CN117866624A - High-brightness rare earth ion europium-activated aluminate fluorescent powder and preparation method and application thereof - Google Patents
High-brightness rare earth ion europium-activated aluminate fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000004645 aluminates Chemical class 0.000 title claims abstract description 33
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 29
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 60
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 59
- 230000009467 reduction Effects 0.000 claims abstract description 40
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229910003668 SrAl Inorganic materials 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 10
- 229910000018 strontium carbonate Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000002284 excitation--emission spectrum Methods 0.000 description 5
- -1 rare earth ion Chemical class 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- 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 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000011240 wet gel Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910017639 MgSi Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000002223 garnet Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/77922—Silicates
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- 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
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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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- Manufacturing & Machinery (AREA)
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- Luminescent Compositions (AREA)
Abstract
The invention discloses high-brightness rare earth ion europium-activated aluminate fluorescent powder, a preparation method and application thereof, and particularly relates to a silicon carbide reduction method-assisted solid phase reaction method. The aluminate fluorescent powder prepared by the method has high quantum efficiency (102.72%) and high luminous intensity, the luminous intensity is 2.30 times of that of a product prepared by a traditional method (a hydrogen reduction method assisted solid phase reaction method), 2.34 times of that of commercial green powder LuAG-520 and the SrAl of commercial long afterglow fluorescent powder 2 O 4 :Eu 2+ /Dy 3+ 3.40 times of (3). The silicon carbide reduction method assisted solid phase reaction method has the advantages of simple process, low equipment requirement, low cost, safety, environmental protection and the like, and the prepared aluminate fluorescent powder has excellent luminous performance and has a large commercial application prospect in the fields of ultraviolet-based white light LED illumination and the like.
Description
Technical Field
The invention relates to a preparation method of luminescent materials, in particular to high-brightness rare earth ion europium-activated aluminate fluorescent powder and a preparation method and application thereof, and belongs to the technical field of inorganic luminescent material preparation.
Background
Because of the great application potential in the aspects of solid-state lighting, display technology, high-energy radiation scintillator, intelligent sensing, biological imaging and the like, people have been on various types in recent decadesThe optical properties of rare earth ion doped inorganic materials have been widely studied. Eu in various rare earth ions 2+ And Ce (Ce) 3+ The activated luminescent material has the excellent properties of wide excitation range, strong luminescent brightness, high quantum efficiency, adjustable light color and the like, and is widely applied to the fields of white light LED illumination, long afterglow, backlight source, scintillator, stress luminescence and the like.
For example: (1) Eu (Eu) 2+ Activated commercial phosphor. White LED lighting (Sr, ba) 2 SiO 4 :Eu 2+ Green powder: U.S. Pat. No. 2B 6809347 (Light source comprising a light-patterning element), baMgAl 10 O 17 :Eu 2+ (BAM) blue powder: the information display society (Journal of the Society for Information Display), 1996, volume 4, page 27, caAlSiN 3 :Eu 2+ Red powder: JP2005239985 (Phosphor, light source and led) and the like; beta-SiAlON to Eu for backlight source 2+ Green powder: US6632379 (Oxynitride phosphor activated by a rare earth element, and sialon type phosphor) and the like; srAl for long afterglow 2 O 4 :Eu 2+ ,Dy 3+ Green powder: european patent EP0622440B2 (Phosphorescent phosphor), sr 2 MgSi 2 O 7 :Eu 2+ ，Dy 3+ Blue powder: journal of Material science communication (Journal of Materials Science Letters), 2001, volume 20, 16, pages 1505-1506, and the like. (2) Ce (Ce) 3+ Activated commercial phosphor. For WLED Y 3 Al 5 O 12 :Ce 3+ (YAG) yellow powder, lu 3 Al 5 O 12 :Ce 3+ (LuAG) green powder: U.S. patent No. US5998925A (Light emitting device having a nitride compound semiconductor and a phosphor containing a garnet fluorescent material), etc.; crystal for scintillator (Lu, Y) 2 SiO 5 :Ce 3+ (LYSO:Ce 3+ ): journal of application physics (Journal of Applied Physics), volume 2000, volume 88, phase 12, pages 7360-7362, and the like. Generally, eu is present in the matrix 3+ And Eu 2+ Ce also has Ce in two stable valence states 3+ And Ce (Ce) 4+ Two valence states to prepare reduced Eu 2+ And Ce (Ce) 3+ Activated luminescent materials require efficient and economical reduction methods, which are critical to improving the quality and performance of the phosphor.
