CN110713834A - Molybdate fluorescent powder and preparation method thereof - Google Patents

Molybdate fluorescent powder and preparation method thereof Download PDF

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Publication number
CN110713834A
CN110713834A CN201911062224.4A CN201911062224A CN110713834A CN 110713834 A CN110713834 A CN 110713834A CN 201911062224 A CN201911062224 A CN 201911062224A CN 110713834 A CN110713834 A CN 110713834A
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fluorescent powder
molybdate
phosphor
preparation
mosio
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江国健
杨璐璐
姜奕辰
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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

Abstract

The invention provides molybdate fluorescent powder and a preparation method thereof. The molybdate phosphor is characterized by comprising: according to the molar ratio of Y, Mo, Si, Eu and Dy of 2: 1: 1: 0.03-0.09: 0.03-0.09, and preparing the molybdate fluorescent powder by adopting a high-temperature solid phase method. Y is2MoSiO8Singly doped Eu3+When excited at 395nm, the fluorescent powder can emit red light with peak values at 618nm and 595 nm. Eu (Eu)3+The concentration of the ions has an important effect on the emission intensity of the phosphor. Y is2MoSiO8：Eu3+，Dy3+When the fluorescent powder is excited at 370nm and 395nm, red light with peak values at 617nm and 611nm can be respectively emitted, and Eu in single doping is widened3+The absorption band of (3) improves the emission intensity. The invention has the advantages of simple preparation, high luminous efficiency of the product and easy industrialization.

