CN109337688B - Double-ion-sensitized up-conversion fluorescent powder and preparation method and application thereof - Google Patents
Double-ion-sensitized up-conversion fluorescent powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to a double-ion-sensitized up-conversion fluorescent powder and a preparation method and application thereof. The upconversion phosphor is made of NaLuF4Is a substrate, Ho3+Yb as an energy trapping center3+And Er3+Both as sensitizing ion and Er3+As the active ion, high intensity red up-conversion luminescence can be obtained. Wherein, high Er doping is performed3+Low doping of Yb3+A mode of (b) is3+And Er3+Meanwhile, as a sensitizing ion, the method can effectively reduce the occurrence probability of concentration quenching, thereby easily realizing high-purity and high-intensity red up-conversion luminescence. By Ho3+As an energy capture center, the Er can be greatly improved3+660nm red up-conversion luminescence intensity. The up-conversion fluorescent powder has the advantages of simple preparation process, short period, low equipment cost, easy operation, no pollution and suitability for large-scale production. The obtained up-conversion fluorescent powder has wide application prospect in the fields of biological imaging, solar cells, solid lasers, device display and the like.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a double-ion-sensitized up-conversion fluorescent powder and a preparation method and application thereof.
Background
The up-conversion luminescence refers to a luminescence phenomenon that the wavelength of emitted light is less than that of excited light, and is mainly a rare earth doped compound at present. The rare earth doped up-conversion luminescent material has the advantages of long fluorescence life, low biotoxicity, high chemical stability, strong light stability and the like, and has wide application prospect in the fields of solid lasers, solar cells, biological imaging and the like. Especially in the field of biological imaging, 980nm excitation light, which can penetrate deeply and reduce tissue damage, is mainly used to excite the upconversion fluorescent material at present. However, under this excitation light, the up-conversion material generally exhibits a plurality of emission peaks. For better application of the upconverting material in biological applications, it is necessary to make the emission peak fall into the range of the "optical window" (red light band (600-700nm) and near infrared band (700-1100nm)) with small absorption (scattering) and high transmittance of biological tissues as much as possible. The conventional up-conversion materials are all Yb3+As sensitizing ions, i.e. by Yb3+Absorption of a 980nm excitation photon followed by energy transfer to an active ion produces up-converted luminescence, but this doped combination of up-converting materials is readily accessibleFluorescence quenching, its luminous intensity is low, and it is difficult to emit a single red light. Therefore, how to develop an upconversion material with high intensity and single red emission is a big problem in the current luminescent material technology field.
In addition, the existing solar cell has a good absorption effect on visible light, but has a weak absorption effect on near infrared light, so if a rare earth doped up-conversion material with high intensity and single red light emission can be obtained, the near infrared light is converted into visible red light, and the conversion efficiency of the solar cell is greatly improved.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a dual ion-sensitized upconversion phosphor. The up-conversion fluorescent powder can emit high-intensity red light by utilizing an energy capture center and double-ion sensitization, and can solve the problems that the existing up-conversion material has a plurality of emission peaks, is impure in luminescence, is insufficient in intensity and the like.
The invention also aims to provide a preparation method of the double-ion-sensitized up-conversion fluorescent powder.
The invention further aims to provide application of the double-ion-sensitized up-conversion fluorescent powder in the fields of solar cells, biological imaging and solid lasers.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a dual-ion sensitized up-conversion fluorescent powder with the chemical expression of NaLuF4Yb/Er/xHo, wherein, NaLuF4As a matrix, Yb3+And Er3+For sensitizing ions while Er3+For activating ions, Ho3+The molar ratio of Lu to Yb to Er to Ho to 4 to 1 to (5-x) to x is 0.05-0.2.
Said x is preferably equal to 0.1. At this time, the up-converting phosphor had the highest intensity of 660nm single red emission.
The invention further provides a preparation method of the double-ion sensitized up-conversion fluorescent powder, which comprises the following steps: uniformly mixing a citric acid solution, a sodium hydroxide solution and water, adding a lutetium nitrate solution, an ytterbium nitrate solution, an erbium nitrate solution and a holmium nitrate solution, uniformly mixing, then adding a sodium fluoride solution and water, uniformly mixing to form a turbid solution, carrying out hydrothermal reaction on the turbid solution, centrifuging the reacted turbid solution to obtain a white precipitate, washing the white precipitate, and drying to obtain the double-ion sensitized up-conversion fluorescent powder.