Currently, in the field of fluorescent powder preparation, carbothermic reduction, H, is mostly adopted 2 、NH 3 Atmosphere reduction and SiC reduction methods. Wherein, carbon powder remained in the fluorescent powder by the carbothermic reduction method can greatly weaken the luminous intensity of the fluorescent powder, H 2 The reduction method has high transportation cost and large danger coefficient in the preparation process, and the glove box and the high-temperature furnace are linked, so that the application of the reduction method in industrial production is greatly limited, and NH (NH) 3 The reduction method has the problems of low reduction rate, large pollution, high risk coefficient and the like, is difficult to be widely applied, and is mainly rare earth ion Eu disclosed in the publication No. CN105441078A 2+ Doped Y 5 Si 3 O 12 N fluorescent powder and preparation method thereof, and directly uses Y (NO) 3 ) 3 、TEOS、Eu(NO 3 ) 3 The Si element is contained in the fluorescent powder matrix synthesized by the method, so that the sample can be directly judged to be impure, the subsequent performance of measuring luminescence and the like is meaningless, and in addition, if the sample is subjected to post-treatment, the preparation process flow is complicated, and the cost is increased.
Therefore, aiming at the problems, the invention provides the high-brightness rare earth ion europium-activated aluminate fluorescent powder prepared by a silicon carbide reduction method assisted solid phase reaction method.
The invention comprises the following steps:
the technical problems to be solved by the invention are as follows: the high-brightness rare earth ion europium activated aluminate fluorescent powder and the preparation method and application thereof are provided, and the specific preparation method is a silicon carbide reduction method assisted solid phase reaction method.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
a high-brightness rare earth ion europium activated aluminate fluorescent powder, the chemical general formula of which is M 1-x- y Al 2 O 4 :xEu 2+ yN, wherein: x is more than or equal to 0.001 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.2, and x, y and z are all mole numbers; m is at least one of Ca, mg, sr and Ba; n is one or two of rare earth or transition metal Dy, nd, er, sm, tm, yb, ce and Cr in an ionic state.
Further, x is more than or equal to 0.005 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.03; m is at least one of Sr and Ba, and N is one or two of Dy, cr and Nd.
Further, x is more than or equal to 0.03 and less than or equal to 0.05.
The preparation method of the high-brightness rare earth ion europium-activated aluminate fluorescent powder comprises the following steps:
s1, the fluorescent powder M 1-x-y Al 2 O 4 :xEu 2+ In yN, M adopts oxide or carbonate thereof as a raw material, al adopts oxide thereof as a raw material, eu adopts oxide thereof as a raw material, N adopts oxide, nitrate and carbonate thereof as a raw material, each element is weighed according to the stoichiometric ratio thereof, a proper amount of fluxing agent is added, and a mixture is obtained after stirring and drying;
s2, placing the mixture into a crucible, sleeving the crucible with the silicon carbide reducing agent, calcining at high temperature, and cooling to obtain the high-brightness rare earth ion europium-activated aluminate fluorescent powder.
In the present invention, the step of S2 is adopted, compared with the SiC, Y (NO) 3 ) 3 、TEOS、Eu(NO 3 ) 3 The method for directly mixing to prepare the fluorescent powder simplifies the process flow, reduces the cost, and does not contain Si element, so that the phase purity is improved, and the performance such as luminescence can be measured.
Preferably, in S1, the fluxing agent is one of boron oxide, boric acid, borate or fluoride, and the fluxing agent accounts for 0-10wt% of the mixture.
Preferably, in S2, the calcination temperature is 1000-1500 ℃, the protective atmosphere is nitrogen or inert gas, the calcination time is 4-8 hours, the silicon carbide reducing agent is essentially a reducing agent, and in order to ensure the sufficient reduction of europium, the dosage is not required to be strictly controlled in the preparation process, if excessive, the unreacted silicon carbide reducing agent can be reused.
Further, the silicon carbide reducing agent is higher than 15-99% of the mass of the mixture.
