CN107892913B - method for improving fluorescence efficiency of impurity-enhanced rare earth up-conversion material - Google Patents
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Abstract
the invention provides a method for improving the fluorescence efficiency of an impurity enhanced rare earth up-conversion material, belonging to the field of optical nano materials. The doping impurities are used as a known mode for enhancing the upconversion fluorescence efficiency of the rare earth, and have the advantages of simple operation, low cost and obvious effect. But the biggest limitation is that impurity ions can introduce defects, namely quenching centers, while reducing the symmetry of crystal lattices, so that the introduction of impurities actually brings the competition of crystal field enhancement and defect quenching. According to the invention, the sensitizing agent and the impurities, and the sensitizing agent and the luminescence center are respectively concentrated in different areas of the core-shell structure through the design of the core-shell structure, so that the side effect caused by the introduction of the impurities is inhibited while the impurity enhancement effect is utilized, the luminescence efficiency of the up-conversion nano material is further improved, the enhancement effect of the traditional impurity enhancement method on the rare earth up-conversion material can be retained, and the up-conversion efficiency is improved.
Description
Technical Field
The invention relates to preparation of an impurity enhanced rare earth up-conversion material, belonging to the field of optical nano materials.
Background
The up-conversion fluorescence phenomenon of rare earth ions has attracted great attention in recent years due to its unique advantages in the fields of biomarkers, solar cells, cancer phototherapy, three-dimensional display and the like. The generation process of the up-conversion fluorescence is as follows: the rare earth ions absorb a plurality of incident near infrared photons, and generate fluorescence by spontaneous radiation after transition to a higher energy level through an excited state absorption or energy transfer process. The multi-photon up-conversion fluorescence efficiency of the current rare earth doped nano material is low, so that research on different synergy schemes is carried out.
Among the various synergy schemes, one can be referred to as impurity enhancement mode, mainly referring to the introduction of transition elements and alkali metal elements into the up-conversion material. For transition elements, researchers find that doping Bi3+ or Zn2+ in an oxide matrix, doping Cd2+ in a fluoride matrix, doping Fe3+ in a fluoride matrix and the like can obviously enhance the up-conversion efficiency. On the other hand, alkali metal is also a very effective upconversion fluorescence synergistic material: researchers found that Li + doped can significantly enhance the upconversion fluorescence of Y2O3 Er3+ nanocrystals, and then the enhancement effect of Li + is also found in BaTiO3, Gd2O3, NaGdF4 and NaYF4 matrixes. In addition, K + of the same family as Li + was also found to enhance the up-conversion fluorescence of rare earth doped NaGdF 4. The mechanism of the impurity enhancement phenomenon is mainly attributed to the fact that impurities cause the reduction of symmetry of a local structure around rare earth ions, so that a local crystal field can be enhanced.
the impurity enhancement method has the advantages of simple operation, low cost and obvious effect, thereby having great practical value. But the biggest limitations of the existing impurity enhancement schemes are:
The impurity ions also introduce lattice defects, namely quenching centers, while reducing the symmetry of the crystal field, so that the introduction of impurities actually brings the mutual competition of crystal field enhancement and defect quenching. For this reason, in impurity-enhanced upconversion systems, the doping concentration is generally low, since too high an impurity concentration significantly increases the number of quenching centers. The conventional impurity enhancement method introduces a defect, namely a quenching center, while doping impurities, and when the energy of a luminescence center is transferred to the quenching center, energy is lost, and fluorescence quenching occurs. The number of quenching centers in the material inevitably and obviously increases along with the increase of the doping concentration, so that the existing impurity enhancement method can only control the concentration of the doped impurities to a lower level, and the method has a limited improvement on the up-conversion fluorescence efficiency.
The invention provides a method for improving the fluorescence efficiency of an impurity enhanced rare earth up-conversion material, which can inhibit quenching of impurities on rare earth up-conversion fluorescence.
