CN116904196A - Up-conversion luminescent material and preparation method thereof - Google Patents
Up-conversion luminescent material and preparation method thereof Download PDFInfo
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 51
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- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
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Abstract
The application provides an up-conversion luminescent material and a preparation method thereof, wherein the up-conversion luminescent material comprises a luminescent core, a luminescent shell coating the luminescent core and an active shell coating the luminescent shell, and the luminescent core has a chemical formula of beta-NaYF 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the luminous shell is beta-NaYF 4 :Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the active shell is beta-NaYF 4 :Yb 3+ ,Nd 3+ . Therefore, the core-shell structured material can emit high-brightness green up-conversion luminescence under the co-excitation of near infrared light with two different wavelengths of 850nm and 1550nm, and the up-conversion luminescent material with a luminescent core-luminescent shell-active shell three-layer structure can remarkably improve the luminescence intensity of double-frequency co-excitation compared with a single-core material.
Description
Technical Field
The application belongs to the technical field of true three-dimensional display, up-conversion luminescence and nano core-shell material preparation intersection, and particularly relates to an up-conversion luminescence material and a preparation method thereof.
Background
With the progress of the information age, people have not satisfied with the image display of two-dimensional planes, and the development of three-dimensional display technology is continuously pursued and promoted. The information quantity expressed by the three-dimensional display is far beyond that of the two-dimensional display, the position of an observer is not limited, and a 360-degree immersive observation image can be realized. Current three-dimensional display technologies fall into several different types, including stereoscopic display, autostereoscopic display, integrated image display, holographic display, volumetric three-dimensional display. The three-dimensional display of the volume is to display a three-dimensional object through volume pixels of a three-dimensional space, is a real stereoscopic image, and can provide all depth information. The development of rare earth up-conversion luminescent materials has also driven the progress of this true three-dimensional display. However, the commercial practical application and development of the three-dimensional display technology have higher requirements on up-conversion luminescent materials, and the display body is fluoride crystal of several rare earths, so that on one hand, the display body is colorless and transparent and does not influence imaging of three-dimensional images; on the other hand, the up-conversion luminescent material is required to have higher luminous intensity, so that the three-dimensional stereoscopic display image has higher resolution. The current up-conversion luminescent material is difficult to meet the requirements.
Therefore, there is a need for an improved up-conversion luminescent material.
Disclosure of Invention
The present application aims to improve at least to some extent at least one of the above technical problems.
In order to solve the problems, the application provides an up-conversion luminescent material, which comprises a luminescent core, a luminescent shell coating the luminescent core, and an active shell coating the luminescent shell, wherein the luminescent core has a chemical formula of beta-NaYF 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the luminous shell is beta-NaYF 4 :Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the active shell is beta-NaYF 4 :Yb 3 + ,Nd 3+ . Therefore, the core-shell structured material can emit high-brightness green up-conversion luminescence under the co-excitation of near infrared light with two different wavelengths of 850nm and 1550nm, and the up-conversion luminescent material with a luminescent core-luminescent shell-active shell three-layer structure can remarkably improve the luminescence intensity of double-frequency co-excitation compared with a single-core material.
According to an embodiment of the present application, in the luminescent core, er 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 0.5% -2% of the total molar amount of (a); in the luminous core, Yb 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ From 0.5% to 2% of the total molar amount.
According to an embodiment of the application, er in the luminescent shell 3+ Is beta-NaYF 4 And Er 3+ From 0.5% to 2% of the total molar amount.
According to an embodiment of the present application, yb in the active shell 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 0.5% -2% of the total molar amount of (a); in the active shell, nd 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ From 0.5% to 1.5% of the total molar amount.
The present application also provides a method of up-converting a luminescent material as described hereinbefore, the method comprising: preparation of luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the The obtained luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ As seed crystal, coating the outer layer of the luminous core with luminous shell beta-NaYF 4 :Er 3+ To obtain the beta-NaYF with the luminous core-luminous shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The obtained luminescent core-luminescent shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ As seed crystal, coating beta-NaYF on the outer layer of the luminous shell 4 :Yb 3+ ,Nd 3+ Forming an active shell to obtain the up-conversion luminescent material beta-NaYF with a core-shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ . Therefore, the up-conversion luminescent material prepared by the method has all the characteristics and advantages of the up-conversion luminescent material, which are not described herein. In addition, the method has the advantages of simple operation and low production cost, and is suitable for large-scale industrial production.
