CN102942923A - Green phosphor and preparation method thereof - Google Patents

Green phosphor and preparation method thereof Download PDF

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Publication number
CN102942923A
CN102942923A CN2012104052792A CN201210405279A CN102942923A CN 102942923 A CN102942923 A CN 102942923A CN 2012104052792 A CN2012104052792 A CN 2012104052792A CN 201210405279 A CN201210405279 A CN 201210405279A CN 102942923 A CN102942923 A CN 102942923A
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emitting phosphor
green emitting
green
phosphor
ion
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刘行仁
蒋鑫
钱元英
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Osram (china) Fluorescent Material Co Ltd
YIXING XINWEI LEESHING RARE EARTH Co Ltd
YIXING XINWEI GROUP CORP Ltd
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Osram (china) Fluorescent Material Co Ltd
YIXING XINWEI LEESHING RARE EARTH Co Ltd
YIXING XINWEI GROUP CORP Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Abstract

The invention relates to a green rare earth phosphor of Tb<3+>, Mn<2+> and Ce<3+> co-activated polyaluminate, and a preparation method thereof. The green phosphor is Tb<3+>, Mn<2+> and Ce<3+> co-activated polyaluminate; the molecular formula has a general formula of the chemical composition of (Ce1-xTbx)(Mg1-yMny)AlmOn, wherein 0<x<=0.50, 0<y<=0.10, 10=<m<=15 and 17=<n<25. The phosphor is synthesized by a two-stage synthesis method and smashed via an airflow mill. The phosphor has high luminescent efficiency under the irradiation of ultraviolet light; the emission spectrum is composed of emission lines of Tb<3+> and emission band a spectrum of Mn<2+> in a blue-green region between 480-532 nm. Therefore, the emission spectrum of the green phosphor is broadened and the y value of chromaticity coordinate is increased, so that the green phosphor is helpful to increase the color rendering index of a fluorescent lamp. The green phosphor with excellent luminescent property and stable physical and chemical properties can be prepared by the two-stage synthesis method. The phosphor can be widely used in energy-saving compact fluorescent lamps and tube fluorescent lamps.

Description

Green emitting phosphor and preparation method thereof
Technical field
The present invention relates to a kind of fluorescent material and preparation method thereof, be specially Tb 3+, Mn 2+And Ce 3+Coactivated many aluminate greens fluorescent RE powder and preparation method thereof.
Technical background
Current energy shortage, energy-conserving and environment-protective become the major issue that various countries are concerned about, some countries ban use of and progressively eliminate incandescent light, promote power saving fluorescent lamp.In recent years, energy-conservation compact type and straight pipe type fluorescent lamp obtained larger development in China.The lamp rare-earth trichromatic fluorescent powder is the critical material of this two classes luminescent lamp, and they determine some key parameters of this class luminescent lamp.
At present lamp with rare-earth trichromatic fluorescent powder in employed green emitting phosphor be Ce 3+And Tb 2+Coactivated (Ce, Tb) MgAl 11O 19(being called for short CAT) many aluminates, its crystalline structure is the magneto plumbite of hexagonal system.This green emitting phosphor luminous efficiency is high, mainly is Tb 3+The 4f electronic energy of ion from 5D 4- 7F jThe transition emission of energy level, main emission peak 545nm, most emitted energies concentrate on yellowish green district.The reference colour coordinate x=0.3269 of this fluorescent material, y=0.5964, people utilize this green emitting phosphor and other luminescent lamps blue and different-colour that red fluorescence powder is prepared, its colour rendering index CRI generally≤80, be difficult to reach CRI〉80 high dominant requirements, this is because the y value of CAT green emitting phosphor is less than normal, lacks bluish-green district spectrum.So one of problem of at present power saving fluorescent lamp technical field existence is under the light efficiency prerequisite of not sacrificing or seldom sacrificing luminescent lamp, how to improve the y value of the chromaticity coordinates of green emitting phosphor.
Summary of the invention
The present invention is directed to the problem that above-mentioned rare earth CAT green emitting phosphor exists, a kind of new green emitting phosphor is provided, utilize Ce in the luminescence 3+, Tb 3+And Mn 2+The principle of luminosity of ion, radiationless transmission ofenergy and crystal field principle are used Mn 2+Ionic replacement is positioned at the part Mg on the tetrahedral sites 2+Ion, effectively absorbing ultraviolet light and Ce occurs 3+-Mn 2+Transmission ofenergy, can produce efficiently green glow, its emmission spectrum is positioned at the bluish-green district of 480-530nm, fills up well the spectrum vacancy, makes the y value of chromaticity coordinates obtain increasing, and is conducive to colour rendering index and improves.