The detailed steps in S2 are as follows: transferring the mixture into a crucible, spreading a silicon carbide reducing agent in the crucible with larger size (the size of the crucible can be designed according to the requirement), sleeving the crucible with the mixture into the large crucible with the silicon carbide reducing agent, placing the crucible into a high-temperature furnace, calcining for 4-8 hours at 1000-1500 ℃ in inert gas atmosphere, and cooling along with the furnace to obtain a target product: high brightness europium activated aluminate fluorescent powder. The specific amount of silicon carbide reducing agent depends on the europium content in the mixture and the form of the designed crucible set, and excessive silicon carbide reducing agent is generally adopted, and the amount of the silicon carbide reducing agent is higher than 15% of the mass of the mixture after exploration.
The main component of the silicon carbide reducing agent is SiC/SiO 2 The compound is a solid phase reducer, siC and SiO in the high temperature calcination (more than 1200℃) process 2 A chemical reaction occurs to produce a strongly reducing gas.
SiC(s)+2SiO 2 (s)→3SiO(g)+CO(g)(>1200℃)
The generated SiO and CO gases have strong reducibility, and can replace the continuously introduced reducing gas flow (N) in the traditional preparation method 2 /H 2 ,NH 3 ) The trivalent europium in the raw material europium oxide is effectively reduced into divalent europium, the luminescence of the prepared product high-brightness aluminate fluorescent powder shows a wide band-shaped excitation-emission spectrum, and no characteristic line spectrum of the trivalent europium proves that the Eu 3+ →Eu 2+ Is fully reduced.
Preferably, in S2, the preparation method of the silicon carbide reducing agent includes the following steps:
a. mixing silicon carbide, tetraethyl orthosilicate, ethanol and distilled water according to a molar ratio, adding concentrated nitric acid, stirring, and heating to obtain an elastic gray wet gel reducing agent precursor mixture;
b. and drying, calcining, cooling and grinding the reducing agent precursor mixture to obtain the silicon carbide reducing agent.
Preferably, the reaction conditions in a are: the molar ratio of the silicon carbide to the tetraethyl orthosilicate to the concentrated nitric acid is 1:2-8:0.1-0.5, and the concentration of the concentrated nitric acid is 65% -98%; the mixed solution is continuously stirred for 1 to 3 hours at the temperature of 80 to 180 ℃.
Further, the molar ratio of the concentrated nitric acid to the tetraethyl orthosilicate is 0.05-0.2: 1.
the reaction process of a is as follows:
under the condition of heating and stirring, tetraethyl orthosilicate can generate hydrolysis and polycondensation reaction in an acid solution to generate a (-O-Si-O-) three-dimensional network structure to form an elastic quasi-wet gel product, and the structure can fix SiC powder in the network structure without sedimentation, so that a uniform liquid-solid homogeneous mixture is formed, namely the elastic gray quasi-wet gel reducing agent precursor mixture.
Preferably, the reaction conditions in b are: the wet gel-like reducing agent precursor mixture is dried for 6 to 30 hours at the temperature of 80 to 180 ℃; the calcination temperature is 400-900 ℃ and the calcination time is 4-8 h.
Through the drying process in b, water and ethanol in the wet gel-like reducing agent precursor mixture can be removed to obtain a blocky xerogel-like product. The silicon polycondensate in the reducing agent precursor mixture may then be oxidized to SiO by high temperature oxidation in a muffle furnace 2 Obtaining SiC/SiO 2 A complex. Because the reducer precursor mixture is prepared by adopting a wet chemical method, siC/SiO is prepared by the structural design of a three-dimensional grid 2 The composite differs from conventional mechanical mixing, siC and SiO 2 Can achieve homogeneous mixing at atomic level and has extremely high reactivity.
The SiC/SiO 2 The compound is the solid phase reducer prepared by the silicon carbide reduction method.
The fluorescent powder is applied to preparing the ultraviolet-based white light LED illumination material.
In a preferred embodiment of the present invention, the green phosphor has a luminous intensity of a conventional method (Ar/H 2 Reduction method assisted solid phase reaction method) 2.30 times, 2.34 times, and commercial long afterglow phosphor SrAl of commercial green powder LuAG-520 (Intermix) 2 O 4 :Eu 2+ /Dy 3+ 3.40 times of the total light-emitting material, has excellent performances of strong light-emitting brightness, high quantum efficiency (up to 102.72 percent) and the like;
subjecting the Sr to 0.95 Al 2 O 4 :0.05Eu 2+ The high-brightness green fluorescent powder is combined with a three-primary-color ultraviolet LED white light source designed by a near ultraviolet LED chip for display, and the white light source has high color rendering index and proper color temperature. Therefore, the prepared fluorescent powder is expected to be applied to ultraviolet-based white light LED illumination.
