CN110724530A - Near-infrared long-afterglow luminescent material, preparation method and application thereof - Google Patents
Near-infrared long-afterglow luminescent material, preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 36
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002223 garnet Substances 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 238000012984 biological imaging Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 62
- 229910000019 calcium carbonate Inorganic materials 0.000 description 31
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 29
- 229910052593 corundum Inorganic materials 0.000 description 24
- 239000010431 corundum Substances 0.000 description 24
- 229910001634 calcium fluoride Inorganic materials 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 4
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 3
- 229910001637 strontium fluoride Inorganic materials 0.000 description 3
- 238000000904 thermoluminescence Methods 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 2
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000006872 improvement Effects 0.000 description 2
- 229910003443 lutetium oxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-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
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910003451 terbium oxide Inorganic materials 0.000 description 2
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 2
- 229940075624 ytterbium oxide Drugs 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910010938 LiGa5O8 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007486 ZnGa2O4 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C09K11/7706—Aluminates
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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
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- 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
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7749—Aluminates
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention relates to the technical field of near-infrared luminescent materials, in particular to a near-infrared long-afterglow luminescent material, a preparation method and application thereof. A near-infrared long afterglow luminescent material has a chemical expression as follows: m2‑xLn1+xSn2‑xAl3+xO12Wherein x is not less than 0<2, M is alkaline earth metal element, Ln is rare earth element. Which does not need to be doped with Cr having toxicity3+The ion can continuously emit intrinsic broad band near infrared light, and the near infrared long afterglow luminescent material has high strength, good chemical stability and difficult deliquescence.
Description
Technical Field
The invention relates to the technical field of near-infrared luminescent materials, in particular to a near-infrared long-afterglow luminescent material, a preparation method and application thereof.
Background
The near-infrared long-afterglow luminescent material is as follows: an afterglow luminescent material which can continuously emit near infrared photons after the excitation of high-energy photons is stopped. The common near-infrared long-afterglow luminescent material mainly contains transition metal Cr3+Doped gallate: ZnGa2O4、Zn3Ga2GeO8、LiGa5O8And the like. The materials have stronger afterglow strength and longer afterglow time, but the materials contain a large amount of expensive gallium and germanium elements and transition metal Cr3+Has toxicity. Therefore, the research on the novel method has lower cost and does not need Cr3+The doped near-infrared long afterglow material has important significance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a near-infrared long-afterglow luminescent material, a preparation method and application thereof. The invention provides a near-infrared long-afterglow luminescent material which does not need to be doped with Cr with toxicity3+The ion can continuously emit intrinsic broad band near infrared light, and the near infrared long afterglow luminescent material has high strength, good chemical stability and difficult deliquescence.
The invention is realized by the following steps:
in a first aspect, an embodiment provides a near-infrared long-afterglow luminescent material, whose chemical expression is: m2-xLn1+ xSn2-xAl3+xO12Wherein x is not less than 0<2, M is alkaline earth metal element, Ln is rare earth element.
In an alternative embodiment, the chemical expression of the near-infrared long-afterglow luminescent material is M2LnSn2Al3O12Wherein M is an alkaline earth metal element, and Ln is a rare earth element.
In an alternative embodiment, the chemical expression of the near-infrared long-afterglow luminescent material is Ca2-xGd1+xSn2- xAl3+xO12Wherein x is not less than 0<2；
Most preferably, the chemical expression of the near-infrared long-afterglow luminescent material is Ca2GdSn2Al3O12。
In an alternative embodiment, the rare earth element is any one of Y, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
In an alternative embodiment, the alkaline earth metal element is any one of Ca, Sr, and Ba.
In an alternative embodiment, the near-infrared long-afterglow luminescent material has a garnet structure.
In a second aspect, the embodiment provides a method for preparing the near-infrared long afterglow luminescent material according to any one of the above embodiments, wherein a mixed raw material containing an alkaline earth metal element, a rare earth element, a tin element and an aluminum element is calcined to form the near-infrared long afterglow luminescent material.
