CN103396800A - Boron aluminate-based blue fluorescent powder, preparation method and application - Google Patents
Boron aluminate-based blue fluorescent powder, preparation method and application Download PDFInfo
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- CN103396800A CN103396800A CN2013103246719A CN201310324671A CN103396800A CN 103396800 A CN103396800 A CN 103396800A CN 2013103246719 A CN2013103246719 A CN 2013103246719A CN 201310324671 A CN201310324671 A CN 201310324671A CN 103396800 A CN103396800 A CN 103396800A
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- 239000000843 powder Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- -1 Boron aluminate Chemical class 0.000 title claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000005424 photoluminescence Methods 0.000 claims abstract 2
- 238000001354 calcination Methods 0.000 claims description 48
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 230000005284 excitation Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 238000003836 solid-state method Methods 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 238000009877 rendering Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000695 excitation spectrum Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910017414 LaAl Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001753 sapphirine Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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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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Abstract
The invention relates to boron aluminate-based blue fluorescent powder, a preparation method and an application, belonging to the technical field of inorganic luminous materials. The fluorescent powder is boron aluminate-based fluorescent powder activated by rare earth ions, the chemical formula is La1-xCexAl2B3O9, x represents the molar percent coefficient of Ce doped in a La position, x is not less than 0.005 and not more than 0.05, and the fluorescent powder is prepared by adopting a high-temperature solid phase method. The rare earth boron aluminate blue fluorescent powder provided by the invention can be effectively excited by ultraviolet light, the range of exciting light is 250-350nm, the emission wavelength is 350-500nm, the luminous intensity is high, the stability is good, and the rare earth boron aluminate blue fluorescent powder becomes an excellent blue component in high color rendering fluorescent powder and can be applied to lighting taking the ultraviolet light as an exciting source, and chromaticity regulation of display devices and photoluminescence. The sintering process of the fluorescent powder provided by the invention is simple, easy to operate and good in reproducibility, and the obtained product is stable in quality and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of phosphor, particularly a kind of by the fluorescent material of ultraviolet excitation, preparation method and application thereof, belong to rare earth luminescent material technical field.
Background technology
The successful research and development of high brightness GaN blue LED and the white light LEDs of realizing thus have been described as maximum light source revolution since the Edison invented incandescent light that continues.Because its photoelectric efficiency that has is high, the life-span is long, volume is little, power is low, the advantage such as solid-state energy-conservation and environmental protection, the white light LEDs product is just attracting increasing the concern.Energy-saving illumination is one of body matter of low-carbon economy.And rare-earth luminescent material is the critical material in electricity-saving lamp and white light LEDs light fixture, and it has great importance for performance index such as the luminous efficiency of improving such LED, work-ing life, colour temperature, colour rendering indexs.
At present, utilize the LED technology to realize that the method for white light mainly contains three kinds: the direct mixed-color method of three-primary color LED, ultraviolet transformation approach and blue chip add the method for yellow fluorescent powder.Wherein, the direct mixed-color method of three-primary color LED is that the three primary colours chip portfolio that directly will launch the red, green, blue wavelength is packaged together, and forms multi-chip type white light LEDs, by spacing color mixed principle, mate in accordance with the appropriate ratio, make the light of three kinds of colors be mixed into white light.But the weakness of this method is its mounting structure more complicated, and the driving voltage of LED of all kinds, luminous efficiency, light distribution characteristic difference need by the intensity of current setting red, green, blue three primary colours, and circuit is more complicated on realizing.The method that blue chip adds yellow fluorescent powder is that the blue light (approximately 450 nanometers) that the GaN base LED chip sends is carried out to excitation rare-earth fluorescent material YAG (Y
3Al
5O
12): Ce
3+Send gold-tinted, thereby form white light.But, because of shortcomings such as it lack the red light portion radiation, and product exists colour rendering index low, and color reducibility is poor, in widespread adoption and the popularization of high-end lighting field, be restricted.And the ultraviolet transformation approach becomes current main flow gradually, because it can be for fluorescent material provides higher excitation energy, by fluorescent material, realizes that wavelength Conversion sends visible light.The combination of ultraviolet LED and three primary colors fluorescent powder, its color developing is best, and the fluorescent material luminous efficiency is lower.Therefore development of new redness, green and blue colour fluorescent powder efficient, Heat stability is good is the key that improves the white light LEDs luminous mass.
