CN104327850B - A kind of low-temperature plasma preparation of Nitride phosphor - Google Patents
A kind of low-temperature plasma preparation of Nitride phosphor Download PDFInfo
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- CN104327850B CN104327850B CN201410609583.8A CN201410609583A CN104327850B CN 104327850 B CN104327850 B CN 104327850B CN 201410609583 A CN201410609583 A CN 201410609583A CN 104327850 B CN104327850 B CN 104327850B
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Abstract
A low-temperature plasma preparation for Nitride phosphor, the chemical general formula of described Nitride phosphor is M
1-xalSiN
3: xEu
2+, wherein M is Ca, Sr or Ba, 0.005≤x≤0.20, synthesizing nitride phosphor material powder under employing carbothermic reduction normal pressure, and then with low-temperature plasma except carbon technique removes carbon residual in material.Advantage of the present invention and positively effect: the preparation method of this Nitride phosphor; the relatively simple raw material of preparation condition obtains easily; decarbonizing technology is efficient, energy-conservation and can available protecting phosphor material powder not be destroyed; the production cost of very big reduction Nitride phosphor, the luminescent properties of guarantee material, be beneficial to nitride phosphor material and throwing light on and showing promoting the use of of field.
Description
[technical field]
The present invention relates to phosphor material powder preparation field, be specifically related to a kind of low-temperature plasma preparation of Nitride phosphor.
[background technology]
Nitride phosphor is obviously better than the advantage of other fluorescent material systems owing to having good luminescence property, thermostability and chemical stability, get the attention and apply in recent years in illumination and display field.The preparation method of Nitride phosphor generally adopts high temperature air pressure sintering method, and firing temperature needs more than 1600 DEG C, requires that 0.1-10MPa nitrogen pressure is to prevent Si simultaneously
3n
4the decomposition of raw material or oxidation.In addition, this high temperature air pressure sintering method is also very harsh to ingredient requirement, such as alkaline-earth nitride, this raw material to the oxygen in air and moisture very responsive, very easily decompose oxidation, need to carry out weighing, batch mixing operation in the case being at hand filled with shielding gas.The more important thing is that this kind of alkaline-earth nitride price is very expensive, greatly add the production cost of Nitride phosphor.Harsh preparation technology and expensive starting material inhibit popularization and the use of Nitride phosphor to a certain extent.
Carbothermic method is equally also prepare a kind of common method of Nitride phosphor.The concrete practice is by carbon source, alkaline earth metal oxide, silicon nitride, and the mixing such as europium sesquioxide, as precursor, at high temperature obtains Nitride phosphor through carbon reduction-nitrogenize-solid state reaction in nitrogen atmosphere.Such as, by Si
3n
4, SrCO
3, Eu
2o
3after mixing with C powder, in 1500 DEG C of normal pressure nitrogen nitrogen atmosphere, there is carbothermal reduction-nitridation reaction prepared Sr
2si
5n
8: Eu
2+nitride phosphor.Compared to high temperature air pressure sintering method, simple, the selected raw material of carbothermic reduction preparation method preparation condition easily obtains, with low cost.Then, carbothermic method prepares product and usually understands residual carbon, affects the luminescent properties of fluorescent material to a great extent, and the application of this kind of method is limited greatly.And at present the most general de-carbon method processes fluorescent material in air or oxygen atmosphere at 500-600 DEG C of temperature, make the carbon that remains and oxygen generation redox reaction.But while removing carbon again, the high temperature of 500-600 DEG C also creates disadvantageous effect to phosphor material powder, such as matrix rare earth ion that is oxidized and doping is oxidized.Low-temperature plasma except carbon technique be that active substance in using plasma (Sauerstoffatom of oxonium ion, activation, molecule and electronics etc.) is oxidized to C0 and C0
2carbon distribution is removed.Because plasma body de-carbon (can be generally several minutes to dozens of minutes) within the very short time, efficient, energy-conservation, be the novel method of Calcination for removing carbon in a kind of very promising alternative conventional air.In addition, because cold plasma has the characteristic that electronic temp is high, gas temperature is low, carbon removal treatment can be carried out to material in a mild condition, avoid the destruction of high-temperature roasting material.
