CN1807549A - Fluorescent powder for white light diode and its production method and usage method - Google Patents
Fluorescent powder for white light diode and its production method and usage method Download PDFInfo
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- CN1807549A CN1807549A CNA2006100385014A CN200610038501A CN1807549A CN 1807549 A CN1807549 A CN 1807549A CN A2006100385014 A CNA2006100385014 A CN A2006100385014A CN 200610038501 A CN200610038501 A CN 200610038501A CN 1807549 A CN1807549 A CN 1807549A
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- 239000000843 powder Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 229910052693 Europium Inorganic materials 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 150000008045 alkali metal halides Chemical class 0.000 claims description 4
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000009877 rendering Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 32
- 239000011575 calcium Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 230000005284 excitation Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910016036 BaF 2 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- AYXYFBLDIAOCIP-UHFFFAOYSA-L potassium;sodium;bromide;chloride Chemical compound [Na+].[Cl-].[K+].[Br-] AYXYFBLDIAOCIP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000003081 coactivator Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
This invention discloses a kind of fluorescence powder used in white light e, whose constitutional formula is : AMXAl10O17.n(Al2O3): Euy, Rz. This invention also discloses a method for manufacturing a kind of fluorescence powder, which is : Firstly, weight up raw materials according to the constitutional formula of fluorescence powder, then weight up secondary solvent that is 10-100 mole percent of raw materials, and mix raw materials with secondary solvent; after these, roast above mixture in the air, and reduction calcinate and final treat to get luorescence powder used in white light light-emitting diode. This invention also discloses a method for mking use of the luorescence powder, and execute electric light source by using the a sort of blue light, ultraviolet or near ultraviolet slice and light-emitting diod luorescence powder as raw materials. The production attained by this invention has stable chemical property and high luminous intensity, and its manufacture technology is simple. The produced electric light source produced has high lighting brilliance and good color rendering.
Description
Technical field
The present invention relates to a kind of fluorescent material and manufacture method thereof and using method, relate in particular to a kind of fluorescent powder for white LED and preparation method thereof and using method.
Background technology
Photodiode is because it has little electric current, room temperature strength height, and is luminous corresponding fast, stable performance, and the life-span is long, and volume is little, and durable in use and shock resistance etc. had a few, and is widely used in fields such as general lighting, pilot lamp, signal lamp, demonstrations.As high-level efficiency, low-cost solid state light emitter, will be expected to existing lighting system is realized substituting.
At present, the method that photodiode is realized mainly contains three kinds: the one, on blue LED chip, apply efficiently, and can be by the yellow fluorescent powder that blue light excited, the mixed back of blue light and gold-tinted forms white light; Second kind is to be coated with to cover blue-light excited and the fluorescent material of transmitting green light and ruddiness the mixed white light that forms of ruddiness, blue light and green glow on blue LED chip; The third is to apply efficiently three primary colors fluorescent powder and make white light emitting diode on purple light or ultraviolet light-emitting diodes chip.
The Ba that US6255670 reported
2(Mg, Zn) Si
2O
7: Eu fluorescent material and preparation method thereof, and the influence that Mg/Zn is compared to quantum yield and synthesis temperature has been proposed, this fluorescent material is the green emitting phosphor with ultraviolet excitation, stable chemical performance, but luminous intensity remains further to be improved; The YAG:Ce fluorescent material of US5998925 report has been mentioned Y/Gd, the situation that influences of Al/Ga comparison fluorescent material emission.There is the problem of color developing in made photodiode.
Summary of the invention
The invention provides a kind of chemical property is stable, luminous intensity is high fluorescent powder for white LED and manufacture method and using method, this fluorescent material manufacturing process is simple, easy handling, environmental protection, steady quality, the electric light source of being made by this fluorescent powder for white LED has the luminosity height, the advantage that color developing is good.
For achieving the above object, the present invention is by the following technical solutions:
A kind of fluorescent powder for white LED, structural formula is: AM
xAl
10O
17N (Al
2O
3): Eu
y, R
z, wherein: A is Ca, Sr, and at least a among the Ba, M is Zn, Ca, Gd, Hf, La, at least a among the Si, R is Dy, Ce, Tb, at least a among the Pr, 0.01＜X＜5,0.01＜y＜0.5,0.002≤z＜0.5,0＜n＜3.