Disclosure of Invention
the invention provides a method for improving the fluorescence efficiency of an impurity enhanced rare earth up-conversion material, and aims to provide an improved impurity enhanced rare earth up-conversion material which utilizes the advantages of impurities such as reduction of crystal field symmetry and enhancement of luminous efficiency and simultaneously inhibits the side effect of fluorescence quenching. The purpose of the invention is realized by the following method:
in order to inhibit fluorescence quenching by impurities, the invention separates a quenching center from a luminescence center: a typical Structure design is shown in fig. 1, and impurities are concentrated in a Core part by using a Core-Shell Structure (Core-Shell Structure); the luminescent rare earth ions are concentrated on the shell part (the positions of the two can be interchanged). Due to the simple energy level structure of the sensitizer ions, it is difficult to match the quenching centers to form an efficient energy transfer, i.e., the proximity of these sensitizers to the quenching centers does not cause significant fluorescence quenching.
compared with the known method, the core-shell structure provided by the invention has obvious advantages in principle, as shown in fig. 2, the left graph is the new structure provided by the invention, namely, the quenching center is concentrated on the core, and the luminescence center is concentrated on the shell layer; the right figure shows the conventional impurity enhancement method, i.e. quenching centers caused by luminescent rare earth ions and impurities are randomly distributed in the crystal lattice, and the arrows in the figure represent the energy transfer from the luminescent centers to the quenching centers, i.e. the fluorescence quenching process. Since the energy transfer process is sharply attenuated with the increase of the distance, the transfer process from the luminescence center to the quenching center only occurs at the adjacent position, and it can be seen that the quenching process is remarkably suppressed in the structure proposed by the present invention. Because the influence of impurity ions on the symmetry of crystal lattices can be utilized in the novel structure, namely the absorption capability of the sensitizer is enhanced, the impurity doping mode for inhibiting fluorescence quenching can realize more efficient upconversion fluorescence.
compared with the prior art, the method provided by the invention has the advantages that:
1. The method can retain the enhancement effect of the traditional impurity enhancement method on the rare earth up-conversion material, and improve the up-conversion efficiency.
2. Can obviously inhibit the side effect caused by the introduction of impurities and optimize the enhancement effect of the impurities.
3. the design scheme based on the core-shell structure has the advantages of mature technology and high product quality.
Drawings
FIG. 1 is a schematic diagram of a structure of a novel impurity doped up-conversion nanocrystal;
FIG. 2 is a schematic diagram of a core-shell structure for suppressing fluorescence quenching;
FIG. 3 is a flow chart of the thermal decomposition method for preparing core-shell structure nanocrystals;
FIG. 4 TEM images of a thermal decomposition method prepared LiY F4, Cd/Yb nanocrystals and core-shell structured LiY F4, Cd/Yb @ LiY F4, Yb/Er nanocrystals synthesized by epitaxial growth, with a scale of 50 nm;
FIG. 5 is a comparison of the upconversion fluorescence spectra of the material prepared according to the present invention and the material prepared according to the known method with the same composition, wherein the fluorescence efficiency of the sample according to the present invention is significantly improved;
FIG. 6 is a flow chart of hydrothermal method for preparing core-shell structure nanocrystals.
Detailed Description
the method for improving the fluorescence efficiency of the impurity enhanced rare earth up-conversion material provided by the invention is further described by combining the accompanying drawings and an example:
Impurities and a sensitizing agent, and the sensitizing agent and luminescent ions in the rare earth up-conversion material are respectively positioned in different parts of the core-shell structure. The rare earth up-conversion nano material is in a four-direction or hexagonal phase and can be excited by laser near 800nm or near 980 nm. The matrix contained in the core-shell structure nano material can be various, wherein the preferred matrix is AmLnF4, wherein Am is Li, Na or K; ln is rare earth ions commonly used as matrixes such as Y, Gd, La, Lu and the like. The core-shell structure nano material has the structure as follows: the sensitizer and the impurity can be in the core region, and the corresponding sensitizer and the luminescent ion are in the shell region; it is also possible to place the sensitizer and the impurity in the shell region and the corresponding sensitizer and luminescent ion in the core region. The sensitizer contained in the core-shell structure nano material is Yb3+, Nd3+, and other rare earth ions with larger near-infrared band absorption cross sections and simpler energy level structures. For Nd3+ ions, an intermediate shell layer only containing Yb3+ needs to be added in the structure to isolate the cross relaxation between Nd3+ and the light-emitting ions (Re3+) and realize the energy transfer of Nd3+ → Yb3+ → Re3 +. Luminescent ions (Re3+) contained in the core-shell structure nano material are rare earth ions such as Er3+, Ho3+, Tm3+ and the like which can form efficient energy transfer with a sensitizer. The type of Impurities (IM) contained in the core-shell structure nanomaterial is ions, such as Cd2+, Fe3+, Bi3+, Li +, and the like, which can cause the symmetry of a local crystal field to be reduced through size mismatch or valence mismatch. The general formula of the core-shell structure nano material comprises:
AmLnF4:IM/Yb@AmLnF4:Yb/Re
AmLnF4:Yb/Re@AmLnF4:IM/Yb
AmLnF4:Im/Nd@AmLnF4:Yb@AmLnF4:Yb/Re
AmLnF4:Yb/Re@AmLnF4:Yb@AmLnF4:Im/Nd
In the general formula, Ln in the same product can be different rare earth matrix elements, and the typical structure is NaYF4: Cd/Yb @ NaGdF4: Yb/Er.