According to an embodiment of the present application, a luminescent core β -NaYF was prepared 4 :Er 3+ ,Yb 3+ Comprising the following steps: mixing the first rare earth salt with oleic acid and 1-octadecene, and reacting to obtain the final productForming a first rare earth oleic acid complex, mixing the first rare earth oleic acid complex with a methanol solution containing a first sodium source and a first fluorine source, volatilizing methanol, and reacting to obtain a luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein the first rare earth salt comprises a Y-containing rare earth salt, an Er-containing rare earth salt and a Yb-containing rare earth salt; preparation of luminescent core-luminescent shell Structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Comprising the following steps: mixing a second rare earth salt with oleic acid and 1-octadecene, reacting to generate a second rare earth oleic acid complex, and carrying out beta-NaYF on the luminescent core 4 :Er 3+ ,Yb 3+ Adding the second rare earth oleic acid complex as seed crystal, adding methanol solution containing a second sodium source and a second fluorine source, volatilizing methanol, and reacting to obtain luminescent core-luminescent shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Wherein the second rare earth salt comprises a Y-containing rare earth salt and an Er-containing rare earth salt; preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Comprising the following steps: mixing the third rare earth salt with oleic acid and 1-octadecene, reacting to generate a third rare earth oleic acid complex, and carrying out beta-NaYF on the luminescent core-luminescent shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Adding the mixed solution as seed crystal into the third rare earth oleic acid complex, adding a methanol solution containing a third sodium source and a third fluorine source, volatilizing methanol, and reacting to obtain the up-conversion luminescent material beta-NaYF with a core-shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Wherein the third rare earth salt comprises a Y-containing rare earth salt, a Yb-containing rare earth salt and an Nd-containing rare earth salt.
According to an embodiment of the present application, a luminescent core β -NaYF was prepared 4 :Er 3+ ,Yb 3+ When the ratio of the first rare earth salt to oleic acid to 1-octadecene is 1mmol (5-10) mL (10-20); preparation of luminescent core-hairLight shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ When the proportion of the second rare earth salt to oleic acid and 1-octadecene is 1mmol (5-10) mL (10-20) mL; preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3 + ,Nd 3+ When the ratio of the third rare earth salt to oleic acid to 1-octadecene is 1mmol (5-10) mL (10-20) mL.
According to an embodiment of the present application, the first rare earth salt, the second rare earth salt, and the third rare earth salt are one of a rare earth chloride salt, a rare earth acetate salt, and a rare earth trifluoroacetate salt; the first sodium source, the second sodium source and the third sodium source are NaOH and CF 3 One of COONa; the first fluorine source, the second fluorine source and the third fluorine source are NH 4 F. One of the nafs.
According to an embodiment of the present application, a luminescent core β -NaYF was prepared 4 :Er 3+ ,Yb 3+ When the ratio of the first rare earth salt to the first sodium source, the first fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL; preparation of luminescent core-luminescent shell Structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ When the ratio of the second rare earth salt to the second sodium source, the second fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL; preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ In the process, the ratio of the third rare earth salt to the third sodium source, the third fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL.
According to an embodiment of the present application, a luminescent core-luminescent shell structure β -NaYF was prepared 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ When the second rare earth salt and the luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ The molar ratio of (2) is 1 (0.8-1.2); preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ When the third rare earth salt is in a light-emitting core-light-emitting shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ The molar ratio of (2) is 1 (0.8-1.2).
Drawings
FIG. 1 is a schematic diagram of an up-conversion luminescent material according to an embodiment of the present application;
FIG. 2 is a flow chart of a method of preparing an up-conversion luminescent material in accordance with an embodiment of the application;
FIG. 3 is a morphology image of a scanning electron microscope photograph of the up-conversion luminescent material prepared in example 1 of the present application;
FIG. 4 is a graph showing the emission spectra of the up-conversion luminescent material prepared in example 1 of the present application for dual-frequency excitation of luminescent core, luminescent core-luminescent shell-active shell.
Detailed Description
Embodiments of the present application are described in detail below. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents used were not manufacturer-identified and were all commercially available conventional products.
The application provides an up-conversion luminescent material, referring to figure 1, the up-conversion luminescent material comprises a luminescent core, a luminescent shell coating the luminescent core and an active shell coating the luminescent shell, wherein the luminescent core has a chemical formula of beta-NaYF 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the luminous shell is beta-NaYF 4 :Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the active shell is beta-NaYF 4 :Yb 3+ ,Nd 3+ . Therefore, the core-shell structured material can emit high-brightness green up-conversion luminescence and uncoated beta-NaYF under the common excitation of near infrared light with two different wavelengths of 850nm and 1550nm 4 :Er 3+ ,Yb 3+ In contrast, the core-shell of the applicationThe luminous intensity of the shell structure material is improved by nearly 6 times. Specifically, the inner layer structure of the application is beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ In which Er is isolated from space by cladding 3+ Reducing Er 3+ The influence of self concentration quenching improves the up-conversion luminous intensity; outer coating active layer beta-NaYF 4 :Yb 3+ ,Nd 3+ On one hand, the surface defect of the material can be reduced, the non-radiative transition is reduced, and on the other hand, the inner layer sensitized ion Yb 3+ And an outer layer sensitized ion Yb 3+ 、Nd 3+ The combined action improves the absorption of the material to near infrared light inside and outside, thereby improving the up-conversion luminous intensity of the dual-frequency co-excitation.
According to an embodiment of the present application, in the luminescent core, er 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 0.5% -2% of the total molar amount of (a); in the luminescent core, yb 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ From 0.5% to 2% of the total molar amount. Therefore, the luminous core has stronger double-frequency excitation up-conversion luminous intensity. If Er in the luminescent core 3+ If the doping ratio is too small, the luminescence center is too small, and the up-conversion luminescence intensity of the dual-frequency excitation is low. If Er in the luminescent core 3+ If the doping ratio of (a) is too large, er is caused 3+ Concentration quenching occurs by itself, resulting in a decrease in the up-conversion luminescence intensity of the dual-frequency excitation. If Yb in the luminescent nucleus 3+ If the doping ratio is too small, the sensitization center is small, the absorption capacity of the luminescent core to near infrared light is reduced, and the up-conversion luminescence intensity of the dual-frequency excitation is low. If Yb in the luminescent nucleus 3+ If the doping ratio is too large, the luminescent core can excessively absorb the energy of 1550nm near infrared light, so that the luminous intensity is increased during 1550nm single-frequency excitation, and the contrast ratio of double-frequency excitation is reduced.
