CN106520119B - A kind of fluorescent powder and preparation method thereof of capable of emitting cyan light - Google Patents
A kind of fluorescent powder and preparation method thereof of capable of emitting cyan light Download PDFInfo
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- CN106520119B CN106520119B CN201610933462.8A CN201610933462A CN106520119B CN 106520119 B CN106520119 B CN 106520119B CN 201610933462 A CN201610933462 A CN 201610933462A CN 106520119 B CN106520119 B CN 106520119B
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- fluorescent powder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7768—Chalcogenides with alkaline earth metals
Abstract
The present invention relates to a kind of fluorescent powder extremely preparation method of the capable of emitting cyan light of LED, prepared fluorescent powder is garnet-base, general formula Ca2A1‑xB2C3O12:xCe, wherein A is one or more of Lu, Y, La or Gd；B is one or both of Hf or Zr；C is one or both of Al or Ga, and 0.01≤x≤0.06.Fluorescent powder crystallinity prepared by the present invention is preferable, and luminous efficiency is high, and brightness is stronger, and chemical property is stablized, and brightness change is small at high temperature, and the service life is long.Preparation method is simple for this, process window mouth width, is suitble to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of phosphor technologies field LED, especially a kind of fluorescent powder of capable of emitting cyan light is extremely
Preparation method.
Background technique
White light LEDs are a kind of new type of solid state light sourcies, now have been used for the principal light source of outdoor lighting.White light LEDs at present
The main commercialization practice is that one layer of YAG fluorescent powder is coated on InGaN blue chip, excites this fluorescent powder using blue chip
The yellow light complementary with blue light is generated, mixing obtains white light.But the luminescent color of device is with driving voltage and fluorescent coating thickness
Variation and change, color reducibility is poor, and colour rendering index is low.Therefore with black light (380~410nm) chip LED technology
Maturation, will be more noticeable with the design of white light LEDs of black light chip excitation redgreenblue fluorescent powder.Due to view
Feel insensitive to ultraviolet light, the white light LEDs of black light chip are than the white light LEDs colour stable that blue chip excites, and color is also
Originality and colour rendering index are high, meanwhile, as the important component of full color spectrum, green light can effectively improve white light LEDs
Colour rendering index, to obtain more good white light.Therefore the green light fluorescent powder of research and development near ultraviolet excitation has important meaning
Justice.Currently, the main application of the fluorescent powder of capable of emitting cyan light (wave-length coverage is 480~490nm) concentrates on the field FED, it is public
The application for a patent for invention that the number of opening is CN101914377A discloses the pastiness color of serial field emission display, green, yellow and white
The luminescent material of coloured light, chemical composition expression are as follows: Li2M1-xEuxSO4And Li2-yM1-xEuxCeySO4.Wherein, M is alkaline earth gold
Belong to ion, is selected from Ca2+、Ba2+、Sr2+；Eu2+(bivalent rare earth europium ion) and Ce3+(trivalent rare earth cerium ion) is active ions；
X, y are active ions Eu2+And Ce3+The molar percentage coefficient that opposite alkaline-earth metal ions M is accounted for, value range: 0.001≤x≤
0.01,0.001≤y≤0.01.Novel rare-earth luminescent material prepared by the invention can be distinguished under denoted low voltage electron beam excitation
Issue stronger cyan, green and sodium yellow and Eu2+And Ce3+The white light for emitting composition, it is glimmering to be introduced into FED three primary colours
Light powder can be significantly expanded the indication range of fluorescent powder.The application for a patent for invention of Publication No. CN102899039A has disclosed one kind
Cyan luminescent material and preparation method thereof, chemical composition expression are as follows: (4-x) SrO4SiO2·4SrCl2XEuO,
In, Eu2+(divalent europium) is active ions；X is the mole that Eu replaces Sr, value range: 0.01≤x≤0.50.This is specially
The preparation method of benefit is simple, is suitable for 3D flat-panel monitor.Green light fluorescent powder is gone back at only in the application of LED field in the prior art
In the starting stage, the green light fluorescent powder of near ultraviolet excitated efficient stable is still very rare, and relevant technology contents rarely have disclosure.
