CN115558493B - High-efficiency heat-stable divalent europium ion green-light fluorescent powder and preparation method and application thereof - Google Patents
High-efficiency heat-stable divalent europium ion green-light fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 115
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000005284 excitation Effects 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 12
- -1 europium ion Chemical class 0.000 claims description 51
- 239000011734 sodium Substances 0.000 claims description 46
- 239000011777 magnesium Substances 0.000 claims description 41
- 239000011575 calcium Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 27
- 108010043121 Green Fluorescent Proteins Proteins 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 2
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical class [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 238000009877 rendering Methods 0.000 abstract description 9
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 238000001194 electroluminescence spectrum Methods 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000005090 crystal field Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HOLUEEOMBYQSAH-UHFFFAOYSA-N magnesium sodium borate Chemical compound [Na+].[Mg+2].[O-]B([O-])[O-] HOLUEEOMBYQSAH-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a high-efficiency and heat-stable divalent europium ion green-light fluorescent powder, a preparation method and application thereofHas a chemical general formula of Na a Ca b Al 11‑c Mg c O 17+d :xEu 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.3, a is more than or equal to 0.5 and less than or equal to 3.5, b is more than or equal to 0 and less than or equal to 1.0,0.1, c is more than or equal to 1.5, and d is more than or equal to 0 and less than or equal to 1.15. The invention is characterized in that the content of each element and Eu are reasonably arranged 2+ Doping concentration and the like, so that the excitation wavelength of the green light fluorescent powder covers the range of 250-450nm, the main peak is positioned in the ultraviolet-near ultraviolet region, the green light fluorescent powder emits the green fluorescence with the peak value of 480-510nm, the half-peak width of an emission band is 80-95nm, the green light fluorescent powder has excellent luminescence property, and meanwhile, the green light fluorescent powder has high internal quantum efficiency and external quantum efficiency and excellent thermal stability; the green-light fluorescent powder can be used for preparing white light LED devices with excellent performance, and has high color rendering index and lumen efficiency.
Description
Technical Field
The invention belongs to the technical field of fluorescent powder, and particularly relates to a high-efficiency and thermally stable divalent europium ion green-light fluorescent powder as well as a preparation method and application thereof.
Background
Blue Light Emitting Diode (LED) and yellow phosphor (Y) 3 Al 5 O 12 :Ce 3+ ) The combination realizes white light emission, and the advantages of energy conservation, high efficiency, long service life and environmental friendliness are achieved, so that the era of solid-state illumination is started. The invention benefits from the high-efficiency red light emitting fluorescent powder, and the color rendering index higher than 80 can be obtained based on the fluorescent conversion type white light LED, so that the white light LED becomes a mainstream product in the current illumination field.
Due to the blue light chip and the yellow phosphor (Y) 3 Al 5 O 12 :Ce 3+ ) The combined LED lacks red light component, has the defects of high color temperature and lower color rendering index, and the white light LED combined by using near ultraviolet or purple light LED chips (the emission wavelength is less than 420 nm) and blue, green and red fluorescent powder with high efficiency not only greatly improves the color rendering index, but also enables the luminous color to be more stable and can obviously reduce glare, but also has the limitation that the emission spectrum (480-520 nm) has a so-called cyan gap, so that the CRI value is prevented from being further improved, so that a new broadband cyan luminescent material is necessary to be explored to fill the cyan blank in order to realize the high CRI white light LED. As one of the components of the white light LED, the fluorescent light has high efficiency and heat stabilityThe light powder is one of the guarantees of obtaining high CIR white light LED.
For illumination, not only the phosphor for manufacturing the white LED is required to have high internal quantum efficiency and high thermal stability, but also high external quantum efficiency and high lumen efficiency, and the green phosphor which has been developed at present does not exist as the phosphor having these excellent properties at the same time, ce 3+ Activating sodium magnesium borate, i.e. NaMgBO 3 :Ce 3+ Is one of the better green fluorescent powder which is discovered at present, the main emission peak is positioned at 480nm, and the half-peak width is 102nm. The external quantum efficiency is more than 90% under the excitation of near ultraviolet light, the intensity is 90% of room temperature at 200K, the internal quantum efficiency and the lumen efficiency are not given, but the external quantum efficiency and the lumen efficiency have great influence on the practical application of the green fluorescent powder.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects in the background art, and provides the high-efficiency and thermally stable divalent europium ion green-light fluorescent powder, and the preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a high-efficiency heat-stable divalent europium ion green light fluorescent powder has a chemical general formula of Na a Ca b Al 11-c Mg c O 17+d :xEu 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.3, a is more than or equal to 0.5 and less than or equal to 3.5, b is more than or equal to 0 and less than or equal to 1.0,0.1, c is more than or equal to 1.5, and d is more than or equal to 0 and less than or equal to 1.15. The d value is used to maintain compound electroneutrality.