The beneficial effects of the invention are as follows: the silicon carbide reduction method is adopted to assist the solid phase reaction method, and the prepared aluminate fluorescent powder has excellent luminous performances of strong luminous brightness, high quantum efficiency and the like. Compared with the conventional reduction method, the method can embody the following advantages:
(1) Full reduction, simple process, low cost, safety, energy conservation and environmental protection;
(2) Reducing gases CO and SiO are generated efficiently, continuously and quantitatively, the reduction is sufficient, and aluminate products have good crystallinity and no impurities;
(3) The aluminate product produced has a luminous intensity and high quantum efficiency superior to commercial powders. Therefore, the preparation method has wide commercial application prospect.
Drawings
FIG. 1 is Sr prepared in example 8 0.95 Al 2 O 4 :0.05Eu 2+ XRD spectra of fluorescent powder at different calcining temperatures;
FIG. 2 shows excitation spectra and emission spectra of the phosphors prepared in examples 1 to 7 at room temperature;
FIG. 3 is Sr prepared in example 8 0.95 Al 2 O 4 :0.05Eu 2+ SEM image of phosphor;
FIG. 4 (a) is a chart of Sr produced by the silicon carbide reduction method in example 8 0.95 Al 2 O 4 :0.05Eu 2+ Phosphor and comparative example 1 in Ar/H 2 (5%) phosphor prepared under atmosphere, luAG-520 (commercial powder))、SrAl 2 O 4 :Eu 2+ Comparison of excitation spectrum and emission spectrum of (domestic commercial powder). FIG. 4 (b) is a graph showing the comparison of the emission spectrum integrals of the above-mentioned phosphors.
FIG. 5 (a) shows Sr produced in example 8 0.95 Al 2 O 4 :0.05Eu 2+ After the fluorescent powder is combined with commercial blue powder and commercial red powder, the fluorescent powder is matched with the electroluminescent spectrum of a white light LED light source designed by a 365nm ultraviolet light LED chip. The illustrations are pictures of the white LED device in daylight and on-state, respectively. Fig. 5 (b) is a CIE color coordinate diagram of the three primary phosphors and the white LED device when illuminated. Fig. 5 (c) and 5 (d) are changes in spectrum, color temperature and color rendering index, respectively, when the white LED device is lit at different currents;
FIG. 6 is a chart of Sr produced by the silicon carbide reduction method of example 10 0.93 Al 2 O 4 :0.05Eu 2+ ,0.02Dy 3+ Phosphor and SrAl 2 O 4 :Eu 2+ ,Dy 3+ Comparison of excitation spectrum and emission spectrum of (domestic commercial powder).
Detailed Description
The invention will be further described with reference to specific drawings and examples in order to provide a better understanding of the technical means, the creation characteristics, the achievement of the objects and the effects of the invention.
The invention adopts a silicon carbide reduction method to assist a solid phase reaction method to prepare the fluorescent powder. The silicon carbide reduction method provides a high-efficiency solid-phase reducing agent, and the aluminate fluorescent powder is prepared by adopting a solid-phase reaction method. The reducing agent provided by the silicon carbide reduction method can realize the full reduction of trivalent europium to divalent europium and promote the crystallization of aluminate into phase.
The silicon carbide reduction method provided by the invention is characterized in that: siC/SiO 2 Calcining the composite at high temperature>SiO and CO gases are generated at 1000 ℃, and the in-situ generated reducing gas has extremely high reducing capability, and can not only effectively reduce Eu in oxidation valence state 3+ And the quality and the performance of the fluorescent powder are greatly improved.
In various fluorescent powder systems, the europium-activated aluminate luminescent material has the advantages of strong ultraviolet absorption, high brightness, long afterglow, high thermal stability, chemical durability, energy conservation, environmental protection and the like, so that the europium-activated aluminate luminescent material is widely researched and applied to various fields. For example: (1) lighting display applications. AC/DC-LED, plant growth light supplement, road traffic safety signs with warning characteristics, novel intelligent fabrics, etc.; (2) sensor-based monitoring applications. Intelligent anti-counterfeiting system, stress distribution sensing, intelligent skin touch sensing, radiation dose sensing, mechanical crack damage health detection and the like; (3) biomedical applications. Biosensing and imaging, biological tracking, targeted photodynamic therapy, drug sustained release, and the like; (4) environmental remediation based application. The method has the advantages of all-weather photocatalysis composite material system, pollutant tracking and monitoring and the like.
