CN102002362B - Fluorescent powder for white light LED, preparation method and application thereof - Google Patents
Fluorescent powder for white light LED, preparation method and application thereof Download PDFInfo
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- CN102002362B CN102002362B CN2010102813272A CN201010281327A CN102002362B CN 102002362 B CN102002362 B CN 102002362B CN 2010102813272 A CN2010102813272 A CN 2010102813272A CN 201010281327 A CN201010281327 A CN 201010281327A CN 102002362 B CN102002362 B CN 102002362B
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Abstract
The invention relates to LED fluorescent powder, and a preparation method and application thereof. The LED fluorescent powder is characterized in that the chemical general formula is RE3-xNbO7:xEu3+, wherein RE is one or more of Y, La and Gd, and x is less than or equal to 1.00 and more than or equal to 0.10. The preparation method comprises the following steps: (1) weighing corresponding raw materials in mol ratio of the chemical general formula RE3-xNbO7:xEu3+, porphyrizing and uniformly mixing; (2) calcining the mixed materials in step (1) in a muffle furnace at high temperature, wherein the calcining temperature of the mixed materials is 1000-1600 DEG C, and the calcining time is 3-24 hours; and (3) carrying out post treatment on the calcined product in step (2). The fluorescent powder can be effectively activated by near ultraviolet light and blue light to glow, and the fluorescent powder can be well matched with near ultraviolet light and blue light LED chips. The fluorescent powder has stable physical/chemical properties, does not react with oxygen, water, carbon dioxide and the like in the environment and has the advantages of heat resistance, no toxicity and no public nuisance. The preparation method is simple and easy to operate and realizes the direct calcination in the air, thereby having good application prospects.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, particularly red fluorescent powder for white radiation LED and its preparation method and application.
Background technology
LED (light-emitting diode) is a kind of New Solid lighting electric light source, have that energy-efficient, environmental protection, overlong service life, volume are little, shock resistance, the advantage such as luminescence response is fast and operating voltage is low, be used widely already in fields such as pilot lamp, signal lamps, white light LEDs has begun now to incandescent light, luminescent lamp the strong challenge of firm status initiation in lighting field now, be expected to progressively replace, thereby present huge market outlook.
White light LEDs produces white light and mainly contains two approach: the first is with three kinds of LED combination results white lights of red, green, blue; the second is to mix with LED de-excitation light conversion phosphor to form white light, this approach has two kinds of implementations, wherein the method for comparative maturity is that blue-light LED chip and YAG:Ce yellow fluorescent powder arrange in pairs or groups to realize white light emission (United States Patent (USP) 5998925), but owing to lacking red light, the compound white light that obtains is cold white light, therefore, this scheme still need be added suitable red fluorescence powder and be improved its colour rendering index, another kind of scheme is with nearly purple LED chip (390-410nm) and red/green/blue three primary colors fluorescent powder combination, red fluorescence powder plays a part very important.
The chip that is used at present White-light LED illumination is mainly the near-ultraviolet light chip of 390～410nm and the blue chip about 465nm.And existing red fluorescence powder effectively excite the scope majority in shortwave UV zone, the launching efficiency under near ultraviolet and blue light is low.Therefore, near-ultraviolet light and the blue-ray LED of development efficient stable seem particularly important with red fluorescence powder.At present, still lack the red fluorescence powder that can be excited by near-ultraviolet light or blue-light LED chip of excellent performance on market, the rouge and powder that especially can be simultaneously excited by near-ultraviolet light and blue led also is in conceptual phase.
