CN102408890A - Silicate green fluorescent powder and preparation method thereof - Google Patents
Silicate green fluorescent powder and preparation method thereof Download PDFInfo
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- CN102408890A CN102408890A CN2011103616399A CN201110361639A CN102408890A CN 102408890 A CN102408890 A CN 102408890A CN 2011103616399 A CN2011103616399 A CN 2011103616399A CN 201110361639 A CN201110361639 A CN 201110361639A CN 102408890 A CN102408890 A CN 102408890A
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Abstract
The invention provides silicate green fluorescent powder which has the advantages of better luminous efficiency, higher brightness and more stable performance. The following technical scheme is adopted: the silicate green fluorescent powder has a chemical formula of M2-xSiO4:xEu, wherein x is greater than or equal to 0.001 and is less than 1; M is one or more of Li, Na, K, Mg, Ca, Sr and Ba elements; and M at least contains one of Sr and Ba elements. The invention provides the silicate fluorescent powder which has better performance and contains europium ions as an activator aiming at the defects in the background art; and the silicate fluorescent powder is suitable to be used as the green fluorescent powder required for manufacturing a white diode and the like, and has higher luminous efficiency, higher brightness and more stable performance. The invention also provides a preparation method of the silicate green fluorescent powder. The synthesis temperature is greatly reduced, energy is saved, and a synthesized product is not required to be subjected to complex subsequent crushing treatment, so that the damage to the surface of the powder is avoided, and higher luminous performance is guaranteed.
Description
Technical field
The present invention relates to europkium-activated silicate fluorescent powder of a kind of REE and preparation method thereof, belong to the technical field of rare earth silicate method of manufacturing fluorescent material.
Background technology
Product and technology become increasingly mature for white light LEDs; And appear at the every aspect of people's daily life, work with the new look of its energy-saving and environmental protection; On market, show powerful growth momentum; Lot of domestic and foreign lamps & lanterns factory, encapsulation factory join this market of solid state lighting one after another, have promoted the development of solid state lighting industry greatly.As the extremely important subsidiary material of white light LEDs product, light-conversion fluorescent powder market is also in continuous development, and more and more flourishing.At present, mainly be coated on the blue-ray LED on the market and produce white light through the complementary color principle with the mixture of cerium activated yttrium aluminum garnet (YAG) fluorescent material and epoxy resin.But because the inclined to one side yellow-green colour of light that YAG fluorescent material sends can only obtain the higher cool tone white light of colour temperature, colour rendering index is lower, and glow color receives the influence of received current and fluorescent coating thickness very big.In order to address the above problem, bring into use near ultraviolet-ultraviolet compound InGaN tube core to excite three primary colors fluorescent powder in the world to realize white light LEDs.Yet the luminous efficiency of the green emitting phosphor of exploitation is not high at present, and actual level of application is lower, and therefore the efficient excellent green emitting phosphor of exploitation has important practical significance.
The silicate of activated by rare earth elements receives much concern because of its excellent property.At present; Preparation fluorescent material generally adopts traditional high temperature solid phase synthesis in the industry; Have many shortcomings though this method is simple,, product big like calcination temperature height, long reaction time, energy consumption needs subsequent disposal very easily to cause crystal impaired, influences powder luminescent properties etc.; According to bibliographical information, the luminosity of the powder after pulverization process approximately is merely 1/4 of original macrobead shape product.
Summary of the invention
The present invention's technical problem at first to be solved provides the silicate green fluorescent powder that a kind of luminous efficiency is better, brightness is higher, performance is more stable.For this reason, the present invention adopts following technical scheme:
Its chemical formula is: M
2-xSiO
4 :XEu, 0.001≤x＜1, wherein M is Li, Na, K, Mg, Ca, Sr, one or more in the Ba element, and M contains a kind of in Sr and the Ba element at least.
Owing to adopt technique scheme of the present invention; The present invention is directed to disadvantages of background technology; Provide a kind of performance better to make the silicate fluorescent powder of activator of europium ion; Be applicable to required green emitting phosphors such as making white light-emitting diodes, its luminous efficiency is better, brightness is higher, performance is more stable.