In an alternative embodiment, preparing the mixed feedstock comprises: uniformly mixing alkaline earth carbonate, rare earth oxide, tin dioxide and aluminum oxide;
preferably, preparing the mixed feedstock further comprises adding an alkaline earth halide, preferably an alkaline earth fluoride;
more preferably, the amount of the alkaline earth fluoride added is 4 to 6% by mass of the mixture of the alkaline earth carbonate, the rare earth oxide, the tin dioxide and the alumina.
In an alternative embodiment, after preparing the mixed raw material, grinding the mixed raw material, and then roasting;
preferably, the milling time is 15-25 minutes.
In an alternative embodiment of the method of the present invention,
the roasting is to raise the temperature to 350-450 ℃ within 1.5-2.5 hours at the temperature raising rate of 180-235 ℃/hour, then to raise the temperature to 1450-1600 ℃ within 4-6 hours at the temperature raising rate of 190-275 ℃/hour, and then to keep the temperature for 2-10 hours.
In a third aspect, the embodiment provides the application of the near-infrared long-afterglow luminescent material as described in any one of the previous embodiments or the near-infrared long-afterglow luminescent material prepared by the preparation method described in any one of the previous embodiments in biological imaging.
The invention has the following beneficial effects: the near-infrared long-afterglow luminescent material can obviously enhance the intensity of the rest glow by selecting the alkaline earth metal elements, the rare earth elements, the aluminum and the tin and regulating the proportion of the alkaline earth metal elements, the rare earth elements, the aluminum and the tin, and has good chemical stability and difficult deliquescence. Meanwhile, the near-infrared long-afterglow luminescent material can emit near-red light under the condition of not doping other exogenous luminescent ions, and has good biological tissue penetrability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an XRD map of a near-infrared long-afterglow luminescent material of embodiment 1 of the present invention;
FIG. 2 is a pyroelectric luminescence curve diagram of the near-infrared long afterglow luminescent material of embodiment 1 of the present invention;
FIG. 3 is a fluorescence spectrum of a near-infrared long afterglow luminescent material of example 1, example 2 and example 9 of the present invention;
FIG. 4 is a detection chart of an afterglow curve of the near-infrared long afterglow luminescent material of embodiment 1 of the present invention;
fig. 5 is a three-dimensional thermoluminescent property detection chart of experimental example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides a near-infrared long-afterglow luminescent material, a preparation method and application thereof.
The invention provides a near-infrared long afterglow luminescent material, which has the chemical expression as follows: m2-xLn1+xSn2-xAl3+xO12Wherein x is not less than 0<2, M is alkaline earth metal element, Ln is rare earth element. The chemical expression shows the elements contained in the near-infrared long-afterglow luminescent material and the proportion of the elements, and the proportion is obtained by calculating the chemical proportion. The afterglow intensity can be obviously enhanced by selecting alkaline earth metal elements, rare earth elements, aluminum and tin and regulating the proportion, the afterglow is more than 12 hours, and the near-infrared long afterglow luminescent material has good chemical stability and is not easy to deliquesce. Meanwhile, the near-infrared long-afterglow luminescent material has the characteristic of being capable of emitting light within the wavelength range of 650-950nm without doping other exogenous luminescent ions (such as chromium, nickel, bismuth and the like), has a longer emission peak wavelength which is about 790nm, has good biological tissue penetrability, and can emit near-infrared light.
Further, the chemical expression of the near-infrared long afterglow luminescent material is M2LnSn2Al3O12Wherein M is an alkaline earth metal element, and Ln is a rare earth element; preferably, the chemical expression of the near-infrared long-afterglow luminescent material is Ca2-xGd1+xSn2- xAl3+xO12Wherein x is not less than 0<2; most preferably, the chemical expression of the near-infrared long-afterglow luminescent material is Ca2GdSn2Al3O12. The proportion of each element is further limited or further limited, so that the near-infrared long-afterglow luminescent material has stronger afterglow intensity, longer afterglow time and more stable chemical properties.
Further, the rare earth element is any one of Y, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. The alkaline earth metal element is any one of Ca, Sr and Ba. The performance of the near-infrared long-afterglow luminescent material can be further improved by specifically adopting the rare earth elements and the alkaline earth metal elements.