According to an embodiment of the application, er in the luminescent shell 3+ Is beta-NaYF 4 And Er 3+ From 0.5% to 2% of the total molar amount. Thus, the inner layer structure beta-NaYF can be made 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Has stronger double-frequency excitation up-conversion luminous intensity. If Er in luminous shell 3+ If the doping ratio is too small, the luminescence center is too small, and the up-conversion luminescence intensity of the dual-frequency excitation is low. If Er in luminous shell 3+ If the doping ratio of (a) is too large, er is caused 3+ Concentration quenching occurs by itself, resulting in a decrease in the up-conversion luminescence intensity of the dual-frequency excitation.
According to an embodiment of the present application, yb in the active shell 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 0.5% -2% of the total molar amount of (a); in the active shell, nd 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ From 0.5% to 1.5% of the total molar amount. Thus, the active shell can exert an optimal sensitization effect. If Yb in active shell 3+ If the doping ratio is too small, the sensitization of the active shell to near infrared light is small, and the effect of enhancing the double-frequency excitation up-conversion luminescence is not obvious. If Yb in active shell 3+ If the doping ratio is too large, the luminous intensity at 1550nm single-frequency excitation is increased, resulting in a decrease in contrast ratio of dual-frequency excitation. If Nd in the active shell 3+ If the doping ratio is too small, the sensitization of the active shell to near infrared light is small, and the effect of enhancing the double-frequency excitation up-conversion luminescence is not obvious. If Nd in the active shell 3+ If the doping ratio is too large, the luminous intensity at 1550nm single-frequency excitation is increased, resulting in a decrease in contrast ratio of dual-frequency excitation.
The present application also provides a method of preparing the up-conversion luminescent material described hereinbefore, with reference to fig. 2, the method comprising:
s100, preparation of luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ ；
According to an embodiment of the present application, the luminescent core β -NaYF may be prepared by a solvothermal method 4 :Er 3+ ,Yb 3+ Specifically, step S100 includes: mixing a first rare earth salt with oleic acid and 1-octadecene, reacting to generate a first rare earth oleic acid complex, mixing the first rare earth oleic acid complex with a methanol solution containing a first sodium source and a first fluorine source, volatilizing methanol, and then reversingAccordingly, a luminescent core beta-NaYF is obtained 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein the first rare earth salt comprises a Y-containing rare earth salt, an Er-containing rare earth salt and a Yb-containing rare earth salt.
According to an embodiment of the present application, in the reaction for producing the first rare earth oleic acid complex, the reaction is performed under the protection of inert gas, the temperature of the reaction is 140 to 170 ℃, the time of the reaction is 40 to 100min, and after the reaction for producing the first rare earth oleic acid complex is completed, the method further includes: cooling the reaction system to 40-60 ℃, adding a methanol solution containing a first sodium source and a first fluorine source under vigorous stirring, and preserving heat for 1-2 h at 40-60 ℃; heating to 100-120 ℃, preserving heat for 10-40 min, and removing methanol; rapidly heating to 300-310 ℃, preserving heat for 1-1.5 h, and cooling to room temperature; centrifuging the reaction solution with ethanol at 9000r/min for 5min, collecting precipitate, washing with mixture of cyclohexane and absolute ethanol for three times, and dispersing the final product in chloroform to obtain beta-NaYF 4 :Er 3+ ,Yb 3+ 。
According to some embodiments of the application, the content of each component of the Y-containing rare earth salt, the Er-containing rare earth salt and the Yb-containing rare earth salt in the first rare earth salt is according to the luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ Is weighed out by the stoichiometric ratio of (2). Specifically, due to the luminescent core, er 3 + Is beta-NaYF 4 、Er 3+ And Yb 3+ 0.5% -2% of the total molar amount of Yb 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ From 0.5% to 2% of the total molar amount of (c), the first rare earth salt should therefore satisfy: the percentage of the sum of the molar amount of Er in the Er-containing rare earth salt and the molar amount of Y in the Y-containing rare earth salt, the molar amount of Er in the Er-containing rare earth salt and the molar amount of Yb in the Yb-containing rare earth salt is 0.5-2%, and the percentage of the sum of the molar amount of Yb in the Yb-containing rare earth salt and the molar amount of Y in the Y-containing rare earth salt, the molar amount of Er in the Er-containing rare earth salt and the molar amount of Yb in the Yb-containing rare earth salt is 0.5-2%.
According to an embodiment of the present application, a luminescent core β -NaYF was prepared 4 :Er 3+ ,Yb 3+ At the time, the ratio of the first rare earth salt to oleic acid and 1-octadeceneExamples are 1mmol (5-10) mL (10-20) mL. Under the condition, the rapid dissolution of the first rare earth salt and the generation of the first rare earth oleic acid complex are facilitated.
