CN103087708B - Red oxynitride fluorescent material and preparation method thereof - Google Patents
Red oxynitride fluorescent material and preparation method thereof Download PDFInfo
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- CN103087708B CN103087708B CN201210492891.8A CN201210492891A CN103087708B CN 103087708 B CN103087708 B CN 103087708B CN 201210492891 A CN201210492891 A CN 201210492891A CN 103087708 B CN103087708 B CN 103087708B
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Abstract
The invention discloses a red oxynitride fluorescent material and a preparation method thereof. The fluorescent material is characterized in that the material is an eutectoid with the chemical formula of pM(1-x)EuxO-qSi3N[4-r]SiO2, wherein M is one or more of Mg, Ca, Sr or Ba, and respectively, p is greater than or equal to 1.5 but less than or equal to 2, q is greater than or equal to 0.25 but less than or equal to 0.4, r is greater than or equal to 0 but less than or equal to 0.25, and x is greater than or equal to 0.001 but less than or equal to 0.5. The preparation method comprises the following steps of: calculating and weighing use levels of raw materials according to the proportion of the components, wherein the raw materials comprise various compounds in oxides containing M, carbonate and oxalate, simple substances, oxides and/or nitrides containing Eu, and oxides containing Si, nitrides and/or compounds which can be converted into oxides or nitrides; mixing the raw materials; heating the mixture under a reducing atmosphere to 1200-1600 DEG C; roasting for 2-24 hours; and cooling to room temperature along with the furnace.
Description
Technical field
The present invention relates to a kind of redness for semiconductor lighting photoluminescence silica-based-nitrogen oxide fluorescent material.
Background technology
Traditional lighting source comprises incandescent light and luminescent lamp.Universal is incandescent light at first, because the cause of its usefulness is substituted by luminescent lamp in large quantities.But with regard to luminescent lamp, because it contains micro-Hg not friendly to the environment; Meanwhile, the efficiency of these conventional light source is relatively low, the life-span is relatively short, is unfavorable for the development of energy saving economy.From last century end, after GaN base blue LED (LED) technological breakthrough, LED application has developed into back lighting, decorative illumination, traffic signals illumination from demonstration field, and has started to enter taking white light LEDs (WLEDs) as main general lighting application.Compared with traditional lighting engineering, white light LEDs (WLEDs) has significant advantage: comprise the advantages such as volume is little, current consumption is low, thermal value is little, the life-span is long, environmental protection.
At present in the world commercial applications the most widely WLEDs technology be to adopt yellow fluorescent powder (as Japanese Ya chemical company has the (Y of patented technology
1-agd
a)
3(Al
1-bga
b)
5o
12: Ce
3+be called for short YAG:Ce) realize with the method for blue led chips incorporate, although the method can obtain efficient white LED light source, but this light source is owing to lacking red (600nm or more long wavelength) composition, so the shortcoming such as have that colour rendering index is on the low side, colour temperature is higher (>5500K) and high temperature light decay is serious, is difficult to meet the demand of general lighting " warm white ".For addressing the aforementioned drawbacks, many schemes propose, and for example scientists is attempted adding red fluorescence material in above-mentioned system or is combined with red, green, blue three fluorescence material by (closely) ultraviolet chip that acquisition colour rendering index is high, while colour temperature low WLEDs.Therefore, no matter use blue light or (closely) purple light chip, all need to research and develop the red fluorescence material of luminescent properties excellence.
Up to the present can be by (closely) ultraviolet or the blue-light excited silica-based nitrogen of redness (oxygen) compound fluorescent material and the rare report of preparation method.Wherein two kinds of best red fluorescence materials of performance are Sr
2si
5n
8and CaAlSiN
3but they prepare difficulty, cost is high, is unfavorable for a large amount of industrial production.Thereby the luminous efficiency of development of new is high, good heat stability, red fluorescence material what the trend requires that preparation method is easy.
