CN1827735A - Alkaline-earth metal silicate fluorescent powder and its preparation method and application - Google Patents
Alkaline-earth metal silicate fluorescent powder and its preparation method and application Download PDFInfo
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- CN1827735A CN1827735A CNA2006100256988A CN200610025698A CN1827735A CN 1827735 A CN1827735 A CN 1827735A CN A2006100256988 A CNA2006100256988 A CN A2006100256988A CN 200610025698 A CN200610025698 A CN 200610025698A CN 1827735 A CN1827735 A CN 1827735A
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Abstract
The invention belongs to the rare-earth luminescent material technical sphere, specifically an alkali earth metal silicate fluorescent powder activated by europium and its process for preparing and its application are disclosed. The chemical formula of the said fluorescent powder is: SrxBa2-x-yEuySizO2+2z, in which 1<x<2, 0.02<=y<=0.2, 0.7<=z<=1.5. The fluorescent powder can be excitated by ultraviolet, purple light and blue light, the range of wavelength of the excitation wave is between 300nm and 520nm, and the wavelength of the emission main peak can be adjusted between 547nm and 585nm along with the variation in component concentration. The white-light LED with a color-temperature between 2800K and 6500K can be prepared by combining fluorescent powder of different concentration with blue-light chip; and the white-light LED with a low color-temperature can be prepared by combining the said fluorescent powder with blue-light LED.
Description
Technical field
The invention belongs to rare earth luminescent material technical field, relate in particular to the white LED light source that a kind of rare-earth europium activated alkaline-earth metal silicate fluorescent powder and its production and application this fluorescent material is made.
Background technology
At present, with led chip and phosphor combination, utilize the optical excitation fluorescent material of LED emission and mix to form a kind of common method that white light is the preparation white light LEDs.Wherein, cooperate the YAG:Ce fluorescent material of jaundice light with the InGaN blue-light LED chip, it is to prepare white light LEDs at present than method in common that the gold-tinted of being launched by the blue light and the fluorescent material of the chip emission that transmits is combined to form white light; Because lack the ruddiness of wavelength greater than 600nm in this white light LEDs spectrum, its colour rendering index (Ra) is not high, correlated(color)temperature is higher and along with angle changes.Expect colour rendering index height, the white light that correlated(color)temperature is low, need to add to glow or the fluorescent material of green glow.But can by blue-light excited red fluorescence powder or light conversion efficiency is low, or character instability.In addition, also there is the problem of light efficiency and stable aspect at present in the white light LEDs of fluorescent material (YAG:Ce) combination of blue chip (InGaN) and jaundice light.There are some researches show that along with the raising of working temperature, InGaN chip light emitting wavelength can be subjected to displacement, not only cause the reduction of YAG:Ce absorption and launching efficiency, can cause that simultaneously white light LEDs look drift and light efficiency takes place along with burning time prolongs significantly descends.Therefore, exploitation good stability, exciting light spectrum width, can the emitted fluorescence powder also be arranged to substitute YAG:Ce and exploitation can be had very important significance to preparing high-quality white light LEDs by purple light excited fluorescent material at red area.
Summary of the invention
The object of the present invention is to provide a kind of wide range excite (360～470nm), emmission spectrum in yellow to orange areas, the simple rare-earth europium activated of preparation technology alkaline-earth metal silicate fluorescent powder and its production and application, to overcome because the problems that correlation technique restriction and shortcoming cause.
Europium provided by the invention activates alkaline-earth metal silicate fluorescent powder, and its moiety can be by following chemical formulation: Sr
xBa
2-x-yEu
ySi
zO
2+2z, 1＜x＜2,0.02≤y≤0.2,0.7≤z≤1.5 wherein.
The preparation method of above-mentioned rare-earth europium activated alkaline-earth metal silicate fluorescent powder provided by the invention may further comprise the steps:
(1) presses chemical formula Sr
xBa
2-x-yEu
ySi
zO
2+2z(wherein 1＜x＜2,0.02≤y≤0.2,0.7≤z≤1.5) take by weighing high-purity chemical reagent Strontium carbonate powder (SrCO of requirement
3), barium carbonate (BaCO
3), silicon-dioxide (SiO
2) and europium sesquioxide (Eu
2O
3), taking by weighing the fusing assistant that accounts for chemical formula 0.3%～3% quality again, mixed grinding (about 2～3 hours) makes its abundant mixing.
(2) above-mentioned uniform mixture is packed into corundum crucible, and place High Temperature Furnaces Heating Apparatus, at air (or H
2/ N
2Atmosphere) 1100～1400 ℃ of sintering are 3～10 hours in; Then at H
2/ N
2Reducing atmosphere (H wherein
2Account in 5～10vol.%) and handled 1～3 hour under 1000～1350 ℃.
