CN105670626B - A kind of super large particle diameter YAG:Ce3+Yellow fluorescent powder and preparation method thereof - Google Patents
A kind of super large particle diameter YAG:Ce3+Yellow fluorescent powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002245 particle Substances 0.000 title abstract description 18
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 54
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 23
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 67
- 239000000376 reactant Substances 0.000 claims description 33
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 claims description 19
- 239000012043 crude product Substances 0.000 claims description 17
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000000498 ball milling Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
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- 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
- C09K11/7792—Aluminates
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- H—ELECTRICITY
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- 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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Abstract
The invention discloses a kind of super large particle diameter YAG:Ce3+Yellow fluorescent powder and preparation method thereof, obtained yellow fluorescent powder are the microballoon of average grain diameter >=40 μm, and its preparation method is to use salt bath process, with YF3And AlF3Raw material of the first mixing and ball milling into fine powder as salt bath, then adds Y2O3、Al2O3And CeO2It is well mixed, 1~15h is sintered in 1300~1500 DEG C in by reducing atmosphere stove, after being cooled to room temperature, is washed for several times by hot salpeter solution washing by soaking and deionized water, final product is produced after 120 DEG C of drying.Fluorescent powder grain pattern prepared by the present invention is developed, few surface defects, crystal face complete display, and even particle distribution, in spherical, chemical stability and heat endurance are good, the yellow fluorescence of 540~565nm peak wavelengths can be launched, and preparation technology is simple, cost is cheap, is easy to industrialized production, is particularly suitable for application to high-power blue light LD light sources.
Description
Technical field
The present invention relates to fluorescent material and preparation method thereof, and in particular to a kind of super large particle diameter YAG:Ce3+Yellow fluorescent powder and
Its preparation method.
Background technology
In recent years, because the continuous development of high-power blue laser (LD) performance, LD are quickly grown as light source, and more
Applied come more in emerging field, such as high power LD illumination, shot-light, stage lighting, laser television, automobile front etc..
Compared with conventional light source device, LD has that low energy-saving and environmental protection, cost, efficiency high, response time are short, service life as light source
The advantages that long, shock resistance and vibration, thus as the ideal chose of light source device of new generation, have broad application prospects and pass through
Ji social benefit.
High power LD is primarily referred to as powerful ultra-blue-light LD and changed by excitated fluorescent powder to launch as light source
Required photochromic light source, the also referred to as scheme of laser fluorescence powder.Three colors of red, green, blue that early stage uses all are to use laser
Light source package caused by coming, there is the defects of with high costs, generation high temperature, hardly enter among average family.And present swash
Emitting phosphor scheme not only largely reduces cost, and solves heat dissipation problem well.YAG at present:Ce3+It is yellow
Color fluorescent material is sodium yellow source important in LD light sources, and is commercialized YAG on the market:Ce3+Yellow fluorescent powder is largely flat
Equal particle diameter is less than 25 μm of powder, and this powder compared with small particle, in the case where high-power blue light LD is excited, hot light decay is more serious, and
And, accelerate the aging of organic gel class the problems such as higher in the temperature that powder surface gathers, have a strong impact on high power LD light source
Optical property.And super large particle diameter (average grain diameter >=40 μm) YAG:Ce3+Yellow fluorescent powder, because particle surface crystallization is completeer
Kind, hot light decay is lower, and radiating is more preferable, is favorably improved the optical property and service life of high power LD light source.Therefore, develop super
Big particle diameter (average grain diameter >=40 μm) YAG:Ce3+Yellow fluorescent powder tool is of great significance.
The content of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, there is provided a kind of super large particle diameter YAG:Ce3+Yellow
Fluorescent material and preparation method thereof, technique is simple, and cost is cheap, is easy to industrialized production, obtained fluorescent material regular shape, especially
It is suitably applied high-power blue light LD light sources.