Summary of the invention
High for existing red fluorescence material preparation difficulty, cost, be unfavorable for mass-produced defect, the present invention proposes a kind of red nitrogen oxide fluorescent material and preparation method thereof, its technical scheme is as follows:
A kind of red nitrogen oxide fluorescent material, it is chemical constitution formula pM
(1-x)o-qSi
3n
4-rSiO
2: the eutectic of xEu, wherein M is Mg, Ca, in Sr or Ba one or more.Wherein p, q, r, x is respectively 1.5≤p≤2,0.25≤q≤0.45,0≤r≤0.25,0.001≤x≤0.5.
As the preferred person of the technical program, can aspect following, embody:
In preferred embodiment, its basic structure of this fluorescent material is by α '-Sr
2siO
4the orthorhombic body structure of composition.
In preferred embodiment, Si wherein can be replaced by the one or more combination part in B, Al, Ga and Ge, and the molar percentage replacing is 0～15%
In preferred embodiment, in emmission spectrum, emission peak wavelength scope is 500nm-700nm, and in excitation spectrum, excitation wavelength range is 300nm-550nm.
In preferred embodiment, in emmission spectrum, emission peak wavelength scope is 600nm-650nm, and in excitation spectrum, excitation wavelength range is 380nm-480nm.
As the basic skills of preparing above-mentioned materials, can embody as follows:
A preparation method for red nitrogen oxide fluorescent material, comprises the following steps:
1) according to chemical constitution formula pM
(1-x)eu
xo-qSi
3n
4-rSiO
2, calculate and take each raw material consumption by each element ratio, p in formula, q, r, x is respectively 1.5≤p≤2,0.25≤q≤0.45,0≤r≤0.25,0.001≤x≤0.5, wherein this raw material comprises:
One or more compounds in the oxide compound that contains M, carbonate, oxalate, wherein M is Mg, Ca, one or more of Sr or Ba;
Containing a kind of or its several combinations in the simple substance of Eu, oxide compound, nitride; And
Containing oxide compound, the nitride of Si, can be converted into the one or more combination in the compound of oxide compound or nitride.
2) above-mentioned raw materials is mixed, under reducing atmosphere, mixture is heated to 1350 DEG C-1500 DEG C, carry out roasting 3-8h, cool to room temperature with the furnace.
This preparation method's preferred person can be by following embodiment:
Described step 2) in this raw material is mixed after, also add fusing assistant, this solubility promoter comprises H
3bO
3, lithium tetraborate and Ba
2+, Sr
2+ca
2+, Mg
2+, Li
+, Al3+, the one or more combination in the fluorochemical of the one or more combination in Eu3+ and Y3+, muriate, carbonate, oxalate.
In preferred embodiment, described step 2) in reducing atmosphere be one or more mixed atmospheres in nitrogen, hydrogen or ammonia.
The beneficial effect that the present invention brings is:
1. red nitrogen oxide fluorescent material provided by the invention, the required red spectrum of high-color rendering in semiconductor lighting is provided, has had high thermostability and chemical stability simultaneously, preparation method is easy, easily a large amount of production, have industry using value, light conversion efficiency is high simultaneously.
2. this programme has very strong suitability, by regulating the Sr of alkaline-earth metal and the ratio of Ba, can obtain the ruddiness of emission wavelength in 610nm-630nm scope, increase phosphor material powder to the particularly absorption of blue region of excitation spectrum, improve the light conversion efficiency of material, can obtain being suitable for easily the scheme of variant production by parameter setting.
Brief description of the drawings
Below in conjunction with accompanying drawing embodiment, the invention will be further described:
Fig. 1: the XRD diffracting spectrum of the embodiment of the present invention 1
Fig. 2: the exciting light spectrogram of the embodiment of the present invention 1
Fig. 3: the utilizing emitted light spectrogram of the embodiment of the present invention 1
Fig. 4: the exciting light spectrogram of the embodiment of the present invention 2
Fig. 5: the utilizing emitted light spectrogram of the embodiment of the present invention 2
Fig. 6: the exciting light spectrogram of the embodiment of the present invention 3
Fig. 7: the utilizing emitted light spectrogram of the embodiment of the present invention 3
Fig. 8: the thermal quenching graphic representation of the embodiment of the present invention 3
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these are described is in order to further illustrate the features and advantages of the present invention, instead of limiting to the claimed invention.