[summary of the invention]
The object of the invention is for above-mentioned existing problems; a kind of low-temperature plasma preparation method of Nitride phosphor is provided; this preparation method's raw material obtains easily, preparation condition is relatively simple; decarbonizing technology is efficient, energy-conservation and can available protecting phosphor material powder not be destroyed; the production cost of very big reduction Nitride phosphor, ensure the luminescent properties of material, be beneficial to nitride phosphor material promoting the use of in illumination and colour developing field.。
Technical scheme of the present invention:
A low-temperature plasma preparation method for Nitride phosphor, the chemical general formula of described Nitride phosphor is M
1-xalSiN
3: xEu
2+, wherein M is Ca, Sr or Ba, 0.005≤x≤0.20, synthesizing nitride phosphor material powder under employing carbothermic reduction normal pressure, and then with low-temperature plasma except carbon technique removes carbon residual in material, step is as follows:
1) by MH
2or MO, Si
3n
4, AlN, Eu
2o
3mix in molar ratio according to chemical general formula with Nano graphite powder, be then placed in boron nitride crucible, at N
2, H
2volume ratio is be warming up to 1550 DEG C with the speed of 5-10 DEG C/min under normal pressure in the nitrogen and hydrogen mixture reducing atmosphere tube furnace of 92:8 and be incubated 6h, after naturally cooling to room temperature, obtains Nitride phosphor coarse fodder;
2) above-mentioned Nitride phosphor coarse fodder is put into dielectric barrier discharge low-temperature plasma equipment, under discharge power is 20-60KW, exposing to the sun according to 2-20 minute in plasma discharge region, obtains Nitride phosphor the finished product.
The mol ratio that the purity of described Nano graphite powder is 99.5%, median size is 40nm, M and Nano graphite powder is 1:1-3.
Advantage of the present invention and positively effect:
The preparation method of this Nitride phosphor; the relatively simple raw material of preparation condition obtains easily; decarbonizing technology is efficient, energy-conservation and can available protecting phosphor material powder not be destroyed; the production cost of very big reduction Nitride phosphor, the luminescent properties of guarantee material, be beneficial to nitride phosphor material and throwing light on and showing promoting the use of of field.
[accompanying drawing explanation]
XRD figure corresponding to the Nitride phosphor sample that Fig. 1 prepares for embodiment 1 carbothermic reduction.
Fig. 2 is electro-plasma experimental installation structural representation, and wherein 1 is top electrode, and 2 is lower electrodes, and 3 is medium layers, and 4 is phosphor material powders.
Fig. 3 is the XRD figure of Nitride phosphor sample after embodiment 2 plasma body de-carbon.
Fig. 4 is the emmission spectrum of Nitride phosphor sample before and after embodiment 3 plasma body de-carbon.
[embodiment]
Describe the preparation method of a kind of Nitride phosphor provided by the invention below in conjunction with accompanying drawing and specific embodiment in detail, explain the present invention, not as limitation of the present invention by schematic embodiment here.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Embodiment 1:
A low-temperature plasma preparation method for Nitride phosphor, the chemical formula of described Nitride phosphor is Ca
0.98alSiN
3: 0.02Eu
2+, synthesizing nitride phosphor material powder under employing carbothermic reduction normal pressure, and then with low-temperature plasma except carbon technique removes carbon residual in material, step is as follows:
1) by CaH
2, AlN, Si
3n
4, Eu
2o
3with purity be 99.5%, median size be the Nano graphite powder of 40nm according to chemical general formula in molar ratio for mixing after 0.98:1:0.33:0.01:1.3 precise, then be placed in boron nitride crucible, be be warming up to 1550 DEG C with the speed of 5 DEG C/min under normal pressure in the nitrogen and hydrogen mixture reducing atmosphere tube furnace of 92:8 and be incubated 6h in volume ratio, after naturally cooling to room temperature, obtain Ca
0.98alSiN
3: 0.02Eu
2+nitride phosphor coarse fodder;
2) above-mentioned Nitride phosphor coarse fodder is put into dielectric barrier discharge low-temperature plasma equipment, pilot plasma device as shown in Figure 2, in figure, 1 be top electrode, 2 are lower electrodes, 3 are medium layers, 4 is phosphor material powders, under discharge power is 40KW, exposing to the sun according to 2 minutes in plasma discharge region, obtains Nitride phosphor Ca
0.98alSiN
3: 0.02Eu
2+.
