CN102888221A - Fluorescent powder for LED and preparation method thereof - Google Patents

Fluorescent powder for LED and preparation method thereof Download PDF

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CN102888221A
CN102888221A CN2012104205800A CN201210420580A CN102888221A CN 102888221 A CN102888221 A CN 102888221A CN 2012104205800 A CN2012104205800 A CN 2012104205800A CN 201210420580 A CN201210420580 A CN 201210420580A CN 102888221 A CN102888221 A CN 102888221A
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fluorescent material
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fluorescent powder
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CN102888221B (en
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符义兵
何锦华
梁超
滕晓明
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Jiangsu Borui Photoelectric Co ltd
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JIANGSU BREE OPTRONICS CO Ltd
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Abstract

The invention relates to a fluorescent powder for LED, which has a chemical structural formula of La1-x-ySr2(Al1-zGaz)O5:Ce3+ x,J3+ yWherein J is one or the combination of more than two of Dy, Nd, Ho, Gd, Sm, Y or Lu in any proportion, x is more than or equal to 0.01 and less than or equal to 0.2, Y is more than or equal to 0.001 and less than or equal to 0.02, and z is more than or equal to 0 and less than or equal to 0.3. The preparation method comprises the following steps: weighing La according to the stoichiometric ratio in the structural formula2O3、Al2O3、Ga2O3、CeO2、SrCO3And J, adding a fluxing agent into the oxide, uniformly mixing, then placing the mixture into a reducing atmosphere furnace, roasting the mixture for 2-8h at the temperature of 1400-1550 ℃, and finally cooling and sieving the obtained product to obtain the catalyst. The fluorescent powder can emit yellow green to orange red light under the excitation of near ultraviolet or blue light, can be used as the fluorescent powder for a white light LED under the excitation of a blue light LED chip, and has the advantages of good luminous performance, high phase purity, simple preparation process and easy operation.

