WO2020024317A1 - Eu3+ ion-activated phosphate-based fluorescent material, preparation therefor and use thereof - Google Patents
Eu3+ ion-activated phosphate-based fluorescent material, preparation therefor and use thereof Download PDFInfo
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- WO2020024317A1 WO2020024317A1 PCT/CN2018/099496 CN2018099496W WO2020024317A1 WO 2020024317 A1 WO2020024317 A1 WO 2020024317A1 CN 2018099496 W CN2018099496 W CN 2018099496W WO 2020024317 A1 WO2020024317 A1 WO 2020024317A1
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- fluorescent material
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- based fluorescent
- activated phosphate
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- 239000000463 material Substances 0.000 title claims abstract description 52
- -1 ion-activated phosphate Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000126 substance Substances 0.000 claims abstract description 19
- 230000005284 excitation Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- 239000010955 niobium Substances 0.000 claims description 34
- 150000002500 ions Chemical class 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 10
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000008040 ionic compounds Chemical class 0.000 claims description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 2
- YEFJHNZIYIHXJQ-UHFFFAOYSA-N [Os+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Os+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YEFJHNZIYIHXJQ-UHFFFAOYSA-N 0.000 claims 1
- 229910000487 osmium oxide Inorganic materials 0.000 claims 1
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 5
- 238000005424 photoluminescence Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 238000000695 excitation spectrum Methods 0.000 description 7
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
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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
- C09K11/7742—Antimonates; Arsenates
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Definitions
- the invention relates to the field of inorganic light-emitting devices, in particular to a Eu 3+ ion-activated phosphate-based fluorescent material, and preparation and application thereof.
- white light-emitting diodes have the advantages of all-solid-state, energy saving, environmental protection, long life, low operating voltage, high luminous efficiency, good shock resistance and safety, and simple light color adjustment.
- the most important process is to coat a blue LED chip (such as InGaN) with a yellow light-emitting fluorescent material (such as YAG: Ce 3+ ) and mix it in an epoxy resin.
- the device can obtain white light emission according to the principle of chromaticity.
- the red-emitting fluorescent materials developed are rare earth Eu 3 + / 2 + or Ce 3+ .
- the rare earth-doped nitride-based red fluorescent materials have excellent fluorescent properties and can also be adapted to most practical application environments.
- the representative red-emitting fluorescent material Y 2 O 2 S: Eu 3+ is a sulfide matrix, the preparation method is complicated, the volatilization of sulfur will cause pollution, and the luminous efficiency is low.
- red fluorescent materials play an important role in modulating the color temperature of white light and improving its color rendering properties, etc. It is very urgent to develop novel red fluorescent materials.
- the purpose of the present invention is to provide an Eu 3+ ion-activated phosphate-based fluorescent material and its preparation and application. It has good light absorption, high luminous efficiency, and is a non-rare-earth-based red fluorescent material.
- the present invention provides a Eu 3+ ion-activated phosphate-based fluorescent material (rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material), which has a chemical formula of Sb 1-x Eu x Nb 3 (PO 4 ) 6 , wherein 0.001 ⁇ x ⁇ 0.1, the Eu 3+ ion-activated phosphate-based fluorescent material emits red fluorescence under the excitation of near-ultraviolet light.
- X in the formula represents the number of moles of Eu 3+ doping.
- x 0.01-0.1.
- Eu 3+ is a typical red light-emitting ion.
- the light emission spectrum is derived from the transition between energy levels in the 4f sublayer. It has obvious sharp line characteristics and high luminous chromaticity.
- the phosphate-based fluorescent material of the present invention does not contain rare earth ions. The preparation cost is low, the matrix skeleton composed of phosphate has high rigidity, good thermal stability, and high luminous efficiency.
- the chemical formula of the Eu 3+ ion-activated phosphate-based phosphor is Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 , Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 , Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 , Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 or Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 .
- the wavelength of near-ultraviolet light is 370-410 nm.
- the wavelength of red fluorescence is 570-720 nm (preferably, the wavelength of red fluorescence is 610-620 nm).
- the fluorescent material of the present invention emits bright red light, the strongest wavelength of light emission is about 615 nm, and the red color is pure.
- the present invention also discloses the application of the Eu 3+ ion-activated phosphate-based fluorescent material in the preparation of a light-emitting device, and the excitation source of the light-emitting device is near-ultraviolet light.