A kind of manufacture method of fluorescent powder for white LED may further comprise the steps:
The first step is formed by the structural formula of fluorescent powder for white LED and to be taken by weighing raw material, and raw material is simple substance, oxide compound or the salt of elements A, M, Al, Eu, R, proportioning is identical in the structural formula of A, M in the raw material, Al, Eu, R proportioning and fluorescent powder for white LED, and wherein A is Ca, Sr, at least a among the Ba, M is Ca, Zn, Gd, Hf, La, at least a among the Si, R is Dy, Ce, Tb, at least a among the Pr
Second step, take by weighing at least a in the halogenide, oxalic acid of halogenide, boric acid, boron oxide, the ammonium of 10～100% alkaline earth metal halide, alkali metal halide, the aluminium of above-mentioned raw materials mole number, and be to mix under the 100-400rpm 5～15 hours with the reaction solubility promoter at rotating speed raw material as solubility promoter;
In the 3rd step, with said mixture roasting in air, maturing temperature is 600～1300 ℃, and roasting time is 0.5～10 hour, forms initial powder mixture;
The 4th step, will above-mentioned initial powder mixture in reducing atmosphere, reduce calcining, the reduction calcining temperature is 1200～1600 ℃, the reduction calcination time is 0.5～10 hour, calcines powder with formation;
The 5th step, will calcine powder and carry out aftertreatment, obtain fluorescent powder for white LED.
A kind of using method of fluorescent powder for white LED is that raw material is made electric light source with a kind of and fluorescent powder for white LED in blue light, ultraviolet, the near ultraviolet light-emitting diode chip for backlight unit.
The resulting fluorescent material of the present invention can be used for making white light emitting diode.This white light emitting diode fluorescent material can be coated with on blue LED chip with fluorescent material covers blue-light excited and the fluorescent material of transmitting green light and ruddiness, the mixed white light that forms of ruddiness, green glow and blue light; Perhaps on purple light or ultraviolet light-emitting diode, apply three primary colors fluorescent powder and make white light emitting diode.Therefore adopt white light emitting diode fluorescent material of the present invention can make the electric light source of white light emitting diode.
The present invention obtains following technique effect:
1) materials chemistry performance of the present invention is stable, through bubble 48 hours, 100 ℃ of heat 10 hours, with in the air 120 ℃ be dried to water ratio less than after 5%, the luminosity fall of fluorescent material is less than 5%.Compare reported can by long wave ultraviolet light～blue light effectively excite (Sr, Mg) (Ga, Al) all there is unstable chemcial property in the fluorescent material of 2S4:Eu fluorescent material or SrS:Eu system, deliquescent deficiency.
2) the present invention is by doping techniques, and the matrix and the excitation center of fluorescent material is optimized.By in matrix, mixing Si, Gd, Zn plasma radius smaller elements, make the spacing of fluorescent material lattice reduce, interatomic distance shortens, thereby has improved the transmission effect of matrix to energy; By adopting the mode of coactivator, can reach the effect of sensitization by the transmission ofenergy between the activator element on the one hand simultaneously; On the other hand, owing to there are two or more luminescence center, thereby can improve the assimilated efficiency of fluorescent material to excitation energy, simultaneously can also improve the emissive porwer of fluorescent material emmission spectrum in long-wave band, promptly make and the excitation spectrum broadening of material of emmission spectrum of fluorescent material in 300～460nm scope, all have stimulation effect preferably.And the YAG:Ce fluorescent material of having reported at present only has two excitation peaks at 340nm and 460nm, therefore can not obtain very high assimilated efficiency to the ultraviolet ray of 380nm and the near-ultraviolet light of 400nm.And for example the specific absorption of the fluorescent material of Ln2O2S:Eu system in 380～400nm wave band is lower, causes luminous intensity not high.
3) because fluorescent material of the present invention adopts high temperature solid-state method to be prepared, under the situation that composition is determined, related controlled variable mainly is synthesis temperature and generated time, simultaneously, owing to adopted the two-step approach synthesis technique, and between the 3rd step and the 4th step, added mixed powder operation, thus can guarantee the reduction effect of excitation center in the homogeneity of powder matrix and the fluorescent material, and then guaranteed the stability of the luminescent properties of final fluorescent material.
