CN113292992A - Efficient red-light fluorescent powder and application thereof in warm white-light LED - Google Patents
Efficient red-light fluorescent powder and application thereof in warm white-light LED Download PDFInfo
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- CN113292992A CN113292992A CN202110662746.9A CN202110662746A CN113292992A CN 113292992 A CN113292992 A CN 113292992A CN 202110662746 A CN202110662746 A CN 202110662746A CN 113292992 A CN113292992 A CN 113292992A
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- 239000000843 powder Substances 0.000 title claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000009877 rendering Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- PYAWNXHHLJLISF-UHFFFAOYSA-N 6-pyran-2-ylidenepyran-3-carboxamide Chemical compound O1C(C=CC(=C1)C(=O)N)=C1OC=CC=C1 PYAWNXHHLJLISF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/676—Aluminates; Silicates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Manufacturing & Machinery (AREA)
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- Inorganic Chemistry (AREA)
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- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the technical field of luminous lighting, and particularly relates to efficient red-light fluorescent powder and application thereof in a warm white-light LED. The invention provides efficient red light fluorescent powder for a warm white light LED, and the chemical expression of the efficient red light fluorescent powder is CaAl12‑x‑yO19X is more than or equal to 0 and less than or equal to 0.01, and y is more than or equal to 0 and less than or equal to 0.02. The substrate selected by the invention is an oxide substrate CaAl12O19，CaO12Polyhedron, AlO4Tetrahedron, AlO5Bipyramid, AlO6The special structure of octahedron alternate laminated arrangement enables Mn4+With Ti4+Can be doped, and the structure is favorable for improving Mn4+With Ti4+The light conversion efficiency of the fluorescent powder is improved, and the application performance of the fluorescent powder is improved. The red fluorescent powder is applied to a warm white LED, and warm white emission of 4037K and 86.3 of color rendering index is realized.
Description
Technical Field
The invention relates to the technical field of luminous lighting, in particular to high-efficiency red-light fluorescent powder and application thereof in a warm white-light LED.
Background
LED lamps, i.e., light emitting diodes, are important devices for converting electrical energy into light energy. The LED lamp is composed of a P-type semiconductor and an N-type semiconductor, and generates photons through electron and hole recombination. The white light LED lamp is obtained by only mixing the LED chips, the cost is high, the adjustment of light color and light intensity of each wavelength is not facilitated, and the application potential is limited. Through blue light LED chip and yellow light phosphor YAG to Ce3+The white light LED lamp is obtained by mixing, and the production cost is effectively reduced. However, the white light emitted by the white light LED lamp is cold white light, and the color temperature is higher, so that the color rendering index is lower. Incorporation of red fluorescence of longer emission wavelengthThe method is simple to operate, the preparation cost of the fluorescent powder is low, and the process is mature, so that the method becomes an effective way for improving the white light LED. However, the existing efficient red phosphor has the problems of high cost, poor stability and the like, and therefore, development of the red phosphor with low cost and high light conversion quantum efficiency is urgently needed to promote development of the warm white LED lamp.
Disclosure of Invention
In order to solve the problems, the invention provides the efficient red fluorescent powder for the warm white LED, and the efficient red fluorescent powder is applied to the warm white LED, so that warm white emission with low color temperature and high color rendering index is realized.
The technical scheme adopted by the invention is as follows:
a high-efficiency red-light fluorescent powder for warm white-light LED has chemical expression of CaAl12-x-yO19:xMn,yTi，0≤x≤0.01，0≤y≤0.02。
The preparation method of the efficient red light fluorescent powder for the warm white light LED comprises the following steps: CaAl according to chemical expression12-x-yO19Accurately weighing CaCO as raw material in stoichiometric ratio of xMn, yTi3、Al2O3、MnCO3、TiO2Adding a fluxing agent, grinding for 30min in an agate mortar, fully mixing uniformly, and then roasting at high temperature in a muffle furnace; wherein x is more than or equal to 0 and less than or equal to 0.01, and y is more than or equal to 0 and less than or equal to 0.02.
Preferably, the fluxing agent is LiF and H3BO3The addition amount is 5 percent of the mass fraction of the system.