Embodiment 1
According to Chemical formula 1 .98SrO-0.4Si
3n
4-0.13SiO
2: 0.02Eu composition takes 2.1960gSrCO
3, 0.0601gSiO
2, 0.4209gSi
3n
4and 0.0220gEu
2o
3, grind 30-60min, raw material is mixed.Mixed powder is put into BN crucible, put into tube-type atmosphere furnace, pass into and mix the N that reducing gas flows
2/ NH
3in (its volume ratio is 5/1) reducing atmosphere, rise to 1000 DEG C with the temperature rise rate of 10 DEG C/min, and then rise to 1450 DEG C with the temperature rise rate of 5 DEG C/min, insulation 4h, then after being down to 500 DEG C with the speed of 10 DEG C/min, naturally cool to room temperature, the powder obtaining is taken out to grinding powdered and obtain required phosphor material powder.Fig. 1 shows the XRD figure spectrum of gained fluorescent material, and its basic structure is by α '-Sr
2siO
4the orthorhombic body structure of composition.Fig. 3 shown, gained fluorescent material by near ultraviolet to blue light wide band particularly the excitation spectrum in Fig. 2 excite and send bright ruddiness, peak wavelength is 617nm.
Embodiment 2
According to Chemical formula 1 .68SrO-0.3BaO-0.45Si
3n
4: 0.02Eu composition takes 1.8638gSrCO
3, 0.4440gBaCO
3, 0.4676gSi
3n
4and 0.0220gEu
2o
3, grind 30mins-60mins, raw material is mixed.Mixed powder is put into BN crucible, put into tube-type atmosphere furnace, pass into and mix the N that reducing gas flows
2/ NH
3in (its volume ratio is 5/1) reducing atmosphere, rise to 1000 DEG C with the temperature rise rate of 8 DEG C/min, and then rise to 1500 DEG C of insulation 5h with the temperature rise rate of 5 DEG C/min, then after being down to 500 DEG C with the speed of 5 DEG C/min, naturally cool to room temperature, after the powder obtaining is taken out, grind powdered and obtain required phosphor material powder.Fig. 5 shown, gained fluorescent material is excited by near ultraviolet to the excitation spectrum of Fig. 4 in blue light wide band, sends bright ruddiness, and peak wavelength is 620nm.Experimental results show that, by regulating the Sr of alkaline-earth metal and the ratio of Ba, can make emission wavelength fluctuate in 625nm-615nm scope, increase phosphor material powder to the particularly absorption of blue region of excitation spectrum, improve the light conversion efficiency of material, can obtain being suitable for easily the scheme of variant production by parameter setting.
Embodiment 3
According to Chemical formula 1 .94SrO-0.4BaO-0.5Si
3n
4: 0.02Eu composition takes 1.8638gSrCO
3, 0.5920gBaCO
3, 0.5196gSi
3n
4, 0.0220gEu
2o
3and add 3at%BaF
2as solubility promoter, jointly grind 30-60mins, raw material is mixed.Mixed powder is put into BN crucible, put into tube-type atmosphere furnace, pass into and mix the N that reducing gas flows
2/ NH
3in (its volume ratio is 5/1) reducing atmosphere, rise to 1000 DEG C with the temperature rise rate of 8 DEG C/min, and then rise to 1400 DEG C of insulation 5h with the temperature rise rate of 5 DEG C/min, then after being down to 500 DEG C with the speed of 5 DEG C/min, naturally cool to room temperature, after the powder obtaining is taken out, grind powdered and obtain required phosphor material powder.Fig. 7 shown, gained fluorescent material is excited by the near ultraviolet shown in Fig. 6 to blue light wide band, sends bright ruddiness, and peak wavelength is 625nm.Experiment showed, solubility promoter BaF
2introducing can reduce the synthetic temperature of powder, industrial production is had to positive effect.
As fully visible, the scheme preparation technology of this fluorescent material is simple, and the Heat stability is good of material, is particularly suitable for scale of mass production.