The multilayer core-shell structure can be prepared to increase the energy transfer of the sensitizer to the luminescence center so as to optimize the luminescence intensity, C-S is used for representing a core-shell structure nanocrystalline unit, and the general formula of the conversion nanomaterial on the multilayer core-shell structure is as follows:
C-S@C-S……@C-S
The Core-Shell structure nano material can be prepared by a thermal decomposition method, a hydrothermal method and other technologies, and the process comprises two main steps of synthesizing a nanocrystalline Core (Core) and then epitaxially growing a Shell layer (Shell).
example 1: the thermal decomposition method is used for synthesizing LiYF4 Cd/Yb @ LiYF4 Yb/Er, the preparation flow is shown in figure 3, and the specific steps are as follows:
Preparation of nanocrystal cores
step 1, adding rare earth chlorides (yttrium chloride, ytterbium chloride and cadmium chloride), impurity raw materials, oleic acid and octadecylene (the proportion is 6: 15) into a three-neck flask, heating the solution to 160 ℃ under the protection of high-purity argon gas, and stirring to form rare earth oleate
and 2, after the product is cooled to room temperature, adding a methanol solution of lithium hydroxide and ammonium fluoride (the ratio of rare earth cations to Li + and F-is 1: 2.5: 4), stirring for 30 minutes, heating to 150 ℃, and keeping the temperature to discharge the methanol in the solution.
And 3, heating the solution to 300 ℃, preserving the temperature for 2 hours, cooling to room temperature, centrifugally cleaning the nanocrystal core product, and dispersing the nanocrystal core product into cyclohexane for later use.
Preparation of stock solution of shell
And 4, selecting rare earth chlorides (yttrium chloride, ytterbium chloride and erbium chloride), oleic acid and octadecene as raw materials, synthesizing according to the steps 1 to 2, keeping the temperature at 150 ℃ to discharge methanol, and naturally cooling the mixed solution to room temperature to obtain a shell layer stock solution for subsequent reaction.
Preparation of core-shell structures
And 5, adding a proper amount of prepared nanocrystal core dispersion liquid into a flask, adding oleic acid and octadecene under the protection of a high-purity argon environment, and heating to 300 ℃.
and 6, after the temperature is stable, injecting the shell layer stock solution into the reaction solution for multiple times for epitaxial growth, cooling to room temperature, and then centrifugally cleaning to obtain the core-shell structure nanocrystal product. The TEM of the sample is shown in FIG. 4, and the spectrum of the novel core-shell structure nanocrystal and the well-known impurity random doping sample is shown in FIG. 5.
Example 2: the preparation flow of NaGdF4 Yb/Er @ NaGdF4 Bi/Yb synthesized by a hydrothermal method is shown in figure 6, and the method comprises the following specific steps:
Preparation of nanocrystal cores
Step 1, adding rare earth nitrate raw materials (erbium nitrate, ytterbium nitrate and nitric acid mill) required by a nanocrystal core, ethylenediamine tetraacetic acid and deionized water into a beaker, stirring until the mixture is clear, and simultaneously adding sodium fluoride and deionized water into another beaker, and stirring until the mixture is clear.
and 2, slowly pouring the sodium fluoride solution into the rare earth nitrate solution, stirring for 30 minutes, and standing for precipitation.
And 3, pouring out supernatant in the beaker, adding the precipitate and deionized water into the reaction kettle, heating to 200 ℃, and preserving heat for 12 hours.
and 4, after the reaction kettle is cooled to room temperature, centrifugally cleaning a product to obtain the nanocrystal core.
Preparation of core-shell structures
step 5, adding a proper amount of the nanocrystal core and sodium fluoride prepared in the step 4 into deionized water and stirring; in addition, nitrate raw materials (ytterbium nitrate, gadolinium nitrate and bismuth nitrate) required by the nanocrystalline shell layer, ethylene diamine tetraacetic acid and deionized water are added into another beaker and stirred until the materials are clear.
And 6, slowly pouring the mixed solution of the nanocrystal core and the sodium fluoride into the rare earth nitrate solution, stirring for 30 minutes, and standing for precipitation.
