CN101760197B - Yellow fluorescent powder used by white light LED and preparation method thereof - Google Patents
Yellow fluorescent powder used by white light LED and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fluorescent powder used for a white light LED and a preparation method thereof. The chemical formula of the fluorescent powder is (A3-x) (Al5-2mBmCm) FnO12-n: xCe, wherein A is one or more of Y, Gd, La and Tb; B is one or more of Ti, Zr and V; C is one or two of Mn, Zn, Mg and Li; x is more than or equal to 0.03 and less than or equal to 0.1; m is more than or equal to 0.01 and less than or equal to 2; and n is more than or equal to 0 and less than or equal to 3x. The preparation method comprises the steps of coating a layer of high-temperature ceramic glaze material at the joint between a crucible cover and a crucible by using a high-temperature solid phase method and a self-pressurization sealing burning technique, putting the crucible into an atmosphere box type furnace to burn for 2 to 5 hours at 1450 to 1550 DEG C in the nitrogen atmosphere, smashing and screening after cooling so as to acquire the finished product of the fluorescent powder. The fluorescent powder of the invention has high radiance. The method of the invention can efficiently lower the burning temperature of the fluorescent powder and increase the relative brightness.
Description
Technical field
The present invention relates to a kind of phosphor for white light LED and preparation method thereof.This fluorescent material can be effectively by blue-light excited, is combined with blue chip and can makes white light LEDs.
Background technology
In recent years, 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.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), the low voltage low current starts the life-span long (more than 1000 hours), speed of response fast (can at high-frequency operation) but and planar package be developed to advantages such as frivolous skilful miscellaneous goods easily.Oneself is through being used as Backlight For Liquid Crystal Display Panels, pilot lamp, general lighting.
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.Yellow fluorescent powder is the important component part of white light LEDs because blue-ray LED excites down efficiently, so blue-light excited luminescent material is significant.Therefore people are carrying out number of research projects aspect the development blue-ray LED excited fluorescent body, and constantly have patent open in succession.United States Patent (USP) 5998925 discloses a kind of blue-light excited yellow fluorescent powder, and 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, lack ruddiness in its emission wavelength and can't obtain the white light LEDs of warm white and high-color rendering.Beijing Non-Ferrous Metal Research General Academy and Grirem Advance Materials Co., Ltd have applied for Chinese patent CN101182416, its chemical constitution chemical formula be LnaMb (0, F)
12: (R
3+, M
2+) X.Wherein, Ln is at least a among Sc, Y, La, Pr, Nd, Gd, Ho, Yb and the Sm, 2.6≤a≤3.4, M is at least a among B, Al and the Ga, 4.5≤b≤5.5, and R is at least a among Ce and the Tb, M ' is Ca, Sr, Ba, and is at least a among Mn and the Zn, 0.001≤x≤O.4.In garnet structure, use F ion substitution O ion, and introduced the divalent metal ion.China CN1861745N a kind of fluorescent material is disclosed, its chemical constitution formula be (Y, Gd)
3A1
5-X(Mg, Si) xO
12: Ce (x=o～3), in garnet structure, introduce Mg and Si ion, its emission wavelength is moved to long wave.China CN101260301 discloses a kind of fluorescent material, and its chemical constitution is: Σ (Ln)
3A1
5-xLi
(x+y)Mg
(x+y)0
12-3yN
3y, atomic fraction is Σ Ln=L (Y+Gd+Ce+Dy+Pr)=1, when this fluorescent material by the-orange subband radiation of visible light of launching λ=538-569nm wavelength when short wavelength light that the InGaN semi-conductor is sent excites.
Introduce a small amount of Ti, Zr among the present invention in the YAG structure, V, Mn, Zn, Mg, Li and alkali earth metal substitute for Al are introduced part F simultaneously and are substituted 0.The introducing of these ions has changed lattice parameter and the crystal potential field of yttrium aluminum garnet, makes the light of its emission different wave length, and these are all different with above-mentioned patent.And the present invention proposes the making method of this kind fluorescent material, gordian technique is to adopt the pressure seal calcination process, and this method is not all mentioned in above-mentioned patent.
