CN107118772B - Eu (Eu)2+Activated phosphor of phosphor aluminate blue luminescence and preparation method - Google Patents
Eu (Eu)2+Activated phosphor of phosphor aluminate blue luminescence and preparation method Download PDFInfo
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- CN107118772B CN107118772B CN201710466128.0A CN201710466128A CN107118772B CN 107118772 B CN107118772 B CN 107118772B CN 201710466128 A CN201710466128 A CN 201710466128A CN 107118772 B CN107118772 B CN 107118772B
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- -1 phosphor aluminate Chemical class 0.000 title claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000002796 luminescence method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 230000005284 excitation Effects 0.000 claims abstract description 11
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000001354 calcination Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 13
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 7
- 238000004020 luminiscence type Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 238000009877 rendering Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 24
- 238000000695 excitation spectrum Methods 0.000 description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 229910001940 europium oxide Inorganic materials 0.000 description 6
- 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 6
- 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
- 238000000227 grinding Methods 0.000 description 6
- 238000001748 luminescence spectrum Methods 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 6
- 235000019799 monosodium phosphate Nutrition 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005090 crystal field Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005286 illumination Methods 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
- 238000000643 oven drying Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 241000083879 Polyommatus icarus Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012423 maintenance Methods 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
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7709—Phosphates
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- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses Eu2+Activated phosphor of phosphor aluminate blue light emission, method for preparing the same, phosphor of phosphor aluminate blue light emissionThe chemical general formula is: cs2‑2xEu2xAlP3O10Wherein x is divalent europium ion Eu2+Substituted Cs+The molar ratio of the ions is within the range of 0.01<x<0.08, the fluorescent powder emits blue light with the dominant wavelength of 450nm under the excitation of ultraviolet light. The pure-phase blue fluorescent powder with excellent luminous performance is obtained by adopting a sol-gel method, and the fluorescent powder emits bright blue light under the excitation of ultraviolet light, and has high luminous intensity, good stability and good color rendering property.
Description
Technical Field
The invention belongs to the technical field of inorganic fluorescent materials and display, and particularly relates to europium ion Eu2+ activated nano phosphoaluminate blue luminescent phosphor and a preparation method thereof.
Background
White LEDs are attracting attention as the next generation of solid state lighting due to their advantages of low power consumption, high efficiency, small size, low maintenance, no mercury, etc. White LEDs have been widely used as backlights for electronic devices, and significant improvements in efficiency and color rendering are expected to replace traditional general illumination for fluorescent lamps. The most common white LED is a combination of blue InGaN chip and Y3Al5O12：Ce3+(YAG:Ce3+) Yellow phosphor. However, this type of white light is poorly colored due to insufficient color in the red and blue-green regions. An effective way to solve this problem is to irradiate red, green and blue phosphors with a UV InGaN led, and to achieve this goal, a blue emitting phosphor is required. The common blue fluorescent powder applied to the ultraviolet white light LED is BaMgAl10O17:Eu2+(BAM). The material has very high luminous efficiency, but is significantly reduced with increasing temperature, which reduces the service life and luminous efficiency of the white LED. Therefore, there is a need to develop a novel blue phosphor which is highly efficient and small in thermal quenching.
Eu doped in inorganic material2+The emission transition (4f65d1 → 4f7) is partially allowed, and in a suitable crystal field environment, the quantum efficiency can be very large, Eu2+The wavelength of the emitted light varies from ultraviolet to red depending on the host lattice. The main characteristics of blue luminescence are associated with a strong crystal field strength, a high degree of covalency of the host lattice and Eu2+5d → 4f of (1) allows the transitions to be coordinated. In a matrix with covalent bonds, Eu, under the action of a strong crystal field2+The 5d orbital is significantly split into several energy levels, which results in rare earthsThe lowest position of the excited state of the ion is moved downwards. It is known that in the host lattice, Eu is responsible for2+The 5d → 4f transition of the ion makes the phosphor show strong broadband absorption at 400nm, which covers the emission wavelength (400nm) of InGaNLED excited by near ultraviolet light. Doping Eu in different compounds2+The spectral position of the absorption and emission bands can be varied. Therefore, a blue phosphor having an absorption band of about 400nm excited by ultraviolet light can be obtained.
