CN108753279B - Europium ion Eu3+Activated red-emitting phosphor and preparation and application thereof - Google Patents
Europium ion Eu3+Activated red-emitting phosphor and preparation and application thereof Download PDFInfo
- Publication number
- CN108753279B CN108753279B CN201810581585.9A CN201810581585A CN108753279B CN 108753279 B CN108753279 B CN 108753279B CN 201810581585 A CN201810581585 A CN 201810581585A CN 108753279 B CN108753279 B CN 108753279B
- Authority
- CN
- China
- Prior art keywords
- fluorescent powder
- ion
- emitting
- europium
- activated red
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 13
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 12
- 230000005284 excitation Effects 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- -1 Europium ion Chemical class 0.000 claims description 23
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 20
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 229910001940 europium oxide Inorganic materials 0.000 claims description 8
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 150000008040 ionic compounds Chemical class 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims 1
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000012190 activator Substances 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 238000000695 excitation spectrum Methods 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 7
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000001748 luminescence spectrum Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- C09K11/774—Borates
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to trivalent europium ion Eu3+Preparation and application of activated red light-emitting fluorescent powder, belonging to the field of luminescent materials. The matrix of the fluorescent powder is LiAlB2O5The activator is Eu3+Ion of the formula Li(1‑x)EuxAl(1‑2x/3)B2O5Wherein x is europium ion Eu3+The doping mole number is more than or equal to 0.001 and less than or equal to 0.1. The red fluorescent powder has strong absorption in a near ultraviolet region, and the wavelength is very consistent with the emission wavelength of a commercial near ultraviolet LED chip. The fluorescent powder of the invention can emit bright red light under the excitation of near ultraviolet light, and has high luminous efficiency and good thermal stability.
Description
Technical Field
The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to a europium ion Eu3+Activated red-emitting phosphor and its preparation and use.
Background
In the development of rare earth functional materials, the development and application of rare earth luminescent materials have received great attention. The rare earth ions have a special electronic layer structure and thus have spectral properties incomparable with common elements, and the rare earth luminescence almost covers the whole solid luminescence range, so long as the luminescence is mentioned, the rare earth is almost not distinguished. Atoms of rare earth elements have unfilled 4f5d electronic configuration shielded by the outside, so that the rare earth elements have abundant electronic energy levels and long-life excited states, energy level transition channels can reach more than 20 and ten thousand, and can generate various radiation absorption and emission, and the rare earth elements are combined with a proper matrix to form a wide range of light-emitting and laser materials.
The luminescence of rare earth compounds is based on their transition of 4f electrons within or between f-f and f-d configurations. Particularly, the transition of electrons from the 4f shell layer is shielded by the outer layer 5d electron layer, so that the transition from the 4f electron energy level has a very narrow spectral line, and therefore, the transition has very pure luminous chromaticity. Especially, the white light LED technology developed in recent years and the application thereof are the fourth generation lighting source following incandescent lamps, fluorescent lamps and energy-saving lamps, are called as the green light source of the 21 st century, and have the characteristics of environmental protection, super-long service life, high efficiency, energy saving, adverse environment resistance, simple structure, small volume, light weight, quick response, good safety and the like.
Among the red-blue-green phosphors, Eu3+Ion-activated red phosphors are the essential chromogenic material. Some current commercial red-emitting phosphors have very low absorption capacity in the near-ultraviolet region, resulting in low luminous efficiency of the final lighting device; in addition, there are typical red-emitting phosphors such as Y2O2S:Eu3+, Y2O3:Eu3+Has the disadvantages of obvious pollution and the like.
Disclosure of Invention
In order to overcome the defects of low excitation efficiency and poor stability of the red fluorescent powder for the white light LED in the prior art in the near ultraviolet and blue light regions, the invention aims to provide a europium ion Eu3+Activated red-emitting phosphor and its preparation and use, the matrix of which is LiAlB2O5The activator is Eu3+Ion, the substrate has a rigid structure and good thermal stability, and is different from the conventional red phosphor Eu3+Ion-substituted trivalent or divalent cation, the red-emitting phosphor of the present invention, Eu3+The position of Li ion is replaced, and the resulting charge imbalance is balanced by Al vacancies. The fluorescent powder has strong absorption in near ultraviolet light, and the red light emission realized by the fluorescent powder has the characteristics of high efficiency and high chromaticity purity. The preparation process is simple and efficient, and has no pollution.
