CN112607775B - Ho3+Activated green down-conversion phosphor and method of making - Google Patents
Ho3+Activated green down-conversion phosphor and method of making Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000000843 powder Substances 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 8
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 7
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 12
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 12
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 7
- 229940044658 gallium nitrate Drugs 0.000 claims description 7
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 7
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 7
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 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 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 4
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 4
- FZKKGPOEHOOXQE-UHFFFAOYSA-H holmium(3+);tricarbonate Chemical compound [Ho+3].[Ho+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O FZKKGPOEHOOXQE-UHFFFAOYSA-H 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 4
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 4
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 32
- 229910052593 corundum Inorganic materials 0.000 description 20
- 239000010431 corundum Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- 230000005284 excitation Effects 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 238000004020 luminiscence type Methods 0.000 description 7
- 229910052715 tantalum Inorganic materials 0.000 description 7
- 238000000695 excitation spectrum Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000012190 activator Substances 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229910004829 CaWO4 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 holmium ion Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction 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
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000004861 thermometry Methods 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
- F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a Ho3+An activated green down-conversion phosphor and a preparation method thereof, wherein the molecular formula of the green down-conversion phosphor is Ho(3‑x‑y)LaxRyTa0.5Ga5.5O14Wherein 0 is<x<3，0≤y≤1，x+y<3, R is one of Gd, Sc, Lu and Y. The fluorescent powder prepared by the invention can be effectively excited by blue light, near ultraviolet light and purple light, emits green light covering the range of 500-585 nm, has the quantum efficiency higher than 10 percent, and can be used in the fields of solid illumination and display.
Description
Technical Field
The invention relates to the technical field of inorganic luminescent materials, in particular to a Ho3+An activated green down-conversion phosphor and a method for making the same.
Background
Trivalent holmium ion (Ho)3+) Has abundant energy levels, and thus has a plurality of different light-emitting wavelengths. Research shows that Ho3 +Is an important up-conversion luminescence activator, and the metastable state energy level of the up-conversion luminescence activator5I6Can be effectively excited by 980 nm wavelength light to obtain green light with shorter wavelength near 535-545nm5F4,5S2 -5I8) And red light(s) located around 640-660nm5F5-5I8). Due to Ho3+The ions have remarkable visible light and intermediate infrared light emission, so the ions are suitable rare earth elements in different photonic application fields such as light emitting diodes and optical thermometry.
Although Ho3+Ion-activated phosphors have been reported, but all have been reported to achieve efficient up-conversion luminescence, and have very low quantum efficiency, and have very limited applications in the fields of solid-state lighting, display, and the like. Such as Ho3+/Yb3+Co-doped CaWO4Up-converting luminescent materials (Xu W, ZHao H, Li Y, et al. optical temporal sensing of the upconversion luminescence from Ho)3+/Yb3+codoped CaWO4[J]. Sensors&The quantum efficiency of the activators B Chemical,2013,188(nov.): 1096-; also as Ho3+/Yb3+Co-dopingHetero photothermal sensitive fluorescent glass phosphor (Yang J X, Li D, Gang L, et al. Photon quantification in Ho)3+/Yb3+co-doped opto-thermalsensitive fluotellurite glass phosphor[J]Applied Optics,2020,59(19), at 6.76W/mm2The quantum efficiency is only 2.970X 10 at the excitation power density of (2)-5。
At present, the number of narrow-band green light trivalent rare earth ions which can be widely applied is not large, and the most common is Tb3+Ions. However, due to Tb3+The synthesis conditions of the doped fluorescent powder are relatively complicated, for example, the control problem of the reduction condition is involved when terbium oxide is used as the raw material, and partial matrix is doped with Tb3+Then it cannot be reduced and cannot emit green light. In addition, Tb3+The price of the ionic raw material is high, for example, the price of terbium oxide is about 3.6 times that of holmium oxide. In contrast, Ho as a green light-emitting center3+The ions have the advantages of low cost, simple synthesis conditions, better excitation position and the like, and can be effectively excited at the excitation position of standard blue light or near ultraviolet light, thereby emitting green light with higher color purity. Therefore, in order to obtain green phosphor which can be excited by blue light or near ultraviolet light, has high luminous efficiency and low cost, Ho is developed and researched3+The activated green down-converting luminescent materials are of great significance.
Disclosure of Invention
The primary object of the present invention is to overcome the above-mentioned disadvantages of the prior art and to provide a Ho3+The green down-conversion phosphor can be effectively excited by blue light, near ultraviolet light or purple light and can generate green down-conversion luminescence under the excitation of exciting light from the near ultraviolet light to a blue light region. In addition, the phosphor can obtain higher quantum efficiency under the excitation of 454nm blue light.
It is a further object of the present invention to provide a Ho3+A preparation method of activated green down-conversion fluorescent powder.
Another object of the present invention is to provide the use of the green down-converting phosphor.
The above object of the present invention is achieved by the following technical solutions:
ho3+An activated green down-conversion phosphor having a molecular formula of Ho(3-x-y)LaxRyTa0.5Ga5.5O14Wherein 0 is<x<3，0≤y≤1，x+y<3, R is one of Gd, Sc, Lu and Y.
Preferably, the molecular formula of the green down-conversion phosphor is Ho(3-x-y)LaxRyTa0.5Ga5.5O14Wherein 2 is< x<3，0≤y≤1，x+y<3, R is one of Gd, Sc, Lu and Y.
The preparation method of the green down-conversion fluorescent powder comprises the following steps:
mixing and grinding a holmium-containing compound, a lanthanum-containing compound, an R-containing compound, tantalum oxide and a gallium-containing compound uniformly according to a proportion, sintering, and cooling to obtain the fluorescent powder; wherein R is one of Gd, Sc, Lu and Y.
Preferably, the holmium-containing compound is selected from one or more of holmium oxide, holmium carbonate and holmium nitrate.
Preferably, the lanthanum-containing compound is selected from one or more of lanthanum oxide, lanthanum carbonate, lanthanum nitrate and lanthanum oxalate.
Preferably, the R-containing compound is an oxide or carbonate or oxalate or nitrate of R.
Preferably, the gallium-containing compound is selected from one or two of gallium oxide and gallium nitrate.
Preferably, the sintering is carried out by raising the temperature to 1000-1500 ℃ at the speed of 5-30 ℃/min and preserving the temperature for 4-10 h.
Preferably, the mixture is pre-sintered before sintering, wherein the pre-sintering is to heat the mixture to 300-900 ℃ at the speed of 5-30 ℃/min and keep the temperature for 2-8 h.
The green down-conversion fluorescent powder can be effectively excited by blue light, near ultraviolet light and purple light, emits green light covering the range of 500-585 nm, meets the performance requirements of the solid illumination and display field on the fluorescent powder, and can be used in the solid illumination and display field. Therefore, the application of the green down-conversion phosphor in the solid illumination and display fields should also be within the scope of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
the green down-conversion fluorescent powder has a wide excitation range, can be effectively excited by blue light, near ultraviolet light and purple light, has a main peak of an excitation spectrum positioned at 454nm, covers excitation of blue light in a range of 430-465 nm, and has strong excitation in the ranges of near ultraviolet light (361nm) and purple light (418 nm). Under the excitation of standard blue light 454nm, the fluorescent powder presents the strongest emission peak at 546nm, and covers green light emission in the range of 500-585 nm to generate bright green light. The color coordinate is (0.2729,0.7163), and the color purity is as high as 99%. In addition, the fluorescent powder has high luminous intensity and quantum efficiency higher than 10%.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the green down-converting phosphor described in example 1.
FIG. 2 is a fluorescence emission spectrum of the green down-converting phosphor described in example 1.
FIG. 3 is a fluorescence excitation spectrum of the green down-conversion phosphor described in example 1.
FIG. 4 is a color coordinate diagram of the green down-converting phosphor of example 1.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
Raw materials are weighed according to the element molar ratio Ho, La, Ta and Ga of 0.045, 2.955, 0.5 and 5.5, wherein the raw materials are holmium oxide, lanthanum oxide, tantalum oxide and gallium oxide. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 400 ℃ for the first step at a heating rate of 10 ℃/min for 4 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 5 ℃/min, and the heat preservation time is 4 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 2
Raw materials are weighed according to the element molar ratio Ho, La, Ta and Ga of 0.03, 2.97, 0.5 and 5.5, wherein the raw materials are holmium oxide, lanthanum oxide, tantalum oxide and gallium oxide. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 300 ℃ for the first step at the heating rate of 5 ℃/min for 3 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1000 ℃, wherein the heating rate is 10 ℃/min, and the heat preservation time is 6 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 3
Raw materials are weighed according to the element molar ratio Ho, La, Ta and Ga of 0.15:2.85:0.5:5.5, wherein the raw materials are holmium oxide, lanthanum oxide, tantalum oxide and gallium oxide. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 600 ℃ for the first step at a heating rate of 10 ℃/min for 2 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 10 ℃/min, and the heat preservation time is 6 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 4
Respectively weighing raw materials according to the element molar ratio Ho, La, Ta and Ga of 1.5:1.5:0.5:5.5, wherein the raw materials are respectively holmium nitrate, lanthanum nitrate, tantalum oxide and gallium nitrate. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 500 ℃ for the first step at a heating rate of 10 ℃/min for 4 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 20 ℃/min, and the heat preservation time is 8 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 5
Weighing raw materials respectively according to the element molar ratio Ho, La, Gd, Ta and Ga of 0.09:2.81:0.1:0.5:5.5, wherein the raw materials respectively comprise holmium carbonate, lanthanum carbonate, gadolinium oxide, tantalum oxide and gallium oxide. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 400 ℃ for the first step at the heating rate of 20 ℃/min for 8 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 20 ℃/min, and the heat preservation time is 8 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 6
Respectively weighing raw materials according to the element molar ratio Ho, La, Y, Ta and Ga of 0.05:2.75:0.2:0.5:5.5, wherein the raw materials are respectively holmium nitrate, lanthanum nitrate, yttrium nitrate, tantalum oxide and gallium nitrate. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 500 ℃ for the first step at a heating rate of 10 ℃/min for 4 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 20 ℃/min, and the heat preservation time is 8 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 7
Weighing raw materials respectively according to the element molar ratio Ho, La, Sc, Ta and Ga of 0.2:2.75:0.05:0.5:5.5, wherein the raw materials respectively comprise holmium nitrate, lanthanum nitrate, scandium nitrate, tantalum oxide and gallium nitrate. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 900 ℃ for the first step at the heating rate of 30 ℃/min for 4 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1500 ℃, wherein the heating rate is 20 ℃/min, and the heat preservation time is 8 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 8
Respectively weighing raw materials according to the element molar ratio Ho, La, Lu, Ta and Ga of 0.2:2.75:0.05:0.5:5.5, wherein the raw materials are holmium nitrate, lanthanum oxalate, lutetium oxide, tantalum oxide and gallium nitrate. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 600 ℃ for the first step at a heating rate of 10 ℃/min for 4 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 10 ℃/min, and the heat preservation time is 4 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 9
Raw materials are weighed according to the mol ratio Ho, La, Sc, Ta and Ga of 0.03, 2.94, 0.03, 0.5 and 5.5, wherein the raw materials are respectively holmium oxide, lanthanum oxide, scandium oxide, tantalum oxide and gallium oxide. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 500 ℃ for the first step at a heating rate of 10 ℃/min for 3 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 30 ℃/min, and the heat preservation time is 10 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Example 10
According to the mol ratio Ho, La, Y, Ta and Ga are 0.25, 2.5, 0.25, 0.5 and 5.5, raw materials are respectively weighed, and the raw materials are respectively holmium carbonate, lanthanum carbonate, yttrium carbonate, tantalum oxide and gallium nitrate. Adding the raw materials into an agate mortar, grinding uniformly, transferring into a corundum crucible, putting the corundum crucible into a high-temperature furnace, and presintering at 400 ℃ for the first step at the heating rate of 5 ℃/min for 4 h. Naturally cooling to room temperature, taking out and grinding, and then carrying out second-step sintering at 1400 ℃, wherein the heating rate is 5 ℃/min, and the heat preservation time is 8 h. And after the reaction is finished, naturally cooling the mixture to room temperature, and uniformly grinding the mixture to obtain the product.
Characterization of
The x-ray powder diffraction results of the product obtained in example 1 are shown in fig. 1, from which it can be seen that the product obtained is a pure phase.
FIG. 2 is a fluorescence emission spectrum of the product obtained in example 1. As can be seen from the figure, under the excitation of 454nm standard blue light, the obtained fluorescent powder can emit green fluorescence with the main peak at 546nm, and the coverage range of the green light is 500-585 nm.
FIG. 3 is a fluorescence excitation spectrum of the product obtained in example 1. As can be seen from the figure, the main peak of the excitation spectrum of the obtained fluorescent powder is located at 454nm, the blue light excitation in the range of 430-465 nm is covered, and the fluorescent powder has stronger excitation in the range of near ultraviolet light (361nm) and violet light (418nm), which indicates that the obtained fluorescent powder can be effectively excited by the blue light, the violet light and the near ultraviolet light. The luminescence of the product obtained in example 1 is shown in FIG. 4 as a color coordinate (0.2729,0.7163) and green light. The x-ray powder diffraction pattern, fluorescence emission spectrum, fluorescence excitation spectrum, and color coordinate pattern of examples 2 to 10 are substantially the same as those of example 1.
The quantum efficiency of the product described in example 1 was evaluated using a hamamatsu C9920-03G absolute quantum yield measurement system, and the evaluation results showed a quantum efficiency of 13.6%. The quantum efficiencies of the products described in examples 2-10 are substantially consistent and all are greater than 10%.
The color purity of the product obtained in example 1 was calculated as 99.56% using color purity calculation software CIE1931 with a version number of v.1.6.0.2. The color purity of the luminescence of the products of the embodiments 2-10 is basically consistent with that of the product of the embodiment 1, and the color purity is more than 99 percent.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. Ho3+An activated green down-conversion phosphor characterized in that said green down-conversion phosphor has a molecular formula of Ho(3-x-y)LaxRyTa0.5Ga5.5O14Wherein 0 is<x<3，0≤y≤1，x+y<3, R is one of Gd, Sc, Lu and Y.
2. The green down-converting phosphor of claim 1, wherein the green down-converting phosphor has a formula of Ho(3-x-y)LaxRyTa0.5Ga5.5O14Wherein 2 is<x<3，0≤y≤1，x+y<3, R is one of Gd, Sc, Lu and Y.
3. The method of making a green down-conversion phosphor of any of claims 1 or 2, comprising the steps of:
mixing and grinding a holmium-containing compound, a lanthanum-containing compound, an R-containing compound, tantalum oxide and a gallium-containing compound uniformly according to a proportion, sintering, and cooling to obtain the fluorescent powder; wherein R is one of Gd, Sc, Lu and Y.
4. The method of claim 3, wherein the holmium-containing compound is selected from one or more of holmium oxide, holmium carbonate, and holmium nitrate.
5. The method of claim 3, wherein the lanthanum containing compound is selected from one or more of lanthanum oxide, lanthanum carbonate, lanthanum nitrate, and lanthanum oxalate.
6. The method of claim 3, wherein the R-containing compound is an oxide or carbonate or oxalate or nitrate of R.
7. The method of claim 3, wherein the gallium-containing compound is selected from one or both of gallium oxide and gallium nitrate.
8. The method of claim 3, wherein the sintering is performed by raising the temperature to 1000-1500 ℃ at a rate of 5-30 ℃/min and maintaining the temperature for 4-10 h.
9. The method for preparing a green down-conversion phosphor as claimed in any one of claims 3 or 8, wherein the mixture is pre-fired before sintering, and the pre-firing is carried out by raising the temperature to 300-900 ℃ at a rate of 5-30 ℃/min and maintaining the temperature for 2-8 h.
10. Use of the green down-converting phosphor of any of claims 1 or 2 in the field of solid state lighting and displays.
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