CN102286281A - Aluminate-based red fluorescent material and preparation method thereof - Google Patents
Aluminate-based red fluorescent material and preparation method thereof Download PDFInfo
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- CN102286281A CN102286281A CN2011102803078A CN201110280307A CN102286281A CN 102286281 A CN102286281 A CN 102286281A CN 2011102803078 A CN2011102803078 A CN 2011102803078A CN 201110280307 A CN201110280307 A CN 201110280307A CN 102286281 A CN102286281 A CN 102286281A
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Abstract
The invention discloses an aluminate-based red fluorescent material and a preparation method thereof. The component of the aluminate-based red fluorescent material is expressed as the following general formula: Sr4-x-y-zMzAlp-m-n-qO25:Mnm, Fen, Clx, Pby, Bq. The preparation method comprises the following steps: mixing all raw materials based on a certain proportion, then crushing and uniformly mixing to obtain a mixed material; then adding a fluxing agent AlF3 or H3BO3; calcining at air or oxidizing atmosphere of 1150-1400 DEG C for 2-8h; and then crushing to the grain size of 3-60mum after cooling to obtain a finished product. The fluorescent material provided by the invention emits red light under ultraviolet light, near ultraviolet light and blue light, thus, the color rendering index of the traditional white light LED (Light Emitting Diode) can be effectively increased. The light-emitting material related to the invention has the advantages of wide excitation wavelength coverage, wide red emitting color range, high brightness, simple and safe preparation method, no pollution, low cost and the like.
Description
One, technical field
The present invention relates to a kind of fluorescent material and preparation method thereof, specifically a kind of aluminate-base red fluorescence material and preparation method thereof.
Two, background technology
Because advantages such as LED have that volume is little, energy-saving and environmental protection, thermal value are low, low current low voltage, life-span are long, white light LEDs more and more is subjected to people's attention as lighting source of new generation.The white light LEDs implementation method that is most widely used in the market is to excite the gold-tinted of YAG:Ce fluorescent material emission and the blue light that is not absorbed fully to be combined into white light with blue chip.As everyone knows, the emission band of this white light LEDs is narrower, and lacks red part in its luminescent spectrum, causes its colour rendering index on the low side, and colour temperature is higher, is difficult to reach the ideal illuminating effect, is not suitable for being used in the demanding occasion of color developing.
For addressing this problem, more effective solution has two kinds: a kind of method is to excite the red-green-blue luminescent material to produce white light with the ultraviolet LED chip; Another kind method is to excite green, red illuminating material with blue-light LED chip, green glow that produces through exciting and ruddiness and the blue light that is not absorbed fully by luminescent material are combined into white light LEDs, can effectively solve like this and lack red wave band in the spectrum and cause LED colour rendering index problem on the low side [Zhang Zhongtai, Junying ZHANG. inorganic embedded photoluminescent material and application. the .2005 of Chemical Industry Press, 3:189].But above-mentioned two kinds of solutions all need be added the material that can produce red emission.At present, widespread use, can be mainly by the red illuminating material that ultraviolet or blue light effectively excite and mix Eu
3+Or Eu
2+Activated luminescent material [Materials Chemistry and Physics.2001,71,179; Mater.Res.Bull, 1996,31,1355.], the red emission peak of this class luminescent material is many in 600nm～630nm scope, and all is narrow emission peak, the rare earths material costliness, limited its application [Phosphor Handbook, CRC Press, 2006 in white light LEDs; Practical Applications of Phosphors, CRC Press, 2006] [Journal of Physics and Chemistry of Solids 61 (12), 2001-2006 (2000) .].Eu wherein
2+Activated nitride or oxynitride not only use rare earth, and synthesis technique complexity, production cost are higher.
Three, summary of the invention
The present invention is for fear of above-mentioned existing in prior technology weak point, aim to provide a kind of color developing height, aluminate-base red fluorescence material that cost is low and preparation method thereof, red fluorescence material of the present invention does not contain rare earth element, the raw material cheapness, the preparation method is simple, can effectively be excited by UV-light and blue light simultaneously.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of aluminate-base red fluorescence material of the present invention are that its composition expressed by following general formula (1):
Sr
4-x-y-zM
zAl
p-m-n-qO
25:Mn
m，Fe
n，Cl
x，Pb
y，B
q……………………(1)
M, n, x, y, z, p, q are each element shared atomic molar per-cent in material component in the general formula (1), 0＜m≤0.2,0≤n≤0.2,13≤p≤15,0≤x≤1,0≤y≤1,0≤z≤1,0≤q≤3; M is one or more among Ca, the Mg.