The green fluorescent powder of the invention is prepared from matrix Na a Ca b Al 11-c Mg c O 17+d And a luminescence center Eu 2+ Two-part structure, emission center Eu 2+ The amount of (2) can be arbitrarily adjusted according to the above x value range, eu of any matrix and any x value 2+ Combining to obtain the final product. Ca. Mg is a matrix structure constituting the phosphor, affects the coordination environment of a luminescence center and the overall covalent and rigid properties of the matrix structure, and is the most importantFinally, the performances of the fluorescent powder such as luminescence color, quantum efficiency, thermal stability and the like are determined. When the content of a, b and c is too high, a large amount of impurity phases can appear in the fluorescent powder, so that the luminous intensity is obviously weakened, or the luminous color/spectrum is obviously changed, and the luminous performance is also reduced.
Preferably, the chemical formula of the divalent europium ion green light fluorescent powder is Na 2.6 Ca 0.5 Al 11-c Mg c O 17+d :xEu 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.3, c is more than or equal to 0.5 and less than or equal to 0.8,0.75, and d is more than or equal to 1.15.
Further preferably, the chemical formula of the divalent europium ion green light fluorescent powder is Na 2.6 Ca 0.5 Al 10.2 Mg 0.8 O 18.1 :0.2Eu 2+ 、Na 2.6 Ca 0.5 Al 10.3 Mg 0.7 O 18.15 :0.2Eu 2+ Or Na (or) 2.6 Al 10.5 Mg 0.5 O 17.75 :0.2Eu 2+ 。
In the green light fluorescent powder, na a Ca b Al 11-c Mg c O 17+d Has a chemical structure with BaMgAl 10 O 17 Similar crystal structure with AlO 4 With AlO 6 The rigid structure of the polyhedron interconnection provides a structural basis for high-heat-stability luminescence. Na (Na) a Ca b Al 11 - c Mg c O 17+d :xEu 2+ Na in a size suitable for a luminescence center Eu 2+ Occupying space and when Eu 2+ Occupying Na + When the lattice site is located, the alien ion substitution is easy to generate a new trap energy level, and the energy level can feed the captured electrons back to the excited state energy level under the action of heat in the light emitting process, so that the light emitting intensity weakening caused by thermal quenching is compensated. Due to excessive Na content, the charge is seriously unbalanced, and Mg is used 2+ Substituted for Al 3+ The unbalanced charge can be properly compensated, so that the luminous performance is greatly improved. Eu (Eu) 2+ Based on 5d-4f transition, while 5d energy level shifts in mass center and crystal field splits due to covalent effect and crystal field effect, resulting in the lowest 5d energy level being changed due to its coordination environment change, blue light fluorescence in the present inventionThe light powder is due to Eu 2+ Occupied polyhedra and AlO 4 AlO (aluminum oxide) 6 Is of a common oxygen atom, and Mg 2+ Radius is larger than Al 3+ Substituted Al/MgO 4 Al/MgO 6 The polyhedral volume expands, so that Eu 2+ The volume of the polyhedron is compressed, thereby increasing the energy of crystal field splitting, and furthermore, due to Mg 2+ Is less electronegative than Al 3+ The reduced covalent nature of Mg-O bonds results in an enhanced covalent nature of Eu-O bonds, which leads to an increased centroid shift, which, from the results of crystal field splitting energy and centroid shift, will lead to emission spectra with Mg 2+ The content increase gradually red shifted to the cyan region of 500 nm.
Preferably, the divalent europium ion green fluorescent powder emits green fluorescent light with the peak value of 480-510nm under the excitation of ultraviolet or purple light with the wavelength of 250-450nm, and the half-peak width of an emission band is 80-95nm.
Preferably, the divalent europium ion blue light fluorescent powder has an internal quantum efficiency of more than 80% and an external quantum efficiency of more than 50% under the excitation of ultraviolet light with a wavelength of 365 nm;
the luminous intensity of the divalent europium ion green fluorescent powder at 150 ℃ is more than 70% of the luminous intensity of the divalent europium ion green fluorescent powder at room temperature, and the integral intensity of the divalent europium ion green fluorescent powder at 150 ℃ is more than 80% of the integral intensity of the divalent europium ion green fluorescent powder at room temperature.
Further preferably, the divalent europium ion green light fluorescent powder has internal quantum efficiency of 91% and external quantum efficiency of 67% under the excitation of near ultraviolet light; when the temperature reaches 150 ℃, the luminous intensity can maintain 85% of the room temperature value, and the integral intensity can maintain 95% of the room temperature value.
