CN102140343A - Synthesis method of red fluorescent powder - Google Patents
Synthesis method of red fluorescent powder Download PDFInfo
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- CN102140343A CN102140343A CN2011100575838A CN201110057583A CN102140343A CN 102140343 A CN102140343 A CN 102140343A CN 2011100575838 A CN2011100575838 A CN 2011100575838A CN 201110057583 A CN201110057583 A CN 201110057583A CN 102140343 A CN102140343 A CN 102140343A
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Abstract
The invention discloses a synthesis method of fluorescent powder capable of emitting red fluorescence. The process proportioning of the material is calculated according to the chemical composition (Ca1-y,Sry)MxS:zEu<2+>; and the method comprises the following steps: performing high temperature solid phase reaction in a weak reducing atmosphere at 1050-1400 DEG C for 3-10 hours and coating with lanthanum phosphate solution. The obtained fluorescent powder has wide excitation spectrum range, good excitation efficiency near 430-490nm of blue light and high luminance, has the functions of increasing the color rendering index of the white LED and the like, and is difficult to oxidize again.
Description
Technical field
The present invention relates to the synthetic method of a kind of white light LEDs with luminophore, particularly (430～490nm) excite the synthetic method of the red fluorescence powder that uses down at blue light.
Background technology
At present, white light LEDs be applied to show or throw light in mainly still produce white light in blue mode with yellow complementary color, just most blue light-emitting chips that adopt add the fluorescent material of the light that turn to be yellow, produce white light afterwards through lighting.Compare differs greatly the emmission spectrum of this white light with natural spectrum (also claiming standard spectrum), so color developing is relatively poor, thereby causes colour rendering index (colour rendering index is represented with Ra) not high.If adopt the chip of sending out UV-light to add the white light that red, green, blue (perhaps using blue chip) is formed respectively, colour rendering index will improve a lot, but the efficient of giving out light but significantly reduces.
No matter be which kind of lighting source, comprise led light source, colour rendering index is all relevant with the distribution of its emmission spectrum.Approaching more natural spectrum (also claiming standard spectrum), its colour rendering index is just high more.In order to improve color developing, promote colour rendering index, can take to replenish the part spectrum that lacks on the spectrum band theoretically, also can cause optical throughput to reduce when still doing like this.The phosphor material powder that chooses when improving the Ra of white light LEDs is quite important, use red and green fluorescent material in the blue led collocation at present, and utilize the technology that in ultraviolet leds, adds red bluish-green fluorescent material to improve the Ra value, reach the target of high-color rendering.The Ra of raising white light LEDs is that good light conversion efficiency should be arranged to the requirement of luminescent material, possesses good ageing resistance again.Analyze from emmission spectrum, at least need a kind of emission main peak at red area (600～680nm) luminescent material, and this luminophore can be excited by near ultraviolet to the light of blue region and launch ruddiness, and this project luminophore characteristics possess above characteristic exactly.A kind of red fluorescence powder is through adding in the fluorescent material of traditional jaundice light, encapsulation is after after blue chip excites, the white light colour rendering index that is produced has obtained significantly improving, also can mix from 2000k～5500k different-colour white light LEDs simultaneously, this series products has good commercial use value.
Summary of the invention
Technical problem to be solved by this invention provides a kind of synthetic method with luminescent material of emission red fluorescence, and particularly a kind of (430～490nm) excite the synthetic method of the red fluorescence powder that uses down at blue light.
In order to solve above-mentioned technical problem, technical scheme of the present invention is: a kind of synthetic method of red fluorescence powder, and it may further comprise the steps:
(1) according to chemical composition (Ca
1-y, Sr
y) M
xS: zEu
2+Calculate processing compound, wherein, M is a kind of among Ga, Al, Mg or the Zn, and 0＜x＜0.3.And 0＜y＜0.5; 0＜z＜0.2;
(2) set by step (1) chemical composition proportioning takes by weighing raw material, and get in the additive of fluxing one or more, the weight of additive of fluxing is 0.5～3% of raw material weight, evenly behind the batch mixing, also cover completely in the corundum crucible of packing into, put into and carry out calcination in the weakly reducing atmosphere stove with the corundum lid, the calcination soaking time was controlled at 3～10 hours, temperature is controlled at 1050～1400 ℃, and it is block that the powder after the calcination becomes, and the powder color is a scarlet;
(3) powder is through crossing 200 order dry screens after the break process, product coats through carrying out lanthanum orthophosphate solution after testing, material is slowly added in the lanthanum orthophosphate solution, stir simultaneously, material adds the back continuation churning time that finishes and was controlled at 1～2 hour, comes regulator solution PH to get final product to neutral according to Property of Acid and Alkali of Solution with ammoniacal liquor at last, treat complete post precipitation removal supernatant liquor after stopping to stir, the throw out taking-up is filtered, put oven for drying into, bake out temperature is controlled at 100～150 ℃;
(4) be finished product, airtight preservation after the powder after will drying sieves through 100 orders.