Furthermore, the near-infrared long-afterglow luminescent material has a garnet structure, so that the near-infrared long-afterglow luminescent material has excellent stability, is not easy to absorb moisture, can be stable in the air for a long time, and can ensure that the luminescent material still has good luminous intensity and time after being placed for a long time.
Further, an embodiment of the present invention further provides a method for preparing a near-infrared long-afterglow luminescent material, including: and roasting the mixed raw material containing alkaline earth metal elements, rare earth elements, tin elements and aluminum elements to form the near-infrared long-afterglow luminescent material.
Specifically, the mass of the required raw materials containing alkaline earth metal elements, rare earth elements, tin elements and aluminum elements is calculated according to the chemical expression of the near-infrared long-afterglow luminescent material, and then mixed to form the mixed raw material.
Specifically, the dosage of the alkaline earth carbonate, the rare earth oxide, the tin dioxide and the aluminum oxide is calculated according to the chemical formula, then the alkaline earth carbonate, the rare earth oxide, the tin dioxide and the aluminum oxide are uniformly mixed, a solvent and alkaline earth halide are also added during mixing, the alkaline earth halide is used as a fluxing agent, the synthesis of the near-infrared long afterglow luminescent material is facilitated, the uniform mixing of all the raw materials is facilitated, and the performance of the near-infrared long afterglow luminescent material is ensured.
Further, the alkaline earth halide is an alkaline earth fluoride, the amount of the alkaline earth fluoride added is 4 to 6% by mass of the mixture of the alkaline earth carbonate, the rare earth oxide, the tin dioxide and the alumina, and the solvent is an alcohol solvent, more preferably a monohydric alcohol, most preferably ethanol. The performance of the near-infrared long-afterglow luminescent material is ensured by adopting the solvent and the alkaline-earth halide.
And then grinding the mixed raw materials for 15-25 minutes, wherein the grinding is carried out in an agate mortar or a ball mill, and the grinding is carried out in the above way, so that the uniform mixing of the materials can be ensured, the near-infrared long-afterglow luminescent material can be ensured to stably form a garnet structure, and the stability of the garnet structure is further ensured.
Further, roasting is carried out after grinding, wherein the roasting is carried out in the air atmosphere, the roasting is carried out by raising the temperature to 350-450 ℃ within 1.5-2.5 hours at the temperature raising rate of 180-275 ℃/hour, then raising the temperature to 1450-1600 ℃ within 4-6 hours at the temperature raising rate of 190-275 ℃/hour and then carrying out heat preservation for 2-10 hours; the temperature rise by adopting the method can reduce the influence of the over-quick temperature rise on the structure or the performance of the near-infrared long-afterglow luminescent material, and then the temperature is kept for 2 to 10 hours, namely the temperature is kept for 2 to 10 hours under the condition of 1450 ℃ and 1600 ℃, so that the roasting effect is ensured, and the improvement of the performance of the near-infrared long-afterglow luminescent material is facilitated.
And then cooling, wherein the cooling adopts a natural cooling mode to room temperature.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2YSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 2.2581g of yttria (Y)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.77g of calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 5 percent of the total weight of calcium carbonate, yttrium oxide, stannic oxide and aluminum oxide. Then, the raw materials are put into an agate mortar to be ground for 20min and are uniformly mixed, then the mixture is put into a corundum crucible, the corundum crucible is put into a high-temperature furnace and is roasted and reacted at high temperature in the air atmosphere, and the specific temperature rise program is as follows: raising the temperature to 400 ℃ within 2 hours at a heating rate of 200 ℃/hour, raising the temperature to 1550 ℃ within 4.6 hours at a heating rate of 250 ℃/hour, preserving the temperature for 5 hours, naturally cooling to room temperature, taking out a sample, and grinding to obtain the productAnd (4) obtaining a product.
Example 2
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2GdSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 3.6250g gadolinium oxide (Gd)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.8358g calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 5 percent of the total weight of calcium carbonate, gadolinium oxide, tin dioxide and aluminum oxide. Then, the raw materials are put into an agate mortar to be ground for 20min and are uniformly mixed, then the mixture is put into a corundum crucible, the corundum crucible is put into a high-temperature furnace and is roasted and reacted at high temperature in the air atmosphere, and the specific temperature rise program is as follows: the temperature is raised to 350 ℃ within 1.5 hours at a temperature raising rate of 235 ℃/hour, then the temperature is raised to 1600 ℃ within 4.6 hours at a temperature raising rate of 275 ℃/hour, then the temperature is kept for 5 hours, then the temperature is naturally cooled to the room temperature, and a sample is taken out and ground to obtain a product.