At present, can be used for being excited the blue colour fluorescent powder of use also few by ultraviolet LED.Wherein the more blue colour fluorescent powder of use adopts divalent europium (Eu usually
2+) as luminescence center, mainly take high temperature solid-state method as main.Blue colour fluorescent powder BaMgAl as commercialization
10O
17: Eu
2+, because its luminous efficiency is low, blue light is easy to, by red and green emitting phosphor absorption etc., affect ultraviolet-near ultraviolet excitated three primary colors fluorescent powder luminescent properties, thereby the white light LEDs performance is reduced; Chinese invention patent CN101497791A discloses a kind of rare earth aluminate blue colour fluorescent powder and preparation method thereof and application, and its chemical formula is Mg
1-x-ySr
yAl
2O
4: Eu
x(in formula, x is the mole number of europium atom, y is the mole number of strontium atom, 0.005≤x≤0.10,0.01≤y≤0.14), it is 463 nanometers that fluorescence spectrum is tested its emission main peak, and the excitation center wavelength is 330 nanometers, sends blue light, but this process relates to the pre-treatment, batching, sintering, washing of raw material etc., and preparation is relatively complicated; Chinese invention patent CN1605612A discloses a kind of RE(rare earth) borate blue colour fluorescent powder and preparation method thereof, and its molecular formula is (EuO)
m(MO)
n(B
2O
3)
p(MX
2)
q(wherein M is a kind of of Mg, Ca, Sr and Ba or its mixing, and X is a kind of or its mixing of Cl and Br and I; M, n, q>=0), this fluorescent material can be by ultraviolet ray excited, the emmission spectrum main peak, between 430～460 nanometers, sends the blue light of higher-strength, but this fluorescent material component is more, can there be a certain amount of dephasign in final product, also relates to the operations such as spraying drying, is unfavorable for actual production; And for example Chinese invention patent CN1190115A discloses BaMgAl
14O
23: the preparation method of Eu blue colour fluorescent powder is that carbon dust is directly covered on starting material, and this preparation method, because carbon dust is directly with starting material, to contact, causes fluorescent material part Prevent Carbon Contamination, thereby causes the waste of starting material in preparation process.Therefore, this preparation method can not meet the needs of actual production well.The europium ion of divalence is not easy reduction fully, so this has also limited its luminescence center as blue colour fluorescent powder.
The substrate material that the aluminium borate system provides, be easy to realize the trivalent reduction of rare earth ion, and trivalent rare earth ions is the energy stable existence in this matrix, also have simultaneously raw material sources abundant, the advantages such as synthesis technique adaptability is extensive, searching, at the high sapphirine aluminium borate system fluorescent material that ultraviolet band is effectively excited, is expected to be used in the white light LEDs field.
Summary of the invention
The deficiency that exists in order to overcome prior art, the purpose of this invention is to provide a kind ofly have stable performance, luminous intensity is high, aluminium borate base blue colour fluorescent powder that manufacturing process is simple, pollution-free, cost is low and preparation method thereof, it can be excited by ultraviolet leds, is applied to the white light LEDs illuminating device.
For reaching above purpose, the technical solution used in the present invention is: a kind of aluminium borate base blue colour fluorescent powder is provided, and its chemical formula is La
1-x Ce
x Al
2B
3O
9, in formula, x represents the molecular fraction coefficient of La position Ce doping, 0.005≤x≤0.05; At wavelength, be that under the ultraviolet excitation of 250～350 nanometers, emission wavelength, between 350～500 nanometers, sends blue-fluorescence.
A kind of method for preparing aluminium borate base blue colour fluorescent powder as above, adopt high temperature solid-state method, comprises the following steps:
1, to contain aluminum ion Al
3+Compound, contain boron ion B
3+Compound, contain lanthanum ion La
3+Compound, contain cerium ion Ce
3+Compound be raw material, by molecular formula La
1-x Ce
x Al
2B
3O
9The stoichiometric ratio of middle corresponding element takes each raw material, and x represents the molecular fraction coefficient of La position Ce doping, 0.005≤x≤0.05; The raw material that takes is ground respectively, and remix is even, obtains mixture;
2, this mixture is calcined under air atmosphere, calcining temperature is 100～500 ℃, and calcination time is 1～12 hour;
3, the mixture naturally cooling after calcining, grind and mix, and under air atmosphere, calcines, and calcining temperature is 400～900 ℃, and calcination time is 1～10 hour;
4, the mixture naturally cooling after calcining, grind and mix, sintering in reducing atmosphere, and calcining temperature is 700～1100 ℃, calcination time is 3～12 hours, obtains a kind of aluminium borate base blue colour fluorescent powder.
