CN112852415B - High-color-purity and high-stability light-emitting green fluorescent powder and preparation method thereof - Google Patents
High-color-purity and high-stability light-emitting green fluorescent powder and preparation method thereof Download PDFInfo
- Publication number
- CN112852415B CN112852415B CN202110032822.8A CN202110032822A CN112852415B CN 112852415 B CN112852415 B CN 112852415B CN 202110032822 A CN202110032822 A CN 202110032822A CN 112852415 B CN112852415 B CN 112852415B
- Authority
- CN
- China
- Prior art keywords
- equal
- compound
- ion
- fluorescent powder
- doping
- 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.)
- Active
Links
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
- C09K11/63—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing boron
-
- 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
Abstract
A luminescent green fluorescent powder with high color purity and high stability and a preparation method thereof, the fluorescent powder has a tetragonal crystal structure and a chemical formula of (Mg) 1‑x‑y Sr x Mn y ) 4 B 6 O 13 In the formula, xIs Sr 2+ Doping with Mg 2+ The molar ratio of the sites, x is more than or equal to 0.1 and less than or equal to 0.3, y is Mn 2+ Doping with Mg 2+ The molar ratio of the sites is more than or equal to 0.005 and less than or equal to 0.02. The preparation method comprises the following steps: weighing the raw materials and the cosolvent, ball-milling and mixing uniformly, placing the mixture in a muffle furnace for drying, then placing the mixture in air for calcination at the calcination temperature of 800-1000 ℃ for 5-7 h, and naturally cooling the mixture to room temperature to obtain the green phosphor. The phosphor prepared by the invention has better dispersibility, complete crystal lattice development, high luminous efficiency and good stability; the whole luminescent system has rich and easily obtained raw material sources, simple and flexible preparation method and low production cost, and can be used in the fields of high-quality backlight sources, projection, illumination and the like.
Description
Technical Field
The invention relates to a fluorescent material and a preparation method thereof, in particular to luminescent green fluorescent powder with high color purity and high stability and a preparation method thereof, belonging to the technical field of luminescent materials.
Background
Phosphor-converted white light emitting diodes (pc-WLEDs) have attracted much attention in the fields of illumination and display due to their advantages of low power consumption, high luminous efficiency, long life, and the like. With the rapid development of the Liquid Crystal Display (LCD) backlight market, the color quality (i.e., wide color gamut) of pc-WLED is increasingly required. Currently, the most widely used light sources in commercial LCD backlights only reach about 80% of the National Television Standards Committee (NTSC)And (4) right. Such as blue LED chips with yellow emitting Y 3 Al 5 O 12 :Ce 3+ Phosphor and red-emitting Sr 2 Si 5 N 8 :Eu 2+ The mixture of phosphors is coupled due to Y 3 Al 5 O 12 :Ce 3+ Insufficient green emission and Y 3 Al 5 O 12 :Ce 3+ And Sr 2 Si 5 N 8 :Eu 2+ The maximum full width at half maximum (FWHM) is greater than 100nm and 90nm, respectively, and therefore, the light source obtained by the above method can only reach 80% of the NTSC standard in the CIE 1931 standard chromaticity system. To achieve a wide color gamut, the development of narrow-band green or red emitting phosphors is imminent. Since the human eye is more sensitive to green than any other color, the green phosphor is a key component to achieve a wide color gamut.
Currently, eu 2+ Doped oxy/nitridosilicates are the most commonly used green materials due to their excellent photoluminescence properties and excellent chemical thermal stability. Such as Ba 2 LiSi 7 AlN 12 ：Eu 2+ (FWHM～61nm)、Ba[Li 2 (Al 2 Si 2 )N 6 ]：Eu 2+ (FWHM-57 nm) and beta-SiAlON: eu (Eu) 2+ (FWHM-55 nm). However, the above phosphor powder still has the following disadvantages: (1) The synthesis needs the coordination of nitride compounds and has harsh conditions, thereby greatly increasing the preparation cost; (2) Wavelengths typically greater than 50nm limit the color gamut of the fabricated device to 90% of the NTSC standard. Therefore, it would be extremely valuable to prepare stable green emitting phosphors with narrower molecular weights under mild synthesis conditions.