Preferably, after the divalent europium ion green fluorescent powder is made into an LED device, the lumen efficiency under 50mA current drive can reach 72.7lm.W -1 。
Preferably, the matrix lattice of the divalent europium ion green light fluorescent powder is hexagonal phase, and the space group of the hexagonal phase is P6 3 /mmc。
As a general inventive concept, the invention provides a preparation method of the high-efficiency and heat-stable divalent europium ion green-light fluorescent powder, which comprises the following steps:
(1) Weighing a sodium-containing compound, a calcium-containing compound, an aluminum-containing compound, a magnesium-containing compound and a europium-containing compound according to stoichiometric ratio, and then weighing a fluxing agent;
(2) Grinding and uniformly mixing the raw materials weighed in the step (1) to obtain a mixture; and heating the mixture to 1200-1500 ℃ in a reducing atmosphere, roasting for 3-6h, naturally cooling to room temperature, and grinding to obtain the divalent europium ion green light fluorescent powder.
Preferably, in the step (1), the sodium-containing compound is any one or a combination of several of sodium carbonate (both of which can be provided with or without crystal water), sodium bicarbonate and sodium oxalate; the calcium-containing compound is any one or the combination of a plurality of calcium carbonates and calcium bicarbonates; the aluminum-containing compound is any one or a combination of a plurality of aluminum hydroxides and aluminum oxides; the magnesium-containing compound is any one or the combination of a plurality of magnesium hydroxide and magnesium oxide; the europium-containing compound is Eu 2 O 3 、EuCl 3 、Eu(NO 3 ) 3 Any one or a combination of a plurality of the above;
the fluxing agent is H 3 BO 3 、NaF、KF、CaF 2 、SrF 2 、BaF 2 、(NH 4 ) 2 CO 3 The mass of the fluxing agent is 3-10% of the total mass of the sodium-containing compound, the calcium-containing compound, the aluminum-containing compound, the magnesium-containing compound and the europium-containing compound. The fluxing agent is a substance which can reduce the reaction temperature, quicken the reaction rate and does not influence the crystal phase of the product, and meanwhile, the fluxing agent can effectively promote the ion diffusion in the reaction and can reduce the reaction temperature and the energy consumption.
Preferably, in the step (2), the temperature is raised to 1200-1500 ℃ at an average temperature rise rate of 3-6 ℃/min; the reducing atmosphere is H 2 And N 2 The mixed gas of H 2 And N 2 The volume ratio of (2) is 5:95-10:90.
As a general inventive concept, the invention provides the divalent europium ion green light fluorescent powder or the application of the divalent europium ion green light fluorescent powder prepared by the preparation method, in particular to the application of the divalent europium ion green light fluorescent powder in the preparation of white light LED devices.
Preferably, in specific application, the green fluorescent powder, blue fluorescent powder and green fluorescent powder (Ba, sr) 2 SiO 4 :Eu 2+ Red phosphor CaAlSiN 3 :Eu 2+ After mixing, packaging the mixture on a near ultraviolet LED chip to manufacture a white light LED device; the blue light fluorescent powder is BaMgAl 10 O 17 :Eu 2+ 、K 1.6 Al 11 O 17.5 :0.20Eu 2+ One or two of the following components;
or the green fluorescent powder and the red fluorescent powder CaAlSiN 3 :Eu 2+ And after mixing, packaging the mixture on a near ultraviolet LED chip to manufacture a white light LED device.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention reasonably sets the content of Mg element, na element, ca element, al element and Eu 2+ Doping concentration and the like, so that the excitation wavelength of the green light fluorescent powder covers the range of 250-450nm, the main peak is positioned in the ultraviolet-near ultraviolet region, the green light fluorescent powder emits the green fluorescence with the peak value of 480-510nm, the half-peak width of the emission band is 80-95nm, the green light fluorescent powder has excellent luminescence property, and meanwhile, the internal quantum efficiency of the green light emission of the green light fluorescent powder can be higher than 91%, and the external quantum efficiency can also be higher than 67%. In addition, the green-light fluorescent powder has excellent thermal stability, the luminous intensity at 150 ℃ can be maintained at 85% of the room temperature value, and the integral intensity can be maintained at 95% of the room temperature value.
2. The synthesis method for preparing the blue light fluorescent powder is simple, the oxide blue light fluorescent powder does not need high-pressure conditions compared with the nitride blue light fluorescent powder, industrial production is easy to realize, and the prepared product has uniform granularity and stable structure.
