CN102337123A - Silicate luminescent material and preparation method thereof - Google Patents

Silicate luminescent material and preparation method thereof Download PDF

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CN102337123A
CN102337123A CN201010232356XA CN201010232356A CN102337123A CN 102337123 A CN102337123 A CN 102337123A CN 201010232356X A CN201010232356X A CN 201010232356XA CN 201010232356 A CN201010232356 A CN 201010232356A CN 102337123 A CN102337123 A CN 102337123A
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luminescent material
preparation
silicate luminescent
raw material
silica aerogel
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CN102337123B (en
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周明杰
马文波
时朝璞
王荣
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention discloses a silicate luminescent material. A general formula of the silicate luminescent material is (Ba1-yAy)2-xSiO4-mFm: Eux, Agn, wherein A presents one or two of Ba, Mg and Ca; x is great than or equal to 0.001 and less than or equal to 0.08; y is great than 0 and less than or equal to 0.7; m is great than 0 and less than or equal to 0.1; and n is great than or equal to 0.00001 and less than or equal to 0.005. The silicate luminescent material has the advantages of high luminescent efficiency. The invention also provides a preparation method of the silicate luminescent material.

Description

Silicate luminescent material and preparation method thereof
[technical field]
The present invention relates to a kind of luminescent material, relate in particular to a kind of silicate luminescent material and preparation method thereof.
[background technology]
LED (Light Emitting Diode) illuminating device has advantages such as volume is little, energy-conservation, vibration resistance, luminous efficiency is high, suitability is strong, pollution-free, and it has become a kind of novel luminous element, is applied to the various luminescent devices that are suitable for changeable environment.For example with third generation semiconductor material gan as semiconductor illuminating light source, current consumption is merely 1/10 of ordinary incandescent lamp under equal brightness, the life-span reached more than 100,000 hours.Therefore, LED is widely used in photoelectron and illuminating engineering technical fields such as various indications, demonstration, decoration, backlight and general lighting.
The White-light LED illumination device of Traditional businessization mainly is to adopt blue-light LED chip to cooperate to receive the blue-light excited fluorescent material that can send yellow or green to generate white light.Yet the traditional silicate series yellow or the luminosity of green emitting phosphor remain further to be improved.
[summary of the invention]
Based on this, be necessary to provide higher silicate luminescent material of a kind of luminosity and preparation method thereof.
A kind of silicate luminescent material, it forms general formula is (Ba 1-yA y) 2-xSiO 4-mF m: Eu x, Ag n, wherein: A is a kind of among Ba, Mg, the Ca or two kinds; 0.001≤x≤0.08; 0＜y≤0.7; 0＜m≤0.1; 0.00001≤n≤0.005.
Wherein, 0.001≤x≤0.06.
Wherein, 0.00001≤n≤0.001.
A kind of preparation method of silicate luminescent material comprises the steps: that preparation contains Ag particulate silica aerogel; According to forming general formula (Ba 1-yA y) 2-xSiO 4-mF m: Eu x, Ag nStoichiometry take by weighing the raw material of Ba, A, F, Eu and contain Ag particulate silica aerogel, mix; Wherein A is a kind of among Sr, Mg, the Ca or two kinds; 0.001≤x≤0.08; 0＜y≤0.7; 0＜m≤0.1; 0.00001≤n≤0.005; Said mixture is heat-treated under reducing atmosphere, be cooled to room temperature.
Wherein, The step that preparation contains Ag particulate silica aerogel comprises: take by weighing silica aerogel and be dissolved in the solution that contains the Ag raw material; Stirred 0.5～3 hour down at 50～75 ℃, carry out supersound process then, dry down in 60～150 ℃ again; Grind evenly, calcined 0.5～3 hour down in 600～1300 ℃.
Wherein, preparation contains in the step of Ag particulate silica aerogel, and the aperture of silica aerogel is 20～100 nanometers, and void content is 92～98%; The Ag raw material is AgNO 3Or the nano colloidal particles of Ag.