- the light emitting device is various illumination display or photoluminescence chromaticity adjusting device using near-ultraviolet light as an excitation light source.
- the present invention also provides a method for preparing the Eu 3+ ion-activated phosphate-based fluorescent material, which is prepared by a wet chemical synthetic sol-gel method, and includes the following steps:
- the amount of the complexing agent and the molar ratio of the cations (Eu 3+ , Sb 3+ , Nb 5+ or P 5+ ) in the added solution are (1.5-2.5): 1;
- the molar ratio of the Sb 3+ ion-containing compound, the Nb 5+ ion-containing compound, the P 5+ ion-containing compound, and the Eu 3+ ion-containing compound is 0.9-0.999: 3: 6: 0.001-0.1;
- the precursor is calcined in an air atmosphere, the calcination temperature is 800-1000 ° C, and the calcination time is 1-10 hours to obtain the Eu 3+ ion-activated phosphate-based fluorescent material.
- the complexing agent is citric acid or oxalic acid.
- the compound containing Sb 3+ ions is antimony trioxide (Sb 2 O 3 ) or antimony trichloride (SbCl 3 ).
- the compound containing Eu 3+ ions is europium oxide (Eu 2 O 3 ) or europium nitrate (Eu (NO 3 ) 3 .6H 2 O).
- the compound containing Nb 5+ ions is niobium pentoxide (Nb 2 O 5 ) or niobium chloride (NbCl 5 ).
- the compound containing a P 5+ ion is diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
- step (2) the reaction is performed under stirring conditions, and the reaction time is 1-3 h.
- the calcination temperature is 850-900 ° C, and the calcination time is 3-5 hours.
- the present invention has at least the following advantages:
- the rare earth Eu 3 + -activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention has good light absorption in the near-ultraviolet light range of 380-410 nm. Under the excitation light of the above wavelength, the fluorescent material emits Bright red light is emitted, the strongest wavelength of light is 615 nanometers, and the red color is pure.
- the rare earth Eu 3 + -activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is a non-rare earth-based phosphate with abundant raw material sources and low prices. It is prepared by a wet chemical sol-gel method. Easy to operate and low sintering temperature.
- the rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention the matrix skeleton composed of phosphate has high rigidity, good thermal stability, and high luminous efficiency, and is suitable for using near-ultraviolet light as an excitation source. Various lighting displays and photoluminescence chromaticity adjustments.
- the rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is excited by near-ultraviolet light, and the emission spectrum is derived from the transition between the energy levels in the 4f sublayer, and the main wavelength is 615 nanometers. , Has obvious sharp line spectrum characteristics, high luminous chromaticity.
- the rare earth Eu 3+ activated SbNb 3 (PO 4 ) 6 -based fluorescent material of the present invention is compared with other red fluorescent materials such as sulfide Y 2 O 2 S: Eu 3+ , halide and the like as host materials.
- the preparation process of the matrix material is simple, the products are easy to collect, there is no waste gas discharge, and the environment is friendly.
- Example 1 is an X-ray powder diffraction pattern of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention
- Example 2 is an electron scanning electron microscope image of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention
- Example 3 is an excitation spectrum of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention under light monitoring at 615 nm;
- Example 4 is a light emission spectrum diagram of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention under 395 nm light excitation;
- Example 5 is a light emission attenuation curve of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 prepared in Example 1 of the present invention
- Example 7 is an electron scanning electron microscope image of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention.
- FIG. 10 is a light emission attenuation curve of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 prepared in Example 3 of the present invention.
- This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 .
- antimony trichloride SbCl 3 was weighed: 2.121 g, europium nitrate Eu (NO 3 ) 3 ⁇ 6H 2 O: 0.312 g, niobium chloride NbCl 5 : 8.1 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 6.9 g.
- the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
- the weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 80 ° C., and continuously stirred until completely dissolved, and then 6.75 g of a complexing agent, oxalic acid, is added and stirred at 90 ° C. to obtain a transparent solution. Recorded as B solution.
- solution C a transparent solution, which is referred to as solution C.
- the obtained A, B, and C solutions were slowly mixed, stirred at a temperature condition of 95 ° C. for 1 hour, and then left to stand and dried to obtain a fluffy precursor.
- the obtained precursor was calcined in an air atmosphere, and the calcination temperature was 1000 ° C., the calcination time was 1 hour, and the mixture was naturally cooled to room temperature to obtain Sb 0.93 Eu 0.07 Nb 3 (PO 4 ) 6 red phosphor.