One of the technical solution adopted for the present invention to solve the technical problems is：
A kind of YAG:Ce3+The preparation method of yellow fluorescent powder, including：
1) by YF3And AlF3According to 1:4~4:1 mass ratio is mixed to prepare YF3-AlF3Mixture, Y is added thereto2O3、
Al2O3And CeO2, it is well mixed, as reactant mixture；Wherein YF3-AlF3Mixture accounts for 18~30wt% of reactant mixture,
As the raw material and additive of salt bath process, Y2O3、Al2O3And CeO2Addition according to YAG:Ce3+Set in yellow fluorescent powder
The stoichiometric proportion of each element determines；
2) reactant mixture for obtaining step 1) carries out salt bath process preparation under reducing atmosphere, and heating-up temperature 1300~
1500 DEG C, 1~15h of heat time, room temperature is subsequently cooled to, obtains the crude product of block shape；
3) crude product for obtaining step 2) is crushed, and is soaked with 60~80 DEG C of 5%~10% hot salpeter solutions
Washing, then be washed with deionized, to remove unreacted YF3-AlF3Mixture；120 DEG C of drying are placed in again, that is, are obtained final
Product YAG:Ce3+Yellow fluorescent powder, its average grain diameter >=40 μm.
In one embodiment：The YAG:Ce3+Yellow fluorescent powder is Y3-xAl5O12:xCe3+, wherein 0.02≤x≤0.2.
In one embodiment：In the step 2), reducing atmosphere H2And N2By volume 1:The gas of 9 mixing.
The two of the technical solution adopted for the present invention to solve the technical problems are：
According to the YAG prepared by above-mentioned preparation method:Ce3+The purposes of yellow fluorescent powder.
In one embodiment：The purposes is the purposes on high-power blue light LD light sources.
Compared with background technology, it has the following advantages that the technical program：
1. in the prior art, YAG:Ce3+Yellow fluorescent powder is largely the powder that average grain diameter is less than 25 μm, because preparing
The phosphor powder of big particle diameter has certain technical difficulty, this mainly due to crystal in growth course, speed is relatively slow,
Growth cycle is long, crystal itself growth is typically small；And the present invention is by adding YF3-AlF3Mixture, and combine each component
Reaction condition with when salt bath, it is successfully realized super large particle diameter (average grain diameter >=40 μm) YAG:Ce3+The system of yellow fluorescent powder
It is standby, and super large particle diameter (average grain diameter >=40 μm) YAG that the present invention is obtained:Ce3+Yellow fluorescent powder, granule-morphology develops,
Few surface defects, particle surface crystallize more perfect, crystal face complete display, and particle size distribution uniformly, in spherical, can
Launch the yellow fluorescence of 540~565nm peak wavelengths, luminous efficiency is higher, and hot light decay is lower, chemical stability and heat endurance
It is good, the high-power blue light LD light sources of 120W are can be applied to, generation temperature is lower, and LD conversion efficiency can be made further to improve.
2. preparation method provided by the present invention is simple, cost is cheap, is easy to industrialized production.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the YAG of embodiment 1:Ce3+The scanning electron microscope (SEM) photograph of yellow fluorescent powder.
Fig. 2 is the YAG of embodiment 1:Ce3+The particle diameter distribution schematic diagram of yellow fluorescent powder.
Fig. 3 is emission spectrum schematic diagram of the fluorescent material of comparative example 1 in the case where 450nm is excited.
Fig. 4 is the YAG of embodiment 1:Ce3+The fluorescent material of yellow fluorescent powder, comparative example 1 and comparative example 2 is in blue light LD light sources
On application apparatus schematic diagram.
Embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1：Prepare YAG:Ce3+Yellow fluorescent powder Y2.9Al5O12:0.1Ce3+
1) by YF3And AlF3According to 1:1 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 12.0g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.83g's respectively
Y2O3, 16.99g Al2O3With 1.15g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 23.1wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to YAG:Ce3+Yellow
Fluorescent material Y2.9Al5O12:0.1Ce3+The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Mixing
Gas) under carry out salt bath process preparation, 1500 DEG C of heating-up temperature, heat time 10h, be subsequently cooled to room temperature, obtain block shape
Crude product；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, obtain final product YAG:Ce3+Yellow fluorescent powder Y2.9Al5O12:0.1Ce3+, its average grain diameter >=40 μm, its
Scanning electron microscope (SEM) photograph and particle diameter distribution schematic diagram difference are as depicted in figs. 1 and 2.