(3) in reducing atmosphere, drop to room temperature after, burned material is crushed to desired particle size, with 70～85 ℃ of deionized water wash, in 120～150 ℃ of baking ovens dry 6～10 hours, can obtain product.
Among the present invention, used fusing assistant can be SrF
2, BaF
2, NH
4HF
2, SrCl
2, BaCl
2, NH
4Cl, H
3BO
3In one or more, its consumption is 0.3%～3%, preferred 1～2% of a fluorescent material chemical formula quality.
Fluorescent material of the present invention can be by ultraviolet, purple light and blue-light excited, and excitation wavelength range is 300～520nm, along with concentration of component changes emission peak wavelength modulation between 547～585nm.
Therefore, by fluorescent material Sr
xBa
2-x-yEu
ySi
zO
2+2z(wherein 1＜x＜2,0.02≤y≤0.2,0.7≤z≤1.5) obtain white LED light source with blue chip or purple light chip portfolio.
According to the present invention, can obtain excitation spectrum and have and depend on that yellow that Ba replacement amount and fusing assistant kind and concentration main peak be easy to move is to the fluorescent orange powder.Therefore, ((emission peak wavelength can be used to prepare the white LED light source of different-colour 360～400nm) to emission peak wavelength with the purple LED chip 450～470nm) fluorescent material of the present invention to be applied to blue-light LED chip.
Description of drawings
Fig. 1 is the exciting light spectrogram of europkium-activated alkaline-earth metal silicate fluorescent powder provided by the invention in the 575nm emission.
Fig. 2 is that several fluorescent material of the present invention is along with forming and the preparation condition variation emmission spectrum figure under 365nm excites.
Fig. 3 is the structure iron of the white light LEDs of application silicate fluorescent powder preparation provided by the invention.
The emmission spectrum figure of the led light source that Fig. 4 obtains for silicate fluorescent powder provided by the invention and blue chip and purple light chip portfolio.
Embodiment
Describe the preferred embodiments of the invention with reference to the accompanying drawings in detail.It is evident that for the person of ordinary skill of the art: under the situation that does not deviate from the spirit and scope of the invention, can therefrom carry out various improvement and variation.Thereby improvement of the present invention and the variation within the scope that is in claims and equivalent thereof contained in the present invention.
The specific embodiments of essence according to the present invention about the manufacture method of europkium-activated alkaline-earth metal silicate fluorescent powder hereinafter will be described.
At first, take by weighing high purity reagent Strontium carbonate powder (SrCO
3), barium carbonate (BaCO
3), silicon-dioxide (SiO
2) and europium sesquioxide (Eu
2O
3).Wherein: the ratio of the total mole number of positively charged ion (Sr+Ba+Eu) and the mole number of Si should be between 2/0.7～1.5, and more excellent is between 2/0.80～1.The mol ratio of Sr/Ba is between 37～4, and more excellent is between 15～20.Eu accounts for cationic molar fraction between 0.02～0.2, and more excellent is between 0.05～0.15.Take by weighing the fusing assistant that accounts for chemical formula 0.3%～3% quality again, more excellent is the fusing assistant of Chemical formula 1～2% quality.They were ground in mortar 2～3 hours, make its abundant mixing.
Afterwards,, and place High Temperature Furnaces Heating Apparatus, be warmed up to 1100～1400 ℃, sintering 3～10 hours with the speed of 8～12 ℃/min with said mixture pack into corundum crucible, compacting.Then at H
2/ N
2Reduction (H
2Volume content 5～10%) 1000～1350 ℃ were reduced 1～3 hour in.Cool to room temperature in the reduction atmosphere, with above-mentioned sinter from High Temperature Furnaces Heating Apparatus, takes out, fragmentation, with 80 ℃ of left and right sides deionized water wash three times (3L water/kg powder), 120～150 ℃ of baking ovens toast and promptly got alleged fluorescent material in 6～10 hours.
Embodiment:
In order to guarantee accuracy, earlier agents useful for same was handled 8 hours in 120 ℃ of baking ovens.Take by weighing the reagent and the fusing assistant of aequum by chemical formula, in mortar, ground 3 hours, make its abundant mixing.Pack into then corundum crucible and compacting.Sintering is 6 hours in 1350 ℃ of air, then at 1300 ℃ of H
2/ N
2(H in the reducing atmosphere
2Account for 10%) reduced 3 hours.After dropping to room temperature in the reducing atmosphere, taking-up from High Temperature Furnaces Heating Apparatus, fragmentation, washing, baking promptly get required product.
