CN104927858A - Nitride fluorescent material capable of emitting green light under excitation of blue light as well as preparation method and application thereof - Google Patents
Nitride fluorescent material capable of emitting green light under excitation of blue light as well as preparation method and application thereof Download PDFInfo
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- CN104927858A CN104927858A CN201510380431.XA CN201510380431A CN104927858A CN 104927858 A CN104927858 A CN 104927858A CN 201510380431 A CN201510380431 A CN 201510380431A CN 104927858 A CN104927858 A CN 104927858A
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- fluorescent material
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- green light
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Abstract
The invention discloses a nitride fluorescent material capable of emitting green light under excitation of blue light as well as a preparation method and application thereof. The fluorescent material consists of the following substances in a molar ratio: 1-3 molar ratio of Gd2O3, 0.3-1.5 molar ratio of SiO2, 0.2-1 molar ratio of Si3N4 and 0.01-0.6 molar ratio of Eu2O3. Besides, the invention further provides the preparation method of the fluorescent material. The preparation method comprises the following steps: after mixing the raw materials, sintering the mixed raw materials in a reducing atmosphere at the high temperature of 1350-1850 DEG C for 2.5-4 hours so as to obtain the nitride fluorescent material. Experiments prove that the prepared fluorescent material disclosed by the invention has a favorable optical characteristic and can translate the blue light into the green light and output white light coordinating with a material capable of emitting red light under the excitation of the blue light, the fluorescent material can be made into a light-emitting device or applied to a display system, and the fluorescent material can also be widely applied to the fields of an office lighting system, a factory lighting system, a house lighting system, a roadway lighting system, a decoration and lighting system, an automobile lighting system, an indicator lighting system and the like.
Description
Technical field
The present invention relates to luminescent material and its production and use, specifically a kind of nitride fluorescent material at blue-light excited emitted green light and its preparation method and application.
Background technology
The output realizing white light in the devices has number of ways, and as excited yellow fluorescent powder by blue chip, blue, yellow light mix obtains white light, or excites red, green, blue three kinds of fluorescent material by purple light (or UV-light), and red, green-blue light is mixed into white light; In addition, blue-ray LED is adopted to excite green glow and red light fluorescent powder to be also a kind of feasible technological approaches.
Nitride fluorescent material has nontoxic, not deliquescence and thermostability advantages of higher because of it, becomes one of focus of luminescent material research field in recent years.Along with deepening continuously of research, in recent years, the research of Nitride phosphor makes red light fluorescent powder progressively be applied to the device such as illumination, display from laboratory study.As M
2si
5n
8: Eu
2+(M=Ca, Sr, Ba), CaAlSiN
3: Eu
2+output ruddiness under the exciting of blue light all can be realized Deng Nitride phosphor.Therefore, exciting green, that red light fluorescent powder realizes white light output object for reaching blue-ray LED, also needing to continually develop more multipotency and being excited the fluorescent material exporting green glow by blue-ray LED.
At present, Eu is realized
2+ionoluminescence, matrix positively charged ion is generally+the alkaline-earth metal ions Ca of divalent
2+, Sr
2+, Ba
2+in one or several, as ZL02155323.8 discloses a kind of preparation method mixing the red fluorescence powder of europium, take alkaline earth metal cation as matrix, be doped with divalent europium by ad hoc approach and prepared fluorescent material, but the fluorescent material prepared by this patent excites lower transmitting at mercury line is ruddiness.In addition, also having scholars to have studied some in industry can the fluorescent material of green light, as ZL201210057383.7 discloses a kind of green fluorescent material for AC-LED and preparation method thereof, the composition general formula wherein for the green fluorescent material of AC-LED is: (M
1-x-yi
xeu
y)al
2o
4; 0 < x≤0.04,0 < y≤0.05.This patent combines interpolation H in synthesis fluorescent material process
3bO
3with rare earth element, effectively SrAl can be suppressed
2o
4the dephasign Sr in half a lifetime of material
4al
14o
25and significantly improve luminous intensity.But the master of this material excites wavestrip to be in ultraviolet region, effectively can not be activated by blue-light LED chip.And for example ZL201110153106.1 discloses fluorescent material of a kind of blue-light excited transmitting red-green glow and preparation method thereof, and this material can by blue-light excited and transmitting green light, but the light emitting ionic of this material is Pr
3+, luminous efficiency is lower than Eu
2+ionoluminescence, and Pr
3+luminescent spectrum be narrow-band spectrum, and White-light LED illumination application on, broad-band illumination be more conducive to human eye colourity display.For another example, ZL201110411784.3 provides a kind of white light LEDs silicate-based green fluorescent material and preparation method thereof, and this fluorescent material is silicate-based fluorescent material, transmitting green light, but it excites wavestrip to be in UV-light wave band, effectively can not be excited by blue-light LED chip.