Summary of the invention
The object of the invention provides a kind of blue-light excited phosphor for white light LED, introduces a small amount of Ti, Zr, Mn, Zn and alkali earth metal and substitute A1 in the YAG crystal, introduces part F simultaneously and substitutes 0.Can adjust position and the optical parametric thereof of fluorescent material emission peak by the ratio of adjusting Ti, Zr, Mn, Zn, Al and alkaline-earth metal and fluorine, the phosphor of high brightness that different application requires is satisfied in preparation.
Another object of the present invention provides a kind of making method of fluorescent material, in the making processes of fluorescent material, adopt 3 valency Ce, and adopt the mode of forvacuum-inflated with nitrogen that raw material is handled, do not need reducing atmosphere during calcining, directly synthetic target product in high pure nitrogen; Adopt sealing pressurization calcination process simultaneously in calcination, namely apply one deck pyroceramic glaze between crucible and crucible cover, in high temperature (about 1300 ℃), the ceramic glaze fusion seals crucible and crucible cover naturally.Compare traditional method, make and effectively to reduce firing temperature 50-100 ℃ in this way, do not need to use hydrogen that reducing atmosphere is provided, solved the safety issue of producing, reduce the requirement to equipment, and can effectively improve the photoluminescence intensity of fluorescent material.
The present invention relates to a kind of phosphor for white light LED and preparation method thereof.
The chemical constitution general formula of related fluorescent material is: (A
3-x) (A1
5-2mB
mC
m) F
n0
12-n: xCe.Wherein A is one or several of Y, Gd, La, Tb, and B is one or more among Ti, Zr, the V, and C is a kind of among Mn, Zn, Mg, the Li or two kinds.Wherein O.03≤x≤0.1,0.01≤m≤2,0≤n≤3x.
Related making method:
The raw material that preparation method of the present invention adopts is Y
20
3, Gd
20
3, La
20
3, Tb
20
3, A1
20
3, ZnO, MnO, MgO, Ti0
2, Zr0
2, V
20
5, CeF
3Perhaps corresponding oxyhydroxide, carbonate, oxalate etc.
In fusing assistant boric acid, Neutral ammonium fluoride, lithium fluoride, aluminum fluoride, the barium fluoride one or more.
Concrete making method is as follows:
1, detect particle diameter and the distribution of various raw materials, the flow of feed gas that particle diameter is bigger be crushed to about 2 scholars of median size O.5um about.
2, according to the chemical ingredients ratio of the chemical formula of above-mentioned fluorescent material, accurately raw materials weighing is carried out pre-mixing.The total amount that adds fusing assistant be described fluorescent material chemical constitution formula mole number 1～10%.Generally with BaF
2As fusing assistant.
2, placed the ball grinder ball milling 2-5 hour.
3, taking out raw material is placed in the crucible, material accounts for about 2/3 of crucible volume, after finishing crucible is added a cover, at crucible cover and crucible junction coating one deck pyroceramic glaze, the amount of fill of glaze is standard with the groove at crucible edge, groove is loaded full getting final product, and the compositional system of glaze is (Li
20, Na
20, MgO, CaO) Si0
2
4, put into vacuum drying oven and vacuumize processing, charge into nitrogen afterwards as shielding gas.
5, the crucible of handling well being put into chamber type electric resistance furnace high temperature synthesizes; speed according to 10 ℃/min is warming up to thermostat temperature; in 1400～1550 ℃ of following calcinations 2～5 hours; be cooled to back below 100 ℃ then and take out, feed high pure nitrogen in the whole process as shielding gas (nitrogen gas purity is greater than 99.99%).
6, adopt the method for cut mechanically, crucible cover is separated with crucible, and further in crucible marginal position machined grooves, recycle after the processing.
7, the block powder fragmentation that will take out, ball milling is to the particle diameter that needs then, the average particle diameter reaches 6-8um, crosses 400 order wet screenings then after overpickling, hot-water soak, washing, and centrifugal back obtains finished product fluorescent material after the oven dry down in 150 ℃ in vacuum drying oven.
The fluor that the present invention obtains is in blue-light excited very strong gold-tinted or the yellow-green light of emission down.It can satisfy the application of white light LEDs preferably, applies this fluorescent powder at blue-light LED chip and can obtain white light; The invention provides simultaneously the preparation this fluor the preparation method, its step and condition are simple, the sealing pressurization calcination process introduced of the present invention particularly, can effectively reduce the firing temperature of fluorescent material, from being down to more than 1550 ℃ below 1500 ℃, compare the synthetic method of conventional high-temperature, the fluorescent material relative brightness has improved 10-20%.The present invention does not use hazardous gases such as hydrogen that reducing atmosphere is provided, and has solved safety problem in the making processes, and reduced the requirement to high temperature service simultaneously, and then cut down the consumption of energy and cost, and easy handling.