The invention prepares the high-brightness rare earth ion europium activated aluminate fluorescent powder by a silicon carbide reduction method assisted solid phase reaction method. The solid reducing agent is prepared by a silicon carbide reduction method, and N is not required to be introduced in the conventional preparation method 2 /H 2 The reducing gas flow can meet the preparation requirement only by taking inert gas flow (nitrogen or argon) as protective atmosphere. The method has the advantages of full reduction, simple process, low equipment dependence, low cost, safety and environmental protection, and the prepared fluorescent powder has the luminous intensity which is about 2.34 times that of commercial green powder LuAG-520 (Intermix) and has the excellent performances of strong luminous brightness, high quantum efficiency (up to 102.72 percent) and the like. Finally, the prepared aluminate green fluorescent powder, commercial blue powder and commercial red powder are mixed and packaged, and a 365nm ultraviolet LED chip is matched to design a white light LED light source, so that the result shows that the white light source has the advantages of high color rendering index, proper color temperature and the like. The results show that the preparation method has wide commercial application prospect, and the prepared fluorescent powder is used as a good candidate of the fluorescent powder for the ultraviolet-based white light LED.
Example 1
Preparation of silicon carbide reducing agent: 4.0110g (0.1000 mol) of silicon carbide, 62.4990g (0.3000 mol) of tetraethyl orthosilicate, 31.2495g (0.6783 mol) of ethanol and 10.8241g (0.6013 mol) of distilled water are respectively added into a beaker, after stirring uniformly, 3mL of 65% concentrated nitric acid is added, stirring is continued at 80 ℃ for about 2 hours until a gray wet gel-like reducing agent precursor mixture with elasticity is formed; and (3) drying the obtained wet gel-like reducing agent precursor mixture at 80 ℃ for 24 hours, transferring the product into an alumina crucible, placing the alumina crucible in a muffle furnace, calcining for 5 hours at 600 ℃ in an air atmosphere, cooling and grinding to obtain the silicon carbide reducing agent for later use.
Preparing aluminate fluorescent powder: the chemical formula of the fluorescent powder is Sr 0.999 Al 2 O 4 :0.001Eu 2+ 2.0392g (0.0200 mol) of alumina (Al 2 O 3 ) 2.9496g (0.01998 mol) strontium carbonate (SrCO) 3 ) 0.0035g (0.00001 mol) of europium oxide (Eu) 2 O 3 ) And (3) uniformly stirring and mixing the raw materials, putting the raw materials into an alumina crucible, putting the crucible into a porcelain boat paved with 5.8g of the silicon carbide reducing agent, putting the porcelain boat into a high-temperature furnace, calcining the porcelain boat at 1300 ℃ for 4 hours under the protection of nitrogen, cooling the porcelain boat along with the furnace, taking out the product, and grinding for 5 minutes to obtain the high-brightness rare earth ion europium-activated aluminate fluorescent powder.
Examples 2-7 were essentially identical to example 1, except that different europium doping concentrations were used, each of the formulas: sr (Sr) 0.995 Al 2 O 4 :0.005Eu 2+ (example 2), sr 0.99 Al 2 O 4 :0.01Eu 2+ (example 3), sr 0.97 Al 2 O 4 :0.03Eu 2+ (example 4), sr 0.95 Al 2 O 4 :0.05Eu 2+ (example 5), sr 0.93 Al 2 O 4 :0.07Eu 2+ (example 6), sr 0.9 Al 2 O 4 :0.1Eu 2+ (example 7), the specific amounts are shown in Table 1.
TABLE 1 raw material ratios and conditions for examples 2-7
Example 8
The preparation method of the silicon carbide reducing agent is the same as in examples 1 to 7.
The phosphor preparation method in this example is substantially the same as that in example 5, except that the phosphor has a chemical formula of Sr 0.95 Al 2 O 4 :0.05Eu 2+ . (1) Based on the starting materials in example 5, 3% by weight of H are also added 3 BO 3 The fluxing agent (0.1506 g), (2) the silicon carbide reducing agent (6 g) is paved in the porcelain boat, and (3) 1200 ℃, 4h and 1400 ℃ and 4h are added on the basis of 1300 ℃ and 4h in the example 5, and the specific see the table II.