Description

A kind of LED fluorescent material and preparation method thereof
Technical field
The present invention relates to a kind of phosphor for white light LED and preparation method thereof, belong to the solid luminescent material technical field.
Background technology
White light LEDs is based on the mixed light principle of colorimetry, LED fluorescent material and GaN blue chip are made up, fluorescent material sends green glow, gold-tinted or the ruddiness of long-wave band behind the blue light that absorption GaN chip sends, with the blue light realization white light emission of GaN chip part transmission.The LED packing forms of main flow is to obtain white light LEDs with blue chip and yellow glimmering powder combination now, and this combination has guaranteed that namely the high light efficiency of LED has guaranteed again the long lifetime of LED.As one of wherein critical material, LED has directly determined the performance index such as luminous efficiency, optical color parameter, aging resistance and working life of white light LEDs with the characteristic index such as light conversion efficiency, spectral composition, bandwidth, diameter of particle and arogel consistency of yellow fluorescent powder, and these parameters are common and structure and the synthetic technology of selected yellow fluorescent powder are closely related.
At present, LED is mainly the aluminate YAG fluorescent material of yttrium aluminum garnet structure with yellow fluorescent powder, and this light-emitting phosphor brightness is high, and light decay is little.Its synthetic method is mainly high temperature solid-state method, usually need the high temperature more than 1600 ℃, synthesis device is had relatively high expectations, simultaneously the peak luminous wavelength adjustable extent (535nm-570nm) less than normal of YAG fluorescent material, particularly after emission wavelength was greater than 560nm, luminescent properties descended obviously.A kind ofly novel excite lower emission wavelength adjustable extent wide and have preferably luminescent properties at blue chip if search out, the relatively simple yellow fluorescent powder of simultaneously preparation will exert far reaching influence to further developing of domestic LED.
Summary of the invention
The purpose of this invention is to provide a kind of good luminous performance, the spectrum adjustable extent is wide and the simple phosphor for white light LED of preparation technology, and provides its preparation method.
Technical scheme of the present invention is: a kind of phosphor for white light LED, chemical structural formula is: La 1-x-ySr 2(Al 1-zGa z) O 5: Ce 3+ x, J 3+ y
Wherein J is the combination of one or more arbitrary proportions among Dy, Nd, Ho, Gd, Sm, Y or the Lu, 0.01≤x≤0.2,0.001≤y≤0.02,0≤z≤0.3.
Preferred J is Nd and the in molar ratio combination of 1:1-1:3 of Gd, and this moment, luminescent properties was best.
In the structural formula of phosphor for white light LED of the present invention, added the Ga element, the adding of Ga element, can change the emission wavelength of fluorescent material, allow the spectrum of fluorescent material produce blue shift, when the mol ratio of Ga and Al reaches 3:7, the emission main peak of fluorescent material is about about 520nm, this moment emission be partially green yellow-green fluorescence, but as the ratio of Ga:Al above 0.3 the time (z〉0.3 time), the luminescent properties of fluorescent material sharply descends.
The add-on of activator is that the x value can change in the 0.01-0.2 scope, and along with the add-on of activator increases gradually, the fluorescent material emission wavelength increases gradually, but in order to guarantee preferably luminescent properties, the x span is preferably 0.02-0.06.
Above-mentioned LED is as follows with the preparation method of yellow-green fluorescence powder:
(1) takes by weighing La by the stoichiometric ratio in the above-mentioned phosphor structure formula 2O 3, Al 2O 3, Ga 2O 3, CeO 2, SrCO 3With the oxide compound of J, get mixing raw material after mixing;
(2) add fusing assistant and mixing in the mixing raw material of step (1), then place the reducing atmosphere stove at 1400-1550 ℃ of roasting 2-8h;
(3) sieve after the product cooling that step (2) is obtained, and get final product.
The add-on of the fusing assistant in the step (2) accounts for the 1-5% of mixing raw material gross weight, and the adding of fusing assistant can promote the luminescent properties of fluorescent material and reduce simultaneously synthesis temperature.Described fusing assistant is selected from NaF, NH 4Cl, AlF 3, H 3BO 3, BaCl 2, SrCl 2Or Na 2CO 3In one or more mixtures that form with arbitrary proportion.Preferred fusing assistant is SrCl 2With AlF 3By weight the mixture that 1:1-1:4 forms, this moment, fluorescent material had best luminescent properties.
The LED that the inventive method obtains has following advantage with fluorescent material:
(1) the light-emitting phosphor performance is good, and phase purity is high;
(2) this fluorescent powder excitation spectrum is wide, can effectively be excited by the blue chip of 440-470nm wave band;
