CN102807865A - Yellow light emitting nitrogen oxide phosphor and method for preparing same - Google Patents
Yellow light emitting nitrogen oxide phosphor and method for preparing same Download PDFInfo
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- CN102807865A CN102807865A CN2012102553842A CN201210255384A CN102807865A CN 102807865 A CN102807865 A CN 102807865A CN 2012102553842 A CN2012102553842 A CN 2012102553842A CN 201210255384 A CN201210255384 A CN 201210255384A CN 102807865 A CN102807865 A CN 102807865A
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- nitric oxide
- yellow emission
- sintering
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Abstract
The invention relates to yellow light emitting nitrogen oxide phosphor and a method for preparing the same. The yellow light emitting nitrogen oxide phosphor is characterized in that the chemical general formula of the phosphor material is Ca1-x-2yAyBySi2O2N2:xEu, wherein A represents Gd or Dy, B represents Li, Na or K, and x is more than or equal to 0.02 and less than or equal to 0.06; and y is more than 0 and less than or equal to 0.1. The phosphor and the preparation method have the advantages that 1, the preparation method is high in operability, raw materials are low in price, the process window is quite wide, and the preparation method is applied to mass industrialized production; and 2, the invention also provides the novel yellow light emitting nitrogen oxide phosphor which is prepared from common low-price compounds, has stable physical and chemical properties and high lighting performance and is motivated by an ultraviolet or near ultraviolet chip.
Description
Technical field
The present invention relates to a kind of yellow emission nitric oxide fluorescent powder and preparation method thereof.
Background technology
White light LEDs has advantages such as environmental protection, volume is little, the life-span is long, speed of response is fast, and aspects such as liquid-crystal display and general lighting demonstrate great application prospect.Light conversion hysteria white light LEDs is the easiest realization industrialization at present, and wherein the most general method is: excite the YAG:Ce3+ yellow fluorescent powder through blue chip, utilize gold-tinted and blue light to obtain white light.It is not good that yet the shortcoming of this kind LED is exactly a color developing.So present research focus has concentrated in the research of burst of ultraviolel three primary colors fluorescent powder, but because three-primary color LED is only used three kinds of powders of RGB, color lacks yellow colour developing still can not reach higher level.
Summary of the invention
One of order of the present invention provide stable, the good yellow emission nitric oxide fluorescent powder of luminescent properties of a kind of physicochemical property;
Two of the object of the invention provides a kind of preparation method who is suitable for the above-mentioned fluorescent material of large-scale industrial production.
A kind of yellow emission nitric oxide fluorescent powder, its special feature is: the chemical general formula of said phosphor material powder is Ca
1-x-2yA
yB
ySi
2O
2N
2: xEu, wherein A represents Gd or Dy, and B represents Li, Na or K, and 0.06>=x>=0.02,0.1>=y>0.
Further, comprise the steps:
(1) according to the chemical general formula Ca of claim 1
1-x-2yA
yB
ySi
2O
2N
2: the mol ratio of each composition takes by weighing oxide compound or the carbonate that contains Ca, the oxide compound of A, B carbonate, SiO respectively among the xEu
2, Si
3N
4, Eu
2O
3, and its ground and mixed obtained mixture;
(2) in the mixture that obtains, add the fusing assistant that accounts for amount of the mixture 2-5wt%, mix then, under the protective atmosphere condition, carry out sintering;
(3) under protective atmosphere, naturally cool to room temperature, the sintered product that obtains is taken out grind then, remove impurity through washing again, promptly get the yellow emission nitric oxide fluorescent powder.
Fusing assistant in the step (2) is H
3BO
3, NaF, SrF
2, BaF
2And CaF
2In one or several mixture.
Sintering in the step (2) is to be that N:H=3:1 is to the N between the 95:5 in volume ratio
2/ H
2Perhaps NH
3Under the protective atmosphere, sintering temperature is at 1450 ℃-1600 ℃, the sintering process of sintering time>=5 hour.
Grind in the step (3) and adopt ball milling, particle size range is that D50 is between 10 microns-20 microns behind the ball milling.
Washing process uses Hydrogen chloride in the step (3), and concentration is between the 5%-10%, and washing time is between the 1h-3h.
Advantage of the present invention and effect are following:
1, preparation method of the present invention is workable, and cost of material is cheap, and process window is wide, is suitable for large-scale industrial production.
2, the present invention provides also that a kind of to adopt common cheap compound be the synthetic physical chemistry stable in properties of starting material, the luminescent properties novel yellow light that good ultraviolet-the near ultraviolet chip excites emission nitric oxide fluorescent powder.