In the report of red fluorescent powder for white radiation LED, can luminous intensity and stable aspect all reach the also rarely found of application requiring.For example: someone attempts Y
2O
2S:Eu
3+Be applied to the WLED field, yet, present commercial red fluorescence powder Y
2O
2S:Eu
3+Have shortcomings: luminous efficiency is low under near ultraviolet excitation, and chemical property is unstable, easily decomposes, and the life-span is short, and separating out of element sulphur can cause corrosive effects to chip, thereby causes the inefficacy of whole device.Several classes that relate in document and patent report are main is expected to also have for the red fluorescence powder of white light LEDs: Ca
3(VO
4)
2: Eu
3+, YVO
4: Eu
3+, Y
2O
3: Eu
3+, Bi
3+, CaO:Eu
3+, CaMoO
4: Eu
3+, (Gd, Y, Eu)
2(MoO
4)
3: Sm
3+, (Sr, Ca) S:Eu
2+, Ca
5(SiO
4)
2Cl
2: Eu
2+, Sr
2Si
5N
8: Eu
2+Deng.Wherein the stable high-luminous-efficiency of rare-earth activated oxynitride is good and come into one's own, as: Sr
2Si
5N
8: Eu
2+, SrSi
2O
2N
2: Eu
2+, need to complete under high temperature (1600-1700 ℃) high nitrogen or ammonia pressure (10atm) but the matrix of this class material is synthetic, very harsh to the requirement of production unit.
At present about with Eu
3+Be active ions, niobate be the bibliographical information of red fluorescent powder for white radiation LED of matrix and patent seldom.Tae-Keun Park etc. has studied the Bi that mixes high density
3+To RNbO
4: Eu
3+The impact of (R=La, Y, Gd) photoluminescence performance (Journal of the Korean Physical Society, 2008,52:431 ↑ 434); Zhou Liya etc. study Eu
3+Concentration is to LaNb
0.70V
0.30O
4: Eu
3+The impact of emmission spectrum, proved V
5+Mix make excitation band to long wave direction broadening (Journal of Alloys and Compounds 2010,495:268-271).Patent of invention CN1239673C and CN1331982C all relate to the phosphor for white light LED take niobate as matrix.
Summary of the invention
The purpose of this invention is to provide a kind of stable chemical performance, illumination effect is good, and ideal color purity can effectively be excited and the phosphor for white light LED of burn red by near-ultraviolet light, blue light.
Another object of the present invention is to provide the preparation method of above-mentioned red fluorescence powder.The preparation method of this fluorescent material is simple, and easy handling is pollution-free, and cost is low.
A further object of the present invention is the application of fluorescent material of the present invention on white light LED electric light source.
For achieving the above object, the present invention is achieved through the following technical solutions:
Adopt stable RE
3-xNbO
7Be matrix, Eu
3+As active ions, its chemical constitution general formula is RE
3-xNbO
7: xEu
3+, wherein RE is Y, La, one or more in Gd, 0.10≤x≤1.00.
The preparation method of the fluorescent material that the present invention relates to is as follows:
(1) according to chemical constitution formula RE
3-xNbO
7: xEu
3+The mol ratio that (wherein RE is Y, La, one or more in Gd, 0.10≤x≤1.00) requires accurately takes raw material, grinds, and makes its mixing;
(2) mixture that step (1) is obtained is put into the high-temperature roasting of retort furnace air atmosphere, and the maturing temperature of mixture is 1000～1600 ℃, and roasting time is 3～24 hours;
(3) product of roasting that obtains in step (2) is passed through last handling process again, namely obtain this red fluorescence powder;
Raw material Nb of the present invention, Y, La, Gd, Eu are simple substance, perhaps its oxide compound, perhaps its corresponding salt.
In step of the present invention (1), can add reaction flux, described reaction flux is one or more in halogenide, vitriol, boron trioxide or the boric acid of Li.
In step of the present invention (1), with respect to the gross weight of the fluorescent material that will synthesize, the add-on of fusing assistant is 0.001～10wt%.
In step of the present invention (2), more than high-temperature roasting can be divided into once or twice; Each maturing temperature is 1000～1600 ℃, and roasting time is 3～24 hours.
In step of the present invention (3), last handling process comprises fragmentation, comminution by gas stream, removal of impurities, oven dry and classification.Described removal of impurities process comprises pickling, alkali cleaning or washing.Described classification process comprises settling methods, method of sieving, hydraulic elutria-tion method or air classification method.
Application on white light LED electric light source of the present invention is to be prepared into electric light source with containing the prepared fluorescent material of the present invention and near ultraviolet or blue-ray LED.
It is wide that the fluorescent material that the present invention synthesized has excitation wavelength range, illumination effect is good, the characteristics such as physical and chemical performance is stable, can effectively be excited and launch red light by near-ultraviolet light, blue light, thereby can be coated in and prepare novel white LED light source on blue-ray LED, also can mate with near-ultraviolet light LED, the fluorescent material that mixes other colors, preparation white light or colored LED light source show application prospect widely, and especially the application potential at the White-light LED illumination technical elements is huge.