3. The green-light fluorescent powder can be used for preparing white light LED devices with excellent performance, and has high color rendering index and lumen efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of cyan fluorescent powder and corresponding standard card in example 1 of the present invention;
FIG. 2 is a graph showing excitation (dotted line) and emission (solid line) spectra of cyan fluorescent powder in example 1 of the present invention;
FIG. 3 is a graph showing the temperature change emission spectrum of the green fluorescent powder in example 1 of the present invention, and the graph showing the relationship between normalized emission intensity and temperature is shown in the inset;
FIG. 4 is a graph showing the internal and external quantum efficiency of green phosphor in example 1 of the present invention;
FIG. 5 is an XRD pattern of green phosphor and corresponding standard card of example 2 of the present invention;
FIG. 6 is a graph showing excitation (broken line) and emission (solid line) spectra of cyan fluorescent powder in example 2 of the present invention;
FIG. 7 is an XRD pattern of green phosphor and corresponding standard card of example 3 of the present invention;
FIG. 8 is a graph showing excitation (broken line) and emission (solid line) spectra of cyan fluorescent powder in example 3 of the present invention;
FIG. 9 is an XRD pattern for the phosphor of comparative example 1 and its corresponding standard card;
FIG. 10 is a graph showing the excitation (broken line) and emission (solid line) spectra of the phosphor of comparative example 1 of the present invention;
FIG. 11 is an XRD pattern for the phosphor of comparative example 2 and its corresponding standard card;
FIG. 12 is a graph showing the excitation (broken line) and emission (solid line) spectra of the phosphor of comparative example 2 of the present invention;
FIG. 13 is an electroluminescence spectrum and a lighting photograph of a 365nm chip based white light LED device in example 4;
FIG. 14 is an electroluminescence spectrum and a lighting photograph of a 395nm chip based white LED device in example 4;
FIG. 15 is an electroluminescence spectrum and a lighting photograph of a 365nm chip based white light LED device in example 5;
FIG. 16 is an electroluminescence spectrum and a lighting photograph of a 395nm chip based white LED device in example 5;
FIG. 17 is an electroluminescence spectrum and a lighting photograph of a 365nm chip based white light LED device in example 6;
FIG. 18 is an electroluminescence spectrum and a lighting photograph of a 395nm chip based white LED device in example 6.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
preparation of Na a Ca b Al 11-c Mg c O 17+d :xEu 2+ Wherein x=0.2, a=2.6, b=0.5, c=0.8, d=1.1, the chemical formula is: na (Na) 2.6 Ca 0.5 Al 10.2 Mg 0.8 O 18.1 :0.2Eu 2+ 。
The preparation method comprises the following steps:
(1) 0.2067g of Na is weighed according to the stoichiometric ratio of elements 2 CO 3 0.0.0751g CaCO 3 1.1934g of Al (OH) 3 0.0484g MgO, 0.0528g Eu 2 O 3 Then 0.797g of fluxing agent H is weighed 3 BO 3 ；
(2) Grinding the raw materials for 30 minutes, and uniformly mixing to obtain a mixture; the mixture is put into a corundum crucible and pushed into a heating zone of a tubular high-temperature furnace, and is heated in H 2 And N 2 Atmosphere of mixed gas (H) 2 And N 2 And the volume ratio of (10:90), the temperature is controlled by a program, the temperature is raised to 1400 ℃ at the average temperature rise rate of 5 ℃/min, and after roasting for 4 hours at 1400 ℃, the temperature is naturally cooled to room temperature, and the divalent europium ion green light fluorescent powder Na is obtained after being taken out and slightly ground 2.6 Ca 0.5 Al 10.2 Mg 0.8 O 18.1 :0.2Eu 2+ 。
The divalent europium ion green light fluorescent powder Na 2.6 Ca 0.5 Al 10.2 Mg 0.8 O 18.1 :0.2Eu 2+ The phase composition of the polymer is shown in FIG. 1, and the space group is P6 3 Na of/mmc 1.22 Al 11 O 17.11 XRD standard card PDF#79-1560 and (CaCe) (AlTiMg) 12 O 19 The standard card PDF#89-7279 is compared, shows that all diffraction peaks of the prepared divalent europium ion green fluorescent powder are matched with diffraction peaks of the standard card in intensity and peak position, and proves that the obtained divalent europium ion green fluorescent powder has P6 3 The pure phase composition of the mmc space group, namely the matrix lattice of the green light fluorescent powder is hexagonal phase, and the space group of the hexagonal phase is P6 3 /mmc。
The excitation and emission spectrum of the divalent europium ion green fluorescent powder is shown in figure 2, the excitation band of the divalent europium ion green fluorescent powder covers 250-450nm (under the excitation of ultraviolet or ultraviolet light with the wavelength of 250-450 nm), the main peak is 371nm, the main peak of the green fluorescent emission is 496nm, the coverage is 420-650nm, and the half-peak width of the emission band is 90nm.
