CN102352245B - Preparation method of Eu-doped aluminum-nitride-based fluorescent powder - Google Patents
Preparation method of Eu-doped aluminum-nitride-based fluorescent powder Download PDFInfo
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- CN102352245B CN102352245B CN2011102619116A CN201110261911A CN102352245B CN 102352245 B CN102352245 B CN 102352245B CN 2011102619116 A CN2011102619116 A CN 2011102619116A CN 201110261911 A CN201110261911 A CN 201110261911A CN 102352245 B CN102352245 B CN 102352245B
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Abstract
The invention relates to a Eu-doped aluminum-nitride-based fluorescent powder and a preparation method thereof. The chemical formula of the fluorescent powder is (1-x-y)AlN:xEu, ySi, wherein x is greater than or equal to 0 and smaller than or equal to 0.01, and y is greater than or equal to 0 and smaller than or equal to 0.1. The preparation method comprises the following steps of: ball-milling and mixing aluminum powder, aluminum nitride, europium oxide and silicon carbide; then, combusting and synthesizing the mixture in low nitrogen atmosphere, and grinding and pulverizing the combusted and synthesized product to obtain the blue Eu-doped aluminum-nitride-based fluorescent powder. In the invention, the aluminum-nitride-based fluorescent powder is prepared by using the combustion synthesis method for the first time. The method has simple process, low cost, good repeatability and no pollution to the environment and is applicable to industrial production.
Description
Technical field:
The present invention relates to a kind of fluorescent material, particularly a kind of preparation method of Eu doped aluminum nitride base fluorescent powder.
Background technology:
In recent years, nitrogen (oxygen) compound fluorescent material is studied widely and is paid close attention in the Application Areas of white light LEDs because of advantages such as its significant thermostability, chemical stability, luminescent spectrum wide coverage and structure diversities.This type of fluorescent material generally can effectively be excited by near-ultraviolet light or blue light, shows the special characteristics of luminescence.Aluminium nitride (AlN) pottery is the important a member in nitrogen (oxygen) compound family, and it has wide band gap (6eV), so the energy level of rare earth element can be positioned at wherein, makes the AlN base fluorescent powder can be applied in photoluminescence and electroluminescent device.That research is more and more ripe at present is rare earth Eu
2+the aluminum-nitride-based fluorescent material of ion doping, this material has demonstrated very strong application prospect in the white light LEDs field.Yet, prepare at present Eu
2+the method of doped aluminum nitride fluorescent material only limits to high temperature solid-state method and carbothermal reduction-nitridation method.As [Hirosaki N, Xie RJ, Inoue K, et al., Appl.Phys.Lett., 2007,91:061101] such as Hirosaki the report with AlN, α-Si
3n
4and Eu
2o
3for raw material, by high temperature solid-state method at 2050 ℃, 1.0MPa N
2react 4h under the condition of pressure, prepare Eu
2+doped aluminum nitride, and Yin etc. [Yin LJ, Xu X, Yu W, et al., J.Am.Ceram.Soc., 2010,93:1702] adopts the carbothermal reduction-nitridation method is prepared this kind of fluorescent material under 1750 ℃, the condition of 8h.But insulation while all needing high temperature and length in preparation process due to these methods, cause preparation cost higher, and production efficiency is too low, has seriously limited its range of application.Therefore be badly in need of exploring a quick and effective synthesis path of economy and prepare Eu
2+doped with Al N fluorescent material, to meet growing industrial production demand.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of AlN:Eu
2+the fluorescent material preparation method, high, the inefficient shortcoming of cost, the method technique is simple, cost is low, speed is fast, required production unit is simple, energy consumption is low, is easy to realize suitability for industrialized production.
The objective of the invention is to be achieved by the following technical programs:
A kind of preparation method of Eu doped aluminum nitride base fluorescent powder comprises following basic step:
(1) aluminium powder, aluminum nitride powder, europium sesquioxide powder and carborundum powder are mixed, put into the ball grinder ball milling and mix;
(2) mixed powder is packed into porous graphite crucible, the porous graphite crucible is put into the reaction chamber of high-pressure combustion synthesizer, after reaction chamber is evacuated to air pressure and is less than 10Pa, is filled with the nitrogen that purity is 99.999%;
(3) by the graphite paper tape, by the powder bottom, being ignited, is 20V at voltage, switches on under the condition that electric current is 60A the graphite paper tape combustion reactions occurs for 10 seconds;
(4) after combustion reactions, product is ground and sieves, obtain Eu doped aluminum nitride fluorescent material.
Further technical scheme of the present invention is that its chemical formula of this fluorescent material is (1-x-y) AlN:xEu, ySi (0.001≤x≤0.01,0.01≤y≤0.1), and aluminium powder and the mixing of the aluminum nitride powder scope that example is 3: 7～7: 3 in molar ratio.
Preferably, described burning is synthetic is to carry out in the ambiance that is 0.5～3MPa at nitrogen pressure.