According to an embodiment of the present application, the first rare earth salt is one of a rare earth chloride salt, a rare earth acetate salt, and a rare earth trifluoroacetate salt; the first sodium source is NaOH, CF 3 One of COONa; the first fluorine source is NH 4 F. One of the nafs.
According to an embodiment of the present application, a luminescent core β -NaYF was prepared 4 :Er 3+ ,Yb 3+ When the rare earth salt is used, the proportion of the first rare earth salt to the first sodium source, the first fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL. Under the condition, the luminescent core beta-NaYF is favored 4 :Er 3+ ,Yb 3+ Is generated.
S200, obtaining the luminous core beta-NaYF 4 :Er 3+ ,Yb 3+ As seed crystal, coating the outer layer of the luminous core with luminous shell beta-NaYF 4 :Er 3+ To obtain the beta-NaYF with the luminous core-luminous shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ ；
According to an embodiment of the present application, the luminescent core-luminescent shell structure β -NaYF may be prepared by a solvothermal method 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Specifically, step S200 includes: mixing a second rare earth salt with oleic acid and 1-octadecene, reacting to generate a second rare earth oleic acid complex, and carrying out beta-NaYF on the luminescent core 4 :Er 3+ ,Yb 3+ Adding the second rare earth oleic acid complex as seed crystal, adding methanol solution containing a second sodium source and a second fluorine source, volatilizing methanol, and reacting to obtain luminescent core-luminescent shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Wherein the second rare earth salt comprises a Y-containing rare earth salt and an Er-containing rare earth salt.
According to an embodiment of the present application, in the reaction for producing the second rare earth oleic acid complex, the reaction is performed under the protection of inert gas, and the temperature of the reaction is 140-170 DEG CThe reaction time is 40-100 min, and after the reaction for producing the second rare earth oleic acid complex is completed, the method further comprises: cooling the reaction system to 40-60 deg.c, adding seed crystal beta-NaYF while stirring vigorously 4 :Er 3+ ,Yb 3+ Stirring for 2-5 min, adding a methanol solution containing a second sodium source and a second fluorine source, and preserving heat for 1-2 h at 40-60 ℃; heating to 100-120 ℃, preserving heat for 10-40 min, and removing methanol; rapidly heating to 300-310 ℃, preserving heat for 1-1.5 h, and cooling to room temperature; centrifuging the reaction solution with ethanol at 9000r/min for 5min, collecting precipitate, washing with mixture of cyclohexane and absolute ethanol for three times, and dispersing the final product in chloroform to obtain luminescent core-luminescent shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ 。
According to some embodiments of the application, the content of each component of the Y-containing rare earth salt and the Er-containing rare earth salt in the second rare earth salt is according to the luminescent shell beta-NaYF 4 :Er 3+ Is weighed out by the stoichiometric ratio of (2). In particular, due to the luminescent shell, er 3+ Is beta-NaYF 4 And Er 3+ From 0.5% to 2% of the total molar amount of (c), the second rare earth salt should therefore satisfy: the percentage of the sum of the molar quantity of Er in the Er-containing rare earth salt and the molar quantity of Y in the Y-containing rare earth salt is 0.5-2 percent.
According to an embodiment of the present application, a luminescent core-luminescent shell structure β -NaYF was prepared 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ When the ratio of the second rare earth salt to oleic acid to 1-octadecene is 1mmol (5-10) mL (10-20) mL. Under the condition, the rapid dissolution of the second rare earth salt and the generation of the second rare earth oleic acid complex are facilitated.
According to an embodiment of the present application, the second rare earth salt is one of a rare earth chloride salt, a rare earth acetate salt, and a rare earth trifluoroacetate salt; the second sodium source is NaOH, CF 3 One of COONa; the second fluorine source is NH 4 F. One of the nafs.
According to an embodiment of the present application, a luminescent core-luminescent shell structure β -NaYF was prepared 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ And the proportion of the second rare earth salt to the second sodium source, the second fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL. Under the condition, the beta-NaYF of the luminescent core-luminescent shell structure is facilitated 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Is generated.
According to an embodiment of the present application, a luminescent core-luminescent shell structure β -NaYF was prepared 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ When the second rare earth salt and the luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ The ratio of (2) is 1 (0.8-1.2). Under the condition, the beta-NaYF of the luminescent core-luminescent shell structure is facilitated 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Is generated.
S300, obtaining the beta-NaYF of the luminous core-luminous shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ As seed crystal, coating beta-NaYF on the outer layer of the luminous shell 4 :Yb 3+ ,Nd 3+ Forming an active shell to obtain the up-conversion luminescent material beta-NaYF with a core-shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ 。
According to an embodiment of the present application, the up-conversion luminescent material β -NaYF of the core-shell structure may be prepared by a solvothermal method 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Specifically, step S300 includes: mixing the third rare earth salt with oleic acid and 1-octadecene, reacting to generate a third rare earth oleic acid complex, and carrying out beta-NaYF on the luminescent core-luminescent shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Adding the mixed solution as seed crystal into the third rare earth oleic acid complex, adding a methanol solution containing a third sodium source and a third fluorine source, volatilizing methanol, and reacting to obtain the up-conversion luminescent material beta-NaYF with a core-shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Wherein the third rare earth salt comprises a Y-containing rare earth salt, a Yb-containing rare earth salt and an Nd-containing rare earth salt.