(3) the light-emitting phosphor peak wavelength is adjustable at 520nm-575nm, and spectrum covers yellow-green colour to orange-colored light, can adapt to the led chip of different-waveband;
(4) preparation method is simple, easy handling, and the production process contamination-free produces, and raw material is easy to get and is with low cost.
Description of drawings
Fig. 1 is the utilizing emitted light spectrogram of the fluorescent material of embodiment of the invention 1-3 gained;
Fig. 2 is the exciting light spectrogram of the fluorescent material of embodiment of the invention 1-3 gained;
Fig. 3 is the utilizing emitted light spectrogram of the fluorescent material of embodiment of the invention 5-7 gained;
Fig. 4 is the scanning electron microscope (SEM) photograph of the fluorescent material of the embodiment of the invention 4 gained.
Embodiment
Embodiment 1
Take by weighing 0.939mol La 2O 3, 1mol Al 2O 3, 0.12mol CeO 2, 4mol SrCO 3, 0.001mol Dy 2O 3And the NH of raw material gross weight 1% 4Cl is as fusing assistant and mix, and places the reducing atmosphere stove in 1400 ℃ of roasting 8h said mixture, after the cooling of coming out of the stove synthetics is sieved and get final product, and this fluorescent material expression formula is La 0.939Sr 2AlO 5: Ce 3+ 0.06, Dy 3+ 0.001
Embodiment 2
Take by weighing 0.94mol La 2O 3, 0.9mol Al 2O 3, 0.1mol Ga 2O 3, 0.08mol CeO 2, 4mol SrCO 3, 0.01molNd 2O 3, 0.01molGd 2O 3And the SrCl of raw material gross weight 1.5% 2AlF with raw material gross weight 1.5% 3As fusing assistant and mix, place the reducing atmosphere stove in 1550 ℃ of roasting 2h said mixture, after the cooling of coming out of the stove synthetics to be sieved and get final product, this fluorescent material expression formula is La 0.94Sr 2Al 0.9Ga 0.1O 5: Ce 3+ 0.04, Nd 3+ 0.01, Gd 3+ 0.01
Embodiment 3
Take by weighing 0.96mol La 2O 3, 0.7mol Al 2O 3, 0.3mol Ga 2O 3, 0.04mol CeO 2, 4mol SrCO 3, 0.005molNd 2O 3, 0.015molGd 2O 3And the SrCl of raw material gross weight 0.4% 2AlF with raw material gross weight 1.6% 3As fusing assistant and mix, place the reducing atmosphere stove in 1500 ℃ of roasting 4h said mixture, after the cooling of coming out of the stove synthetics to be sieved and get final product, this fluorescent material expression formula is La 0.96Sr 2Al 0.7Ga 0.3O 5: Ce 3+ 0.02, Nd 3+ 0.005, Gd 3+ 0.015
Utilizing emitted light spectrogram and the exciting light spectrogram of the fluorescent material of embodiment 1-3 gained are seen respectively Fig. 1 and Fig. 2, can find out from Fig. 1 and Fig. 2, and the consumption of regulating Ga can change best excitation peak and the emission peak position of fluorescent material.
Embodiment 4
Take by weighing 0.96mol La 2O 3, 0.8mol Al 2O 3, 0.2mol Ga 2O 3, 0.06mol CeO 2, 4mol SrCO 3, 0.005molSm 2O 3, 0.005molHo 2O 3, 0.01molY 2O 3And the H of raw material gross weight 1% 3BO 3, raw material gross weight 2% AlF 3, raw material gross weight 2% BaCl 2As fusing assistant and mix, place the reducing atmosphere stove in 1480 ℃ of roasting 6h said mixture, after the cooling of coming out of the stove synthetics being sieved namely gets LED fluorescent material, and this fluorescent material expression formula is La 0.96Sr 2Al 0.8Ga 0.2O 5: Ce 3+ 0.03, Sm 3+ 0.005, Ho 3+ 0.005, Y 3+ 0.005
The scanning electron microscope (SEM) photograph of the fluorescent material of embodiment 4 gained as shown in Figure 4, the about 6-8 μ of fluorescent powder grain particle diameter m, pattern is regular, is evenly distributed.
Embodiment 5
Take by weighing 0.982mol La 2O 3, 0.8mol Al 2O 3, 0.2mol Ga 2O 3, 0.02mol CeO 2, 4mol SrCO 3, 0.005molSm 2O 3, 0.001molLu 2O 3, 0.001Dy 2O 3, 0.001molHo 2O 3And the H of raw material gross weight 1% 3BO 3, raw material gross weight 1% Na 2CO 3, raw material gross weight 1% SrCl 2, raw material gross weight 1% NH 4Cl is as fusing assistant and mix, and places the reducing atmosphere stove in 1450 ℃ of roasting 7h said mixture, after the cooling of coming out of the stove synthetics is sieved and get final product, and gained fluorescent material expression formula is La 0.982Sr 2Al 0.8Ga 0.2O 5: Ce 3+ 0.03, Sm 3+ 0.005, Ho 3+ 0.001, Lu 3+ 0.001, Dy 3+ 0.001The utilizing emitted light spectrogram of gained fluorescent material is seen Fig. 3.
Embodiment 6
Take by weighing 0.799mol La 2O 3, 1mol Al 2O, 0.40mol CeO 2, 4mol SrCO 3, 0.01molY 2O 3And the BaCl of raw material gross weight 2% 2As fusing assistant and mix, place the reducing atmosphere stove in 1480 ℃ of roasting 6h said mixture, after the cooling of coming out of the stove synthetics being sieved namely gets LED fluorescent material, and its expression formula is La 0.799Sr 2AlO 5: Ce 3+ 0.2, Y 3+ 0.01The utilizing emitted light spectrogram of gained fluorescent material is seen Fig. 3.
Embodiment 7
Take by weighing 0.835mol La 2O 3, 0.8mol Al 2O, 4mol SrCO 3, 0.015molLu 2O 3And the SrCl of raw material gross weight 2% 2As fusing assistant and mix, place the reducing atmosphere stove in 1470 ℃ of roasting 6.5h said mixture, after the cooling of coming out of the stove synthetics being sieved namely gets LED fluorescent material, and this fluorescent material expression formula is La 0.835Sr 2AlO 5: Ce 3+ 0.15, Lu 3+ 0.015The utilizing emitted light spectrogram of gained fluorescent material is seen Fig. 3.