Another technical problem to be solved of the present invention provides a kind of preparation method of above-mentioned silicate green fluorescent powder.For this reason, the present invention adopts following preparation method:
1) obtain solution
Take by weighing the nitrate salt of europium nitrate, M with the pairing stoichiometric ratio of the said chemical formula of claim 1, be dissolved in the absolute ethyl alcohol, the back that stirs adds tetraethoxy (TEOS) and Hydrocerol A;
The purity of europium nitrate is more than 99.99%, and the purity of the nitrate salt of M is more than 99.7%, and the purity of tetraethoxy is more than 99.7%, and the purity of absolute ethyl alcohol is more than 99.7%;
2) form colloidal sol
The solution use nitre acid for adjusting pH value that step 1) is made is 1 ~ 5, and 20 ~ 60min forms transparent complex sol in 60 ~ 70oC stirred in water bath;
3) spraying drying
With step 2) colloidal sol that forms carries out heating atomization with spray-dryer, and the colloid flow is 10 ~ 25ml/min, and the carrier gas temperature is 140 ~ 180oC, and the material outlet temperature is 55 ~ 70oC, obtains translucent xerogel sample;
4) high-temperature calcination
The translucent xerogel sample that will pass through step 3) is in the H of 1/5 ~ 1/10 (volume ratio)
2/ N
2Be heated to 900 ~ 1200oC under the atmosphere, heat-up rate is: 3 ~ 6oC/min, soaking time is 2 ~ 5h, come out of the stove after being cooled to room temperature, fluorescent powder.
Further, TEOS and alcoholic acid volume ratio are 1:2 ~ 2:1 during the step 1) obtain solution.
Further, add that all metal ions sum (comprises Eu in amount and the solution of Hydrocerol A during the step 1) obtain solution
3+With the M ion) etc. amount of substance.
Because adopt technical scheme of the present invention, compared with prior art, the present invention has following advance:
Preparing method provided by the present invention has adopted that rational chemical substance is selected, proportioning, dissolving, spraying drying, calcination, cooling; Nitrate salt with basic metal or earth alkali metal is raw material; With the tetraethoxy is the silicon source, is activator with the europium nitrate, is solvent with the absolute ethyl alcohol; With the Hydrocerol A is additive, finally obtains the europkium-activated silicate green high purity of REE fluorescent material.The pattern of this fluorescent material is a form of spherical particles, and its particulate medium particle diameter on average is about 5 ~ 8 μ m, its good luminous performance, and stability is high, and excitation wavelength range is at 300 ~ 500nm, and emission wavelength is between 490 ~ 600nm.
Compare with high temperature solid-state method; The particulate that preparation method of the present invention makes reacts by being suspended in aerial drop, thus can prepare the very solid spherical phosphor of rule, very even on composition and size; Narrow diameter distribution; Not only help improving the luminous intensity of material, can also improve the coating performance of fluorescent material, and improve the resolving power of luminous demonstration.And utilize this method, synthesis temperature is low than the homophase method, does not need fusing assistant, and inclusion-free is introduced, and the product that makes is formed and the equal may command of particle diameter, and this method is simple to operate, but continuous production, and cost is lower.
In addition, synthesis temperature of the present invention reduces greatly, has saved the energy, and the product that generates needn't pass through complicated follow-up pulverization process, has therefore avoided the damage of powder surface, has guaranteed higher luminescent properties.
Description of drawings
Fig. 1 prepares for embodiment among the present invention 2
(Sr 0.370 Ba 1.580 ) SiO 4 : 0.050EuThe excitation spectrum of fluorescent material, wherein X-coordinate is an excitation wavelength range, and unit is nanometer (nm), and ordinate zou is the relative intensity of this material absorption peak under different wave length light excites.
Fig. 2 prepares for embodiment among the present invention 2
(Sr 0.370 Ba 1.580 ) SiO 4 : 0.050EuThe emmission spectrum of fluorescent material; Wherein X-coordinate is the emmission spectrum wavelength region, and unit is nanometer (nm), and ordinate zou is the relative intensity of this material emission peak under 460nm is blue-light excited, and maximum emission peak is 526nm, is the green light launching phase.
Fig. 3 prepares for embodiment among the present invention 3
Ba 1.930 SiO 4 : 0.070EuThe SEM of fluorescent material (sem) figure, powder granule is evenly distributed, and is spherical in shape.
Fig. 4 prepares for embodiment among the present invention 4
(Sr 1.390 Mg 0.530 ) SiO 4 : 0.080EuThe XRD of fluorescent material (x XRD X) figure, wherein X-coordinate is an x ray input angle, ordinate zou is the relative intensity of diffraction peak.
Embodiment
Be described in detail in the face of the present invention does down, said content is to explanation of the present invention rather than qualification.
Embodiment 1
The nitrate salt that takes by weighing corresponding weight according to the pairing stoichiometric ratio of fluorescent material chemical formula is dissolved in the absolute ethyl alcohol; Add tetraethoxy (TEOS) (with the absolute ethyl alcohol equal-volume) and Hydrocerol A (with amount of substance such as all metal ions sum in the solution) then, mixing the back, to use the pH value of nitric acid regulator solution be 1.5,2.0,2.5,3.0,3.5,4.0 or 4.5.Wherein, the purity of tetraethoxy is more than 99.7%, and the purity of absolute ethyl alcohol is more than 99.7%.