According to an embodiment of the present application, in the reaction for producing the third rare earth oleic acid complex, the reaction is performed under the protection of inert gas, the temperature of the reaction is 140 to 170 ℃, the time of the reaction is 40 to 100min, and after the reaction for producing the third rare earth oleic acid complex is completed, the method further includes: cooling the reaction system to 40-60 deg.c, adding seed crystal beta-NaYF while stirring vigorously 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Stirring for 2-5 min, adding a methanol solution containing a third sodium source and a third fluorine source, and preserving heat for 1-2 h at 40-60 ℃; heating to 100-120 ℃, preserving heat for 10-40 min, and removing methanol; rapidly heating to 300-310 ℃, preserving heat for 1-1.5 h, and cooling to room temperature; centrifuging the reaction solution with ethanol at 9000r/min for 5min, collecting precipitate, washing with mixture of cyclohexane and absolute ethanol for three times, and dispersing the final product in chloroform to obtain core-shell up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ 。
According to some embodiments of the application, the content of each component of the Y-containing rare earth salt, the Yb-containing rare earth salt and the Nd-containing rare earth salt in the third rare earth salt is according to the active shell beta-NaYF 4 :Yb 3+ ,Nd 3+ Is weighed out by the stoichiometric ratio of (2). Specifically, yb is contained in the active shell 3 + Is beta-NaYF 4 、Yb 3+ And Nd 3+ From 0.5% to 2% of the total molar amount of Nd 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ From 0.5% to 1.5% of the total molar amount of (c), therefore, the third rare earth salt should satisfy: the percentage of the sum of the molar amount of Yb in the Yb-containing rare earth salt and the molar amount of Y in the Y-containing rare earth salt, the molar amount of Yb in the Yb-containing rare earth salt, and the molar amount of Nd in the Nd-containing rare earth salt is 0.5-2%, the molar amount of Nd in the Nd-containing rare earth salt and the molar amount of Y in the Y-containing rare earth salt, and the Yb-containing rare earth saltThe percentage of the sum of the molar amount of Yb in the Nd-containing rare earth salt and the molar amount of Nd in the Nd-containing rare earth salt is 0.5% -1.5%.
According to an embodiment of the present application, a core-shell structured up-conversion luminescent material β -NaYF is prepared 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ When the ratio of the third rare earth salt to oleic acid to 1-octadecene is 1mmol (5-10) mL (10-20) mL. Under the condition, the rapid dissolution of the third rare earth salt and the generation of the third rare earth oleic acid complex are facilitated.
According to an embodiment of the present application, the third rare earth salt is one of a rare earth chloride salt, a rare earth acetate salt, and a rare earth trifluoroacetate salt; the third sodium source is NaOH, CF 3 One of COONa; the third fluorine source is NH 4 F. One of the nafs.
According to an embodiment of the present application, a core-shell structured up-conversion luminescent material β -NaYF is prepared 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ In the process, the ratio of the third rare earth salt to the third sodium source, the third fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL. Under the condition, the up-conversion luminescent material beta-NaYF of the core-shell structure is facilitated 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Is generated.
According to an embodiment of the present application, a core-shell structured up-conversion luminescent material β -NaYF is prepared 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ When the third rare earth salt is in a light-emitting core-light-emitting shell structure beta-NaYF 4 :Er 3+ ,Yb 3 + @β-NaYF 4 :Er 3+ The molar ratio of (2) is 1 (0.8-1.2). Under the condition, the up-conversion luminescent material beta-NaYF of the core-shell structure is facilitated 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Is generated by (a)。
The rare earth luminescent material is coated layer by a solvothermal method, so that the structure of each coating layer is complete and uniform, the thickness and the number of layers of the coating layer are directionally controlled, and the structure of the up-conversion luminescent material can be flexibly adjusted and optimized.
The application will be further illustrated with reference to specific examples. The starting materials for both examples and comparative examples can be obtained commercially or prepared by known methods.
