CN101798510A - Nitride phosphor material and preparation method thereof - Google Patents
Nitride phosphor material and preparation method thereof Download PDFInfo
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- CN101798510A CN101798510A CN 201010124165 CN201010124165A CN101798510A CN 101798510 A CN101798510 A CN 101798510A CN 201010124165 CN201010124165 CN 201010124165 CN 201010124165 A CN201010124165 A CN 201010124165A CN 101798510 A CN101798510 A CN 101798510A
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Abstract
The invention provides a nitride phosphor material and a preparation method thereof. The nitride phosphor material is characterized in that the general chemical formula is M2-xSi5-yZyN8:xEu, wherein M is one or a combination of two of the alkaline-earth metals including Mg, Ca, Sr and Ba, and Z is one of Al and Ge; x is not less than 0.01 and not more than 0.3; and y is not less than 0 and not more than 1.0. The nitride phosphor material has low-price synthetic raw materials, stable performance and simple synthesis technology and is suitable for industrialized volume production.
Description
Technical field
The invention belongs to LED fluorescent material technical field, relate to a kind of Nitride phosphor and preparation method thereof.
Background technology
Along with the progress of LED correlation technique, white light LEDs has all been obtained very big progress at luminous efficiency, work-ing life, aspect such as reduce cost.Be accompanied by manifesting of energy problem, energy-efficient free of contamination LED has a wide range of applications, and the LED illumination also is the long-range objectives that researcher is pursued.But the white light LEDs product on the market mainly is to adopt the GaN chip to excite yellow fluorescent powder to realize white light, and it is exactly to lack red composition that there is a serious deficiency in the generation white light of this pattern, has hindered LED especially in the promotion and application of lighting field.
At present, the method that the solution white light LEDs lacks red composition adds red fluorescence powder exactly in white fluorescent powder, to improve its colour rendering index.But the common red fluorescence powder based on the sulfide system exists that luminous efficiency is low, the shortcoming of poor chemical stability on the market, has limited its application in white light LEDs.
Eu activated Nitride phosphor has high luminous efficiency and chemical stability is good, and excitation wavelength range is wide, is a kind of ideal LED red fluorescence powder.The method of conventional synthesizing nitride fluorescent material adopts the metal direct nitridation method; this method is raw materials used for costing an arm and a leg; the metal of poor chemical stability carries out synthesizing after the nitrogenize; perhaps direct purchase price is expensive more and extremely unsettled metal nitride is synthetic; above-mentioned two kinds of methods must be operated under inert atmosphere protection in glove box; cost high technology complexity is unfavorable for industrialized mass production.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nitride phosphor material, adopting cheapness, stable compound is raw material, synthesis technique is simple, is suitable for industrialized mass production.
To achieve these goals, the present invention adopts following technical scheme: a kind of nitride phosphor material, its chemical general formula are M
2-xSi
5-yZ
yN
8: xEu, wherein, M represents one or both the combination among alkaline-earth metal Mg, Ca, Sr, the Ba; Z represents a kind of among Al, the Ge; 0.01≤x≤0.3,0≤y≤1.0.
To achieve these goals, making method of the present invention adopts following technical scheme: a kind of preparation method of nitride phosphor material may further comprise the steps: 1) will contain oxide compound, carbonate, nitrate, the acetate of M, SiO
2, contain nitride or the oxide compound of X, α-Si
3N
4, the oxide compound of Eu, nitrate, and the carbon containing reducing substances is that raw material is even through the ball milling thorough mixing; 2) step 1) gained mixture is first at N
2In carry out low-temperature sintering, and then it is synthetic to improve the further high temperature sintering of sintering temperature in shielding gas; 3) with step 2) sintered product that obtains washs and is drying to obtain nitride phosphor material of the present invention.
Described carbon containing reducing substances is carbon dust, C
3H
6N
6, C
2H
4N
4, a kind of in the polyethylene.
Described sintering process is carried out in tube furnace, before the sintering burner hearth is carried out deoxygenation, dehumidification treatments.
Described low sintering temperature is 800 ℃-1000 ℃, and sintering time is 16-24 hour.
Shielding gas is N in the described high temperature sintering building-up process
2, N
2-NH
3Mixed gas or N
2-CH
4A kind of in the mixed gas.