Example 9
The preparation method of the silicon carbide reducing agent is the same as in examples 1 to 7.
The phosphor preparation method in this example is basically the same as that in example 8, except that the phosphor has a chemical formula of Ba 0.95 Al 2 O 4 :0.05Eu 2+ . (1) 3.7500g (0.0190 mol) of barium carbonate (BaCO 3 ) Instead of 2.8050g (0.0190 mol) of strontium carbonate (SrCO) 3 ) (2) 7g of the silicon carbide reducing agent is paved in a porcelain boat; (3) the calcination temperature was 1400℃and the details are shown in Table II.
Example 10
The preparation method of the silicon carbide reducing agent is the same as in examples 1 to 7.
The phosphor preparation method in this example is substantially the same as that in example 8, except that (1) the phosphor has a chemical formula of Sr 0.93 Al 2 O 4 :0.05Eu 2+ ,0.02Dy 3+ 。(2)2.7460g(0.0186mol)SrCO 3 Instead of 2.8050g (0.0190 mol) SrCO 3 0.0746g (0.0002 mol) Dy was added 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the (3) 6.5g of the silicon carbide reducing agent is paved in the porcelain boat; (4) the calcination temperature was 1500 ℃, see in particular Table II.
Example 11
The preparation method of the silicon carbide reducing agent is the same as in examples 1 to 7.
The phosphor preparation method in this example is substantially the same as that in example 8,the difference is that (1) the chemical formula of the fluorescent powder is Sr 0.92 Al 2 O 4 :0.05Eu 2+ ,0.02Nd 3+ ,0.01Cr 3+ 。(2)2.7164g(0.0184mol)SrCO 3 Instead of 2.8050g (0.0190 mol) SrCO 3 0.1350g (0.0002 mol) of Nd are added 2 O 3 、0.0200g(0.0001mol)Cr 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the (3) 6.5g of the silicon carbide reducing agent is paved in the porcelain boat, and the concrete is shown in a second table.
Comparative example 1
Aluminate fluorescent powder is prepared by adopting a traditional hydrogen reduction method and a solid phase reaction method, namely 95 percent of argon (Ar) and 5 percent of hydrogen (H) are continuously introduced 2 ) The mixed gas stream acts as a reducing agent. The chemical formula of the fluorescent powder is Sr 0.95 Al 2 O 4 :0.05Eu 2+ . 2.0392g (0.0200 mol) of alumina (Al 2 O 3 ) 2.8050g (0.0190 mol) strontium carbonate (SrCO) 3 ) 0.1760g (0.0005 mol) europium oxide (Eu) 2 O 3 ). Stirring and mixing the above materials, loading into an alumina crucible, and placing the crucible into a high temperature furnace, ar/H 2 (95%/5%) under a mixed gas flow, calcination was carried out for 4 hours at 1300 ℃. Cooling with furnace, grinding for 5 min to obtain Sr 0.95 Al 2 O 4 :0.05Eu 2+ The luminous powder is shown in the table II.
Table II raw material ratios and conditions in examples 8 to 11 and comparative example 1
As shown in FIG. 1, the pure phase and highly crystalline aluminate product was obtained by the silicon carbide reduction method assisted solid phase reaction method under the calcination conditions of 1200 ℃, 1400 ℃,1300 ℃ in example 8.
As shown in FIG. 2, in examples 1 to 7, fluorescence was generated when the doping concentration of europium was 5mol% (example 5)The luminous intensity of the powder is the greatest. The excitation-emission spectra of the prepared products are all broadband emission and come from Eu 2+ Typical 4f 6 5d 1 →4f 7 Transition, indicates the full reduction of trivalent europium-divalent europium. Samples with europium doping concentrations of 5mol% will follow, i.e.: sr (Sr) 0.95 Al 2 O 4 :0.05Eu 2+ (example 5) light emitting performance comparison with commercial materials.
As shown in FIG. 3, the aluminate fluorescent powder product prepared is of a random polyhedral structure.
As shown in fig. 4 (a) and (b), the phosphor (example 5) prepared by the silicon carbide reduction method has extremely high luminous intensity, and is specifically expressed as: the fluorescent powder prepared by the silicon carbide reduction method is Ar/H 2 2.30 times of the fluorescent powder prepared by the reduction method is 2.34 times of the commercial powder LuAG-520 and is the commercial powder SrAl 2 O 4 :Eu 2+ /Dy 3+ 3.40 times of (3). Meanwhile, the fluorescent powder has excellent quantum efficiency (up to 102.72%). The result shows that the high-brightness rare earth ion europium-activated aluminate fluorescent powder prepared by the silicon carbide reduction method has excellent luminous performance.