Use method for preparing and have chemical formula Sr
1.89Ba
0.01Eu
0.1Si
0.9O
3.8Fluorescent material at the excitation spectrum of 575nm emission as shown in Figure 1.As can be seen from the figure, this powder all can effectively be excited to have very wide excitation spectrum in 300～520nm scope, and wherein there are two peak values at 343nm and 418nm place.Illustrate that this fluorescent material can be used for long wave ultraviolet, purple light and blue-light LED chip to make white LED light source.
Fig. 2 demonstrates by above-mentioned preparation method, the emmission spectrum of four alkaline-earth metal silicate fluorescent powders under 365nm excites of preparing by the concentration, fusing assistant and the sintering condition that change Sr/Ba ratio, Eu.These four fluorescent material are respectively Sr
1.5Ba
0.4Eu
0.1Si
1.1O
4.2, Sr
1.7Ba
0.2Eu
0.1Si
0.95O
3.9, Sr
1.7Ba
0.17Eu
0.13SiO
4, Sr
1.84Ba
0.04Eu
0.12Si
0.9O
3.8This fluorescent material shows the emmission spectrum of broad as can be seen, and the red area more than 600nm all has emission, and its emission peak wavelength can be between 547～585nm modulation.So, use this silicate fluorescent powder can prepare white light LEDs, its correlated(color)temperature can change between 2800～6500K.
Use silicate fluorescent powder Sr of the present invention
1.89Ba
0.01Eu
0.1Si
0.9O
3.8Make white light LEDs with purple light chip (peak wavelength 400nm) and blue chip (peak wavelength 453nm) by structure iron encapsulation shown in Figure 3, the emmission spectrum of two kinds of led light sources is shown in Fig. 4.As can be seen from Figure 4, purple light and blue chip all can effectively excite this alkaline-earth metal silicate fluorescent powder.
By changing the encapsulation condition, the ratio that promptly changes the packaging plastic of fluorescent material of the present invention and use can prepare the LED of different colors coordinate.Table 1 has provided the illuminant colour coordinate figure of the LED that different fluorescent material that blue chip and purple light chip excite and packaging plastic ratio make.The led light source that can prepare the different colors coordinate by the ratio that adopts different fluorescent material of forming of the present invention and different powder and packaging plastic.And because silicate fluorescent powder of the present invention has very wide excitation spectrum, can under the shooting conditions of broad, work, help preparing the led light source of high stability.
The illuminant colour coordinate figure example of some led light sources that table 1 wherein three kinds of fluorescent material of the present invention and purple light and blue chip encapsulation make
| 365nm excites down the emission peak wavelength (nm) of fluorescent material | Encapsulation condition and the luminous coordinate of corresponding LED | ||||||
| 400nm chip | 453nm chip | ||||||
| Fluorescent material accounts for the ratio (%) of packaging plastic | x | y | Fluorescent material accounts for the ratio (%) of packaging plastic | x | y | ||
| No.1 | 550 | 5 | 0.3992 | 0.4180 | 30 | 0.3143 | 0.3016 |
| 40 | 0.4670 | 0.5210 | 40 | 0.3551 | 0.3616 | ||
| No.2 | 565 | 5 | 0.4145 | 0.3979 | 40 | 0.3518 | 0.3177 |
| 40 | 0.4920 | 0.4990 | 50 | 0.3887 | 0.3653 | ||
| No.3 | 585 | 40 | 0.4920 | 0.4270 | 80 | 0.3424 | 0.2568 |
| 60 | 0.5210 | 0.4560 | 100 | 0.3749 | 0.2884 | ||
Claims (6)
1. one kind with rare-earth europium activated alkaline-earth metal silicate fluorescent powder, it is characterized in that moiety is by following chemical formulation: Sr
xBa
2-x-yEu
ySi
zO
2+2z, 1＜x＜2 wherein, O.02≤y≤O.2,0.7≤z≤1.5.
2. according to the described rare-earth europium activated of claim 1 alkaline-earth metal silicate fluorescent powder, it is characterized in that launching peak wavelength and between 547～585nm, change.
3. a rare-earth europium activates the preparation method of alkaline-earth metal silicate fluorescent powder, it is characterized in that concrete steps are as follows:
(1) presses chemical formula Sr
xBa
2-x-yEu
ySi
zO
2+2z, 1＜x＜2,0.02≤y≤0.2, O.7≤z≤1.5 take by weighing Strontium carbonate powder, barium carbonate, silicon-dioxide and the europium sesquioxide of requirement, take by weighing the fusing assistant that accounts for chemical formula 0.3%～3% quality again, with the abundant mixing of these components;
(2) said mixture is packed into corundum crucible, and to place High Temperature Furnaces Heating Apparatus sintering, atmosphere be air or N
2/ H
2, sintering temperature is 1100～1400 ℃, sintering time is 3～10 hours;
(3) with sinter pyroprocessing under reducing atmosphere, treatment temp is 1000～1350 ℃, and the treatment time is 1～3 hour;
(4) in reducing atmosphere, drop to room temperature, sinter is crushed to desired particle size,, dry under 120～150 ℃ of temperature, promptly obtain required product with 70～85 ℃ of deionized water wash.
