CN113549455B - Up-conversion luminescent material, and preparation and application thereof - Google Patents
Up-conversion luminescent material, and preparation and application thereof Download PDFInfo
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- 239000000126 substance Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000090 biomarker Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 64
- 238000001035 drying Methods 0.000 claims description 54
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 18
- 238000006862 quantum yield reaction Methods 0.000 abstract description 10
- 238000005286 illumination Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 154
- 238000003756 stirring Methods 0.000 description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 57
- 239000008367 deionised water Substances 0.000 description 45
- 229910021641 deionized water Inorganic materials 0.000 description 45
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 40
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 39
- 229910017604 nitric acid Inorganic materials 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000002253 acid Substances 0.000 description 31
- 238000007599 discharging Methods 0.000 description 28
- 238000005406 washing Methods 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 19
- 239000011684 sodium molybdate Substances 0.000 description 19
- 235000015393 sodium molybdate Nutrition 0.000 description 19
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 18
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 description 16
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- -1 rare earth ions Chemical class 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 2
- 229940075613 gadolinium oxide Drugs 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 2
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 2
- 229940075624 ytterbium oxide Drugs 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 150000000922 Holmium Chemical class 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001225 Ytterbium Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to an up-conversion luminescent material, and preparation and application thereof. The chemical formula of the up-conversion luminescent material provided by the invention is SrGd 2‑x‑y (MoO 4 ) 4 :yYb 3+ ,xHo 3+ The method comprises the steps of carrying out a first treatment on the surface of the X is more than or equal to 0.01 and less than or equal to 0.03,0.03, and y is more than or equal to 0.07. The up-conversion luminescent material provided by the invention can realize high-efficiency red light and green light emission under the excitation of an external excitation light source, has high luminous intensity, high color purity and high quantum yield, can greatly reduce the damage to living cells when being applied to the preparation of biological markers, and can further improve the high-quality flat panel display capability, the solid laser and the high-performance illumination product efficiency.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to an up-conversion luminescent material, and preparation and application thereof.
Background
In recent years, along with the rapid development of the electronic industry, novel efficient up-conversion luminescent materials are more and more paid attention to, and the materials can convert 980nm near infrared light into visible light and have great application prospects in the fields of high-quality flat panel display, solid lasers, biological markers and high-performance illumination products.
The molybdate material has lower phonon energy, so that the non-radiative transition of the excited state energy level can be effectively inhibited, and the improvement of the luminous efficiency of the rare earth ions is facilitated. And the peculiar ABO of the material 4 The tetrahedral structure of the type (a=ca, sr, ba, mg, pb, zn, mn, ni, fe, co, etc.; b=mo or W) has excellent optical, electromagnetic properties and chemical stability. The research on the structure and the performance of molybdate materials is carried out by the hydrothermal synthesis method of rare earth doped tungsten molybdate fluorescent powder (Wei Yanyan et al, volume 10, page 1758, functional materials in 2011) to obtain that molybdate is typicalThe conclusion of the self-excited luminescent material is that the unique tetrahedral structure has extremely high stability and application value when being used as a luminescent matrix material.
However, rare earth activated ions used in the current up-conversion luminescent materials based on molybdate are Er 3+ For the main research object, for example, chinese patent CN104031644B discloses molybdate up-conversion luminescent material, preparation method and application thereof, and Er 3+ And Yb 3+ ZnGd doped 4 Mo 3 O 16 Wherein Yb 3+ Ions as sensitizers to enhance Er 3+ But the prior art uses molybdate as matrix double-doped material has poor luminous performance.
Disclosure of Invention
In view of the above, the present invention provides an up-conversion luminescent material, and its preparation and application, wherein the up-conversion luminescent material has a chemical formula of SrGd 2-x-y (MoO 4 ) 2 :yYb 3+ ,xHo 3+ Can emit red and green double light, and has high luminous intensity, high color purity and high quantum yield.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an up-conversion luminescent material, the chemical formula of which is shown as formula I:
SrGd 2-x-y (MoO 4 ) 4 :yYb 3+ ,xHo 3+ a formula I;
x is more than or equal to 0.01 and less than or equal to 0.03,0.03, and y is more than or equal to 0.07.