4) compare (matrix is synthesized and reduction is once finished) with one-step synthesis process, the luminosity increase rate of synthetic fluorescent material reaches more than 10%.
5) in whole synthesis procedure, do not have the generation of toxicity waste liquid substantially, thereby guaranteed the present technique security, pollution-free.
6) in addition, simultaneously because the fluorescent material of washing is directly sent in the fluidized bed drying system dries with warm air, therefore avoided the problem of the powder unity that general oven drying technology occurs easily, its reason is to have avoided in the static drying course existence owing to water to cause the generation of " bridge formation " bonding.
Embodiment
1 one kinds of fluorescent powder for white LED of embodiment, structural formula is: AM
xAl
10O
17N (Al
2O
3): Eu
y, R
z, wherein: A is Ca, Sr, and a kind of among the Ba also can be two or more mixture, the proportioning of mixture can be any proportioning, and M is Zn, Gd, Ca, Hf, La, a kind of among the Si also can be two or more mixture, and the proportioning of mixture can be any proportioning, and R is Dy, Ce, Tb, a kind of among the Pr also can be two or more mixture, the proportioning of mixture can be any proportioning, 0.01＜X＜5, X can be 0.02,0.035,0.56,1.05,1.34,1.48,1.58,1.66,1.75,1.83,1.95,1.98,2,2.5,3,3.6,4,4.7,0.01＜y＜0.5, y can be 0.01,0.025,0.07,0.09,0.12,0.18,0.23,0.28,0.37,0.42,0.47,0.49,0.002≤z＜0.5, z can be 0.0023,0.041,0.25,0.33,0.45,0.48,0≤n＜3, n can be 0,0.5,0.8,1,1.5,2,2.5, AM
xAl
10O
17N (Al
2O
3) be matrix, Eu
y, R
zBe excitation center.
2 one kinds of manufacture method according to the fluorescent powder for white LED of embodiment 1 of embodiment comprise:
The first step is formed by the structural formula of fluorescent powder for white LED and to be taken by weighing raw material, and raw material is an elements A, M, Al, Eu, the simple substance of R, also can be A, M, Al, Eu, the oxide compound of R, also can be A, M, Al, Eu, the salt of R, A in the raw material, M, Al, Eu, proportioning is identical in the structural formula of R proportioning and fluorescent powder for white LED, and wherein A is Ca, Sr, at least a (if multiple, its proportioning can be any proportioning) among the Ba, M is Zn, Gd, Hf, La, at least a (if multiple among the Si, its proportioning can be any proportioning), R is Dy, Ce, Tb, at least a (if multiple, its proportioning can be any proportioning) among the Pr;
Second step, take by weighing 10～100% of above-mentioned raw materials mole number and (for example can be chosen for 15%, 30%, 38%, 52%, 66%, 78%, 85%, 99%) alkaline earth metal halide (for example can be chosen for calcium chloride, magnesium bromide), alkali metal halide (for example can be chosen for sodium-chlor, Potassium Bromide), the halogenide of aluminium (for example can be chosen for aluminum chloride, aluminum bromide), boric acid, boron oxide, the halogenide of ammonium (for example can be chosen for ammonium chloride, brometo de amonio), at least a in the oxalic acid as solubility promoter, and with raw material to put into the V-arrangement mixer be to mix under 100-400 rev/min 5～15 hours at rotating speed with the reaction solubility promoter, if the two or more mixture of solubility promoter, its proportioning can be any proportioning;
In the 3rd step, with said mixture roasting in air, maturing temperature is 600～1300 ℃, for example can be chosen for 650 ℃, 800 ℃, 940 ℃, 1100 ℃, 1230 ℃, roasting time is 0.5～10 hour, for example can be chosen for 0.5 hour, 1.8 hours, 2.8 hours, 4.3 hour, 6 hours, 8.3 hours, 9 hours, form initial powder mixture;
The 4th step, will above-mentioned initial powder mixture in reducing atmosphere, reduce calcining, the calcining temperature of reducing is 1200～1600 ℃, and the calcination time that reduces is 0.5～10 hour, and reducing atmosphere is N
2With H
2Mixed atmosphere, carbon dust atmosphere, pure H
2Among the atmosphere three any one is to form the calcining powder;
The 5th step, will calcine powder washing 2～5 times, oven dry obtains fluorescent powder for white LED, and oven dry is adopted in the fluidized bed drying system and is carried out, and is that 99.9% diameter is the Al of 5mm by high-pressure hot air with fluorescent material slurry and purity degree of depositing promptly
2O
3Ceramic Balls blows afloat in fluidized-bed and is violent rolling condition, has guaranteed the decentralized of powder by the mechanical force of Ceramic Balls, and best by the effect that fluorescent material is dried with warm air, and the effect of a conventional oven is relatively poor.