Claims (7)

1. a LED fluorescent material is characterized in that, chemical structural formula is: La 1-x-ySr 2(Al 1-zGa z) O 5: Ce 3+ x, J 3+ y, wherein J is the combination of one or more arbitrary proportions among Dy, Nd, Ho, Gd, Sm, Y or the Lu, 0.01≤x≤0.2,0.001≤y≤0.02,0≤z≤0.3.
2. LED fluorescent material as claimed in claim 1 is characterized in that, J is Nd and the in molar ratio combination of 1:1-1:3 of Gd.
3. LED fluorescent material as claimed in claim 1 is characterized in that, the span of x is 0.02-0.06.
4. claim 1 or 2 or 3 described LED is characterized in that with the preparation method of fluorescent material, comprise the steps:
(1) takes by weighing La by the stoichiometric ratio in claim 1 structural formula 2O 3, Al 2O 3, Ga 2O 3, CeO 2, SrCO 3With the oxide compound of J, get mixing raw material after mixing;
(2) add fusing assistant and mixing in the mixing raw material of step (1), then place the reducing atmosphere stove at 1400-1550 ℃ of roasting 2-8h;
(3) sieve after the product cooling that step (2) is obtained, and get final product.
5. LED is characterized in that with the preparation method of fluorescent material the consumption of used fusing assistant is that the mixing raw material gross weight gets 1-5% as claimed in claim 4.
6. such as the preparation method of LED as described in claim 4 or 5 with fluorescent material, it is characterized in that used fusing assistant is selected from NaF, NH 4Cl, AlF 3, H 3BO 3, BaCl 2, SrCl 2Or Na 2CO 3In one or more mixtures that form with arbitrary proportion.
7. LED is characterized in that with the preparation method of fluorescent material used fusing assistant is SrCl as claimed in claim 6 2With AlF 3Mixture by weight 1:1-1:4 formation.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104087299A (en) * 2014-06-19 2014-10-08 南京航空航天大学 Blue light-excited aluminate-based red fluorescent material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101113333A (en) * 2007-08-28 2008-01-30 厦门大学 Method for preparing cerium-activated yttrium aluminium garnet fluorescent powder
US20090212314A1 (en) * 2008-02-27 2009-08-27 The Regents Of The University Of California YELLOW EMITTING PHOSPHORS BASED ON Ce3+-DOPED ALUMINATE AND VIA SOLID SOLUTION FOR SOLID-STATE LIGHTING APPLICATIONS
CN102352248A (en) * 2011-09-19 2012-02-15 上海穗杉实业有限公司 Fluorescent powder for white light-emitting diodes (LEDs) and backlight LEDs
WO2012020341A1 (en) * 2010-08-10 2012-02-16 Koninklijke Philips Electronics N.V. Converter material for solar cells

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101113333A (en) * 2007-08-28 2008-01-30 厦门大学 Method for preparing cerium-activated yttrium aluminium garnet fluorescent powder
US20090212314A1 (en) * 2008-02-27 2009-08-27 The Regents Of The University Of California YELLOW EMITTING PHOSPHORS BASED ON Ce3+-DOPED ALUMINATE AND VIA SOLID SOLUTION FOR SOLID-STATE LIGHTING APPLICATIONS
WO2012020341A1 (en) * 2010-08-10 2012-02-16 Koninklijke Philips Electronics N.V. Converter material for solar cells
CN102352248A (en) * 2011-09-19 2012-02-15 上海穗杉实业有限公司 Fluorescent powder for white light-emitting diodes (LEDs) and backlight LEDs

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOO HYUN KIM,ET AL: "Luminescence characteristics and optimization of (La,Gd)Sr2(Al,B)O5:Ce phosphor for white light emitting diodes", 《JOURNAL OF LUMINESCENCE》, vol. 132, 30 January 2012 (2012-01-30), pages 1376 - 1381, XP028403380, DOI: doi:10.1016/j.jlumin.2012.01.029 *
JOO HYUN KIM,ET AL: "Preparation and luminescence characterization of fine-sized LaSr2AlO5:Ce phosphor prepared by spray pyrolysis", 《JOURNAL OF LUMINESCENCE》, vol. 131, 31 March 2011 (2011-03-31), pages 1487 - 1491, XP028197312, DOI: doi:10.1016/j.jlumin.2011.03.054 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104087299A (en) * 2014-06-19 2014-10-08 南京航空航天大学 Blue light-excited aluminate-based red fluorescent material and preparation method and application thereof
CN104087299B (en) * 2014-06-19 2016-08-31 南京航空航天大学 A kind of blue light activated aluminate-based red fluorescent material and preparation method and application

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Address after: 211100 Building 5, No. 69, Liquan Road, Jiangning high tech Zone, Nanjing, Jiangsu Province

Patentee after: Jiangsu Borui photoelectric Co.,Ltd.

Address before: 211100 No.69 Liquan Road, Science Park, Shangfang Town, Jiangning District, Nanjing City, Jiangsu Province

Patentee before: JIANGSU BREE OPTRONICS Co.,Ltd.

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