CN101486910B - Green phosphor for white light LED and preparation thereof - Google Patents
Green phosphor for white light LED and preparation thereof Download PDFInfo
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- CN101486910B CN101486910B CN2009100089368A CN200910008936A CN101486910B CN 101486910 B CN101486910 B CN 101486910B CN 2009100089368 A CN2009100089368 A CN 2009100089368A CN 200910008936 A CN200910008936 A CN 200910008936A CN 101486910 B CN101486910 B CN 101486910B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- -1 compound carbonate Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000009877 rendering Methods 0.000 claims description 5
- 108010043121 Green Fluorescent Proteins Proteins 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000013467 fragmentation Methods 0.000 claims description 4
- 238000006062 fragmentation reaction Methods 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000005049 combustion synthesis Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 23
- 230000005284 excitation Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052733 gallium Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910052788 barium Inorganic materials 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910052700 potassium Inorganic materials 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 25
- 238000009413 insulation Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 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
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 241001025261 Neoraja caerulea Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RLMMPAFGVXFLEB-UHFFFAOYSA-N O[Si](O)(O)Cl.P Chemical compound O[Si](O)(O)Cl.P RLMMPAFGVXFLEB-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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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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- Luminescent Compositions (AREA)
Abstract
The invention relates to green phosphor powder for white light LED and a preparation method thereof. The chemical composition general formula of the involved phosphor powder is as follows: (A9-m-u-vBm)(Si4-nMn)O16-m/2-n/2X2:uEu, vR, wherein, A is one or a plurality of alkaline earth metals such as Mg, Ca, Sr and Ba; R is one or a plurality of metals such as Zn, Mn, Y, Gd, Tb, Yb, Dy, Ce, Ho, Pr, Bi, Sn and Ti; B is one or a plurality of alkali metals such as Li, Na and K; M is one or a plurality of B, Al and Ga, and X is one or a plurality of F, Cl, Br and I; wherein, m is more than or equal to 0.0001 and less than or equal to 1; n is more than or equal to 0 and less than or equal to 1; u is more than or equal to 0.03 and less than or equal to 0.6; v is more than or equal to 0 and less than or equal to 0.5; the boric acid and excessive alkaline earth metal halide serve as latent solvent; the hydroxide, oxide or corresponding salt in the above structure is selected to be raw material, burned for 2 to 5 hours in the reducing gas of 1000 to 1300 DEG C, and cooled to obtain phosphor powder for white light LED after final treatment. The phosphor powder emits green light under the excitation of the ultraviolet light, near ultraviolet light or blue light, and can serve as phosphor powder for white light LED excitated by blue light or ultraviolet light. The phosphor powder has the advantages of high luminous intensity, simple manufacturing method, wide excitation wavelength, no pollution, low cost, etc.
Description
Technical field
The present invention relates to a kind of green phosphor for white light LED and preparation method thereof.
Background technology
LED has lot of advantages: energy-conservation (20% of the incandescent light of same luminosity, fluorescent lamp 50%), environmental protection (shatter-proof shock-resistant be difficult for broken refuse recyclable), volume is little, all solid state, thermal value is low (do not have thermal radiation, current consumption little), low voltage low current Start-up life long (more than 1000 hours), speed of response fast (can at high-frequency operation) but and planar package be developed to easily the advantages such as frivolous skilful miscellaneous goods.Backlight, pilot lamp, the general lighting of liquid-crystal display have been used as.Along with rise in the whole world of the semiconductor lighting cause of photodiode (LED), white light LEDs has caused that as light source of new generation people pay close attention to greatly.