In addition to the lanthanide ion doped oxide/nitride described above, the transition metal Mn 2+ Ion-doped oxides have attracted attention as green-emitting phosphor powders in light-emitting diodes because of their low-cost preparation methods. Benefit from Mn 2+ Specific spectral characteristics (d-d transition), mn 2+ FWHM-18-45 nm of doped green phosphor powder is higher than rare earth Eu 2+ /Ce 3+ The activated green emitting phosphor is narrower. It is well known that green emission can be derived from Mn 2+ OccupyThe tetrahedral cation sites in the host lattice are obtained, thus developing a Mn 2+ The ion-doped oxide is especially important as narrow-band green fluorescent powder and a preparation method thereof.
Disclosure of Invention
The invention aims to provide the luminescent green fluorescent powder with high color purity and high stability and the preparation method thereof, the method is simple to operate and low in production cost, and the prepared green fluorescent powder has the advantages of high color purity, excellent thermal stability and the like and can be used in the fields of high-quality backlight sources, projection, illumination and the like.
In order to realize the purpose, the invention adopts the technical scheme that: a high-purity and high-stability luminous green fluorescent powder with tetragonal crystal structure and chemical formula (Mg) 1-x-y Sr x Mn y ) 4 B 6 O 13 In the formula, strontium ion Sr 2+ As crystal phase stabilizer, x is Sr 2+ Doping with Mg 2+ The molar ratio of x is more than or equal to 0.1 and less than or equal to 0.3, and manganese ions Mn 2+ For activating ions, y is Mn 2+ Doping with Mg 2 + The molar ratio of the sites is more than or equal to 0.005 and less than or equal to 0.02.
The preparation method of the luminescent green fluorescent powder with high color purity and high stability comprises the following steps:
(1) By containing magnesium ions Mg 2+ Compound of (2), containing strontium ion Sr 2+ Compound (b) containing manganese ion Mn 2+ Compound of (2), containing boron ion B 3+ Is prepared from the compound of formula (Mg) 1-x-y Sr x Mn y ) 4 B 6 O 13 Weighing the raw materials according to the stoichiometric ratio of the corresponding elements, wherein x is Sr 2+ Doping with Mg 2+ The mole ratio of the sites, x is more than or equal to 0.1 and less than or equal to 0.3, y is Mn 2+ Doping with Mg 2+ The molar ratio of the sites, and y is more than or equal to 0.005 and less than or equal to 0.02; weighing a fluxing agent, wherein the adding amount of the fluxing agent is 30-45 wt% of the total mass of the raw material powder;
(2) Ball-milling the weighed raw materials and the cosolvent until the raw materials are fully and uniformly mixed;
(3) Placing the uniformly mixed raw materials in a muffle furnace for drying;
(4) And (4) calcining the mixture dried in the step (3) in the air at the calcining temperature of 800-1000 ℃ for 5-7 h, naturally cooling to room temperature, and grinding again to obtain the luminescent green fluorescent powder with high color purity and high stability.
Preferably, said magnesium ions contain Mg 2+ The compound of (b) is magnesium oxide; the strontium ion Sr 2+ The compound of (a) is strontium oxide; the manganese ion Mn is contained 2+ The compound of (1) is manganese carbonate; the boron ion B 3+ The compound of (a) is boric acid.
Preferably, the cosolvent is ammonium chloride.
Preferably, the pre-calcination temperature in the step (4) is 800 ℃, and the calcination time is 5h.
Compared with the prior art, the invention has the following advantages:
(1) The green fluorescent powder prepared according to the technical scheme of the invention has the advantages of good dispersibility, more complete crystal lattice development, high luminous efficiency and good stability;
(2) The whole luminescent system does not contain any rare earth element, the adopted matrix element raw materials are rich and easily available, the preparation method is simple, feasible and flexible, and the production cost is low;
(3) Under the excitation of the wavelength of 450nm of ultraviolet light or blue light, the center of the emission wavelength is positioned near 540nm, the full width at half maximum is only 18-20nm, the color purity is as high as 90-95%, the green fluorescence has more pure chromaticity, and bright green fluorescence can be emitted; meanwhile, the prepared powder has inhibited non-radiative transition, presents excellent thermal stability, has luminous attenuation of only 5-10% at 150 ℃, and can be used in the fields of high-quality backlight sources, projection, illumination and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a sample prepared according to one embodiment of the invention;
FIG. 2 is a photograph of a sample prepared according to an embodiment of the present invention under UV irradiation;
FIG. 3 is a photograph of a sample prepared according to example two of the present invention under UV irradiation;
FIG. 4 is a photograph of a sample prepared according to a third embodiment of the present invention under UV irradiation;
FIG. 5 is a graph of the emission spectrum of samples prepared in the first to third embodiments of the present invention under 450nm wavelength excitation.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Example one
Preparation (Mg) 0.895 Sr 0.1 Mn 0.005 ) 4 B 6 O 13 : according to the formula (Mg) 0.895 Sr 0.1 Mn 0.005 ) 4 B 6 O 13 The stoichiometric ratio of each element in the raw materials is respectively called as: magnesium oxide MgO:3.65g, strontium oxide SrO:1.05g of manganese carbonate MnCO 3 :0.06g of boric acid H 3 BO 3 :9.37g, 4.25g of NH as a flux was added 4 Cl, wherein the addition amount of the Cl is 30% of the total mass of the raw material powder; adding the raw materials and the cosolvent into a ball mill, fully and uniformly mixing the raw materials, and then placing the mixture into a muffle furnace for drying; and after drying, calcining the mixture in the air at 800 ℃ for 5h, naturally cooling to room temperature, and grinding again to obtain the luminescent green fluorescent powder with high color purity and high stability.