It is raw material that aluminium powder, aluminium nitride, europium sesquioxide, silicon carbide are take in the present invention, by after the raw material ball milling, under low nitrogen atmosphere, burn and synthesize, prepares blue Eu doped aluminum nitride fluorescent material; The method not only technique is simple, reproducible, and cost is low, pollution-free, and the blue Eu doped aluminum nitride fluorescent material excellent performance of preparing.
Beneficial effect of the present invention is, the raw material used in the preparation method is comparatively cheap metallic aluminium powder, aluminum nitride powder, carborundum powder and nitrogen, and preparation time is short, and energy consumption is low, and cost is low, and efficiency is high; Due to non-volatile, without decomposing, so environmentally friendly; And method is simple, reproducible; The output of product is high, purity is high; Powder diameter distributes comparatively even.The Eu doped aluminum nitride fluorescent material synthesized has wide application prospect in the white light LEDs field.
The accompanying drawing explanation
Fig. 1 is the combustion and synthesis device structural representation that the present invention uses;
Fig. 2 is the XRD figure of Eu doped aluminum nitride fluorescent material;
Fig. 3 is the SEM figure of Eu doped aluminum nitride fluorescent material;
Fig. 4 is the luminescent properties figure of Eu doped aluminum nitride fluorescent material.
Embodiment:
Below in conjunction with accompanying drawing, invention is described in further detail.
As shown in Figure 1, in figure, 1 is reaction chamber; 2 is electrode; 3 is the porous graphite crucible; 4 is the reactant powder; 5 is the graphite paper tape; 6 is inlet mouth; 7 is venting port; 8 for vacuumizing gas port; 9 is direct supply; 10 is weather gage; Preparation process of the present invention completes in combustion and synthesis device, under suitable nitrogen pressure condition, makes aluminium powder directly and nitrogen generation combustion reactions, obtains Eu doped aluminum nitride fluorescent powder.
Embodiment 1:
Form (1-x-y) AlN:xEu according to chemical formula, ySi, get x=0.01, y=0.1, the molar ratio of aluminium powder and aluminum nitride powder is got 5: 5, be about to put into ball grinder (not vacuumizing) ball mill mixing 2 hours after aluminium powder 6.07 grams, aluminum nitride powder 9.22 grams, europium sesquioxide 0.79 gram, silicon carbide 1.80 grams mixing, rotating speed is 400 rev/mins, within dry 8 hours under 110 ℃ subsequently, also crosses 100 eye mesh screens.By the mixed powder porous graphite crucible of packing into, the porous graphite crucible is put into the reaction chamber of high-pressure combustion synthesizer, after reaction chamber is evacuated to air pressure and is less than 10Pa, is filled with the high pure nitrogen of 2.0MPa purity 99.99%; By the graphite paper tape, by the powder bottom, being ignited, is 20V at voltage, switches on under the condition that electric current is 60A the graphite paper tape and makes for 10 seconds combustion reactions occur.After reaction, the product in the porous graphite crucible is taken out and grinds and sieve, obtain Eu doped aluminum nitride fluorescent material.
Utilize X-ray diffractometer (XRD), scanning electronic microscope (SEM) and spectrophotofluorometer (PL) to be characterized resulting product.Fig. 2 is the XRD figure spectrum of product, and all spectrums peak index turns to six side's aluminium nitride phases, the spectrum peak of any impurity phase do not occur.Fig. 3 is the SEM photo of product, and visible particle size were is between 0.5～3 μ m.Fig. 4 is the luminescent properties collection of illustrative plates of fluorescent material, and the excitation peak position is at 290nm and 330nm, and emission peak is positioned at 470nm.
Embodiment 2:
Form (1-x-y) AlN:xEu according to chemical formula, ySi, get x=0.001, y=0.01, the molar ratio of aluminium powder and aluminum nitride powder is got 3: 7, be about to put into ball grinder (not vacuumizing) ball mill mixing 2 hours after aluminium powder 3.90 grams, aluminum nitride powder 13.80 grams, europium sesquioxide 0.09 gram, silicon carbide 0.20 gram mixing, rotating speed is 400 rev/mins, within dry 8 hours under 110 ℃ subsequently, also crosses 100 eye mesh screens.By the mixed powder porous graphite crucible of packing into, the porous graphite crucible is put into the reaction chamber of high-pressure combustion synthesizer, after reaction chamber is evacuated to air pressure and is less than 10Pa, is filled with the high pure nitrogen of 3.0MPa purity 99.99%; By the graphite paper tape, by the powder bottom, being ignited, is 20V at voltage, switches on under the condition that electric current is 60A the graphite paper tape and makes for 10 seconds combustion reactions occur.After reaction, the product in the porous graphite crucible is taken out and grinds and sieve, obtain Eu doped aluminum nitride fluorescent material.