Can be by blue-light excited yellow fluorescent powder in the blue-light LED chip coating, gold-tinted and the remaining blue light of fluorescent material emission are combined into white light.Because it is the important component part of white light LEDs that blue-ray LED excites lower efficient yellow fluorescent powder, so blue-light excited luminescent material is significant.Therefore carry out a large amount of research work aspect the fluor that people excite at the development blue-ray LED, and constantly had patent in succession open, as, United States Patent (USP) 5998925 discloses a kind of blue-light excited yellow fluorescent powder, they consist of (Y, Gd)
3(Al, Ga)
5O
12: Ce, combining with blue chip obtains white light LEDs.Although it has higher luminous efficiency, but lacking ruddiness in its emission wavelength and can't obtain the white light LEDs of warm white and high-color rendering. other method of planting that realizes white light LEDs is exactly that blue-light LED chip adds green and red fluorescence powder, and obtains the white light LEDs of the low colour temperature of high-color rendering.As, a kind of nitrogen oxide green fluorescent powder is disclosed among the Chinese patent CN01029230A, it and nitride red fluorescent material Sr
2Si
5N
8Red fluorescence powder can produce the high-performance white light LEDs of the low colour temperature of high-color rendering.But the luminosity of nitrogen oxide green fluorescent powder and nitride red fluorescent powder is lower, and cost is high.Also has significant limitation as the white-light LED fluorescence material.China CN1186103A discloses a kind of Chlorosilicate phosphor powder, and composition can be expressed as Ca
8Mg
1-aZn
a(SiO
4)
4Cl
2: xEu, yM.Wherein M is Ce and Mn, a small amount of Sr, and Ba can replace Ca.0≤a in the formula≤1,0≤x≤0.2,0≤y≤0.1.Wherein do not contain basic metal and B, Al, Ga etc.China CN101235286A discloses a kind of similar green emitting phosphor, and its composition can be expressed as: (M
1-y 1R
y)
aMgM
b 2M
c 3O
A+2b+ (3/2) cX
2, M
1Be selected from Ca, Sr, Ba, Zn, Mn at least a, M
2Be selected from Si, Ge, Sn at least a, M
3Be selected from B, Al, Ga, In at least a, X be selected from rare earth element must have that Eu's is at least a.0.0001≤y≤0.3，7.0≤a≤10.0，3.0≤b≤5.0，0≤c≤1.0。Wherein do not contain alkali metal yet.
Summary of the invention
One of one object of the present invention provides a kind of white light LEDs fluor, its excitation wavelength range is wide, synthesis temperature is low, a kind of blue light that chemical substance is stable and the emission main peak can move in very wide scope or the phosphor for white light LED of ultraviolet excitation.
The chemical constitution general formula of fluorescent material involved in the present invention is: (A
9-m-u-vB
m) (Si
4-nM
n) O
16-m/2-n/2X
2: uEu, vR.Wherein A is one or more of Mg, Ca in the alkaline-earth metal, Sr, Ba, R be among Metal Zn, Mn, Y, Gd, Tb, Yb, Dy, Ce, Ho, Pr, Bi, Sn, the Ti one or several, B be among basic metal Li, Na, the K one or several, M is one or several among B, Al, the Ga, X be among F, Cl, Br, the I one or several.0.001≤m≤1,0≤n≤1,0.03≤u≤0.6,0≤v≤0.5 wherein is take boric acid and excessive alkaline earth metal halide as solubility promoter.
In addition, the change in concentration of Eu ion and foreign cation R affects the lattice parameter of fluorescent material among the present invention among the present invention, thereby has changed crystal field strength.So that the peak position of the emmission spectrum of fluorescent material changes.By the concentration of adjusting Eu ion and foreign cation among the present invention can be meticulous the position of emission peak of adjusting fluorescent material.
The purpose of having introduced R among the present invention is, utilize between rare earth ion or the transition metal ion for the transmission ofenergy of luminescence center.After luminescence center was excited, excitation energy can be delivered to another luminescence center from a luminescence center, so that the luminous enhancing of Eu ion (perhaps Mn) is played sensibilized for active ions.Thereby obtain efficient fluorescent material.R ion among the present invention can and active ions Eu ion (perhaps Mn) between efficient radiationless transmission ofenergy occurs.
Another object of the present invention provides the preparation method of the fluor that a kind of white light LEDs uses.Its step and condition are as follows:
The raw material that preparation method of the present invention adopts is at least a in alkaline earth metal oxide, the compound carbonate that can change into alkaline earth metal oxide, the oxyhydroxide etc.; At least a in rare-earth oxide, the compound carbonate that can change into rare-earth oxide or the vitriol etc.; A kind of in silicic acid or the silicon-dioxide.At least a in halogenation ammonia or the metal halide.
Fusing assistant is boric acid and excessive alkaline earth metal halide, and these two kinds of solubility promoters all are both as base starting material, and excessive part plays again fusing assistant simultaneously;
(1) according to the chemical ingredients ratio of the chemical constitution formula of above-mentioned fluor, accurate weighing above-mentioned raw materials, the mole number of described fusing assistant is 0～5% with the ratio of the mole number of the chemical constitution formula of described fluorescent powder.Wherein halogenation ammonia or metal halide excessive 5%～200%.
(2) with the raw material that mixes in air, be 1000～1300 ℃ in temperature, calcination 2～5 hours.
(3) with above-mentioned product cooling, fragmentation, then ball milling is distributed in the dehydrated alcohol, through centrifugal, 90 ℃ of oven dry.