Concrete technical scheme is:
Green emitting phosphor is Tb 3+, Mn 2+And Ce 3+Coactivated many aluminates, molecular formula are that the chemical constitution general formula is (Ce 1-xTb x) (Mg 1-yMn y) Al mO n, 0＜x≤0.50,0＜y≤0.10,10≤m≤15,17≤n＜25 wherein.
Preferred (the Ce that forms 1-xTb x) (Mg 1-yMn y) Al 11O 19, 0.30≤x≤0.41,0.005≤y≤0.05 wherein.
This green emitting phosphor is transmitting green light under ultraviolet excitation, in visible spectrum range mainly by Tb 3+The emmission spectrum of ion and Mn 2+The emmission spectrum of ion forms.
Wherein, Tb 3+Ion be emitted as by force main peak 545nm, Mn 2+The emission main peak of ion is 515nm.
Chromaticity coordinates x and y value and Mn 2+Concentration is relevant, control Mn 2+Ionic concn can be modulated the relation of light efficiency and chromaticity coordinates x and y value, with Mn 2+Concentration increases, and the x value slightly reduces, and the y value increases, and can realize not reducing or seldom reducing the light efficiency of green emitting phosphor, and improves the purpose of chromaticity coordinates y value.Under ultraviolet photon excites, remove at the yellowish green district of spectrum Tb 3+The strong emission of ion (main peak 545nm) and the very weak Ce in long wave ultraviolet region 3+Outside the emission, also present a Mn in the bluish-green district of 480nm-530nm spectrum 2+Stronger emission, its main peak is 515nm, its emissive porwer and Mn 2+Ionic concn is relevant.This spectrum is just in time filled up the blank in the CAT green emitting phosphor emmission spectrum in the past, makes the emmission spectrum broadening of fluorescent material.
The preparation method of this green emitting phosphor may further comprise the steps:
(1) according to the mole metering ratio of each element in the chemical constitution of right 1, takes by weighing the solid chemical compound and the fusing assistant that contain Ce, Tb, Mg, Mn, Al element, be mixed above-mentioned solid chemical compound mill even;
(2) material of mill after mixed is in high temperature air calcination 3-7 hour, then is cooled to room temperature;
(3) after the cooling this product is pulverized, then used the hot deionized water washing and drying;
(4) product with oven dry is placed in the high temperature reduction gas calcination 3-7 hour again, then is cooled to room temperature;
(5) be cooled to room temperature after, product is pulverized, then use the hot deionized water washing and drying, the sorting of sieving.
The condition of above process need is specially, and calcination temperature is 1450-1600 ℃ in the high temperature air; Calcination temperature is 1100-1500 ℃ in the high temperature reduction gas; Reducing gas is the combination of ammonia or hydrogen and nitrogen, and hydrogen content is 5-20% in the combination of hydrogen and nitrogen, and a nitrogen content is 95-80%.
Fusing assistant is AlF 3, H 3BO 3, BaF 2, NH 4Cl and H 3BO 3Mixture, MgF 2In one or more mixing.
Green emitting phosphor of the present invention adopts twice synthesis method and airflow milling to pulverize.
For the first time calcination in high temperature air mainly makes starting material that solid state reaction at high temperature occurs, and guarantees to generate six side's pure phase (Ce, Tb) (Mg, Mn) Al 11O 19The magneto plumbite crystal; In low-temperature reduction atmosphere, anneal for the second time, make on the one hand remaining Ce 4+, Tb 4+And Mn 4+Ion is reduced to Ce fully 3+, Tb 3+And Mn 2+, luminous intensity improves, and the body colour of product is whiter, reduces Optical Absorption, has dephasign to be eliminated in the product if make on the other hand, further guarantees it is pure hexagonal.
Adopt airflow milling to pulverize the dispersion of agglomerated fluorescent material and classification, and do not destroy the crystal grain of fluorescent material, guarantee the physical property of fluorescent material.And mechanical ball milling can destroy fluorescent material crystal grain, causes luminous intensity to descend.
The used raw material of the present invention comprises the CeO of purity 4N 2And Tb 4O 7, or the salt of Ce, Tb, such as nitrate, carbonate, oxalate and muriate etc., the α-Al of Fluorescence Grade 2O 3, the BaCO that analytical pure or top grade are pure 3And MgO.Raw materials of magnesium oxide can be lightweight, or magnesium basic carbonate, magnesiumcarbonate etc.And Mn 2+Ion source can comprise AR or GR level MnCO 3, MnO 2, MnX 2(X=F, Cl) and Mn(NO 3) 2Deng.