In addition, how to obtain the scheme that there is the green light fluorescent powder of good brightness and colour stability there is no solution at high temperature, belong to
In the project to be solved of this field one.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is good bright to propose that one kind can obtain having at high temperature
The preparation method of the green light fluorescent powder and this fluorescent powder of degree and colour stability.
The fluorescent powder of the capable of emitting cyan light of a kind of LED of the invention, it is characterised in that the general formula of the fluorescent powder is
Ca2A1-xB2C3O12:xCe；Wherein A is one or more of Lu, Y, La or Gd；B is one or both of Hf or Zr；C is
One or both of Al or Ga；Activator is Ce ion；Wherein, 0.01≤x≤0.06.Garnet structure stability is good, is
A kind of excellent luminous host, thus obtained this light-emitting phosphor intensity is high, and strength retrogression is slow at high temperature, has
Good brightness and colour stability, function admirable.
Further, LED of the invention is with the chemical composition of the fluorescent powder of capable of emitting cyan light
Ca2Lu0.97Ce0.03Hf2Al3O12。
Further, LED of the invention is with the chemical composition of the fluorescent powder of capable of emitting cyan light
Ca2Lu0.5Y0.49Ce0.01HfZrAl3O12。
Further, LED of the invention is with the chemical composition of the fluorescent powder of capable of emitting cyan light
Ca2Lu0.5Y0.44Ce0.06Hf2Ga3O12。
Further, LED of the invention is with the chemical composition of the fluorescent powder of capable of emitting cyan light
Ca2La0.97Ce0.03HfZrAl3O12。
Further, LED of the invention is with the chemical composition of the fluorescent powder of capable of emitting cyan light
Ca2Gd0.97Ce0.03Hf2Al3O12。
Further, the LED of the invention preparation method of the fluorescent powder of capable of emitting cyan light, includes the following steps:
1) according to chemical general formula Ca2A1-xB2C3O12:xCe weighs raw material, and wherein Ca is introduced by its carbonate or oxide,
A, B and C is introduced by its oxide, and Ce is also introduced in the form of its oxide；
2) weighed raw material is sufficiently mixed grinding and obtains mixed raw material powder；
3) raw material powder obtained is fitted into corundum crucible, is placed in reducing atmosphere, keep the temperature 4 at 1400~1500 DEG C
~8h, cools to room temperature with the furnace；
4) the product taking-up of sintering is ground up, sieved, obtains the fluorescent powder of the capable of emitting cyan light for LED of the invention
Ca2A1-xB2C3O12:xCe。
Further, the preparation method of the LED of the invention fluorescent powder of capable of emitting cyan light, the reduction in reducing atmosphere
Property gas be H2, volume content is 5%~10%.
Compared with prior art, the invention has the following beneficial technical effects:
LED provided by the invention is a kind of fluorescent powder of garnet-base with the fluorescent powder of capable of emitting cyan light, and use is common
Metal carbonate or oxide be raw material preparation, prepared garnet-base hanced cyan fluorescent powder crystallinity is preferable, shine
High-efficient, brightness is stronger, and chemical property is stablized, and brightness change is small under high temperature, and the service life is long.This method is simple and easy, process window
Width is suitble to large-scale industrial production.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrogram of embodiment 1.
Fig. 2 is the excitation and launching light spectrogram of embodiment 1.
Fig. 3 is the emission spectrum variation with temperature figure of embodiment 1, and wherein excitation wavelength is 410nm.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail.