Example 1
The dual-frequency excitation up-conversion luminescent material with a core-shell structure consists of a luminescent core, a luminescent shell and an active shell, wherein the luminescent core structure is beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ The luminous shell structure is beta-NaYF 4 :1％Er 3+ The active shell structure is beta-NaYF 4 :2％Yb 3+ ,1％Nd 3+ . The chemical expression of the dual-frequency excitation up-conversion luminescent material with the core-shell structure is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
The preparation method of the core-shell structure dual-frequency excitation up-conversion luminescent material comprises the following steps:
(1) Preparation of luminescent core beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ ；
Will be 0.97mmol YCl 3 ·6H 2 O、0.02mmol ErCl 3 ·6H 2 O、0.01mmol YbCl 3 ·6H 2 O is added into a mixed solvent of 6mL of oleic acid and 15mL of 1-octadecene, inert gas is introduced to deoxidize, the temperature is kept at 150 ℃ for 40min until the rare earth salt is completely dissolved to obtain a rare earth oleic acid complex, and the temperature is reduced to 50 ℃; 10mL containing 2.5mmol NaOH and 4mmol NH was added with vigorous stirring 4 F, preserving the temperature of the methanol solution at 50 ℃ for 1h; heating to 120deg.C, maintaining the temperature for 20min, and removing methanol; quickly heating to 305 ℃, preserving heat for 1h, and cooling to room temperature; centrifuging the reaction solution with ethanol at 9000r/min for 5min, collecting precipitate, washing with mixture of cyclohexane and absolute ethanol for three times, and dispersing the final product in 4mL chloroform to obtain luminescent core beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ 。
(2) Preparation of luminescent core-luminescent shell Structure beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ ；
Luminescent core beta-NaYF prepared in step (1) 4 2% Er,1% Yb as seed crystal, and preparing beta-NaYF with luminous core-luminous shell structure by solvothermal method 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ . Specifically, beta-NaYF of luminescent core-luminescent shell structure is prepared 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ Comprising the following steps:
will be 0.99mmol YCl 3 ·6H 2 O、0.01mmol ErCl 3 ·6H 2 O is added into a mixed solvent of 6mL of oleic acid and 15mL of 1-octadecene, inert gas is introduced to deoxidize, the temperature is kept at 150 ℃ for 40min until the rare earth salt is completely dissolved to obtain a rare earth oleic acid complex, and the temperature is reduced to 50 ℃; seed crystal beta-NaYF dissolved in 4mL chloroform in step (1) was added with vigorous stirring 4 :2％Er 3+ ,1％Yb 3+ Stirring for 2min, adding 10mL containing 2.5mmol NaOH and 4mmol NH 4 F, preserving the temperature of the methanol solution at 50 ℃ for 1h; heating to 120deg.C, maintaining the temperature for 20min, and removing methanol; quickly heating to 305 ℃, preserving heat for 1h, and cooling to room temperature; centrifuging the reaction solution with ethanol at 9000r/min for 5min, collecting precipitate, washing with mixture of cyclohexane and absolute ethanol for three times, and dispersing the final product in 4mL chloroform to obtain luminescent core-luminescent shell structure beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ 。
(3) Preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
beta-NaYF with luminescent core-luminescent shell structure prepared in step (2) 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ As seed crystal, prepared by solvothermal methodβ-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Will be 0.97mmol YCl 3 ·6H 2 O、0.02mmol YbCl 3 ·6H 2 O and 0.01mmol NdCl 3 ·6H 2 O is added into a mixed solvent of 6mL of oleic acid and 15mL of 1-octadecene, inert gas is introduced to deoxidize, the temperature is kept at 150 ℃ for 40min until the rare earth salt is completely dissolved to obtain a rare earth oleic acid complex, and the temperature is reduced to 50 ℃; seed crystal beta-NaYF dissolved in 4mL chloroform in step (2) was added with vigorous stirring 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ Stirring for 2min, adding 10mL containing 2.5mmol NaOH and 4mmol NH 4 F, preserving the temperature of the methanol solution at 50 ℃ for 1h; heating to 120deg.C, maintaining the temperature for 20min, and removing methanol; quickly heating to 305 ℃, preserving heat for 1h, and cooling to room temperature; centrifuging the reaction solution with ethanol at 9000r/min for 5min, collecting precipitate, washing with mixture of cyclohexane and absolute ethanol for three times, and dispersing the final product in 4mL chloroform to obtain core-shell up-conversion luminescent material beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
As can be seen from fig. 3, the dual-frequency excitation luminescence intensity of the up-conversion luminescent material of the core-shell structure is greater than the luminescence intensity of the core-shell structure material and greater than the luminescence intensity of the luminescent core material. And uncoated beta-NaYF 4 Up-conversion luminescent material beta-NaYF with core-shell structure compared with 2% Er and 1% Yb 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ The luminous intensity at 540nm is increased by approximately 6 times.
Example 2
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by referring to the method of example 1, except that Er in the luminescent core prepared in example 2 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 0.5% of the total molar amount of Yb 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 0.5% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in example 2 is as follows: beta-NaYF 4 :0.5％Er 3+ ,0.5％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Example 3
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by referring to the method of example 1, except that Er in the luminescent core prepared in example 3 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 2% of the total molar amount of Yb 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 2% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in example 3 is as follows: beta-NaYF 4 :2％Er 3+ ,2％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Example 4
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by referring to the method of example 1, except that Er in the luminescent shell prepared in example 4 3+ Is beta-NaYF 4 And Er 3+ 0.5% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in example 4 is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :0.5％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Example 5
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by referring to the method of example 1, except that Er in the luminescent shell prepared in example 5 3+ Is beta-NaYF 4 And Er 3+ 2% of the total molar amount. Example 5 preparationThe chemical expression of the dual-frequency excitation up-conversion luminescent material with the core-shell structure is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :2％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Example 6
A core-shell structured dual-frequency excitation up-conversion luminescent material was prepared by the method of example 1, except that Yb in the active shell prepared in example 6 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 0.5% of the total molar amount of Nd 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 0.5% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in example 6 is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :0.5％Yb 3+ ,0.5％Nd 3+ 。
Example 7
