CN108822842B - Red strontium magnesium phosphate fluorescent material and preparation method and application thereof - Google Patents
Red strontium magnesium phosphate fluorescent material and preparation method and application thereof Download PDFInfo
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- CN108822842B CN108822842B CN201810559802.4A CN201810559802A CN108822842B CN 108822842 B CN108822842 B CN 108822842B CN 201810559802 A CN201810559802 A CN 201810559802A CN 108822842 B CN108822842 B CN 108822842B
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- 239000000463 material Substances 0.000 title claims abstract description 61
- BTEPQKGGXUMBRS-UHFFFAOYSA-K magnesium;strontium;phosphate Chemical compound [Mg+2].[Sr+2].[O-]P([O-])([O-])=O BTEPQKGGXUMBRS-UHFFFAOYSA-K 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 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
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 14
- 238000001228 spectrum Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000009877 rendering Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 13
- 238000000695 excitation spectrum Methods 0.000 description 10
- 238000000227 grinding Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7737—Phosphates
- C09K11/7738—Phosphates with alkaline earth metals
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
- H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
- H10H20/8512—Wavelength conversion materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
一种红色锶镁磷酸盐荧光材料及其制备方法和应用，该红色锶镁磷酸盐荧光材料为Sr19(1‑x)Eu19xMg2(PO4)14，按照原料中各元素摩尔比Sr:Eu:Mg＝19(1‑x):19x:2；Mg:P＝1:7称取原料，混合后在还原气氛下，先加热至900℃保温4h,再升温至1200℃保温6h，随炉冷却至室温。优点是：Eu2+离子掺杂后，Sr19Mg2(PO4)14；Eu2+在激发波长在400nm处可以获得发射波长在625nm的红光，提供了半导体照明中高显色性所需的红色光谱，并具有高的发光效率、良好的热稳定性和化学稳定性。产品制备方法简单，合成条件温和，适用于大批量生产，极具产业应用价值。
A red strontium magnesium phosphate fluorescent material and a preparation method and application thereof, the red strontium magnesium phosphate fluorescent material is Sr 19(1-x) Eu 19x Mg 2 (PO 4 ) 14 , and the molar ratio of each element in the raw material is Sr :Eu:Mg=19(1-x):19x:2; Mg:P=1:7 Weigh the raw materials, after mixing, in a reducing atmosphere, first heat to 900°C for 4h, then heat up to 1200°C for 6h, Cool to room temperature with the oven. The advantages are: after doping with Eu 2+ ions, Sr 19 Mg 2 (PO 4 ) 14 ; Eu 2+ can obtain red light with an emission wavelength of 625 nm at an excitation wavelength of 400 nm, which provides the required high color rendering in semiconductor lighting. The red spectrum, and has high luminous efficiency, good thermal stability and chemical stability. The product has a simple preparation method and mild synthesis conditions, is suitable for mass production, and has great industrial application value.
Description
Technical Field
The invention relates to a red strontium magnesium phosphate fluorescent material, a preparation method and application thereof, in particular to a red phosphate fluorescent material for photoluminescence in semiconductor illumination, and a preparation method and application thereof.
Background
The WLEDs lamp has unique advantages in the aspects of energy conservation, environmental protection, long service life and the like, is the development requirement of jointly advocating and participating in energy conservation and environmental protection all over the world, and in addition, the LED lamp is a real environment-friendly product because the LED lamp does not contain pollutants such as lead, mercury and the like.
White WLEDs light source can be obtained by combining a (near) ultraviolet chip with red, green and blue fluorescent materials, and has high color rendering index and low color temperature, and in order to improve the color rendering property and stability of the final WLEDs, the fluorescent material excited by the (near) ultraviolet chip is required to have good chip wavelength matching property, stability and higher luminous efficiency. Therefore, there is a need to develop a novel efficient and stable light emitting material.
