CN113549455A - 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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- 239000008367 deionised water Substances 0.000 description 45
- 229910021641 deionized water Inorganic materials 0.000 description 45
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- 229910017604 nitric acid Inorganic materials 0.000 description 39
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 38
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- 239000002253 acid Substances 0.000 description 28
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- 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
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 19
- 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 16
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- 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
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- 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
- 239000000203 mixture Substances 0.000 description 2
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- 238000004020 luminiscence type Methods 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
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- 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
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- 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 up-conversion luminescent material provided by the invention has a chemical formula of SrGd2‑x‑y(MoO4)4:yYb3+,xHo3+(ii) a X is more than or equal to 0.01 and less than or equal to 0.03, and y is more than or equal to 0.03 and less than or equal to 0.07. The up-conversion luminescent material provided by the invention can realize high-efficiency emission of red light and green light 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 biomarkers, and can further improve the capability of a high-quality flat panel display, and the efficiency of a solid laser and a high-performance lighting product.
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, with the rapid development of the electronic industry, novel efficient up-conversion luminescent materials are more and more valued by people, can convert 980nm near-infrared light into visible light, and have great application prospects in the fields of high-quality flat panel displays, solid lasers, biomarkers and high-performance lighting products.
The molybdate material has lower phonon energy, so that the non-radiative transition of the excited state energy level can be effectively inhibitedAnd the improvement of the luminous efficiency of the rare earth ions is facilitated. And the ABO specific to the material4The tetrahedron structure of type (A ═ Ca, Sr, Ba, Mg, Pb, Zn, Mn, Ni, Fe, Co, etc.; B ═ Mo or W) has excellent optical, electromagnetic and chemical stability. The research on the structure and the performance of molybdate materials is carried out by 'hydrothermal synthesis and structure and performance research of rare earth doped tungsten molybdate fluorescent powder' (Wei Yan et al, vol. 10 of 2011, page 1758, functional materials), the conclusion that molybdate is a typical self-excited light material is obtained, and the specific tetrahedral structure of the molybdate has extremely high stability and application value when being used as a luminescent matrix material.
However, the rare earth active ions used in the current molybdate-based up-conversion luminescent materials are Er3+For the main research object, for example, Chinese patent CN104031644B discloses molybdate up-conversion luminescent material, preparation method and application thereof, and Er3+And Yb3+Doped ZnGd4Mo3O16In which Yb3+Ion as sensitizer to increase Er3+The green light emitting intensity of the material is low, but the double-doped material taking molybdate as a substrate in the prior art has poor light emitting performance.
Disclosure of Invention
In view of this, the present invention provides an up-conversion luminescent material, and a preparation method and an application thereof, wherein the up-conversion luminescent material provided by the present invention has a chemical formula of SrGd2-x-y(MoO4)2:yYb3+,xHo3+The red light and the green light can be emitted, and the luminescent intensity, the color purity and the quantum yield are high.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an up-conversion luminescent material, which has a chemical formula shown as a formula I:
SrGd2-x-y(MoO4)4:yYb3+,xHo3+formula I;
x is more than or equal to 0.01 and less than or equal to 0.03, and y is more than or equal to 0.03 and less 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 an up-conversion luminescent material in the technical scheme, which comprises the following steps:
sr according to the stoichiometric ratio of the chemical formula shown in the formula I2+Solution, Gd3+Solution, MoO4 2-Solution, Yb3+Solution, Ho3+And 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, said Sr2+Sr in solution2+The amount concentration of the substance(s) is 0.04-0.08 mol/L.
Preferably, said Sr2+Sr in solution2+The mass ratio of the amount of the substance(s) to the complexing agent(s) is (0.01 to 0.02) mol:0.5 g.
Preferably, a crystallized product is obtained after the crystallization reaction, 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 an application of the up-conversion luminescent material in the technical scheme or the up-conversion luminescent material obtained by the preparation method in the technical scheme in flat panel display, solid laser, preparation of biomarkers or illumination products.