White light emitting diodes fabricated with uv chips have been in common use for the past decades and have been reported to be suitable for uv excitation including orthosilicates, aluminates, sulfides and oxynitrides/nitrides, molybdates, etc. The patent relates to a europium ion Eu2+The research of the literature indicates that the activated nano phosphoaluminate blue luminescent phosphor has not been reported before.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a luminescent material which has high chemical purity, good luminescent quality, simple preparation process and no pollution and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: eu (Eu)2+The activated phosphor of the phosphor aluminate blue light emission has a chemical general formula: cs2-2xEu2xAlP3O10Wherein x is divalent europium ion Eu2+Substituted Cs+The molar ratio of the ions is within the range of 0.01<x<0.08, the fluorescent powder emits blue luminescence with the dominant wavelength of 450nm under the excitation of ultraviolet light.
Eu (Eu)2+The preparation method of the activated phosphor of phosphor aluminate blue luminescence adopts sol-gel method synthesis, comprising the following steps:
(1) cesium ion compound, europium ion compound, aluminum ion compound, phosphorus ion compound are expressed by the general formula Cs2- 2xEu2xAlP3O10Corresponding cesium ion, europium ion and aluminum ionWeighing the phosphorus ions according to the stoichiometric ratio; dissolving the weighed raw materials in deionized water or dilute nitric acid respectively, diluting with deionized water, and adding a complexing agent into each solution respectively;
(2) slowly mixing the raw material solutions added with the complexing agent obtained in the step 1 together, heating and stirring, standing, and drying to obtain a fluffy precursor;
(3) placing the precursor obtained in the step 2 in a muffle furnace protected by reducing atmosphere for calcining to obtain Eu2+Activated phosphor of phosphoaluminate blue luminescence.
Further, the cesium ion compound in step 1 is CsNO3Or CsCl.
Further, the europium ion compound in step 1 is Eu2O3Or Eu (NO)3)3·6H2O。
Further, the aluminum ion compound in step 1 is Al (NO)3)3·9H2O or AlCl3。
Further, the phosphorus ion compound in the step 1 is NaH2PO4·2H2O or NH4H2PO4。
Further, the complexing agent in the step 1 is citric acid or oxalic acid, and the addition amount of the complexing agent is 1.5-2 times of the molar amount of cesium ions, europium ions, aluminum ions or phosphorus ions in the raw material solution.
Further, the heating temperature of the step 2 is 50-100 ℃, and the stirring time is 1-2 hours.
Further, the calcination in the step 3 is divided into two times, the temperature of the first calcination is 200-500 ℃, and the temperature is kept for 1-8 hours; the temperature of the second calcination is 500-850 ℃, and the temperature is kept for 1-10 hours. Preferably: the first calcination temperature is 250-450 ℃, and the calcination time is 2-7 hours; the second calcination temperature is 550-800 ℃, and the calcination time is 4-9 hours.
Further, the reducing atmosphere in step 3 is one of the following two atmospheres:
(1) a mixed gas atmosphere of 5% by volume of hydrogen and 95% by volume of nitrogen;
(2) the gaseous atmosphere resulting from the combustion of carbon granules or various activated carbons in air.
The invention has the beneficial effects that:
1. the matrix material provided by the technical scheme of the invention can easily realize the reduction of the divalent rare earth ions, and the divalent rare earth ions can stably exist in the matrix.
2. The blue fluorescent material has a wider excitation area, is matched with the currently used ultraviolet excitation area (280-315nm), and is suitable for ultraviolet type illumination and display.
3. The prepared fluorescent powder has high luminous intensity, good stability and color rendering property and uniform granularity, and is beneficial to realizing the preparation of high-power lighting equipment.
4. The preparation process of the matrix material is simple, and the preparation temperature is low. The product is easy to collect, has no waste water and gas emission, is environment-friendly, and is particularly suitable for continuous production.
Drawings
FIG. 1 is a sample Cs of the prepared material1.98Eu0.02AlP3O10X-ray powder diffraction pattern of (a).
FIG. 2 is a sample Cs of the prepared material1.98Eu0.02AlP3O10SEM image of (d).
FIG. 3 is a sample Cs of the prepared material1.98Eu0.02AlP3O10Excitation spectra obtained under optical monitoring at 440 nm.
FIG. 4 is a sample Cs of the prepared material1.98Eu0.02AlP3O10The luminescence spectrum is obtained under the excitation of 300 nm ultraviolet light. And the chromaticity coordinates x-0.1501042 and y-0.0517480 were obtained, which fell in the blue region.