It is very important to choose suitable fusing assistant, can be from AlF 3, H 3BO 3, BaF 2Deng in choose one or more composite fluxing agents.Fusing assistant adds, and favourable fluorescent material synthesis temperature reduces, the control of relative brightness raising and grain-size and the raising of quality.
Advantage of the present invention and effect: the present invention utilizes Ce3+ to intensify Tb3+, strengthen the yellow green light emission of Tb3+ ion, and utilize the effective absorbing ultraviolet light of Ce3+, with radiationless transmission ofenergy mechanism absorbed energy is passed to the Mn2+ ion, greatly strengthen the Mn2+ green emitting, thereby the bluish-green district (480-530nm) in visible spectrum increases newly emission, the emmission spectrum scope broadening of green emitting phosphor, this causes the chromaticity coordinates y value of fluorescent material to improve, and the luminescent lamp colour rendering index that utilizes this fluorescent material to make can obtain to improve.(2) fluorescent material of the present invention prepares workable.At a suitable Mn 2+In the concentration range and do not mix Mn in the past 2+The CAT green emitting phosphor compare, luminous intensity does not change, even slightly is improved.(3) need not increase any new installation and technique, utilize related process and the equipment of original production CAT green emitting phosphor can realize scale operation, cost does not increase yet.
Description of drawings
(1) (a) among Fig. 1, (b) and (c) curve be respectively embodiment 1, the XRD figure spectrum of comparative example 1 and international crystalline diffraction standard card JCPDS88-2135;
(2) Fig. 2 is the emmission spectrum of comparative example 1;
(3) Fig. 3 is the prepared emmission spectrum of sample under the 253.7nm ultraviolet excitation of embodiment 1, and it is by Tb 3+The emmission spectrum of ion (main peak 545nm) and Mn 2+The emmission spectrum of ion (main peak 515nm) forms;
(4) Fig. 4 is the emmission spectrum of embodiment 2;
(5) Fig. 4 is the emmission spectrum of embodiment 3;
(6) Fig. 6 is chromaticity coordinates x and y value and the Mn of comparative example 1 and embodiment 1-3 2+Concentration relationship figure;
(7) Fig. 7 is the emmission spectrum of embodiment 9.
Embodiment
For making more clear and reliable enforcement of this experiment, the below describes the present invention.
Prepare first the comparative example product, then compare according to technical scheme Preparation Example product provided by the invention.
Comparative example 1:
Accurately take by weighing the CeO of 13.367g purity 4N 2, the Tb of 7.150g purity 4N 4O 7, the analytically pure MgO of 4.562g, 65.000g Fluorescence Grade α-Al 2O 3And 0.385g analytical pure boric acid.The preparation method of the green emitting phosphor that provides of the present invention is provided, that is, with above-mentioned raw materials fully grind be mixed even, then mixed raw material is put into alumina crucible, the crucible of charge is placed in the automatic tunnel kiln calcination in 1600 ℃ of air, insulation calcination 5 hours.Then with the kiln cooling, take out.This product is carried out fragmentation, cross 100 mesh sieves, then use airflow milling to grind, then clean with hot deionized water, clean rear 120 ℃ of oven dry.
The above-mentioned product that high temperature synthesizes in air is placed in the alumina crucible, is that 20%H2 mixes the calcination of annealing in the reducing gas with 80%N2 1200 ℃ volume ratios, is incubated 5 hours.After annealing is finished, be cooled to room temperature.Put the product taking-up in ball grinder ball milling.Product after taking-up grinds with the hot deionized water washing, filters after the washing, product is placed in 120 ℃ of baking ovens dries, the sorting of at last product of drying being sieved.
Qualified the obtaining of sorting consists of (Ce 0.67Tb 0.33) MgAl 11O 19Green emitting phosphor.
(XRD) measures and analyzes its crystalline structure by the x x ray diffractometer x.Test result is shown in (b) curve among Fig. 1, and (c) curve among Fig. 1 is the XRD spectra of international crystalline diffraction standard card JCPDS88-2135; Fig. 1 (a) curve is example 1 (Ce 0.67Tb 0.33) (Mg 0.995Mn 0.005) Al 11O 19XRD spectra.