It should be noted that, in this embodiment, the temperature is raised to 350 ℃ within 1.5 hours at a temperature raising rate of 235 ℃/hour, theoretically, the temperature is raised to 235 ℃/hour within 1.5 hours, and should be 352.5 ℃, but the present invention is expressed as raising the temperature to 350 ℃ within 1.5 hours, that is, within 1.5 hours (time may be less than 1.5 hours) at a temperature raising rate of 235 ℃/hour, and the temperature is raised to 350 ℃ only when the temperature is raised to 350 ℃ and certainly just 1.5 hours. Hereinafter, the temperature raising process is performed in the same manner as the case where the time is slightly different from the theoretical time.
Example 3
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2TbSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 3.7385g Terbium oxide (Tb)4O7) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.84g of calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 5 percent of the total weight of calcium carbonate, terbium oxide, tin dioxide and aluminum oxide. Then, the raw materials are put into an agate mortar to be ground for 20min and are uniformly mixed, then the mixture is put into a corundum crucible, the corundum crucible is put into a high-temperature furnace and is roasted and reacted at high temperature in the air atmosphere, and the specific temperature rise program is as follows: the temperature is raised to 450 ℃ within 2.5 hours at a heating rate of 180 ℃/hour, then raised to 1450 ℃ within 4 hours at a heating rate of 250 ℃/hour, then kept warm for 5 hours, then naturally cooled to room temperature, and the sample is taken out and ground to obtain the product.
Example 4
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2DySn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 3.7300g dysprosium oxide (Dy)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.67g of calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 4 percent of the total weight of calcium carbonate, dysprosium oxide, tin dioxide and aluminum oxide. Then, the raw materials are put into an agate mortar to be ground for 15min and are uniformly mixed, then the mixture is put into a corundum crucible, the corundum crucible is put into a high-temperature furnace and is roasted and reacted at high temperature in the air atmosphere, and the specific temperature rise program is as follows: raising the temperature to 400 ℃ within 2 hours at a heating rate of 200 ℃/hour, raising the temperature to 1550 ℃ within 4.2 hours at a heating rate of 275 ℃/hour, preserving the temperature for 10 hours, naturally cooling to room temperature, taking out and grinding a sampleThe product is obtained.
Example 5
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2HoSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 3.7786g of holmium oxide (Ho)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 1.01g of calcium fluoride (CaF)2) Calcium carbonate (CaCO)3) Holmium oxide (Ho)2O3) Tin dioxide (SnO)2) And alumina (Al)2O3) Calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 6 percent of the total weight of calcium carbonate, holmium oxide, tin dioxide and aluminum oxide. Then, the raw materials are put into an agate mortar to be ground for 25min and are uniformly mixed, then the mixture is put into a corundum crucible, the corundum crucible is put into a high-temperature furnace and is roasted and reacted at high temperature in the air atmosphere, and the specific temperature rise program is as follows: the temperature is raised to 350 ℃ within 2 hours at a heating rate of 180 ℃/hour, then is raised to 1450 ℃ within 5.3 hours at a heating rate of 190 ℃/hour, then is kept for 2 hours, and then is naturally cooled to the room temperature, and a sample is taken out and ground to obtain a product.
Example 6
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2ErSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 3.8252g erbium oxide (Er)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.85g of calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent,the amount of calcium fluoride is 5% of the total weight of calcium carbonate, erbium oxide, tin dioxide and aluminum oxide. Then, the raw materials are put into an agate mortar to be ground for 20min and are uniformly mixed, then the mixture is put into a corundum crucible, the corundum crucible is put into a high-temperature furnace and is roasted and reacted at high temperature in the air atmosphere, and the specific temperature rise program is as follows: the temperature is raised to 400 ℃ within 2 hours at a heating rate of 200 ℃/hour, then the temperature is raised to 1550 ℃ within 4.6 hours at a heating rate of 250 ℃/hour, then the temperature is kept for 5 hours, and then the sample is naturally cooled to the room temperature, taken out and ground to obtain the product.