In the present embodiment, the initial powder mixture that above-mentioned the 3rd step is formed mixed roasting again in air then 5～15 hours under 100-400rpm, roasting condition is identical with the 3rd step, so, mixes powder and roasting and hockets, 1-3 time altogether, carry out FOUR EASY STEPS then.
The using method of 3 one kinds of fluorescent powder for white LED of embodiment covers fluorescent material of the present invention by cladding process on the chip of blue light, UV-light or near ultraviolet photodiode and makes electric light source.Making method is with common electrical light source manufacture method.
4 one kinds of fluorescent powder for white LED of embodiment, structural formula is: AM
xAl
10O
17N (Al
2O
3): Eu
y, R
z, wherein: A is Ca, Sr, and a kind of among the Ba also can be two or more mixture, the proportioning of mixture can be any proportioning, and M is Zn, Gd, Ca, Hf, La, a kind of among the Si also can be two or more mixture, and the proportioning of mixture can be any proportioning, and R is Dy, Ce, Tb, a kind of among the Pr also can be two or more mixture, the proportioning of mixture can be any proportioning, 0.01＜X＜5, X can be 0.02,0.035,0.56,1.05,1.34,1.48,1.58,1.66,1.75,1.83,1.95,1.98,2,2.5,3,3.6,4,4.7,0.01＜y＜0.5, y can be 0.01,0.025,0.07,0.09,0.12,0.18,0.23,0.28,0.37,0.42,0.47,0.49,0.002≤z＜0.5, z can be 0.0023,0.041,0.25,0.33,0.45,0.48,0≤n＜3, n can be 0,0.5,0.8,1,1.5,2,2.5.Its structure and luminescent properties shown in example in the table 17,8,9,10,11,12,13, can the making by the following method of this fluorescent powder for white LED, this method may further comprise the steps:
The first step is formed by the structural formula of fluorescent powder for white LED and to be taken by weighing raw material, and raw material is an elements A, M, Al, Eu, the simple substance of R, also can be A, M, Al, Eu, the oxide compound of R, also can be A, M, Al, Eu, the salt of R, A in the raw material, M, Al, Eu, proportioning is identical in the structural formula of R proportioning and fluorescent powder for white LED, and wherein A is Ca, Sr, at least a (if multiple, its proportioning can be any proportioning) among the Ba, M is Zn, Gd, Hf, La, at least a (if multiple among the Si, its proportioning can be any proportioning), R is Dy, Ce, Tb, at least a (if multiple, its proportioning can be any proportioning) among the Pr;
Second step, take by weighing 10～100% of above-mentioned raw materials mole number and (for example can be chosen for 15%, 30%, 38%, 52%, 66%, 78%, 85%, 99%) alkaline earth metal halide (for example can be chosen for calcium chloride, magnesium bromide), alkali metal halide (for example can be chosen for sodium-chlor, Potassium Bromide), the halogenide of aluminium (for example can be chosen for aluminum chloride, aluminum bromide), boric acid, boron oxide, the halogenide of ammonium (for example can be chosen for ammonium chloride, brometo de amonio), at least a in the oxalic acid as solubility promoter, and with raw material to put into the V-arrangement mixer be to mix under 100-400 rev/min 5～15 hours at rotating speed with the reaction solubility promoter, if the two or more mixture of solubility promoter, its proportioning can be any proportioning;
The 3rd the step, with said mixture in air roasting once, maturing temperature is 600～1300 ℃, for example can be chosen for 650 ℃, 800 ℃, 940 ℃, 1100 ℃, 1230 ℃, roasting time is 0.5～10 hour, for example can be chosen for 0.5 hour, 1.8 hours, 2.8 hours, 4.3 hour, 6 hours, 8.3 hours, 9 hours, form initial powder mixture;
The 4th step, will above-mentioned initial powder mixture in reducing atmosphere, reduce calcining, the calcining temperature of reducing is 1200～1600 ℃, and the calcination time that reduces is 0.5～10 hour, and reducing atmosphere is N
2With H
2Mixed atmosphere, carbon dust atmosphere, pure H
2Among the atmosphere three any one is to form the calcining powder;
The 5th step, will calcine powder washing 2～5 times, to filter, oven dry obtains fluorescent powder for white LED, and oven dry adopts the effect of drying with warm air in the fluidized bed drying system best, and the effect of a conventional oven is relatively poor.