Fig. 2 is the emmission spectrum of this fluorescent material under the 253.7nm ultraviolet excitation.It only is that Tb is arranged 3+Ion 5D 4- 7F jThe energy level transition spectral line of emission forms, main emission peak 545nm.The chromaticity coordinates x=0.3298 of this green emitting phosphor, y=0.5958.
Comparative example 2:
Take by weighing corresponding raw material by comparative example 1 method.For the first time calcination 5 hours in 1550 ℃ of air after mill is mixed is for the second time at 1450 ℃ volume ratio 20%H 2With 80%N 2Calcination is 5 hours in the mixing reducing atmosphere.The composition of the green emitting phosphor that finally obtains is identical with comparative example 1 with luminescent properties, its chromaticity coordinates x=0.3322, y=0.5916.
Embodiment 1:
Accurately take by weighing the CeO of 16.451g purity 4N 2, the Tb of 8.800g purity 4N 4O 7, the analytically pure MgO of 5.722g, 0.389g analytical pure boric acid, 0.082g analytical pure MnCO 3And 80.00g Fluorescence Grade α-Al 2O 3
Above-mentioned raw materials fully ground be mixed evenly, then mixed raw material is put into alumina crucible, the crucible of charge is placed in the automatic tunnel kiln calcination in 1600 ℃ of air, insulation calcination 5 hours.Then with the kiln cooling, take out.Product is broken, crosses 100 mesh sieves, then uses airflow milling to grind, and then cleans with hot deionized water, cleans rear 120 ℃ of oven dry.
The above-mentioned product that high temperature synthesizes in air is placed in the alumina crucible, is 20%H 1250 ℃ volume ratios 2With 80%N 2Mix the calcination of annealing in the reducing gas, be incubated 5 hours.After annealing is finished, be cooled to room temperature, product taken out put ball milling in the ball grinder into.The taking-up ground product with the hot deionized water washing, is filtered after the washing, product is placed in 120 ℃ of baking ovens dries, the sorting of at last product of drying being sieved.Final prepared group of products becomes (Ce 0.67Tb 0.33) (Mg 0.995Mn 0.005) Al 11O 19Green emitting phosphor.
Its crystalline structure is measured and analyzed to this green emitting phosphor by x x ray diffractometer x (XRD), its result is (a) curve among Fig. 1, its diffraction peak is very sharp, clear, with (c) curve among Fig. 1 be that international crystalline diffraction standard card JCPDS88-2135 contrast shows in full accord.The crystalline structure of green emitting phosphor of the present invention is the magneto plumbite structure of hexagonal system, and LaMgAl 11O 19Isomorphism.
Adopt fluorescent material optical color parameter overall analysis system (three look Instr Ltd. of Zhejiang University) to the Photochromic Properties test of this green emitting phosphor.Fig. 3 is the emmission spectrum of this green emitting phosphor under the 253.7nm ultraviolet excitation.It is by Tb 3+Ion 5D 4- 7F jEnergy level transition emission spectrum (main peak 545nm) and Mn 2+Emmission spectrum (main peak 515nm) in bluish-green district forms.
The chromaticity coordinates x=0.3163 of this new green fluorescent material, y=0.6078 is with the Mn that do not have of comparative example 1 2+(the Ce that mixes altogether 0.67Tb 0.33) MgAl 11O 19Green emitting phosphor is compared, and emmission spectrum and chromaticity coordinates x and y value all change, and particularly the y value increases, and luminous intensity also slightly is improved.This shows that the green emitting phosphor that this embodiment 1 provides can improve colour rendering index CRI, and do not reduce luminous intensity..
Embodiment 2:
Carefully take by weighing 41.127g purity 4NCeO 2, the Tb of 22.000g purity 4N 4O 7, the analytically pure MgO of 14.233g, 0.310g analytical pure MnO and 200.00g Fluorescence Grade α-Al 2O 3With an amount of boric acid, mill is mixed even, prepares fluorescent material by the method for implementing 1, i.e. first calcination 5 hours in 1600 ℃ of air; Process rear at 1200 ℃ of 20%H 2-80%N 2Calcination is 5 hours in (volume ratio) reducing atmosphere; Product carries out aftertreatment.Prepared green emitting phosphor consist of (Ce 0.67Tb 0.33)(Mg 0.99Mn 0.01) Al 11O 19
Adopt fluorescent material optical color parameter overall analysis system (three look Instr Ltd. of Zhejiang University) to the Photochromic Properties test of this green emitting phosphor, the emmission spectrum of this green emitting phosphor under 253.7nm excites is illustrated among Fig. 4, the spectral results of it and Fig. 3 is compared, their spectrum composition is identical with shape, is both Tb 3+And Mn 2+Emission, Mn just 2+Emissive porwer strengthen, and chromaticity coordinates x and y value become respectively x=0.3021, y=0.6204, and embodiment 1 and without Mn 2+The fluorescent material of codoped is compared, and the x value reduces, and the y value further increases, and luminous intensity slightly has decline.Mn 2+Emission of ions is filled up the blank of bluish-green district (480-530nm) emmission spectrum, makes colour gamut broadening, and favourable color rendering properties of light source improves.