The preparation method's of aluminate-base red fluorescence material of the present invention characteristics are to operate according to the following steps: oxide compound, carbonate, oxalate, acetate, oxyhydroxide or muriate with Sr, Ca, Mg, Al, Mn, Fe, B and Pb are raw material, can not form compound except, by proportional quantity pulverize and mix compound, add the fusing assistant AlF of mixture quality 0.1-5% then
3Or H
3BO
3, in air atmosphere or oxidizing atmosphere, calcined 2-8 hour down in 1150-1400 ℃, be crushed to particle diameter 3-60 μ m after the cooling and get product.
Described proportional quantity is the amount that takes by weighing after measuring in the ratio of composition shown in the general formula (1) and qualification thereof.
With respect to the rare earths material of costliness, the Mn among the present invention
4+The activated luminescent material is cheap, and near the scarlet red light district of emission peak 650nm, with Eu
2+/ Eu
3+Adulterated LED luminescent powder (460-620nm) is compared, and this luminescent powder has been expanded the spectral range of white light LEDs, makes it more near sunlight, can be used to develop the white LED light source that has than high-color rendering.And Mn
4+In air atmosphere or weak oxide atmosphere, can obtain, not need reducing atmosphere, therefore greatly reduce requirement and cost, also improve the security in the production process production unit.In the present invention, also mix auxiliary activators such as a spot of Fe, Cl, Pb, increased substantially luminous intensity.
With respect to application number 200810218742.6 the related luminescent material principal phase CaAl of patent of invention
12O
19: Mn
4+, synthetic matrix of materials principal phase of the present invention is Sr
4Al
14O
25, and the synthetic method that adopts also has a great difference, and in addition, the present invention has increased auxiliary activator ions such as Fe, Cl, Pb, can significantly improve Mn
4+Luminosity.And the material of the application number generation scarlet emission that to be 201010550332.9 patent related is a Mn doping germanic acid magnesium, Mg
4GeO
6: Mn, the aluminate based luminescent material mentioned with the present invention has different greatly.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the emission band of red fluorescence material of the present invention is between 625-700nm, and peak-peak has the ideal scarlet near 652nm.
2, red fluorescence material of the present invention can effectively be excited at the 300-500nm wave band, can mate with ultraviolet chip or blue chip preferably.
3, used fusing assistant is AlF in the preparation process of the present invention
3Or H
3BO
3, wherein with AlF
3The luminescent material hardness that obtains for fusing assistant is lower, be easy to pulverize and the grain graininess that obtains even.
Can obviously reduce the hardness of calcining back fluorescent material when 4, the present invention uses the oxalate of Sr, Ca, Mg, Al, Mn, Fe, B and Pb, muriate, oxide compound or carbonate that acetate partly or entirely replaces above-mentioned element as raw material.
5, the present invention does not contain precious metal raw materials such as rare earth, and does not need reducing atmosphere, the raw material cheapness, preparation technology is low for equipment requirements, safe, have market potential using value and higher competitive power, help realizing the large-scale application of White LED with high color rendering property.
Four, description of drawings
Fig. 1 is the excitation spectrum of the red fluorescence material of the embodiment of the invention 4 preparations.The excitation peak of fluorescent material of the present invention belongs to broadband excitation between 250-500nm as can be seen from Figure 1, and promptly ultraviolet and visible waveband all can excite.
Fig. 2 is the emmission spectrum of red fluorescence material under ultraviolet excitation of the embodiment of the invention 4 preparations.As shown in Figure 2, the transmitting boundary of fluorescent material of the present invention is the broad peak between the 630-690nm, has comprised a peak position and has been positioned at the wire peak of 651nm and peak position and is positioned near the 665nm acromion.
Fig. 3 is the emmission spectrum of red fluorescence material under blue light (460nm) excites of the embodiment of the invention 4 preparations.As shown in Figure 3, matrix doped with Mg
2+After, exciting down at 460nm, considerable change does not take place in emission peak peak position and peak shape.
Fig. 4 is the excitation spectrum of the red fluorescence material of the embodiment of the invention 6 preparations.As shown in Figure 4, behind the matrix doped F e ion, considerable change does not all take place in the excitation spectrum peak position and the peak shape of sample, promptly still can effectively be excited by the 250-500nm wave band.
Fig. 5 is the emmission spectrum of red fluorescence material under ultraviolet excitation of the embodiment of the invention 6 preparations.As shown in Figure 5, behind the doped F e ion, under the 360nm ultraviolet excitation, sample can produce bright scarlet (630-690nm) emission.
Fig. 6 is the emmission spectrum of red fluorescence material under blue-light excited of the embodiment of the invention 6 preparation.As shown in Figure 6, behind the doped F e ion, under the 460nm excited by visible light, sample can produce bright scarlet (630-690nm) emission.