The concentration of the citric acid solution is preferably 2 mol.L-1。
The concentration of the sodium hydroxide solution is preferably 4 mol.L-1。
Further preferably, when the citric acid solution, the sodium hydroxide solution and the water are uniformly mixed, the volume ratio of the citric acid solution to the sodium hydroxide solution to the water is 1.5:1.25: 10.
Wherein, citric acid is used as a chelating agent, and sodium hydroxide is used for adjusting the pH value of the solution.
The preparation method of the lutetium nitrate solution, the ytterbium nitrate solution, the erbium nitrate solution or the holmium nitrate solution is preferably to obtain the lutetium oxide (99.99%), the ytterbium oxide (99.99%), the erbium oxide (99.99%) or the holmium oxide (99.99%) by dissolving the lutetium oxide, the ytterbium nitrate, the erbium nitrate or the holmium nitrate in the dilute nitric acid with the mass fraction of 30%.
The concentration of the lutetium nitrate solution is preferably 1 mol.L-1。
The concentration of the ytterbium nitrate solution is preferably 0.5 mol.L-1。
The concentration of the erbium nitrate solution is preferably 1 mol.L-1。
The concentration of the holmium nitrate solution is preferably 0.1 mol.L-1。
Further preferably, the volume ratio of the lutetium nitrate solution, the ytterbium nitrate solution, the erbium nitrate solution and the holmium nitrate solution is Lu: Yb: Er: Ho: 4:2: y: x, wherein x is 0.5-2, and y is 4.8-4.95.
The concentration of the sodium fluoride solution is preferably 1 mol.L-1。
Further preferably, the volume ratio of the added lutetium nitrate solution to the added ytterbium nitrate solution to the added sodium fluoride solution to the added water is 2:1:50: 30.
The water is preferably deionized water.
The turbid liquid is milky white.
The hydrothermal reaction is preferably carried out at 200 ℃ for 10 hours.
The hydrothermal reaction vessel is preferably a stainless steel reaction kettle.
The mother liquor of the reacted turbid solution is clear, and white precipitate is at the bottom.
The centrifugation condition is preferably centrifugation for 10min at 10000 r/min, and the centrifugation is carried out twice.
The washing mode is preferably washing with deionized water and alcohol in sequence.
The drying mode is preferably drying at 60 ℃ for 12 h.
The invention further provides application of the double-ion-sensitized up-conversion fluorescent powder in the fields of solar cells, biological imaging and solid lasers. For example, the existing solar cell has strong absorption in the visible light band but weak absorption in the near infrared band, and the double-ion-sensitized up-conversion phosphor can efficiently convert near infrared light into visible red light, which is beneficial to improving the conversion efficiency of the solar cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the upconversion fluorescent powder prepared by the invention is NaLuF4Is a substrate, Ho3+Yb as an energy trapping center3+And Er3+Both as sensitizing ion and Er3+As an active ion, high-intensity single red light emission can be obtained under the excitation of 980 nm. Relative to single Er3+Sensitization due to Yb3+Can efficiently absorb 980nm near infrared light, so the high Er doping is adopted3+Low doping of Yb3+A mode of (b) is3+And Er3+Meanwhile, as a sensitizing ion, the method can effectively reduce the occurrence probability of concentration quenching, thereby easily realizing high-purity and high-intensity red up-conversion luminescence. Furthermore, with Ho3+As an energy capture center, the Er can be greatly improved3+660nm red up-conversion luminescence intensity.
(2) According to the preparation method of the double-ion-sensitized up-conversion fluorescent powder, citric acid is used as a chelating agent, the pH value of the solution is adjusted by using sodium hydroxide, and the double-ion-sensitized up-conversion fluorescent powder can be prepared under the hydrothermal reaction by adjusting the proportion of Lu ions, Yb ions, Er ions and Ho ions in the solution. The preparation method has the advantages of simple process, low equipment cost, easy operation, no environmental pollution, short preparation period and suitability for mass production.
(3) The upconversion fluorescent powder prepared by the invention is used in the field of biological imaging, and can also be used in the fields of solar cells, solid lasers and the like by absorbing near infrared light and emitting high-intensity visible 660nm red light.
Drawings
FIG. 1 shows the fluorescence spectra of the upconversion phosphors prepared in examples 1-3.
FIG. 2 is an energy transition diagram of the upconversion phosphors prepared in examples 1-3.