Embodiment 3:
Carefully take by weighing 18.507g purity 4NCeO 2, the Tb of 9.900g purity 4N 4O 7, the analytically pure MgO of 6.340g, 0.369g analytical pure MnCO 3And 90g Fluorescence Grade α-Al 2O 3With an amount of boric acid, mill is mixed even, by the preparation of 1 method of enforcement, obtains to consist of (Ce 0.67Tb 0.33) (Mg 0.98Mn 0.02) Al 11O 19Green emitting phosphor.
Utilize above-mentioned same testing method, the emmission spectrum of this green emitting phosphor under the 253.7nm ultraviolet excitation is illustrated among Fig. 5, and the spectral results of Fig. 4 of Fig. 3, the embodiment 2 of it and embodiment 1 is compared, and their spectrum composition is identical with shape, is both Tb 3+And Mn 2+Emission.Just at bluish-green spectral region (480-530nm) Mn 2+The emissive porwer of ion significantly strengthens, and chromaticity coordinates x and y value become respectively x=0.2799, and y=0.6415 compares with embodiment 1, embodiment 2, and the x value further reduces, and the y value enlarges markedly, and luminous intensity descends to some extent.
Embodiment 4,5,6:
Embodiment 4,5,6 is the composition of corresponding embodiment 1,2,3 phosphor raw material respectively, on manufacture method, only high temperature reduction gas calcination temperature is changed into 1450 ℃Condition.
Utilize above-mentioned same testing method, the luminescent spectrum of embodiment 4 resulting fluorescent material is compared with embodiment 1, and their spectrum composition is identical with shape, is both Tb 3+And Mn 2+Emission, its chromaticity coordinates x=0.3198, y=0.6086; Both chromaticity coordinatess are very approaching.
The performance of embodiment 5 resulting green emitting phosphors is compared with embodiment 2, and their spectrum composition is identical with shape, is both Tb 3+And Mn 2+Emission, chromaticity coordinates x=0.3076, y=0.6190;
And the luminescent spectrum of embodiment 6 resulting green emitting phosphors is compared with embodiment 3, and their spectrum composition is identical with shape, is both Tb 3+And Mn 2+Emission, its chromaticity coordinates x=0.2875, y=0.6375.
Compare with comparative example 2, embodiment 4,5,6 x value reduce, but the y value enlarges markedly.
At (Ce 0.67Tb 0.33) (Mg 1-aMn a) Al 11O 19(a=0.005,0.008,0.01,0.02mol) in the green emitting phosphor, during by above embodiment 1-3 and Mn=0.008mol, their its chromaticity coordinates x and y value and Mn 2+The relation table of concentration (at) is shown among Fig. 6, obviously with Mn 2+Ionic concn increases, and the x value reduces gradually, and the y value increases gradually.
Embodiment 4,5, the emmission spectrum of 6 samples under the 253.7nm ultraviolet excitation also are by Tb 3+And Mn 2+The emmission spectrum of ion forms, and they are different from the spectrum of comparative example 2.
Embodiment 7:
Take by weighing the CeO of 18.44g 4N 2, the Tb of 8.999g purity 4N 4O 7, the analytically pure MgO of 6.197g, 0.179g analytical pure MnCO 3And 95.000g Fluorescence Grade α-Al 2O 3With a small amount of analytical pure boric acid, mill is mixed even.Light calcination 5 hours in 1550 ℃ of air; Then at 1100 ℃ 20%H 2-80%N 2Calcination is 5 hours in (volume ratio) mixing reducing atmosphere, and other steps are processed product by example 1 method.Its product composition is (Ce 0.69Tb 0.31) (Mg 0.99Mn 0.01) Al 11O 19
The luminosity of this fluorescent material is identical with embodiment 2 with embodiment 1, its chromaticity coordinates x=0.3067, y=0.6156.The y value is than not mixing altogether Mn 2+The ion same sample is high, and relative brightness is 98.8%
Embodiment 8:
Prescription by embodiment 7 takes by weighing raw material, mixes, and presses the synthetic green emitting phosphor of embodiment 4 methods.Its luminosity is identical with embodiment 7 with embodiment 5, its chromaticity coordinates x=0.3093, y=0.6135.The y value is than not mixing altogether Mn 2+Same sample high, relative brightness 99.3%.