And 7, pouring out supernatant in the beaker, adding the precipitate and deionized water into the reaction kettle, heating to 200 ℃, and preserving heat for 12 hours.
And 8, after the reaction kettle is cooled to room temperature, centrifugally cleaning the product to obtain the core-shell structure nanocrystal product.
Example 3: thermal decomposition method for synthesizing NaNdF4, Cd @ NaYF4, Yb @ NaGdF4 and Yb/Er
preparation of nanocrystal cores
step 1, neodymium chloride, cadmium chloride, oleic acid and octadecylene (ratio 6: 15) are added into a three-neck flask, and under the protection of high-purity argon gas environment, the solution is heated to 150 ℃ and stirred to form rare earth oleate
And 2, after the product is cooled to room temperature, adding a methanol solution of sodium hydroxide and ammonium fluoride (the ratio of rare earth cations to Na + and F-is 1: 2.5: 4), stirring for 30 minutes, heating to 100 ℃, and keeping the temperature to discharge the methanol in the solution.
step 3, heating the solution to 320 ℃, preserving the heat for 2 hours, cooling to room temperature, centrifugally cleaning a nanocrystal core product (NaNdF4: Cd), and dispersing into cyclohexane for later use.
preparation of stock solution of shell
And 4, selecting yttrium chloride, ytterbium chloride, oleic acid and octadecylene required by the intermediate shell layer, synthesizing according to the steps 1-2, keeping the temperature at 100 ℃ to discharge methanol, and naturally cooling the mixed solution to room temperature to obtain the intermediate shell layer stock solution required by the subsequent reaction.
And 5, selecting gadolinium chloride, ytterbium chloride, erbium chloride, oleic acid and octadecene raw materials required by the shell layer, synthesizing according to the steps 1-2, keeping the temperature at 100 ℃ to discharge methanol, and naturally cooling the mixed solution to room temperature to obtain the shell layer stock solution required by the subsequent reaction.
Epitaxial growth of intermediate shell
And step 6, adding a proper amount of the nanocrystal core dispersion prepared in the step 3 into a flask, adding oleic acid and octadecene under the protection of a high-purity argon environment, and heating to 320 ℃.
And 7, after the temperature is stable, injecting the shell stock solution synthesized in the step 4 into the reaction solution for epitaxial growth for multiple times, cooling to room temperature, then centrifugally cleaning to obtain a NaNdF4 Cd @ NaYF4 Yb precursor, and dispersing with cyclohexane for later use.
Epitaxial growth of the crust layer
And 8, adding a proper amount of the precursor dispersion liquid prepared in the step 7 into a flask, adding oleic acid and octadecene under the protection of high-purity argon, and heating to 320 ℃.
and 9, after the temperature is stable, injecting the shell stock solution synthesized in the step 5 into the reaction solution for multiple times for epitaxial growth, and after the temperature is reduced to room temperature, centrifugally cleaning to obtain a final reactant NaNdF4: Cd @ NaYF4: Yb @ NaGdF4: Yb/Er.
The above-described embodiments are intended to illustrate the objects, principles, aspects and advantages of the present invention in detail, and not to limit the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for improving the fluorescence efficiency of an impurity enhanced rare earth up-conversion material is characterized by comprising the following steps: impurities and a sensitizing agent, the sensitizing agent and luminescent ions in the rare earth up-conversion material are respectively positioned in different parts of a core-shell structure, the impurities and the sensitizing agent are enriched in one area, the sensitizing agent and the luminescent rare earth ions are enriched in the other area, the two areas are constructed into a whole through the design of the core-shell structure, quenching centers are concentrated in a core, luminescent centers are concentrated in a shell layer, or the luminescent centers are concentrated in the core, and the quenching centers are concentrated in the shell layer; the general formula of the nano material with the core-shell structure comprises:
AmLnF4:IM/Yb@AmLnF4:Yb/Re
AmLnF4:Yb/Re@AmLnF4:IM/Yb
AmLnF4:IM/Nd@AmLnF4:Yb@AmLnF4:Yb/Re
AmLnF4:Yb/Re@AmLnF4:Yb@AmLnF4:IM/Nd
In the general formula, Ln in the same product is the same or different rare earth matrix elements;
The matrix contained in the core-shell structure nano material is AmLnF4, wherein Am is Li, Na or K; ln is Y, Gd, La or Lu;
the sensitizer contained in the core-shell structure nano material is Yb3+, Nd3+, and Nd3+ ions, a middle shell layer only containing Yb3+ needs to be added in the structure, the luminescent ions Re contained in the core-shell structure nano material are Er3+, Ho3+ and Tm3+, and the impurities IM contained in the core-shell structure nano material are ions Cd2+, Fe3+, Bi3+ and Li + which can cause the symmetry reduction of a local crystal field through size mismatch or valence mismatch.