FIG. 3 is an X-ray diffraction pattern of the upconversion phosphor prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
The embodiment provides a double-ion sensitized up-conversion fluorescent powder and a preparation method thereof.
1.5mL of the solution was added at a concentration of 2 mol. L-11.25mL of citric acid solution (4 mol. L)-1The sodium hydroxide solution and 10mL of deionized water were mixed, stirred for 10 minutes, and then 0.4mL of 1 mol. L in sequence was added-10.2mL of lutetium nitrate solution with a concentration of 0.5 mol.L-10.495mL of ytterbium nitrate solution (1 mol. L)-1And 0.05mL of erbium nitrate solution having a concentration of 0.1 mol. L-1Stirring the holmium nitrate solution for 30 minutes, and adding 10mL of 1 mol.L solution-1And 6mL of deionized water, and stirring for 30 minutes to form a milky turbid solution. Transferring the turbid liquid to a white lining of a stainless steel reaction kettle, sealing, and putting the stainless steel reaction kettle into an ovenIn (b), the hydrothermal reaction was carried out at 200 ℃ for 10 hours. And performing centrifugal separation on the reacted turbid solution twice, wherein the rotation speed of each time is 10000 rpm, and the time is 10 minutes, so as to obtain a white precipitate. And washing the white precipitate with deionized water and alcohol in sequence, and drying at 60 ℃ for 12 hours to obtain the up-conversion fluorescent powder.
A fluorescence analyzer is adopted to analyze the fluorescence intensity of the up-conversion fluorescent powder under the excitation of 980nm near infrared light and draw an energy level transition diagram of the up-conversion fluorescent powder, and a fluorescence spectrogram and the energy level transition diagram are respectively shown in figures 1 and 2, so that the up-conversion fluorescent powder can emit single red light with high intensity under the excitation of 980nm near infrared light.
Example 2
The embodiment provides a double-ion sensitized up-conversion fluorescent powder and a preparation method thereof.
1.5mL of the solution was added at a concentration of 2 mol. L-11.25mL of citric acid solution (4 mol. L)-1The sodium hydroxide solution and 10mL of deionized water were mixed, stirred for 10 minutes, and then 0.4mL of 1 mol. L in sequence was added-10.2mL of lutetium nitrate solution with a concentration of 0.5 mol.L-10.49mL of a 1 mol. L ytterbium nitrate solution-1And 0.1mL of erbium nitrate solution having a concentration of 0.1 mol. L-1Stirring the holmium nitrate solution for 30 minutes, and adding 10mL of 1 mol.L solution-1And 6mL of deionized water, and stirring for 30 minutes to form a milky turbid solution. Transferring the turbid solution into a white lining of a stainless steel reaction kettle, sealing, putting into an oven, and carrying out hydrothermal reaction for 10 hours at 200 ℃. And performing centrifugal separation on the reacted turbid solution twice, wherein the rotation speed of each time is 10000 rpm, and the time is 10 minutes, so as to obtain a white precipitate. And washing the white precipitate with deionized water and alcohol in sequence, and drying at 60 ℃ for 12 hours to obtain the up-conversion fluorescent powder.
The obtained up-conversion phosphor was subjected to phase composition analysis by XRD, and the results are shown in FIG. 3, which proves that the crystal form and hexagonal crystal NaLuF of the obtained phosphor4And (5) performing anastomosis. The fluorescence intensity of the upconversion fluorescent powder under the excitation of 980nm near infrared light is analyzed by a fluorescence analyzer and an energy level transition diagram is drawn, as shown in figures 1 and 2, the upconversion fluorescent powder can be seen to be near to 980nmUnder the excitation of infrared light, a single red light with high intensity can be emitted.
Example 3
The embodiment provides a double-ion sensitized up-conversion fluorescent powder and a preparation method thereof.
1.5mL of the solution was added at a concentration of 2 mol. L-11.25mL of citric acid solution (4 mol. L)-1The sodium hydroxide solution and 10mL of deionized water were mixed, stirred for 10 minutes, and then 0.4mL of 1 mol. L in sequence was added-10.2mL of lutetium nitrate solution with a concentration of 0.5 mol.L-10.48mL of a 1 mol. L ytterbium nitrate solution-1And 0.2mL of erbium nitrate solution having a concentration of 0.1 mol. L-1Stirring the holmium nitrate solution for 30 minutes, and adding 10mL of 1 mol.L solution-1And 6mL of deionized water, and stirring for 30 minutes to form a milky turbid solution. Transferring the turbid solution into a white lining of a stainless steel reaction kettle, sealing, putting into an oven, and carrying out hydrothermal reaction for 10 hours at 200 ℃. And performing centrifugal separation on the reacted turbid solution twice, wherein the rotation speed of each time is 10000 rpm, and the time is 10 minutes, so as to obtain a white precipitate. And washing the white precipitate with deionized water and alcohol in sequence, and drying at 60 ℃ for 12 hours to obtain the up-conversion fluorescent powder.