Five, embodiment
The invention will be further described below in conjunction with drawings and Examples, and non-limiting examples is as follows.
Embodiment 1:
The chemical formula of the red fluorescence material of present embodiment preparation is: Sr
4Al
13.98O
25: Mn
0.01
Take by weighing SrCO
31.570g, Al
2O
31.844g, MnCO
30.006g and AlF
33H
2O 0.089g puts into the agate mortar grinding and makes it the even compound that gets of thorough mixing, then compound is put into corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 3h, temperature rise rate is 2-10 ℃/min, keep air atmosphere or weak oxide atmosphere in the whole process, insulation finishes postcooling to room temperature, grinds after the taking-up and obtains the luminescent material finished product.
Embodiment 2:
The chemical formula of the red fluorescence material of present embodiment preparation is: Sr
4Al
14.14O
25: Mn
0.07
Take by weighing SrCO
31.586g, Al
2O
31.917g, MnCO
30.012g and H
3BO
3Make it the even compound that gets of thorough mixing 0.181g put into the agate mortar grinding, then compound is put into corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 3h, temperature rise rate is 2-10 ℃/min, keep air atmosphere or weak oxide atmosphere in the whole process, insulation finishes postcooling to room temperature.Grind after the taking-up and obtain the luminescent material finished product.
Embodiment 3:
The chemical formula of the red fluorescence material of present embodiment preparation is: Sr
3.93Ca
0.07Al
13.74O
25: Mn
0.07
Take by weighing SrCO
31.586g, CaCO
30.02g, Al
2O
31.917g, MnCO
30.004g and H
3BO
3Make it the even compound that gets of thorough mixing 0.089g put into the agate mortar grinding, then compound is put into corundum crucible, in tube type resistance furnace, calcine, at 1000 ℃ of insulation 5h postcooling, take out and grind, at 1300 ℃ of insulation 7h, temperature rise rate is 2-10 ℃/min then, keep air atmosphere or weak oxide atmosphere in the whole process, insulation finishes postcooling to room temperature.Grind after the taking-up and obtain the luminescent material finished product.
Embodiment 4:
The chemical formula of the red fluorescence material of present embodiment preparation is: Sr
3.91Mg
0.09Al
13.69O
25: Mn
0.01
Take by weighing SrCO
31.586g, MgO 0.01g, Al
2O
31.898g, MnCO
30.004g and H
3BO
3Make it the even compound that gets of thorough mixing 0.089g put into the agate mortar grinding, then compound is put into corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, keeps air atmosphere in the whole process, and insulation finishes postcooling to room temperature.Grind after the taking-up and obtain the luminescent material finished product.
Embodiment 5:
The chemical formula of the red fluorescence material of present embodiment preparation is: Sr
3.99Al
14O
25: Mn
0.01, Pb
0.007
Take by weighing SrCO
31.586g, Al
2O
31.898g, MnCO
30.004g, H
3BO
30.089g and PbC
4H
6O
43H
2O 0.0067g puts into the agate mortar grinding and makes it the even compound that gets of thorough mixing, then compound is put into corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, keep air atmosphere or weak oxide atmosphere in the whole process, insulation finishes postcooling to room temperature.Grind after the taking-up and obtain the luminescent material finished product.
Embodiment 6:
The chemical formula of the red fluorescence material of present embodiment preparation is: Sr
4Al
14O
25: Mn
0.01, Fe
0.008
Take by weighing SrCO
31.586g, Al
2O
31.898g, MnCO
30.004g, H
3BO
30.089g and Fe (NO
3)
39H
2O 0.009g puts into the agate mortar grinding and makes it the even compound that gets of thorough mixing, then compound is put into corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, keep air atmosphere or weak oxide atmosphere in the whole process, insulation finishes postcooling to room temperature.Grind after the taking-up and obtain the luminescent material finished product.
Embodiment 7:
The chemical formula of the red fluorescence material of present embodiment preparation is: Sr
3.95Al
14O
25: Mn
0.01, Cl
0.05
Take by weighing SrCO
31.586g, Al
2O
31.898g, MnCO
30.004g, H
3BO
30.089g and NH
4Cl 0.0071g puts into the agate mortar grinding and makes it the even compound that gets of thorough mixing, then compound is put into corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, keep air atmosphere or weak oxide atmosphere in the whole process, insulation finishes postcooling to room temperature.Grind after the taking-up and obtain the luminescent material finished product.
Claims (2)
1. aluminate-base red fluorescence material is characterized in that its composition expressed by following general formula (1):
Sr
4-x-y-zM
zAl
p-m-n-qO
25:Mn
m，Fe
n，Cl
x，Pb
y，B
q……………………(1)
M, n, x, y, z, p, q are each element shared atomic molar per-cent in material component in the general formula (1), 0＜m≤0.2,0≤n≤0.2,13≤p≤15,0≤x≤1,0≤y≤1,0≤z≤1,0≤q≤3; M is one or more among Ca, the Mg.