Adopt following main raw material in the synthetic method of emitting red light material of the present invention: fluorescence europium oxide (Eu
2O
3), analytical pure sulfuric acid calcium (CaSO
4), high-purity strontium carbonate (SrCO
3), high-purity calcium carbonate (CaCO
3), high-purity magnesium oxide (MgO), high-purity zinc oxide (ZnO), high purity aluminium oxide (Al
2O
3), high-purity gallium oxide (Ga
2O
3).Other trace additive of fluxing is selected barium fluoride (BaF for use
2), strontium fluoride (SrF
2), lithium chloride (LiCl), lithium fluoride (LiF), get wherein one or more.
The present invention is by the mix synthetic method of Ga, Al, Mg or one kind of Zn and micro-fusing assistant of component, final by handling in coating to particle surface, having solved the sulfidic material that the general technology skill produced causes the sulphur to separate out problem easily, and powder granularity is evenly distributed, good fluidity, product has also obtained significantly improving on luminous intensity and heatproof degree are aging, and remarkable effect has also been played in the lifting of white light LEDs color developing.
Description of drawings
Accompanying drawing is luminophore emmission spectrum figure of the present invention.
Embodiment
Embodiment 1
With raw material: europium sesquioxide 0.01g, calcium sulfate 89.44g, lime carbonate 5.22g, Strontium carbonate powder 11.48g, magnesium oxide 2.10g, barium fluoride 0.541g mix grinding 1.5 hours in the ball grinder of the corundum material of 1 liter capacity, abrasive substance uses diameter to be about the 10mm agate ball, the material that mix grinding is good is packed into to put in the corundum crucible and was carried out pyroreaction under the hydrogen and nitrogen gas reducing atmosphere 3 hours, reduction temperature is controlled at 1400 ℃, after the pyroreaction lumpy material through after the break process through 200 mesh sieves, then carrying out the lanthanum orthophosphate coating handles, product coats through carrying out lanthanum orthophosphate solution after testing, material is slowly added in the lanthanum orthophosphate solution, stir simultaneously, material adds the back continuation churning time that finishes and was controlled at 1.0 hours, come regulator solution PH to get final product according to Property of Acid and Alkali of Solution with ammoniacal liquor at last to neutral, treat complete post precipitation removal supernatant liquor after stopping to stir, the throw out taking-up is filtered, put oven for drying into, bake out temperature is controlled at 100 ℃; Oven dry back finished product sieves, tests.The emission characteristic spectrum of this luminophore process ultraviolet excitation as shown in drawings.
Embodiment 2
With raw material: europium sesquioxide 0.01g, calcium sulfate 85.72g, Strontium carbonate powder 14.17g, magnesium oxide 2.70g, barium fluoride 2.55g, strontium fluoride 0.528g mix grinding 1.5 hours in the ball grinder of the corundum material of 1 liter capacity, abrasive substance uses diameter to be about the 10mm agate ball, the material that mix grinding is good is packed into to put in the corundum crucible and was carried out pyroreaction under the hydrogen and nitrogen gas reducing atmosphere 5 hours, reduction temperature is controlled at 1300 ℃, after the pyroreaction lumpy material through after the break process through 200 mesh sieves, then carrying out the lanthanum orthophosphate coating handles, product coats through carrying out lanthanum orthophosphate solution after testing, material is slowly added in the lanthanum orthophosphate solution, stir simultaneously, material adds the back continuation churning time that finishes and was controlled at 1.5 hours, come regulator solution PH to get final product according to Property of Acid and Alkali of Solution with ammoniacal liquor at last to neutral, treat complete post precipitation removal supernatant liquor after stopping to stir, the throw out taking-up is filtered, put oven for drying into, bake out temperature is controlled at 120 ℃; Oven dry back finished product sieves, tests.The emission characteristic spectrum of this luminophore process ultraviolet excitation as shown in drawings.