Embodiment 2：Prepare YAG:Ce3+Yellow fluorescent powder Y2.92Al5O12:0.08Ce3+
1) by YF3And AlF3According to 2:1 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 15.0g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.98g's respectively
Y2O3, 16.99g Al2O3With 0.92g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 27.3wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to Y2.92Al5O12:
0.08Ce3+The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Mixing
Gas) under carry out salt bath process preparation, 1500 DEG C of heating-up temperature, heat time 6h, be subsequently cooled to room temperature, obtain the thick of block shape
Product；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, obtain final product YAG:Ce3+Yellow fluorescent powder Y2.92Al5O12:0.08Ce3+, its average grain diameter >=40 μm.
Embodiment 3：Prepare YAG:Ce3+Yellow fluorescent powder Y2.88Al5O12:0.12Ce3+
1) by YF3And AlF3According to 1:2 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 17.2g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.68g's respectively
Y2O3, 16.99g Al2O3With 1.38g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 30wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to Y2.88Al5O12:
0.12Ce3+The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Mixing
Gas) under carry out salt bath process preparation, 1500 DEG C of heating-up temperature, heat time 2h, be subsequently cooled to room temperature, obtain the thick of block shape
Product；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, obtain final product YAG:Ce3+Yellow fluorescent powder Y2.88Al5O12:0.12Ce3+, its average grain diameter >=40 μm.
Embodiment 4：Prepare YAG:Ce3+Yellow fluorescent powder Y2.9Al5O12:0.1Ce3+
1) by YF3And AlF3According to 1:4 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 10.0g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.83g's respectively
Y2O3, 16.99g Al2O3With 1.15g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 20wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to Y2.9Al5O12:0.1Ce3 +The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Mixing
Gas) under carry out salt bath process preparation, 1400 DEG C of heating-up temperature, heat time 14h, be subsequently cooled to room temperature, obtain block shape
Crude product；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, obtain final product YAG:Ce3+Yellow fluorescent powder Y2.9Al5O12:0.1Ce3+, its average grain diameter >=40 μm.
Embodiment 5：Prepare YAG:Ce3+Yellow fluorescent powder Y2.94Al5O12:0.06Ce3+
1) by YF3And AlF3According to 1:1 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 8.8g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.13g's respectively
Y2O3, 16.99g Al2O3With 0.69g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 18.1wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to Y2.94Al5O12:
0.06Ce3+The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Mixing
Gas) under carry out salt bath process preparation, 1500 DEG C of heating-up temperature, heat time 6h, be subsequently cooled to room temperature, obtain the thick of block shape
Product；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, obtain final product YAG:Ce3+Yellow fluorescent powder Y2.94Al5O12:0.06Ce3+, its average grain diameter >=40 μm.
Embodiment 6：Prepare YAG:Ce3+Yellow fluorescent powder Y2.85Al5O12:0.15Ce3+
1) by YF3And AlF3According to 1:1 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 16.0g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.45g's respectively
Y2O3, 16.99g Al2O3With 1.72g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 28.5wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to Y2.85Al5O12:
0.15Ce3+The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Mixing
Gas) under carry out salt bath process preparation, 1350 DEG C of heating-up temperature, heat time 8h, be subsequently cooled to room temperature, obtain the thick of block shape
Product；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, obtain final product YAG:Ce3+Yellow fluorescent powder Y2.85Al5O12:0.15Ce3+, its average grain diameter >=40 μm.
Comparative example 1：By chemical formula Y2.9Al5O12:0.1Ce3+Prepare fluorescent material
1) by YF3And AlF3According to 1:1 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 8.0g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.83g's respectively
Y2O3, 16.99g Al2O3With 1.15g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 16.7wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to Y2.9Al5O12:
0.1Ce3+The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Mixing
Gas) under carry out salt bath process preparation, 1500 DEG C of heating-up temperature, heat time 5h, be subsequently cooled to room temperature, obtain the thick of block shape
Product；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, final product fluorescent material is obtained, its emission spectrum schematic diagram in the case where 450nm is excited is as shown in Figure 3.