FIG. 5 is a sample Cs of the prepared material1.98Eu0.02AlP3O10The light attenuation curve of (1) has a decay time of 550 ns.
FIG. 6 is a sample of material Cs prepared according to the present technique1.9Eu0.1AlP3O10X-ray powder diffraction pattern of (a).
FIG. 7 is a sample Cs of the prepared material1.9Eu0.1AlP3O10SEM image of (d).
FIG. 8 sample Cs of a material prepared according to the inventive technique1.9Eu0.1AlP3O10Excitation spectra obtained under optical monitoring at 450 nm.
FIG. 9 is a sample of material Cs prepared in accordance with the present technique1.9Eu0.1AlP3O10The luminescence spectrum is obtained under the excitation of 300 nm ultraviolet light. And the chromaticity coordinates x-0.1498474 and y-0.0544204 were obtained, which fell in the blue region.
FIG. 10 is a sample of material Cs prepared in accordance with the present technique1.9Eu0.1AlP3O10The attenuation curve of (1) has a decay time of 830 ns.
Detailed Description
The invention is further described below with reference to the figures and examples.
Example 1:
according to the formula Cs1.98Eu0.02AlP3O10The stoichiometric ratio of each element in the formula (I) is respectively weighed: cesium nitrate CsNO3: 1.2864 g, europium oxide Eu2O3: 0.0117 g, aluminum nitrate Al (NO)3)3·9H2O: 1.2504 g of sodium dihydrogen phosphate NaH2PO4·2H2O: 1.5601 g, adding cesium nitrate CsNO3Dissolving in deionized water, adding 0.8914 g of oxalic acid, and stirring until the solution is completely transparent; europium oxide Eu2O3Dissolving in dilute nitric acid, adding 0.0045 g of oxalic acid, and stirring until the solution is completely transparent; adding aluminum nitrate Al (NO)3)3·9H2O is dissolved in deionized water, 0.4502 g of oxalic acid are added, sodium dihydrogen phosphate NaH is added2PO4·2H2O was dissolved in deionized water, 1.3506 grams of oxalic acid was added and stirred until completely clear to form a clear sol.
Mixing the above solutions, stirring at 65 deg.C for 5 hr, standing for a certain time, and slowly oven drying in oven to obtain herba Potentillae AnserinaeA loose precursor; putting the obtained precursor into a corundum crucible and calcining in a muffle furnace in reducing atmosphere at the temperature of 300 ℃ for 3 hours; naturally cooling the obtained pre-calcined product, placing the pre-calcined product in a mortar for grinding and uniformly mixing, and then calcining the pre-calcined product in a muffle furnace in reducing atmosphere at the calcining temperature of 550 ℃ for 4 hours to obtain europium ion Eu2+Activated nano phosphoaluminate blue luminescent phosphor.
FIG. 1 is a sample Cs of a material prepared according to the present technique1.98Eu0.02AlP3O10X-ray powder diffraction pattern of (a);
FIG. 2 is a sample Cs of material prepared according to the present technique1.98Eu0.02AlP3O10SEM picture of (1);
FIG. 3 is a sample Cs of material prepared according to the present technique1.98Eu0.02AlP3O10An excitation spectrum obtained under the monitoring of light at 440 nm;
FIG. 4 is a sample Cs of material prepared according to the present technique1.98Eu0.02AlP3O10The luminescence spectrum is obtained under the excitation of 300 nm ultraviolet light. And the chromaticity coordinates x-0.1501042 and y-0.0517480 were obtained, which fell in the blue region.
FIG. 5 is a sample of material Cs prepared according to the present technique1.98Eu0.02AlP3O10The light attenuation curve of (1) has a decay time of 550 ns.
Example 2:
according to the formula Cs1.96Eu0.04AlP3O10The stoichiometric ratio of each element in the formula (I) is respectively weighed: cesium chloride CsCl: 1.1000 g, europium nitrate Eu (NO3) 3.6H 2O: 0.0595 g, aluminium chloride AlCl 3: 0.4445 g of ammonium dihydrogen phosphate NH4H2PO4: 1.1503 g, cesium chloride CsCl was dissolved in deionized water, 0.8824 g of oxalic acid was added, and stirring was carried out until it was completely transparent; europium nitrate Eu (NO)3)3·6H2Dissolving O in deionized water, adding 0.0180 g of oxalic acid, and stirring until the solution is completely transparent; will chloridizeAluminium AlCl3Dissolving in deionized water, adding 0.4502 g of oxalic acid, and dissolving sodium dihydrogen phosphate NaH2PO4·2H2O was dissolved in deionized water, 1.3506 grams of oxalic acid was added and stirred until completely clear to form a clear sol.