As shown in fig. 5 (b), based on the aluminate green powder prepared (example 5), the blue powder was prepared by a trichromatic design (commercial blue powder BaMgAl 10 O 17 Eu and commercial red CaAlSiN 3 Eu) and an ultraviolet LED chip, the white light source (0.3310, 0.3542) shown in the figure 5 (a) has the advantages of high color rendering property (95.9), proper color temperature (5615K), balanced and increased electroluminescent spectrum intensity along with the current increase shown in the figure 5 (c), stability along with the current change of the color temperature and the color rendering index shown in the figure 5 (d), and the like, and the screened aluminate product is expected to become high-quality green fluorescent powder for ultraviolet LED illumination.
As shown in FIG. 6, sr produced by silicon carbide reduction 0.93 Al 2 O 4 :0.05Eu 2+ The 0.02Dy phosphor (example 10) has a luminous intensity of the commercial powder SrAl 2 O 4 :Eu 2+ /Dy 3+ Is 2.02 times as large as the above.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be appreciated by persons skilled in the art that the present invention is not limited to the embodiments described above, but is capable of numerous variations and modifications without departing from the spirit and scope of the invention as hereinafter claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A preparation method of high-brightness rare earth ion europium-activated aluminate fluorescent powder, wherein the chemical general formula of the fluorescent powder is M 1-x-y Al 2 O 4 :xEu 2+ yN, wherein: x is more than or equal to 0.001 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.2, and x, y and z are all mole numbers; m is at least one of Ca, mg, sr and Ba; n is one or two of rare earth or transition metal Dy, nd, er, sm, tm, yb, ce and Cr, and is characterized in that the preparation method is a silicon carbide reduction method assisted solid phase reaction method, and comprises the following steps:
s1, the fluorescent powder M 1-x-y Al 2 O 4 :xEu 2+ In yN, M adopts oxide or carbonate thereof as a raw material, al adopts oxide thereof as a raw material, eu adopts oxide thereof as a raw material, N adopts oxide, nitrate and carbonate thereof as a raw material, each element is weighed according to the stoichiometric ratio thereof, fluxing agent is added, and the mixture is obtained after stirring and drying;
s2, placing the mixture into a crucible, sleeving the crucible with the silicon carbide reducing agent, calcining at high temperature, and cooling to obtain the high-brightness rare earth ion europium-activated aluminate fluorescent powder.
2. The method of manufacturing according to claim 1, characterized in that: in S1, the fluxing agent is one of boron oxide, boric acid, borate or fluoride, and the fluxing agent accounts for 0-10wt% of the mixture.
3. The method of manufacturing according to claim 1, characterized in that: in S2, the calcination temperature is 1000-1500 ℃, the protective atmosphere is nitrogen or inert gas, the calcination time is 4-8 h, and the silicon carbide reducing agent is higher than 15-99% of the mass of the mixture.
4. The method of manufacturing according to claim 1, characterized in that: in S2, the preparation method of the silicon carbide reducing agent includes the following steps:
a. mixing silicon carbide, tetraethyl orthosilicate, ethanol and distilled water according to a molar ratio, adding concentrated nitric acid, stirring and heating to obtain a reducer precursor mixture;
b. and drying, calcining, cooling and grinding the reducing agent precursor mixture to obtain the silicon carbide reducing agent.
5. The process of claim 4, wherein the reaction conditions in a are: the molar ratio of the silicon carbide to the tetraethyl orthosilicate to the concentrated nitric acid is 1:2-8:0.1-0.5, and the concentration of the concentrated nitric acid is 65% -98%; the mixed solution is continuously stirred for 1 to 3 hours at the temperature of 80 to 180 ℃.
6. The process of claim 4, wherein the reaction conditions in b are: the reducing agent precursor mixture is dried for 6 to 30 hours at the temperature of 80 to 180 ℃; the calcination temperature is 400-900 ℃ and the calcination time is 4-8 h.
7. A high brightness rare earth ion europium activated aluminate phosphor prepared by the preparation method of claims 1 to 6.
8. The use of the phosphor of claim 7 for the preparation of an ultraviolet-based white LED lighting material.
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