Described N
2-NH
3The volume ratio of mixed gas is 90: 10, described N
2-CH
4The volume ratio of mixed gas is 95: 5.
Sintering temperature is 1000 ℃-1800 ℃ in the described high temperature sintering building-up process.
Sintered sample is washed the employing Virahol, and the volume of Virahol is more than 3 times of sintered product volume.
Compared with prior art, the present invention has the following advantages:
1, luminescent material of the present invention is an Eu activated nitride, the quantum yield height, and physical and chemical performance is stable, and anti-decay property is good.
2, luminescent material excitation wavelength range of the present invention is wide, can be suitable for multiple wave band excitaton source and excite.
3, the present invention adopts carbon reduction method synthesizing nitride fluorescent material, used starting material are stable, the cheap material of chemical property, price costliness and the extremely unsettled starting material of chemical property such as the pure metal that has replaced using in the current synthesizing nitride fluorescent material process, metal nitride, make process more simple, process window is wide, is beneficial to the stable performance of each batch products.
4, saved the nitride metal process in the ordinary method, avoided hyperbaric environment required in experimentation, whole experiment can be carried out at conventional tube furnace, and product cost significantly reduces.
Description of drawings
Fig. 1 is the Sr of preparation in the embodiment of the invention 1
1.96Si
5N
8: the XRD of 0.04Eu fluorescent material (X-ray diffraction) figure.
Fig. 2 is the Sr of preparation in the embodiment of the invention 1
1.96Si
5N
8: the emmission spectrum figure of 0.04Eu fluorescent material.
Embodiment
Below by specific embodiment the present invention is done detailed description.
Embodiment 1:Sr
1.96Si
5N
8: the preparation of 0.04Eu fluorescent material
With SrCO
3, SiO
2, α-Si
3N
4, Eu
2O
3, carbon dust is starting material, the ratio of the amount of substance of above-mentioned substance is SrCO
3: SiO
2: α-Si
3N
4: Eu
2O
3: carbon dust=1.96: 2: 1: 0.02: 1.96, above-mentioned starting material are carried out abundant ball milling mix the back taking-up, put into the Mo crucible, at N
2800 ℃ of sintering are after 24 hours in the atmosphere, and ℃ continuation of rising sintering temperature to 1500 is at N
2Sintering is 15 hours in the atmosphere, and cooling is taken out, and washs 3 times with 5 times of Virahols to sample volume, promptly gets Sr after the drying
1.96Si
5N
8: 0.04Eu fluorescent material, its XRD figure and emmission spectrum figure see also Fig. 1 and Fig. 2.
Embodiment 2:Sr
1.92Ba
0.07Si
5N
8: the preparation of 0.01Eu fluorescent material
With SrCO
3, Ba (NO
3)
2, SiO
2, α-Si
3N
4, Eu
2O
3, C
3H
6N
6Be starting material, the ratio of the amount of substance of above-mentioned substance is SrCO
3: Ba (NO
3)
2: SiO
2: α-Si
3N
4: Eu
2O
3: C
3H
6N
6=1.92: 0.07: 2: 1: 0.005: 0.33, above-mentioned starting material are carried out abundant ball milling mix the back taking-up, put into the Mo crucible, at N
2900 ℃ of sintering are after 16 hours in the atmosphere, and ℃ continuation of rising sintering temperature to 1800 is at N
2Sintering is 10 hours in the atmosphere, and cooling is taken out, and washs 3 times with 6 times of Virahols to sample volume, promptly gets Sr after the drying
1.92Ba
0.07Si
5N
8: 0.01Eu fluorescent material.
Embodiment 3:Sr
1.7Si
4.5Al
0.5N
8: the preparation of 0.3Eu fluorescent material
With SrCO
3, AlN, SiO
2, α-Si
3N
4, Eu
2O
3, C
2H
4N
4Be starting material, the ratio of the amount of substance of above-mentioned substance is SrCO
3: AlN: SiO
2: α-Si
3N
4: Eu
2O
3: C
2H
4N
4=1.7: 0.5: 1.5: 1: 0.15: 0.49, above-mentioned starting material are carried out abundant ball milling mix the back taking-up, put into the Mo crucible, at N
21000 ℃ of sintering are after 20 hours in the atmosphere, and ℃ continuation of rising sintering temperature to 1500 is at N
2-NH
3Sintering is 12 hours in (volume ratio is 90: 10) atmosphere, and cooling is taken out, and washs 3 times with 8 times of Virahols to sample volume, promptly gets Sr after the drying
1.7Si
4.5Al
0.5N
8: 0.3Eu fluorescent material.