- FIG. 1 is an X-ray powder diffraction pattern of the above product.
- the XRD test results show that the prepared material is a pure phase substance and has no heterogeneous phase.
- FIG. 2 is a SEM image of the above product.
- FIG. 2 shows that the material has good crystallization performance, uniform particle size, and a size of about 100 nm.
- FIG. 3 is an excitation spectrum obtained by monitoring the emitted light of the above product at 615 nanometers. It can be seen that the excitation source of red light emission is mainly 395 nanometers, so the phosphor can be used to prepare near-ultraviolet excited fluorescent lamps.
- Fig. 4 is a luminescence spectrum obtained by exciting the above product with near-ultraviolet light at 395 nanometers. It can be seen from the figure that the main central luminescence wavelength of the material is in the red luminescence band of 615 nanometers.
- Fig. 5 is the luminescence decay curve of the above product at 615 nanometers. It can be seen from the figure that the decay time of the material is 1.37 milliseconds.
- This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 .
- antimony trioxide Sb 2 O 3 1.312 g
- samarium Eu 2 O 3 0.176 g
- niobium oxide Nb 2 O 5 3.987 g
- Diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 7.92 g.
- the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
- solution C Dissolve 7.92 grams of the weighed diammonium hydrogen phosphate reagent in dilute nitric acid, add 17 grams of citric acid, and stir at 60 ° C to obtain a transparent solution, which is referred to as solution C.
- the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 60 ° C. for 3 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
- the obtained precursor was calcined in an air atmosphere at a temperature of 800 ° C. for a period of 10 hours, and was naturally cooled to room temperature to obtain Sb 0.9 Eu 0.1 Nb 3 (PO 4 ) 6 red phosphor. Its structure test, surface morphology, excitation spectrum, luminescence spectrum and attenuation curve are similar to those of Example 1.
- This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 .
- antimony trichloride SbCl 3 was weighed: 1.77 g, europium nitrate Eu (NO 3 ) 3 ⁇ 6H 2 O: 0.107 g, and niobium chloride NbCl 5 : 6.484 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 5.521 g.
- the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
- Dissolve antimony trichloride and thorium nitrate in a dilute nitric acid solution and continue to stir vigorously until a transparent solution is obtained after complete dissolution.
- Weigh 1.45 g of oxalic acid into the transparent solution stir it at 80 ° C, and record it as solution A.
- the weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 75 ° C., and continuously stirred until completely dissolved, and then 4.32 g of a complexing agent, oxalic acid, is added and stirred at 85 ° C. to obtain a transparent solution. Recorded as B solution.
- solution C The obtained ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent was dissolved in dilute nitric acid, 8.6 g of oxalic acid was added, and the solution was stirred at 75 ° C. to obtain a transparent solution, which is referred to as solution C.
- the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 90 ° C. for 2 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
- the obtained precursor was calcined in an air atmosphere at a temperature of 850 ° C. for a period of 3 hours and naturally cooled to room temperature to obtain Sb 0.97 Eu 0.03 Nb 3 (PO 4 ) 6 red phosphor.
- FIG. 6 is an X-ray powder diffraction pattern of the above product.
- the XRD test results show that the prepared material is a pure phase substance without a heterogeneous phase.
- FIG. 7 is a SEM image of the above product, and FIG. 2 shows that the material has good crystallization performance, uniform particle size, and a size between 100-150 nm.
- FIG. 8 is an excitation spectrum chart of the above product under the monitored emission light of 615 nanometers. It can be seen that the excitation source of red light emission is mainly 395 nanometers, so the phosphor can be used to prepare near-ultraviolet excited fluorescent lamps.
- FIG. 10 is a luminescence decay curve of the above product at 615 nanometers. It can be seen from the figure that the decay time of the material is 1.6 ms.
- This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 .
- antimony trichloride SbCl 3 was weighed: 2.26 g, europium nitrate Eu (NO 3 ) 3 ⁇ 6H 2 O: 0.05 g, niobium chloride NbCl 5 : 8.1 g, ammonium dihydrogen phosphate NH 4 H 2 PO 4 : 6.9 g.
- the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
- the weighed niobium chloride NbCl 5 is dissolved in a hydrofluoric acid solution, heated in a water bath at 70 ° C., and continuously stirred until completely dissolved, and then 5.4 g of a complexing agent, oxalic acid, is added and stirred at 80 ° C. to obtain a transparent solution. Recorded as B solution.