The invention provides an up-conversion luminescent material, which has a chemical formula as follows: SrGd2-x-y(MoO4)4:yYb3+,xHo3+(ii) a X is more than or equal to 0.01 and less than or equal to 0.03, and y is more than or equal to 0.03 and less than or equal to 0.07. The up-conversion luminescent material provided by the invention takes molybdate as a matrix material and Yb is added3+And Ho3+Obtaining the molecular formula of SrGd2-x-y(MoO4)2:yYb3+,xHo3+The invention provides Yb in the upconversion luminescent material3+And Ho3+The specific 4f electronic layer structure can realize high-efficiency emission of red light and green light in a 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 light and green light under the excitation of a 980nm long-wavelength light source when the up-conversion luminescent material provided by the invention is used for preparing the biomarker, so that compared with the luminescent material excited by short wavelength, the up-conversion luminescent material provided by the invention has less damage to living cells and higher application value; and 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 under the excitation light of 0.55W and 980nm, the green light emission peak intensity is 984.787, the red light emission peak intensity is 450.349, the color purity is 97.7-99.3%, and the quantum yield is 1.3-1.7%.
The preparation method of the up-conversion luminescent material provided by the technical scheme is easy to operate and low in cost.
Drawings
FIG. 1 is an XRD pattern of an up-converted luminescent material prepared in example 1 of the present invention;
FIG. 2 is a normalized excitation spectrum of the products of examples 1-5 of the present invention under 0.55W excitation light;
FIG. 3 is a normalized emission spectrum of the products of examples 2, 6-9 of the present invention under 0.75W excitation light.
Detailed Description
The invention provides an up-conversion luminescent material, which has a chemical formula shown as a formula I:
SrGd2-x-y(MoO4)4:yYb3+,xHo3+formula I;
x is more than or equal to 0.01 and less than or equal to 0.03, and y is more than or equal to 0.03 and less than or equal to 0.07.
The up-conversion luminescent material provided by the invention has a chemical formula of SrGd2-x-y(MoO4)2:yYb3+,xHo3+X is more than or equal to 0.01 and less than or equal to 0.03, y is more than or equal to 0.03 and less than or equal to 0.07, and 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.
Yb in the up-conversion luminescent material provided by the invention3+And Ho3+The specific 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 biomarkers, and can further improve the capability of a high-quality flat panel display, a solid laser and the efficiency of high-performance illumination products.
The invention provides a preparation method of an up-conversion luminescent material in the technical scheme, which comprises the following steps:
sr according to the stoichiometric ratio of the chemical formula shown in the formula I2+Solution, Gd3+Solution, MoO4 2-Solution, Yb3+Solution, Ho3+And 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 starting materials used are commercially available products well known to those skilled in the art, unless otherwise specified.
In the present invention, said Sr2+The solution is preferably an aqueous solution of a water soluble strontium salt, more preferably an aqueous solution of strontium nitrate. In the present invention, said Sr2+Sr in solution2+The amount concentration of the substance(s) is 0.04-0.08 mol/L, preferably 0.041-0.079 mol/L.
In the present invention, the Gd3+The solution is preferably an aqueous solution of a water-soluble gadolinium salt, more preferably an aqueous gadolinium nitrate solution. In the present invention, the Gd3+Gd in solution3+The amount concentration of the substance(s) is 0.05-0.08 mol/L, preferably 0.058-0.079 mol/L.
The invention has no special requirement on the source of the 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 a gadolinium nitrate solution; in the invention, the mass percentage concentration of the concentrated nitric acid is preferably 60-65%; the dissolving temperature is preferably 75-85 ℃. The invention has no special requirements on the mass ratio of the gadolinium oxide to the concentrated nitric acid, and the excess of the concentrated nitric acid in the dissolving process is ensured; in the present invention, it is preferable that the post-treatment is performed on the dissolved mixed solution to obtain gadolinium nitrate, and in the present invention, the post-treatment preferably includes: and sequentially performing acid discharge and drying. In the invention, the mixed solution is preferably heated, in the invention, the heating temperature is preferably 75-85 ℃, and the acid discharge is finished when the solid matters precipitated in the mixed solution are not increased any more. In the invention, the drying is preferably evaporation drying, the temperature of the evaporation drying is not specially required, in the specific embodiment of the invention, the temperature of the evaporation drying is preferably 70-90 ℃, the time of the evaporation drying is not specially required, and the moisture can be completely evaporated.
