CN102286281B - Aluminate-based red fluorescent material and preparation method thereof - Google Patents

Aluminate-based red fluorescent material and preparation method thereof Download PDF

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CN102286281B
CN102286281B CN2011102803078A CN201110280307A CN102286281B CN 102286281 B CN102286281 B CN 102286281B CN 2011102803078 A CN2011102803078 A CN 2011102803078A CN 201110280307 A CN201110280307 A CN 201110280307A CN 102286281 B CN102286281 B CN 102286281B
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fluorescent material
preparation
aluminate
light
red
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CN102286281A (en
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王雷
许育东
王迪
陈翌庆
徐进章
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Hefei University of Technology
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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

A kind of aluminate-based red fluorescent material and preparation method thereof
One, technical field
The present invention relates to a kind of fluorescent material and preparation method thereof, specifically a kind of aluminate-based red fluorescent material and preparation method thereof.
Two, background technology
Because LED has that volume is little, the advantage such as low, the low current low voltage of energy-saving and environmental protection, thermal value, life-span be long, white light LEDs more and more receives people's concern as lighting source of new generation.The white light LEDs implementation method be most widely used in the market is to excite the gold-tinted of YAG:Ce fluorescent material emission and the blue light be not completely absorbed 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 the illuminating effect that reaches desirable, is not suitable for being used in color developing and requires high occasion.
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, the green glow produced through exciting and ruddiness and the blue light do not absorbed fully by luminescent material are combined into white light LEDs, can effectively solve in spectrum like this and lack red wave band and cause LED colour rendering index problem on the low side [Zhang Zhongtai, Junying ZHANG. inorganic fluorescent substances and application. the .2005 of Chemical Industry Press, 3:189].But above-mentioned two kinds of solutions all need to add the material that can produce red emission.At present, widespread use, can be mainly and mix Eu by the red illuminating material that ultraviolet or blue light effectively excite 3+Or Eu 2+Luminescent material [Materials Chemistry and Physics.2001,71,179 activated; Mater.Res.Bull, 1996,31,1355.], the red emission peak of this class luminescent material is many in 600nm～630nm scope, and is all 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+The nitride or the oxynitride that activate are not only used rare earth, and synthesis technique is complicated, production cost is higher.
Three, summary of the invention
The present invention is for fear of the existing weak point of above-mentioned prior art, aim to provide aluminate-based red fluorescent material that a kind of color developing is high, 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 by UV-light and blue light, effectively be excited simultaneously.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of aluminate-based red fluorescent 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 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 in Ca, Mg.
The preparation method's of aluminate-based red fluorescent material of the present invention characteristics are to operate according to the following steps: oxide compound, carbonate, oxalate, acetate, oxyhydroxide or the muriate of Sr, Ca, Mg, Al, Mn, Fe, B and Pb of take is raw material, can not form compound except, by proportional quantity, pulverize and mix and to obtain compound, then add the fusing assistant AlF of mixture quality 0.1-5% 3Or H 3BO 3, in air atmosphere or oxidizing atmosphere under 1150-1400 ℃ calcining 2-8 hour, be crushed to particle diameter 3-60 μ m after cooling and get product.
Described proportional quantity is the amount taken after the ratio metering in the composition shown in general formula (1) and restriction thereof.
With respect to expensive rare earths material, the Mn in the present invention 4+The luminescent material activated is cheap, and near the scarlet red light district of emission peak 650nm, with Eu 2+/ Eu 3+The LED luminescent powder (460-620nm) of doping is compared, and this luminescent powder has been expanded the spectral range of white light LEDs, makes it more near sunlight, can have the white LED light source than high-color rendering for exploitation.And Mn 4+In air atmosphere or weak oxide atmosphere, can obtain, not need reducing atmosphere, therefore greatly reduce requirement and the cost to production unit, also improve the security in the production process.In the present invention, also mix the auxiliary activators such as a small amount of Fe, Cl, Pb, increased substantially luminous intensity.
With respect to application number, be 200810218742.6 the related luminescent material principal phase CaAl of patent of invention 12O 19: Mn 4+, the matrix of materials principal phase that the present invention synthesizes is Sr 4Al 14O 25, and the synthetic method adopted also has a great difference, and in addition, the present invention has increased the auxiliary activator ions such as Fe, Cl, Pb, can significantly improve Mn 4+Luminosity.And the material that the related generation scarlet of patent that application number is 201010550332.9 is launched is Mn doping germanic acid magnesium, Mg 4GeO 6: Mn, the aluminate based luminescent material mentioned from the present invention has greatly different.
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, near 652nm, has desirable scarlet.
2, red fluorescence material of the present invention can effectively be excited at the 300-500nm wave band, can with ultraviolet chip or blue chip, mate preferably.
3, in preparation process of the present invention, fusing assistant used is AlF 3Or H 3BO 3, wherein with AlF 3The luminescent material hardness obtained for fusing assistant is lower, be easy to pulverize and the grain graininess that obtains even.
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, can obviously reduce the hardness of fluorescent material after calcining.
5, the present invention does not contain the 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, be conducive to realize the large-scale application of White LED with high color rendering property.
Four, accompanying drawing explanation
Fig. 1 is the excitation spectrum of the red fluorescence material of the embodiment of the present invention 4 preparations.The excitation peak of fluorescent material of the present invention, between 250-500nm, belongs to broadband excitation as can be seen from Figure 1, and namely 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 present invention 4 preparations.As shown in Figure 2, the transmitting boundary of fluorescent material of the present invention is the broad peak between 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 acromion 665nm.
Fig. 3 is the emmission spectrum of red fluorescence material under blue light (460nm) excites of the embodiment of the present invention 4 preparations.As shown in Figure 3, host doped Mg 2+After, under 460nm excited, considerable change did not occur in emission peak peak position and peak shape.
Fig. 4 is the excitation spectrum of the red fluorescence material of the embodiment of the present invention 6 preparations.As shown in Figure 4, after host doped Fe ion, considerable change does not all occur in excitation spectrum peak position and the peak shape of sample, namely 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 present invention 6 preparations.As shown in Figure 5, after 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 present invention 6 preparation.As shown in Figure 6, after 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 red fluorescence material prepared by the present embodiment is: Sr 4Al 13.98O 25: Mn 0.01.
Take 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 fully to mix to obtain compound, then compound is put into to corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 3h, temperature rise rate is 2-10 ℃/min, in whole process, keep air atmosphere or weak oxide atmosphere, insulation is cooled to room temperature after finishing, and after taking-up, grinds and obtains the luminescent material finished product.
Embodiment 2:
The chemical formula of red fluorescence material prepared by the present embodiment is: Sr 4Al 14.14O 25: Mn 0.07.
Take SrCO 31.586g, Al 2O 31.917g, MnCO 30.012g and H 3BO 30.181g put into the agate mortar grinding, make it fully to mix to obtain compound, then compound is put into to corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 3h, temperature rise rate is 2-10 ℃/min, in whole process, keep air atmosphere or weak oxide atmosphere, insulation is cooled to room temperature after finishing.After taking-up, grind and obtain the luminescent material finished product.
Embodiment 3:
The chemical formula of red fluorescence material prepared by the present embodiment is: Sr 3.93Ca 0.07Al 13.74O 25: Mn 0.07.
Take SrCO 31.586g, CaCO 30.02g, Al 2O 31.917g, MnCO 30.004g and H 3BO 30.089g put into the agate mortar grinding, make it fully to mix to obtain compound, then compound is put into to corundum crucible, in tube type resistance furnace, calcine, cooling after 1000 ℃ of insulation 5h, take out and grind, then at 1300 ℃ of insulation 7h, temperature rise rate is 2-10 ℃/min, in whole process, keep air atmosphere or weak oxide atmosphere, insulation is cooled to room temperature after finishing.After taking-up, grind and obtain the luminescent material finished product.
Embodiment 4:
The chemical formula of red fluorescence material prepared by the present embodiment is: Sr 3.91Mg 0.09Al 13.69O 25: Mn 0.01.
Take SrCO 31.586g, MgO 0.01g, Al 2O 31.898g, MnCO 30.004g and H 3BO 30.089g put into the agate mortar grinding, make it fully to mix to obtain compound, then compound is put into to corundum crucible, calcine in tube type resistance furnace, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, keeps air atmosphere in whole process, and insulation is cooled to room temperature after finishing.After taking-up, grind and obtain the luminescent material finished product.
Embodiment 5:
The chemical formula of red fluorescence material prepared by the present embodiment is: Sr 3.99Al 14O 25: Mn 0.01, Pb 0.007.
Take 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 fully to mix to obtain compound, then compound is put into to corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, in whole process, keep air atmosphere or weak oxide atmosphere, insulation is cooled to room temperature after finishing.After taking-up, grind and obtain the luminescent material finished product.
Embodiment 6:
The chemical formula of red fluorescence material prepared by the present embodiment is: Sr 4Al 14O 25: Mn 0.01, Fe 0.008.
Take 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 fully to mix to obtain compound, then compound is put into to corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, in whole process, keep air atmosphere or weak oxide atmosphere, insulation is cooled to room temperature after finishing.After taking-up, grind and obtain the luminescent material finished product.
Embodiment 7:
The chemical formula of red fluorescence material prepared by the present embodiment is: Sr 3.95Al 14O 25: Mn 0.01, Cl 0.05.
Take 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 fully to mix to obtain compound, then compound is put into to corundum crucible, in tube type resistance furnace, calcine, at 1300 ℃ of insulation 4h, temperature rise rate is 2-10 ℃/min, in whole process, keep air atmosphere or weak oxide atmosphere, insulation is cooled to room temperature after finishing.After taking-up, grind and obtain the luminescent material finished product.