Preferably, x is 0.01, 0.015, 0.02, 0.025 or 0.03, and y is 0.03, 0.04, 0.05, 0.06 or 0.07.
Preferably, when x is 0.01, y is 0.05;
when x is 0.01, y is 0.03;
when x is 0.01, y is 0.04;
when x is 0.01, y is 0.06;
when x is 0.01, y is 0.07;
when x is 0.015, y is 0.05;
when x is 0.025, y is 0.05;
when x is 0.02, y is 0.05;
when x is 0.03, y is 0.05.
The invention provides a preparation method of the up-conversion luminescent material, which comprises the following steps:
according to the stoichiometric ratio of the chemical formula shown in the formula I, sr is added 2+ Solution, gd 3+ Solution, moO 4 2- Solution Yb 3+ Solution, ho 3+ Mixing the solution with a complexing agent, and carrying out crystallization reaction under the condition that the pH value is 1-3 to obtain the up-conversion luminescent material.
Preferably, the temperature of the crystallization reaction is 170-200 ℃, and the time of the crystallization reaction is 20-30 h.
Preferably, the Sr 2+ Sr in solution 2+ The concentration of the substances is 0.04 to 0.08mol/L.
Preferably, the Sr 2+ Sr in solution 2+ The ratio of the amount of the substance to the mass of the complexing agent is (0.01-0.02) mol/0.5 g.
Preferably, the crystallization reaction is followed by obtaining a crystallized product, and the method further comprises drying the crystallized product to obtain the up-conversion luminescent material, wherein the drying temperature is 50-70 ℃, and the drying time is 5-8 hours.
Preferably, the complexing agent comprises polyethylene glycol and/or EDTA.
The invention provides application of the up-conversion luminescent material in flat panel display, solid laser, biomarker preparation or illumination product preparation.
The invention provides an up-conversion luminescent material, which has the chemical formula: srGd 2-x-y (MoO 4 ) 4 :yYb 3+ ,xHo 3+ The method comprises the steps of carrying out a first treatment on the surface of the X is more than or equal to 0.01 and less than or equal to 0.03,0.03, and y is more than or equal to 0.07. The up-conversion luminescent material provided by the invention takes molybdate as a matrix material and Yb is added 3+ And Ho 3+ Obtaining SrGd of molecular formula 2-x-y (MoO 4 ) 2 :yYb 3+ ,xHo 3+ Up-conversion luminescent material of (2), yb in the up-conversion luminescent material provided by the invention 3+ And Ho 3+ The special 4f electronic layer structure can realize high-efficiency red light and green light emission in the range of 540-660 nm under the excitation of an external excitation light source, has high luminous intensity, high color purity and high quantum yield, and can emit red and green double lights under the excitation of a 980nm long-wavelength light source when being used for preparing a biomarker and the up-conversion luminescent material provided by the invention is used for preparing the biomarker, so that compared with the luminescent material excited by a short wavelength, the up-conversion luminescent material provided by the invention has less damage to living cells and higher application value; the capability of a high-quality flat panel display, the efficiency of a solid laser and a high-performance illumination product can be further improved. The results of the examples show that the up-conversion luminescent material provided by the invention has the peak intensity of green light luminescence of up to 984.787, the peak intensity of red light luminescence of up to 450.349, the color purity of 97.7-99.3% and the quantum yield of 1.3-1.7% in the range of 540-660 nm under the excitation light of 0.55W and 480 nm.
The invention provides the preparation method of the up-conversion luminescent material, which is easy to operate and low in cost.
Drawings
FIG. 1 is an XRD pattern of an up-conversion luminescent material prepared in example 1 of the present invention;
FIG. 2 is a graph showing normalized excitation spectra of the products of examples 1 to 5 of the present invention at 0.55W excitation light;
FIG. 3 is a graph showing normalized emission spectra of the products of examples 2 and 6 to 9 of the present invention at 0.75W excitation light.
Detailed Description
The invention provides an up-conversion luminescent material, the chemical formula of which is shown as formula I:
SrGd 2-x-y (MoO 4 ) 4 :yYb 3+ ,xHo 3+ a formula I;
x is more than or equal to 0.01 and less than or equal to 0.03,0.03, and y is more than or equal to 0.07.