Wherein, take by weighing in the step of raw material of Ba, A, F, Eu, the raw material of Ba and A is a kind of in the carbonate, oxalate of Ba and A; The raw material of Eu is a kind of in the oxide compound, acetate, carbonate, oxalate of Eu.
Wherein, the raw material of F is NH 4F.
Wherein, said reducing atmosphere is 95%N 2+ 5%H 2The mixing reducing atmosphere.
Wherein, said thermal treatment is in 1000～1350 ℃ of heat preservation sinterings 1～10 hour.
The performance test results shows that the stability of above-mentioned silicate luminescent material is better, and has higher light emission intensity at the range of wavelengths of 450～600 nanometers.Advantages such as in addition, the preparation method of above-mentioned silicate luminescent material has that technology is simple, equipment requirements is low and preparation cycle is short.
[description of drawings]
Fig. 1 is the silicate luminescent material of embodiment 4 and the exciting light spectrogram of traditional silicate luminescent material.
[embodiment]
To combine accompanying drawing and embodiment that silicate luminescent material and preparation method thereof is specified below.
The composition general formula of the silicate luminescent material of this embodiment is (Ba 1-yA y) 2-xSiO 4-mF m: Eu x, Ag n, wherein: A is a kind of among Sr, Mg, the Ca or two kinds; 0.001≤x≤0.08; 0＜y≤0.7; 0＜m≤0.1; 0.00001≤n≤0.005.
More preferred embodiment, 0.001≤x≤0.06; 0.00001≤n≤0.001.
The preparation method of above-mentioned silicate luminescent material can use high temperature solid-state method, and it comprises following several steps:
(1) preparation contains Ag particulate silica aerogel.Can at first take by weighing a certain amount of silica aerogel is dissolved in the ethanolic soln that contains the Ag raw material; And under 50～75 ℃, stirred 0.5～3 hour; Used ultrasonication then 10 minutes, dry under 60～150 ℃ again, grind evenly; Calcined 0.5～3 hour down in 600～1300 ℃, promptly obtain containing Ag particulate silica aerogel.Wherein, the aperture of employed silica aerogel is preferably 20～100 nanometers, and void content is preferably 92～98%.The Ag raw material is preferably AgNO 3Or the nano colloidal particles of Ag.
(2) according to forming general formula (Ba 1-yA y) 2-xSiO 4-mF m: Eu x, Ag nThe stoichiometry raw material and step (1) synthetic that take by weighing Ba, A, F, Eu contain Ag particulate silica aerogel, mix.Wherein A is a kind of among Sr, Mg, the Ca or two kinds.The raw material of Ba, A is preferably a kind of in the carbonate, oxalate of Sr and A.The raw material of F is a fluorochemical, is preferably NH 4F.The raw material of Eu is preferably a kind of in the oxide compound, acetate, carbonate, oxalate of Eu.0.001≤x≤0.08；0＜y≤0.7；0＜m≤0.1；0.00001≤n≤0.005。
(3) said mixture is heat-treated under reducing atmosphere, be cooled to room temperature, promptly obtain silicate luminescent material.Wherein, reducing atmosphere is preferably 95%N 2+ 5%H 2The mixing reducing atmosphere.Heat treated step is 1000～1350 ℃ of heat preservation sinterings 1～10 hour.
Be described further through the preparation method of various embodiments below above-mentioned silicate luminescent material.Following all reagent are analytical pure.
Embodiment 1 high temperature solid-state method prepares Ba 1.999SiO 4: Eu 0.001, Ag 0.00001
At first take by weighing silica aerogel 0.3g, be dissolved into 5ml and contain AgNO 31 * 10 -5In the ethanolic soln of mol/L, stirred 3 hours down at 50 ℃, ultrasonic then 10 minutes, again 60 ℃ of dryings, dried sample is ground evenly, 600 ℃ of following precalcinings 3 hours, take by weighing BaCO then 31.5776g, Eu 2(CO 3) 30.0010g mix with the silica aerogel 0.2404g that contains Ag, again at 95%N 2+ 5%H 2The following 1000 ℃ of heat preservation sinterings of weakly reducing atmosphere 10 hours, resultant product is cooled to room temperature, promptly obtains Ba 1.999SiO 4: Eu 0.001, Ag 0.00001Luminescent material.It excites transmitting green light down at 420nm.
Embodiment 2 high temperature solid-state methods preparation (Ba 0.9Ga 0.1) 1.92SiO 3.95F 0.05: Eu 0.08, Ag 0.005