The fluorescence intensity of the upconversion phosphor under the excitation of 980nm near infrared light is analyzed by a fluorescence analyzer and an energy level transition diagram is depicted, as shown in fig. 1 and 2. As can be seen from FIG. 1, the upconversion phosphors prepared in examples 1-3 all emit high-purity red light with a wavelength of 660nm, and the upconversion phosphor prepared in example 2 has the highest red light emission intensity. As can be seen from FIG. 2, the upconversion phosphors prepared in examples 1-3 are highly Er-doped3+Low doping of Yb3+In such a manner that Yb3+And Er3+Can simultaneously and efficiently absorb 980nm near-infrared excitation photons and can use Ho3+As an energy capture center, high-intensity red up-conversion luminescence under double-ion sensitization is realized.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A double-ion sensitized up-conversion fluorescent powder is characterized in that: the chemical expression is NaLuF4:Yb/Er/xHo, wherein, NaLuF4As a matrix, Yb3+And Er3+For sensitizing ions while Er3+For activating ions, Ho3+The molar ratio of Lu to Yb to Er to Ho = 4 to 1 to x, and x = 0.1, is used as the energy trapping center.
2. The method of preparing the diionic sensitized upconversion phosphor of claim 1, comprising the steps of: uniformly mixing a citric acid solution, a sodium hydroxide solution and water, adding a lutetium nitrate solution, an ytterbium nitrate solution, an erbium nitrate solution and a holmium nitrate solution, uniformly mixing, then adding a sodium fluoride solution and water, uniformly mixing to form a turbid solution, carrying out hydrothermal reaction on the turbid solution, centrifuging the reacted turbid solution to obtain a white precipitate, washing the white precipitate, and drying to obtain the double-ion sensitized up-conversion fluorescent powder.
3. The method of claim 2, wherein the method comprises:
the concentration of the lutetium nitrate solution is 1 mol.L-1；
The concentration of the ytterbium nitrate solution is 0.5 mol.L-1；
The concentration of the erbium nitrate solution is 1 mol.L-1；
The concentration of the holmium nitrate solution is 0.1 mol.L-1。
4. The method of claim 3, wherein the method comprises: the volume ratio of the lutetium nitrate solution, the ytterbium nitrate solution, the erbium nitrate solution and the holmium nitrate solution is Lu to Yb to Er to Ho = 4 to 2 to 4.9 to 1.
5. The method of claim 3, wherein the method comprises:
the concentration of the sodium fluoride solution is 1 mol.L-1；
The volume ratio of the added lutetium nitrate solution to the added ytterbium nitrate solution to the added sodium fluoride solution to the added water is 2:1:50: 30.
6. The method of claim 2, wherein the method comprises:
the concentration of the citric acid solution is 2 mol.L-1；
The concentration of the sodium hydroxide solution is 4 mol.L-1。
7. The method of claim 6, wherein the method comprises: when the citric acid solution, the sodium hydroxide solution and the water are uniformly mixed, the volume ratio of the citric acid solution to the sodium hydroxide solution to the water is 1.5:1.25: 10.
8. The method for preparing the diionic-sensitized upconversion phosphor according to any one of claims 2 to 7, characterized in that: the hydrothermal reaction is carried out for 10 hours at 200 ℃.
9. The use of the diionic sensitized upconversion phosphor of claim 1, wherein: the double-ion sensitized up-conversion fluorescent powder is used in the fields of solar cells, biological imaging and solid lasers.
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Non-Patent Citations (2)
| Title |
|---|
| Combinatorial Discovery of Lanthanide-Doped Nanocrystals with Spectrally Pure Upconverted Emission;Emory M. Chan et al.;《Nano Letters》;20120619;第12卷;第3839-3845页 * |
| Morphology evolution and pure red upconversion mechanism of β-NaLuF4 crystals;Hao Lin et al.;《Scientific Reports》;20160616;第6卷;第28051页 * |
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