Embodiment
Illustrate: the related fluorescent material component of following example is as shown in table 1.
Following example 1-4 adopts diverse ways to make, the difference of the fluorescent material performance that the method for pointing out in the sign patent and traditional method are made.
Example 1
Fluorescent material consist of Y
2.94Al
5(0, F)
12: 0.06Ce, making method is as follows: accurately take by weighing raw material Y
20
366.39g, A1
20
350.98g, Ce0
22.01g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, be divided into 2 parts after material is taken out, put into 2 alumina crucibles respectively, a crucible is not added a cover (sample number into spectrum Y1-1), and an other crucible is added a cover (sample number into spectrum Yl-2), puts into the calcination of atmosphere box-type furnace then simultaneously, be incubated 4h down at 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance NH that feeds of whole calcination process
3Divide (the 75%H that vents one's spleen
2+ 25%N
2).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, and numbering is respectively Y1-1 and Y1-2.
Example 2
Fluorescent material consist of Y
2.94Al
5(0, F)
12: 0.06Ce, making method is as follows: accurately take by weighing raw material Y
20
366.39g, A1
20
350.98g, CeF
32.37g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, and crucible is added a cover but is not used the ceramic glaze sealing, puts into the calcination of atmosphere box-type furnace, be incubated 4h down at 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance NH that feeds of whole calcination process
3Divide (the 75%H that vents one's spleen
2+ 25%N
2).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y2.
Example 3
Fluorescent material consist of Y
2.94Al
5(0, F)
12: 0.06Ce, making method is as follows: accurately take by weighing raw material Y
20
366.39g, A1
20
350.98g, CeF
32.37g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down at 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, ball milling to median size reaches 8.0 scholar 0.5um after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y3.
Example 4
Fluorescent material consist of Y
2.94Al
5(0, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
350.98g, CeF
33.15g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down at 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, ball milling to median size reaches 8.0 scholar 0.5um after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y4.
Example 1-4 shows the luminous that adopts the method that proposes in the present patent application can effectively improve fluorescent material
Can, so following example all adopts this method to make fluorescent material.Example 5-7 adopts V, Li to replace part A l.
Example 5
Fluorescent material consist of Y
2.92Al
4.9Li
0.05V
0.05(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
349.96g, CeF
33.15g, Li
2C0
30.37g, V
20
50.91g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um the broken liquor-saturated back of machinery ball milling to median size reaches 8.0 scholars, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y5.
Example 6
Fluorescent material consist of Y
2.92Al
4.8Li
0.1V
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
348.94g, CeF
33.15g, Li
2C0
30.74g, V
20
51.82g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards and carry out the vacuum nitrogen filling gas disposal, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um the broken liquor-saturated back of machinery ball milling to median size reaches 8.0 scholars, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y6.
Example 7
Fluorescent material consist of Y
2.92Al
4.4Li
0.3V
0.3(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
344.86g, CeF
33.15g, Li
2C0
32.22g, V
20
55.46g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the atmosphere box-type furnace after disposing and calcine, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um the broken liquor-saturated back of machinery ball milling to median size reaches 8.0 scholars, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y7.
Example 8-11 adopts the method that proposes in the present patent application to make, and uses Mg, Zn, Mn, and Ti, Zr replace part A 1.
Embodiment 8
Fluorescent material consist of Y
2.92Al
4.8Zn
0.1Ti
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
348.94g, CeF
33.15g, ZnO1.63g, Ti0
21.60g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y8.
Example 9
Fluorescent material consist of Y
2.92Al
4.8Mn
0.1Ti
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
348.94g, CeF
33.15g, MnO1.42g, Ti0
21.60g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y9.
Example 10
Fluorescent material consist of Y
2.92Al
4.8Mg
0.1Ti
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
348.94g, CeF
33.15g, MgO0.81g, Ti0
21.60g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, tear is closed uniform material pack in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y10.