XRD figure corresponding to the Nitride phosphor sample that Fig. 1 prepares for carbothermic reduction.Show in figure: the principal crystalline phase of the product that carbothermic reduction obtains is CaAlSiN
3phase, the carbothermic reduction process illustrating under normal pressure also can be prepared synthesis and obtain Nitride phosphor.
Embodiment 2:
A low-temperature plasma preparation method for Nitride phosphor, the chemical formula of described Nitride phosphor is Ca
0.96alSiN
3: 0.04Eu
2+, synthesizing nitride phosphor material powder under employing carbothermic reduction normal pressure, and then with low-temperature plasma except carbon technique removes carbon residual in material, step is as follows:
1) by CaH
2, AlN, Si3N4, Eu
2o
3with purity be 99.5%, median size be the Nano graphite powder of 40nm according to chemical general formula in molar ratio for mixing after 0.96:1:0.33:0.02:1.4 precise, then be placed in boron nitride crucible, be be warming up to 1550 DEG C with the speed of 10 DEG C/min under normal pressure in the nitrogen and hydrogen mixture reducing atmosphere tube furnace of 92:8 and be incubated 6h in volume ratio, after naturally cooling to room temperature, obtain Ca
0.96alSiN
3: 0.04Eu
2+nitride phosphor coarse fodder;
2) above-mentioned Nitride phosphor coarse fodder is put into dielectric barrier discharge low-temperature plasma equipment (see embodiment 1), under discharge power is 40KW, exposing to the sun according to 2 minutes in plasma discharge region, obtains Nitride phosphor Ca
0.96alSiN
3: 0.04Eu
2+.
Fig. 3 is the XRD figure of Nitride phosphor sample after plasma body de-carbon, shows in figure: sample is still CaAlSiN
3principal crystalline phase, illustrates that low-temperature plasma decarbonizing technology does not cause the thing of phosphor material powder to change mutually.
Embodiment 3:
A low-temperature plasma preparation method for Nitride phosphor, the chemical formula of described Nitride phosphor is Ca
0.96alSiN
3: 0.04Eu
2+, synthesizing nitride phosphor material powder under employing carbothermic reduction normal pressure, and then with low-temperature plasma except carbon technique removes carbon residual in material, step is as follows:
1) by Ca0, AlN, Si3N4, Eu
2o
3with purity be 99.5%, median size be the Nano graphite powder of 40nm according to chemical general formula in molar ratio for mixing after 0.96:1:0.33:0.02:2.2 precise, then be placed in boron nitride crucible, be be warming up to 1550 DEG C with the speed of 8 DEG C/min under normal pressure in the nitrogen and hydrogen mixture reducing atmosphere tube furnace of 92:8 and be incubated 6h in volume ratio, after naturally cooling to room temperature, obtain Ca
0.96alSiN
3: 0.04Eu
2+nitride phosphor coarse fodder;
2) above-mentioned Nitride phosphor coarse fodder is put into dielectric barrier discharge low-temperature plasma equipment (see embodiment 1), under discharge power is 50KW, exposing to the sun according to 4 minutes in plasma discharge region, obtains Nitride phosphor Ca
0.96alSiN
3: 0.04Eu
2+.
Fig. 4 is the emmission spectrum of Nitride phosphor sample before and after embodiment 3 plasma body de-carbon, shows in figure: after plasma de-carbon, the sample of fluorescent material strengthens about 30%.