The thermal stability results are shown in FIG. 3, and the interpolated graph shows that the luminous intensity is maintained at 85% of the room temperature value at 150℃and the integrated intensity is maintained at 95% of the room temperature value at 150 ℃.
As shown in fig. 4, the quantum efficiency was 91% or more, and the external quantum efficiency was 67% or more.
Example 2:
preparation of Na a Ca b Al 11-c Mg c O 17+d :xEu 2+ Wherein x=0.2, a=2.6, b=0.5, c=0.7, d=1.15, the chemical formula is: na (Na) 2.6 Ca 0.5 Al 10.3 Mg 0.7 O 18.15 :0.2Eu 2+ 。
The preparation method comprises the following steps:
(1) 0.2067g of Na is weighed according to the stoichiometric ratio of elements 2 CO 3 0.0.0751g CaCO 3 1.2051g of Al (OH) 3 0.0423g MgO, 0.0528g Eu 2 O 3 Then 0.797g of fluxing agent H is weighed 3 BO 3 ；
(2) Grinding the raw materials for 30 minutes, and uniformly mixing to obtain a mixture; the mixture is put into a corundum crucible and pushed into a heating zone of a tubular high-temperature furnace, and is heated in H 2 And N 2 Atmosphere of mixed gas (H) 2 And N 2 And the volume ratio of (10:90), the temperature is controlled by a program, the temperature is raised to 1400 ℃ at the average temperature rise rate of 5 ℃/min, and after roasting for 4 hours at 1400 ℃, the temperature is naturally cooled to room temperature, and the divalent europium ion green light fluorescent powder Na is obtained after being taken out and slightly ground 2.6 Ca 0.5 Al 10.3 Mg 0.7 O 18.15 :0.2Eu 2+ 。
Divalent europium ion green light fluorescent powder Na 2.6 Ca 0.5 Al 10.3 Mg 0.7 O 18.15 :0.2Eu 2+ The phase composition of (C) is shown in FIG. 5, and the space group is P6 3 Na of/mmc 1.22 Al 11 O 17.11 XRD standard card PDF#79-1560 and (CaCe) (AlTiMg) 12 O 19 The standard card PDF#89-7279 is compared, which shows that all diffraction peaks of the prepared fluorescent powder are matched with the diffraction peaks of the standard card in intensity and peak position, and the obtained fluorescent powder is proved to have P6 3 The pure phase composition of the mmc space group, namely the matrix lattice of the green light fluorescent powder is hexagonal phase, and the space group of the hexagonal phase is P6 3 /mmc。
The excitation and emission spectra are shown in figure 6, the excitation band of the divalent europium ion green light fluorescent powder is covered with 250-450nm (under the excitation of ultraviolet or ultraviolet light with the wavelength of 250-450 nm), the main peak is 371nm, the green light fluorescence emission main peak is 488nm, the coverage is 420-650nm, and the half-peak width of the emission band is 90nm.
Example 3:
preparation of Na a Ca b Al 11-c Mg c O 17+d :xEu 2+ Wherein x=0.2, a=2.6, b=0, c=0.5, d=0.75, the chemical formula is: na (Na) 2.6 Al 10.5 Mg 0.5 O 17.75 :0.2Eu 2+ 。
The preparation method comprises the following steps:
(1) 0.2067g of Na is weighed according to the stoichiometric ratio of elements 2 CO 3 1.2285g of Al (OH) 3 0.0302g MgO, 0.0528g Eu 2 O 3 Then 0.797g of fluxing agent H is weighed 3 BO 3 ；
(2) Grinding the raw materials for 30 minutes, and uniformly mixing to obtain a mixture; the mixture is put into a corundum crucible and pushed into a heating zone of a tubular high-temperature furnace, and is heated in H 2 And N 2 Atmosphere of mixed gas (H) 2 And N 2 And the volume ratio of (10:90), the temperature is controlled by a program, the temperature is raised to 1400 ℃ at the average temperature rise rate of 5 ℃/min, and after roasting for 4 hours at 1400 ℃, the temperature is naturally cooled to room temperature, and the divalent europium ion green light fluorescent powder Na is obtained after being taken out and slightly ground 2.6 Al 10.5 Mg 0.5 O 17.75 :0.2Eu 2+ 。
Divalent europium ion green light fluorescent powder Na 2.6 Al 10.5 Mg 0.5 O 17.75 :0.2Eu 2+ The phase composition of (C) is shown in FIG. 7, and the space group is P6 3 Na of/mmc 1.22 Al 11 O 17.11 XRD standard card PDF#79-1560 and (CaCe) (AlTiMg) 12 O 19 The standard card PDF#89-7279 is compared, which shows that all diffraction peaks of the prepared fluorescent powder are matched with the diffraction peaks of the standard card in intensity and peak position, and the obtained fluorescent powder is proved to have P6 3 The pure phase composition of the mmc space group, namely the matrix lattice of the green light fluorescent powder is hexagonal phase, and the space group of the hexagonal phase is P6 3 /mmc。
The excitation and emission spectra are shown in figure 8, the excitation band of the divalent europium ion green light fluorescent powder is covered with 250-450nm (under the excitation of ultraviolet or ultraviolet light with the wavelength of 250-450 nm), the main peak is 340nm, the green light fluorescence emission main peak is 500nm, the coverage is 420-650nm, and the half-peak width of the emission band is 90nm.