Referring to FIG. 1, a sample (Mg) prepared according to the protocol of this example is shown 0.895 Sr 0.1 Mn 0.005 ) 4 B 6 O 13 Scanning Electron Microscopy (SEM) of (A), as can be seen in the figure, provides (Mg) 0.895 Sr 0.1 Mn 0.005 ) 4 B 6 O 13 The green fluorescent powder particles are uniformly dispersed, the dispersibility is better, and the crystal lattice development is complete, which indicates that the reaction is completely carried out.
Referring to FIG. 2, the sample (Mg) prepared according to the embodiment 0.895 Sr 0.1 Mn 0.005 ) 4 B 6 O 13 The picture of the real object under the ultraviolet light shows that the crystal lattice is completely developed, which indicates that the reaction is completely performed.
Referring to FIG. 5, a sample (Mg) prepared according to the protocol of this example is shown 0.895 Sr 0.1 Mn 0.005 ) 4 B 6 O 13 The luminescence spectrum under the excitation of 450nm wavelength shows that the sample has the highest luminescence peak at 540nm wavelength under the excitation of 450nm wavelength light, the full width at half maximum is only 18nm, the color purity is as high as 90 percent, and the sample can be used in the fields of high-quality backlight source, projection, illumination and the like.
Example two
Preparation (Mg) 0.88 Sr 0.1 Mn 0.02 ) 4 B 6 O 13 : according to the formula (Mg) 0.88 Sr 0.1 Mn 0.02 ) 4 B 6 O 13 The stoichiometric ratio of each element in the raw materials is respectively called as: magnesium oxide MgO:3.57g, strontium oxide SrO:0.26g of manganese carbonate MnCO 3 :0.23g of boric acid H 3 BO 3 :9.32, 4.7g of flux NH were added 4 Cl, wherein the addition amount of the Cl is 35% of the total mass of the raw material powder; adding the raw materials and the cosolvent into a ball mill, fully and uniformly mixing the raw materials, and then placing the mixture into a muffle furnace for drying; and after drying, calcining the mixture in air at 850 ℃ for 6h, naturally cooling to room temperature, and grinding again to obtain the luminescent green fluorescent powder with high color purity and high stability.
SEM images of samples prepared in this example are consistent with those prepared in example 1.
Referring to FIG. 3, a sample (Mg) prepared according to the embodiment 0.88 Sr 0.1 Mn 0.02 ) 4 B 6 O 13 The physical photograph under UV irradiation shows that the lattice is completely developed, indicating that the reaction is complete.
Referring to FIG. 5, a sample (Mg) prepared according to the embodiment 0.88 Sr 0.1 Mn 0.02 ) 4 B 6 O 13 The luminescence spectrum under the excitation of 450nm wavelength shows that the sample has the highest luminescence peak at 540nm wavelength under the excitation of 450nm wavelength light, the full width at half maximum is only 20nm, and the color purity is as high as90 percent, can be used in the fields of high-quality backlight, projection, illumination and the like.