Example 9:
Take by weighing the CeO of 31.871g purity 4N 2, the Tb of 24.052g purity 4N 4O 7, 12.019g analytical pure MgO, 1.804g analytical pure MnCO 3, 120g Fluorescence Grade α-Al 2O 3, 0.759g analytical pure boric acid.It is even that the above-mentioned raw materials mill is mixed, and the raw material that mixes is put into alumina crucible, and this crucible is put into the automatic tunnel kiln, and calcination in 1550 ℃ of air is incubated 5 hours under the temperature again.Then with the kiln cooling, take out.Press example 1 method aftertreatment.
The above-mentioned product that high temperature synthesizes in air is put into alumina crucible, 1150 ℃20%H 2-80%N 2(volume ratio) mixes the calcination of annealing in the reducing gas, again is incubated 5 hours under the temperature.Then by the method for example 1 product is carried out aftertreatment.The group of products that obtains becomes (Ce 0.59Tb 0.41) (Mg 0.95Mn 0.05) Al 15O 25Green emitting phosphor.
Press embodiment 1 testing method, measure the luminescent properties of this fluorescent material.Fig. 7 provides the emmission spectrum of this fluorescent material under the 253.7nm ultraviolet excitation, and it also is by Tb 3+And Mn 2+The emmission spectrum of ion forms, relatively Mn 2+Emission band increases.Because Mn 2+Concentration increases, and chromaticity coordinates x=0.2375 further reduces, and y=0.6806 further increases.

Claims (9)

1. green emitting phosphor is characterized in that, described green emitting phosphor is Tb 3+, Mn 2+And Ce 3+Coactivated many aluminates, molecular formula are that the chemical constitution general formula is (Ce 1-xTb x) (Mg 1-yMn y) Al mO n, 0＜x≤0.50,0＜y≤0.10,10≤m≤15,17≤n＜25 wherein.
2. green emitting phosphor according to claim 1 is characterized in that, the preferred (Ce that forms 1-xTb x) (Mg 1-yMn y) Al 11O 19, 0.30≤x≤0.50,0.005≤y≤0.05 wherein.
3. green emitting phosphor according to claim 1 and 2 is characterized in that, described green emitting phosphor is transmitting green light under ultraviolet excitation, in visible spectrum range mainly by Tb 3+The emmission spectrum of ion and Mn 2+The emmission spectrum of ion forms.
4. green emitting phosphor according to claim 3 is characterized in that, Tb 3+The strong emission main peak of ion is 545nm, Mn 2+The emission main peak of ion is 515nm.
5. prepare the method for green emitting phosphor as claimed in claim 1, it is characterized in that, may further comprise the steps:
(1) according to the mole metering ratio of each element in the chemical constitution of right 1, takes by weighing the solid chemical compound and the fusing assistant that contain Ce, Tb, Mg, Mn, Al element, be mixed above-mentioned solid chemical compound mill even;
(2) material of mill after mixed is in high temperature air calcination 3-7 hour, then is cooled to room temperature;
(3) after the cooling this product is pulverized, then used the hot deionized water washing and drying;
(4) product with oven dry is placed in the high temperature reduction gas calcination 3-7 hour again, then is cooled to room temperature;
(5) be cooled to room temperature after, product is pulverized, then use the hot deionized water washing and drying, the sorting of sieving.
6. the preparation method of green emitting phosphor according to claim 5 is characterized in that, (3) step used airflow milling to pulverize.
7. the preparation method of green emitting phosphor according to claim 5 is characterized in that, calcination temperature is 1450-1600 ℃ in the described high temperature air.
8. the preparation method of green emitting phosphor according to claim 5 is characterized in that, calcination temperature is 1100-1500 ℃ in the described high temperature reduction gas.
9. the preparation method of green emitting phosphor according to claim 5 is characterized in that, described fusing assistant is AlF 3, H 3BO 3, BaF 2, NH 4Cl and H 3BO 3Mixture, MgF 2In one or more mixtures.
CN2012104052792A 2012-11-21 2012-11-21 Green phosphor and preparation method thereof Pending CN102942923A (en)

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Cited By (1)

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