A core-shell structured dual-frequency excitation up-conversion luminescent material was prepared by the method of example 1, except that Yb in the active shell prepared in example 7 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 2% of the total molar amount of Nd 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 1.5% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in example 7 is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1.5％Nd 3+ 。
Comparative example 1
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by the method of example 1, except that Er in the luminescent core prepared in comparative example 1 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 3% of the total molar amount. Dual-frequency excitation of core-shell Structure prepared in comparative example 1The chemical expression of the up-conversion luminescent material is: beta-NaYF 4 :3％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Comparative example 2
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by the method of example 1, except that Yb in the luminescent core prepared in comparative example 2 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 3% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in comparative example 2 is as follows: beta-NaYF 4 :2％Er 3+ ,3％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Comparative example 3
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by referring to the method of example 1, except that Er in the luminescent shell prepared in comparative example 3 3+ Is beta-NaYF 4 And Er 3+ 3% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in comparative example 3 is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :3％Er 3+ @β-NaYF 4 :2％Yb 3+ ,1％Nd 3+ 。
Comparative example 4
A dual-frequency excitation up-conversion luminescent material of a core-shell structure was prepared by the method of example 1, except that Yb in the active shell prepared in comparative example 4 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 3% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in comparative example 4 is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :3％Yb 3+ ,1％Nd 3+ 。
Comparative example 5
A dual-frequency excitation up-conversion luminescent material of core-shell structure was prepared by the method of example 1, except that Nd in the active shell prepared in comparative example 5 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 2% of the total molar amount. The chemical expression of the core-shell structure dual-frequency excitation up-conversion luminescent material prepared in comparative example 5 is as follows: beta-NaYF 4 :2％Er 3+ ,1％Yb 3+ @β-NaYF 4 :1％Er 3+ @β-NaYF 4 :2％Yb 3+ ,2％Nd 3+ 。
Performance tests were performed on the up-conversion luminescent materials prepared in examples 1 to 7 and comparative examples 1 to 5.
The testing method comprises the following steps: the light-emitting intensity of the double-frequency excitation of the up-conversion luminescent material is obtained by testing in a self-made fluorescence spectrum acquisition system, the excitation light sources are jointly excited by infrared lasers of 850nm (1W) and 1550nm (2W), and the emission spectrum signals are collected and recorded by an optical fiber spectrometer. The contrast is: at 540nm, the ratio of the luminous intensity of the 850nm and 1550nm dual-frequency excitation to the luminous intensity of the 1550nm single-frequency excitation.
The test results of examples 1 to 7 and comparative examples 1 to 5 are shown in Table 1 below.
TABLE 1
As can be seen from table 1, the up-conversion luminescent materials prepared in examples 1 to 7 can have higher luminescence intensity of dual-frequency excitation and higher contrast ratio at the same time, while the up-conversion luminescent materials prepared in comparative examples 1 to 7 cannot have higher luminescence intensity of dual-frequency excitation and higher contrast ratio at the same time, which indicates that the performance of the up-conversion luminescent materials prepared in examples 1 to 7 is significantly better than that of the up-conversion luminescent materials prepared in comparative examples 1 to 5.
From the test results of example 1, example 2, example 3, comparative example 1 and comparative example 2, it can be seen that Er, when present in the luminescent core 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 0.5% -2% of the total molar amount of Yb 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ The up-conversion luminescent material prepared by the method has better performance when the total molar quantity is 0.5-2%, and the up-conversion luminescent material prepared by the method can have higher luminous intensity of double-frequency excitation and higher contrast. As can be seen from the test results of comparative example 1, er was found in the luminescent core 3+ When the doping ratio is too large, the up-conversion luminescence intensity of the dual-frequency excitation is reduced. As can be seen from the test results of comparative example 2, yb in the luminescent core 3+ If the doping ratio is too large, the contrast ratio of the dual-frequency excitation is lowered.
From the test results of example 1, example 4, example 5 and comparative example 3, it can be seen that Er, when in the luminescent shell 3+ Is beta-NaYF 4 And Er 3+ The up-conversion luminescent material prepared by the method has better performance when the total molar quantity is 0.5-2%, and at the moment, the up-conversion luminescent material can have higher luminous intensity of double-frequency excitation and higher contrast. As can be seen from the test results of comparative example 3, er was found in the luminescent case 3+ When the doping ratio of (2) is too large, er can be caused 3+ Concentration quenching occurs by itself, resulting in a decrease in the up-conversion luminescence intensity of the dual-frequency excitation.
From the test results of example 1, example 6, example 7, comparative example 4 and comparative example 5, it can be seen that Yb is found in the active shell 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 0.5% -2% of the total molar amount of Nd 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ When the total molar quantity of the up-conversion luminescent material is 0.5% -1.5%, the prepared up-conversion luminescent material has better performance, and at the moment, the active shell can play an optimal sensitization role, and at the moment, the up-conversion luminescent material can have higher luminescent intensity of double-frequency excitation and higher contrast. As can be seen from the test results of comparative examples 4 and 5, when the doping ratio of the sensitizer in the active shell is too large, the luminous intensity at 1550nm single-frequency excitation is increased, resulting in contrast ratio of dual-frequency excitationAnd (3) lowering.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (10)
1. An up-conversion luminescent material is characterized by comprising a luminescent core, a luminescent shell coating the luminescent core and an active shell coating the luminescent shell, wherein the luminescent core has a chemical formula of beta-NaYF 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the luminous shell is beta-NaYF 4 :Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the active shell is beta-NaYF 4 :Yb 3+ ,Nd 3+ 。
2. The up-conversion luminescent material according to claim 1, wherein Er in the luminescent core 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ 0.5% -2% of the total molar amount of (a);
in the luminescent core, yb 3+ Is beta-NaYF 4 、Er 3+ And Yb 3+ From 0.5% to 2% of the total molar amount of (C)。
3. The up-conversion luminescent material according to claim 1, wherein Er in the luminescent shell 3+ Is beta-NaYF 4 And Er 3+ From 0.5% to 2% of the total molar amount.