Example 7
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2TmSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 3.8587g Thulium oxide (Tm)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.85g of calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 5 percent of the total weight of calcium carbonate, thulium oxide, tin dioxide and aluminum oxide. And then, putting the raw materials into an agate mortar, grinding for 20min, uniformly mixing, then putting into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and carrying out high-temperature roasting reaction in air atmosphere, wherein the specific temperature rise procedure is as follows, the temperature rise procedure is consistent as that of example 6, after the temperature rises to 1550 ℃, the temperature is kept for 5 hours, then, the temperature is naturally cooled to room temperature, and the sample is taken out and ground to obtain the product.
Example 8
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2YbSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
weighing 4.0 according to the stoichiometric ratio036g calcium carbonate (CaCO)3) 3.9408g ytterbium oxide (Yb)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.85g of calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 5 percent of the total weight of calcium carbonate, ytterbium oxide, tin dioxide and alumina. And then, putting the raw materials into an agate mortar, grinding for 20min, uniformly mixing, then putting into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and carrying out high-temperature roasting reaction in air atmosphere, wherein the specific temperature rise procedure is as follows, the temperature rise procedure is consistent as that of example 6, after the temperature rises to 1550 ℃, the temperature is kept for 5 hours, then, the temperature is naturally cooled to room temperature, and the sample is taken out and ground to obtain the product.
Example 9
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ca2LuSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
4.0036g of calcium carbonate (CaCO) were weighed out in a stoichiometric ratio3) 3.9798g lutetium oxide (Lu)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.85g of calcium fluoride (CaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of calcium fluoride is 5 percent of the total weight of calcium carbonate, lutetium oxide, tin dioxide and aluminum oxide. And then, putting the raw materials into an agate mortar, grinding for 20min, uniformly mixing, then putting into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and carrying out high-temperature roasting reaction in air atmosphere, wherein the specific temperature rise procedure is as follows, the temperature rise procedure is consistent as that of example 6, after the temperature rises to 1550 ℃, the temperature is kept for 5 hours, then, the temperature is naturally cooled to room temperature, and the sample is taken out and ground to obtain the product.
Example 10
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: sr2YSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
5.9052g of strontium carbonate (SrCO) are weighed according to the stoichiometric ratio3) 2.2581g of yttria (Y)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.86g of strontium fluoride (SrF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of strontium fluoride is 5 percent of the total weight of strontium carbonate, yttrium oxide, stannic oxide and aluminum oxide. And then, putting the raw materials into an agate mortar, grinding for 20min, uniformly mixing, then putting into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and carrying out high-temperature roasting reaction in air atmosphere, wherein the specific temperature rise procedure is as follows, the temperature rise procedure is consistent as that of example 6, after the temperature rises to 1550 ℃, the temperature is kept for 5 hours, then, the temperature is naturally cooled to room temperature, and the sample is taken out and ground to obtain the product.
Example 11
The embodiment provides a near-infrared long-afterglow luminescent material, which has a chemical composition expression as follows: ba2YSn2Al3O12。
The embodiment also provides a preparation method of the near-infrared long-afterglow luminescent material, which comprises the following steps:
7.8936g of barium carbonate (BaCO) were weighed out in a stoichiometric ratio3) 2.2581g of yttria (Y)2O3) 6.0284g of tin dioxide (SnO)2) And 3.0588g of alumina (Al)2O3) 0.96g of barium fluoride (BaF)2) As a fluxing agent, ethanol is used as a solvent, and the dosage of strontium fluoride is 5 percent of the total weight of barium carbonate, yttrium oxide, tin dioxide and aluminum oxide. And then, putting the raw materials into an agate mortar, grinding for 20min, uniformly mixing, then putting into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and carrying out high-temperature roasting reaction in air atmosphere, wherein the specific temperature rise procedure is as follows, the temperature rise procedure is consistent as that of example 6, after the temperature rises to 1550 ℃, the temperature is kept for 5 hours, then, the temperature is naturally cooled to room temperature, and the sample is taken out and ground to obtain the product.