The blue-light excited lower green glow that realizes exports and needs less Stokes displacement, and lower to realize the fluorescent material kind that green glow exports less blue-light excited, and lower to realize the Nitride phosphor that green glow exports very few especially blue-light excited.Therefore, be necessary very much to develop more multipotency and, at the fluorescent material of blue-light excited lower transmitting green light, provide more more options for applying.
Summary of the invention
The object of this invention is to provide a kind of nitride fluorescent material at blue-light excited emitted green light and its preparation method and application, with develop a greater variety of can at the nitride fluorescent material of blue-light excited emitted green light, for application provide more more options further.
The object of the invention is to be achieved through the following technical solutions:
At a nitride fluorescent material for blue-light excited emitted green light, this fluorescent material is made up of the material of following mol ratio:
Gd
2O
3 1-3
SiO
2 0.3-1.5
Si
3N
4 0.2-1
Eu
2O
30.01-0.6。
Preferably, in described fluorescent material, the mol ratio of each material is:
Gd
2O
3 1.5-2.5
SiO
2 0.5-1.2
Si
3N
4 0.3-0.5
Eu
2O
30.01-0.2。
Fluorescent material provided by the invention is the sosoloid of high temperature solid state reaction generation under reducing atmosphere; Under described reducing atmosphere, high temperature solid state reaction refers to and react 2.5-4 h under 1350-1850 DEG C of high temperature and in reducing atmosphere.
Present invention also offers a kind of preparation method of the nitride fluorescent material at blue-light excited emitted green light, comprise the following steps:
A () is by each raw material of molar ratio weighing according to claim 1;
B raw material mixing is placed in reducing atmosphere by (), at 1350-1850 DEG C of high temperature sintering 2.5-4h, obtain fluorescent material.
In step (a) described in preparation method provided by the invention, the mol ratio of each raw material is preferably: Gd
2o
3: 1.5-2.5, SiO
2: 0.5-1.2, Si
3n
4: 0.3-0.5, Eu
2o
3: 0.01-0.2.Under this optimum condition, its luminescence is more bright.
Reducing atmosphere described in the present invention refers to N
2, H
2the reducing atmosphere that mixed gas is formed, in addition, this reducing atmosphere also comprises other conventional reduction atmosphere that those skilled in the art can expect, as carbon granules embedding, CO, NH
3and the reducing atmosphere that its mixed gas provides at a certain temperature.
The preferred 1550-1650 DEG C of sintering temperature in preparation method of the present invention, more preferably 1600 DEG C; Sintering time is 2.5-3.5h, more preferably 3h.
The present invention, by selecting specific raw material and formula rate, adopts high temperature solid-state method one-step synthesis can effectively absorb the concurrent fluorescent material penetrating green glow of luminous energy at blue wave band under reducing atmosphere.This material does not contain+divalent alkaline earth metal cation, and raw material directly adopts trivalent rare earth oxide compound, works as Eu
2+after ion doping enters, can be excited under blue-ray LED and launch green glow.Not only raw materials used kind cost that is few, preparation is low, not containing any toxic substance, in process of production without potential safety hazard for this material, and the physicochemical property of its product are stablized, Heat stability is good, luminescent properties is good, brightness is high, reproducible, is easy to suitability for industrialized production and applies.Preparation method's technique of the present invention is simple, and preparation time is short, handling good, for manufacturing various Eu
2+luminous gadolinium silica nitrogen fluorescent material provides Research idea.