With above-mentioned solution 60,65 or 70oC stirred in water bath 20,30,40,50 or 60min after make the rare earth complex sol.
Prepare xerogel with spray-dryer heating atomization colloidal sol, the colloid flow is set is 10,15,20 or 25ml/min, the carrier gas temperature is 140,145,150,155,160,170 or 180oC, and the material outlet temperature is 55,60,65 or 70oC.
Xerogel is inserted tube furnace in H
2-N
2Mixed atmosphere in 900,950,1000,1050,1100,1150 or 1200oC calcination 2,2.5,3,3.5,4 or 4.5h, heat-up rate is 5oC/min.
Cool to room temperature at last with the furnace, obtain good dispersivity, concentrated, the subglobose high-purity fluorescent powder of size-grade distribution.
Embodiment 2 (Sr
0.370Ba
1.580) SiO
4: the preparation of 0.050Eu fluorescent material
Take by weighing a certain amount of strontium nitrate, nitrate of baryta and europium nitrate by the pairing stoichiometric ratio of this chemical formula and be dissolved in the absolute ethyl alcohol, add tetraethoxy (TEOS) (with the absolute ethyl alcohol equal-volume) and Hydrocerol A then (with Sr
2+, Ba
2+And Eu
3+Three kinds of amount of substances such as ion sum), mixing afterwards, the pH value of use nitric acid regulator solution is 2.5.Wherein, the purity of tetraethoxy is more than 99.7%, and the purity of absolute ethyl alcohol is more than 99.7%.
Above-mentioned solution is made the rare earth complex sol behind 65oC stirred in water bath 30min.
Prepare xerogel with spray-dryer heating atomization colloidal sol, it is 15ml/min that the colloid flow is set, and the carrier gas temperature is 155oC, and the material outlet temperature is 60oC.
Xerogel is inserted tube furnace in H
2-N
2(H wherein
2Volume ratio be 5%) mixed atmosphere at 1000 oC calcination 3.5h, heat-up rate is 4oC/min.
Cool to room temperature at last with the furnace, obtain good dispersivity, concentrated, the subglobose (Sr of size-grade distribution
0.370Ba
1.580) SiO
4: 0.050Eu fluorescent material.
Embodiment 3 Ba
1.930SiO
4: the preparation of 0.070Eu fluorescent material
Take by weighing a certain amount of nitrate of baryta and europium nitrate is dissolved in the absolute ethyl alcohol by the pairing stoichiometric ratio of this chemical formula, add tetraethoxy (TEOS) (with the absolute ethyl alcohol equal-volume) and Hydrocerol A then (with Ba
2+And Eu
3+Two kinds of amount of substances such as ion sum), mixing afterwards, the pH value of use nitric acid regulator solution is 2.5.Wherein, the purity of tetraethoxy is more than 99.7%, and the purity of absolute ethyl alcohol is more than 99.7%.
Above-mentioned solution is made the rare earth complex sol behind 70oC stirred in water bath 25min.
Prepare xerogel with spray-dryer heating atomization colloidal sol, it is 20ml/min that the colloid flow is set, and the carrier gas temperature is 160oC, and the material outlet temperature is 60oC.
Xerogel is inserted tube furnace in H
2-N
2(H wherein
2Volume ratio be 5%) mixed atmosphere at 900oC calcination 3h, heat-up rate is 5oC/min.
Cool to room temperature at last with the furnace, obtain good dispersivity, concentrated, the subglobose Ba of size-grade distribution
1.930SiO
4: 0.070Eu fluorescent material.
Embodiment 4 (Sr
1.390Mg
0.530) SiO
4: the preparation of 0.080Eu fluorescent material
Take by weighing a certain amount of strontium nitrate, magnesium nitrate and europium nitrate by the pairing stoichiometric ratio of this chemical formula and be dissolved in the absolute ethyl alcohol, add tetraethoxy (TEOS) (with the absolute ethyl alcohol equal-volume) and Hydrocerol A then (with Sr
2+, Mg
2+And Eu
3+Three kinds of amount of substances such as ion sum), mixing afterwards, the pH value of use nitric acid regulator solution is 2.5.Wherein, the purity of tetraethoxy is more than 99.7%, and the purity of absolute ethyl alcohol is more than 99.7%.
Above-mentioned solution is made the rare earth complex sol behind 65oC stirred in water bath 25min.
