CN112852415A - 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
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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‑ySrxMny)4B6O13In the formula, x is Sr2+Doping with Mg2+The molar ratio of x is more than or equal to 0.1 and less than or equal to 0.3, and y is Mn2+Doping with Mg2+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 fluorescent powder prepared by the invention has good 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 demand for pc-WLED color quality (i.e., wide color gamut) is increasing. Currently, the most widely used light sources in commercial LCD backlights only reach around 80% of the National Television Standards Committee (NTSC). Such as blue LED chips with yellow emitting Y3Al5O12:Ce3+Phosphor and red-emitting Sr2Si5N8:Eu2+The phosphor mixture is coupled due to Y3Al5O12:Ce3+Insufficient green emission and Y3Al5O12:Ce3+And Sr2Si5N8:Eu2+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.
At present, Eu2+Doped oxy/nitridosilicates are the most commonly used green materials due to their excellent photoluminescence properties and excellent chemical thermal stability. Such as Ba2LiSi7AlN12：Eu2+(FWHM～61nm)、Ba[Li2(Al2Si2)N6]：Eu2+(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) the wavelength is typically greater than 50nm, limiting 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 Mn2+Ion-doped oxides have attracted attention as green-emitting phosphor powders in light-emitting diodes because of their low-cost preparation process. Benefiting from Mn2+Specific spectral characteristics (d-d transition), Mn2+FWHM-18-45 nm of doped green phosphor powder is higher than rare earth Eu2+/Ce3+The activated green emitting phosphor is narrower. It is well known that green emission can be derived from Mn2+Occupying the cationic sites of the tetrahedra in the host lattice, thus developing a Mn2+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 achieve 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-ySrxMny)4B6O13In the formula, strontium ion Sr2+Is a crystal phase stabilizer, x is Sr2+Doping with Mg2+The molar ratio of x is more than or equal to 0.1 and less than or equal to 0.3, and manganese ions Mn2+For activating the ions, y is Mn2+Doping with Mg2 +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 Mg2+Compound of (5), containing strontium ion Sr2+Compound of (2), containing manganese ion Mn2+Compound of (2), containing boron ion B3+Is prepared from the compound of formula (Mg)1-x-ySrxMny)4B6O13Weighing the raw materials according to the stoichiometric ratio of the corresponding elements, wherein x is Sr2+Doping with Mg2+The molar ratio of the sites, x is more than or equal to 0.1 and less than or equal to 0.3, and y is Mn2+Doping with Mg2+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 (3) calcining the mixture dried in the step (3) in the air at 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 containing Mg2+The compound of (a) is magnesium oxide; the strontium ion Sr2+The compound of (a) is strontium oxide; the manganese ion Mn is contained2+The compound of (1) is manganese carbonate; the boron ion B3+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 5 h.
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 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 up to 90-95%, the chromaticity of green fluorescence is more pure, 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 luminescence spectrum of samples prepared in the first to third examples of the present invention under the excitation of a wavelength of 450 nm.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Example one
Preparation (Mg)0.895Sr0.1Mn0.005)4B6O13: according to the formula (Mg)0.895Sr0.1Mn0.005)4B6O13The 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 MnCO3: 0.06g of boric acid H3BO3: 9.37g of flux NH 4.25g was added4Cl, wherein the addition amount of the Cl is 30% of the total mass of the raw material powder; mixing the above raw materials and dissolving assistantAdding the agent 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 shown0.895Sr0.1Mn0.005)4B6O13As can be seen from the Scanning Electron Micrograph (SEM) of (Mg)0.895Sr0.1Mn0.005)4B6O13The 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, a sample (Mg) prepared according to the protocol of this example is shown0.895Sr0.1Mn0.005)4B6O13The 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 shown0.895Sr0.1Mn0.005)4B6O13The 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)0.88Sr0.1Mn0.02)4B6O13: according to the formula (Mg)0.88Sr0.1Mn0.02)4B6O13The 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 MnCO3: 0.23g of boric acid H3BO3: 9.32, 4.7g of flux NH were added4Cl, wherein the addition amount of the Cl is 35% of the total mass of the raw material powder; mixing the above raw materials and dissolving assistantAdding the agent 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 protocol of this example is shown0.88Sr0.1Mn0.02)4B6O13The 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 shown0.88Sr0.1Mn0.02)4B6O13The 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, 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.
EXAMPLE III
Preparation (Mg)0.68Sr0.3Mn0.02)4B6O13: according to the formula (Mg)0.68Sr0.3Mn0.02)4B6O13The 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 MnCO3: 0.21g of boric acid H3BO3: 8.27, 5.15g of flux NH were added4Cl, wherein the addition 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 in 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, a sample (Mg) prepared according to the protocol of this example is shown0.68Sr0.3Mn0.02)4B6O13The 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 shown0.68Sr0.3Mn0.02)4B6O13The 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)1-x-ySrxMny)4B6O13In the formula, strontium ion Sr2+Is a crystal phase stabilizer, x is Sr2+Doping with Mg2+The molar ratio of x is more than or equal to 0.1 and less than or equal to 0.3, and manganese ions Mn2+For activating the ions, y is Mn2+Doping with Mg2+The molar ratio of the sites is more than or equal to 0.005 and less than or equal to 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 Mg2+Compound of (5), containing strontium ion Sr2+Compound of (2), containing manganese ion Mn2+Compound of (2), containing boron ion B3+Is prepared from the compound of formula (Mg)1-x-ySrxMny)4B6O13Weighing the raw materials according to the stoichiometric ratio of the corresponding elements, wherein x is Sr2+Doping with Mg2+The molar ratio of the sites, x is more than or equal to 0.1 and less than or equal to 0.3, and y is Mn2+Doping with Mg2+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 (3) calcining the mixture dried in the step (3) in the air at 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 of claim 2, wherein the phosphor contains Mg ions2+The compound of (a) is magnesium oxide; the strontium ion Sr2+The compound of (a) is strontium oxide; the manganese ion Mn is contained2+The compound of (1) is manganese carbonate; the boron ion B3+The compound of (a) is boric acid.
4. The method for preparing a high-color-purity high-stability light-emitting green phosphor according to claim 2 or 3, wherein the cosolvent 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 pre-calcination temperature in step (4) is 800 ℃ and the calcination time is 5 h.
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