Fluorescent material prepared by the present invention proves by experiment, and its excitation spectrum is broadband spectral, excites wavestrip to be in 300-520nm, 400-520nm wave band be blue light mainly excite wave band; Its emmission spectrum is unimodal broadband spectral, wavelength emissions band is in 450-650nm, this fluorescent material has High Efficiency Luminescence at 500-560nm green light band, therefore, this fluorescent material can coordinate red-luminescing material, at blue-light excited lower output white light, luminescent device can be made into or be applied to indicating system, also can in field widespread uses such as Office lighting systems, factory illumination system, home lighting systems, roadway lighting system, decorative lightening system, automobile lighting system and telltale lighting systems.
Accompanying drawing explanation
Fig. 1 is excitation spectrum and the emmission spectrum of the fluorescent material that embodiment 1 obtains; This fluorescent material can effectively be excited in 300-520nm wavelength region; Its emission band is in 450-650nm scope, launches peak position and is about 535nm.
Fig. 2 is the excitation spectrum of the fluorescent material that embodiment 2 obtains, and this fluorescent material can effectively be excited in 300-500nm wavelength region.
Fig. 3 is the emmission spectrum of the fluorescent material that embodiment 2 obtains, and bands of a spectrum are in 450-650nm scope, launches peak position and is about 525nm.
Embodiment
Embodiment is for further describing the present invention below, but does not limit the present invention in any form.
Embodiment 1
Be Gd in molar ratio
2o
3: SiO
2: Si
3n
4: Eu
2o
3=1.5:0.5:0.5:0.01 weighs each analytical pure raw material, puts into graphite furnace after fully being mixed by each raw material, passes into hydrogen and nitrogen mixture atmosphere, is warming up to 1600 DEG C, insulation calcining 3 hours, and furnace cooling, takes out and grind and obtain fluorescent material.
Embodiment 2
Be Gd in molar ratio
2o
3: SiO
2: Si
3n
4: Eu
2o
3=2.5:1.2:0.3:0.2 weighs each analytical pure raw material, puts into graphite furnace after fully being mixed by each raw material, passes into hydrogen and nitrogen mixture atmosphere, is warming up to 1600 DEG C, is incubated 3 hours, furnace cooling, takes out and grinds and obtain fluorescent material.
Embodiment 3
Be Gd in molar ratio
2o
3: SiO
2: Si
3n
4: Eu
2o
3=1:0.3:0.2:0.01 weighs each analytical pure raw material, puts into graphite furnace after fully being mixed by each raw material, passes into hydrogen and nitrogen mixture atmosphere, is warming up to 1350 DEG C, is incubated 4 hours, furnace cooling, takes out and grinds and obtain fluorescent material.
Embodiment 4
Be Gd in molar ratio
2o
3: SiO
2: Si
3n
4: Eu
2o
3=3:1.5:1:0.06 weighs each analytical pure raw material, puts into graphite furnace after fully being mixed by each raw material, passes into hydrogen and nitrogen mixture atmosphere, is warming up to 1850 DEG C, is incubated 2.5 hours, furnace cooling, takes out and grinds and obtain fluorescent material.
Embodiment 5
Be Gd in molar ratio
2o
3: SiO
2: Si
3n
4: Eu
2o
3=2:1:0.4:0.02 weighs each analytical pure raw material, puts into graphite furnace after fully being mixed by each raw material, passes into hydrogen and nitrogen mixture atmosphere, is warming up to 1700 DEG C, is incubated 3.5 hours, furnace cooling, takes out and grinds and obtain fluorescent material.
Embodiment 6
Be Gd in molar ratio
2o
3: SiO
2: Si
3n
4: Eu
2o
3=1:0.8:0.7:0.04 weighs each analytical pure raw material, puts into graphite furnace after fully being mixed by each raw material, passes into hydrogen and nitrogen mixture atmosphere, is warming up to 1650 DEG C, is incubated 3 hours, furnace cooling, takes out and grinds and obtain fluorescent material.
The Performance Detection of the fluorescent material prepared by embodiment 7 the present invention
For fluorescent material prepared by embodiment 1 and embodiment 2, be that excitation light source measures its excitation and emission spectra figure with blue-light LED chip, its detected result is shown in Fig. 1, Fig. 2 and Fig. 3 respectively.