In order to achieve the purpose, the invention adopts the technical scheme that:
europium ion Eu3+An activated red-emitting phosphor having the chemical formula Li(1-x)EuxAl(1-2x/3)B2O5Wherein x is europium ion Eu3+The doping mole number of x is more than or equal to 0.001 and less than or equal to 0.1, and the fluorescent powder can realize the conversion of near ultraviolet light to emit red fluorescence.
Preferably, it has the formula Li0.97Eu0.03Al0.98B2O5、Li0.99Eu0.01Al0.993B2O5、 Li0.999Eu0.001Al0.9993B2O5、Li0.95Eu0.05Al0.9666B2O5、Li0.93Eu0.07Al0.9533B2O5Or Li0.9Eu0.1Al0.9333B2O5。
The invention also provides the europium ion Eu3+The preparation method of the activated red-emitting fluorescent powder comprises the following steps:
(1) according to the chemical formula Li(1-x)EuxAl(1-2x/3)B2O5The stoichiometric ratio of each element in the alloy is measured to contain Li+、 Eu3 +、Al3+And B3+Dissolving an ionic compound in a proper amount of deionized water or dilute nitric acid solution to obtain a transparent solution;
(2) weighing a complexing agent, adding the complexing agent into the transparent solution, and stirring for a period of time at a certain temperature for aging; then placing the precursor in a drying oven for drying to obtain a fluffy precursor;
(3) placing the precursor obtained in the step (2) in a muffle furnace for calcining, and then naturally cooling to room temperature to obtain the europium ion Eu3+Activated red emitting phosphor.
Preferably, in the step (1), lithium ion Li is contained+The compound of (A) is lithium oxide (Li)2O), lithium nitrate (LiNO)3) Or lithium carbonate (Li)2CO3) (ii) a Containing europium ion Eu3+Is europium oxide (Eu)2O3) Or europium nitrate (Eu (NO)3)3·6H2O); containing Al ions3+The compound of (A) is aluminum nitrate (Al (NO)3)3·9H2O), or aluminum hydroxide (Al (OH)3) (ii) a Containing boron ions B3+The compound of (A) is boron trioxide (B)2O3) Or boric acid(H3BO3)。
Preferably, in the step (2), the complexing agent is used in an amount of Li+、Eu3+、Al3+And B3+The amount of ionic compound is 1.0-2.0 wt%.
Preferably, in the step (2), the complexing agent is citric acid, and the temperature for stirring and aging is 60-80 ℃.
Preferably, in the step (3), the calcining temperature is 700-800 ℃ and the time is 2-8 hours.
The europium ion Eu of the invention3+The activated red-emitting phosphor can be applied to materials for fluorescent lighting and displays. For example, the europium ion Eu may be3+The activated red-emitting fluorescent powder is coated on the inner wall of the vacuum fluorescent tube, and under the irradiation of ultraviolet rays emitted by an ultraviolet lamp, the illumination of the ultraviolet fluorescent lamp is realized; alternatively, the europium ion Eu may be3+The activated red-emitting fluorescent powder and other fluorescent powder are used together, mixed in transparent resin and packaged around a semiconductor chip, and white-light LED illumination is realized under the excitation of chip emitting light.
Compared with the prior art, the invention has the beneficial effects that:
1. the matrix material provided by the technical scheme of the invention has a rigid matrix structure, good physical and chemical properties and high thermal stability.
2. With conventional red phosphors, e.g. Y2O2S:Eu3+,Y2O3:Eu3+Compared with the luminescent material, the red fluorescent powder prepared by the technical scheme of the invention has stronger excitation at near ultraviolet of about 400 nm.
3. Compared with red fluorescent powder taking other sulfides and halides as matrix materials, the preparation process of the matrix material has no pollution and no waste water and gas emission; the process can be completed on common equipment, and has low requirement on the equipment.
Drawings
FIG. 1: the X-ray powder diffraction pattern of the phosphor was prepared according to the protocol of example 1.
FIG. 2 is a drawing: SEM images of samples prepared according to the technical scheme of the invention example 1. The particles are fine and uniform.
FIG. 3: the sample was prepared according to the protocol of example 1 and the excitation spectrum obtained at 613 nm of luminescence was monitored.