Example 11
Fluorescent material consist of Y
2.92Al
4.8Mg
0.1Zr
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
365.94g, A1
20
348.94g, CeF
33.15g, MgO0.81g, Zr0
22.46g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at edge is collapsed in the Pu, fill ceramic glaze, put into vacuum drying oven afterwards and carry out the vacuum nitrogen filling gas disposal, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation naturally cools to room temperature after finishing, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y11.
Example 12-15 adopts the method that proposes in the present patent application to make, and on the basis of example 10 components prescription, uses Gd, La, Tb to replace part Y.
Example 12
Fluorescent material consist of Y
2.82Gd
0.1A1
4.8Mg
0.1Ti
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
363.68g, Gd
20
33.63g, A1
20
348.94g, CeF
33.15g, MgO0.81g, Ti0
21.60g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation so is cooled to room temperature after finishing in vain, the omnidistance feeding of whole calcination process high-purity N 2 (purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y12.
Example 13
Fluorescent material consist of Y
2.82Gd
0.3A1
4.8Mg
0.1Ti
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
359.16g, Gd
20
310.88g, A1
20
348.94g, CeF
33.15g, MgO0.81g, Ti0
21.60g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation so is cooled to room temperature after finishing in vain, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y13.
Example 14
Fluorescent material consist of Y
2.62La
0.3A1
4.8Mg
0.1Ti
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
363.68g, La
20
39.77g, A1
20
348.94g, CeF
33.15g, MgO0.81g, Ti0
21.60g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards to vacuumize-the inflated with nitrogen processing, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation so is cooled to room temperature after finishing in vain, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y14.
Example 15
Fluorescent material consist of Y
2.62Tb
0.3A1
4.8Mg
0.1Ti
0.1(O, F)
12: 0.08Ce, making method is as follows: accurately take by weighing raw material Y
20
363.68g, La
20
310.98g, A1
20
348.94g, CeF
33.15g, MgO0.81g, Ti0
21.60g, BaF
23.51g, above-mentioned raw materials is carried out pre-mixing, put into 500ml ball grinder ball milling then 3 hours, the material that mixes is packed in the alumina crucible, crucible is added a cover, in the groove at crucible edge, fill ceramic glaze, put into vacuum drying oven afterwards and carry out the vacuum nitrogen filling gas disposal, put into the calcination of atmosphere box-type furnace after disposing, be incubated 4h down in 1500 ℃, the about 10 ℃/min of heat-up rate, insulation so is cooled to room temperature after finishing in vain, the omnidistance high-purity N that feeds of whole calcination process
2(purity〉99.99%).After the cooling block powder is taken out, O.5um ball milling to median size reaches 8.0 scholars after the Mechanical Crushing, to remove impurity, crosses 400 order wet screenings through 80 ℃ of hot-water soaks afterwards, and the oven dry of centrifugal back obtains the fluorescent material finished product, is numbered Y15.
The corresponding component table of each example of table 1 yellow fluorescent powder
| Sequence number | Component | Example | Sample number into spectrum |
| 1 | Y 2.94Al 5(0，F) 12:0.06Ce | Example 1 | Y1-1,Yl-2 |
| 2 | Y 2.94Al 5(0，F) 12:0.06Ce | Example 2 | Y2 |
| 3 | Y 2.94Al 5(0，F) 12:0.06Ce | Example 3 | Y3 |
| 4 | Y 2.92Al 5(0，F) 12:0.08Ce | Example 4 | Y4 |
| ? | ? | ? | ? |
| 5 | Y 2.92Al 4.9Li 0.05V 0.05(O，F) 12:0.08Ce | Example 4 | Y5 |
| 6 | Y 2.92Al 4.8Li 0.1V 0.1(O，F) 12:0.08Ce | Example 5 | Y6 |
| 7 | Y 2.92Al 4.4Li 0.3V 0.3(O，F) 12:0.08Ce | Example 6 | Y7 |
| ? | ? | ? | ? |
| 8 | Y 2.92Al 4.8Zn 0.1Ti 0.1(O，F) 12:0.08Ce | Example 7 | Y8 |
| 9 | Y 2.92Al 4.8Mn 0.1Ti 0.1(O，F) 12:0.08Ce | Example 8 | Y9 |
| 10 | Y 2.92Al 4.8Mg 0.1Ti 0.1(O，F) 12:0.08Ce | Example 9 | Y10 |
| 11 | Y 2.92Al 4.8Mg 0.1Zr 0.1(O，F) 12:0.08Ce | Example 10 | Y11 |
| ? | ? | ? | ? |
| 12 | Y 2.82Gd 0.1A1 4.8Mg 0.1Ti 0.1(O，F) 12:0.08Ce | Example 11 | Y12 |
| 13 | Y 2.62Gd 0.3A1 4.8Mg 0.1Ti 0.1(O，F) 12:0.08Ce | Example 12 | Y13 |
| 14 | Y 2.62La 0.3A1 4.8Mg 0.1Ti 0.1(O，F) 12:0.08Ce | Example 13 | Y14 |
| 15 | Y 2.62Tb 0.3A1 4.8Mg 0.1Ti 0.1(O，F) 12:0.08Ce | Example 14 | Y15 |
Fig. 1 is the exciting light spectrogram of example 4 counter sample Y4.Because crystalline structure is YAG, trace doped its excitation peak position that do not change, all samples exciting light spectrogram is basic identical, so the exciting light spectrogram of employing Y4 is as representative.