Embodiment 3:
Form (1-x-y) AlN:xEu according to chemical formula, ySi, get x=0.005, y=0.05, the molar ratio of aluminium powder and aluminum nitride powder is got 7: 3, be about to put into ball grinder (not vacuumizing) ball mill mixing 2 hours after aluminium powder 8.58 grams, aluminum nitride powder 5.59 grams, europium sesquioxide 0.96 gram, silicon carbide 0.42 gram mixing, rotating speed is 400 rev/mins, within dry 8 hours under 110 ℃ subsequently, also crosses 100 eye mesh screens.By the mixed powder porous graphite crucible of packing into, the porous graphite crucible is put into the reaction chamber of high-pressure combustion synthesizer, after reaction chamber is evacuated to air pressure and is less than 10Pa, is filled with the high pure nitrogen of 0.5MPa purity 99.99%; By the graphite paper tape, by the powder bottom, being ignited, is 20V at voltage, switches on under the condition that electric current is 60A the graphite paper tape and makes for 10 seconds combustion reactions occur.After reaction, the product in the porous graphite crucible is taken out and grinds and sieve, obtain Eu doped aluminum nitride fluorescent material.
Embodiment 4:
Form (1-x-y) AlN:xEu according to chemical formula, ySi, get x=0.005, y=0.06, the molar ratio of aluminium powder and aluminum nitride powder is got 6: 4, be about to put into ball grinder (not vacuumizing) ball mill mixing 2 hours after aluminium powder 7.29 grams, aluminum nitride powder 7.38 grams, europium sesquioxide 0.41 gram, silicon carbide 1.15 grams mixing, rotating speed is 400 rev/mins, within dry 8 hours under 110 ℃ subsequently, also crosses 100 eye mesh screens.By the mixed powder porous graphite crucible of packing into, the porous graphite crucible is put into the reaction chamber of high-pressure combustion synthesizer, after reaction chamber is evacuated to air pressure and is less than 10Pa, is filled with the high pure nitrogen of 1.0MPa purity 99.99%; By the graphite paper tape, by the powder bottom, being ignited, is 20V at voltage, switches on under the condition that electric current is 60A the graphite paper tape and makes for 10 seconds combustion reactions occur.After reaction, the product in the porous graphite crucible is taken out and grinds and sieve, obtain Eu doped aluminum nitride fluorescent material.
Claims (2)
1. the preparation method of an Eu doped aluminum nitride base fluorescent powder, is characterized in that, comprises following preparation process:
(1) according to chemical formula (1-x-y) AlN:xEu ySi, 0.001≤x≤0.01,0.06<y≤0.1, aluminium powder, aluminum nitride powder, europium sesquioxide powder and carborundum powder are mixed, put into the ball grinder ball milling and mix, wherein, the molar ratio of aluminium powder and aluminum nitride powder is 3:7～7:3;
(2) mixed powder is packed into porous graphite crucible, the porous graphite crucible is put into the reaction chamber of high-pressure combustion synthesizer, after reaction chamber is evacuated to air pressure and is less than 10Pa, is filled with the nitrogen that purity is 99.999%;
(3) by the graphite paper tape, by the powder bottom, being ignited, is 20V at voltage, switches on under the condition that electric current is 60A the graphite paper tape combustion reactions occurs for 10 seconds;
(4) after combustion reactions, product is ground and sieves, obtain Eu doped aluminum nitride base fluorescent powder.
2. the preparation method of a kind of Eu doped aluminum nitride base fluorescent powder as claimed in claim 1, is characterized in that, in described step (2), nitrogen pressure is 0.5～3MPa.
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| CN102827600A (en) * | 2012-07-17 | 2012-12-19 | 西安交通大学 | Mn-doped aluminum nitride-based red phosphor powder and preparation method of red phosphor powder |
| CN105462579A (en) * | 2015-12-04 | 2016-04-06 | 许昌学院 | Long-afterglow red fluorescent material and preparation method thereof |
| WO2017157157A1 (en) * | 2016-03-18 | 2017-09-21 | 深圳市绎立锐光科技开发有限公司 | Method for preparing fluorescent ceramic provided with aluminum nitride substrate, and related fluorescent ceramic |
| CN109054816A (en) * | 2018-07-24 | 2018-12-21 | 北京科技大学 | A kind of preparation method of the aluminium nitride fluorescent powder of europium ion activation |
| WO2021206151A1 (en) * | 2020-04-09 | 2021-10-14 | 日亜化学工業株式会社 | Sintered body, light emitting device, wavelength conversion member, and method for manufacturing sintered body |
| CN111748343B (en) * | 2020-06-29 | 2022-09-02 | 新余学院 | Rare earth ion doped silicon oxynitride-based fluorescent powder, preparation method thereof and combustion synthesis device |
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Non-Patent Citations (4)
| Title |
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| Benjamin Dierre et al..Role of Si in the Luminescence of AlN:Eu,Si Phosphors.《J. Am. Ceram. Soc.》.2009,第92卷(第6期),第1272-1275页. |
| Role of Si in the Luminescence of AlN:Eu,Si Phosphors;Benjamin Dierre et al.;《J. Am. Ceram. Soc.》;20090630;第92卷(第6期);第1272-1275页 * |
| 氮化铝的燃烧合成及反应机理;江国健等;《第十届全国高技术陶瓷学术年会论文集》;19980901;第208-213页 * |
| 江国健等.氮化铝的燃烧合成及反应机理.《第十届全国高技术陶瓷学术年会论文集》.1998,第208-213页. |
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