Above to a kind of redness provided by the present invention silica-based-detailed introduction that nitrogen oxide fluorescent material and preparation method thereof carries out.Applied specific case herein embodiments of the present invention are set forth, the explanation of above embodiment is only for helping to understand method of the present invention and core concept thereof.It should be pointed out that the ordinary person for the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (7)
1. a red nitrogen oxide fluorescent material, is characterized in that: it is chemical constitution formula pM
(1-x)eu
xo-qSi
3n
4-rSiO
2eutectic, wherein M is Mg, Ca, in Sr or Ba one or more; Wherein p, q, r, x is respectively 1.5≤p≤2,0.25≤q≤0.45,0≤r≤0.25,0.001≤x≤0.5; Fluorescent material basic structure is by α '-Sr
2siO
4the orthorhombic body structure of composition.
2. a red nitrogen oxide fluorescent material, is characterized in that: it is chemical constitution formula pM
(1-x)eu
xo-qSi
3n
4-rSi
(1-y)z
yo
2eutectic, wherein M is Mg, Ca, in Sr or Ba one or more; Wherein p, q, r, x is respectively 1.5≤p≤2,0.25≤q≤0.45,0≤r≤0.25,0.001≤x≤0.5; Wherein Z is the one or more combination in B, Al, Ga and Ge, 0≤y≤0.15; Fluorescent material basic structure is by α '-Sr
2siO
4the orthorhombic body structure of composition.
3. according to the red nitrogen oxide fluorescent material of the one described in claim 2, it is characterized in that: in emmission spectrum, peak wavelength scope is 500nm-700nm, in excitation spectrum, excitation wavelength range is 300nm-550nm.
4. according to the red nitrogen oxide fluorescent material of the one described in claim 2, it is characterized in that: in emmission spectrum, peak wavelength scope is 600nm-650nm, in excitation spectrum, excitation wavelength range is 380nm-480nm.
5. a preparation method for red nitrogen oxide fluorescent material, is characterized in that, comprises the following steps:
1) according to chemical constitution formula pM
(1-x)eu
xo-qSi
3n
4-rSiO
2, calculate and take each raw material consumption by each element ratio, p in formula, q, r, x is respectively 1.5≤p≤2,0.25≤q≤0.45,0≤r≤0.25,0.001≤x≤0.5, wherein this raw material comprises:
One or more compounds in the oxide compound that contains M, carbonate, oxalate, wherein M is Mg, Ca, one or more of Sr or Ba;
Containing a kind of or its several combinations in the simple substance of Eu, oxide compound, nitride; And
Containing oxide compound, the nitride of Si, can be converted into the one or more combination in the compound of oxide compound or nitride;
2) above-mentioned raw materials is mixed, under reducing atmosphere, mixture is heated to 1200 DEG C-1600 DEG C, carry out roasting 2-24h, cool to room temperature with the furnace, fluorescent material basic structure is by α '-Sr
2siO
4the orthorhombic body structure of composition.
6. according to the preparation method of a kind of red nitrogen oxide fluorescent material of claim 5, it is characterized in that: described step 2) in this raw material is mixed after, also add fusing assistant, this solubility promoter comprises H
3bO
3, lithium tetraborate and Ba
2+, Sr
2+ca
2+, Mg
2+, Li
+, Al
3+, Eu
3+and Y
3+in one or more combination in one or more fluorochemical, muriate, carbonate, oxalate.
7. according to the preparation method of claim 5 or 6, it is characterized in that: described step 2) in reducing atmosphere be one or more mixed atmospheres in nitrogen, hydrogen or ammonia.
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| CN103087708B true CN103087708B (en) | 2014-11-05 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044222A (en) * | 2004-09-22 | 2007-09-26 | 独立行政法人物质·材料研究机构 | Phospher, process for producing the same and luminescence apparatus |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044222A (en) * | 2004-09-22 | 2007-09-26 | 独立行政法人物质·材料研究机构 | Phospher, process for producing the same and luminescence apparatus |
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Granted publication date: 20141105 Termination date: 20171127 |