparation of near-infrared luminescent Yb and Tm co-doped core-shell structure nanocrystal and application of nanocrystal in immunochromatography detection |
| CN114015446A (en) * | 2021-12-08 | 2022-02-08 | 甘肃农业大学 | Application method of up-conversion luminescent material in optical invisible anti-counterfeiting aspect |
| CN114015446B (en) * | 2021-12-08 | 2023-08-11 | 甘肃农业大学 | Application method of up-conversion luminescent material in optical invisible anti-counterfeiting |
| CN115537200A (en) * | 2022-10-10 | 2022-12-30 | 上海交通大学 | Ultra-wideband response lanthanum series nanocrystalline and preparation method and application thereof |
| CN115537200B (en) * | 2022-10-10 | 2023-08-25 | 上海交通大学 | Ultra-wideband response lanthanide nanocrystalline and preparation method and application thereof |
| CN116515488A (en) * | 2023-04-17 | 2023-08-01 | 华中科技大学 | Up-conversion luminescent material with double abrupt interfaces and preparation method thereof |
| CN116515488B (en) * | 2023-04-17 | 2024-05-14 | 华中科技大学 | Up-conversion luminescent material with double abrupt interfaces and preparation method thereof |
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