Description of drawings
Fig. 1 is the fixing doping of Eu, changes a series of fluorescent material emmission spectrum figure that the doping of Dy and Li is done, comprising the fluorescent material for preparing among the embodiment 1;
Fig. 2 is the fixing doping of Eu, changes a series of fluorescent material emmission spectrum figure that the doping of Gd and Li is done, comprising the fluorescent material for preparing among the embodiment 2.
Embodiment
Embodiment 1:
According to Ca
0.96Dy
0.01Li
0.01Si
2O
2N
2: the 0.02Eu stoichiometric ratio takes by weighing CaCO
3, Dy
2O
3, Li
2CO
3, SiO
2, Si
3N
4, Eu
2O
3And the fusing assistant H of raw material total mass 3wt%
3BO
3, taking by weighing raw material more than inciting somebody to action and all put among the mortar, grinding mixes it, then is put in the alumina crucible, crucible is placed tube furnace, at shielding gas N
2: H
2Among=the 9:1 (volume ratio) with 1600 ℃ of temperature sintering 12 hours; Be cooled to room temperature afterwards and take out that to obtain particle diameter D50 after ball milling sieves be 15 microns powder; Through 5% (massfraction) Hydrogen chloride washing 3h, and under 80 degrees centigrade, baking 4h promptly obtains yellow fluorescent powder Ca in the air to drying
0.96Dy
0.01Li
0.01Si
2O
2N
2: 0.02Eu.
Fig. 1 is 0.02 for the fixing doping mol ratio of Eu, a series of fluorescent material emmission spectrum figure that the doping of change Dy and Li is done, wherein powder emmission spectrum correspondence one group of luminous the best wherein among the embodiment 1.
Embodiment 2:
According to Ca
0.86Gd
0.06Li
0.06Si
2O
2N
2: the 0.02Eu stoichiometric ratio takes by weighing CaCO
3, Gd
2O
3, Li
2CO
3, SiO
2, Si
3N
4, Eu
2O
3And the fusing assistant NaF of raw material total mass ratio 1wt%, taking by weighing raw material more than inciting somebody to action and all put among the mortar, grinding mixes it, then is put in the alumina crucible, crucible is placed tube furnace, at shielding gas N
2: H
2Among=the 3:1 (volume ratio) with 1580 ℃ of temperature sintering 8 hours; Being cooled to afterwards and obtaining particle diameter D50 after room temperature taking-up ball milling sieves is the powder about 15 microns; Through 10% Hydrogen chloride washing 1h, and under 80 degrees centigrade, baking 4h promptly obtains yellow fluorescent powder Ca in the air to drying
0.86Gd
0.06Li
0.06Si
2O
2N
2: 0.02Eu.
Fig. 2 is 0.02 for the fixing doping mol ratio of Eu, a series of fluorescent material emmission spectrum figure that the doping of change Gd and Li is done, wherein powder emmission spectrum correspondence one group of luminous the best wherein among the embodiment 2.
Embodiment 3:
According to Ca
0.86Dy
0.04Na
0.04Si
2O
2N
2: the 0.06Eu stoichiometric ratio takes by weighing CaO, Dy
2O
3, Na
2CO
3, SiO
2, Si
3N
4, Eu
2O
3And the fusing assistant BaF of raw material total mass ratio 5wt%
2, taking by weighing raw material more than inciting somebody to action and all put among the mortar, ground and mixed is even, then is put in the alumina crucible, and crucible is placed tube furnace, at shielding gas NH
3In with 1450 ℃ of temperature sintering 6 hours, be cooled to room temperature afterwards and take out that to obtain particle diameter D50 after ball milling sieves be the powder about 15 microns, through 6% Hydrogen chloride washing 2h, and under 80 degrees centigrade, baking 4h promptly obtains yellow fluorescent powder Ca in the air to drying
0.86Dy
0.04Na
0.04Si
2O
2N
2: 0.06Eu.
Embodiment 4:
According to Ca
0.76Gd
0.1Na
0.1Si
2O
2N
2: the 0.04Eu stoichiometric ratio takes by weighing CaO, Gd
2O
3, Na
2CO
3, SiO
2, Si
3N
4, Eu
2O
3And the fusing assistant CaF of raw material total mass ratio 3wt%
2, taking by weighing raw material more than inciting somebody to action and all put among the mortar, ground and mixed is even, then is put in the alumina crucible, and crucible is placed tube furnace, at shielding gas N
2: H
2With 1500 ℃ of temperature sintering 10 hours, be cooled to room temperature afterwards and take out that to obtain particle diameter D50 after ball milling sieves be the powder about 15 microns among the=95:5, through 7% Hydrogen chloride washing 3h, and under 80 degrees centigrade, baking 4h promptly obtains yellow fluorescent powder Ca in the air to drying
0.76Gd
0.1Na
0.1Si
2O
2N
2: 0.04Eu.