Embodiment 4:Sr
1.72Mg
0.08Si
5N
8: the preparation of 0.2Eu fluorescent material
With SrO, MgO, SiO
2, α-Si
3N
4, Eu
2O
3, C
3H
6N
6Be starting material, the ratio of the amount of substance of above-mentioned substance is SrO: MgO: SiO
2: α-Si
3N
4: Eu
2O
3: C
3H
6N
6=1.72: 0.08: 2: 1: 0.1: 0.33, above-mentioned starting material are carried out abundant ball milling mix the back taking-up, put into the Mo crucible, at N
2900 ℃ of sintering are after 16 hours in the atmosphere, and ℃ continuation of rising sintering temperature to 1800 is at N
2Sintering is 10 hours in the atmosphere, and cooling is taken out, and washs 3 times with 6 times of Virahols to sample volume, promptly gets Sr after the drying
1.72Mg
0.08Si
5N
8: 0.2Eu fluorescent material
Embodiment 5:Sr
1.9Si
4GeN
8: the preparation of 0.1Eu fluorescent material
With SrCO
3, GeN, SiO
2, α-Si
3N
4, Eu
2O
3, C
2H
4N
4Be starting material, the ratio of the amount of substance of above-mentioned substance is SrCO
3: GaN: SiO
2: α-Si
3N
4: Eu
2O
3: C
3H
6N
6=1.9: 1: 1: 1: 0.05: 0.49, above-mentioned starting material are carried out abundant ball milling mix the back taking-up, put into the Mo crucible, at N
2900 ℃ of sintering are after 24 hours in the atmosphere, and ℃ continuation of rising sintering temperature to 1700 is at N
2-CH
4Sintering is 20 hours in (volume ratio is 95: 5) atmosphere, and cooling is taken out, and washs 3 times with 5 times of Virahols to sample volume, promptly gets Sr after the drying
1.9Si
4GeN
8: 0.1Eu fluorescent material.
Claims (9)
1. a nitride phosphor material is characterized in that, its chemical general formula is M
2-xSi
5-yZ
yN
8: xEu, wherein,
M represents one or both the combination among alkaline-earth metal Mg, Ca, Sr, the Ba; Z represents a kind of among Al, the Ge; 0.01≤x≤0.3,0≤y≤1.0.
2. the preparation method of a nitride phosphor material is characterized in that, may further comprise the steps:
1) will contain one or both combination in the oxide compound, carbonate, nitrate, acetate of M, SiO
2, contain nitride or the oxide compound of Z, α-Si
3N
4, the oxide compound of Eu, nitrate, and the carbon containing reducing substances is that raw material is even through the ball milling thorough mixing;
2) step 1) gained mixture is first at N
2In carry out low-temperature sintering, and then it is synthetic to improve the further high temperature sintering of sintering temperature in shielding gas;
3) with step 2) sintered product that obtains washs and is drying to obtain nitride phosphor material of the present invention.
3. as the preparation method of a kind of nitride phosphor material as described in the claim 2, it is characterized in that: the carbon containing reducing substances is carbon dust, C
3H
6N
6, C
2H
4N
4, a kind of in the polyethylene.
4. as the preparation method of a kind of nitride phosphor material as described in the claim 2, it is characterized in that: sintering process is carried out in tube furnace, before the sintering burner hearth is carried out deoxygenation, dehumidification treatments.
5. as the preparation method of a kind of nitride phosphor material as described in the claim 2, it is characterized in that: low sintering temperature is 800 ℃-1000 ℃, and sintering time is 16-24 hour.
6. as the preparation method of a kind of nitride phosphor material as described in the claim 2, it is characterized in that: shielding gas is N in the high temperature sintering building-up process
2, N
2-NH
3Mixed gas or N
2-CH
4A kind of in the mixed gas.
7. as the preparation method of a kind of nitride phosphor material as described in the claim 6, it is characterized in that: described N
2-NH
3The volume ratio of mixed gas is 90: 10, described N
2-CH
4The volume ratio of mixed gas is 95: 5.