2. The method of claim 1, wherein the method comprises the steps of: the rare earth up-conversion nano material is in a tetragonal phase or a hexagonal phase and can be excited by laser near 800nm or near 980 nm.
3. The method of claim 1, wherein the method comprises the steps of: a multilayer core-shell structure can be prepared, C-S is used for representing a core-shell structure nanocrystalline unit, and the general formula of the up-conversion nanomaterial of the multilayer core-shell structure is as follows:
C-S@C-S……@C-S。
4. The method of claim 1, wherein the method comprises the steps of: the core-shell structure nano material is prepared by a thermal decomposition method or a hydrothermal method, and the process comprises two main steps of synthesizing a nanocrystalline core and subsequently epitaxially growing a shell.
5. The method of claim 4, wherein the method comprises the steps of: the thermal decomposition method is used for synthesizing core-shell structure nano material LiYF4 Cd/Yb @ LiYF4 Yb/Er, and comprises the following specific steps:
(1) preparation of nanocrystal cores
step 1, adding rare earth chloride, impurity raw materials, oleic acid and octadecene into a three-neck flask, heating the solution to 160 ℃ under the protection of high-purity argon, and stirring to form rare earth oleate;
Step 2, after the product is cooled to room temperature, adding a methanol solution of lithium hydroxide and ammonium fluoride, stirring for 30 minutes, heating to 150 ℃, and keeping the temperature to discharge the methanol in the solution;
Step 3, heating the solution to 300 ℃, preserving the heat for 2 hours, cooling to room temperature, centrifugally cleaning the nanocrystal core product, and dispersing the nanocrystal core product into cyclohexane for later use;
(2) Preparation of stock solution of shell
Step 4, selecting rare earth chloride, oleic acid and octadecylene as raw materials, synthesizing according to the steps 1 to 2, keeping the temperature at 150 ℃ to discharge methanol, and naturally cooling the mixed solution to room temperature to obtain a shell stock solution for subsequent reaction;
(3) Preparation of core-shell structures
step 5, adding a proper amount of prepared nanocrystal core dispersion liquid into a flask, adding oleic acid and octadecene under the protection of a high-purity argon environment, and heating to 300 ℃;
And 6, after the temperature is stable, injecting the shell layer stock solution into the reaction solution for multiple times for epitaxial growth, cooling to room temperature, and then centrifugally cleaning to obtain the core-shell structure nanocrystal product.
6. The method of claim 4, wherein the method comprises the steps of: the hydrothermal method is used for synthesizing the core-shell structure nano material NaGdF4 Yb/Er @ NaGdF4 Bi/Yb, and comprises the following specific steps:
(1) Preparation of nanocrystal cores
Step 1, adding a rare earth nitrate raw material required by a nanocrystal core, ethylenediamine tetraacetic acid and deionized water into a beaker, stirring until the mixture is clear, and simultaneously adding sodium fluoride and deionized water into another beaker, and stirring until the mixture is clear;
Step 2, slowly pouring the sodium fluoride solution into the rare earth nitrate solution, stirring for 30 minutes, and standing for precipitation;
step 3, pouring out supernatant in the beaker, adding the precipitate and deionized water into a reaction kettle, heating to 200 ℃, and preserving heat for 12 hours;
step 4, after the reaction kettle is cooled to room temperature, centrifugally cleaning a product to obtain a nanocrystal core;
(2) Preparation of core-shell structures
Step 5, adding a proper amount of the nanocrystal core and sodium fluoride prepared in the step 4 into deionized water and stirring; in addition, nitrate raw materials, ethylene diamine tetraacetic acid and deionized water which are needed by the nanocrystalline shell layer are added into another beaker and stirred until the mixture is clear;
Step 6, slowly pouring the mixed solution of the nanocrystal core and the sodium fluoride into the rare earth nitrate solution, stirring for 30 minutes, and standing for precipitation;
Step 7, pouring out supernatant in the beaker, adding the precipitate and deionized water into a reaction kettle, heating to 200 ℃, and keeping the temperature for 12 hours;
And 8, after the reaction kettle is cooled to room temperature, centrifugally cleaning the product to obtain the core-shell structure nanocrystal product.
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