Comparative example 2：By chemical formula Y2.9Al5O12:0.1Ce3+Prepare fluorescent material
1) by YF3And AlF3According to 1:1 mass ratio mixing, ball milling obtain YF into the fine powder of micron level3-AlF3Mixing
Thing, the raw material as salt bath process；
2) YF for obtaining 6g steps 1)3-AlF3Mixture loads mixing tank, then is charged with 21.83g's respectively
Y2O3, 16.99g Al2O3With 1.15g CeO2, it is placed in batch mixer and mixes 4h with well mixed, as reactant mixture；Its
Middle YF3-AlF3Mixture accounts for the 13.1wt% of reactant mixture, Y2O3、Al2O3And CeO2Addition according to Y2.9Al5O12:
0.1Ce3+The stoichiometric proportion of middle each element determines；
3) by the reactant mixture that step 2) obtains, in reducing atmosphere, (reducing atmosphere is volume ratio 1:9 H2And N2Gaseous mixture
Body) under carry out salt bath process preparation, 1450 DEG C of heating-up temperature, heat time 4h, be subsequently cooled to room temperature, obtain the crude product of block shape；
4) crude product for obtaining step 3) is put into double-roll crusher and crushed, with 60~80 DEG C of 10% hot nitre
Acid solution washing by soaking 2 times, then be washed with deionized 4 times, to remove unreacted YF3-AlF3Mixture；120 DEG C are placed in again
After drying 4h, that is, obtain final product fluorescent material.
Experimental example
By the YAG of embodiment 1:Ce3+Yellow fluorescent powder Y2.9Al5O12:0.1Ce3+, comparative example 1 and comparative example 2 fluorescent material
Properties be compared.
As shown in table 1, it is the YAG of embodiment 1:Ce3+The performance of the fluorescent material of yellow fluorescent powder, comparative example 1 and comparative example 2
Parameter and the application performance contrast on blue light LD.
The application performance of the embodiment 1 of table 1, comparative example 1 with the performance parameter of comparative example 2 and on blue light LD contrasts
Various characteristics shown in table 1, wherein CIE chromaticity coordinates, brightness and external quantum efficiency are that fluorescent material passes through fluorescence spectrum
Instrument, determined with 450nm blue light to excite, and efficiency and temperature are to be excited by 120W 445nm blue lasers to survey
Fixed.In table 1, brightness and efficiency are with the YAG of embodiment 1:Ce3+Yellow fluorescent powder is 100% to represent its relative value.
As shown in table 2, it is the YAG of embodiment 1:Ce3+The heat of the fluorescent material of yellow fluorescent powder, comparative example 1 and comparative example 2 declines
Subtract characteristic.
The heat fade characteristic of the embodiment 1 of table 2, comparative example 1 and comparative example 2
The heat fade characteristic of fluorescent material shown in table 2 is as the rise of temperature is determined with 450nm blue light to excite
's.In table 2, brightness with the fluorescent material that embodiment 1, comparative example 1 and comparative example 2 are each obtained at 30 DEG C for 100%
Represent its relative value.The YAG of embodiment 1 as shown in Table 2:Ce3+Yellow fluorescent powder has more preferably hot compared with comparative example 1 and comparative example 2
Fade performance.
Fig. 4 represents the YAG of embodiment 1:Ce3+The fluorescent material of yellow fluorescent powder, comparative example 1 and comparative example 2 is in blue light LD light
Application apparatus on source.Wherein fluorescent wheel be by embodiment 1, comparative example 1 and 2 respective fluorescent material of comparative example and organic silica gel with
And aerosil is according to 60：39：1 mass ratio, it is 0.2 millimeter in the thickness that minute surface aluminium surface is prepared into, internal-and external diameter
Respectively 52 millimeters and 60 millimeters of annulus phosphor laminate.Temperature as shown in table 1, it is that phosphor laminate surface measurement is arrived
Temperature, and the YAG of embodiment 1:Ce3+Yellow fluorescent powder, applied to the high-power blue light LD of 120W, with higher efficiency and more
Low temperature.
