CN103013506A - Nitride fluorescent powder material and preparation method thereof - Google Patents
Nitride fluorescent powder material and preparation method thereof Download PDFInfo
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- CN103013506A CN103013506A CN2012105278851A CN201210527885A CN103013506A CN 103013506 A CN103013506 A CN 103013506A CN 2012105278851 A CN2012105278851 A CN 2012105278851A CN 201210527885 A CN201210527885 A CN 201210527885A CN 103013506 A CN103013506 A CN 103013506A
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Abstract
The invention relates to the technical field of fluorescent powder for LED (Light Emitting Diode), and in particular relates to a nitride fluorescent powder material and a preparation method thereof. The nitride fluorescent powder material is characterized in that the chemical formula is M2-xSi5-yAlyN8:xEu, wherein M refers to one or combination of two of alkaline-earth metals Mg, Ca, Sr and Ba; and x is larger than or equal to 0.01 and is less than or equal to 0.3, and y is larger than 0 and less than or equal to 1.0. The nitride fluorescent powder material has the benefits that firstly, the luminescent material is Eu activated nitride with high quantum efficiency, stable physical and chemical properties and excellent antidumping property; secondly, the luminescent material is wide in wavelength range and is applicable to excitation of various wave band excitation sources; thirdly, metals (or non-metal) of high activity are smelted into an alloy body with good stability through an alloy smelting process, and the process window is wide, thereby being beneficial for the performance stability of products of different batches; and fourthly, the metal nitriding process in an ordinary method is saved, so that the cost of a product is greatly reduced.
Description
Technical field
The present invention relates to LED fluorescent material technical field, especially a kind of nitride phosphor material and preparation method thereof.
Background technology
Along with the progress of LED correlation technique, white light LEDs all makes great progress at aspects such as luminous efficiency, work-ing life, reduction costs.Be accompanied by manifesting of energy problem, the LED of high-efficiency energy-saving pollution-free 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 red fluorescence powder, to improve its colour rendering index.But luminous efficiency is low, the shortcoming of poor chemical stability in common existing take the sulfide system as main red fluorescence powder on the market, has limited its application in white light LEDs.
The Nitride phosphor that Eu activates has high luminous efficiency and chemical stability is good, and excitation wavelength range is wide, is a kind of desirable LED red fluorescence powder.The method of conventional synthesizing nitride fluorescent material adopts the metal direct nitridation method; the method is raw materials used to be with expensive; the metal of poor chemical stability carries out synthesizing after the nitrogenize; perhaps directly more expensive the and extremely unsettled metal nitride of purchase price is synthetic; above-mentioned two kinds of methods must operate under inert atmosphere protection in glove box; the cost high technology is complicated, is unfavorable for industrialized mass production.
Summary of the invention
One of purpose of the present invention provides a kind of nitride phosphor material, and this phosphor material powder is fit to ultraviolet, near ultraviolet or blue light equal excitation source excitation, and emission wavelength is a kind of LED fluorescent material of excellent property at the emitting red light of 600-680nm;
Two of purpose of the present invention provides a kind of preparation method of above-mentioned phosphor material powder, and the method adopts alloy prior with the elemental metals of less stable or the alloy of nonmetal melting formation good stability, is suitable for industrialized mass production.
A kind of nitride phosphor material, its special feature is: chemical general formula is M
2-xSi
5-yAl
yN
8: xEu, wherein, M represents one or both the combination among alkaline-earth metal Mg, Ca, Sr, the Ba, and above-mentioned x, y satisfy 0.01≤x≤0.3,0＜y≤1.0.
A kind of preparation method of aforementioned nitride phosphor material, its special feature is, comprises the steps:
(1) according to aforesaid chemical general formula, one or both combination and simple substance Si, metal A l, the metal Eu among alkaline-earth metal Mg, Ca, Sr, the Ba carried out melting by stoichiometric ratio in arc-melting furnace, form alloy;
(2) with behind the broken ball milling of the alloy that obtains under protective atmosphere high temperature sintering, after cooling is taken out washing dry, namely obtain nitride phosphor material of the present invention.
Each elementary composition derives from metal or non-metal simple-substance in the chemical general formula.
The mixing of each elementary composition is finished by the mode that arc-melting furnace forms alloy in the chemical general formula.
Protective atmosphere is the nitrogen greater than 3N in the step (2).
Sintering temperature is 1400 ℃-1800 ℃ in the middle high temperature sintering building-up process of step (2), sintering time 5-10h.