FIG. 4 is a drawing: the fluorescence spectrum under 395 nm excitation of the sample prepared according to the technical scheme of example 1.
FIG. 5: the luminescence decay curve of the sample is prepared according to the technical scheme of the invention example 1.
FIG. 6: the X-ray powder diffraction pattern of the fluorescent powder is prepared according to the technical scheme of the embodiment 4
FIG. 7: the sample was prepared according to the protocol of example 4 and the excitation spectrum obtained at 613 nm of luminescence was monitored.
FIG. 8: the fluorescence spectrogram of the sample prepared according to the technical scheme of the example 4 under the excitation of 395 nm
FIG. 9: the luminescence decay curve of the sample is prepared according to the technical scheme of the invention embodiment 4.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples.
Example 1:
according to the chemical formula Li0.97Eu0.03Al0.98B2O5Respectively weighing lithium nitrate Li (NO) according to the stoichiometric ratio of Li, Eu, Al and B3): 0.737 g of europium oxide Eu2O3: 0.264 g, aluminum nitrate Al (NO)3)3·9H2O: 18.37 g of boron trioxide B2O3: 3.5 g, and 0.03 g of citric acid accounting for 1.0-2.0 wt% of the mass of each sample, dissolving europium oxide and boron trioxide in dilute nitric acid, adding lithium nitrate and aluminum nitrate, finally adding weighed citric acid, magnetically stirring in a water bath at 60 ℃ to obtain a clear solution, placing the clear solution in a drying oven, drying to obtain a precursor, placing the precursor in a muffle furnace for calcination, wherein the sintering temperature is 700 ℃, the calcination time is 8 hours, cooling to room temperature, taking out and fully grinding to obtain the sample.
Referring to the attached figure 1, the X-ray powder diffraction pattern of the fluorescent powder prepared according to the technical scheme of the embodiment 1 is shown; the test results show that the prepared sample is a pure phase material with perfect crystallinity.
Referring to fig. 2, a SEM image of a sample prepared according to the embodiment of the invention example 1 is shown. The particles are fine and uniform.
Referring to FIG. 3, a sample is prepared according to the technical scheme of example 1, and the excitation spectrum obtained under the condition of emitting light of 613 nm is monitored. The test result shows that the fluorescent powder has strong light absorption in the interval of ultraviolet and near ultraviolet wavelength, and is suitable for being used as semiconductor lighting equipment.
Referring to FIG. 4, the fluorescence spectrum under 395 nm excitation of the sample prepared according to the embodiment of example 1 is shown. As can be seen, the prepared material can effectively convert near ultraviolet light into red light.
Referring to fig. 5, a luminescence decay curve of a sample prepared according to the technical scheme of the invention example 1 is calculated to obtain a decay time of 1.4 milliseconds.
Example 2:
according to the chemical formula Li0.99Eu0.01Al0.993B2O5Respectively weighing lithium nitrate Li (NO) according to the stoichiometric ratio of Li, Eu, Al and B3): 3.317 g, europium oxide Eu2O3: 0.223 g of aluminum hydroxide Al (OH)3: 3.873 g of boric acid HBO3: 6.2 g, and 1.0-2.0 wt% of citric acid in the mass of each sample: 0.28 g, europium oxide and boric acid are dissolved in dilute nitric acid, lithium nitrate and aluminum hydroxide are added, weighed citric acid is finally added, magnetic stirring is carried out in a water bath at the temperature of 80 ℃ to obtain a clear solution, the solution is placed in a drying oven and dried to obtain a precursor, the precursor is placed in a muffle furnace to be calcined, the sintering temperature is 800 ℃, the calcining time is 2 hours, the precursor is cooled to the room temperature, and the sample is taken out and fully ground to obtain the sample.
The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 1.
Example 3:
according to the chemical formula Li0.999Eu0.001Al0.9993B2O5Respectively weighing lithium nitrate Li (NO) according to the stoichiometric ratio of Li, Eu, Al and B3): 3.347 g, europium nitrate Eu (NO)3)3·6H2O: 0.223 g of aluminum hydroxide Al (OH)3: 3.897 g of boron trioxide B2O3: 3.5 g, and 1.0-2.0 wt% of citric acid in the mass of each sample: 0.23 g, dissolving diboron trioxide in dilute nitric acid, adding lithium nitrate, europium nitrate and aluminum hydroxide, finally adding weighed citric acid, magnetically stirring in a water bath at 70 ℃ to obtain a clear solution, placing the clear solution in a drying oven, drying to obtain a precursor, placing the precursor in a muffle furnace for calcination, wherein the sintering temperature is 750 ℃, the calcination time is 5 hours, cooling to room temperature, taking out and fully grinding to obtain a sample.