In embodiment 1 according to Ca2Lu0.97Ce0.03Hf2Al3O12Stoichiometric ratio weighs CaCO3、Lu2O3、HfO2、Al2O3
And CeO2, mixed, be fully ground after be put in alumina crucible；Crucible is placed in tube furnace, in protective gas N2/H2=
It in 9:1 (volume ratio), is sintered 2 hours with 900 DEG C of temperature, then proceedes to be cooled to after being warming up to 1500 DEG C of temperature sintering 5 hours
Room temperature；Fluorescent powder Ca is obtained after taking out smashing and grinding sieving2Lu0.97Ce0.03Hf2Al3O12。
Fig. 1 is Ca2Lu0.97Ce0.03Hf2Al3O12X-ray diffraction spectrogram, as seen from the figure the sample have it is good
Crystal structure.Fig. 2 is Ca2Lu0.97Ce0.03Hf2Al3O12Excitation and launching light spectrogram, the excitation wavelength of the fluorescent powder between
300~450nm, preferable excitation wavelength are located at 340 ± 10nm and 410 ± 10nm；Transmitting light dominant wavelength is located at 484nm.Fig. 3 is
Ca2Lu0.97Ce0.03Hf2Al3O12Emission spectrum variation with temperature figure, wherein excitation wavelength be 410nm, it can be found that this is glimmering
There is good brightness and colour stability under light powder high temperature.It is a kind of excellent shine because garnet structure stability is good
Matrix, therefore 87% when luminous intensity of the garnet-base fluorescent powder at 150 DEG C prepared is room temperature, and be it is commercial (Sr,
Ba)2SiO4:Eu2+1.1 times of light-emitting phosphor intensity.
In example 2 according to Ca2Lu0.5Y0.49Ce0.01HfZrAl3O12Stoichiometric ratio weighs CaCO3、Lu2O3、Y2O3、
HfO2、ZrO2、Al2O3And CeO2, mixed, be fully ground after be put in alumina crucible；Crucible is placed in tube furnace, is being protected
Protect gas N2/H2It in=46:4 (volume ratio), is sintered 2 hours with 900 DEG C of temperature, then proceedes to be warming up to 1450 DEG C of temperature sintering 6
It is cooled to room temperature after hour；Hanced cyan fluorescent powder Ca is obtained after taking out smashing and grinding sieving2Lu0.5Y0.49Ce0.01HfZrAl3O12。
According to Ca in embodiment 32Lu0.5Y0.44Ce0.06Hf2Ga3O12Stoichiometric ratio weighs CaCO3、Lu2O3、Y2O3、
HfO2、Ga2O3And CeO2, mixed, be fully ground after be put in alumina crucible；Crucible is placed in tube furnace, in protection gas
Body N2/H2It in=46:4 (volume ratio), is sintered 2 hours with 900 DEG C of temperature, then proceedes to be warming up to 1425 DEG C of temperature sintering 6 hours
After be cooled to room temperature；Fluorescent powder Ca is obtained after taking out smashing and grinding sieving2Lu0.5Y0.44Ce0.06Hf2Ga3O12。
According to Ca in embodiment 42La0.97Ce0.03HfZrAl3O12Stoichiometric ratio weighs CaCO3、La2O3、HfO2、ZrO2、
Al2O3And CeO2, mixed, be fully ground after be put in alumina crucible；Crucible is placed in tube furnace, in protective gas N2/
H2It in=46:4 (volume ratio), is sintered 2 hours with 900 DEG C of temperature, then proceedes to be warming up to cold after 1450 DEG C of temperature are sintered 6 hours
But to room temperature；Fluorescent powder Ca is obtained after taking out smashing and grinding sieving2La2HfZrAl3O12。
Embodiment 5, according to Ca2Gd0.97Ce0.03Hf2Al3O12Stoichiometric ratio weighs CaCO3、Gd2O3、HfO2、Al2O3And
CeO2, mixed, be fully ground after be put in alumina crucible；Crucible is placed in tube furnace, in protective gas N2/H2=46:
It in 4 (volume ratios), is sintered 2 hours with 900 DEG C of temperature, then proceedes to be cooled to room after being warming up to 1450 DEG C of temperature sintering 6 hours
Temperature；Fluorescent powder Ca is obtained after taking out smashing and grinding sieving2Gd0.97Ce0.03Hf2Al3O12。
Claims (2)
1. a kind of LED fluorescent powder of capable of emitting cyan light, it is characterised in that the chemical composition of the fluorescent powder is
Ca2Lu0.97Ce0.03Hf2Al3O12, luminous intensity of the fluorescent powder at 150 DEG C be its room temperature when 87%.