In the present embodiment, the initial powder mixture that above-mentioned the 3rd step is formed mixed roasting again in air then 5～15 hours under 100-400rpm, roasting condition is identical with the 3rd step, so, mixes powder and roasting and hockets, 1-3 time altogether, carry out FOUR EASY STEPS then.
Embodiment 4 takes by weighing BaCO
33.97g, SiO
20.30g, Al
2O
310.2g, Eu
2O
30.14g, Dy
2O
30.04g, get BaF
23.46g as solubility promoter, above raw material is analytical pure, after above raw material is evenly mixed, after 2 hours, promptly obtain initial powder 1200 ℃ of roastings, again after mixing, with roasting 3h under 1350 ℃ of reductive conditions, the powder that roasting obtains is washed 120 ℃ of oven dry 3 times.Promptly get molecule and consist of BaSiO
5Al
10O
17: Eu
0.04, Dy
0.01Sample.
Embodiment 5 takes by weighing BaCO
33.94g, CaCO
30.40g, Al
2O
314.3g, Eu
2O
30.11g and Dy
2O
30.94g, get BaF
21.64g and NH
4Cl2.38 is as solubility promoter, and its manufacture method is identical with embodiment 1, and obtaining molecular composition is BaCa
0.2Al
14O
23: Eu
0.03Dy
0.025
Embodiment 6 is except that forming by the molecular formula of each embodiment in the table 1 and stoichiometry takes by weighing the raw material, and remaining making step is identical with embodiment, obtains molecular composition and luminous intensity sees Table 1, and its intensity is higher than comparative example.
Comparative example takes by weighing BaCO
33.94g, MgO 0.32g; Al
2O
310.2g, Eu
2O
30.14g, MnCO
30.03g, get BaF
22.13g as solubility promoter, its making method is identical with example 1, obtains ingredient and consists of BaMg
0.8Al
10O
17: Eu
0.04, Mn
0.015Sample.Its luminosity sees the following form, and its intensity is lower than each embodiment.
Table 1 molecular formula and illumination effect
| The embodiment of the invention | Molecular formula | Relative intensity (%) | |
| 460nm excites | 400nm excites | ||
| 1 | BaSiO 5Al 10O 17:Eu 0.04，Dy 0.01 | 118 | 139 |
| 2 | BaCa 0.2Al 14O 23:Eu 0.03，Dy 0.025 | 113 | 141 |
| 3 | Ba 2Ca 0.01Al 10O 17:Eu 0.03，Tb 0.02 | 106 | 109 |
| 4 | Ba 2Ca 0.01Gd 0.03Al 10O 17:Eu 0.02，Tb 0.02 | 120 | 134 |
| 5 | BaHf 0.20Si 0.03Al 10O 17:Eu 0.02，Tb 0.02 | 109 | 129 |
| 6 | SrZn 0.02Al 10O 17:Eu 0.07，Pr 0.02 | 104 | 129 |
| 7 | Sr 4Gd 0.06Al 11.5O 19.3:Eu 0.02，Pr 0.001 | 106 | 136 |
| 8 | Sr 4Gd 0.02Si 0.015Al 10O 17:Eu 0.03，Dy 0.04 | 118 | 140 |
| 9 | Sr 2Si 2La 0.06Al 14O 23:Eu 0.025，Tb 0.025 | 105 | 126 |
| 10 | Sr 4Gd 0.02Si 0.015Al 10O1 7:Eu 0.03，Dy 0.04 | 124 | 129 |
| 11 | Ca 5Zn 0.06Al 10O 17:Eu 0.05，Pr 0.03 | 126 | 146 |
| 12 | Ca 4Si 0.012Gd 0.024Al 14O 23:Eu 0.04，Dy 0.015 | 109 | 124 |
| 13 | Ca 2Si 0.012Gd 0.024Al 14O 23:Eu 0.04，Tb 0.015 | 113 | 121 |
| Comparative example | BaMg 0.8Al 10O 17:Eu 0.04，Mn 0.015 | 100 | 114 |
Claims (6)
1, a kind of fluorescent powder for white LED is characterized in that structural formula is: AM
xAl
10O
17N (Al
2O
3): Eu
y, R
z, wherein: A is Ca, Sr, and at least a among the Ba, M is Zn, Ca, Gd, Hf, La, at least a among the Si, R is Dy, Ce, Tb, at least a among the Pr, 0.01＜X＜5,0.01＜y＜0.5,0.002≤z＜0.5,0＜n＜3.