At first take by weighing silica aerogel 0.37g, be dissolved into 20ml and contain nanometer Ag micelle 1.5 * 10 -3In the ethanolic soln of mol/L, stirred 2 hours down at 60 ℃, ultrasonic then 10 minutes, again 90 ℃ of dryings, dried sample is ground evenly, 800 ℃ of following precalcinings 2 hours, take by weighing BaC then 2O 41.5576g, CaC 2O 40.0983g, Eu 2(C 2O 4) 30.0908g, NH 4F 0.0074g and the silica aerogel 0.2404g that contains Ag mix, again at 95%N 2+ 5%H 2The following 1100 ℃ of heat preservation sinterings of weakly reducing atmosphere 8 hours, resultant product is cooled to room temperature, promptly obtains (Ba 0.9Ca 0.1) 1.92SiO 3.95F 0.05: Eu 0.08, Ag 0.005Luminescent material.It excites emission yellow green light down at 440nm.
Embodiment 3 high temperature solid-state methods preparation (Ba 0.5Sr 0.4Mg 0.1) 1.94SiO 3.9F 0.1: Eu 0.06, Ag 0.001
At first take by weighing silica aerogel 0.6g, be dissolved into 30ml and contain nanometer Ag micelle 3.3 * 10 -4In the ethanolic soln of mol/L, stirred 0.5 hour down at 70 ℃, ultrasonic then 10 minutes, again 150 ℃ of dryings, dried sample is ground evenly, 1000 ℃ of following precalcinings 1.5 hours, take by weighing BaCO then 30.7655g, SrC 2O 40.5452g, MgO 0.0313g, Eu (CH 3CO 2) 30.0790g, NH 4F 0.0148g and the silica aerogel 0.2404g that contains Ag mix, again at 95%N 2+ 5%H 2The following 1300 ℃ of heat preservation sinterings of weakly reducing atmosphere 4 hours, resultant product is cooled to room temperature, promptly obtains (Ba 0.5Sr 0.4Mg 0.1) 1.94SiO 3.9F 0.1: Eu 0.06, Ag 0.001Luminescent material.It excites emission yellow green light down at 440nm.
Embodiment 4 high temperature solid-state methods preparation (Ba 0.7Sr 0.3) 1.98SiO 3.92F 0.08: Eu 0.02, Ag 0.00005
At first take by weighing silica aerogel 0.37g, be dissolved into 15ml and contain AgNO 32 * 10 -5In the ethanolic soln of mol/L, stirred 1 hour down at 65 ℃, ultrasonic then 10 minutes, again 80 ℃ of dryings, dried sample is ground evenly, 1200 ℃ of following precalcinings 1 hour, take by weighing BaCO then 31.0938g, SrCO 30.3507g, Eu 2O 30.0141g, NH 4Silica aerogel 0.2404g after F 0.0118g and the calcining mixes, again at 95%N 2+ 5%H 2The following 1250 ℃ of heat preservation sinterings of weakly reducing atmosphere 4 hours, resultant product is cooled to room temperature, promptly obtains (Ba 0.7Sr 0.3) 1.98SiO 3.92F 0.08: Eu 0.02, Ag 0.00005Luminescent material.It excites transmitting green light down at 440nm.
Embodiment 5 high temperature solid-state methods preparation (Ba 0.3Sr 0.3Ca 0.4) 1.99SiO 3.9F 0.1: Eu 0.01, Ag 0.0005
At first take by weighing silica aerogel 0.43g, be dissolved into 25ml and contain AgNO 31.4 * 10 -4In the ethanolic soln of mol/L, stirred 0.5 hour down at 75 ℃, ultrasonic then 10 minutes, again 120 ℃ of dryings, dried sample is ground evenly, 1300 ℃ of following precalcinings 0.5 hour, take by weighing BaCO then 30.4711g, SrCO 30.3524g, CaCO 30.3187g, Eu 2O 30.0070g, NH 4Silica aerogel 0.2404g after F 0.0148g and the calcining mixes, again at 95%N 2+ 5%H 2The following 1350 ℃ of heat preservation sinterings of weakly reducing atmosphere 1 hour, resultant product is cooled to room temperature, promptly obtains (Ba 0.3Sr 0.3Ca 0.4) 1.99SiO 3.9F 0.1: Eu 0.01, Ag 0.0005Luminescent material.It excites emission yellow green light down at 440nm.
Fig. 1 is traditional (Ba 0.7Sr 0.3) 1.98SiO 3.92F 0.08: Eu 0.02The luminescent spectrum comparison diagram of the silicate luminescent material of fluorescent material and embodiment 4 preparations.Test the instrument that this spectrum uses and be Tianjin, island RF-5301PC XRF, the excitation wavelength of emmission spectrum is 440nm.10 representatives is the silicate luminescent material of embodiment 4 preparation among Fig. 1,11 representatives be the conventional fluorescent powder.Can find out by Fig. 1; The luminescent material of embodiment 4 has stronger broadband emission spectrum in 450～600nm; Peak value is at 514nm; Luminous intensity exceeds 10% of conventional fluorescent powder, explains that thus this silicate luminescent material has good stability, luminous efficiency advantage of higher, can be applied in the white LED light source device preferably.
In addition, those skilled in the art can also do other variation in spirit of the present invention, and certainly, these are included within the scope of requirement protection of the present invention according to the variation that the present invention's spirit is done.