Further, the roasting temperature is 1000-1500 ℃, and the roasting time is 3-6 h.
Preferably, the roasting temperature is 1500 ℃, and the roasting time is 5 h.
Preferably, the atmosphere of the calcination is an air atmosphere.
A warm white LED lamp comprises 365nm ultraviolet LED chip and BaMgAl10O17:Eu2+Blue light phosphor, (Ba, Sr)2SiO4:Eu2+Green light fluorescent powder and warm white light L using sameThe efficient red fluorescent powder of ED.
Compared with the prior art, the invention has the following beneficial effects:
the substrate selected by the invention is an oxide substrate CaAl12O19，CaO12Polyhedron, AlO4Tetrahedron, AlO5Bipyramid, AlO6The special structure of octahedron alternate laminated arrangement enables Mn4+With Ti4+Can be doped, and the structure is favorable for improving Mn4+With Ti4+The light conversion efficiency of the fluorescent powder is improved, and the application performance of the fluorescent powder is improved. The invention is doped with Mn4+Ti is doped as red light emitting ions4+Mn is converted by photon energy transfer4+The luminous intensity of the red light is improved by nearly 2 times. The red fluorescent powder is applied to a warm white LED, and warm white emission of 4037K and 86.3 of color rendering index is realized.
Drawings
FIG. 1 is an X-ray diffraction chart of the phosphors prepared in examples 1 to 4.
FIG. 2 shows Ti of phosphor prepared in example 14+Emission spectrum and Mn of phosphor prepared in example 24+Excitation spectrum.
FIG. 3 is an emission spectrum of the phosphor prepared in examples 2 to 4 under 365nm light excitation.
FIG. 4 is a graph of the electroluminescence spectrum of a warm white LED lamp prepared in example 5.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A blue-light fluorescent powder with chemical composition formula of CaAl11.99O190.01 Ti. 0.2002g of CaCO were accurately weighed3、1.2225g Al2O3、0.0016g TiO2H is added in an amount of 5 percent of the mass fraction of the system3BO3And LiF as a fluxing agent,grinding in agate mortar for 30min, mixing, placing in muffle furnace, calcining at 1500 deg.C in air atmosphere for 5h, cooling to room temperature, taking out, and grinding to obtain fluorescent powder CaAl11.998O19:0.002Mn。
Example 2
A red-light fluorescent powder with chemical composition formula of CaAl11.998O190.002 Mn. 0.2001g of CaCO were accurately weighed3、1.2233g Al2O3、0.00046g MnCO3H is added in an amount of 5 percent of the mass fraction of the system3BO3Grinding the powder and LiF serving as a fluxing agent in an agate mortar for 30min, fully and uniformly mixing, placing the mixture in a muffle furnace, roasting the mixture for 5h at 1500 ℃ in an air atmosphere, cooling the mixture to room temperature, taking out the cooled mixture and grinding the mixture to obtain the fluorescent powder CaAl11.99O19:0.01Ti。
Example 3
A red-light fluorescent powder with chemical composition formula of CaAl11.988O190.002Mn and 0.01 Ti. 0.2001g of CaCO were accurately weighed3、1.2223g Al2O3、0.00045g MnCO3、0.0017g TiO2H is added in an amount of 5 percent of the mass fraction of the system3BO3Grinding the powder and LiF serving as a fluxing agent in an agate mortar for 30min, fully and uniformly mixing, placing the mixture in a muffle furnace, roasting the mixture for 5h at 1500 ℃ in an air atmosphere, cooling the mixture to room temperature, taking out the cooled mixture and grinding the mixture to obtain the fluorescent powder CaAl11.988O19:0.002Mn,0.01Ti。
Example 4
A red-light fluorescent powder with chemical composition formula of CaAl11.978O190.002Mn and 0.02 Ti. 0.2003g of CaCO were accurately weighed3、1.2213g Al2O3、0.00047g MnCO3、0.0032g TiO2H is added in an amount of 5 percent of the mass fraction of the system3BO3Grinding the powder and LiF serving as a fluxing agent in an agate mortar for 30min, fully and uniformly mixing, placing the mixture in a muffle furnace, roasting the mixture for 5h at 1500 ℃ in an air atmosphere, cooling the mixture to room temperature, taking out the cooled mixture and grinding the mixture to obtain the fluorescent powder CaAl11.978O19:0.002Mn,0.02Ti。