2, a kind of manufacture method of fluorescent powder for white LED according to claim 1 is characterized in that may further comprise the steps:
The first step is formed by the structural formula of fluorescent powder for white LED and to be taken by weighing raw material, and raw material is simple substance, oxide compound or the salt of elements A, M, Al, Eu, R, proportioning is identical in the structural formula of A, M in the raw material, Al, Eu, R proportioning and fluorescent powder for white LED, and wherein A is Ca, Sr, at least a among the Ba, M is Ca, Zn, Gd, Hf, La, at least a among the Si, R is Dy, Ce, Tb, at least a among the Pr
Second step, take by weighing at least a in the halogenide, oxalic acid of halogenide, boric acid, boron oxide, the ammonium of 10～100% alkaline earth metal halide, alkali metal halide, the aluminium of above-mentioned raw materials mole number, and be to mix under the 100-400rpm 5～15 hours with the reaction solubility promoter at rotating speed raw material as solubility promoter;
In the 3rd step, with said mixture roasting in air, maturing temperature is 600～1300 ℃, and roasting time is 0.5～10 hour, forms initial powder mixture;
The 4th step, will above-mentioned initial powder mixture in reducing atmosphere, reduce calcining, the reduction calcining temperature is 1200～1600 ℃, the reduction calcination time is 0.5～10 hour, calcines powder with formation;
The 5th step, will calcine powder and carry out aftertreatment, obtain fluorescent powder for white LED.
3, the manufacture method of fluorescent powder for white LED according to claim 2, the measure that it is characterized in that aftertreatment in the 5th step is sent into fluidized-bed and is dried with warm air for calcining powder washing 2～5 times.
4, the manufacture method of fluorescent powder for white LED according to claim 2 is characterized in that reducing atmosphere is N in the 4th step
2With H
2Mixed atmosphere, carbon dust atmosphere, pure H
2A kind of among the atmosphere three.
5, the manufacture method of fluorescent powder for white LED according to claim 2, it is characterized in that after the 3rd step, the initial powder mixture that forms was mixed under 100-400rpm 5～15 hours, roasting in air then, roasting condition is identical with the 3rd step, mix powder and roasting and hocket, 1-3 time altogether.
6, a kind of using method of fluorescent powder for white LED according to claim 1 is characterized in that a kind of and fluorescent powder for white LED in blue light, ultraviolet, the near ultraviolet light-emitting diode chip for backlight unit is made electric light source.
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| CN101824318A (en) * | 2010-04-27 | 2010-09-08 | 东北师范大学 | Cerium-doped dodecacalcium heptaluminate blue light emitting fluorescent powder and preparation method thereof |
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| CN1150296C (en) * | 2000-06-22 | 2004-05-19 | 大连路明科技集团有限公司 | Light-accumulation long-afterglow luminous material |
| US6809781B2 (en) * | 2002-09-24 | 2004-10-26 | General Electric Company | Phosphor blends and backlight sources for liquid crystal displays |
| US7077978B2 (en) * | 2004-05-14 | 2006-07-18 | General Electric Company | Phosphors containing oxides of alkaline-earth and group-IIIB metals and white-light sources incorporating same |
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