2. the LED according to claim 1 fluorescent powder of capable of emitting cyan light, preparation method are as follows:
1) raw material is weighed according to chemical general formula, wherein Ca is introduced by its carbonate or oxide, and Lu, Hf and Al are aoxidized by it
Object introduces, and Ce is also introduced in the form of its oxide；
2) weighed raw material is sufficiently mixed grinding and obtains mixed raw material powder；
3) raw material powder obtained is fitted into corundum crucible, is placed in reducing atmosphere, at 1400~1500 DEG C keep the temperature 4~
8h cools to room temperature with the furnace；
4) the product taking-up of sintering is ground up, sieved, obtains garnet-base hanced cyan fluorescent powder.
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| CN201610933462.8A CN106520119B (en) | 2016-10-24 | 2016-10-24 | A kind of fluorescent powder and preparation method thereof of capable of emitting cyan light |
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| CN201610933462.8A CN106520119B (en) | 2016-10-24 | 2016-10-24 | A kind of fluorescent powder and preparation method thereof of capable of emitting cyan light |
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| CN106520119B true CN106520119B (en) | 2018-12-07 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107459990B (en) * | 2017-08-17 | 2020-09-08 | 河北华人信通建设有限公司 | Green fluorescent powder and preparation method thereof |
| CN107722983A (en) * | 2017-09-20 | 2018-02-23 | 木林森股份有限公司 | L ED fluorescent powder and preparation method thereof |
| US11326099B2 (en) * | 2019-10-30 | 2022-05-10 | GE Precision Healthcare LLC | Ceramic scintillator based on cubic garnet compositions for positron emission tomography (PET) |
| CN111908910B (en) * | 2020-08-18 | 2022-04-22 | 新沂市锡沂高新材料产业技术研究院有限公司 | High-color-rendering-index transparent ceramic for warm white lighting and preparation method thereof |
| CN114149259A (en) * | 2021-11-24 | 2022-03-08 | 海南钇坤智能科技有限公司 | Laser ceramic material for inhibiting ion conversion |
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| CN104918892A (en) * | 2012-12-20 | 2015-09-16 | 松下知识产权经营株式会社 | Rare earth aluminum garnet-type inorganic oxide, phosphor and light-emitting device using same |
| EP3053987A1 (en) * | 2013-09-30 | 2016-08-10 | Panasonic Intellectual Property Management Co., Ltd. | Phosphor, light-emitting device using same, illumination light source, and illumination device |
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Patent Citations (2)
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| CN104918892A (en) * | 2012-12-20 | 2015-09-16 | 松下知识产权经营株式会社 | Rare earth aluminum garnet-type inorganic oxide, phosphor and light-emitting device using same |
| EP3053987A1 (en) * | 2013-09-30 | 2016-08-10 | Panasonic Intellectual Property Management Co., Ltd. | Phosphor, light-emitting device using same, illumination light source, and illumination device |
Non-Patent Citations (3)
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| Novel Garnet-Structure Ca2GdZr2(AlO4)3:Ce3+ Phosphor and Its Structural Tuning of Optical Properties;Xinghong Gong等;《Inorg. Chem. 》;20140610;6607?6614 * |
| Synthesis, Crystal Structures, and Photoluminescence Properties of Ce3+-Doped Ca2LaZr2Ga3O12: New Garnet Green-Emitting Phosphors for White LEDs;Jiyou Zhong等;《J. Phys. Chem. C》;20150624;5562?5569 * |
| Synthesis, Structure, and Photoluminescence Properties of Ce3+-Doped Ca2YZr2Al3O12: A Novel Garnet Phosphor for White LEDs;Xicheng Wang等;《J. Phys. Chem. C》;20141110;16208?16214 * |
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