4. preparation method according to claim 3 is characterized in that described fusing assistant is SrF
2, BaF
2, NH
4HF
2, SrCl
2, BaCl
2, NH
4Cl, H
3BO
3In one or more.
5. the application of rare-earth europium activated alkaline-earth metal silicate fluorescent powder as claimed in claim 1 in the preparation white LED light source.
6. the application in the preparation white LED light source according to claim 5 is characterized in that described fluorescent material and ultraviolet, purple light chip or blue chip combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100256988A CN100427566C (en) | 2006-04-13 | 2006-04-13 | Alkaline-earth metal silicate fluorescent powder and its preparation method and application |
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|---|---|---|---|
| CNB2006100256988A CN100427566C (en) | 2006-04-13 | 2006-04-13 | Alkaline-earth metal silicate fluorescent powder and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1827735A true CN1827735A (en) | 2006-09-06 |
| CN100427566C CN100427566C (en) | 2008-10-22 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818063A (en) * | 2010-05-14 | 2010-09-01 | 中国科学技术大学 | Method for preparing silicon-based oxynitride fluorescent powder |
| CN101130690B (en) * | 2007-07-12 | 2011-12-14 | 复旦大学 | Bivalence europium enabled alkaline earth metal silicate fluorescent powder and method of producing the same |
| CN102585805A (en) * | 2012-01-19 | 2012-07-18 | 杭州杭科光电有限公司 | Multi-emission-peak LED (light emitting diode) white light fluorescent powder and preparation method thereof |
| CN104109536A (en) * | 2013-04-19 | 2014-10-22 | 四川新力光源股份有限公司 | Nitrogen oxide luminescent material, preparation method and LED light source prepared from same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0552513B1 (en) * | 1992-01-07 | 1996-12-04 | Koninklijke Philips Electronics N.V. | Low-pressure mercury discharge lamp |
| CN1032921C (en) * | 1992-09-19 | 1996-10-02 | 杨丽馨 | Undark |
| CN1126746A (en) * | 1994-01-06 | 1996-07-17 | 肖志国 | Luminous material |
| US6429583B1 (en) * | 1998-11-30 | 2002-08-06 | General Electric Company | Light emitting device with ba2mgsi2o7:eu2+, ba2sio4:eu2+, or (srxcay ba1-x-y)(a1zga1-z)2sr:eu2+phosphors |
| KR100665299B1 (en) * | 2004-06-10 | 2007-01-04 | 서울반도체 주식회사 | Luminescent material |
-
2006
- 2006-04-13 CN CNB2006100256988A patent/CN100427566C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130690B (en) * | 2007-07-12 | 2011-12-14 | 复旦大学 | Bivalence europium enabled alkaline earth metal silicate fluorescent powder and method of producing the same |
| CN101818063A (en) * | 2010-05-14 | 2010-09-01 | 中国科学技术大学 | Method for preparing silicon-based oxynitride fluorescent powder |
| CN101818063B (en) * | 2010-05-14 | 2013-03-06 | 中国科学技术大学 | Method for preparing silicon-based oxynitride fluorescent powder |
| CN102585805A (en) * | 2012-01-19 | 2012-07-18 | 杭州杭科光电有限公司 | Multi-emission-peak LED (light emitting diode) white light fluorescent powder and preparation method thereof |
| CN104109536A (en) * | 2013-04-19 | 2014-10-22 | 四川新力光源股份有限公司 | Nitrogen oxide luminescent material, preparation method and LED light source prepared from same |
| WO2014169834A1 (en) * | 2013-04-19 | 2014-10-23 | 四川新力光源股份有限公司 | Oxynitride luminescent material, preparation method, and led light source manufactured thereby |
| CN104109536B (en) * | 2013-04-19 | 2016-03-02 | 四川新力光源股份有限公司 | Oxynitride luminescent material, preparation method and the LED light source be made up of it |
| US9909059B2 (en) | 2013-04-19 | 2018-03-06 | Sichuan Sunfor Light Co., Ltd. | Oxynitride luminescent material, preparation method, LED light source manufactured thereby |
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| Publication number | Publication date |
|---|---|
| CN100427566C (en) | 2008-10-22 |
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