In the present invention, the MoO4 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 MoO4 2-MoO in solution4 2-The amount concentration of the substance(s) is 0.05-0.08 mol/L, preferably 0.062-0.079 mol/L.
In the present invention, Yb is3+The solution is preferably an aqueous solution of a water-soluble ytterbium salt, more preferably an aqueous solution of ytterbium nitrate. In the present invention, Yb is3+Yb in solution3+The amount concentration of the substance(s) is 0.008 to 0.02mol/L, preferably 0.001 to 0.0018 mol/L.
The invention has no special requirement on the source of the ytterbium nitrate in the ytterbium nitrate aqueous solution, and can adopt the commercially available ytterbium nitrate or self-made ytterbium nitrate.
In a specific embodiment of the present invention, the preparation method of ytterbium nitrate preferably includes the following steps: dissolving ytterbium oxide 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 dissolving temperature is preferably 75-85 ℃. The invention has no special requirement on the mass ratio of the ytterbium oxide to the concentrated nitric acid, and ensures that the concentrated nitric acid is excessive in the dissolving process. The protection range of the post-treatment of the mixed solution in the invention is preferably the same as the protection range of the post-treatment of the mixed solution in the preparation method of gadolinium nitrate, and is not described herein again.
In the present invention, the Ho3+The solution is preferably an aqueous solution of water-soluble holmium salt, more preferably an aqueous solution of holmium nitrate. In the present invention, the Ho3+Ho in solution3+The amount concentration of the substance(s) is 0.003-0.01 mol/L, preferably 0.004-0.009 mol/L.
The method has no special requirement on the source of the holmium nitrate in the holmium nitrate aqueous solution, and can adopt commercially available holmium nitrate or self-made holmium nitrate.
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 dissolving temperature is preferably 75-85 ℃.
The invention has no special requirement on the mass ratio of the holmium oxide and the concentrated nitric acid, and the excessive concentrated nitric acid in the dissolving process is ensured; the protection range of the post-treatment of the mixed solution in the invention is preferably the same as the protection range of the post-treatment of the mixed solution in the preparation method of gadolinium nitrate, and is not described herein again.
In the present invention, the complexing agent preferably includes 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 invention has no special requirement on the source of the complexing agent.
In the present invention, said Sr2+Sr in solution2+The mass ratio of the amount of the substance(s) to the complexing agent(s) is preferably (0.01 to 0.02) mol:0.5g, and more preferably (0.012 to 0.017) mol:0.5 g.
In the present invention, the mixing preferably comprises the steps of:
sr is2+Solution and MoO4 2-Carrying out first mixing on the solution to obtain a first solution;
mixing the first solution with Gd3+Carrying out second mixing on the solution to obtain a second solution;
mixing the second solution with Yb3+Solutions and Ho3+Carrying out third mixing on the solution to obtain a third solution;
and performing fourth mixing on the third solution and the complexing agent.
In the invention, the first mixing, the second mixing, the third mixing and the fourth mixing are preferably carried out at room temperature, the time of the first mixing, the second mixing, the third mixing and the fourth mixing is not particularly required, and the materials can be uniformly mixed.
In the invention, the temperature of the crystallization reaction is preferably 170-200 ℃, and more preferably 172-180 ℃; the time of the crystallization reaction is preferably 20-30 h, and more preferably 22-24 h; in the invention, the pH value of the crystallization reaction is 1-3, the pH value of a fourth solution obtained by fourth mixing is preferably adjusted by a pH adjusting agent, the pH adjusting agent 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 invention, a crystallized product is obtained after the crystallization reaction, the invention preferably dries the crystallized product to obtain the up-conversion luminescent material, in the invention, the invention preferably washes the crystallized product before the drying, in the invention, the washing preferably sequentially carries out water washing and alcohol washing, the number of times of the water washing is preferably 1-3, the invention has no special requirement on the amount of water used for the water washing, in the invention, the solvent used for the alcohol washing is preferably ethanol, the number of times of the alcohol washing is preferably 1-3, and the invention has no special requirement on the amount of alcohol used for the alcohol washing.