The up-conversion luminescence provided by the inventionThe chemical formula of the material is SrGd 2-x-y (MoO 4 ) 2 :yYb 3+ ,xHo 3+ X is more than or equal to 0.01 and less than or equal to 0.03,0.03, y is more than or equal to 0.07, and when x is 0.01 in the invention, y is 0.05; when x is 0.01, y is 0.03; when x is 0.01, y is 0.04; when x is 0.01, y is 0.06; when x is 0.01, y is 0.07; when x is 0.015, y is 0.05; when x is 0.025, y is 0.05; when x is 0.02, y is 0.05; when x is 0.03, y is 0.05.
Yb in the up-conversion luminescent material provided by the invention 3+ And Ho 3+ The special 4f electronic layer structure can efficiently emit red light and green light within the range of 540-660 nm under the excitation of an external excitation light source, has high luminous intensity, high color purity and high quantum yield, can greatly reduce the damage to living cells when being applied to the preparation of biological markers, and can further improve the capability of a high-quality flat panel display, the efficiency of a solid laser and a high-performance illumination product.
The invention provides a preparation method of the up-conversion luminescent material, which comprises the following steps:
according to the stoichiometric ratio of the chemical formula shown in the formula I, sr is added 2+ Solution, gd 3+ Solution, moO 4 2- Solution Yb 3+ Solution, ho 3+ Mixing the solution with a complexing agent, and carrying out crystallization reaction under the condition that the pH value is 1-3 to obtain the up-conversion luminescent material.
In the present invention, the raw materials used are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the Sr 2+ The solution is preferably an aqueous strontium nitrate solution, more preferably an aqueous strontium nitrate solution. In the present invention, the Sr 2+ Sr in solution 2+ The concentration of the substances is 0.04 to 0.08mol/L, preferably 0.041 to 0.079mol/L.
In the present invention, the Gd 3+ The solution is preferably an aqueous gadolinium nitrate solution, more preferably an aqueous gadolinium nitrate solution. In the present invention, the Gd 3+ SolutionGd in (a) 3+ The concentration of the substances is 0.05 to 0.08mol/L, preferably 0.058 to 0.079mol/L.
The invention has no special requirement on the source of gadolinium nitrate in the gadolinium nitrate aqueous solution, and can adopt commercially available gadolinium nitrate or self-made gadolinium nitrate.
In a specific embodiment of the present invention, the preparation method of gadolinium nitrate preferably includes the following steps: dissolving gadolinium oxide in excessive concentrated nitric acid to obtain gadolinium nitrate solution; in the invention, the mass percentage concentration of the concentrated nitric acid is preferably 60-65%; the temperature of the dissolution is preferably 75 to 85 ℃. The invention has no special requirement on the mass ratio of the gadolinium oxide to the concentrated nitric acid, and ensures that the concentrated nitric acid is excessive in the dissolving process; the present invention preferably performs a post-treatment on the dissolved mixed solution to obtain gadolinium nitrate, and in the present invention, the post-treatment preferably includes: acid discharging and drying are sequentially carried out. In the present invention, the acid discharge is preferably performed by heating the mixed solution, and in the present invention, the heating temperature is preferably 75 to 85 ℃, and the acid discharge is completed when the solid matter precipitated in the mixed solution is not increased any more. In the present invention, the drying is preferably evaporation drying, the temperature of the evaporation drying is not specifically required, in a specific embodiment of the present invention, the temperature of the evaporation drying is preferably 70 to 90 ℃, the time of the evaporation drying is not specifically required, and the evaporation of the moisture is complete.
In the present invention, the MoO 4 2- The solution is preferably an aqueous solution of a water-soluble molybdate, preferably an alkali metal molybdate, more preferably sodium molybdate. In the present invention, the MoO 4 2- MoO in solution 4 2- The concentration of the substances is 0.05 to 0.08mol/L, preferably 0.062 to 0.079mol/L.
In the present invention, the Yb 3+ The solution is preferably an aqueous ytterbium salt solution, more preferably an aqueous ytterbium nitrate solution. In the present invention, the Yb 3+ Yb in solution 3+ The concentration of the substance is 0.008 to 0.02mol/L, preferably 0.001 to 0.0018mol/L.