Mixing the solutions, stirring for 5 hours at the temperature of 70 ℃, standing for a period of time, and then slowly drying in an oven to obtain a fluffy precursor; putting the obtained precursor into a corundum crucible and calcining in a muffle furnace in reducing atmosphere at the calcining temperature of 400 ℃ for 4 hours; naturally cooling the obtained pre-calcined product, placing the pre-calcined product in a mortar for grinding and uniformly mixing, and then calcining the pre-calcined product in a muffle furnace in reducing atmosphere at the calcining temperature of 650 ℃ for 5 hours to obtain europium ion Eu2+Activated nano phosphoaluminate blue luminescent phosphor.
The main structural properties, excitation spectrum, light emission spectrum and light attenuation curve are similar to those of example 1.
Example 3:
according to the formula Cs1.92Eu0.08AlP3O10Respectively weighing cesium nitrate CsNO according to the stoichiometric ratio of each element3: 1.2474 g, europium nitrate Eu (NO)3)3·6H2O: 0.1189 g of AlCl3: 0.44445 g of ammonium dihydrogen phosphate NH4H2PO4: 1.5601 g, adding cesium nitrate CsNO3Dissolving in deionized water, adding 0.8644 g of oxalic acid, and stirring until the solution is completely transparent; europium nitrate Eu (NO)3)3·6H2Dissolving O in deionized water, adding 0.0360 g of oxalic acid, and stirring until the solution is completely transparent; mixing aluminum chloride AlCl3Dissolving in deionized water, adding 0.4502 g of oxalic acid, and dissolving sodium dihydrogen phosphate NaH2PO4·2H2O was dissolved in deionized water, 1.3506 grams of oxalic acid was added and stirred until completely clear to form a clear sol.
Mixing the above solutions, stirring at 65 deg.C for 4 hr, standing for a certain time, and slowly oven drying in ovenObtaining a fluffy precursor; putting the obtained precursor into a corundum crucible and calcining in a muffle furnace in reducing atmosphere at the temperature of 250 ℃ for 6 hours; naturally cooling the obtained pre-calcined product, placing the pre-calcined product in a mortar for grinding and uniformly mixing, and then calcining the pre-calcined product in a muffle furnace in reducing atmosphere at the calcining temperature of 700 ℃ for 6 hours to obtain europium ion Eu2+Activated nano phosphoaluminate blue luminescent phosphor.
The main structural properties, excitation spectrum, light emission spectrum and light attenuation curve are similar to those of example 1.
Example 4:
according to the formula Cs1.9Eu0.1AlP3O10And (3) weighing cesium chloride CsCl: 1.0663 g, europium oxide Eu2O3: 0.0587 g, aluminum nitrate Al (NO)3)3·9H2O: 1.2504 g of ammonium dihydrogen phosphate NH4H2PO4: 1.1503 g, cesium chloride CsCl was dissolved in deionized water, 1.8241 g of citric acid was added, and stirring was carried out until complete transparency; europium oxide Eu2O3Dissolving in dilute nitric acid, adding 0.0480 g of citric acid, and stirring until the solution is completely transparent; adding aluminum nitrate Al (NO)3)3·9H2O in DI water, 0.9607 g of citric acid was added and ammonium dihydrogen phosphate NH was added4H2PO4·2H2O was dissolved in deionized water, 2.8821 grams of citric acid was added, and stirred until completely clear to form a clear sol.
Mixing the solutions, stirring for 4 hours at the temperature of 65 ℃, standing for a period of time, and then slowly drying in an oven to obtain a fluffy precursor; putting the obtained precursor into a corundum crucible and calcining in a muffle furnace protected by reducing atmosphere at the temperature of 450 ℃ for 4 hours; naturally cooling the obtained pre-calcined product, placing the pre-calcined product in a mortar for grinding and uniformly mixing, and then calcining the pre-calcined product in a muffle furnace in reducing atmosphere at the calcining temperature of 750 ℃ for 7 hours to obtain europium ion Eu2+Activated nano phosphoaluminate blue luminescent phosphor.