EXAMPLE III
Preparation (Mg) 0.68 Sr 0.3 Mn 0.02 ) 4 B 6 O 13 : according to the formula (Mg) 0.68 Sr 0.3 Mn 0.02 ) 4 B 6 O 13 The stoichiometric ratio of each element in the raw materials is respectively called as: magnesium oxide MgO:2.44g, strontium oxide SrO:0.69g of manganese carbonate MnCO 3 :0.21g of boric acid H 3 BO 3 :8.27, 5.15g of flux NH were added 4 Cl, wherein the adding amount of the Cl is 44% of the total mass of the raw material powder; adding the raw materials and the cosolvent into a ball mill, fully and uniformly mixing the raw materials, and then placing the mixture into a muffle furnace for drying; and after drying, calcining the mixture in the air at the calcining temperature of 1000 ℃ for 7h, naturally cooling to room temperature, and grinding again to obtain the luminescent green fluorescent powder with high color purity and high stability.
SEM images of samples prepared in this example are consistent with those prepared in example 1.
Referring to FIG. 4, the sample (Mg) prepared according to the embodiment 0.68 Sr 0.3 Mn 0.02 ) 4 B 6 O 13 The picture of the real object under the ultraviolet light shows that the crystal lattice is completely developed, which indicates that the reaction is completely performed.
Referring to FIG. 5, a sample (Mg) prepared according to the protocol of this example is shown 0.68 Sr 0.3 Mn 0.02 ) 4 B 6 O 13 The luminescence spectrum under the excitation of 450nm wavelength shows that the sample has the highest luminescence peak at 540nm wavelength under the excitation of 450nm wavelength light, the full width at half maximum is only 19nm, the color purity is up to 90 percent, and the sample can be used in the fields of high-quality backlight sources, projection, illumination and the like.
Claims (5)
1. A high-purity and high-stability luminous green fluorescent powder is characterized in that the fluorescent powder has a tetragonal crystal structure and has a chemical formula of (Mg) x-y1- Sr x Mn y ) 4 B 6 O 13 In the formula, strontium ion Sr 2+ Is a crystal phase stabilizer and is used as a crystal phase stabilizer,xis Sr 2+ Doping with Mg 2+ The molar ratio of the units is more than or equal to 0.1xLess than or equal to 0.3, manganese ion Mn 2+ In order to activate the ions, the ion beam is irradiated,yis Mn 2+ Doping with Mg 2+ The molar ratio of the units is more than or equal to 0.005y≤0.02。
2. The method for preparing the high color purity and high stability light-emitting green phosphor of claim 1, comprising the steps of:
(1) By containing magnesium ions Mg 2+ Compound of (5), containing strontium ion Sr 2+ Compound of (2), containing manganese ion Mn 2+ Compound of (2), containing boron ion B 3+ Is prepared from the compound of formula (Mg) x-y1- Sr x Mn y ) 4 B 6 O 13 Weighing the raw materials according to the stoichiometric ratio of the corresponding elements, whereinxIs Sr 2+ Doping with Mg 2+ The mole ratio of the units is more than or equal to 0.1x≤0.3，yIs Mn 2+ Doping with Mg 2+ The mole ratio of the units is more than or equal to 0.005yLess than or equal to 0.02; weighing a fluxing agent, wherein the adding amount of the fluxing agent is 30-45 wt% of the total mass of the raw material powder;
(2) Ball-milling the weighed raw materials and a fluxing agent until the raw materials are fully and uniformly mixed;
(3) Placing the uniformly mixed raw materials in a muffle furnace for drying;
(4) And (4) calcining the mixture dried in the step (3) in the air at the calcining temperature of 800-1000 ℃ for 5-7 h, naturally cooling to room temperature, and grinding again to obtain the luminescent green fluorescent powder with high color purity and high stability.
3. The method for preparing a high purity, high stability green emitting phosphor according to claim 2, wherein said phosphor contains magnesium ion Mg 2+ The compound of (a) is magnesium oxide; the strontium ion Sr 2+ The compound of (A) isStrontium oxide; the manganese ion Mn is contained 2+ The compound of (1) is manganese carbonate; the boron ion B 3+ The compound of (a) is boric acid.