The invention has no special requirement on the source of the ytterbium nitrate in the ytterbium nitrate aqueous solution, and can adopt the ytterbium nitrate sold in the market or self-made.
In a specific embodiment of the present invention, the preparation method of ytterbium nitrate preferably includes the following steps: ytterbium oxide is dissolved in excessive concentrated nitric acid to obtain ytterbium nitrate solution; in the invention, the mass percentage concentration of the concentrated nitric acid is preferably 60-65%; the temperature of the dissolution is preferably 75 to 85 ℃. The invention has no special requirement on the mass ratio of ytterbium oxide and concentrated nitric acid, and ensures that the concentrated nitric acid is excessive in the dissolving process. The protection range of the mixed solution after-treatment is preferably the same as that of the mixed solution in the preparation method of gadolinium nitrate, and is not repeated here.
In the present invention, the Ho 3+ The solution is preferably a water-soluble holmium salt aqueous solution, more preferably a holmium nitrate aqueous solution. In the present invention, the Ho 3+ Ho in solution 3+ The concentration of the substance (C) is 0.003 to 0.01mol/L, preferably 0.004 to 0.009mol/L.
The source of the holmium nitrate in the holmium nitrate aqueous solution is not particularly required, and the holmium nitrate sold in the market or the holmium nitrate can be adopted for self-control.
In a specific embodiment of the present invention, the preparation method of holmium nitrate preferably includes the following steps: dissolving holmium oxide in excessive concentrated nitric acid to obtain holmium nitrate solution; in the invention, the mass percentage concentration of the concentrated nitric acid is preferably 60-65%, and the dissolution temperature is preferably 75-85 ℃.
The invention has no special requirement on the mass ratio of the holmium oxide to the concentrated nitric acid, and ensures that the concentrated nitric acid is excessive in the dissolving process; the protection range of the mixed solution after-treatment is preferably the same as that of the mixed solution in the preparation method of gadolinium nitrate, and is not repeated here.
In the present invention, the complexing agent preferably comprises polyethylene glycol and/or EDTA, and in the present invention, the polyethylene glycol is preferably one or more of PEG1000, PEG 1500, and PEG 4000.
The source of the complexing agent is not particularly required in the invention.
In the present invention, the Sr 2+ Sr in solution 2+ The ratio of the amount of the substance to the mass of the complexing agent is preferably (0.01 to 0.02) mol/0.5 g, more preferably (0.012 to 0.017) mol/0.5 g.
In the present invention, the mixing preferably includes the steps of:
sr is added 2+ Solution and MoO 4 2- Carrying out first mixing on the solution to obtain a first solution;
mixing the first solution with Gd 3+ Carrying out second mixing on the solution to obtain a second solution;
subjecting the second solution, yb 3+ Solution and Ho 3+ Thirdly, mixing the solutions to obtain a third solution;
and fourth mixing the third solution and the complexing agent.
In the present invention, the first mixing, the second mixing, the third mixing and the fourth mixing are preferably performed at room temperature, and there is no special requirement on the time of the first mixing, the second mixing, the third mixing and the fourth mixing, so that the materials are uniformly mixed.
In the present invention, the temperature of the crystallization reaction is preferably 170 to 200 ℃, more preferably 172 to 180 ℃; the crystallization reaction time is preferably 20 to 30 hours, more preferably 22 to 24 hours; in the present invention, the pH value of the fourth solution obtained by the fourth mixing is preferably adjusted by using a pH adjuster, wherein the pH adjuster is preferably a sodium hydroxide solution, and the mass concentration of the sodium hydroxide solution is preferably 45-50%.
In a specific embodiment of the present invention, the crystallization reaction is preferably performed in a reaction vessel.
In the present invention, the crystallization product is obtained after the crystallization reaction, the present invention preferably dries the crystallization product to obtain the up-conversion luminescent material, in the present invention, the present invention preferably washes the crystallization product before the drying, in the present invention, the washing is preferably sequentially performed with water washing and alcohol washing, the number of times of the water washing is preferably 1 to 3, the amount of the water washing is not particularly required, in the present invention, the solvent for the alcohol washing is preferably ethanol, the number of times of the alcohol washing is preferably 1 to 3, and the amount of the alcohol washing is not particularly required.