FIG. 6 is a sample of material Cs prepared according to the present technique1.9Eu0.1AlP3O10X-ray powder diffraction pattern of (a);
FIG. 7 is a sample of material Cs prepared in accordance with the present technique1.9Eu0.1AlP3O10SEM picture of (1);
FIG. 8 sample Cs of a material prepared according to the inventive technique1.9Eu0.1AlP3O10An excitation spectrum obtained under the monitoring of light of 450 nm;
FIG. 9 is a sample of material Cs prepared in accordance with the present technique1.9Eu0.1AlP3O10The luminescence spectrum is obtained under the excitation of 300 nm ultraviolet light. And obtaining chromaticity coordinates of x-0.1498474 and y-0.0544204, which fall in a blue region;
FIG. 10 is a sample of material Cs prepared in accordance with the present technique1.9Eu0.1AlP3O10The attenuation curve of (1) has a decay time of 830 ns.
Example 5:
according to the formula Cs1.88Eu0.12AlP3O10And (3) weighing cesium chloride CsCl: 1.0551 g, europium oxide Eu2O3: 0.0704 g, aluminium chloride AlCl 3: 0.0445 g of sodium dihydrogen phosphate NaH2PO4·2H2O: 1.5601 g, cesium chloride CsCl was dissolved in deionized water, 1.8061 g of citric acid was added, and stirring was carried out until complete transparency; europium oxide Eu2O3Dissolving in dilute nitric acid, adding 0.0384 g of citric acid, and stirring until the solution is completely transparent; mixing aluminum chloride AlCl3Dissolving in deionized water, adding 0.9607 g of citric acid, and adding sodium dihydrogen phosphate NaH2PO4·2H2O was dissolved in deionized water, 2.8821 grams of citric acid was added, and stirred until completely clear to form a clear sol.
Mixing the above solutions, stirring at 65 deg.C for 4 hr, standing for a certain period of time, and standingSlowly drying in a drying oven to obtain a fluffy precursor; putting the obtained precursor into a corundum crucible and calcining in a muffle furnace in reducing atmosphere at the temperature of 450 ℃ for 4 hours; naturally cooling the obtained pre-calcined product, placing the pre-calcined product in a mortar for grinding and uniformly mixing, and then calcining the pre-calcined product in a muffle furnace in reducing atmosphere at the calcining temperature of 800 ℃ for 9 hours to obtain europium ion Eu2+Activated nano phosphoaluminate blue luminescent phosphor.
The main structural properties, excitation spectrum, luminescence spectrum and light attenuation curves are similar to example 4.
Example 6:
according to the formula Cs1.84Eu0.16AlP3O10Respectively weighing cesium nitrate CsNO according to the stoichiometric ratio of each element3: 1.1954 g, europium nitrate Eu (NO)3)3·6H2O: 0.2379 g, aluminum nitrate Al (NO)3)3·9H2O: 1.2504 g of ammonium dihydrogen phosphate NH4H2PO4: 1.1503 g, adding cesium nitrate CsNO3Dissolving in deionized water, adding 1.7677 g of citric acid, and stirring until the solution is completely transparent; europium nitrate Eu (NO)3)3·6H2Dissolving O in deionized water, adding 0.1537 g of citric acid, and stirring until the solution is completely transparent; adding aluminum nitrate Al (NO)3)3·9H2O in DI water, 0.9607 g of citric acid was added and ammonium dihydrogen phosphate NH was added4H2PO4Dissolved in deionized water, 2.8821 grams of citric acid was added and stirred until completely clear to form a clear sol.
Mixing the solutions, stirring for 3 hours at the temperature of 75 ℃, standing for a period of time, and then slowly drying in an oven to obtain a fluffy precursor; putting the obtained precursor into a corundum crucible and calcining in a muffle furnace in reducing atmosphere at the temperature of 300 ℃ for 5 hours; the obtained pre-calcined product is naturally cooled, then is put into a mortar for grinding and is uniformly mixed, and then is calcined in a muffle furnace with reducing atmosphere, and the calcination temperature is highThe temperature is 600 ℃, the calcination time is 5 hours, and the europium ion Eu is obtained2+Activated nano phosphoaluminate blue luminescent phosphor.
The main structural properties, excitation spectrum, luminescence spectrum and light attenuation curves are similar to example 4.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Any simple modifications, equivalent variations and modifications of the above examples, which are in accordance with the principles of the present technology and methods, remain within the scope of the technical and method solutions of the present invention.