FIG. 1 is an X-ray of the phosphors obtained in examples 1 to 4Diffraction pattern, from which it can be seen that Ti is being doped4+With Mn4+One or two ions of CaAl12O19The lattice structure of (A) is still consistent, no significant phase change occurs, or no hetero-phase occurs, which indicates that Ti4+With Mn4+Has been successfully doped with CaAl12O19In the crystal lattice. FIG. 2 shows Ti of phosphor prepared in example 14+Emission spectrum and Mn of phosphor prepared in example 24+Excitation spectrum diagram showing Ti4+Emission light region of (2) and Mn4+Are mostly coincident with the excitation light region of (A), Ti4+With Mn4+There is efficient photon energy transfer therebetween. FIG. 3 is an emission spectrum of the phosphor prepared in examples 2 to 4 under 365nm light excitation, doped with Ti4+After, Mn4+The red emission of Ti is significantly enhanced, but when Ti is used4+When the amount is too large, Mn is caused4+The light intensity is reduced because Ti4+Too high a concentration results in an increased non-radiative energy loss of the system.
Example 5
A warm white LED lamp comprises 365nm ultraviolet LED chip and BaMgAl10O17:Eu2+Blue light phosphor, (Ba, Sr)2SiO4:Eu2+Green phosphor and the red phosphor prepared in example 3. Mixing the three kinds of fluorescent powder in proportion, adding organic silica gel for packaging, fully mixing, putting into an ultrasonic machine for ultrasonic treatment for 10min, and finally putting into an oven for drying for 6h at 50 ℃.
FIG. 4 is an electroluminescence spectrum of a warm white LED lamp prepared in example 5 by adjusting a blue phosphor BaMgAl10O17:Eu2+Green phosphor (Ba, Sr)2SiO4:Eu2+And red phosphor CaAl11.988O190.002Mn and 0.01Ti, the warm white LED lamp can emit high-quality warm white light with 4037K color temperature and 86.3 color rendering index.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The utility model provides a can be used to warm white light LED's high-efficient red light phosphor powder which characterized in that: the chemical expression of the fluorescent powder is CaAl12-x-yO19:xMn,yTi，0≤x≤0.01，0≤y≤0.02。
2. The method for preparing the efficient red phosphor for warm white LED according to claim 1, wherein the method comprises the following steps: the method comprises the following steps: CaAl according to chemical expression12-x-yO19Accurately weighing CaCO as raw material in stoichiometric ratio of xMn, yTi3、Al2O3、MnCO3、TiO2Adding a fluxing agent, grinding for 30min in an agate mortar, fully mixing uniformly, and then roasting at high temperature in a muffle furnace; wherein x is more than or equal to 0 and less than or equal to 0.01, and y is more than or equal to 0 and less than or equal to 0.02.
3. The method of claim 2, wherein: the fluxing agent is LiF and H3BO3The addition amount is 5 percent of the mass fraction of the system.
4. The method of claim 2, wherein: the roasting temperature is 1000-1500 ℃, and the roasting time is 3-6 h.
5. The method of claim 2, wherein: the roasting atmosphere is air atmosphere.
6. A warm white light LED lamp characterized in that: the warm white LED lamp consists of a 365nm ultraviolet LED chip and BaMgAl10O17:Eu2+Blue light phosphor, (Ba, Sr)2SiO4:Eu2+A green phosphor and the high efficiency red phosphor of claim 1 useful in warm white LEDs.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110662746.9A CN113292992A (en) | 2021-06-15 | 2021-06-15 | Efficient red-light fluorescent powder and application thereof in warm white-light LED |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110662746.9A CN113292992A (en) | 2021-06-15 | 2021-06-15 | Efficient red-light fluorescent powder and application thereof in warm white-light LED |
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| CN113292992A true CN113292992A (en) | 2021-08-24 |
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Application publication date: 20210824 |
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