Claims (10)

1. a silicate luminescent material is characterized in that, the composition general formula is (Ba 1-yA y) 2-xSiO 4-mF m: Eu x, Ag n, wherein:
A is a kind of among Sr, Mg, the Ca or two kinds;
0.001≤x≤0.08；
0＜y≤0.7；
0＜m≤0.1；
0.00001≤n≤0.005。
2. silicate luminescent material as claimed in claim 1 is characterized in that: 0.001≤x≤0.06.
3. silicate luminescent material as claimed in claim 1 is characterized in that: 0.00001≤n≤0.001.
4. the preparation method of a silicate luminescent material as claimed in claim 1 is characterized in that, comprises the steps:
Preparation contains Ag particulate silica aerogel;
According to forming general formula (Ba 1-yA y) 2-xSiO 4-mF m: Eu x, Ag nStoichiometry take by weighing raw material and the said Ag of the containing particulate silica aerogel of Ba, A, F, Eu, mix; Wherein A is a kind of among Sr, Mg, the Ca or two kinds; 0.001≤x≤0.08; 0＜y≤0.7; 0＜m≤0.1; 0.00001≤n≤0.005;
Said mixture is heat-treated under reducing atmosphere, be cooled to room temperature.
5. the preparation method of silicate luminescent material as claimed in claim 4; It is characterized in that the step that said preparation contains Ag particulate silica aerogel comprises: take by weighing silica aerogel and be dissolved in the solution that contains the Ag raw material, stirred 0.5～3 hour down at 50～75 ℃; Carry out supersound process then; Dry under 60～150 ℃ again, grind evenly, calcined 0.5～3 hour down in 600～1300 ℃.
6. the preparation method of silicate luminescent material as claimed in claim 5 is characterized in that, said preparation contains in the step of Ag particulate silica aerogel, and the aperture of said silica aerogel is 20～100 nanometers, and void content is 92～98%; The Ag raw material is AgNO 3Or the nano colloidal particles of Ag.
7. the preparation method of silicate luminescent material as claimed in claim 4 is characterized in that, in the step of the said raw material that takes by weighing Ba, A, F, Eu, the raw material of Ba and A is a kind of in the carbonate, oxalate of Ba and A; The raw material of Eu is a kind of in the oxide compound, acetate, carbonate, oxalate of Eu.
8. the preparation method of silicate luminescent material as claimed in claim 4 is characterized in that, in the step of the said raw material that takes by weighing Ba, A, F, Eu, the raw material of F is NH 4F.
9. the preparation method of silicate luminescent material as claimed in claim 4 is characterized in that, said reducing atmosphere is 95%N 2+ 5%H 2The mixing reducing atmosphere.
10. the preparation method of silicate luminescent material as claimed in claim 4 is characterized in that, said thermal treatment is in 1000～1350 ℃ of heat preservation sinterings 1～10 hour.
CN201010232356XA 2010-07-20 2010-07-20 Silicate luminescent material and preparation method thereof Expired - Fee Related CN102337123B (en)

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WO2014040220A1 (en) * 2012-09-11 2014-03-20 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method thereof
CN104736665A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN104736666A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN104946254A (en) * 2015-06-02 2015-09-30 杭州萤鹤光电材料有限公司 Rare earth ion-activated multiphase fluorescent material
CN105112045A (en) * 2015-08-20 2015-12-02 桂林市环境监测中心站 Luminescent material containing dielectric layer and metal nanoparticles and preparation method therefor

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014040220A1 (en) * 2012-09-11 2014-03-20 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method thereof
CN104619811A (en) * 2012-09-11 2015-05-13 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method thereof
JP2015531413A (en) * 2012-09-11 2015-11-02 オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー Silicate luminescent material and manufacturing method thereof
CN104736665A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN104736666A (en) * 2012-10-31 2015-06-24 海洋王照明科技股份有限公司 Silicate luminescent material and preparation method therefor
CN104946254A (en) * 2015-06-02 2015-09-30 杭州萤鹤光电材料有限公司 Rare earth ion-activated multiphase fluorescent material
CN104946254B (en) * 2015-06-02 2017-04-12 杭州萤鹤光电材料有限公司 Rare earth ion-activated multiphase fluorescent material
CN105112045A (en) * 2015-08-20 2015-12-02 桂林市环境监测中心站 Luminescent material containing dielectric layer and metal nanoparticles and preparation method therefor

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