Characteristics of the present invention:
(1) the present invention is with RE
3-xNO
7Niobate is matrix, with Eu
3+(wherein RE is Y for excitation center, La, one or more in Gd, 0.10≤x≤1.00), made and effectively to have been excited and the fluorescent material of the light that glows by near-ultraviolet light, blue light, this powder can mate with near-ultraviolet light and blue-light LED chip well, is a kind of red fluorescent powder for white radiation LED of new high-efficiency.
(2) red fluorescence powder physical and chemical performance of the present invention is stable, and with the oxygen in environment, water, carbonic acid gas etc. do not react, and are heat-resisting, nontoxic, nuisanceless.
(3) red fluorescence powder, preparation method thereof of the present invention is simple and easy in operation, does not also use the special gas protection, and directly roasting in air has good application prospect.
Description of drawings
Fig. 1 is the Y of embodiment 1 preparation
1.5NbO
7:
1.5Eu
3+The excitation spectrum (left side) under 612nm monitoring and the emmission spectrum under 395nm excites (right side) respectively, as shown in the figure, this fluorescent material can effectively be excited by the near-ultraviolet light of 350～550nm scope, blue light and green glow and send the ruddiness that peak wavelength is positioned at about 612nm, wherein near-ultraviolet light has higher excitation intensity, and red purity is very high.
Fig. 2 is the Gd of embodiment 2 preparations
1.8NbO
7:
1.2Eu
3+The excitation spectrum (left side) under 612nm monitoring and the emmission spectrum (right side) under 395nm and 465nm excite respectively, as shown in the figure, this fluorescent material can effectively be excited by the near-ultraviolet light of 350～550nm scope, blue light and green glow and send the ruddiness that peak wavelength is positioned at about 612nm, wherein near-ultraviolet light has higher excitation intensity, and red purity is very high.
Fig. 3 is the La of embodiment 3 preparations
1.5NbO
7:
1.5Eu
3+The excitation spectrum (left side) under 612nm monitoring and the emmission spectrum (right side) under 395nm and 465nm excite respectively, as shown in the figure, this fluorescent material can effectively be excited by the near-ultraviolet light of 350～550nm scope, blue light and green glow and send the ruddiness that peak wavelength is positioned at about 612nm, wherein near-ultraviolet light has higher excitation intensity, and red purity is very high.
Embodiment
The present invention will be described further by following examples.
Embodiment 1:Y
1.5NbO
7:
1.5Eu
3+The Preparation Example of fluorescent material
Take respectively 1.3969 gram Y
2O
3(99.999%), 1.0962 gram Nb
2O
5(99.999%), 2.1771 gram Eu
2O
3(99.999%), 0.4000 gram LiCl (analytical pure), wherein LiCl is as reaction flux, in agate mortar ground and mixed evenly after, the alumina crucible of packing into, 1200 ℃ of roastings are 8 hours in air atmosphere, cool to room temperature with the furnace, washing removal of impurities, drying, levigate namely get the Y in the present invention
1.5NbO
7:
1.5Eu
3+Red fluorescence powder.Its excitation and emission spectra is seen Fig. 1.
Embodiment 2:Gd
1.8NbO
7:
1.2Eu
3+The Preparation Example of fluorescent material
Take respectively 2.2966 gram Gd
2O
3(99.999%), 0.93558 gram Nb
2O
5(99.999%), 1.4864 gram Eu
2O
3(99.999%), 0.4000 gram LiCl (analytical pure), wherein LiCl is as reaction flux, in agate mortar ground and mixed evenly after, the alumina crucible of packing into, 1200 ℃ of roastings are 8 hours in air atmosphere, cool to room temperature with the furnace, washing removal of impurities, drying, levigate namely get the Gd in the present invention
1.8NbO
7:
12Eu
3+Red fluorescence powder.Its excitation and emission spectra is seen Fig. 2.