In the present invention, the drying temperature is preferably 50 to 70 ℃, more preferably 55 to 65 ℃; the drying time is preferably 5 to 8 hours, more preferably 5.5 to 7 hours.
The invention provides application of the up-conversion luminescent material in flat panel display, solid laser, biomarker preparation or illumination product preparation.
When the up-conversion luminescent material provided by the invention is applied to flat panel display (including high-performance display), the up-conversion luminescent material can be used for preparing a luminescent coating of flat panel display (including high-performance display) equipment, and the characteristics of no excitation of a visible light source, high luminescent color purity, high luminous efficiency and quick response are realized, so that no visible backlight display of the current OLED product can be completely realized.
The up-conversion luminescent material provided by the invention can excite red and green light under the excitation of 980nm long wavelength, so that the up-conversion luminescent material provided by the invention only needs the excitation of long wavelength light and has low toxicity, and therefore, the up-conversion luminescent material has little damage to living cells when being used for preparing biological markers and high application value.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Take 0.20989gGd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.0591gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
take 0.0227gHo 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 deg.C for 22h to obtain crystallized product, washing with water for 3 times, washing with ethanol for 3 times, and drying at 60 deg.C for 6h to obtain up-conversion luminescent material with chemical formula SrGd 1.93 (MoO 4 ) 4 :0.05Yb 3+ ,0.02Ho 3+ 。
Example 2
Take 0.21098gGd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
0.0591g is takenYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
take 0.01134gHo 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 deg.C for 22h to obtain crystallized product, washing with water for 3 times, washing with ethanol for 3 times, and drying at 60 deg.C for 6h to obtain up-conversion luminescent material with chemical formula SrGd 1.94 (MoO 4 ) 4 :0.05Yb 3+ ,0.01Ho 3+ 。
Example 3
Take 0.21043gGd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.0591gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
0.01701g Ho 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 deg.C for 22h to obtain crystallized product, washing with water for 3 times, washing with ethanol for 3 times, and drying at 60 deg.C for 6h to obtain up-conversion luminescent material with chemical formula SrGd 1.935 (MoO 4 ) 4 :0.05Yb 3+ ,0.015Ho 3+ 。
Example 4
0.20934g Gd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.0591gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
0.02835g Ho 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolvingDissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 ℃ for 22h to obtain crystallized product, washing the crystallized product with water for 3 times, washing with ethanol for 3 times, and drying at 60 ℃ for 6h to obtain up-conversion luminescent material with chemical formula SrGd 1.925 (MoO 4 ) 4 :0.05Yb 3+ ,0.025Ho 3+ 。
Example 5
0.2088g Gd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.0591gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
0.03402g Ho 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing the sodium molybdate solution and the strontium nitrate solution for 10min, and adding the nitrateStirring and mixing gadolinium acid solution for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating the pH value of the reaction solution to be 2 by using sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 ℃ for 22h to obtain crystallized product, washing the crystallized product with water for 3 times, washing with ethanol for 3 times, and drying at 60 ℃ for 6h to obtain the up-conversion luminescent material with the chemical formula SrGd 1.92 (MoO 4 ) 4 :0.05Yb 3+ ,0.03Ho 3+ 。
Example 6
0.21315g Gd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.03546gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
0.01134g Ho 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 deg.C, and crystallizingAfter 22h, obtaining crystallized product, washing the crystallized product with water for 3 times and ethanol for 3 times, drying at 60 ℃ for 6h to obtain up-conversion luminescent material with a chemical formula of SrGd 1.96 (MoO 4 ) 4 :0.03Yb 3+ ,0.01Ho 3+ 。
Example 7
0.2121g Gd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.04728gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
0.01134g Ho 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 ℃ for 22h to obtain crystallized product, washing the crystallized product with water for 3 times, washing with ethanol for 3 times, and drying at 60 ℃ for 6h to obtain up-conversion luminescent material with chemical formula SrGd 1.95 (MoO 4 ) 4 :0.04Yb 3+ ,0.01Ho 3+ 。
Example 8