When the present invention adopted high temperature solid-state method, the described calcining temperature of step 2 was 200～400 ℃, and calcination time is 3～10 hours; The described calcining temperature of step 3 is 600～800 ℃, and calcination time is 4～9 hours; The described calcining temperature of step 4 is 800～1000 ℃, and calcination time is 4～10 hours.
The aluminum ion Al that contains of the present invention
3+Compound comprise a kind of in aluminum oxide, aluminium hydroxide; Contain boron ion B
3+Compound comprise a kind of in boron trioxide, boric acid; Contain lanthanum ion La
3+Compound comprise a kind of in lanthanum trioxide, lanthanum nitrate; The described cerium ion Ce that contains
4+Compound be cerium oxide.Reducing atmosphere described in step 4 is the active carbon granule reducing atmosphere.
Aluminium borate base blue colour fluorescent powder prepared take UV-light as excitaton source by the present invention can coordinate appropriate redness, green emitting phosphor, applies and is packaged in outside the InGaN diode, prepares the white light LEDs illuminating device.
Compared with prior art, the advantage of technical solution of the present invention is:
1, the substrate material that provides of the aluminium borate base fluorescent powder for preparing of the present invention, be easy to realize rare earth ion Ce
4+Reduction, and trivalent rare earth ions can stablize and deposit in this matrix, sulfur-bearing not, environmental friendliness, have higher luminous efficiency.
2, fluorescent material provided by the invention, its excitation spectrum is wider, this fluorescent material excite scope in 250～350 nanometers, emission wavelength is between 350～500 nanometers, suitable ultraviolet LED excites, and can stick on the ultraviolet leds chip and obtain efficient blue-light-emitting.
3, aluminium borate base blue colour fluorescent powder, preparation method thereof provided by the invention is simple, easy handling, and preparation process is not added solubility promoter, is easy to suitability for industrialized production.With simple aluminates system fluorescent material relatively, synthesis temperature low (800～1000 ℃), thus obviously reduce energy consumption and product cost, the material preparation for the requirement of equipment well below similar fluorescent material.
4, synthesis material wide material sources used in the present invention, reactive behavior is high, and application prospect is extensive.The product easily collecting, discharge without waste water and gas simultaneously, and environmental friendliness especially is suitable for serialization production.
The accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction collection of illustrative plates of the material sample for preparing by the embodiment of the present invention 1 technical scheme;
Fig. 2 is the luminescent spectrum figure of material sample under the ultraviolet excitation of 310 nanometers for preparing by the embodiment of the present invention 1 technical scheme;
Fig. 3 is the exciting light spectrogram of the ultraviolet region that obtains under the light detection of 380 nanometers by material sample prepared by the embodiment of the present invention 1 technical scheme.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further described.
Embodiment 1:
Preparation La
0.995Ce
0.005Al
2B
3O
9
According to chemical formula La
0.995Ce
0.005Al
2B
3O
9In the stoichiometric ratio of each element take respectively aluminium oxide Al
2O
3: 1.020 grams, boric acid H
3BO
3: 1.855 grams, lanthanum trioxide La
2O
3: 1.621 grams, cerium oxide CeO
2: 0.009 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 200 ℃, calcination time 10 hours, then be cooled to room temperature, takes out sample; Fully mixed grinding is even again by the raw material of calcining for the first time, sintering again under air atmosphere, and 800 ℃ of temperature, calcination time 4 hours, then be chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on reducing atmosphere sintering (being embedded in activated carbon powder) in retort furnace, calcining temperature is 1000 ℃, and calcination time is 4 hours, namely obtains powder shaped aluminium borate base blue colour fluorescent powder.
Referring to accompanying drawing 1, it is the X-ray powder diffraction collection of illustrative plates of the material sample for preparing by the present embodiment technical scheme, and the XRD test result shows, prepared material is aluminium borate LaAl
2B
3O
9Monophase materials.
Referring to accompanying drawing 2, it is 0.5% concentration C e
3+Ion doping La
3+La prepared by position
0.995Ce
0.005Al
2B
3O
9In fluorescent material, with UV-light 310 nanometers, excite the luminescent spectrum that obtains, emission wavelength is between 300～500 nanometers, the main center emission wavelength of this material is about the blue-light-emitting wave band of 450 nanometers, by CIE, calculate simultaneously, the coordinate of learning it is x=0.152, y=0.071, also just in time drop on blue region, is applicable to the white light LEDs that UV-light is excitation light source.
Referring to accompanying drawing 3, from the spectrogram of the exciting light at ultraviolet region that the monitoring of the material sample to preparing by the technology of the present invention utilizing emitted light 380 nanometers obtain, finding out, excitation area is handed over wide, the blue-light-emitting of this material excite source mainly between 250～350 nanometers, can mate well the ultraviolet LED chip.
Embodiment 2:
Preparation La
0.99Ce
0.01Al
2B
3O
9
According to chemical formula La
0.99Ce
0.01Al
2B
3O
9In the stoichiometric ratio of each element take respectively aluminium hydroxide Al (OH)
3: 1.560 grams, boric acid H
3BO
3: 1.855 grams, lanthanum nitrate La (NO
3)
3: 3.217 grams, cerium oxide CeO
2: 0.018 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 400 ℃, calcination time 3 hours, then be cooled to room temperature, takes out sample; Fully mixed grinding is even again by the raw material of calcining for the first time, sintering again under air atmosphere, and 600 ℃ of temperature, calcination time 9 hours, then be chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on reducing atmosphere sintering (being embedded in activated carbon powder) in retort furnace, calcining temperature is 800 ℃, and calcination time is 10 hours, namely obtains powder shaped aluminium borate base blue colour fluorescent powder.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 1.
Embodiment 3:
Preparation La
0.97Ce
0.03Al
2B
3O
9
According to chemical formula La
0.97Ce
0.03Al
2B
3O
9In the stoichiometric ratio of each element take respectively aluminium oxide Al
2O
3: 1.020 grams, boron oxide B
2O
3: 1.045 grams, lanthanum trioxide La
2O
3: 1.581 grams, cerium oxide CeO
2: 0.052 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 300 ℃, calcination time 7 hours, then be cooled to room temperature, takes out sample; Fully mixed grinding is even again by the raw material of calcining for the first time, sintering again under air atmosphere, and 700 ℃ of temperature, calcination time 8 hours, then be chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on reducing atmosphere sintering (being embedded in activated carbon powder) in retort furnace, calcining temperature is 900 ℃, and calcination time is 8 hours, namely obtains powder shaped aluminium borate base blue colour fluorescent powder.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 1.
Embodiment 4:
Preparation La
0.95Ce
0.05Al
2B
3O
9
According to chemical formula La
0.95Ce
0.05Al
2B
3O
9In the stoichiometric ratio of each element take respectively aluminium hydroxide Al (OH)
3: 1.560 grams, boron oxide B
2O
3: 1.045 grams, lanthanum nitrate La (NO
3)
3: 3.087 grams, cerium oxide CeO
2: 0.087 gram, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 350 ℃, calcination time 8 hours, then be cooled to room temperature, takes out sample; Fully mixed grinding is even again by the raw material of calcining for the first time, sintering again under air atmosphere, and 750 ℃ of temperature, calcination time 9 hours, then be chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on reducing atmosphere sintering (being embedded in activated carbon powder) in retort furnace, calcining temperature is 850 ℃, and calcination time is 10 hours, namely obtains powder shaped aluminium borate base blue colour fluorescent powder.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 1.
Claims (10)
1. aluminium borate base blue colour fluorescent powder, it is characterized in that: its chemical formula is La
1-x Ce
x Al
2B
3O
9, in formula, x is the molar percentage coefficient of La position Ce doping, 0.005≤x≤0.05; Described fluorescent material is under the ultraviolet excitation of 250～350 nanometers at wavelength, and emission wavelength is the blue light between 350～500 nanometers.
2. the preparation method of an aluminium borate base blue colour fluorescent powder as claimed in claim 1, is characterized in that adopting high temperature solid-state method, comprises the following steps:
(1) to contain aluminum ion Al
3+Compound, contain boron ion B
3+Compound, contain lanthanum ion La
3+Compound, contain cerium ion Ce
4+Compound be raw material, by molecular formula La
1-x Ce
x Al
2B
3O
9The stoichiometric ratio of middle corresponding element takes each raw material, and in formula, x represents the molar percentage coefficient of La position Ce doping, 0.005≤x≤0.05; The raw material that takes is ground respectively, and remix is even, obtains mixture;
(2) mixture is calcined under air atmosphere, calcining temperature is 100～500 ℃, and calcination time is 1～12 hour;
(3) the mixture naturally cooling after calcining, grind and mix, and under air atmosphere, calcines, and calcining temperature is 400～900 ℃, and calcination time is 1～10 hour;
(4) the mixture naturally cooling after calcining, grind and mix, sintering in reducing atmosphere, and calcining temperature is 700～1100 ℃, calcination time is 3～12 hours, obtains a kind of aluminium borate base blue colour fluorescent powder.