Claims (2)

1. aluminate-based red fluorescent 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 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 in Ca, Mg;
Described fluorescent material is the fluorescent material prepared by the following method:
Oxide compound, carbonate, oxalate, acetate, oxyhydroxide or the muriate of Sr, Ca, Mg, Al, Mn, Fe, B and Pb of take is raw material, pulverizes and mix and to obtain compound by proportional quantity, then adds the fusing assistant AlF of mixture quality 0.1-5% 3Or H 3BO 3, in air atmosphere or oxidizing atmosphere under 1150-1400 ℃ calcining 2-8 hour, be crushed to particle diameter 3-60 μ m after cooling and get product.
2. the preparation method of an aluminate-based red fluorescent material claimed in claim 1, it is characterized in that operating according to the following steps: oxide compound, carbonate, oxalate, acetate, oxyhydroxide or the muriate of Sr, Ca, Mg, Al, Mn, Fe, B and Pb of take is raw material, by proportional quantity, pulverize and mix and to obtain compound, then add the fusing assistant AlF of mixture quality 0.1-5% 3Or H 3BO 3, in air atmosphere or oxidizing atmosphere under 1150-1400 ℃ calcining 2-8 hour, be crushed to particle diameter 3-60 μ m after cooling and get product.
CN2011102803078A 2011-09-21 2011-09-21 Aluminate-based red fluorescent material and preparation method thereof Expired - Fee Related CN102286281B (en)

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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
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
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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