Description

Molybdate fluorescent powder and preparation method thereof
Technical Field
The invention belongs to the field of white light LEDs, and particularly relates to preparation of molybdate fluorescent powder for the white light LEDs.
Background
LEDs are the most valuable light sources in the twenty-first century, being able to convert electrical energy into light energy. The current commercial white light LED is manufactured by using a blue LED chip and yellow phosphor (YAG: Ce)3+) The method has simple process and low cost, and the prepared material has high efficiency, but the LED emits light with red colorThe emitted light is cold white light, and has poor color rendering and low color rendering index. When the product is packaged, a proper amount of red fluorescent powder is doped into YAG (yttrium aluminum garnet): Ce3+Therefore, the search of the novel red fluorescent powder becomes a hot point of research, and has very important significance for improving the performance of the white light LED. In order to develop efficient and stable red fluorescent powder required by white light LEDs for illumination and further improve red light performance, researchers make a great deal of research. At present, the widely studied and mature red phosphor systems mainly include: garnet systems, sulfide systems, nitride systems, tungsten/molybdate systems, and the like. The fluorescent powder taking sulfide as a matrix is easy to decompose SO2Toxic gas and synthesis conditions which are not easy to reach by the silicon-based nitrogen oxide fluorescent powder, and the fuzzy understanding of the crystal structure and the like limit the wide application of the fluorescent powder.
Molybdate phosphor is a phosphor for LED developed in recent years. The luminescent material taking molybdate as the matrix has simple preparation method, and simultaneously, the molybdate has good physical and chemical stability and lower phonon energy, so the molybdate is an important matrix material in the field of luminescent materials. Molybdate is a self-activated luminescent material, has strong absorption in a near ultraviolet region, and can effectively transfer energy. Fluorescent powder using molybdate system as matrix also has the advantages of good luminescence property, stability and color purity, etc., so it has been receiving much attention in recent years. Current white LED has high thermal stability Y2MoSiO8：Eu3+Red phosphors have been reported to emit red light at 618nm and 595nm when excited at 395 nm. The luminous intensity and luminous efficiency of the fluorescent powder are the key points for using the same matrix. Eu (Eu)3+The activated fluorescent powder, particularly molybdate substrate fluorescent powder has the characteristics of high luminescent color purity, stable luminescent property and the like, so that the activated fluorescent powder is most hopeful to become red fluorescent powder for white light LED, but is Eu-coated3+Limited by narrow band absorption of Eu3+The activated red fluorescent powder has the problem of low luminous intensity. Thus, broadening Eu3+Absorption band of (2) to increase luminous intensityThe development of efficient and stable fluorescent powder is an important problem to be solved at present.
The molybdate has unique self-activating characteristic, wide intrinsic luminous band and pure-phase structure Y2MoSiO8：Eu3+The fluorescent powder can effectively excite the fluorescent powder under 395nm, red light is emitted at 595nm and 618nm, and the main peaks are 595nm and 618nm respectively. Can dope Eu in the matrix lattice3+And Dy3+The ions can make the luminous material have good luminous intensity and luminous efficiency. When excited below 395nm, Y2MoSiO8：Eu3+，Dy3+The phosphor can emit red light at a higher peak, so Eu3+And Dy3+The concentration of the ions has an important influence on the emission intensity of the phosphor.
Reference documents:
[1] white light LED status quo and related problems consider [ J ] science and technology perspectives, 2015,25(13):165.
[2].H.M.Zhu,C.C.Lin,W.Q.Luo,S.T.Shu,Z.G.Liu,Y.S.Liu,J.T.Kong,E.Ma,Y.G.Cao,R.S.Liu,X.Y.Chen,Highly efficient non-rare-earth red emittingphosphor for warm white light-emitting diodes,Nat.Commun.5(2014)4312.
Disclosure of Invention
The invention aims to provide molybdate fluorescent powder with high luminous intensity and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing molybdate phosphor, comprising: according to the molar ratio of Y, Mo, Si, Eu and Dy of 2: 1: 1: 0.03-0.09: 0.03-0.09, and preparing the molybdate fluorescent powder by adopting a high-temperature solid phase method.
Preferably, the raw material consists of Y2O3、MoO3、SiO2、Eu2O3And Dy2O3And (4) forming.
Preferably, the high temperature solid phase method comprises: mixing the raw materials, adding 1.5-2.0 wt% of NH4Grinding and mixing the F fluxing agent, putting the mixture into a corundum crucible, then putting the corundum crucible into a muffle furnace for high-temperature calcination, and then automatically calciningThen cooling and grinding to obtain the molybdate fluorescent powder.
More preferably, the high-temperature calcination temperature is 1200-1500 ℃, and the time is 4-6 hours.
The invention also provides the molybdate fluorescent powder prepared by the preparation method.
Furthermore, the molybdate fluorescent powder is Dy3+And Eu3+Doped Y2MoSiO8And (3) fluorescent powder.
Further, Dy is described3+The doping amount of the Eu is 5-9 percent3+The doping amount of the catalyst is 5 to 9 percent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention has low synthesis temperature and low cost.
(2) The powder has high luminous intensity, high luminous efficiency and good luminous performance.
(3) The fluorescent powder has good stability and excellent physical property and chemical property, and can be applied to white light LEDs.
(5) The preparation method of the invention is a high-temperature solid phase method, has simple process, does not need special equipment, has environment-friendly production process, small harm to operators and environment, low total organic matter amount, low production cost and easy control, and has the core of grinding and needs to uniformly mix various raw materials for reaction. The fluorescent powder prepared by the method has high brightness and simple process, and is suitable for mass production.
Drawings
FIG. 1 is Y after doping2MoSiO8：Dy3+，Eu3+XRD pattern of (a).
FIG. 2 is Y after doping2MoSiO8：Dy3+，Eu3+Spectrum of (a).
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Each raw material used in the following examples is a commercially available product.
Example 1