Washing process is to adopt deionized water to embathe until washings Ph value is neutrality in the step (2).
Drying temperature is 120 ℃ in the step (2).
The beneficial effect of the inventive method is:
1, luminescent material of the present invention is the nitride that Eu activates, and quantum yield is high, 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 alloyage synthesizing nitride fluorescent material, form the alloy body of good stability by the alloy smelting process metal that activity is high (or nonmetal) melting, avoid price costliness and the extremely unsettled starting material of chemical property such as 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, product cost significantly reduces.
Description of drawings
Fig. 1 is the Sr of preparation in the embodiment of the invention 1
1.96Si
4.5Al
0.5N
8: the XRD of 0.04Eu fluorescent material (X-ray diffraction) figure, wherein X-coordinate is the X ray input angle, ordinate zou is the relative intensity of diffraction peak;
Fig. 2 is the Sr of preparation in the embodiment of the invention 1
1.96Si
4.5Al
0.5N
8: the utilizing emitted light spectrogram of 0.04Eu fluorescent material.
Embodiment
The below is described in detail the present invention, and the explanation of the invention is not limited.
Embodiment 1:
Sr
1.96Si
4.5Al
0.5N
8: the preparation of 0.04Eu fluorescent material.
Take Sr, Si, Al, Eu as starting material, the ratio of the amount of substance of above-mentioned substance is Sr:Si:Al:Eu=1.96:4.5:0.5:0.04, with above-mentioned metal (or nonmetal), put into arc-melting furnace and carry out moment high arc temperature formation alloy body, to obtain powdered alloy behind the broken ball milling of gained alloy body, powdered alloy is put into the zirconium white crucible, at the N greater than 3N
21400 ℃ of sintering are 10 hours in the atmosphere, take out behind the naturally cooling, embathe with deionized water, until washings Ph value is neutral, namely get Sr after 120 ℃ of dry 2h dryings again
1.96Si
4.5Al
0.5N
8: 0.04Eu fluorescent material.
Embodiment 2:
Sr
1.95Ca
0.04Si
4.5Al
0.5N
8: the preparation of 0.01Eu fluorescent material.
Take Sr, Ca, Si, Al, Eu as starting material, the ratio of the amount of substance of above-mentioned substance is Sr:Ca:Si:Al:Eu=1.95:0.04:4.5:0.5:0.01, with above-mentioned metal (or nonmetal), put into arc-melting furnace and carry out moment high arc temperature formation alloy body, to obtain powdered alloy behind the broken ball milling of gained alloy body, powdered alloy is put into the zirconium white crucible, at N
21500 ℃ of sintering are 8 hours in the atmosphere, and naturally cooling takes out, and embathe with deionized water, until washings Ph value is neutrality, namely get Sr behind 120 ℃ of dry 2h
1.95Ca
0.04Si
4.5Al
0.5N
8: 0.01Eu fluorescent material.
Embodiment 3:
Sr
1.5Ba
0.2Si
5N
8: the preparation of 0.3Eu fluorescent material.
Take Sr, Ba, Si, Eu as starting material, the ratio of the amount of substance of above-mentioned substance is Sr:Ba:Si:Eu=1.5:0.2:5:0.3, with above-mentioned metal (or nonmetal), put into arc-melting furnace and carry out moment high arc temperature formation alloy body, to obtain powdered alloy behind the broken ball milling of gained alloy body, powdered alloy is put into the zirconium white crucible, at N
21800 ℃ of sintering are 8 hours in the atmosphere, and naturally cooling takes out, and embathe with deionized water, until washings Ph value is neutrality, namely get Sr behind 120 ℃ of dry 2h
1.5Ba
0.2Si
5N
8: 0.3Eu fluorescent material.
Embodiment 4:
Sr
1.92Mg
0.04Si
4AlN
8: the preparation of 0.04Eu fluorescent material.
Take Sr, Mg, Si, Al, Eu as starting material, the ratio of the amount of substance of above-mentioned substance is Sr:Mg:Si:Eu=1.92:0.04:4:1:0.04, with above-mentioned metal (or nonmetal), put into arc-melting furnace and carry out moment high arc temperature formation alloy body, to obtain powdered alloy behind the broken ball milling of gained alloy body, powdered alloy is put into the zirconium white crucible, at N
21600 ℃ of sintering are 12 hours in the atmosphere, and naturally cooling takes out, and embathe with deionized water, until washings Ph value is neutrality, namely get Sr behind 120 ℃ of dry 2h
1.92Mg
0.04Si
4AlN
8: 0.04Eu fluorescent material.
Embodiment 5:
Ca
1.96Si
4AlN
8: the preparation of 0.04Eu fluorescent material.
Take Ca, Si, Al, Eu as starting material, the ratio of the amount of substance of above-mentioned substance is Ca:Si:Al:Eu=1.96:4:1:0.04, with above-mentioned metal (or nonmetal), put into arc-melting furnace and carry out moment high arc temperature formation alloy body, to obtain powdered alloy behind the broken ball milling of gained alloy body, powdered alloy is put into the zirconium white crucible, at N
21700 ℃ of sintering are 10 hours in the atmosphere, and naturally cooling takes out, and embathe with deionized water, until washings Ph value is neutrality, namely get Ca behind 120 ℃ of dry 2h
1.96Si
4AlN
8: 0.04Eu fluorescent material.
Claims (8)
1. nitride phosphor material, it is characterized in that: chemical general formula is M
2-xSi
5-yAl
yN
8: xEu, wherein, M represents one or both the combination among alkaline-earth metal Mg, Ca, Sr, the Ba, and above-mentioned x, y satisfy 0.01≤x≤0.3,0＜y≤1.0.
2. the preparation method of the described nitride phosphor material of claim 1 is characterized in that, comprises the steps:
(1) according to the chemical general formula of claim 1, one or both combination and simple substance Si, metal A l, the metal Eu among alkaline-earth metal Mg, Ca, Sr, the Ba carried out melting by stoichiometric ratio in arc-melting furnace, form alloy;
(2) with behind the broken ball milling of the alloy that obtains under protective atmosphere high temperature sintering, after cooling is taken out washing dry, namely obtain nitride phosphor material of the present invention.
3. the preparation method of a kind of nitride phosphor material as claimed in claim 2, it is characterized in that: each elementary composition derives from metal or non-metal simple-substance in the chemical general formula.
4. the preparation method of a kind of nitride phosphor material as claimed in claim 2 is characterized in that: the mixing of each elementary composition is finished by the mode that arc-melting furnace forms alloy in the chemical general formula.
5. the preparation method of a kind of nitride phosphor material as claimed in claim 2 is characterized in that: protective atmosphere is nitrogen in the step (2).
6. the preparation method of a kind of nitride phosphor material as claimed in claim 2 is characterized in that: in the step (2) in the high temperature sintering building-up process sintering temperature be 1400 ℃-1800 ℃, sintering time 5-10h.
7. the preparation method of a kind of nitride phosphor material as claimed in claim 2 is characterized in that: washing process is to adopt deionized water wash until washings Ph value is neutrality in the step (2).
8. the preparation method of a kind of nitride phosphor material as claimed in claim 2 is characterized in that: drying temperature is 120 ℃ in the step (2).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327854A (en) * | 2014-11-11 | 2015-02-04 | 河北利福化工科技有限公司 | Red luminescent fluorescent powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005226000A (en) * | 2004-02-13 | 2005-08-25 | Shoei Chem Ind Co | Nitride phosphor, manufacturing method of nitride phosphor, white light emitting element and pigment |
| CN101171321A (en) * | 2005-04-01 | 2008-04-30 | 三菱化学株式会社 | Alloy powder for raw material of inorganic functional material and phosphor |
| CN101798510A (en) * | 2010-03-15 | 2010-08-11 | 彩虹集团公司 | Nitride phosphor material and preparation method thereof |
-
2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005226000A (en) * | 2004-02-13 | 2005-08-25 | Shoei Chem Ind Co | Nitride phosphor, manufacturing method of nitride phosphor, white light emitting element and pigment |
| CN101171321A (en) * | 2005-04-01 | 2008-04-30 | 三菱化学株式会社 | Alloy powder for raw material of inorganic functional material and phosphor |
| CN101798510A (en) * | 2010-03-15 | 2010-08-11 | 彩虹集团公司 | Nitride phosphor material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327854A (en) * | 2014-11-11 | 2015-02-04 | 河北利福化工科技有限公司 | Red luminescent fluorescent powder and preparation method thereof |
| CN104327854B (en) * | 2014-11-11 | 2016-05-18 | 河北利福化工科技有限公司 | A kind of red luminescence phosphor and preparation method thereof |
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Application publication date: 20130403 |