4. The method according to claim 2 or 3, wherein the flux is ammonium chloride.
5. The method for preparing a high color purity and high stability light-emitting green phosphor according to claim 2 or 3, wherein the calcination temperature in the step (4) is 800 ℃ and the calcination time is 5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110032822.8A CN112852415B (en) | 2021-01-11 | 2021-01-11 | High-color-purity and high-stability light-emitting green fluorescent powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110032822.8A CN112852415B (en) | 2021-01-11 | 2021-01-11 | High-color-purity and high-stability light-emitting green fluorescent powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112852415A CN112852415A (en) | 2021-05-28 |
| CN112852415B true CN112852415B (en) | 2023-04-07 |
Family
ID=76002534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110032822.8A Active CN112852415B (en) | 2021-01-11 | 2021-01-11 | High-color-purity and high-stability light-emitting green fluorescent powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112852415B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102559179B (en) * | 2011-12-31 | 2014-11-05 | 浙江工业大学 | Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof |
| CN103468255B (en) * | 2013-09-26 | 2015-03-25 | 苏州大学 | Chlorine borate luminescent material and preparation method thereof |
| CN104845617B (en) * | 2015-04-30 | 2016-08-24 | 陕西师范大学 | A kind of Zn4b6o13: Eu3+the simple method for preparing of luminescent material |
| CN106947473B (en) * | 2017-03-30 | 2019-10-08 | 厦门理工学院 | A kind of praseodymium doped borate red luminescent material and preparation method and its usage |
| CN109536161A (en) * | 2018-12-21 | 2019-03-29 | 厦门理工学院 | A kind of compound aluminate red luminescent material of additive Mn and its preparation method and application |
| CN110041921A (en) * | 2019-05-08 | 2019-07-23 | 南京邮电大学 | A kind of manganese ion activated green emitting phosphor and preparation method thereof |
| CN110591707B (en) * | 2019-09-05 | 2021-03-02 | 常州工程职业技术学院 | Mn (manganese)2+Activated vanadium phosphate inorganic fluorescent powder and preparation method and application thereof |
-
2021
- 2021-01-11 CN CN202110032822.8A patent/CN112852415B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112852415A (en) | 2021-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7755276B2 (en) | Aluminate-based green phosphors | |
| US8951440B2 (en) | Nitride-based red-emitting phosphors in RGB (red-green-blue) lighting systems | |
| KR101812997B1 (en) | Silicate phosphor, method of manufacturing silicate phosphor, and light-generating device having silicate phosphor | |
| US8158026B2 (en) | Method for preparing B-Sialon phosphor | |
| JP5970534B2 (en) | Oxynitride phosphor | |
| US20130140490A1 (en) | Silicon Nitride Powder for Siliconnitride Phosphor, CaAlSiN3 Phosphor Using Same, Sr2Si5N8 Phosphor Using Same, (Sr, Ca)AlSiN3 Phosphor Using Same, La3Si6N11Phosphor Using Same, and Methods for Producing the Phosphors | |
| US7618556B2 (en) | Phosphor for white light-emitting device and white light-emitting device including the same | |
| CN103314074B (en) | Sialon phosphor, method for producing same, and light-emitting device package using same | |
| CN113444521B (en) | Red fluorescent powder and light-emitting device with same | |
| US20130140491A1 (en) | Green to Yellow Light-Emitting Aluminate Phosphors | |
| WO2013056408A1 (en) | Red light-emitting nitride material, and light-emitting part and light-emitting device comprising same | |
| CN107722982A (en) | Silicon substrate nitrogen oxides hanced cyan fluorescent powder of Fluorescence Increasing and preparation method thereof | |
| US20230159824A1 (en) | Green-Emitting Phosphors and Devices Thereof | |
| US20100219376A1 (en) | Red phosphor material and manufacturing method thereof | |
| CN110591711A (en) | Gallate red fluorescent powder for white light LED and preparation method thereof | |
| CN112852415B (en) | High-color-purity and high-stability light-emitting green fluorescent powder and preparation method thereof | |
| CN102399554B (en) | Nitride red luminescence material, and luminescent part and luminescent device containing the same | |
| CN101717638A (en) | Fluorescent powder for field emission and method for preparing same | |
| KR20130057157A (en) | Oxinitride phosphor and light emitting device comprising the same | |
| JP2011202002A (en) | Phosphor | |
| KR101335522B1 (en) | Phosphors for blue-light excitation, a method for producing the same and white light emitting diode comprising the same | |
| KR101617690B1 (en) | Oxide Red Phosphor and Method for Preparing the Same | |
| KR20180120611A (en) | Excitation light property improved Ba-Al-O based phosphor, manufacturing method of the same and light emitting device comprising the same | |
| JP2017206599A (en) | Phosphor, light emitting device, illumination device and image display device | |
| KR20120106468A (en) | Silicate-based phosphor and light emitting device having the same |
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 |