Prepare xerogel with spray-dryer heating atomization colloidal sol, it is 20ml/min that the colloid flow is set, and the carrier gas temperature is 160oC, and the material outlet temperature is 65oC.
Xerogel is inserted tube furnace in H
2-N
2(H wherein
2Volume ratio be 5%) mixed atmosphere at 1100oC calcination 3h, heat-up rate is 5oC/min.
Cool to room temperature at last with the furnace, obtain good dispersivity, concentrated, the subglobose (Sr of size-grade distribution
1.390Mg
0.530) SiO
4: 0.080Eu fluorescent material.
Claims (7)
1. a silicate fluorescent powder is characterized in that its chemical formula is: M
2-xSiO
4 :XEu, 0.001≤x＜1, wherein M is Li, Na, K, Mg, Ca, Sr, one or more in the Ba element.
2. a kind of silicate fluorescent powder according to claim 1, the M that it is characterized in that this fluorescent material contain a kind of in Sr, the Ba element at least, and in fluorescent material, meet following mol ratio content range: 1≤Sr＜2,1≤Ba＜2 or 1≤Sr+Ba＜2.
3. the preparation method of the described a kind of silicate fluorescent powder of claim 1 is characterized in that it may further comprise the steps:
1) obtain solution
Take by weighing europium nitrate (Eu (NO with the pairing stoichiometric ratio of the said chemical formula of claim 1
3)
3), the nitrate salt of M, be dissolved in the absolute ethyl alcohol, the back that stirs adds tetraethoxy (TEOS) and Hydrocerol A;
The purity of europium nitrate is more than 99.99%, and the purity of the nitrate salt of M is more than 99.7%, and the purity of tetraethoxy is more than 99.7%, and the purity of absolute ethyl alcohol is more than 99.7%;
2) form colloidal sol
The solution use nitre acid for adjusting pH value that step 1) is made is 1 ~ 5, and 20 ~ 60min forms transparent complex sol in 60 ~ 70oC stirred in water bath;
3) spraying drying
With step 2) colloidal sol that forms carries out heating atomization with spray-dryer, and the colloid flow is 10 ~ 25ml/min, and the carrier gas temperature is 140 ~ 180oC, and the material outlet temperature is 55 ~ 70oC, obtains translucent xerogel sample;
4) high-temperature calcination
The translucent xerogel sample that will pass through step 3) is in the H of 1/5 ~ 1/10 volume ratio
2/ N
2Be heated to 900 ~ 1200oC under the atmosphere, heat-up rate is 3 ~ 6oC/min, and soaking time is 2 ~ 5h, come out of the stove after being cooled to room temperature, fluorescent powder.
4. the preparation method of a kind of silicate fluorescent powder according to claim 3, TEOS and alcoholic acid volume ratio are 1:2 ~ 2:1 when it is characterized in that the step 1) obtain solution.
5. the preparation method of a kind of silicate fluorescent powder according to claim 3 adds in amount and the solution of Hydrocerol A amount of substances such as all metal ions sum when it is characterized in that the step 1) obtain solution.
6. the preparation method of a kind of silicate fluorescent powder according to claim 3 is characterized in that step 2) in, regulating the pH value is 2.5.
7. a kind of silicate fluorescent powder according to claim 1 is characterized in that the emission of this fluorescent material
Wave band is positioned between 490 ~ 600nm.
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| EP1236784A1 (en) * | 1999-12-01 | 2002-09-04 | Kasei Optonix, Ltd. | Method for producing phosphor |
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| US20100033074A1 (en) * | 2007-02-23 | 2010-02-11 | Fujito Nakakawaji | Phosphor, method for production thereof, wavelength converter, light emitting device and luminaire |
| CN101851508A (en) * | 2010-06-30 | 2010-10-06 | 江苏博睿光电有限公司 | Europium activated silicate green fluorescent powder and application thereof in white light emitting diode |
| CN102191057A (en) * | 2011-03-28 | 2011-09-21 | 彩虹集团公司 | Method for optimizing crystalline form of silicate green fluorescent powder material |
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2011
- 2011-11-15 CN CN2011103616399A patent/CN102408890A/en active Pending
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| EP1236784A1 (en) * | 1999-12-01 | 2002-09-04 | Kasei Optonix, Ltd. | Method for producing phosphor |
| US20030209693A1 (en) * | 2000-04-20 | 2003-11-13 | Kasei Optonix, Ltd. | Phosphor consisting of hollow particles, phosphor slurry, phosphor beads for analysis using tracer technique and their production processes |
| US20040017154A1 (en) * | 2002-07-24 | 2004-01-29 | Satoshi Ito | Phosphor, method for producing phosphor and its precursor, and display device |
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Application publication date: 20120411 |