Comparative example 1:
preparation of Na a Ca b Al 11-c Mg c O 17+d :xEu 2+ Wherein x=0.2, a=2, b=0.3, c=0, d=1, the chemical formula is: na (Na) 2 Ca 0.3 Al 11 O 18 :0.2Eu 2+ 。
The preparation method comprises the following steps:
(1) Weighing 0.1060g of Na according to the stoichiometric ratio of elements 2 CO 3 CaCO 0.03g 3 0.8580g of Al (OH) 3 Eu 0.0352g 2 O 3 Then, 0.0516g of flux H was weighed 3 BO 3 ；
(2) Grinding the raw materials for 30 minutes, and uniformly mixing to obtain a mixture; the mixture is put into a corundum crucible and pushed into a heating zone of a tubular high-temperature furnace, and is heated in H 2 And N 2 Atmosphere of mixed gas (H) 2 And N 2 And the volume ratio of (1) is 10:90), the temperature is controlled by a program, the temperature is raised to 1400 ℃ at the average temperature rise rate of 5 ℃/min, the mixture is roasted for 4 hours at 1400 ℃, and the mixture is naturally cooled to room temperature and then is taken out to be slightly ground, thus obtaining the green fluorescent powder Na 2 Ca 0.3 Al 11 O 17.8 :0.2Eu 2+ 。
Blue light fluorescent powder Na 2 Ca 0.3 Al 11 O 17.8 :0.2Eu 2+ The phase composition of (C) is shown in FIG. 9, and the space group is P6 3 Na of/mmc 1.22 Al 11 O 17.11 XRD standard card PDF#38-0470 and CaAl 12 O 19 The standard card PDF#89-7279 is compared, which shows that all diffraction peaks of the prepared fluorescent powder are matched with the diffraction peaks of the standard card in intensity and peak position, and the obtained fluorescent powder is proved to have P6 3 Two phase composition of/mmc space group, caAl 12 O 19 (Standard card PDF#89-7279) is a hybrid phase.
The excitation and emission spectrum of the green light fluorescent powder is shown in figure 10, the excitation band of the green light fluorescent powder is covered with 250-450nm (under the excitation of ultraviolet or purple light with the wavelength of 250-450 nm), the main peak is 340 and 371nm, the green light fluorescence emission main peak is 465nm, the excitation band is covered with 420-650nm, the half-peak width of the emission band is 63nm, the green light gap can be made up when the white light LED is manufactured, and the color rendering index of the device can be further improved.
Comparative example 2:
preparation of Na a Ca b Al 11-c Mg c O 17+d :xEu 2+ Wherein x=0.2, a=0, b=0.8, c=0.8, d=0.1, the chemical formula is: ca (Ca) 0.8 Al 10.2 Mg 0.8 O 17.1 :0.2Eu 2+ 。
The preparation method comprises the following steps:
(1) 0.0801g of CaCO is weighed according to the stoichiometric ratio of elements 3 0.8736g of Al (OH) 3 0.0201g MgO, 0.0352g Eu 2 O 3 0.0505g of fluxing agent H is weighed again 3 BO 3 ；
(2) Grinding the raw materials for 30 minutes, and uniformly mixing to obtain a mixture; the mixture is put into a corundum crucible and pushed into a heating zone of a tubular high-temperature furnace, and is heated in H 2 And N 2 Atmosphere of mixed gas (H) 2 And N 2 And the volume ratio of (10:90), the temperature is controlled by a program, the temperature is raised to 1400 ℃ at the average temperature rise rate of 5 ℃/min, and after roasting for 4 hours at 1400 ℃, the temperature is naturally cooled to room temperature, and then the fluorescent powder Ca activated by europium ions is obtained after being taken out and slightly ground 0.8 Al 10.2 Mg 0.8 O 16.9 :0.2Eu 2+ 。
Phosphor Ca 0.8 Al 10.2 Mg 0.8 O 16.9 The phase composition of 0.2Eu is shown in FIG. 11, and the space group is P6 3 CaAl of/mmc 12 O 19 The standard card PDF#89-7279 is compared, which shows that all diffraction peaks of the prepared fluorescent powder are matched with the diffraction peaks of the standard card in intensity and peak position, and the obtained fluorescent powder is proved to have P6 3 Pure phase composition of/mmc space group.