Embodiment 4:
A low-temperature plasma preparation method for Nitride phosphor, the chemical formula of described Nitride phosphor is Sr
0.96alSiN
3: 0.04Eu
2+, synthesizing nitride phosphor material powder under employing carbothermic reduction normal pressure, and then with low-temperature plasma except carbon technique removes carbon residual in material, step is as follows:
1) by Sr0, AlN, Si
3n
4, Eu
2o
3with purity be 99.5%, median size be the Nano graphite powder of 40nm according to chemical general formula in molar ratio for mixing after 0.96:1:0.33:0.02:2.5 precise, then be placed in boron nitride crucible, be be warming up to 1550 DEG C with the speed of 5 DEG C/min under normal pressure in the nitrogen and hydrogen mixture reducing atmosphere tube furnace of 92:8 and be incubated 6h in volume ratio, after naturally cooling to room temperature, obtain Sr
0.96alSiN
3: 0.04Eu
2+nitride phosphor coarse fodder;
2) above-mentioned Nitride phosphor coarse fodder is put into dielectric barrier discharge low-temperature plasma equipment (see embodiment 1), under discharge power is 50KW, exposing to the sun according to 4 minutes in plasma discharge region, obtains Nitride phosphor Sr
0.96alSiN
3: 0.04Eu
2+.
Claims (2)
1. a low-temperature plasma preparation method for Nitride phosphor, is characterized in that: the chemical general formula of described Nitride phosphor is M
1-xalSiN
3: xEu
2+, wherein M is Ca, Sr or Ba, 0.005≤x≤0.20, synthesizing nitride phosphor material powder under employing carbothermic reduction normal pressure, and then with low-temperature plasma except carbon technique removes carbon residual in material, step is as follows:
1) by MH
2or MO, Si
3n
4, AlN, Eu
2o
3mix in molar ratio according to chemical general formula with Nano graphite powder; Then be placed in boron nitride crucible, at N
2, H
2volume ratio is be warming up to 1550 DEG C with the speed of 5-10 DEG C/min under normal pressure in the nitrogen and hydrogen mixture reducing atmosphere tube furnace of 92:8 and be incubated 6h, after naturally cooling to room temperature, obtains Nitride phosphor coarse fodder;
2) above-mentioned Nitride phosphor coarse fodder is put into dielectric barrier discharge low-temperature plasma equipment, under discharge power is 20-60kW, exposing to the sun according to 2-20 minute in plasma discharge region, obtains Nitride phosphor the finished product.
2. according to the low-temperature plasma preparation method of Nitride phosphor shown in claim 1, it is characterized in that: described Nano graphite powder is purity is 99.5%, median size is the Nano graphite powder of 40nm, and the mol ratio of M and Nano graphite powder is 1:1-3.
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| CN106206873A (en) * | 2016-08-08 | 2016-12-07 | 雷春生 | A kind of preparation method of high light efficiency LED lamp flourescent sheet |
| CN106524077B (en) * | 2016-10-07 | 2019-01-29 | 嘉兴市南湖区翊轩塑料五金厂（普通合伙） | A kind of preparation method of indoor lamp fluorescence cover |
| CN112920799B (en) * | 2021-02-03 | 2022-04-15 | 江南大学 | Method for preparing rare earth doped yttrium oxide fluorescent nanoparticles by DBD technology |
| CN114958356B (en) * | 2022-06-20 | 2023-12-19 | 深圳瑞欧光技术有限公司 | Nitride red fluorescent powder and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102760798A (en) * | 2011-04-29 | 2012-10-31 | 清华大学 | Manufacturing method of LED |
| CN103681600A (en) * | 2012-09-05 | 2014-03-26 | 三星电子株式会社 | Integrated circuit device, semiconductor device, and method of manufacturing integrated circuit device and semiconductor device |
| CN104087293A (en) * | 2014-07-23 | 2014-10-08 | 中国科学院上海硅酸盐研究所 | Red fluorophor as well as carbothermal reduction nitridation preparation method and application of red fluorophor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102760798A (en) * | 2011-04-29 | 2012-10-31 | 清华大学 | Manufacturing method of LED |
| CN103681600A (en) * | 2012-09-05 | 2014-03-26 | 三星电子株式会社 | Integrated circuit device, semiconductor device, and method of manufacturing integrated circuit device and semiconductor device |
| CN104087293A (en) * | 2014-07-23 | 2014-10-08 | 中国科学院上海硅酸盐研究所 | Red fluorophor as well as carbothermal reduction nitridation preparation method and application of red fluorophor |
Non-Patent Citations (1)
| Title |
|---|
| "Sr2Si5N8:Eu2+荧光粉的制备与发光性能";柏朝晖等，;《无机化学学报》;20100630;第26卷(第6期);第1003-1007页 * |
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