Embodiment 3
With raw material: europium sesquioxide 0.01g, calcium sulfate 86.13g, Strontium carbonate powder 10.50g, magnesium oxide 1.70g, zinc oxide 0.66g, barium fluoride 0.154g, lithium chloride 0.85g mix grinding 1.5 hours in the ball grinder of the corundum material of 1 liter capacity, abrasive substance uses diameter to be about the 10mm agate ball, the material that mix grinding is good is packed into to put in the corundum crucible and was carried out pyroreaction under the hydrogen and nitrogen gas reducing atmosphere 5 hours, reduction temperature is controlled at 1300 ℃, after the pyroreaction lumpy material through after the break process through 200 mesh sieves, then carrying out the lanthanum orthophosphate coating handles, product coats through carrying out lanthanum orthophosphate solution after testing, material is slowly added in the lanthanum orthophosphate solution, stir simultaneously, material adds the back continuation churning time that finishes and was controlled at 1.5 hours, come regulator solution PH to get final product according to Property of Acid and Alkali of Solution with ammoniacal liquor at last to neutral, treat complete post precipitation removal supernatant liquor after stopping to stir, the throw out taking-up is filtered, put oven for drying into, bake out temperature is controlled at 130 ℃; Oven dry back finished product sieves, tests.The emission characteristic spectrum of this luminophore process ultraviolet excitation as shown in drawings.
Embodiment 4
With raw material: europium sesquioxide 0.01g, calcium sulfate 83.61g, Strontium carbonate powder 7.34g, gallium oxide 2.71g, lithium fluoride 1.25g, lithium chloride 0.50g mix grinding 1.5 hours in the ball grinder of the corundum material of 1 liter capacity, abrasive substance uses diameter to be about the 10mm agate ball, the material that mix grinding is good is packed into to put in the corundum crucible and was carried out pyroreaction under the hydrogen and nitrogen gas reducing atmosphere 8 hours, reduction temperature is controlled at 1200 ℃, after the pyroreaction lumpy material through after the break process through 200 mesh sieves, then carrying out the lanthanum orthophosphate coating handles, product coats through carrying out lanthanum orthophosphate solution after testing, material is slowly added in the lanthanum orthophosphate solution, stir simultaneously, material adds the back continuation churning time that finishes and was controlled at 2 hours, come regulator solution PH to get final product according to Property of Acid and Alkali of Solution with ammoniacal liquor at last to neutral, treat complete post precipitation removal supernatant liquor after stopping to stir, the throw out taking-up is filtered, put oven for drying into, bake out temperature is controlled at 120 ℃; Oven dry back finished product sieves, tests.The emission characteristic spectrum of this luminophore process ultraviolet excitation as shown in drawings.
Embodiment 5
With raw material: europium sesquioxide 0.01g, calcium sulfate 87.29g, lime carbonate 7.34g, Strontium carbonate powder 5.26g, gallium oxide 0.71g, aluminum oxide 1.98g, barium fluoride 1.75g, strontium fluoride 0.262g mix grinding 1.5 hours in the ball grinder of the corundum material of 1 liter capacity, abrasive substance uses diameter to be about the 10mm agate ball, the material that mix grinding is good is packed into to put in the corundum crucible and was carried out pyroreaction under the hydrogen and nitrogen gas reducing atmosphere 10 hours, reduction temperature is controlled at 1050 ℃, after the pyroreaction lumpy material through after the break process through 200 mesh sieves, then carrying out the lanthanum orthophosphate coating handles, product coats through carrying out lanthanum orthophosphate solution after testing, material is slowly added in the lanthanum orthophosphate solution, stir simultaneously, material adds the back continuation churning time that finishes and was controlled at 2 hours, come regulator solution PH to get final product according to Property of Acid and Alkali of Solution with ammoniacal liquor at last to neutral, treat complete post precipitation removal supernatant liquor after stopping to stir, the throw out taking-up is filtered, put oven for drying into, bake out temperature is controlled at 150 ℃; Oven dry back finished product sieves, tests.The emission characteristic spectrum of this luminophore process ultraviolet excitation as shown in drawings.