The excitation and emission spectra are shown in FIG. 12, the excitation main peak of the europium ion activated fluorescent powder is located at 320nm, the emission main peak is located at 592 and 615nm, which is typical of Eu 3+ Is provided.
Example 4:
selecting Na prepared in example 1 2.6 Ca 0.5 Al 10.2 Mg 0.8 O 18.1 :0.2Eu 2+ Commercial red phosphor CaAlSiN 3 :Eu 2+ And manufacturing a white light LED device with the 365nm or 395nm near ultraviolet chip.
In this example, a 1W high power chip was used, and the emission peak was 365 or 395nm. The specific method comprises the following steps:
uniformly mixing the two kinds of fluorescent powder according to the mass ratio of 30:1 to obtain mixed fluorescent powder; uniformly mixing the mixed fluorescent powder and the silica gel for encapsulation according to the mass ratio of 1:3, dripping the mixed material to the periphery of the near ultraviolet chip and covering the chip and the lead, and then placing the chip and the lead in a vacuum drying oven for curing at 120 ℃ to obtain the white light LED device.
The color rendering indices of the devices combined with 365nm chip and 395nm chip were 88.3, 86.4, respectively, and lumen efficiencies were 62.599lm/W, 55.559lm/W, respectively. The electroluminescence spectrogram and the lighting photo of the white light LED device based on the 365nm near ultraviolet chip are shown in FIG. 13; the electroluminescence spectrum and the lighting photo of the white light LED device based on 395nm near ultraviolet chip are shown in FIG. 14.
Example 5:
selecting Na prepared in example 1 2.6 Ca 0.5 Al 10.2 Mg 0.8 O 18.1 :0.2Eu 2+ Blue light fluorescent powder K 1.6 Al 11 O 17.5 :0.20Eu 2+ Commercial green light fluorescent powder (Ba, sr) 2 SiO 4 :Eu 2+ Commercial red phosphor CaAlSiN 3 :Eu 2+ And manufacturing a white light LED device with the 365nm or 395nm near ultraviolet chip.
In this example, a 1W high power chip was used, and the emission peak was 365 or 395nm. The specific method comprises the following steps:
uniformly mixing the three kinds of fluorescent powder according to the mass ratio of 6:20:1:1 to obtain mixed fluorescent powder; uniformly mixing the mixed fluorescent powder and the silica gel for encapsulation according to the mass ratio of 1:5, dripping the mixed material to the periphery of the near ultraviolet chip and covering the chip and the lead, and then placing the chip and the lead in a vacuum drying oven for curing at 120 ℃ to obtain the white light LED device.
The color rendering indices of the devices combined with 365nm chips and 395nm chips were 94.4, 95.6, respectively, and lumen efficiencies were 72.731lm/W, 62.467lm/W, respectively. The electroluminescence spectrogram and the lighting photo of the white light LED device based on the 365nm near ultraviolet chip are shown in FIG. 15; the electroluminescence spectrum and the lighting photo of the white light LED device based on 395nm near ultraviolet chip are shown in FIG. 16.
Example 6:
selecting Na prepared in example 1 2.6 Ca 0.5 Al 10.2 Mg 0.8 O 18.1 :0.2Eu 2+ Commercial blue light fluorescent powder BaMgAl 10 O 17 :Eu 2+ Commercial green light fluorescent powder (Ba, sr) 2 SiO 4 :Eu 2+ Commercial red phosphor CaAlSiN 3 :Eu 2+ And manufacturing a white light LED device with the 365nm or 395nm near ultraviolet chip.
In this example, a 1W high power chip was used, and the emission peak was 365 or 395nm. The specific method comprises the following steps:
uniformly mixing the three kinds of fluorescent powder according to the mass ratio of 10:30:4:3 to obtain mixed fluorescent powder; uniformly mixing the mixed fluorescent powder and the silica gel for encapsulation according to the mass ratio of 1:5, dripping the mixed material to the periphery of the near ultraviolet chip and covering the chip and the lead, and then placing the chip and the lead in a vacuum drying oven for curing at 120 ℃ to obtain the white light LED device.
The color rendering indices of the devices combined with 365nm chips and 395nm chips were 94, respectively, and lumen efficiencies were 67.615lm/W and 64.955lm/W, respectively. The electroluminescence spectrogram and the lighting photo of the white light LED device based on the 365nm near ultraviolet chip are shown in FIG. 17; the electroluminescence spectrum and the lighting photo of the white light LED device based on 395nm near ultraviolet chip are shown in FIG. 18.