2. the preparation method of the described aluminate-base red fluorescence material of claim 1, it is characterized in that operating according to the following steps: oxide compound, carbonate, oxalate, acetate, oxyhydroxide or muriate with Sr, Ca, Mg, Al, Mn, Fe, B and Pb are raw material, by proportional quantity pulverize and mix compound, add the fusing assistant AlF of mixture quality 0.1-5% then
3Or H
3BO
3, in air atmosphere or oxidizing atmosphere, calcined 2-8 hour down in 1150-1400 ℃, be crushed to particle diameter 3-60 μ m after the cooling and get product.
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|---|---|---|---|
| CN2011102803078A CN102286281B (en) | 2011-09-21 | 2011-09-21 | Aluminate-based red fluorescent material and preparation method thereof |
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|---|---|
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| CN102286281B CN102286281B (en) | 2013-11-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146381A (en) * | 2013-01-29 | 2013-06-12 | 广州有色金属研究院 | Aluminate red phosphor activated by manganese ion and preparation method thereof |
| WO2014202311A1 (en) * | 2013-06-17 | 2014-12-24 | Osram Gmbh | Red phosphor, white light source, light emitting device, and method for forming the red phosphor |
| CN105602556A (en) * | 2015-12-30 | 2016-05-25 | 中国人民大学 | Na/Mn co-doped Sr4Al14O25 red fluorescent powder as well as preparation method and application of Na/Mn co-doped Sr4Al14O25 red fluorescent powder |
| CN116103039A (en) * | 2022-09-08 | 2023-05-12 | 赣州中蓝稀土新材料科技有限公司 | Novel Li and Mn codoped aluminate matrix red fluorescent powder and preparation method thereof |
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| CN1362466A (en) * | 2000-12-22 | 2002-08-07 | 住友化学工业株式会社 | Aluminate phosphorus production method |
| CN1574192A (en) * | 2003-06-02 | 2005-02-02 | 电灯专利信托有限公司 | Discharge lamp with phosphor |
| WO2006072919A2 (en) * | 2005-01-10 | 2006-07-13 | Philips Intellectual Property & Standards Gmbh | Illumination system comprising barium magnesium aluminate phosphor |
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2011
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| CN1362466A (en) * | 2000-12-22 | 2002-08-07 | 住友化学工业株式会社 | Aluminate phosphorus production method |
| CN1574192A (en) * | 2003-06-02 | 2005-02-02 | 电灯专利信托有限公司 | Discharge lamp with phosphor |
| WO2006072919A2 (en) * | 2005-01-10 | 2006-07-13 | Philips Intellectual Property & Standards Gmbh | Illumination system comprising barium magnesium aluminate phosphor |
Non-Patent Citations (1)
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146381A (en) * | 2013-01-29 | 2013-06-12 | 广州有色金属研究院 | Aluminate red phosphor activated by manganese ion and preparation method thereof |
| CN103146381B (en) * | 2013-01-29 | 2015-07-01 | 广州有色金属研究院 | Aluminate red phosphor activated by manganese ion and preparation method thereof |
| WO2014202311A1 (en) * | 2013-06-17 | 2014-12-24 | Osram Gmbh | Red phosphor, white light source, light emitting device, and method for forming the red phosphor |
| CN104232082A (en) * | 2013-06-17 | 2014-12-24 | 欧司朗有限公司 | Red phosphor, white light source, light-emitting device and red phosphor forming method |
| US20160137917A1 (en) * | 2013-06-17 | 2016-05-19 | Osram Gmbh | Red Phosphor, White Light Source, Light Emitting Device, and Method for Forming the Red Phosphor |
| US9862884B2 (en) * | 2013-06-17 | 2018-01-09 | Osram Gmbh | Red phosphor, white light source, light emitting device, and method for forming the red phosphor |
| CN105602556A (en) * | 2015-12-30 | 2016-05-25 | 中国人民大学 | Na/Mn co-doped Sr4Al14O25 red fluorescent powder as well as preparation method and application of Na/Mn co-doped Sr4Al14O25 red fluorescent powder |
| CN105602556B (en) * | 2015-12-30 | 2018-07-13 | 中国人民大学 | A kind of Sr that Na/Mn is co-doped with4Al14O25Red fluorescence powder and the preparation method and application thereof |
| CN116103039A (en) * | 2022-09-08 | 2023-05-12 | 赣州中蓝稀土新材料科技有限公司 | Novel Li and Mn codoped aluminate matrix red fluorescent powder and preparation method thereof |
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