Difference when this figure of Fig. 2 is intended to employing is described without manufacture craft between the luminescent properties of fluorescent material, corresponding example 1 of the present invention, example 2, example 3 and example 4.Example 1 and example 2 adopt traditional method to make, and example 3 and example 4 adopt the method for describing among the present invention to make, and concrete manufacture craft flow process such as invention example are described.Sample Y1-1 and Y1-2 corresponding instance 1, Y2 corresponding instance 2, Y3 corresponding instance 3, Y4 corresponding instance 4 as seen from the figure, adopt manufactured samples Y4 of the present invention to have the highest luminous intensity.When characterizing the fluorescent material performance afterwards with Y4 as reference.
This figure of Fig. 3 is intended to illustrate the light-emitting phosphor changes of properties of using V and Li to replace part A l.Sample Y5 corresponding instance 5, Y6 corresponding instance 6, Y7 corresponding instance 7.As seen from the figure, Y6 has the highest luminous intensity, shows to use V, Li to replace the luminous intensity that part A l can effectively improve fluorescent material simultaneously.
This figure of Fig. 4 is intended to explanation and uses Ti, Zr, Mg, Zn, light-emitting phosphor changes of properties when Mn replaces Al.As seen from the figure, Y10 has the highest luminous intensity, shows Ti, and the luminescent properties of fluorescent material was best when Mg replaced Al, and Zr, Mg replace the luminous intensity that Al also can significantly strengthen fluorescent material simultaneously, and be good but effect does not have Ti, Mg to replace Al simultaneously.
This figure of Fig. 5 is intended to illustrate light-emitting phosphor changes of properties when elements such as using Gd, La, Tb replace Y, and Y12 sample luminous intensity is the highest as seen from the figure, and Y15 sample emission peak predominant wavelength is the longest, but relative brightness is low slightly than Y12.
This figure of Fig. 6 is the structural map of extraordinary crucible, and a is that crucible, b are crucible cover.
Claims (2)
1. Yellow fluorescent powder used by white light LED, its chemical formula is: (A
3-x) (A1
5-2mB
mC
m) F
n0
12-n: xCe; Wherein A is one or several of Y, Gd, La, Tb, and B is one or more among Ti, Zr, the V, and C is a kind of among Mn, Zn, Mg, the Li or two kinds; Ce wherein adopts trivalent Ce; Wherein O.03≤x≤O.1, O.01≤m≤2,0＜n≤3x.