Claims (9)
1. A high-efficiency heat-stable divalent europium ion green light fluorescent powder is characterized in that the chemical formula of the divalent europium ion green light fluorescent powder is Na 2.6 Ca 0.5 Al 11-c Mg c O 17+d :xEu 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.3, c is more than or equal to 0.5 and less than or equal to 0.8,0.75, and d is more than or equal to 1.15.
2. The divalent europium ion blue light fluorescent powder according to claim 1, wherein the divalent europium ion blue light fluorescent powder emits blue fluorescence with a peak value of 480-510nm under the excitation of ultraviolet or ultraviolet light with a wavelength of 250-450nm, and the half-peak width of the emission band is 80-95nm.
3. The divalent europium ion blue light phosphor according to claim 1, wherein the internal quantum efficiency of the divalent europium ion blue light phosphor is 80% or more and the external quantum efficiency thereof is 50% or more;
the luminous intensity of the divalent europium ion green fluorescent powder at 150 ℃ is more than 70% of the luminous intensity of the divalent europium ion green fluorescent powder at room temperature, and the integral intensity of the divalent europium ion green fluorescent powder at 150 ℃ is more than 80% of the integral intensity of the divalent europium ion green fluorescent powder at room temperature.
4. The divalent europium ion blue light phosphor according to claim 1, wherein the matrix lattice of the divalent europium ion blue light phosphor is hexagonal phase and the space group of the hexagonal phase is P6 3 /mmc。
5. The method for preparing the high-efficiency and thermally stable divalent europium ion blue light phosphor according to any one of claims 1 to 4, which comprises the following steps:
(1) Weighing a sodium-containing compound, a calcium-containing compound, an aluminum-containing compound, a magnesium-containing compound and a europium-containing compound according to stoichiometric ratio, and then weighing a fluxing agent;
(2) Grinding and uniformly mixing the raw materials weighed in the step (1) to obtain a mixture; and heating the mixture to 1200-1500 ℃ in a reducing atmosphere, roasting for 3-6h, naturally cooling to room temperature, and grinding to obtain the divalent europium ion green light fluorescent powder.
6. The method according to claim 5, wherein in the step (1), the sodium-containing compound is any one or a combination of sodium carbonate, sodium bicarbonate, and sodium oxalate; the calcium-containing compound is any one or the combination of a plurality of calcium carbonates and calcium bicarbonates; the aluminum-containing compound is any one or a combination of a plurality of aluminum hydroxides and aluminum oxides; the magnesium-containing compound is any one or the combination of a plurality of magnesium hydroxide and magnesium oxide; the europium-containing compound is Eu 2 O 3 、EuCl 3 、Eu(NO 3 ) 3 Any one or a combination of a plurality of the above;
the fluxing agent is H 3 BO 3 、CaF 2 、SrF 2 、NaF、KF、BaF 2 、(NH 4 ) 2 CO 3 The mass of the fluxing agent is 3-10% of the total mass of the sodium-containing compound, the calcium-containing compound, the aluminum-containing compound, the magnesium-containing compound and the europium-containing compound.
7. The method according to claim 5 or 6, wherein in the step (2), the temperature is raised to 1200 to 1500 ℃ at an average temperature raising rate of 3 to 6 ℃/min; the reducing atmosphere is H 2 And N 2 The mixed gas of H 2 And N 2 The volume ratio of (2) is 5:95-10:90.
8. The use of the divalent europium ion blue light phosphor according to any one of claims 1 to 4 or the divalent europium ion blue light phosphor prepared by the preparation method according to any one of claims 5 to 7, wherein the divalent europium ion blue light phosphor is used for manufacturing a white LED device.
9. The use according to claim 8, characterized in that theThe blue light fluorescent powder, the blue light fluorescent powder and the green light fluorescent powder (Ba, sr) 2 SiO 4 :Eu 2+ Red phosphor CaAlSiN 3 :Eu 2+ After mixing, packaging the mixture on a near ultraviolet LED chip to manufacture a white light LED device; the blue light fluorescent powder is BaMgAl 10 O 17 :Eu 2+ 、K 1.6 Al 11 O 17.5 :0.20Eu 2+ One or two of the following components;
or the green fluorescent powder and the red fluorescent powder CaAlSiN 3 :Eu 2+ And after mixing, packaging the mixture on a near ultraviolet LED chip to manufacture a white light LED device.
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| JP4854106B2 (en) * | 1999-10-08 | 2012-01-18 | 大電株式会社 | UV or vacuum UV excited blue phosphor |
| JP4396016B2 (en) * | 2000-09-21 | 2010-01-13 | 三菱化学株式会社 | Aluminate phosphor, phosphor paste composition, and vacuum ultraviolet light-excited light emitting device |
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