Claims (10)
1. Eu (Eu)2+Activated phosphor of phosphoaluminate blue luminescence characterized in that: the chemical general formula of the phosphor is as follows: cs2-2xEu2xAlP3O10Wherein x is divalent europium ion Eu2+Substituted Cs+The molar ratio of the ions is within the range of 0.01<x<0.08, under the excitation of ultraviolet light, the fluorescent powder emits blue light with the dominant wavelength of 450 nm; the phosphor is prepared and synthesized by a sol-gel method.
2. Eu according to claim 12+The preparation method of the activated phosphor is characterized in that the phosphor is synthesized by a sol-gel method, and comprises the following steps:
(1) cesium ion compound, europium ion compound, aluminum ion compound, phosphorus ion compound are expressed by the general formula Cs2- 2xEu2xAlP3Weighing the O10 according to the stoichiometric ratio of cesium ions, europium ions, aluminum ions and phosphorus ions; dissolving the weighed raw materials in deionized water or dilute nitric acid respectively, diluting with deionized water, and adding a complexing agent into each solution respectively;
(2) slowly mixing the raw material solutions added with the complexing agent obtained in the step 1 together, heating and stirring, standing, and drying to obtain a fluffy precursor;
(3) putting the precursor obtained in the step 2 in a reducing atmosphere for protectionCalcining in a muffle furnace to obtain Eu2+Activated phosphor of phosphoaluminate blue luminescence.
3. The method of claim 2, wherein: the cesium ion compound in the step 1 is CsNO3Or CsCl.
4. The method of claim 2, wherein: the europium ion compound in the step 1 is Eu2O3Or Eu (NO)3)3·6H2O。
5. The method of claim 2, wherein: the aluminum ion compound in the step 1 is Al (NO)3)3·9H2O or AlCl3。
6. The method of claim 2, wherein: the phosphorus ion compound in the step 1 is NaH2PO4·2H2O or NH4H2PO4。
7. The method of claim 2, wherein: the complexing agent in the step 1 is citric acid or oxalic acid, and the adding amount of the complexing agent is 1.5-2 times of the molar amount of cesium ions, europium ions, aluminum ions or phosphorus ions in the raw material solution.
8. The method of claim 2, wherein: the heating temperature of the step 2 is 50-100 ℃, and the stirring time is 1-2 hours.
9. The method of claim 2, wherein: the calcination in the step 3 is divided into two times, the temperature of the first calcination is 200-500 ℃, and the temperature is kept for 1-8 hours; the temperature of the second calcination is 500-850 ℃, and the temperature is kept for 1-10 hours.
10. The method of claim 2, wherein: the reducing atmosphere in the step 3 is one of the following two atmospheres:
(1) a mixed gas atmosphere of 5% by volume of hydrogen and 95% by volume of nitrogen;
(2) the gaseous atmosphere resulting from the combustion of carbon granules or various activated carbons in air.
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| CN102277167A (en) * | 2011-08-26 | 2011-12-14 | 昆明理工大学 | Europium ion-doped aluminum magnesium phosphate fluorescent powder and preparation method thereof |
| CN102286283A (en) * | 2011-08-26 | 2011-12-21 | 昆明理工大学 | Aluminium magnesium phosphate blue fluorescent powder doped with europium ions and preparation method thereof |
| CN105199725A (en) * | 2015-09-17 | 2015-12-30 | 盐城工学院 | Alkali-metal-ion-reinforced red light type fluorescent powder formed by adulterating titanate in rare earth and preparation method |
| CN105331363A (en) * | 2015-12-01 | 2016-02-17 | 昆明学院 | Phosphorus aluminate fluorescent powder and preparation method thereof |
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| CN102277167A (en) * | 2011-08-26 | 2011-12-14 | 昆明理工大学 | Europium ion-doped aluminum magnesium phosphate fluorescent powder and preparation method thereof |
| CN102286283A (en) * | 2011-08-26 | 2011-12-21 | 昆明理工大学 | Aluminium magnesium phosphate blue fluorescent powder doped with europium ions and preparation method thereof |
| CN105199725A (en) * | 2015-09-17 | 2015-12-30 | 盐城工学院 | Alkali-metal-ion-reinforced red light type fluorescent powder formed by adulterating titanate in rare earth and preparation method |
| CN105331363A (en) * | 2015-12-01 | 2016-02-17 | 昆明学院 | Phosphorus aluminate fluorescent powder and preparation method thereof |
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