2. the preparation method of a kind of Yellow fluorescent powder used by white light LED according to claim 1, in the making processes of fluorescent material, adopt trivalent Ce, and adopt the mode of forvacuum-inflated with nitrogen that raw material is handled, do not need reducing atmosphere during calcining, directly synthetic target product in high pure nitrogen; Adopt sealing pressurization calcination process simultaneously in calcination, namely apply one deck pyroceramic glaze between crucible and crucible cover, in 1300 ℃ of high temperature, the ceramic glaze fusion seals crucible and crucible cover naturally; Concrete making method is as follows:
A) particle diameter and the distribution of the various raw materials of detection, O.5um the flow of feed gas that particle diameter is bigger is crushed to median size 2 scholars;
B) according to the chemical ingredients ratio of the chemical formula of fluorescent material, accurately raw materials weighing is carried out pre-mixing, the total amount that adds fusing assistant be described fluorescent material chemical constitution formula mole number 1～10%, with BaF
2As fusing assistant;
C) placed the ball grinder ball milling 2-5 hour;
D) taking out raw material is placed in the crucible, material accounts for about 2/3 of crucible volume, after finishing crucible is added a cover, at crucible cover and crucible junction coating one deck pyroceramic glaze, the amount of fill of glaze is standard with the groove at crucible edge, groove is loaded full getting final product, and the compositional system of glaze is (Li
20, Na
20, MgO, CaO) Si0
2
E) put into vacuum drying oven and vacuumize processing, charge into nitrogen afterwards as shielding gas;
F) crucible of handling well being put into chamber type electric resistance furnace high temperature synthesizes, speed according to 10 ℃/min is warming up to thermostat temperature, in 1400～1550 ℃ of following calcinations 2～5 hours, being cooled to back below 100 ℃ then takes out, feed high pure nitrogen in the whole process as shielding gas, nitrogen gas purity is greater than 99.99%;
G) method of employing cut mechanically is separated crucible cover, and further in crucible marginal position machined grooves, is recycled after the processing with crucible;
H) the block powder fragmentation that will take out, ball milling is to the particle diameter that needs then, the average particle diameter reaches 6-8um, crosses 400 order wet screenings then after overpickling, hot-water soak, washing, and centrifugal back obtains finished product fluorescent material after the oven dry down in 150 ℃ in vacuum drying oven.
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| US8529791B2 (en) * | 2006-10-20 | 2013-09-10 | Intematix Corporation | Green-emitting, garnet-based phosphors in general and backlighting applications |
| CN102173771A (en) * | 2010-11-29 | 2011-09-07 | 天津理工大学 | Method for preparing yttrium and aluminum garnet luminous ceramic body for white light light-emitting diode (LED) |
| CN102206488B (en) * | 2011-03-29 | 2014-04-09 | 李�瑞 | Blue fluorescent powder used for white light LEDs and its preparation method |
| EP2730637B1 (en) * | 2011-07-05 | 2017-06-14 | Panasonic Corporation | Rare-earth aluminum garnet type fluorescent substance and light-emitting device obtained using same |
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| CN102936497B (en) * | 2012-11-08 | 2014-12-31 | 广州有色金属研究院 | Main emission peak changeable and adjustable fluorescent material and preparation method thereof |
| CN104342156B (en) * | 2013-07-30 | 2016-08-10 | 宁波升谱光电股份有限公司 | A kind of fluorescent material and preparation method thereof and the luminescent device containing this fluorescent material |
| DE102013109313A1 (en) * | 2013-08-28 | 2015-03-05 | Leuchtstoffwerk Breitungen Gmbh | Improved garnet phosphor and process for its preparation |
| US9335011B2 (en) * | 2014-07-02 | 2016-05-10 | General Electric Company | Oxyfluoride phosphor compositions and lighting apparatus thereof |
| CN109135751A (en) * | 2018-09-14 | 2019-01-04 | 赣南师范大学 | A kind of LED light fluorescent powder and preparation method thereof being stimulated by blue light |
| CN109233835A (en) * | 2018-09-18 | 2019-01-18 | 江苏锐阳照明电器设备有限公司 | A kind of LED light fluorescent powder and preparation method thereof can be reduced the reaction time |
| CN114806577A (en) * | 2021-01-22 | 2022-07-29 | 中强光电股份有限公司 | Wavelength conversion material, method for producing same, wavelength conversion device, and projection device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998925A (en) * | 1996-07-29 | 1999-12-07 | Nichia Kagaku Kogyo Kabushiki Kaisha | Light emitting device having a nitride compound semiconductor and a phosphor containing a garnet fluorescent material |
| CN101182416A (en) * | 2006-11-13 | 2008-05-21 | 北京有色金属研究总院 | Aluminate phosphor containing divalent metal element as well as manufacturing method and luminescent device |
-
2009
- 2009-10-27 CN CN2009101803980A patent/CN101760197B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998925A (en) * | 1996-07-29 | 1999-12-07 | Nichia Kagaku Kogyo Kabushiki Kaisha | Light emitting device having a nitride compound semiconductor and a phosphor containing a garnet fluorescent material |
| CN101182416A (en) * | 2006-11-13 | 2008-05-21 | 北京有色金属研究总院 | Aluminate phosphor containing divalent metal element as well as manufacturing method and luminescent device |
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