The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 1.
Example 4:
according to the chemical formula Li0.95Eu0.05Al0.9666B2O5In the stoichiometric ratio of Li, Eu, Al and B, respectively weighing lithium oxide Li2O: 0.713 g, europium oxide Eu2O3: 0.44 g, aluminum nitrate Al (NO)3)3·9H2O: 18.123 g of boron trioxide B2O3: 3.5 g, and 1.0-2.0 wt% of citric acid in the mass of each sample: 0.5 g, dissolving lithium oxide, europium oxide and boron trioxide in dilute nitric acid, adding weighed aluminum nitrate and citric acid, magnetically stirring in a water bath at 70 ℃ to obtain a clear solution, placing the clear solution in a drying oven, drying to obtain a precursor, placing the precursor in a muffle furnace for calcination, wherein the sintering temperature is 780 ℃, the calcination time is 4 hours, cooling to room temperature, taking out and fully grinding to obtain a sample.
Referring to FIG. 6, the X-ray powder diffraction pattern of the phosphor prepared according to the technical scheme of example 4 is shown; XRD test results show that the prepared sample is a pure phase material with perfect crystallinity.
Referring to FIG. 7, a sample is prepared according to the technical scheme of example 4, and the excitation spectrum obtained under the condition of emitting light of 613 nm is monitored. The test result shows that the fluorescent powder has strong light absorption in the interval of ultraviolet and near ultraviolet wavelength, and is suitable for being used as semiconductor lighting equipment.
Referring to FIG. 8, the fluorescence spectrum under 395 nm excitation of the sample prepared according to the embodiment of example 4 is shown. As can be seen, the prepared material can also effectively convert near ultraviolet light into red light.
Referring to fig. 9, a luminescence decay curve of a sample prepared according to the embodiment of the present invention 4 is calculated to obtain a decay time of 3.0 ms.
Example 5
According to the chemical formula Li0.93Eu0.07Al0.9533B2O5Respectively weighing lithium nitrate Li (NO) according to the stoichiometric ratio of Li, Eu, Al and B3): 3.3165 g, europium nitrate Eu (NO)3)3·6H2O: 1.561 g, aluminum hydroxide Al (OH)3: 3.718 g, boric acid HBO3: 6.2 g, and 1.0-2.0 wt% of citric acid in the mass of each sample: 0.3 g, dissolving lithium nitrate, europium nitrate, aluminum hydroxide and boric acid in dilute nitric acid, adding a proper amount of deionized water, finally adding weighed citric acid, magnetically stirring in a water bath at 80 ℃ to obtain a clear solution, placing the solution in an oven, drying to obtain a precursor, placing the precursor in a muffle furnace for calcination, wherein the sintering temperature is 750 ℃, the calcination time is 6 hours, cooling to room temperature, taking out and fully grinding to obtain a sample.
The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 4.
Example 6:
according to the chemical formula Li0.9Eu0.1Al0.9333B2O5The stoichiometric ratio of Li, Eu, Al and B is measured, lithium carbonate Li is weighed respectively2CO3: 1.665 g, europium nitrate Eu (NO)3)3·6H2O: 2.23 g, aluminum hydroxide Al (OH)3: 3.64 g boric acid HBO3: 6.2 g, and 1.0-2.0 wt% of citric acid in the mass of each sample: 0.3 g of lithium carbonate, europium nitrate and oxyhydrogenDissolving aluminum oxide and boric acid in a proper amount of dilute nitric acid solution, adding weighed citric acid, magnetically stirring in a water bath at 70 ℃ to obtain a clear solution, placing the clear solution in a drying oven, drying to obtain a precursor, placing the precursor in a muffle furnace for calcination at the sintering temperature of 800 ℃ for 3 hours, cooling to room temperature, taking out, and fully grinding to obtain the sample.
The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 4.