Preparation of molybdate fluorescent powder (Eu) by high-temperature solid-phase method3+，Dy3+The doping amount of 3 percent) comprises the following specific steps: according to the molar ratio of Y, Mo, Si, Eu and Dy of 2: 1: 1: 0.03: 0.03, weigh 1.1291gY2O3，0.7197gMoO3，0.3004gSiO2，0.05280gEu2O3，0.05595gDy2O3Mixing the raw materials, and adding 1.5 wt% of NH into the mixture4F fluxing agent is fully ground in an agate mortar for 1 hour to be uniformly mixed and then put into a corundum crucible, then the corundum crucible is put into a muffle furnace, the mixture is subjected to heat preservation and calcination at 1200 ℃ for 4 hours, and the molybdate fluorescent powder (Y) is obtained after the mixture is naturally cooled and then taken out and ground2MoSiO8：Dy3+，Eu3+). The particle size diameter is 2.3 μm, the sample powder is put into a sample chamber, an excitation wavelength is selected for emission spectrum scanning, and the emission main peak of the emission spectrum is read. And (3) giving an emission main peak of the emission spectrum, scanning the excitation spectrum, and reading out the peak wavelength of the excitation spectrum. Reloading, testing for 3 times, taking the arithmetic mean value of the difference of peak wavelength between each time not more than +1 nm. The strongest excitation wavelength was 370nm and the strongest emission wavelength was 617 nm. After sample powder is filled, the sample powder is placed in a sample chamber, an excitation wavelength is selected, the fluorescent powder is excited to emit light, and the emission spectrum power distribution of the fluorescent powder is obtained through testing by a spectrum radiation analyzer. And calculating the quantum efficiency of the fluorescent powder at the excitation wavelength. The samples were reloaded and tested 3 times for relative differences between each time. The quantum efficiency was 18.3%. The XRD results are shown in FIG. 1, and the spectrogram results are shown in FIG. 2.
Example 2
Preparation of molybdate fluorescent powder (Eu) by high-temperature solid-phase method3+，Dy3+The doping amount of 5 percent) comprises the following specific steps: according to the molar ratio of Y, Mo, Si, Eu and Dy of 2: 1: 1: 0.05: 0.05, title toAmount 1.1291gY2O3，0.7197gMoO3，0.3004gSiO2，0.0879gEu2O3，0.09325gDy2O3Mixing the raw materials, and adding 1.6 wt% of NH into the mixture4F fluxing agent is fully ground in an agate mortar for 1 hour to be uniformly mixed and then put into a corundum crucible, then the corundum crucible is put into a muffle furnace, the mixture is subjected to heat preservation and calcination at 1300 ℃ for 5 hours, and the mixture is naturally cooled and then taken out to be ground to obtain molybdate fluorescent powder (Y)2MoSiO8：Dy3+，Eu3+) The particle size diameter is 2.5 μm. After sample powder is filled, the sample powder is put into a sample chamber, an excitation wavelength is selected, emission spectrum scanning is carried out, and the emission main peak of the emission spectrum is read. And (3) giving an emission main peak of the emission spectrum, scanning the excitation spectrum, and reading out the peak wavelength of the excitation spectrum. Reloading, testing for 3 times, taking the arithmetic mean value of the difference of peak wavelength between each time not more than +1 nm. The strongest excitation wavelength was 395nm and the strongest emission wavelength was 611 nm. After sample powder is filled, the sample powder is placed in a sample chamber, an excitation wavelength is selected, the fluorescent powder is excited to emit light, and the emission spectrum power distribution of the fluorescent powder is obtained through testing by a spectrum radiation analyzer. And calculating the quantum efficiency of the fluorescent powder at the excitation wavelength. The samples were reloaded and tested 3 times for relative differences between each time. The quantum efficiency was 28.6%.
Example 3
Preparation of molybdate fluorescent powder (Eu) by high-temperature solid-phase method3+，Dy3+The doping amount of 7 percent) comprises the following specific steps: according to the molar ratio of Y, Mo, Si, Eu and Dy of 2: 1: 1: 0.07: 0.07, weigh 1.1291gY2O3，0.7197gMoO3，0.3004gSiO2，0.1231gEu2O3，0.1305gDy2O3Mixing the raw materials, and adding 1.8 wt% of NH into the mixture4F fluxing agent is fully ground in an agate mortar for 1 hour to be uniformly mixed and then put into a corundum crucible, then the corundum crucible is put into a muffle furnace to be thermally insulated and calcined at 1400 ℃ for 5 hours, and the molybdate fluorescent powder (Y) is obtained after being naturally cooled and then taken out and ground2MoSiO8：Dy3+，Eu3+) The particle size diameter was 2.6. mu.m. Putting the sample powder into the sampleIn the room, an excitation wavelength is selected, emission spectrum scanning is carried out, and the emission main peak of the emission spectrum is read. And (3) giving an emission main peak of the emission spectrum, scanning the excitation spectrum, and reading out the peak wavelength of the excitation spectrum. Reloading, testing for 3 times, taking the arithmetic mean value of the difference of peak wavelength between each time not more than +1 nm. The strongest excitation wavelength was 370nm and the strongest emission wavelength was 617 nm. After sample powder is filled, the sample powder is placed in a sample chamber, an excitation wavelength is selected, the fluorescent powder is excited to emit light, and the emission spectrum power distribution of the fluorescent powder is obtained through testing by a spectrum radiation analyzer. And calculating the quantum efficiency of the fluorescent powder at the excitation wavelength. The samples were reloaded and tested 3 times for relative differences between each time. The quantum efficiency was 24.0%.
Example 4
Preparation of molybdate fluorescent powder (Eu) by high-temperature solid-phase method3+，Dy3+The doping amount of 9 percent) comprises the following specific steps: according to the molar ratio of Y, Mo, Si, Eu and Dy of 2: 1: 1: 0.09: 0.09, weigh 1.1291gY2O3，0.7197gMoO3，0.3004gSiO2，0.1583gEu2O3，0.1678gDy2O3Mixing the raw materials, and adding 2.0 wt% of NH into the mixture4F fluxing agent is fully ground in an agate mortar for 1 hour to be uniformly mixed and then put into a corundum crucible, then the corundum crucible is put into a muffle furnace to be thermally insulated and calcined at 1500 ℃ for 6 hours, and the molybdate fluorescent powder (Y) is obtained after being taken out and ground after natural cooling2MoSiO8：Dy3+，Eu3+) The particle size diameter is 2.8 μm. After sample powder is filled, the sample powder is put into a sample chamber, an excitation wavelength is selected, emission spectrum scanning is carried out, and the emission main peak of the emission spectrum is read. And (3) giving an emission main peak of the emission spectrum, scanning the excitation spectrum, and reading out the peak wavelength of the excitation spectrum. Reloading, testing for 3 times, taking the arithmetic mean value of the difference of peak wavelength between each time not more than +1 nm. The strongest excitation wavelength was 370nm and the strongest emission wavelength was 617 nm. After sample powder is filled, the sample powder is placed in a sample chamber, an excitation wavelength is selected, the fluorescent powder is excited to emit light, and the emission spectrum power distribution of the fluorescent powder is obtained through testing by a spectrum radiation analyzer. Calculating the quantum of the fluorescent powder under the excitation wavelengthEfficiency. The samples were reloaded and tested 3 times for relative differences between each time. The quantum efficiency was 24.0%. The quantum efficiency was 43.1%.