4. The up-conversion luminescent material according to claim 1, wherein in the active shell, yb 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ 0.5% -2% of the total molar amount of (a);
in the active shell, nd 3+ Is beta-NaYF 4 、Yb 3+ And Nd 3+ From 0.5% to 1.5% of the total molar amount.
5. A method of preparing the up-conversion luminescent material as claimed in any one of claims 1 to 4, the method comprising:
preparation of luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ ；
The obtained luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ As seed crystal, coating the outer layer of the luminous core with luminous shell beta-NaYF 4 :Er 3+ To obtain the beta-NaYF with the luminous core-luminous shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ ；
The obtained luminescent core-luminescent shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ As seed crystal, coating beta-NaYF on the outer layer of the luminous shell 4 :Yb 3+ ,Nd 3+ Forming an active shell to obtain the up-conversion luminescent material beta-NaYF with a core-shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ 。
6. The method of claim 5, wherein the luminescent core β -NaYF is prepared 4 :Er 3+ ,Yb 3+ Comprising the following steps: mixing a first rare earth salt with oleic acid and 1-octadecene, reacting to generate a first rare earth oleic acid complex, mixing the first rare earth oleic acid complex with a methanol solution containing a first sodium source and a first fluorine source, volatilizing methanol, and reacting to obtain a luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein the first rare earth salt comprises a Y-containing rare earth salt, an Er-containing rare earth salt and a Yb-containing rare earth salt;
preparation of luminescent core-luminescent shell Structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Comprising the following steps: mixing a second rare earth salt with oleic acid and 1-octadecene, reacting to generate a second rare earth oleic acid complex, and carrying out beta-NaYF on the luminescent core 4 :Er 3+ ,Yb 3+ Adding the second rare earth oleic acid complex as seed crystal, adding methanol solution containing a second sodium source and a second fluorine source, volatilizing methanol, and reacting to obtain luminescent core-luminescent shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Wherein the second rare earth salt comprises a Y-containing rare earth salt and an Er-containing rare earth salt;
preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Comprising the following steps: mixing the third rare earth salt with oleic acid and 1-octadecene, reacting to generate a third rare earth oleic acid complex, and carrying out beta-NaYF on the luminescent core-luminescent shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ Adding the mixed solution as seed crystal into the third rare earth oleic acid complex, adding a methanol solution containing a third sodium source and a third fluorine source, volatilizing methanol, and reacting to obtain the up-conversion luminescent material beta-NaYF with a core-shell structure 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ Wherein the third rare earth salt comprises a Y-containing rare earth salt, a Yb-containing rare earth salt and an Nd-containing rare earth salt.
7. The method of claim 6, wherein the luminescent core β -NaYF is prepared 4 :Er 3+ ,Yb 3+ When the ratio of the first rare earth salt to oleic acid to 1-octadecene is 1mmol (5-10) mL (10-20);
preparation of luminescent core-luminescent shell Structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ When the proportion of the second rare earth salt to oleic acid and 1-octadecene is 1mmol (5-10) mL (10-20) mL;
preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ When the ratio of the third rare earth salt to oleic acid to 1-octadecene is 1mmol (5-10) mL (10-20) mL.
8. The method of claim 6, wherein the first rare earth salt, the second rare earth salt, and the third rare earth salt are one of a rare earth chloride salt, a rare earth acetate salt, and a rare earth trifluoroacetate salt;
the first sodium source, the second sodium source and the third sodium source are NaOH and CF 3 One of COONa;
the first fluorine source, the second fluorine source and the third fluorine source are NH 4 F. One of the nafs.
9. The method of claim 7, wherein the luminescent core β -NaYF is prepared 4 :Er 3+ ,Yb 3+ When the ratio of the first rare earth salt to the first sodium source, the first fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL;
preparation of luminescent core-luminescent shell Structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ When the ratio of the second rare earth salt to the second sodium source, the second fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL;
preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ In the process, the ratio of the third rare earth salt to the third sodium source, the third fluorine source and the methanol is 1 mmol:2-3 mmol:3.5-4.5 mmol:5-10 mL.
10. The method of claim 6, wherein the luminescent core-luminescent shell structure β -NaYF is prepared 4 :Er 3+ ,Yb 3 + @β-NaYF 4 :Er 3+ When the second rare earth salt and the luminescent core beta-NaYF 4 :Er 3+ ,Yb 3+ The molar ratio of (2) is 1 (0.8-1.2);
preparation of core-shell structured up-conversion luminescent material beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ @β-NaYF 4 :Yb 3+ ,Nd 3+ When the third rare earth salt is in a light-emitting core-light-emitting shell structure beta-NaYF 4 :Er 3+ ,Yb 3+ @β-NaYF 4 :Er 3+ The molar ratio of (2) is 1 (0.8-1.2).
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