8. as the preparation method of a kind of nitride phosphor material as described in the claim 2, it is characterized in that sintering temperature is 1000 ℃-1800 ℃ in the high temperature sintering building-up process.
9. as the preparation method of a kind of nitride phosphor material as described in the claim 2, it is characterized in that sintered sample is washed the employing Virahol, the volume of Virahol is more than 3 times of sintered product volume.
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965104A (en) * | 2012-10-31 | 2013-03-13 | 彩虹集团公司 | Nitride fluorescent powder material and preparation method thereof |
| CN103013506A (en) * | 2012-12-10 | 2013-04-03 | 彩虹集团公司 | Nitride fluorescent powder material and preparation method thereof |
| CN103305214A (en) * | 2013-06-16 | 2013-09-18 | 桂林理工大学 | Preparation method of color-regulatable Eu-doped fluorescent powder |
| CN105295903A (en) * | 2015-11-03 | 2016-02-03 | 江苏罗化新材料有限公司 | Preparation method of nitride red fluorescent powder for high-foregrounding white light and backlight source LED (light emitting diode) |
| CN105885839A (en) * | 2012-07-18 | 2016-08-24 | 英特曼帝克司公司 | RED-EMITTING NITRIDE-BASED PHOSPHORS, and white light source comprising same |
| JP2017509735A (en) * | 2014-01-09 | 2017-04-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Europium-doped alkaline earth metal silicooxynitride-based phosphor |
| US10174246B2 (en) | 2012-07-18 | 2019-01-08 | Intematix Corporation | Red-emitting nitride-based calcium-stabilized phosphors |
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| CN1522291A (en) * | 2002-03-22 | 2004-08-18 | ���ǻ�ѧ��ҵ��ʽ���� | Nitride phosphor and method for preparation thereof, and light emitting device |
| WO2009050171A2 (en) * | 2007-10-15 | 2009-04-23 | Leuchtstoffwerk Breitungen Gmbh | Rare-earth doped alkaline-earth silicon nitride phosphor, method for producing and radiation converting device comprising such a phosphor |
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Patent Citations (2)
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| CN1522291A (en) * | 2002-03-22 | 2004-08-18 | ���ǻ�ѧ��ҵ��ʽ���� | Nitride phosphor and method for preparation thereof, and light emitting device |
| WO2009050171A2 (en) * | 2007-10-15 | 2009-04-23 | Leuchtstoffwerk Breitungen Gmbh | Rare-earth doped alkaline-earth silicon nitride phosphor, method for producing and radiation converting device comprising such a phosphor |
Non-Patent Citations (2)
| Title |
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| 《APPLIED PHYSICS LETTERS》 20060418 Xianqing Piao, et al., Characterization and luminescence properties of Sr2Si5N8:Eu2+ phosphor for white light-emitting-diode illumination 第161908页 , * |
| 《Materials Science and Engineering》 20091231 T Horikawa, et al., Preparation of Sr2Si5N8:Eu2+ Phosphors using Various Novel Reducing Agents and Their Luminescent Properties 第1-6页 , * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885839A (en) * | 2012-07-18 | 2016-08-24 | 英特曼帝克司公司 | RED-EMITTING NITRIDE-BASED PHOSPHORS, and white light source comprising same |
| US10174246B2 (en) | 2012-07-18 | 2019-01-08 | Intematix Corporation | Red-emitting nitride-based calcium-stabilized phosphors |
| CN102965104A (en) * | 2012-10-31 | 2013-03-13 | 彩虹集团公司 | Nitride fluorescent powder material and preparation method thereof |
| CN103013506A (en) * | 2012-12-10 | 2013-04-03 | 彩虹集团公司 | Nitride fluorescent powder material and preparation method thereof |
| CN103305214A (en) * | 2013-06-16 | 2013-09-18 | 桂林理工大学 | Preparation method of color-regulatable Eu-doped fluorescent powder |
| JP2017509735A (en) * | 2014-01-09 | 2017-04-06 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Europium-doped alkaline earth metal silicooxynitride-based phosphor |
| CN105295903A (en) * | 2015-11-03 | 2016-02-03 | 江苏罗化新材料有限公司 | Preparation method of nitride red fluorescent powder for high-foregrounding white light and backlight source LED (light emitting diode) |
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Application publication date: 20100811 |