- solution C The obtained ammonium dihydrogen phosphate NH 4 H 2 PO 4 reagent was dissolved in dilute nitric acid, 10.8 g of oxalic acid was added, and the solution was stirred at 70 ° C. to obtain a transparent solution, which is referred to as solution C.
- the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 80 ° C. for 2 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
- the obtained precursor was calcined in an air atmosphere at a temperature of 900 ° C. for a period of 3 hours, and was naturally cooled to room temperature to obtain Sb 0.99 Eu 0.01 Nb 3 (PO 4 ) 6 red phosphor. Its excitation spectrum, emission spectrum and attenuation curve are similar to those of the third embodiment.
- This embodiment provides an Eu 3+ ion-activated phosphate-based phosphor having a chemical formula of Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 .
- antimony trichloride SbCl 3 1.3 g
- niobium chloride NbCl 5 4.86 g
- ammonium dihydrogen phosphate NH 4 H 2 PO 4 4.14 g.
- the above Eu 3+ ion-activated phosphate-based phosphor was prepared as follows:
- Dissolve the weighed niobium chloride NbCl 5 in the hydrofluoric acid solution heat it in a water bath at 80 ° C, continue to stir until completely dissolved, and then add 4.05 g of the complexing agent oxalic acid. Stir at 80 ° C to obtain a transparent solution, which is referred to as solution B.
- the obtained A, B, and C solutions were slowly mixed, stirred at a temperature of 90 ° C. for 3 hours, and then allowed to stand and then dried to obtain a fluffy precursor.
- the obtained precursor was calcined in an air atmosphere at a temperature of 860 ° C. for a period of 4 hours, and was naturally cooled to room temperature to obtain Sb 0.95 Eu 0.05 Nb 3 (PO 4 ) 6 red phosphor. Its excitation spectrum, emission spectrum and attenuation curve are similar to those of the third embodiment.
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Abstract
Description
Claims (10)
- 一种Eu 3+离子激活的磷酸盐基荧光材料,其特征在于:其化学式为Sb 1-xEu xNb 3(PO 4) 6,其中0.001≤x≤0.1,所述Eu 3+离子激活的磷酸盐基荧光材料在近紫外光的激发下发出红色荧光。 A Eu 3+ ion-activated phosphate-based fluorescent material, characterized in that its chemical formula is Sb 1-x Eu x Nb 3 (PO 4 ) 6 , where 0.001 ≦ x ≦ 0.1, the Eu 3+ ion-activated Phosphate-based fluorescent materials emit red fluorescence when excited by near-ultraviolet light.
- 根据权利要求1所述的Eu 3+离子激活的磷酸盐基荧光材料,其特征在于:所述近紫外光的波长为370-410nm。 The Eu 3+ ion-activated phosphate-based fluorescent material according to claim 1, wherein the wavelength of the near-ultraviolet light is 370-410 nm.
- 根据权利要求1所述的Eu 3+离子激活的磷酸盐基荧光材料,其特征在于:所述红色荧光的波长为570-720nm。 The Eu 3+ ion-activated phosphate-based fluorescent material according to claim 1, wherein the wavelength of the red fluorescence is 570-720 nm.
- 权利要求1-3中任一项所述的Eu 3+离子激活的磷酸盐基荧光材料在制备发光器件中的应用,所述发光器件的激发源为近紫外光。 The application of the Eu 3+ ion-activated phosphate-based fluorescent material according to any one of claims 1 to 3 in the preparation of a light emitting device, wherein the excitation source of the light emitting device is near-ultraviolet light.