Skilled person will appreciate that when the technical parameter of the present invention changes in following scope, it is contemplated that obtain
Same as the previously described embodiments or similar technique effect：
A kind of YAG:Ce3+The preparation method of yellow fluorescent powder, including：
1) by YF3And AlF3According to 1:4~4:1 mass ratio is mixed to prepare YF3-AlF3Mixture, Y is added thereto2O3、
Al2O3And CeO2, it is well mixed, as reactant mixture；Wherein YF3-AlF3Mixture accounts for 18~30wt% of reactant mixture,
Y2O3、Al2O3And CeO2Addition according to YAG:Ce3+The stoichiometric proportion of each element set in yellow fluorescent powder determines；
2) reactant mixture for obtaining step 1) carries out salt bath process preparation under reducing atmosphere, and heating-up temperature 1300~
1500 DEG C, 1~15h of heat time, room temperature is subsequently cooled to, obtains the crude product of block shape；
3) crude product for obtaining step 2) is crushed, and is soaked with 60~80 DEG C of 5%~10% hot salpeter solutions
Washing, then be washed with deionized, to remove unreacted YF3-AlF3Mixture；120 DEG C of drying are placed in again, that is, are obtained final
Product YAG:Ce3+Yellow fluorescent powder, its average grain diameter >=40 μm.
The YAG:Ce3+Yellow fluorescent powder is Y3-xAl5O12:xCe3+, wherein 0.02≤x≤0.2.
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still it belong in the range of the present invention covers.
Claims (4)
- A kind of 1. YAG:Ce3+The preparation method of yellow fluorescent powder, it is characterised in that：Including：1) by YF3And AlF3According to 1:4~4:1 mass ratio is mixed to prepare YF3-AlF3Mixture, Y is added thereto2O3、Al2O3 And CeO2, it is well mixed, as reactant mixture；Wherein YF3-AlF3Mixture accounts for 18~30wt% of reactant mixture, Y2O3、 Al2O3And CeO2Addition according to YAG:Ce3+The stoichiometric proportion of each element set in yellow fluorescent powder determines；2) reactant mixture for obtaining step 1) carries out salt bath process preparation, heating-up temperature 1300~1500 under reducing atmosphere DEG C, 1~15h of heat time, room temperature is subsequently cooled to, obtains the crude product of block shape；3) crude product for obtaining step 2) is crushed, with 60~80 DEG C of 5%~10% hot salpeter solution washing by soaking, It is washed with deionized again, to remove unreacted YF3-AlF3Mixture；120 DEG C of drying are placed in again, that is, obtain final product YAG:Ce3+Yellow fluorescent powder, its average grain diameter >=40 μm.
- A kind of 2. YAG according to claim 1:Ce3+The preparation method of yellow fluorescent powder, it is characterised in that：The YAG: Ce3+Yellow fluorescent powder is Y3-xAl5O12:xCe3+, wherein 0.02≤x≤0.2.
- A kind of 3. YAG according to claim 1:Ce3+The preparation method of yellow fluorescent powder, it is characterised in that：The step 2) in, reducing atmosphere H2And N2By volume 1:The gas of 9 mixing.
- 4. the YAG prepared by preparation method according to any one of claim 1 to 3:Ce3+The purposes of yellow fluorescent powder, It is characterized in that：The purposes is the purposes on high-power blue light LD light sources.
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| US6409938B1 (en) * | 2000-03-27 | 2002-06-25 | The General Electric Company | Aluminum fluoride flux synthesis method for producing cerium doped YAG |
| CN101041775A (en) * | 2006-03-24 | 2007-09-26 | 北京有色金属研究总院 | Fluorescent powder and manufacturing method and electric light source produced thereby |
| CN103980901A (en) * | 2014-04-30 | 2014-08-13 | 福建省长汀金龙稀土有限公司 | Preparation method of YAG:Ce<3+> yellow fluorescent powder for white light LED |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6409938B1 (en) * | 2000-03-27 | 2002-06-25 | The General Electric Company | Aluminum fluoride flux synthesis method for producing cerium doped YAG |
| CN101041775A (en) * | 2006-03-24 | 2007-09-26 | 北京有色金属研究总院 | Fluorescent powder and manufacturing method and electric light source produced thereby |
| CN103980901A (en) * | 2014-04-30 | 2014-08-13 | 福建省长汀金龙稀土有限公司 | Preparation method of YAG:Ce<3+> yellow fluorescent powder for white light LED |
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