Comparative example 1
This comparative example provides a garnet Material M2-xLn1+xSn2-xAl3+xO12And Ln ═ Y and x ═ 2, and the chemical composition expression is as follows: y is3Al5O12And the fluorescence spectrum and the afterglow spectrum of the fluorescent material are tested to show that the fluorescent material does not have the near infrared luminescence and afterglow performances at all.
This comparative example also provides Y3Al5O12The preparation method comprises the following steps:
3.3872g of yttrium oxide (Y) were weighed out in a stoichiometric ratio2O3) And 2.5490g of alumina (Al)2O3) And ethanol is used as a solvent, then the raw materials are put into an agate mortar to be ground for 20min and are uniformly mixed, then the mixture is put into a corundum crucible, the corundum crucible is put into a high-temperature furnace and is roasted at high temperature in air atmosphere for reaction, the specific temperature rise procedure is consistent as the temperature rise procedure of example 6, the temperature is raised to 1550 ℃, then the temperature is kept for 5 hours, then the mixture is naturally cooled to room temperature, and a sample is taken out and ground to obtain a product.
Comparative example 2
This comparative example provides a garnet material containing Zr (the compound Ca of example 12YSn2Al3O12Wherein Sn is replaced by Zr), and the chemical composition expression is as follows: ca2YZr2Al3O12And the fluorescence spectrum and the afterglow spectrum of the fluorescent material are tested to show that the fluorescent material does not have the near infrared luminescence and afterglow performances at all.
Ca of this comparative example2YZr2Al3O12The preparation process of (a) was identical to that of example 1, except that 6.0284g of tin dioxide (SnO)2) Replacement was made with 4.9288g of zirconium dioxide (ZrO)2)。
Comparative example 3
This comparative example provides that M2-xLn1+xSn2-xAl3+xO12Wherein M is replaced by an alkali metal element Na, and the chemical composition expression is as follows: na (Na)2YSn2Al3O12The resulting product is a molten, mixed-phase, non-garnet product.
This comparative example also provides Na2YSn2Al3O12The preparation process of (A) was identical to that of example 1, except that 4.0036g of calcium carbonate (CaCO)3) Replacement was with 2.1198g sodium carbonate (Na)2CO3)。
Experimental example 1
The near-infrared long-afterglow luminescent material of example 1 was subjected to X-ray diffraction, thermoluminescence, fluorescence spectroscopy and afterglow curve detection, and the detection results are shown in fig. 1, 2, 3 and 4.
As can be seen from fig. 1, example 1 has a garnet structure in which Ca and Y mixedly occupy a 24c site of 8 coordination, Sn occupies a 16a site of 6 coordination, and Al occupies a 24d site of 4 coordination, and a schematic diagram of a unit cell obtained by structure refinement is shown in an inset in the upper right corner.
According to fig. 2, the sample can store the energy absorbed when the energy is charged, and the strongest heat release temperature peak is about 90 ℃, which meets the requirement of the long afterglow material.
As can be seen from FIG. 3, the maximum excitation wavelength of the material of example 1 is about 280nm, and the maximum emission wavelength is in the near infrared region of about 790 nm.
As can be seen from FIG. 4, after the sample of example 1 is charged for 10min (254nm), the excitation light is removed, and the sample can still continuously emit near infrared light for more than 12 h.
Experimental example 2
The fluorescence spectrum detection was performed on the near-infrared long afterglow luminescent materials of example 1, example 2 and example 9, and the detection results are shown in fig. 3. The three-dimensional thermoluminescent performance of example 2 was examined and the characterization results are shown in fig. 5.
As can be seen from fig. 3, the strongest excitation wavelength of the materials of examples 1, 2 and 9 is located at about 280nm, and the strongest emission wavelength is located in the near infrared region of about 790 nm.