Embodiment 5:
According to Ca
0.95Gd
0.01K
0.01Si
2O
2N
2: the 0.03Eu stoichiometric ratio takes by weighing CaCO
3, Gd
2O
3, K
2CO
3, SiO
2, Si
3N
4, Eu
2O
3And the H of fusing assistant raw material total mass ratio 2wt%
3BO
3And 2wt%SrF
2, taking by weighing raw material more than inciting somebody to action and all put among the mortar, ground and mixed is even, then is put in the alumina crucible, and crucible is placed tube furnace, at shielding gas N
2: H
2Among=the 19:1 (volume ratio) with 1500 ℃ of temperature sintering 10 hours; Being cooled to afterwards and obtaining particle diameter D50 after room temperature taking-up ball milling sieves is the powder about 15 microns; Through 9% Hydrogen chloride washing 1h, and under 80 degrees centigrade, baking 4h promptly obtains yellow fluorescent powder Ca in the air to drying
0.95Gd
0.01K
0.01Si
2O
2N
2: 0.03Eu.
Claims (6)
1. yellow emission nitric oxide fluorescent powder, it is characterized in that: the chemical general formula of said phosphor material powder is Ca
1-x-2yA
yB
ySi
2O
2N
2: xEu, wherein A represents Gd or Dy, and B represents Li, Na or K, and 0.06>=x>=0.02,0.1>=y>0.
2. the preparation method of a yellow emission nitric oxide fluorescent powder is characterized in that, comprises the steps:
(1) according to the chemical general formula Ca of claim 1
1-x-2yA
yB
ySi
2O
2N
2: the mol ratio of each composition takes by weighing oxide compound or the carbonate that contains Ca, the oxide compound of A, B carbonate, SiO respectively among the xEu
2, Si
3N
4, Eu
2O
3, and its ground and mixed obtained mixture;
(2) in the mixture that obtains, add the fusing assistant that accounts for amount of the mixture 2-5wt%, mix then, under the protective atmosphere condition, carry out sintering;
(3) under protective atmosphere, naturally cool to room temperature, the sintered product that obtains is taken out grind then, remove impurity through washing again, promptly get the yellow emission nitric oxide fluorescent powder.
3. the preparation method of a kind of yellow emission nitric oxide fluorescent powder as claimed in claim 2 is characterized in that: the fusing assistant in the step (2) is H
3BO
3, NaF, SrF
2, BaF
2And CaF
2In one or several mixture.
4. the preparation method of a kind of yellow emission nitric oxide fluorescent powder as claimed in claim 2 is characterized in that: the sintering in the step (2) is to be that N:H=3:1 is to the N between the 95:5 in volume ratio
2/ H
2Perhaps NH
3Under the protective atmosphere, sintering temperature is at 1450 ℃-1600 ℃, the sintering process of sintering time>=5 hour.
5. the preparation method of a kind of yellow emission nitric oxide fluorescent powder as claimed in claim 2 is characterized in that: grind in the step (3) and adopt ball milling, particle size range is that D50 is between 10 microns-20 microns behind the ball milling.
6. the preparation method of a kind of yellow emission nitric oxide fluorescent powder as claimed in claim 2 is characterized in that: washing process uses Hydrogen chloride in the step (3), and concentration is between the 5%-10%, and washing time is between the 1h-3h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102553842A CN102807865A (en) | 2012-07-23 | 2012-07-23 | Yellow light emitting nitrogen oxide phosphor and method for preparing same |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108485655A (en) * | 2018-04-04 | 2018-09-04 | 陕西师范大学 | Ca4Si4N2O9Crystal and fluorescent powder and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948690A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Preparation method of nitrogen oxide yellow fluorescent powder material |
| CN102618261A (en) * | 2012-03-09 | 2012-08-01 | 东华大学 | A CaSi2O2N2: eu2+, dy3+, li+phosphor and its preparation method |
-
2012
- 2012-07-23 CN CN2012102553842A patent/CN102807865A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948690A (en) * | 2010-09-29 | 2011-01-19 | 彩虹集团公司 | Preparation method of nitrogen oxide yellow fluorescent powder material |
| CN102618261A (en) * | 2012-03-09 | 2012-08-01 | 东华大学 | A CaSi2O2N2: eu2+, dy3+, li+phosphor and its preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108485655A (en) * | 2018-04-04 | 2018-09-04 | 陕西师范大学 | Ca4Si4N2O9Crystal and fluorescent powder and preparation method |
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Effective date of abandoning: 20121205 |
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