0.20989g Gd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.7092gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
0.01134g Ho 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding deionized water to obtain 90mL Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 deg.C for 22h to obtain crystallized product, washing with water for 3 times, washing with ethanol for 3 times, and drying at 60 deg.C for 6h to obtain up-conversion luminescent material with chemical formula SrGd 1.93 (MoO 4 ) 4 :0.06Yb 3+ ,0.01Ho 3+ 。
Example 9
0.2088g Gd 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Gd (NO) 3 ) 3 A solution;
take 0.08274gYb 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Yb (NO) 3 ) 3 A solution;
0.01134g Ho 2 O 3 Stirring and dissolving in 20mL of concentrated nitric acid (68% by mass concentration), completely dissolving at 75deg.C, discharging acid at 75deg.C, drying at 90deg.C, adding 20mL of deionized water to obtain Ho (NO) 3 ) 3 A solution;
0.265g Sr (NO) 3 ) 2 Stirring and dissolving in 20mL of deionized water to obtain strontium nitrate solution;
1.03g of Na 2 MoO 4 Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing sodium molybdate solution and strontium nitrate solution for 10min, adding gadolinium nitrate solution, stirring and mixing for 10min, adding ytterbium nitrate solution and holmium nitrate solution, stirring and mixing for 10min, adding 0.5g PEG1000, stirring and mixing uniformly, regulating pH value of reaction solution to 2 with 45% sodium hydroxide solution, stirring and mixing uniformly, transferring into a reaction kettle, crystallizing at 182 deg.C for 22h to obtain crystallized product, washing with water for 3 times, washing with ethanol for 3 times, and drying at 60 deg.C for 6h to obtain up-conversion luminescent material with chemical formula SrGd 1.92 (MoO 4 ) 4 :0.07Yb 3+ ,0.01Ho 3+ 。
Test example 1
The product of example 1 was structurally identified by means of an X-ray diffractometer (XRD) model Rigaku D/max 2600, with a test range of 10 DEG.ltoreq.2θ.ltoreq.70°, the detection results being shown in FIG. 1. As can be seen from FIG. 1, all diffraction peaks of the product prepared in example 1 are compared with SrMoO 4 Standard card 08-0482 was consistent, indicating that the product of example 1 was structured to conform to SrMoO 4 The crystal structure of the material can not generate any impurity phase by doped rare earth ions, and can not cause a matrix SrGd 2 (MoO 4 ) 4 Significant changes in structure.
Test example 2
The normalized excitation spectra at 650nm and 540nm of the products of examples 1 to 5 were measured at room temperature using a Fluoromax-4 fluorescence spectrophotometer, the results are shown in FIG. 2 and Table 1, the color purity of the products of examples 1 to 5 is shown in Table 2, and the quantum yield is shown in Table 3.
TABLE 1 peak intensities of green and Red light at excitation light Source Power of 0.55W for the products of examples 1-5
TABLE 2 color purity at excitation light source power of 0.55W for the products of examples 1 to 5
| Sequence number | Color purity |
| Example 2 | 97.7％ |
| Example 3 | 97.9％ |
| Example 1 | 99.3％ |
| Example 4 | 98.7％ |
| Example 5 | 98.3％ |
TABLE 3 Quantum yield at excitation light Source Power of 0.55W for the products of examples 1-5
| Sequence number | Quantum yield |
| Example 2 | 1.4％ |
| Example 3 | 1.5％ |
| Example 1 | 1.7％ |
| Example 4 | 1.6％ |
| Example 5 | 1.3％ |
As is apparent from the results of the luminescence intensity, color purity and quantum yield of FIGS. 2 and tables 1 to 3, yb 3+ And Ho 3+ The fluorescence intensity, color purity and quantum yield were maximized at a molar ratio of 5:2 (example 1). Ho 3+ Ion concentration of 0.02 Yb 3+ At an ion concentration of 0.05, the green and red emission intensities of the product of example 1 both reached a maximum, mainly because: due to Ho 3+ As the ion doping concentration increases, more Ho is caused 3+ The ions are excited to 5 F 4 ( 5 S 2 ) At the energy level. At the position of 5 F 4 ( 5 S 2 ) Ho at energy level 3+ Ion quantity increasesAdding, resulting in a transition from this energy level back 5 I 8 Ho of ground state energy level 3+ The number of ions increases with the intensity of green light emission corresponding to the energy level transition process being significantly enhanced. 5 F 4 ( 5 S 2 ) Ho at energy level 3+ The ion number increases, resulting in more Ho 3+ Ion beam 5 F 4 ( 5 S 2 ) Transition of energy level to 5 F 5 At the energy level. When (when) 5 F 5 Ho at energy level 3+ Ion transition back 5 I 8 At the ground state energy level, the red light emission intensity corresponding to the energy level transition process is significantly enhanced. But Ho 3+ When the ion concentration is more than 0.02, the concentration continues to increase, which instead causes the green and red light emission intensity of the up-conversion luminescent material to decrease, and the decrease is caused by the concentration quenching phenomenon of rare earth luminescence center ions.