3. the preparation method of a kind of aluminium borate base blue colour fluorescent powder according to claim 2, is characterized in that: the described aluminum ion Al that contains
3+Compound comprise a kind of in aluminum oxide, aluminium hydroxide.
4. the preparation method of a kind of aluminium borate base blue colour fluorescent powder according to claim 2, is characterized in that: the described boron ion B that contains
3+Compound comprise a kind of in boron trioxide, boric acid.
5. the preparation method of a kind of aluminium borate base blue colour fluorescent powder according to claim 2, is characterized in that: the described lanthanum ion La that contains
3+Compound comprise a kind of in lanthanum trioxide, lanthanum nitrate.
6. the preparation method of a kind of aluminium borate base blue colour fluorescent powder according to claim 2, is characterized in that: the described cerium ion Ce that contains
4+Compound be cerium oxide.
7. the preparation method of a kind of aluminium borate base blue colour fluorescent powder according to claim 2, it is characterized in that: the described calcining temperature of step (2) is 200～400 ℃, and calcination time is 3～10 hours; The described calcining temperature of step (3) is 600～800 ℃, and calcination time is 4～9 hours; The described calcining temperature of step (4) is 800～1000 ℃, and calcination time is 4～10 hours.
8. the preparation method of a kind of aluminium borate base blue colour fluorescent powder according to claim 2, it is characterized in that: the described reducing atmosphere of step (4) is the active carbon granule reducing atmosphere.
9. the application of an aluminium borate base blue colour fluorescent powder as claimed in claim 1 is characterized in that: the colourity for the preparation of the illumination take UV-light as excitaton source, display device and photoluminescence is regulated.
10. the application of an aluminium borate base blue colour fluorescent powder as claimed in claim 1 is characterized in that: described fluorescent material is coordinated to appropriate redness, green emitting phosphor, apply and be packaged in outside the InGaN diode, prepare the white light LEDs illuminating device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310324671.9A CN103396800B (en) | 2013-07-30 | 2013-07-30 | Boron aluminate-based blue fluorescent powder, preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446573A (en) * | 2017-08-18 | 2017-12-08 | 苏州轻光材料科技有限公司 | A kind of UV excited white lights LED fluorescent material and preparation method thereof |
| CN108822836A (en) * | 2018-06-08 | 2018-11-16 | 南通纺织丝绸产业技术研究院 | A kind of Eu2+And Eu3+The fluorescent powder of europium ion mixing activation, preparation method and application |
| CN111996002A (en) * | 2020-09-18 | 2020-11-27 | 中国科学院长春应用化学研究所 | Single-matrix white light fluorescent powder, and preparation method and application thereof |
| CN116875303A (en) * | 2023-06-02 | 2023-10-13 | 常熟理工学院 | Aluminate-based red luminescent material and preparation method and application thereof |
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2013
- 2013-07-30 CN CN201310324671.9A patent/CN103396800B/en not_active Expired - Fee Related
Non-Patent Citations (1)
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| GIANCARLO DELLA VENTURA ET AL.: "Peprossiite-(Ce), a new mineral from Campagnano (Italy): the first anhydrous rare-earth-element borate", 《EUR. J. MINERAL.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446573A (en) * | 2017-08-18 | 2017-12-08 | 苏州轻光材料科技有限公司 | A kind of UV excited white lights LED fluorescent material and preparation method thereof |
| CN108822836A (en) * | 2018-06-08 | 2018-11-16 | 南通纺织丝绸产业技术研究院 | A kind of Eu2+And Eu3+The fluorescent powder of europium ion mixing activation, preparation method and application |
| CN111996002A (en) * | 2020-09-18 | 2020-11-27 | 中国科学院长春应用化学研究所 | Single-matrix white light fluorescent powder, and preparation method and application thereof |
| CN116875303A (en) * | 2023-06-02 | 2023-10-13 | 常熟理工学院 | Aluminate-based red luminescent material and preparation method and application thereof |
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| CN103396800B (en) | 2014-09-17 |
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