The foregoing description and reference sample related data synopsis:
Annotate: the reference sample is that domestic conventional fabrication processes is produced sulfurated lime: europium (CaS:Eu) rouge and powder, being decided to be normal brightness is 100%.
The foregoing description does not limit the present invention in any way, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops in protection scope of the present invention.
Claims (1)
1. the synthetic method of a red fluorescence powder is characterized in that may further comprise the steps:
(1) according to chemical composition (Ca
1-y, Sr
y) M
xS: zEu
2+Calculate processing compound, wherein, M is a kind of among Ga, Al, Mg or the Zn, and 0＜x＜0.3, and 0＜y＜0.5,0＜z＜0.2;
(2) set by step (1) chemical composition proportioning takes by weighing raw material, and takes by weighing barium fluoride (BaF
2), strontium fluoride (SrF
2), in the lithium chloride (LiCl), lithium fluoride (LiF) one or more are as fluxing additive, the weight of additive of fluxing is 0.5～3% of raw material weight, evenly behind the batch mixing, pack in the corundum crucible and cover completely with the corundum lid, put into and carry out calcination in the weakly reducing atmosphere stove, the calcination soaking time was controlled at 3～10 hours, and temperature is controlled at 1050～1400 ℃, it is block that powder after the calcination becomes, and the powder color is a scarlet;
(3) powder is through crossing 200 order dry screens after the break process, product coats through carrying out lanthanum orthophosphate solution after testing, material is slowly added in the lanthanum orthophosphate solution, stir simultaneously, material adds the back continuation churning time that finishes and was controlled at 1～2 hour, comes regulator solution PH to get final product to neutral according to Property of Acid and Alkali of Solution with ammoniacal liquor at last, treat complete post precipitation removal supernatant liquor after stopping to stir, the throw out taking-up is filtered, put oven for drying into, bake out temperature is controlled at 100～150 ℃;
(4) be finished product, airtight preservation after the powder after will drying sieves through 100 orders.
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| CN 201110057583 CN102140343B (en) | 2011-03-10 | 2011-03-10 | Synthesis method of red fluorescent powder |
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|---|---|---|---|
| CN 201110057583 CN102140343B (en) | 2011-03-10 | 2011-03-10 | Synthesis method of red fluorescent powder |
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|---|---|
| CN102140343A true CN102140343A (en) | 2011-08-03 |
| CN102140343B CN102140343B (en) | 2013-02-27 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045241A (en) * | 2013-01-15 | 2013-04-17 | 重庆希晨科技有限公司 | Sulphide red fluorescent material for white-light LED (light-emitting diode) and preparation method for same |
| CN106967431A (en) * | 2017-03-22 | 2017-07-21 | 安徽师范大学 | Fluorescent material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070023734A1 (en) * | 2005-07-28 | 2007-02-01 | Sony Corporation | Phosphor, optical device, and display device |
| CN101009341A (en) * | 2006-01-27 | 2007-08-01 | 亿光电子工业股份有限公司 | Fluorescent body and its white light LED |
| CN101120204A (en) * | 2005-02-14 | 2008-02-06 | 三菱化学株式会社 | Light source, solid-state light-emitting element module, phosphor module, light distribution element module, illumination device and image display device, and light control method for the light source |
-
2011
- 2011-03-10 CN CN 201110057583 patent/CN102140343B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101120204A (en) * | 2005-02-14 | 2008-02-06 | 三菱化学株式会社 | Light source, solid-state light-emitting element module, phosphor module, light distribution element module, illumination device and image display device, and light control method for the light source |
| US20070023734A1 (en) * | 2005-07-28 | 2007-02-01 | Sony Corporation | Phosphor, optical device, and display device |
| CN101009341A (en) * | 2006-01-27 | 2007-08-01 | 亿光电子工业股份有限公司 | Fluorescent body and its white light LED |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045241A (en) * | 2013-01-15 | 2013-04-17 | 重庆希晨科技有限公司 | Sulphide red fluorescent material for white-light LED (light-emitting diode) and preparation method for same |
| CN106967431A (en) * | 2017-03-22 | 2017-07-21 | 安徽师范大学 | Fluorescent material and preparation method thereof |
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|---|---|
| CN102140343B (en) | 2013-02-27 |
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