Test example 3
The normalized excitation spectra at 650nm and 540nm of the products of examples 2, 6-9 when excited with excitation light at 0.75W, 480 nm were measured at room temperature using a Fluoomax-4 fluorescence spectrophotometer, and the results are shown in FIG. 3 and Table 2.
TABLE 2 peak intensities of green and Red light at 0.75W excitation light Source powers for the products of examples 2, 6-9
As can be seen from the results of the light emission intensities of fig. 3 and table 2, it can be seen from fig. 3 and table 2: increasing Yb 3+ The ion concentration and the luminous intensity are gradually enhanced, because with Yb 3+ Ion concentration increase, ho 3+ The ions receive more from Yb 3+ Energy emitted by the ions. Therefore, the luminous intensity (green and red) of the product will gradually increase. When Yb 3+ :Ho 3+ Maximum light intensity at 5:2 (example 1)Along with Yb 3+ Ion concentration is further increased and is in Yb 3+ Of ions 2 F 5/2 The number of particles at the energy level is rather reduced due to the concentration quenching phenomenon, and thus the luminous intensity of the product is reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. An up-conversion luminescent material is characterized in that the chemical formula is shown as formula I:
SrGd 2-x-y (MoO 4 ) 4 :yYb 3+ ,xHo 3+ a formula I;
x is 0.02 and y is 0.05;
the preparation method of the up-conversion luminescent material comprises the following steps:
according to the stoichiometric ratio of the chemical formula shown in the formula I, sr is added 2+ Solution, gd 3+ Solution, moO 4 2- Solution Yb 3+ Solution, ho 3+ Mixing the solution with a complexing agent, and carrying out crystallization reaction under the condition that the pH value is 2 to obtain the up-conversion luminescent material; the temperature of the crystallization reaction is 182 ℃;
the crystallization reaction is carried out to obtain a crystallization product, and the method further comprises the step of drying the crystallization product to obtain the up-conversion luminescent material, wherein the drying temperature is 50-70 ℃, and the drying time is 5-8 hours.
2. The method for preparing the up-conversion luminescent material according to claim 1, comprising the steps of:
according to the stoichiometric ratio of the chemical formula shown in the formula I, sr is added 2+ Solution, gd 3+ Solution, moO 4 2- Solution Yb 3+ Solution, ho 3+ Mixing the solution with a complexing agent, and carrying out crystallization reaction under the condition that the pH value is 2 to obtain the up-conversion luminescent material; the crystallization reactionThe temperature is 182 ℃;
the crystallization reaction is carried out to obtain a crystallization product, and the method further comprises the step of drying the crystallization product to obtain the up-conversion luminescent material, wherein the drying temperature is 50-70 ℃, and the drying time is 5-8 hours.
3. The method according to claim 2, wherein the crystallization reaction time is 20 to 30 hours.
4. The method of preparation of claim 2, wherein the Sr 2+ Sr in solution 2+ The mass concentration of the substances is 0.04-0.08 mol/L.
5. The method of preparation of claim 2 or 4, wherein the Sr 2+ Sr in solution 2+ The ratio of the amount of the substance to the mass of the complexing agent is (0.01-0.02) mol/0.5 g.
6. The method of claim 2, wherein the complexing agent comprises polyethylene glycol and/or EDTA.
7. Use of the up-conversion luminescent material according to claim 1 or the up-conversion luminescent material obtained by the preparation method according to any one of claims 2 to 6 in flat panel displays, solid state lasers, in the preparation of biomarkers or in lighting products.
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