Claims (8)
1. Europium ion Eu3+An activated red-emitting phosphor characterized in that it has a chemical formula of Li(1-x)EuxAl(1-2x/3)B2O5Wherein x is europium ion Eu3+The doping mole number of x is more than or equal to 0.001 and less than or equal to 0.1, and the fluorescent powder can realize the conversion of near ultraviolet light to emit red fluorescence.
2. The europium ion Eu of claim 13+The preparation method of the activated red-emitting fluorescent powder is characterized by comprising the following steps:
(1) according to the chemical formula Li(1-x)EuxAl(1-2x/3)B2O5The stoichiometric ratio of each element in the alloy is measured to contain Li+、Eu3+、Al3+And B3+Dissolving an ionic compound in a proper amount of deionized water or dilute nitric acid solution to obtain a transparent solution;
(2) weighing a complexing agent, adding the complexing agent into the transparent solution, and stirring for a period of time at a certain temperature for aging; then placing the precursor in a drying oven for drying to obtain a fluffy precursor;
(3) placing the precursor obtained in the step (2) in a muffle furnace for calcining, and then naturally cooling to room temperature to obtain the europium ion Eu3+Activated red emitting phosphor.
3. The Eu ion Eu according to claim 23+The preparation method of the activated red-emitting fluorescent powder is characterized in that the step (1) containsWith lithium ions Li+The compound of (A) is lithium oxide (Li)2O), lithium nitrate (LiNO)3) Or lithium carbonate (Li)2CO3) (ii) a Containing europium ion Eu3+Is europium oxide (Eu)2O3) Or europium nitrate hexahydrate (Eu (NO)3)3•6H2O); containing Al ions3+The compound of (A) is aluminum nitrate nonahydrate (Al (NO)3)3•9H2O), or aluminum hydroxide (Al (OH)3) (ii) a Containing boron ions B3+The compound of (A) is boron trioxide (B)2O3) Or boric acid (H)3BO3）。
4. The Eu ion Eu according to claim 23+The preparation method of the activated red-emitting fluorescent powder is characterized in that in the step (2), the dosage of the complexing agent is Li+、Eu3+、Al3+And B3+The amount of ionic compound is 1.0-2.0 wt%.
5. The Eu ion Eu according to claim 23+The preparation method of the activated red-emitting fluorescent powder is characterized in that in the step (2), the complexing agent is citric acid, and the temperature for stirring and aging is 60-80 ℃.
6. The Eu ion Eu according to claim 23+The preparation method of the activated red-emitting fluorescent powder is characterized in that in the step (3), the calcination temperature is 700-800 ℃ and the time is 2-8 hours.
7. The europium ion Eu of claim 13+Use of activated red-emitting phosphors for materials for fluorescent lighting and displays.
8. The use according to claim 7, wherein said europium ion Eu is selected3+The activated red-emitting fluorescent powder is coated on the inner wall of the vacuum fluorescent tube, and under the irradiation of ultraviolet rays emitted by an ultraviolet lamp, the illumination of the ultraviolet fluorescent lamp is realized;or, the europium ion Eu3+The activated red-emitting fluorescent powder and other fluorescent powder are used together, mixed in transparent resin and packaged around a semiconductor chip, and white-light LED illumination is realized under the excitation of chip emitting light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810581585.9A CN108753279B (en) | 2018-06-05 | 2018-06-05 | Europium ion Eu3+Activated red-emitting phosphor and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810581585.9A CN108753279B (en) | 2018-06-05 | 2018-06-05 | Europium ion Eu3+Activated red-emitting phosphor and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108753279A CN108753279A (en) | 2018-11-06 |
| CN108753279B true CN108753279B (en) | 2021-03-26 |
Family
ID=63999354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810581585.9A Expired - Fee Related CN108753279B (en) | 2018-06-05 | 2018-06-05 | Europium ion Eu3+Activated red-emitting phosphor and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108753279B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957403B (en) * | 2019-04-28 | 2021-08-27 | 江苏师范大学 | Eu (Eu)3+Activated barium strontium fluoborate red fluorescent powder and preparation and application thereof |
| CN116875303A (en) * | 2023-06-02 | 2023-10-13 | 常熟理工学院 | Aluminate-based red luminescent material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343541A (en) * | 2008-08-26 | 2009-01-14 | 江苏技术师范学院 | Red fluorescent powder for white radiation LED and preparation thereof |