(4) be reaction atmosphere with carbon or graphite at the reducing gas that combustion synthesis in air produces then, or be the H of 1～10%:99～90% with volume ratio
2And N
2The reaction atmosphere of mixed gas is 1000～1300 ℃ in temperature, calcination 2～5 hours.
(5) with above-mentioned product cooling, fragmentation, then ball milling is distributed in the dehydrated alcohol, and process is centrifugal, and obtains final product 120 ℃ of oven dry, and body colour is green fluorescent material.
Advantage of the present invention: 1. can obtain the green emitting phosphor that halfwidth changes by the composition that changes the matrix element and the ratio of regulating each element.And consider that alkaline-earth metal forms solid solution structure to the impact of its emissive porwer.2. make in matrix and introduce alkalimetal ion and rare earth element ion strengthens its green emission.3. adding transition metal and rare earth ion in activator does with improving its emissive porwer by its emission sensitization.4. improved the crystal property of fluorescent material by double sintering, and considered that washing is on the impact employing washing with alcohol of its luminous intensity.
The fluor that the present invention obtains is in blue light or the very strong green light of the near ultraviolet excitated lower emission of ultraviolet.It can be satisfied with the application of white light LEDs preferably, and the fluorescent material that coats this fluorescent powder and red-emitting at blue-light LED chip can obtain the white light that high-color rendering hangs down colour temperature; Simultaneously, the invention provides the preparation this fluor the preparation method, its step and condition are simple, temperature of reaction is low, easy handling.
Description of drawings
Figure one is the comparison diagram of example 2 and example 6
Embodiment
Embodiment 1
Take by weighing CaO 3.8974 grams, SiO
22.4034 gram, MgO 0.403 gram, CaCl
22.2197 gram, Eu
2O
30.176 gram, MnCl
24H
2O 0.0099 gram, Li
2CO
30.0032 gram carries out abundant ground and mixed, then the material that mixes is put into alumina crucible, puts into together afterwards a larger crucible, places an amount of activated carbon between two crucibles, outer crucible is added a cover.Put into chamber type electric resistance furnace and calcine, at 1250 ℃ of lower insulation 4h, the about 5 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing.Block powder after the calcining is taken out, use distilled water wash after the Mechanical Crushing, then 90 ℃ of lower dryings, be crushed to median size with micronizer mill at last and reach 4 ± 0.5um, obtain the fluorescent material finished product.
Embodiment 2
Take by weighing CaO 3.8974 grams, SiO
22.4034 gram, MgO 0.403 gram, CaCl
22.2197 gram, Eu
2O
30.176 gram, Dy
2O
30.0186 gram, Li
2CO
30.0035 gram carries out abundant ground and mixed, then the material that mixes is put into alumina crucible, puts into together afterwards a larger crucible, places an amount of activated carbon between two crucibles, outer crucible is added a cover.Put into chamber type electric resistance furnace and calcine, at 1250 ℃ of lower insulation 4h, the about 5 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing.Block powder after the calcining is taken out, use distilled water wash after the Mechanical Crushing, then 90 ℃ of lower dryings, be crushed to median size with micronizer mill at last and reach 4 ± 0.5um, obtain the fluorescent material finished product.
Embodiment 3
Take by weighing CaCO
34.14 gram, SiO
21.44 gram, MgO 0.2418 gram, CaCl
21.332 gram, Eu
2O
30.1056 gram, BaF
20.0726 gram, boric acid 0.1452 gram, Li
2CO
30.0041 gram carries out abundant ground and mixed, then the material that mixes is put into alumina crucible, puts into together afterwards a larger crucible, places an amount of activated carbon between two crucibles, outer crucible is added a cover.Put into chamber type electric resistance furnace and calcine, at 1250 ℃ of lower insulation 4h, the about 5 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing.Block powder after the calcining is taken out, use distilled water wash after the Mechanical Crushing, then 90 ℃ of lower dryings, be crushed to median size with micronizer mill at last and reach 4 ± 0.5um, obtain the fluorescent material finished product.
Embodiment 4
Take by weighing CaCO
37.95 gram, SiO
22.4034 gram, CaCl
21.332 gram, Eu
2O
30.088 gram, Li
2CO
30.0052 gram carries out abundant ground and mixed, then the material that mixes is put into alumina crucible, puts into together afterwards a larger crucible, places an amount of activated carbon between two crucibles, outer crucible is added a cover.Put into chamber type electric resistance furnace and calcine, at 1250 ℃ of lower insulation 4h, the about 5 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing.Block powder after the calcining is taken out, use distilled water wash after the Mechanical Crushing, then 90 ℃ of lower dryings, be crushed to median size with micronizer mill at last and reach 4 ± 0.5um, obtain the fluorescent material finished product.