Embodiment 3:La
1.5NbO
7:
1.5Eu
3+The Preparation Example of fluorescent material
Take respectively 1.7936 gram La
2O
3(99.999%), 0.9756 gram Nb
2O
5(99.999%), 1.9374 gram Eu
2O
3(99.999%), 0.4000 gram LiCl (analytical pure), wherein LiCl is as reaction flux, in agate mortar ground and mixed evenly after, the alumina crucible of packing into, 1200 ℃ of roastings are 8 hours in air atmosphere, cool to room temperature with the furnace, washing removal of impurities, drying, levigate namely get the Gd in the present invention
1.8NbO
7:
1.2Eu
3+Red fluorescence powder.Its excitation and emission spectra is seen Fig. 3.
Claims (8)
1. LED fluorescent material is characterized in that its chemical constitution general formula is:
RE
3-xNbO
7:xEu
3+
Wherein, RE is Y, La, one or more in Gd, 0.10≤x≤1.00.
2. the preparation method of a fluorescent material claimed in claim 1 is characterized in that:
(1) according to chemical constitution formula RE
3-xNbO
7: xEu
3+Mol ratio take raw material, porphyrize mixes;
(2) mixture that step (1) is obtained is put into the retort furnace high-temperature roasting, and the maturing temperature of mixture is 1000-1600 ℃, and roasting time is 3-24 hour;
(3) product of roasting that obtains in step (2) is passed through last handling process again, namely obtain this fluorescent material.
3. preparation method according to claim 2, is characterized in that described Nb, Y, La, Gd, Eu are simple substance, perhaps its oxide compound, perhaps its corresponding salt.
4. preparation method according to claim 2, is characterized in that adding reaction flux in step (1), and described reaction flux is one or more in halogenide, vitriol, boron trioxide or the boric acid of Li.
5. preparation method according to claim 4, is characterized in that the gross weight with respect to the fluorescent material that will synthesize, and the add-on of fusing assistant is 0.001～10wt%.
6. preparation method according to claim 2, is characterized in that in described step (2), and more than high-temperature roasting can be divided into once or twice, each maturing temperature 1000-1600 ℃, roasting time was 3-24 hour.
7. preparation method according to claim 2, in the described step of its feature (3), last handling process comprises fragmentation, removal of impurities, dries and sieves.
8. fluorescent material claimed in claim 1 and near ultraviolet or the blue-ray LED application on the preparation electric light source.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102813272A CN102002362B (en) | 2010-09-14 | 2010-09-14 | Fluorescent powder for white light LED, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102813272A CN102002362B (en) | 2010-09-14 | 2010-09-14 | Fluorescent powder for white light LED, preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102002362A CN102002362A (en) | 2011-04-06 |
| CN102002362B true CN102002362B (en) | 2013-05-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260501B (en) * | 2011-05-17 | 2013-12-04 | 内蒙古大学 | Method for preparing red nano-fluorescent material |
| CN116814263B (en) * | 2023-06-07 | 2024-05-28 | 云南大学 | Single-phase white light fluorescent material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539914A (en) * | 2003-10-23 | 2004-10-27 | 北京有色金属研究总院 | Red luminescent powder in use for LED, preparing method and electric light source produced |
| CN1760326A (en) * | 2004-10-11 | 2006-04-19 | 北京有色金属研究总院 | Phosphor powder of composite oxide in use for white light LED and fabricated electric light source |
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|---|---|---|---|---|
| JP4309242B2 (en) * | 2003-12-19 | 2009-08-05 | Ｎｅｃライティング株式会社 | Red phosphor material, white light emitting diode using red phosphor material, and lighting device using white light emitting diode |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1539914A (en) * | 2003-10-23 | 2004-10-27 | 北京有色金属研究总院 | Red luminescent powder in use for LED, preparing method and electric light source produced |
| CN1760326A (en) * | 2004-10-11 | 2006-04-19 | 北京有色金属研究总院 | Phosphor powder of composite oxide in use for white light LED and fabricated electric light source |
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Effective date of registration: 20210423 Address after: 226200 No. 500 Linyang Road, Qidong Economic Development Zone, Nantong City, Jiangsu Province Patentee after: QIDONG SHENGHAN MEDICAL TECHNOLOGY Co.,Ltd. Address before: 999 No. 330031 Jiangxi province Nanchang Honggutan University Avenue Patentee before: Nanchang University |
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