- 一种权利要求1-3中任一项所述的Eu 3+离子激活的磷酸盐基荧光材料的制备方法,其特征在于,包括以下步骤: A method for preparing an Eu 3+ ion-activated phosphate-based fluorescent material according to any one of claims 1-3, comprising the following steps:(1)将含有Sb 3+离子的化合物和含有Eu 3+离子的化合物溶于稀硝酸中,在络合剂的存在下在60-90℃下混匀,得到A溶液;将含有Nb 5+离子的化合物溶于氢氟酸,然后在60-90℃下与所述络合剂混匀,得到B溶液;将含有P 5+离子的化合物溶于稀硝酸中,然后在60-80℃下与所述络合剂混匀,得到C溶液; (1) Dissolve the compound containing Sb 3+ ions and the compound containing Eu 3+ ions in dilute nitric acid, mix in the presence of a complexing agent at 60-90 ° C to obtain A solution; and include Nb 5+ The ionic compound is dissolved in hydrofluoric acid, and then mixed with the complexing agent at 60-90 ° C to obtain a solution B; the compound containing P 5+ ions is dissolved in dilute nitric acid, and then at 60-80 ° C Mix with the complexing agent to obtain a C solution;其中,所述络合剂的用量和所加入溶液之中阳离子的摩尔比为1.5-2.5:1;Wherein, the amount of the complexing agent and the molar ratio of cations in the added solution are 1.5-2.5: 1;所述含有Sb 3+离子的化合物、含有Nb 5+离子的化合物、含有P 5+离子的化合物、含有Eu 3+离子的化合物的摩尔比为0.9-0.999:3:6:0.001-0.1; The molar ratio of the Sb 3+ ion-containing compound, the Nb 5+ ion-containing compound, the P 5+ ion-containing compound, and the Eu 3+ ion-containing compound is 0.9-0.999: 3: 6: 0.001-0.1;(2)将所述A溶液、B溶液和C溶液混匀后在60-95℃下反应,反应完全后干燥产物,得到前驱体;(2) the A solution, the B solution and the C solution are mixed and reacted at 60-95 ° C; after the reaction is completed, the product is dried to obtain a precursor;(3)将所述前驱体在空气气氛中煅烧,煅烧温度为800-1000℃,得到所述Eu 3+离子激活的磷酸盐基荧光材料。 (3) The precursor is calcined in an air atmosphere, and the calcination temperature is 800-1000 ° C to obtain the Eu 3+ ion-activated phosphate-based fluorescent material.
- 根据权利要求5所述的制备方法,其特征在于:在步骤(1)中,所述络合剂为柠檬酸或草酸。The method according to claim 5, wherein in step (1), the complexing agent is citric acid or oxalic acid.
- 根据权利要求5所述的制备方法,其特征在于:在步骤(1)中,所述含有Sb 3+离子的化合物为三氧化二锑或三氯化锑。 The preparation method according to claim 5, wherein in the step (1), the compound containing Sb 3+ ions is antimony trioxide or antimony trichloride.
- 根据权利要求5所述的制备方法,其特征在于:在步骤(1)中,所述含有Eu 3+离子的化合物为氧化铕或硝酸铕。 The method according to claim 5, wherein in step (1), the compound containing Eu 3+ ions is osmium oxide or osmium nitrate.
- 根据权利要求5所述的制备方法,其特征在于:在步骤(1)中,所述含有Nb 5+离子的化合物为五氧化二铌或氯化铌。 The preparation method according to claim 5, wherein in the step (1), the compound containing Nb 5+ ions is niobium pentoxide or niobium chloride.
- 根据权利要求5所述的制备方法,其特征在于:在步骤(1)中,所述含有P 5+离子的化合物为磷酸氢二铵或磷酸二氢铵。 The preparation method according to claim 5, wherein in step (1), the compound containing P 5+ ions is diammonium phosphate or diammonium phosphate.
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Non-Patent Citations (3)
Title |
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A. JOUANNEAUX: "The (MIII1/2M'V3/2)(P04) 3 compounds, M=Sb, Nd, Eu, Bi; M'=Sb, Nb, Ta. Preparation and Structure", EUR. J. SOLID STATE INORG. CHEM., vol. 30, 31 December 1993 (1993-12-31), pages 1 - 2, ISSN: 0992-4361 * |
ABDERRAHIM AATIQ: "Preparation and crystal structure of SbV 1.50InIII0.50(PO4)3 and (SbV 0.50InIII0.50)P2O7", POWDER DIFFRACTION, vol. 23, no. 3, 1 September 2008 (2008-09-01), pages 232 - 240, XP009178902, ISSN: 0885-7156, DOI: 10.1154/1.2955583 * |
KENZO KASAHARA ET AL: "Preparation and Crystal Structure of a New Form of Sb2(PO4)3 and M1/2SbV3/2(PO4)3 (M = Y, In, and Sc)", JOURNAL OF SOLID STATE CHEMISTRY, vol. 118, no. 1, 1 August 1995 (1995-08-01), pages 104 - 111, XP055683783, ISSN: 0022-4596, DOI: 10.1006/jssc.1995.1317 * |
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