Claims (7)

1. A preparation method of molybdate fluorescent powder is characterized by comprising the following steps: according to the molar ratio of Y, Mo, Si, Eu and Dy of 2: 1: 1: 0.03-0.09: 0.03-0.09, and preparing the molybdate fluorescent powder by adopting a high-temperature solid phase method.
2. The method of claim 1, wherein the source material is Y2O3、MoO3、SiO2、Eu2O3And Dy2O3And (4) forming.
3. The method of claim 1, wherein the high temperature solid phase method comprises: mixing the raw materials, adding 1.5-2.0 wt% of NH4And F, grinding and mixing the fluxing agent, placing the mixture into a corundum crucible, then placing the corundum crucible into a muffle furnace for high-temperature calcination, naturally cooling, and grinding to obtain the molybdate fluorescent powder.
4. The method of claim 3, wherein the high temperature calcination is at 1500 ℃ and 1200 ℃ for 4-6 hours.
5. The molybdate phosphor of claim 1.
6. The molybdate phosphor of claim 5, wherein the molybdate phosphor is Dy3+And Eu3+Doped Y2MoSiO8And (3) fluorescent powder.
7. The molybdate phosphor of claim 5, wherein Dy is present3+The doping amount of the Eu is 5-9 percent3+Amount of doping5 to 9 percent.
CN201911062224.4A 2019-11-02 2019-11-02 Molybdate fluorescent powder and preparation method thereof Pending CN110713834A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285986A (en) * 2022-01-28 2023-06-23 有研稀土新材料股份有限公司 Luminescent material and luminescent device comprising same

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
G. RAMAKRISHNA ET AL.: "White light emission and energy transfer (Dy3+→Eu3+) in combustion synthesized YSO: Dy3+, Eu3+ nanophosphors", 《OPTIK》 *
GUOYI DONG ET AL.: ""A novel red Y2MoSiO8:Eu3+ phosphor with high thermal stability for white LEDs", 《CERAMICS INTERNATIONAL》 *
JING WAN ET AL.: "Energy transfer and colorimetric properties of Eu3+/Dy3+ co-doped Gd2(MoO4)3 phosphors", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285986A (en) * 2022-01-28 2023-06-23 有研稀土新材料股份有限公司 Luminescent material and luminescent device comprising same
CN116285986B (en) * 2022-01-28 2024-02-27 有研稀土新材料股份有限公司 Luminescent material and luminescent device comprising same

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Application publication date: 20200121