At present, few red luminescent materials with high efficiency and excellent thermal stability, which can be excited by (near) ultraviolet light, are reported. Wherein the red fluorescent material with better performance is represented by Y2O2S:Eu3+However, they cause environmental pollution due to the formation of sulfide as a by-product in the sulfate production process, and have poor chemical stability at a specific temperature, which directly affects the light conversion efficiency, Y2O2S:Eu3+The stability of the composition is to be further improved. Further, Eu3+The f-f transition absorption belongs to a linear absorption peak, and has a certain difference with the matching of the emission peak of the current commercial LED chip (365 nm-410 nm), thereby seriously influencing the light conversion efficiency of the device. The development and development of nitride fluorescent powder have received great attention from the scientific and industrial fields due to its unique excitation spectrum (the excitation range covers ultraviolet, near ultraviolet, blue light and even green light) and excellent luminescence characteristics. The nitride fluorescent material has high luminous efficiency, good wavelength matching performance and stability, and is widely concerned by people in recent years, however, the preparation process of the nitride fluorescent material needs harsh conditions such as high temperature (more than 1600 ℃), high pressure (0.1-10 MPa), atmosphere protection and the like, and the wide application and popularization of the fluorescent powder are greatly limited.
Disclosure of Invention
The invention aims to provide a red strontium magnesium phosphate fluorescent material which is good in spectrum matching, high in luminous efficiency, simple and convenient in preparation method and low in synthesis temperature, and a preparation method and application thereof.
The technical solution of the invention is as follows:
red wineStrontium magnesium phosphate fluorescent material of chemical composition formula Sr19(1-x)Eu19xMg2(PO4)14Wherein x is more than or equal to 0.001 and less than or equal to 0.09.
A preparation method of a red strontium magnesium phosphate fluorescent material comprises the following steps:
1) according to the chemical composition formula Sr19(1-x)Eu19xMg2(PO4)14According to the mol ratio of the elements Sr, Eu, Mg, 19(1-x), 19x and 2; weighing raw materials in a ratio of Mg to P of 1 to 7, wherein x is more than or equal to 0.001 and less than or equal to 0.09, and the raw materials comprise:
an Sr-containing oxide (SrO) or a compound capable of being converted to the oxide as an Sr source;
an oxide containing Mg (MgO) or a compound capable of being converted to the oxide as a Mg source;
the Eu source comprises a simple substance, an oxide and a nitrate of Eu;
an oxide containing P or a compound capable of being converted to an oxide of P as a source of P;
2) mixing the raw materials to obtain a mixture, heating the mixture to 900 ℃ in a reducing atmosphere, preserving heat for 4 hours, then heating to 1200 ℃ and preserving heat for 6 hours, and cooling to room temperature along with the furnace.
The Sr source is SrO and SrCO3、Sr(NO3)2·4H2O、SrC2O4Or Sr (CH)3COO)2。
The Mg source is MgO and MgCO3、4MgCO3·Mg(OH)2·5H2O。
The P source is (NH)4)2HPO4、NH4H2PO4、H3PO4Or P2O5。
The Eu source is Eu simple substance and Eu2O3Or Eu (NO)3)3·6H2O。
In the step 2, the reducing atmosphere is one or a mixture of nitrogen, hydrogen or ammonia.
An application of a red strontium magnesium phosphate fluorescent material in the preparation of a white light LED.
The invention has the beneficial effects that:
(1) phosphate materials with Whitlockite-type crystal structures are widely applied to various fields such as laser materials, biological materials, luminescent materials and the like due to the advantages of low synthesis temperature, good physical and chemical stability and the like. The Eu is synthesized by adjusting the experimental conditions and the raw material ratio for the first time2+Ion-doped red fluorescent material Sr19Mg2(PO4)14:Eu2+. The red phosphate fluorescent material belongs to a white phosphorite crystal structure, and the space group is R-3 m. Eu (Eu)2+After ion doping, Sr19Mg2(PO4)14；Eu2+Red light with an emission wavelength of 625nm can be obtained at an excitation wavelength of 400nm, a red spectrum required for high color rendering in semiconductor illumination is provided, and high luminous efficiency, good thermal stability and good chemical stability are achieved. The product has simple preparation method, can be synthesized under normal pressure, has lower calcining temperature, is suitable for mass production, and has great industrial application value.
(2) Preparing Eu in reducing atmosphere by adjusting the ratio of Sr and Eu2+The fluorescent material has a wide excitation range from 365nm to 410nm, can be well matched with a near ultraviolet LED chip, and can obtain red light with an emission wavelength of 625nm at an excitation wavelength of 400 nm. Meanwhile, the scheme suitable for different products can be conveniently obtained by adjusting the doping proportion parameter, has strong applicability, and Sr is under the excitation condition of 400nm18.81Eu0.19Mg2(PO4)14The luminous brightness can reach 68.3% of that of commercial powder, and compared with the commercial powder, Sr19Mg2(PO4)14The red phosphate fluorescent material has the advantages of low price, simple production and preparation and the like, and has potential to become a novel red fluorescent material.
Drawings
The invention is further illustrated by the following examples in conjunction with the accompanying drawings:
FIG. 1 is an XRD diffraction pattern of a red phosphate fluorescent material in example 1 of the present invention;
FIG. 2 is a graph showing an excitation spectrum and an emission spectrum of a red phosphate fluorescent material in example 1 of the present invention;
FIG. 3 is a thermal quenching graph of a red phosphate fluorescent material in example 1 of the present invention;
FIG. 4 is an XRD diffraction pattern of the red phosphate fluorescent material in example 2 of the present invention;
FIG. 5 is a graph showing an excitation spectrum and an emission spectrum of a red phosphate fluorescent material in example 2 of the present invention;
FIG. 6 is a thermal quenching graph of a red phosphate fluorescent material in example 2 of the present invention;
FIG. 7 is an XRD diffraction pattern of the red phosphate fluorescent material in example 3 of the present invention;
FIG. 8 is a graph showing an excitation spectrum and an emission spectrum of a red phosphate fluorescent material in example 3 of the present invention;
FIG. 9 is a thermal quenching graph of a red phosphate fluorescent material in example 3 of the present invention;
FIG. 10 shows a red phosphate phosphor and a current commercial red phosphor Y in example 2 of the present invention2O2S:Eu3+And (4) comparing the emission intensity.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention, and not to limit the scope of the appended claims.
Example 1
(1) According to the chemical formula Sr19Mg2(PO4)14：0.005Eu2+(Sr18.905Eu0.095Mg2(PO4)14) The composition was weighed 0.9153g SrCO3，0.0264g MgO，0.6063g(NH4)2HPO4And 0.0054g Eu2O3Grinding for 30min to uniformly mix the raw materials to obtain mixed powder;
(2) mixing the powdersPlacing the corundum crucible into a tubular atmosphere furnace, introducing mixed reducing gas, namely flowing N2/H2(the volume ratio is 9/1), heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4h, then heating to 1200 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 6h, then cooling to 500 ℃ at the heating rate of 5 ℃/min, naturally cooling to room temperature, taking out the obtained powder, and grinding into powder to obtain the required fluorescent powder material.
As shown in the figure, FIG. 1 shows a sample Sr obtained in example 118.905Eu0.095Mg2(PO4)14The basic structure of the XRD pattern of (1) is a scheelite crystal structure and has an R-3m space group.
FIG. 2 shows an excitation spectrum and an emission spectrum of the fluorescent material obtained in example 1; it can be seen that the excitation spectrum of the fluorescent material under the monitoring of 625nm shows a broadband excitation peak in the range of 300 to 450nm, and has stronger excitation near 400nm, which indicates that the fluorescent material can be applied to the white light LED excited by an ultraviolet LED chip. Under the excitation of 400nm, the sample shows red light emission, the range extends from 550nm to about 750nm, the wavelength of the main emission peak is about 625nm, and the sample can be well matched with a near ultraviolet LED chip.
FIG. 3 shows the thermal quenching spectrum of the fluorescent material obtained in example 1, and shows that the emission peak of the sample is somewhat reduced with increasing temperature, and the emission intensity remains 36.27% of the initial intensity when the temperature is reduced to 413K (140 ℃).
The Sr is discovered by testing the quantum efficiency of the strontium titanate18.905Eu0.095Mg2(PO4)14The absolute quantum yield of the fluorescent powder material can reach 75%.
Example 2
(1) According to the chemical formula Sr19Mg2(PO4)14:0.01Eu2+(Sr18.81Eu0.19Mg2(PO4)14) Weighing 1.7465g Sr (NO)3)2·4H2O，0.0636g 4MgCO3·Mg(OH)2·5H2O，0.4490g H3PO4And 0.0109g Eu2O3Grinding for 45min to uniformly mix the raw materials;
(2) putting the mixed powder into a corundum crucible, putting the corundum crucible into a tubular atmosphere furnace, and introducing mixed reducing gas, namely flowing N2/H2In a reducing atmosphere of a mixed atmosphere (the volume ratio of nitrogen to hydrogen is 9/1), raising the temperature to 900 ℃ at the rate of 5 ℃/min, preserving the heat for 4h, then raising the temperature to 1200 ℃ at the rate of 5 ℃/min, preserving the heat for 6h, then lowering the temperature to 500 ℃ at the rate of 5 ℃/min, naturally cooling to room temperature, taking out the obtained powder, and grinding the powder into powder to obtain the required fluorescent powder material. FIG. 4 shows Sr of a sample obtained in example 218.81Eu0.19Mg2(PO4)14The basic structure of the XRD pattern of (1) is a scheelite crystal structure and has an R-3m space group. FIG. 5 shows the excitation spectrum and emission spectrum of the fluorescent material obtained in example 2; it can be seen that the excitation spectrum of the fluorescent material under the monitoring of 625nm shows a broadband excitation peak in the range of 300 to 450nm, and the fluorescent material has stronger excitation near 400nm and can have better matching with a near ultraviolet LED chip. The sample exhibited red emission, with monitoring at 400nm, ranging from 550nm to around 750nm, with the main peak wavelength of emission lying around 625 nm. FIG. 6 shows the thermal quenching spectrum of the fluorescent material obtained in example 2, and shows that the emission peak of the sample is somewhat reduced with increasing temperature, and the emission intensity is maintained at 40.94% of the initial intensity when the temperature is reduced to 413K (140 ℃). The absolute quantum yield of the sample can reach 79% by testing the quantum efficiency of the sample.
Example 3
(1) According to the chemical formula Sr19Mg2(PO4)14:0.02Eu2+(Sr18.62Eu0.38Mg2(PO4)14) Weighing 0.6290g of SrO, 0.0263g of MgO and 0.5250g of NH4H2PO4And 0.0552g Eu (NO)3)3·6H2O, grinding for 60min to uniformly mix the raw materials;
(2) putting the mixed powder into a corundum crucible, putting the corundum crucible into a tubular atmosphere furnace, and introducingMixed reducing gases, i.e. flowing N2/H2(the volume ratio is 9/1), heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 4h, then heating to 1200 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 6h, then cooling to 500 ℃ at the heating rate of 5 ℃/min, naturally cooling to room temperature, taking out the obtained powder, and grinding into powder to obtain the required fluorescent powder material. FIG. 7 shows Sr of a sample obtained in example 318.62Eu0.38Mg2(PO4)14The basic structure of the XRD pattern of (1) is a scheelite crystal structure and has an R-3m space group. FIG. 8 shows an excitation spectrum and an emission spectrum of the fluorescent material obtained in example 3; it can be seen that the excitation spectrum of the fluorescent material under the monitoring of 625nm shows a broadband excitation peak in the range of 300 to 450nm, and the fluorescent material has stronger excitation near 400nm and can have better matching with a near ultraviolet LED chip. The sample exhibited red emission, with monitoring at 400nm, ranging from 550nm to around 750nm, with the main peak wavelength of emission lying around 625 nm. FIG. 9 shows the thermal quenching spectrum of the fluorescent material obtained in example 3, and shows that the emission peak of the sample is somewhat reduced with increasing temperature, and the emission intensity remains 46.43% of the initial intensity when the temperature is reduced to 413K (140 ℃). The absolute quantum yield of the sample can reach 74% by testing the quantum efficiency of the sample.
FIG. 10 is a comparison of the emission intensity of the red phosphate phosphor of example 2 of the present invention and the emission intensity of the commercial phosphors currently on the market. It can be seen that Sr is under the excitation condition of 400nm18.81Eu0.19Mg2(PO4)14The luminous brightness can reach 68.3 percent of that of commercial powder, and the red fluorescent material has the potential to be the most novel red fluorescent material. The luminous intensity of the fluorescent material is expected to be further improved through subsequent process treatment.
The above description is only exemplary 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 (8)
1. A red strontium magnesium phosphate fluorescent material is characterized in that: chemical composition formula Sr19(1-x)Eu19xMg2(PO4)14，Wherein x is more than or equal to 0.001 and less than or equal to 0.09.
2. A preparation method of a red strontium magnesium phosphate fluorescent material is characterized by comprising the following steps: the method comprises the following steps:
1) according to the chemical composition formula Sr19(1-x)Eu19xMg2(PO4)14According to the mol ratio of the elements in the raw materials, Sr: Eu: Mg =19(1-x):19x: 2; weighing raw materials according to the ratio of Mg to P =1 to 7, wherein x is more than or equal to 0.001 and less than or equal to 0.09, and the raw materials comprise:
an oxide SrO containing Sr or a compound capable of being converted to the oxide as a Sr source;
an oxide MgO containing Mg or a compound capable of being converted to the oxide as a Mg source;
the Eu source comprises a simple substance, an oxide and a nitrate of Eu;
an oxide containing P or a compound capable of being converted to an oxide of P as a source of P;
2) mixing the raw materials to obtain a mixture, heating the mixture to 900 ℃ in a reducing atmosphere, preserving heat for 4 hours, then heating to 1200 ℃ and preserving heat for 6 hours, and cooling to room temperature along with the furnace.
3. The method for preparing a red strontium magnesium phosphate fluorescent material according to claim 2, wherein the method comprises the following steps: the Sr source is SrO and SrCO3、Sr(NO3)2·4H2O、SrC2O4Or Sr (CH)3COO)2。
4. The method for preparing a red strontium magnesium phosphate fluorescent material according to claim 2, wherein the method comprises the following steps: the Mg source is MgO and MgCO3、4MgCO3·Mg(OH)2·5H2O。
5. According to the claimsThe preparation method of the red strontium magnesium phosphate fluorescent material according to claim 2 is characterized by comprising the following steps: the P source is (NH)4)2HPO4、NH4H2PO4、H3PO4Or P2O5。
6. The method for preparing a red strontium magnesium phosphate fluorescent material according to claim 2, wherein the method comprises the following steps: the Eu source is Eu simple substance and Eu2O3Or Eu (NO)3)3·6H2O。
7. The method for preparing a red strontium magnesium phosphate fluorescent material according to claim 2, wherein the method comprises the following steps: in the step 2, the reducing atmosphere is one or a mixture of nitrogen, hydrogen or ammonia.
8. Use of the red strontium magnesium phosphate fluorescent material according to claim 1 in the fabrication of a white LED.
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| Novel orange light emitting phosphor Sr9(Li, Na, K)Mg(PO4)7: Eu2+ excited by NUV light for white LEDs;Xin Ding et al.;《Acta Materialia》;20160901;第120卷;第281-291页 * |
| Synthesis, crystal structure and luminescence characteristics of a novel red phosphor Ca19Mg2(PO4)14:Eu3+ for light emitting diodes and field emission displays;Ge Zhu et al.;《Journal of Materials Chemistry C》;20130729;第1卷;第5960-5969页 * |
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