In the invention, the drying temperature is preferably 50-70 ℃, and more preferably 55-65 ℃; the drying time is preferably 5-8 h, and more preferably 5.5-7 h.
The invention provides an application of the up-conversion luminescent material in the technical scheme or the up-conversion luminescent material obtained by the preparation method in the technical scheme in flat panel display, solid laser, preparation of biomarkers or illumination products.
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 has the characteristics of no visible light source excitation, high luminescent color purity, high luminescent efficiency and quick reaction, and can completely realize the non-visible backlight display of the current OLED product.
The up-conversion luminescent material provided by the invention can excite red and green double light under the excitation of 980nm long wavelength, so that the up-conversion luminescent material provided by the invention only needs the excitation of the long wavelength light, has low toxicity, and has small harm to living cells when used for preparing a biomarker, and high application value.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Get 0.20989gGd2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.0591gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
take 0.0227gHo2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, transferring the reaction solution into a reaction kettle, performing crystallization reaction for 22h at 182 ℃ to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an up-conversion luminescent material, and converting the luminescence material into a chemical substanceHas a chemical formula of SrGd1.93(MoO4)4:0.05Yb3+,0.02Ho3+。
Example 2
Get 0.21098gGd2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.0591gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
get 0.01134gHo2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, transferring the reaction solution into a reaction kettle, performing crystallization reaction at 182 ℃ for 22h to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an up-conversion luminescent material with the chemical formula of SrGd1.94(MoO4)4:0.05Yb3+,0.01Ho3+。
Example 3
Get 0.21043gGd2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percent concentration is 68 percent), and dissolving at 75 DEG CAfter the completion of the decomposition, the mixture was subjected to acid discharge at 75 ℃ and then dried at 90 ℃, and 20mL of deionized water was added to obtain Gd (NO)3)3A solution;
get 0.0591gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
0.01701g of Ho are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, moving the reaction solution into a reaction kettle, performing crystallization reaction for 22h at 182 ℃ to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an up-conversion luminescent material with the chemical formula of SrGd1.935(MoO4)4:0.05Yb3+,0.015Ho3+。
Example 4
0.20934g of Gd are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.0591gYb2O3Stirring and dissolving in 20mL concentrated nitric acid (mass percent concentration is 68%), dissolving completely at 75 deg.C, and dissolving in waterAcid removal is carried out at 75 ℃, then drying is carried out at 90 ℃, and 20mL of deionized water is added to obtain Yb (NO)3)3A solution;
0.02835g of Ho are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, moving the reaction solution into a reaction kettle, performing crystallization reaction for 22h at 182 ℃ to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an up-conversion luminescent material with the chemical formula of SrGd1.925(MoO4)4:0.05Yb3+,0.025Ho3+。
Example 5
0.2088g of Gd are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.0591gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
0.03402g of Ho are taken2O3Stirring and dissolving in 20mL concentrated nitric acid (mass percentage concentration is 68%), dissolving completely at 75 deg.C, and discharging acid at 75 deg.CThen dried at 90 ℃ and added with 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, moving the reaction solution into a reaction kettle, performing crystallization reaction for 22h at 182 ℃ to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an up-conversion luminescent material with the chemical formula of SrGd1.92(MoO4)4:0.05Yb3+,0.03Ho3+。
Example 6
0.21315g of Gd are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.03546gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
0.01134g of Ho are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, transferring the reaction solution into a reaction kettle, performing crystallization reaction for 22h at 182 ℃ to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an up-conversion luminescent material with the chemical formula of SrGd1.96(MoO4)4:0.03Yb3+,0.01Ho3+。
Example 7
0.2121g of Gd are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.04728gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
0.01134g of Ho are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring 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, adding the gadolinium nitrate solution, stirring and mixing for 10min, then adding the ytterbium nitrate solution and the holmium nitrate solution, stirring and mixing for 10min, and finally adding 05g PEG1000 is stirred and mixed uniformly, then the pH value of the reaction solution is adjusted to 2 by sodium hydroxide solution with the mass concentration of 45%, the mixture is stirred and mixed uniformly and then is moved into a reaction kettle, crystallization reaction is carried out for 22h at 182 ℃ to obtain a crystallization product, the crystallization product is washed by water for 3 times, washed by ethanol for 3 times and dried at 60 ℃ for 6h to obtain the up-conversion luminescent material with the chemical formula of SrGd1.95(MoO4)4:0.04Yb3+,0.01Ho3+。
Example 8
0.20989g of Gd are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.7092gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
0.01134g of Ho are taken2O3Stirring and dissolving in 20mL concentrated nitric acid (mass percent concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding deionized water to obtain 90mL Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, transferring the reaction solution into a reaction kettle, performing crystallization reaction at 182 ℃ for 22h to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an upconversion productA luminescent material of the formula SrGd1.93(MoO4)4:0.06Yb3+,0.01Ho3+。
Example 9
0.2088g of Gd are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (with a mass percent concentration of 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Gd (NO)3)3A solution;
get 0.08274gYb2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68 percent), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Yb (NO)3)3A solution;
0.01134g of Ho are taken2O3Stirring and dissolving in 20mL of concentrated nitric acid (the mass percentage concentration is 68%), completely dissolving at 75 ℃, discharging acid at 75 ℃, drying at 90 ℃, and adding 20mL of deionized water to obtain Ho (NO)3)3A solution;
taking 0.265g Sr (NO)3)2Stirring and dissolving in 20mL of deionized water to obtain a strontium nitrate solution;
collecting 1.03g of Na2MoO4Stirring and dissolving in 20mL of deionized water to obtain a sodium molybdate solution;
stirring and mixing a sodium molybdate solution and a strontium nitrate solution for 10min, adding a gadolinium nitrate solution, stirring and mixing for 10min, adding an ytterbium nitrate solution and a holmium nitrate solution, stirring and mixing for 10min, finally adding 0.5g of PEG1000, stirring and mixing uniformly, adjusting the pH value of a reaction solution to 2 by using a sodium hydroxide solution with the mass concentration of 45%, stirring and mixing uniformly, transferring the reaction solution into a reaction kettle, performing crystallization reaction for 22h at 182 ℃ to obtain a crystallization product, washing the crystallization product for 3 times by water, washing the crystallization product for 3 times by ethanol, and drying the crystallization product for 6h at 60 ℃ to obtain an up-conversion luminescent material with the chemical formula of SrGd1.92(MoO4)4:0.07Yb3+,0.01Ho3+。
Test example 1
The product of example 1 was subjected to structural characterisation using an X-ray diffractometer (XRD) of the type Rigaku D/max 2600,the test range is 10 degrees to 2 degrees and 70 degrees, and the detection result is shown in figure 1. As can be seen from FIG. 1, all diffraction peaks and SrMoO of the product prepared in example 14Standard cards 08-0482 are in agreement, indicating that the product of example 1 is in the structure of SrMoO4The crystal structure of the material, the doped rare earth ions do not generate any impurity phase and do not cause the matrix SrGd2(MoO4)4Significant changes in structure.
Test example 2
The normalized excitation spectra at 650nm and 540nm of the products of examples 1-5 when excited with 0.55W, 980nm excitation light were measured at room temperature using a Fluoromax-4 spectrofluorometer, and the results are shown in FIG. 2 and Table 1, the color purity of the products of examples 1-5 is shown in Table 2, and the quantum yield is shown in Table 3.
TABLE 1 Peak intensity of Green light and Red light at 0.55W excitation light source power for products of examples 1-5
TABLE 2 color purity of products of examples 1-5 with excitation light source power of 0.55W
| Serial 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 yields of products of examples 1 to 5 with excitation light source power of 0.55W
| Serial 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 clear from FIG. 2 and the results of Table 1 to 3 in terms of luminous intensity, color purity and quantum yield, Yb3+And Ho3+Fluorescence intensity at a molar ratio of 5:2 (example 1)The degree, color purity and quantum yield are the greatest. Ho3+Ion concentration of 0.02, Yb3+When the ion concentration is 0.05, the green and red light emission intensities of the product of example 1 reach the maximum values, mainly because: due to Ho3+When the ion doping concentration is increased, more Ho is caused3+The ions are excited to5F4(5S2) At energy level. At the position of5F4(5S2) Ho at energy level3+The number of ions increases, resulting in a transition back from this energy level5I8Ho of ground state energy level3+The number of ions is increased, and the green light emission intensity corresponding to the energy level transition process is obviously enhanced.5F4(5S2) Ho at energy level3+The ion number increases, resulting in more Ho3+Ion is composed of5F4(5S2) Transition of energy level to5F5At energy level. When in use5F5Ho at energy level3+Ion jump back5I8In the ground state energy level, the emission intensity of red light corresponding to the transition process of the energy level is obviously enhanced. But Ho3+When the ion concentration is more than 0.02, the concentration is continuously increased to cause the reduction of the green light and red light emission intensity of the up-conversion luminescent material, which is caused by the concentration quenching phenomenon of the 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 by excitation light of 0.75W and 980nm were measured at room temperature using a Fluoromax-4 spectrofluorometer, and the results are shown in FIG. 3 and Table 2.
Table 2 products of examples 2, 6-9 peak intensities of green and red light at 0.75W excitation light source power
As can be seen from the results of the emission intensities in fig. 3 and table 2, it can be seen from fig. 3 and table 2 that: increase Yb3+The ion concentration, the luminous intensity, is gradually increased because of Yb3+Increase in ion concentration, Ho3+The ions will receive more from Yb3+The energy emitted by the ions. Therefore, the luminous intensity (green and red) of the product will gradually increase. When Yb3+:Ho3+At 5:2 (example 1) the light intensity is maximal with Yb3+The ion concentration is further increased and is in Yb3+Of ions2F5/2The population of 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 only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An upconversion luminescent material having a chemical formula as shown in formula I:
SrGd2-x-y(MoO4)4:yYb3+,xHo3+formula I;
x is more than or equal to 0.01 and less than or equal to 0.03, and y is more than or equal to 0.03 and less than or equal to 0.07.
2. The upconverting luminescent material of claim 1, wherein 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.
3. The upconverting luminescent material according to claim 1 or 2,
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.
4. A method for preparing an up-conversion luminescent material as claimed in any one of claims 1 to 3, comprising the steps of:
sr according to the stoichiometric ratio of the chemical formula shown in the formula I2+Solution, Gd3+Solution, MoO4 2-Solution, Yb3+Solution, Ho3+And 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.
5. The method according to claim 4, wherein the temperature of the crystallization reaction is 170 to 200 ℃ and the time of the crystallization reaction is 20 to 30 hours.
6. The production method according to claim 4, wherein the Sr is2+Sr in solution2+The amount concentration of the substance(s) is 0.04-0.08 mol/L.
7. The production method according to claim 4 or 6, wherein the Sr is2+Sr in solution2+The mass ratio of the amount of the substance(s) to the complexing agent(s) is (0.01 to 0.02) mol:0.5 g.
8. The preparation method according to claim 4, wherein a crystallized product is obtained after the crystallization reaction, and further comprising 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.
9. The method of claim 4, wherein the complexing agent comprises polyethylene glycol and/or EDTA.
10. Use of the upconversion luminescent material according to any one of claims 1 to 3 or the upconversion luminescent material obtained by the preparation method according to any one of claims 4 to 9 in flat panel displays, solid lasers, preparation of biomarkers or illumination products.
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| CN106085430A (en) * | 2016-06-13 | 2016-11-09 | 岭南师范学院 | A kind of up-conversion phosphor and its preparation method and application |
| CN113462390A (en) * | 2021-07-27 | 2021-10-01 | 上海同晔科技有限公司 | Europium-doped tungsten molybdate red fluorescent powder and preparation method and application thereof |
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