As can be seen from FIG. 5, the sample has strong thermoluminescence, the maximum thermoluminescence temperature peak is similar to that in FIG. 1 (about 90 ℃), and meets the requirements of the long afterglow material; in addition, its main peak of pyroelectric emission is located at about 790nm, which is consistent with the emission spectrum of FIG. 3, and it is demonstrated that the afterglow of the sample actually originates from the near-infrared light intrinsic to the material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A near-infrared long afterglow luminescent material is characterized in that the chemical expression is as follows: m2-xLn1+xSn2-xAl3+xO12Wherein x is not less than 0<2, M is alkaline earth metal element, Ln is rare earth element.
2. The near-infrared long-afterglow luminescent material of claim 1, wherein the chemical expression of the near-infrared long-afterglow luminescent material is M2LnSn2Al3O12Wherein M is an alkaline earth metal element, and Ln is a rare earth element.
3. The near-infrared long-afterglow luminescent material as claimed in claim 1 or 2, wherein the chemical expression of the near-infrared long-afterglow luminescent material is Ca2-xGd1+xSn2-xAl3+xO12Wherein x is not less than 0<2；
Most preferably, the chemical expression of the near-infrared long-afterglow luminescent material is Ca2GdSn2Al3O12。
4. The near-infrared long-afterglow luminescent material of claim 3, wherein the rare earth element is any one of Y, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
preferably, the alkaline earth metal element is any one of Ca, Sr, and Ba.
5. The near-infrared long-afterglow luminescent material of claim 1, wherein the near-infrared long-afterglow luminescent material has a garnet structure.
6. The method for preparing a near-infrared long-afterglow luminescent material as claimed in any one of claims 1 to 5, wherein a mixed raw material containing an alkaline earth metal element, a rare earth element, a tin element and an aluminum element is calcined to form the near-infrared long-afterglow luminescent material.
7. The method of claim 6, wherein preparing the mixed feedstock comprises: uniformly mixing alkaline earth carbonate, rare earth oxide, tin dioxide and aluminum oxide;
preferably, preparing the mixed feedstock further comprises adding an alkaline earth halide, preferably an alkaline earth fluoride;
more preferably, the alkaline earth fluoride is added in an amount of 4 to 6% by mass of a mixture formed of the alkaline earth carbonate, the rare earth oxide, the tin dioxide and the alumina;
preferably, forming the mixed feedstock further comprises adding a solvent, preferably the solvent is an alcoholic solvent, more preferably a monohydric alcohol, most preferably ethanol.
8. The production method according to claim 7, wherein after the mixed raw material is produced, the mixed raw material is ground and then fired;
preferably, the milling time is 15-25 minutes.
9. The method according to any one of claims 6-8, wherein the baking is performed by raising the temperature to 350-450 ℃ within 1.5-2.5 hours at a temperature-raising rate of 180-235 ℃/hour, then raising the temperature to 1450-1600 ℃ within 4-6 hours at a temperature-raising rate of 190-275 ℃/hour, and then maintaining the temperature for 2-10 hours;
preferably, the firing is followed by cooling.
10. The near-infrared long-afterglow luminescent material as defined in any one of claims 1 to 5 or the near-infrared long-afterglow luminescent material prepared by the preparation method as defined in any one of claims 6 to 9 for use in biological imaging.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745847A (en) * | 2021-01-08 | 2021-05-04 | 广东省科学院稀有金属研究所 | Calcium samarium tin aluminum garnet-based orange yellow fluorescent powder and preparation method thereof |
| CN114717001A (en) * | 2022-04-24 | 2022-07-08 | 江西离子型稀土工程技术研究有限公司 | Oxide near-infrared luminescent material and preparation method and application thereof |
| CN115353884A (en) * | 2022-07-21 | 2022-11-18 | 广东省科学院资源利用与稀土开发研究所 | Garnet-based long-afterglow luminescent material for alternating-current LED and preparation method thereof |