| CN105623660A (en) * | 2016-03-17 | 2016-06-01 | 中南大学 | Warm white fluorescent powder excited by ultraviolet LED |
| CN106634977A (en) * | 2016-11-18 | 2017-05-10 | 厦门大学 | Green phosphor excited by near ultraviolet light and preparation method of green phosphor |
| CN106753347A (en) * | 2016-11-18 | 2017-05-31 | 厦门大学 | A kind of near ultraviolet excitated red fluorescence powder and preparation method thereof |
-
2018
- 2018-06-05 CN CN201810581585.9A patent/CN108753279B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343541A (en) * | 2008-08-26 | 2009-01-14 | 江苏技术师范学院 | Red fluorescent powder for white radiation LED and preparation thereof |
| CN105623660A (en) * | 2016-03-17 | 2016-06-01 | 中南大学 | Warm white fluorescent powder excited by ultraviolet LED |
| CN106634977A (en) * | 2016-11-18 | 2017-05-10 | 厦门大学 | Green phosphor excited by near ultraviolet light and preparation method of green phosphor |
| CN106753347A (en) * | 2016-11-18 | 2017-05-31 | 厦门大学 | A kind of near ultraviolet excitated red fluorescence powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Photoluminescence properties of Tb3+ doped lithium alumino-borate phosphor,LiAlB2O5:Tb3+;R.S.Palaspagar等;《International Journal of Luminescence and applications》;20160228;第6卷;第85-88页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108753279A (en) | 2018-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109777404B (en) | Europium ion Eu3+Activated aluminate red fluorescent powder and preparation method thereof | |
| BR112013003416B1 (en) | SILICATE LUMINOPHOR WITH MODIFIED SURFACE | |
| CN103627392B (en) | A kind of stibnate base red fluorescent powder and its preparation method and application | |
| CN102604638A (en) | Eu<3+>-activated phosphate red phosphor powder as well as preparation method and application thereof | |
| CN113403074A (en) | Mn4+ activated antimonate narrow-band red fluorescent powder and preparation method thereof | |
| CN103242830B (en) | Fluorosilicate-based blue-green fluorescent powder as well as preparation method and applications of fluorescent powder | |
| CN105694886A (en) | Eu (Eu)2+Preparation method and application of doped fluosilicate-based luminescent material | |
| CN108753279B (en) | Europium ion Eu3+Activated red-emitting phosphor and preparation and application thereof | |
| CN109957403B (en) | Eu (Eu)3+Activated barium strontium fluoborate red fluorescent powder and preparation and application thereof | |
| CN109370580B (en) | Bismuth ion activated titanium aluminate fluorescent powder and preparation method and application thereof | |
| CN103059838B (en) | Eu<2+> activated silicate yellow fluorescent powder as well as preparation method and application thereof | |
| CN104073255A (en) | Zirconium silicate salt blue fluorescent powder, preparation method and application thereof | |
| CN110129050A (en) | It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method | |
| CN102199429B (en) | Fluophosphate-based light-emitting material and preparation method thereof | |
| CN109957402B (en) | Trivalent europium ion activated red-emitting fluorescent powder and preparation and application thereof | |
| CN110003901B (en) | Eu (Eu)3+And Ti4+Ion-codoped niobium tantalate red fluorescent powder, and preparation method and application thereof | |
| CN102660286B (en) | Vanadate up-conversion light-emitting material activated by erbium ions Er<3+> and preparation method thereof | |
| CN105419798B (en) | A kind of preparation method and application of orange red antimonate luminescent materials | |
| CN109957397B (en) | Tb3+ activated barium strontium fluoborate green fluorescent powder and preparation and application thereof | |
| CN104804731B (en) | Magnesium silicate potassium blue-green fluorescent powder that a kind of Eu2+ activates and its preparation method and application | |
| CN106867524B (en) | A kind of preparation and application of alkaline earth aluminate blue fluorescent material | |
| CN109233826B (en) | Europium ion activated titanium aluminate fluorescent powder and preparation method and application thereof | |
| CN101942301B (en) | Phosphate red fluorescent powder for light-emitting diode and preparation method thereof | |
| CN112521944B (en) | Rare earth Eu 3+ Ion activated red luminescent material, preparation method and application | |
| CN109593527A (en) | A kind of orange red barium phosphate yttrium fluorescent powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210326 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |