CN102660284B - Manufacturing method of red nitride fluorescent powder for LED - Google Patents
Manufacturing method of red nitride fluorescent powder for LED Download PDFInfo
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- CN102660284B CN102660284B CN2012101133054A CN201210113305A CN102660284B CN 102660284 B CN102660284 B CN 102660284B CN 2012101133054 A CN2012101133054 A CN 2012101133054A CN 201210113305 A CN201210113305 A CN 201210113305A CN 102660284 B CN102660284 B CN 102660284B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention relates to a manufacturing method of red nitride fluorescent powder for LED. The manufacturing method comprises the following steps of weighing raw materials, carrying out ball milling of one or more fluxing agents, sieving, mixing, sintering, crushing, washing, sieving and carrying out packaging. Compared with the existing high-temperature solid-state technology, the manufacturing method has the advantages that only one high-temperature sintering process on the raw materials is carried out and thus sintering hardness of powder is reduced obviously and sintered powder blocks are incompact so that processes and energy consumption are reduced and product quality is improved; and the one or more fluxing agents are subjected to ball milling in advance so that ball milling time of an initial product is greatly reduced and crystal brightness of a final product is improved.
Description
Technical field
The present invention relates to the manufacture method of a kind of LED with fluorescent material, more particularly relate to the manufacture method that a kind of nitride is manufactured red fluorescence powder.
Background technology
LED refers to photodiode, be a kind of can be the solid-state semiconducter device of visible light by electric energy conversion, it can directly be converted into light to electricity; It has changed the luminous principle luminous with the electricity-saving lamp tricolor powder of incandescent light tungsten filament, and adopts electroluminescence.The characteristics of LED are very obvious, the life-span is long, light efficiency is high, radiationless and reduce power consumption, stability is high, volume is little, shock-resistant, thereby in multi-field widespread use.Traditional implementation of white light LEDs is blue chip stack yellow fluorescent powder, the white light color developing that this mode obtains is poor, and employing blue chip or many colour system of ultraviolet chip stack fluorescent material, such as: red fluorescence powder, green emitting phosphor etc., can realize the LED that color developing is better, so nitride red fluorescent powder is applicable to the white light LEDs of the various high-performance high-color renderings of preparation.At present superior on the performances such as the chemical stability of nitride red fluorescent powder, thermostability, make its application comparatively extensive.
Nitride red fluorescent powder mostly is alkali earth metal and rare earth compound, because the chemical property of alkali earth metal and rare earth metal is active, with the easy formation impurity such as water, oxygen, affect the component of synthetic product, and then have influence on the use properties of final product.Therefore the atmosphere in building-up process, processing conditions have all been proposed to higher requirement, difficulty of processing is strengthened, tooling cost improves.
Its processing step of high temperature solid-state method of the prior art is: batching → batch mixing → high temperature pre-burning → detect → pulverize → primary dcreening operation → high temperature reduction → detect → pulverize → primary dcreening operation → ball milling → washing → wet screening → centrifugal dewatering → dry → dusting cover → comprehensive detection → finished product.Although the crystallite crystal mass that this method obtains is good, few surface defects, luminous efficiency is high, be beneficial to suitability for industrialized production, but also there is certain defect, as twice high temperature sintering of needs, warm-up time is long etc. in reducing atmosphere, not only waste energy and the finished particle that generates is large, size distribution is wide, easy agglomerate, needs long ball milling could reduce particle diameter, but simultaneously the twinkler crystalline form is damaged, luminosity factor descends.
Summary of the invention
For above-mentioned technical problem, purpose of the present invention be just to provide a kind of without by twice calcination and in inert atmosphere heat-up time short LED by the manufacture method of nitride red fluorescent powder fluorescent material.
To achieve these goals, the present invention adopts following technical scheme:
A kind of manufacture method of Nitride phosphor of doped with rare-earth elements is characterized in that comprising the following steps:
A) take respectively aluminium nitride, silicon nitride, CaCl2, strontium nitride, fusing assistant, the weight taken is calculated according to the stoichiometric ratio of nitride red fluorescent powder general formula, and described general formula is Ca
1-x-3y/2A
xB
ySiAlN
3, wherein A is one or more in alkaline earth element Be, Ba, Mg, Sr, Ra; , B is one or more in rare earth element Pr, Gd, Sm, Tb, Eu, Er, Ce, Lu; The span of its doping x is 0≤x≤0.1, and the span of y is 0<y≤0.1;
B) difference that obtains fluorescent material particle diameter size and wavelength according to plan is chosen different fusing assistants, described fusing assistant is one or more in boric acid, strontium fluoride, Calcium Fluoride (Fluorspan), aluminum fluoride, will account for a) fusing assistant of the described general formula 0.5-3% of step mole and carry out crossing 250 eye mesh screens after dry bulb mill 2-10h;
C) by a) and b) starting material that obtain of step put into planetary ball mill and fully mix, mixing time is 10-20h;
D) by c) pack into crucible put into the high-temperature tubular atmosphere furnace of the mixture that obtains of step;
E) in high-temperature atmosphere furnace, pass into the inert atmosphere of pure nitrogen gas, burn 4.5h at 1700 ℃ of lower constant temperature;
F) by e) head product that obtains of step is from crucible, taking out, and after being down to room temperature, first with excellent pestle, carries out coarse breaking, then roller pair breaking 2 times, finally carries out ball milling 2.5h;
G) by f) head product that obtains of step is with after the deionized water washing of 90 ℃ 5 times, and put into baking oven and dry;
H) by g) head product that obtains of step crosses 300 eye mesh screens, and packing, obtain finished product.
The present invention compares and has following features with existing high temperature solid-state law technology:
Because the present invention only carries out a high temperature to raw material, burn, thereby the sintered material hardness of powder obviously reduces, the powder agglomates of sintering is loose, and the time of burning is short, has not only reduced technological process, and save energy and quality product go up not down; Fusing assistant is carried out to ball-milling processing in advance, make the Ball-milling Time of head product greatly reduce, thereby increased the launching efficiency of the finished product.
Embodiment
Embodiment 1: chemical formula is: Ca
0.96Mg
0.01Gd
0.02SiAlN
3
A) accurately take the CaCl2 of 142.3g, the magnesium nitride of 1.0g, the nitrogenize gadolinium of 5.1g, the silicon nitride of 140.2g, the aluminium nitride of 122.9g;
B) accurately take 8.2g boric acid and carry out crossing 250 eye mesh screens after dry bulb mill 5h;
C) by a) and b) starting material that obtain of step put into ball mill and fully mix, mixing time is 10h;
D) by c) pack into crucible put into high-temperature atmosphere furnace of the mixture that obtains of step;
E) in high-temperature atmosphere furnace, pass into the inert atmosphere of pure nitrogen gas, burn 4.5h at 1700 ℃ of lower constant temperature;
F) by e) head product that obtains of step is from crucible, taking out, and after being down to room temperature, first with excellent pestle, carries out coarse breaking, then roller pair breaking 2 times, finally carries out ball milling 1.5h;
G) by f) head product that obtains of step is with after the deionized water washing of 90 ℃ 5 times, and put into baking oven and dry;
H) by f) head product that obtains of step crosses 300 eye mesh screens, and packing, obtain finished product.
Embodiment 2: chemical formula is: Ca
0.96Ba
0.01Gd
0.02SiAlN
3
I) accurately take the nitrogenize gadolinium, the silicon nitride of 280.4g, the aluminium nitride of 245.8g of nitrogenize barium 10.2g of CaCl2, the 8.8g of 284.6g;
J) accurately take 16.6g boric acid and carry out crossing 250 eye mesh screens after dry bulb mill 5h;
K) by a) and b) starting material that obtain of step put into planetary ball mill and fully mix, mixing time is 10h;
L) by c) pack into crucible put into high-temperature atmosphere furnace of the mixture that obtains of step;
M) in high-temperature atmosphere furnace, pass into the inert atmosphere of pure nitrogen gas, burn 4.5h at 1700 ℃ of lower constant temperature;
N) by e) head product that obtains of step is from crucible, taking out, and after being down to room temperature, first with excellent pestle, carries out coarse breaking, then roller pair breaking 2 times, finally carries out ball milling 1.5h;
O) by f) head product that obtains of step is with after the deionized water washing of 90 ℃ 5 times, and put into baking oven and dry;
P) by f) head product that obtains of step crosses 300 eye mesh screens, and packing, obtain finished product.
Embodiment 3: chemical formula is: Ca
0.93Mg
0.04Ce
0.02SiAlN
3
Q) accurately take CaCl2, the magnesium nitride of 5.4g, the cerium nitride of 12.3g, the silicon nitride of 187.0g, the 163.96g aluminium nitride of 183.8g;
R) accurately take 11.0g boric acid and carry out crossing 250 eye mesh screens after dry bulb mill 5h;
S) by a) and b) starting material that obtain of step put into planetary ball mill and fully mix, mixing time is 17h;
T) by c) pack into crucible put into high-temperature atmosphere furnace of the mixture that obtains of step;
U) in high-temperature atmosphere furnace, pass into the inert atmosphere of going back of pure nitrogen gas, burn 4.5h at 1700 ℃ of lower constant temperature;
V) by e) head product that obtains of step is from crucible, taking out, and after being down to room temperature, first with excellent pestle, carries out coarse breaking, then roller pair breaking 2 times, finally carries out ball milling 1.5h;
W) by f) head product that obtains of step is with after the deionized water washing of 90 ℃ 5 times, and put into baking oven and dry;
X) by f) head product that obtains of step crosses 300 eye mesh screens, and packing, obtain finished product.
Be understandable that, in this specification sheets, only provided the part embodiment of this invention.According to above-mentioned principle, the present invention can also carry out suitable change and modification to above-mentioned embodiment.Therefore, the present invention is not limited to embodiment disclosed and described above, to modifications and changes more of the present invention, also should fall in the protection domain of claim of this patent.In addition, although in this specification sheets, used some specific terms, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (1)
1. a LED is by the manufacture method of nitride red fluorescent powder
,It is characterized in that comprising the following steps:
A) take respectively aluminium nitride, silicon nitride, CaCl2, strontium nitride, fusing assistant, the weight taken is calculated according to the stoichiometric ratio of nitride red fluorescent powder general formula, and described general formula is Ca
1-x-3y/2A
xB
ySiAlN
3, wherein A is one or more in alkaline earth element Be, Ba, Mg, Sr, Ra; B is one or more in rare earth element Pr, Gd, Sm, Tb, Eu, Er, Ce, Lu; The span of its doping x is 0≤x≤0.1, and the span of y is 0<y≤0.1;
B) difference that obtains fluorescent material particle diameter size and wavelength according to plan is chosen different fusing assistants, described fusing assistant is one or more in boric acid, strontium fluoride, Calcium Fluoride (Fluorspan), aluminum fluoride, will account for a) fusing assistant of the described general formula 0.5-3% of step mole and carry out crossing 250 eye mesh screens after dry bulb mill 2-10h;
C) by a) and b) starting material that obtain of step put into planetary ball mill and fully mix, mixing time is 10-20h;
D) by c) pack into crucible put into the high-temperature tubular atmosphere furnace of the mixture that obtains of step;
E) in high-temperature atmosphere furnace, pass into the inert atmosphere of pure nitrogen gas, burn 4.5h at 1700 ℃ of lower constant temperature;
F) by e) head product that obtains of step is from crucible, taking out, and after being down to room temperature, first with excellent pestle, carries out coarse breaking, then roller pair breaking 2 times, finally carries out ball milling 2.5h;
G) by f) head product that obtains of step is with after the deionized water washing of 90 ℃ 5 times, and put into baking oven and dry;
H) by g) head product that obtains of step crosses 300 eye mesh screens, and packing, obtain finished product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2644465C1 (en) * | 2017-03-14 | 2018-02-12 | Общество с ограниченной ответственностью "Монокристалл Пасты" | Method for production of finely-dispersed red luminescent material for generation of resulting white light in light emitting diodes |
Families Citing this family (5)
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| WO2016199406A1 (en) * | 2015-06-12 | 2016-12-15 | 株式会社 東芝 | Phosphor and method for producing same, and led lamp |
| WO2017013867A1 (en) * | 2015-07-22 | 2017-01-26 | パナソニックＩｐマネジメント株式会社 | Garnet compound and method for producing same, light emitting device and decorative article using garnet compound, and methodof using garnet compound |
| CN107200588B (en) * | 2016-03-18 | 2020-10-20 | 深圳光峰科技股份有限公司 | Preparation method of aluminum nitride matrix fluorescent ceramic and related fluorescent ceramic |
| CN110627024A (en) * | 2019-09-16 | 2019-12-31 | 中国科学院上海硅酸盐研究所 | Aluminum-doped silicon nitride material, aluminum-doped silicon nitride-based orange-red fluorescent material and preparation method thereof |
| CN111187617B (en) * | 2020-03-06 | 2022-11-11 | 英特美光电（苏州）有限公司 | Preparation method of nitride red fluorescent powder |
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| JP3837588B2 (en) * | 2003-11-26 | 2006-10-25 | 独立行政法人物質・材料研究機構 | Phosphors and light emitting devices using phosphors |
| CN101698800A (en) * | 2009-10-30 | 2010-04-28 | 聊城大学 | Preparation method of alpha-Sialon fluorescent powder |
| CN101851510A (en) * | 2010-05-26 | 2010-10-06 | 厦门大学 | Co-precipitation method for preparing rare earth cerium ion-doped yttrium aluminum garnet fluorescent powder |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2644465C1 (en) * | 2017-03-14 | 2018-02-12 | Общество с ограниченной ответственностью "Монокристалл Пасты" | Method for production of finely-dispersed red luminescent material for generation of resulting white light in light emitting diodes |
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