| CN116283271A (en) * | 2023-03-07 | 2023-06-23 | 宁波大学 | Gd with high refractive index and high optical quality 2 Sn 2 O 7 Method for preparing pyrochlore type transparent ceramic |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2194736C2 (en) * | 2000-12-05 | 2002-12-20 | Сощин Наум Пинхасович | Photoluminescent phosphor with overlong-duration afterglow |
| US20040062699A1 (en) * | 2002-09-25 | 2004-04-01 | Matsushita Electric Industrial Co. | Inorganic oxide and phosphor |
| CN103396796A (en) * | 2013-07-30 | 2013-11-20 | 苏州大学 | Antimonate long-afterglow fluorescent powder and preparation method thereof |
| CN104498029A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院长春应用化学研究所 | Long-afterglow luminescent material and preparation method thereof |
| CN106635014A (en) * | 2016-12-02 | 2017-05-10 | 浙江工业大学 | Garnet-structure single-matrix white-light fluorescent powder and preparation method and application thereof |
| CN109666481A (en) * | 2017-10-13 | 2019-04-23 | 江西理工大学 | A kind of long after glow luminous material and preparation method thereof |
| CN110028967A (en) * | 2019-05-15 | 2019-07-19 | 山东大学 | A kind of ultraviolet long after glow luminous material of garnet-base and preparation method thereof |
| CN110257067A (en) * | 2019-06-25 | 2019-09-20 | 山东大学 | A kind of trivalent bismuth ion doping ultraviolet long after glow luminous material of yttrium lutetium gallium-aluminum garnet and preparation method thereof |
-
2019
- 2019-10-31 CN CN201911050032.1A patent/CN110724530B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2194736C2 (en) * | 2000-12-05 | 2002-12-20 | Сощин Наум Пинхасович | Photoluminescent phosphor with overlong-duration afterglow |
| US20040062699A1 (en) * | 2002-09-25 | 2004-04-01 | Matsushita Electric Industrial Co. | Inorganic oxide and phosphor |
| CN103396796A (en) * | 2013-07-30 | 2013-11-20 | 苏州大学 | Antimonate long-afterglow fluorescent powder and preparation method thereof |
| CN104498029A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院长春应用化学研究所 | Long-afterglow luminescent material and preparation method thereof |
| CN106635014A (en) * | 2016-12-02 | 2017-05-10 | 浙江工业大学 | Garnet-structure single-matrix white-light fluorescent powder and preparation method and application thereof |
| CN109666481A (en) * | 2017-10-13 | 2019-04-23 | 江西理工大学 | A kind of long after glow luminous material and preparation method thereof |
| CN110028967A (en) * | 2019-05-15 | 2019-07-19 | 山东大学 | A kind of ultraviolet long after glow luminous material of garnet-base and preparation method thereof |
| CN110257067A (en) * | 2019-06-25 | 2019-09-20 | 山东大学 | A kind of trivalent bismuth ion doping ultraviolet long after glow luminous material of yttrium lutetium gallium-aluminum garnet and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| I. O. GALUSKINA ET AL.: "Irinarassite Ca3Sn2SiAl2O12-new garnet from the Upper Chegem Caldera, Northern Caucasus, Kabardino-Balkaria, Russia", 《MINERALOGICAL MAGAZINE》 * |
| T. JANSEN ET AL.: "Thermal quenching of Mn4+ luminescence in Sn4+-containing garnet hosts", 《OPTICAL MATERIALS》 * |
| 王洪杰 等: "Pr3+离子激活的新型长余辉发光材料GdY1.46Lu0.5Ga3Al2O12:0.04Pr3+的发光性质研究", 《化工新型材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745847A (en) * | 2021-01-08 | 2021-05-04 | 广东省科学院稀有金属研究所 | Calcium samarium tin aluminum garnet-based orange yellow fluorescent powder and preparation method thereof |
| CN114717001A (en) * | 2022-04-24 | 2022-07-08 | 江西离子型稀土工程技术研究有限公司 | Oxide near-infrared luminescent material and preparation method and application thereof |
| CN115353884A (en) * | 2022-07-21 | 2022-11-18 | 广东省科学院资源利用与稀土开发研究所 | Garnet-based long-afterglow luminescent material for alternating-current LED and preparation method thereof |
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| CN116283271A (en) * | 2023-03-07 | 2023-06-23 | 宁波大学 | Gd with high refractive index and high optical quality 2 Sn 2 O 7 Method for preparing pyrochlore type transparent ceramic |
| CN116283271B (en) * | 2023-03-07 | 2024-03-12 | 宁波大学 | Gd with high refractive index and high optical quality 2 Sn 2 O 7 Method for preparing pyrochlore type transparent ceramic |
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