Claims (9)
1. at a nitride fluorescent material for blue-light excited emitted green light, it is characterized in that, this fluorescent material is made up of the material of following mol ratio:
Gd
2O
3 1-3
SiO
2 0.3-1.5
Si
3N
4 0.2-1
Eu
2O
30.01-0.6。
2. the nitride fluorescent material at blue-light excited emitted green light according to claim 1, is characterized in that, described fluorescent material is made up of the material of following mol ratio:
Gd
2O
3 1.5-2.5
SiO
2 0.5-1.2
Si
3N
4 0.3-0.5
Eu
2O
30.01-0.2。
3. the nitride fluorescent material at blue-light excited emitted green light according to claim 1 and 2, is characterized in that, described fluorescent material is the sosoloid of high temperature solid state reaction generation under reducing atmosphere.
4. the nitride fluorescent material at blue-light excited emitted green light according to claim 3, is characterized in that, under described reducing atmosphere, high temperature solid state reaction refers to and react 2.5-4 h under 1350-1850 DEG C of high temperature and in reducing atmosphere.
5. the nitride fluorescent material at blue-light excited emitted green light according to claim 4, is characterized in that, described reducing atmosphere refers to N
2, H
2the reducing atmosphere that mixed gas is formed.
6. in a preparation method for the nitride fluorescent material of blue-light excited emitted green light, it is characterized in that, comprise the following steps:
A () is by each raw material of molar ratio weighing according to claim 1;
B raw material mixing is placed in reducing atmosphere by (), at 1350-1850 DEG C of high temperature sintering 2.5-4h, obtain fluorescent material.
7. the preparation method of the nitride fluorescent material at blue-light excited emitted green light according to claim 6, is characterized in that, in step (a), the mol ratio of each raw material is: Gd
2o
3: 1.5-2.5, SiO
2: 0.5-1.2, Si
3n
4: 0.3-0.5, Eu
2o
3: 0.01-0.2.
8. the preparation method of the nitride fluorescent material at blue-light excited emitted green light according to claim 7, is characterized in that, the reducing atmosphere described in step (b) refers to N
2, H
2the reducing atmosphere that mixed gas is formed.
9. the application of nitride fluorescent material in illumination or indicating system at blue-light excited emitted green light according to claim 1.
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|---|---|---|---|
| CN201510380431.XA CN104927858A (en) | 2015-07-02 | 2015-07-02 | Nitride fluorescent material capable of emitting green light under excitation of blue light as well as preparation method and application thereof |
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| CN1839192A (en) * | 2003-10-03 | 2006-09-27 | 独立行政法人物质·材料研究机构 | Oxynitride phosphor and light-emitting device |
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| KR20100087934A (en) * | 2009-01-29 | 2010-08-06 | 한국화학연구원 | Europium oxynitride phosphor material |
| CN103003390A (en) * | 2010-07-22 | 2013-03-27 | 通用电气公司 | Oxynitride phosphors, method of preparation, and light emitting instrument |
| CN103146386A (en) * | 2013-03-15 | 2013-06-12 | 河北大学 | Europium doped lanthanide silicon oxynitride and preparation method thereof |
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2015
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1839192A (en) * | 2003-10-03 | 2006-09-27 | 独立行政法人物质·材料研究机构 | Oxynitride phosphor and light-emitting device |
| CN101195744A (en) * | 2006-08-15 | 2008-06-11 | 大连路明科技集团有限公司 | Nitrogen-containing compound luminescent material, manufacturing method and illuminating device used thereof |
| KR20100087934A (en) * | 2009-01-29 | 2010-08-06 | 한국화학연구원 | Europium oxynitride phosphor material |
| CN103003390A (en) * | 2010-07-22 | 2013-03-27 | 通用电气公司 | Oxynitride phosphors, method of preparation, and light emitting instrument |
| CN103146386A (en) * | 2013-03-15 | 2013-06-12 | 河北大学 | Europium doped lanthanide silicon oxynitride and preparation method thereof |
| CN104371722A (en) * | 2014-10-31 | 2015-02-25 | 电子科技大学 | Eu<2+>-doped Y4Si2O7N2 blue fluorescent powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| FA-CHUN LU等: "Synthesis and Photoluminescence of a Novel Green-Emitting La5Si3O12N:Eu2+ Phosphor", 《J. AM. CERAM. SOC.》 * |
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Application publication date: 20150923 |