Embodiment 5
Take by weighing CaCO
36.95 gram, SiO
22.4034 gram, MgO 0.403 gram, CaCl
21.332 gram, Eu
2O
30.088 gram, Li
2CO
30.1118 gram carries out abundant ground and mixed, then the material that mixes is put into alumina crucible, puts into together afterwards a larger crucible, places an amount of activated carbon between two crucibles, outer crucible is added a cover.Put into chamber type electric resistance furnace and calcine, at 1250 ℃ of lower insulation 4h, the about 5 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing.Block powder after the calcining is taken out, use distilled water wash after the Mechanical Crushing, then 90 ℃ of lower dryings, be crushed to median size with micronizer mill at last and reach 4 ± 0.5um, obtain the fluorescent material finished product.
Embodiment 6
Take by weighing CaCO
36.65 gram, SiO
22.4034 gram, MgO 0.403 gram, CaCl
21.332 gram, Eu
2O
30.088 gram, Li
2CO
30.0018 gram, Gd
2O
30.5438 gram carries out abundant ground and mixed, then the material that mixes is put into alumina crucible, puts into together afterwards a larger crucible, places an amount of activated carbon between two crucibles, outer crucible is added a cover.Put into chamber type electric resistance furnace and calcine, at 1250 ℃ of lower insulation 4h, the about 5 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing.Block powder after the calcining is taken out, use distilled water wash after the Mechanical Crushing, then 90 ℃ of lower dryings, be crushed to median size with micronizer mill at last and reach 4 ± 0.5um, obtain the fluorescent material finished product.
Chemical formula and the characteristics of luminescence thereof of table one embodiment 7-20
| Embodiment | Chemical formula | Relative brightness |
| 7 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.03Li | 108 |
| 8 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.05Li | 105 |
| 9 | Ca 7.9Mg(SiO 4) 4Cl 2:Eu，0.05Li，0.05Y | 112 |
| 10 | Ca 7.9Mg(SiO 4) 4Cl 2:Eu，0.1Gd | 109 |
| 11 | Ca 7.9Mg(SiO 4) 4Cl 2:Eu，Li0.05，0.05Gd | 113 |
| 12 | Ca 7.7Mg(SiO 4) 4Cl 2:Eu，0.3Gd | 102 |
| 13 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.02Tb，0.02Na | 110 |
| 14 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.02Yb，0.02Na | 115 |
| 15 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.02Dy，0.02Na | 119 |
| 16 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.01Ce，0.01Li | 110 |
| 17 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.01Bi，0.01Li | 103 |
| 18 | Ca 8Mg 0.9Zn 0.1(SiO 4) 4Cl 2:Eu，0.02Dy，0.02Na | 103 |
| 19 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.01Ce，0.04Li，0.3Dy | 104 |
| 20 | Ca 8Mg(SiO 4) 4Cl 2:Eu，0.03 Y，0.06Li，0.3Dy | 108 |
| Comparative example | Ca 8Mg(SiO 4) 4Cl 2:Eu | 100 |
Chemical formula and the characteristics of luminescence thereof of table two embodiment 21-28
| Embodiment | Chemical formula | Relative brightness |
| 21 | Ca 9(SiO 4) 4Cl 2:Eu，0.03Li | 103 |
| 22 | Ca 9(SiO 4) 4Cl 2:Eu，0.05Li | 106 |
| 23 | Ca 9(SiO 4) 4Cl 2:Eu，0.05Dy | 110 |
| 24 | Ca 9(SiO 4) 4Cl 2:Eu，0.05Ce | 105 |
| 25 | Ca 9(SiO 4) 4Cl 2:Eu，0.01Y | 102 |
| 26 | Ca 9(SiO 4) 4Cl 2:Eu，0.02Tb | 106 |
| 27 | Ca 9(SiO 4) 4Cl 2:Eu，0.05Na，0.05Dy | 112 |
| 28 | Ca 9(SiO 4) 4Cl 2:Eu，0.05K，0.05Dy | 115 |
| Comparative example | Ca 9(SiO 4) 4Cl 2:Eu | 100 |
Claims (2)
1. the green phosphor material of an alkali-metal-doped is characterized in that chemical formula is:
(A
9-m-u-vB
m)(Si
4-nM
n)O
16-m/2-n/2X
2:uEu，vR，
Wherein A is one or more of Mg, Ca in the alkaline-earth metal, Sr, Ba, R be among Metal Zn, Mn, Y, Gd, Tb, Yb, Dy, Ce, Ho, Pr, Bi, Sn, the Ti one or several, B be among basic metal Li, Na, the K one or several, M is one or several among B, Al, the Ga, X be among F, Cl, Br, the I one or several;
0.001≤m≤1 wherein; 0＜n≤1; 0.03≤u≤0.6; 0＜v≤0.5; And wherein take boric acid and excessive alkaline earth metal halide as fusing assistant, excessive degree is 5%～200%;
Wherein, the preparation process of described green phosphor material and condition are as follows:
The raw material that adopts is: at least a in alkaline earth metal oxide, the compound carbonate that can change into alkaline earth metal oxide, the oxyhydroxide; At least a in rare-earth oxide, the compound carbonate that can change into rare-earth oxide or the vitriol; A kind of in silicic acid or the silicon-dioxide; And at least a in halogenation ammonia or the metal halide;
Fusing assistant is described boric acid and excessive alkaline earth metal halide, and these two kinds of fusing assistants all are both as base starting material, and excessive part plays again fusing assistant simultaneously;
(1) according to the chemical ingredients ratio of the chemical constitution formula of above-mentioned fluor, accurate weighing above-mentioned raw materials, the mole number of described fusing assistant is 0～5% with the ratio of the mole number of the chemical constitution formula of described fluor; Wherein halogenation ammonia or metal halide excessive 5%～200%;
(2) with the raw material that mixes in air, be 1000～1300 ℃ in temperature, calcination 2～5 hours;
(3) with above-mentioned product cooling, fragmentation, then ball milling is distributed in the dehydrated alcohol, through centrifugal, 90 ℃ of oven dry;
(4) be reaction atmosphere with carbon at the reducing gas that combustion synthesis in air produces then, or be 1～10%: 99～90% H with volume ratio
2And N
2The reaction atmosphere of mixed gas is 1000～1300 ℃ in temperature, calcination 2～5 hours;
With above-mentioned product cooling, fragmentation, then ball milling is distributed in the dehydrated alcohol, and process is centrifugal, and obtains final product 120 ℃ of oven dry, and body colour is green fluorescent material;
The fluorescent material of wherein said green is applied to White LED, wherein hangs down the white light of colour temperature to obtain high-color rendering at the fluorescent material of the described green of blue-light LED chip coating and the fluorescent material of red-emitting.
2. the green phosphor material of a kind of alkali-metal-doped according to claim 1, it is characterized in that: carbon is specially graphite described in the step (4).
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| JP5310087B2 (en) * | 2009-02-26 | 2013-10-09 | 日亜化学工業株式会社 | Phosphor and light emitting device using the same |
| CN102925975A (en) * | 2011-08-09 | 2013-02-13 | 上海祥羚光电科技发展有限公司 | Making method for YAG single crystal for white light LED |
| CN102637792A (en) * | 2012-05-14 | 2012-08-15 | 上海祥羚光电科技发展有限公司 | Method for preparing fluorescent powder prefabricated thin film for white-light LED (Light-Emitting Diode) |
| CN102709448A (en) * | 2012-06-26 | 2012-10-03 | 上海祥羚光电科技发展有限公司 | White light LED packaging structure and method |
| CN103050609A (en) * | 2012-07-17 | 2013-04-17 | 上海祥羚光电科技发展有限公司 | Preparation method of white chip for LED (Light Emitting Diode) |
| CN115261017B (en) * | 2022-08-14 | 2024-01-26 | 湘潭大学 | Blue light luminescent material capable of being excited by purple light and preparation method thereof |
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| CN101092561A (en) * | 2007-07-25 | 2007-12-26 | 沈阳化工学院 | Method for preparing calcium magnesium chloro-silicate for green emitting phosphor |
| CN101134895A (en) * | 2006-08-15 | 2008-03-05 | 大连路明科技集团有限公司 | Wide-spectrum excitation fluorescent material and synthesizing method and light-emitting apparatus using the same |
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| CN101092561A (en) * | 2007-07-25 | 2007-12-26 | 沈阳化工学院 | Method for preparing calcium magnesium chloro-silicate for green emitting phosphor |
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Effective date of registration: 20160612 Address after: 215316 Jiangsu Province, Kunshan high tech Industrial Park of St No. 28 Patentee after: Kunshan art all luminous Mstar Technology Ltd Address before: 215316 Jiangsu Province, Kunshan high tech Industrial Park of St No. 28 Patentee before: Li Rui |