CN110684527A - Mn-doped blue light excitation4+Hexafluoroferrite red luminescent material and synthetic method thereof - Google Patents
Mn-doped blue light excitation4+Hexafluoroferrite red luminescent material and synthetic method thereof Download PDFInfo
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- CN110684527A CN110684527A CN201910670906.7A CN201910670906A CN110684527A CN 110684527 A CN110684527 A CN 110684527A CN 201910670906 A CN201910670906 A CN 201910670906A CN 110684527 A CN110684527 A CN 110684527A
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
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Abstract
The invention relates to the field of inorganic functional materials, and discloses a blue light excited Mn-doped material4+The hexafluoroferrite red luminescent material and the synthesis method thereof. The invention relates to Mn-doped with blue light excitation4+The chemical composition of the hexafluoroferrite red luminescent material is Cs2KFe1‑xF6:xMn4+(ii) a x is the corresponding doping Mn4+Ion relative to Fe3+Molar percentage coefficient of ion, 0<x is less than or equal to 0.10. The red luminescent material provided by the invention mainly emits red light of about 633 nm under the excitation of blue light, and has high luminous efficiency. The invention relates to blue light excited Mn-doped4+The preparation method of the hexafluoroferrite red luminescent material is a liquid phase method, is carried out at normal temperature, has simple synthesis process and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to Mn-doped material excited by blue light4+The hexafluoroferrite red luminescent material and the preparation method thereof belong to the field of inorganic functional material synthesis.
Background
The solid-state illumination light source based on the blue light GaN chip is widely applied to daily life and work of people due to a series of advantages of energy conservation, high efficiency, low starting voltage and the like. In order to obtain a warm white LED with low color temperature and high color rendering index for better application to indoor lighting or other special fields, a certain amount of red phosphor is often required to be added during the manufacturing process of the white LED device to enhance the emission of the white LED in the red region. Therefore, the luminous efficiency of the red fluorescent powder seriously influences the luminous performance of the warm white LED device.
In recent years, Mn4+Has been widely used as a red light emission center in various luminescent materials. Such as Mn4+The activated fluoride red luminescent materials can be perfectly matched with blue light emission of a GaN chip because the strongest excitation band of the activated fluoride red luminescent materials is positioned in a blue light region, so that the red luminescent materials have high red emission efficiency and high color purity. For example hexafluoro compound A2XF6(A is Na, K, Rb, etc.; X is Ti, Si, Sn, Ge, etc.) Mn-doped4+The luminescence property of red phosphor has been widely reported.
In the present invention, we report the successful development of a new blue-light efficiently excited Mn in hydrofluoric acid solution4+Activated hexafluoroferrite red luminescent material Cs2KFe1-xF6:xMn4+(x is the corresponding doping Mn4+Ion relative to Fe3+Molar percentage coefficient of ion, 0<x is less than or equal to 0.10) and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a blue light excited Mn-doped alloy4+The hexafluoroferrite red luminescent material.
Another object of the present invention is to provide a method for preparing the above red light emitting material.
In order to achieve the above objects, the present invention relates to blue light excited Mn-doped4+The hexafluoroferrite red luminescent material comprises the following chemical components: cs2KFe1-xF6:xMn4+(ii) a x is the corresponding doping Mn4+Ion relative to Fe3+Ion stationCoefficient of mole percent, 0<x is less than or equal to 0.10, the raw materials used by the invention comprise, by mass, 58.0 ~ 63.0.0% of cesium fluoride, 8.0 ~ 11.0.0% of potassium fluoride, 0.2 ~ 10.0.0% of potassium hexafluoromanganate, 14.0 ~ 20% of ferric oxide and 8.0 ~ 15.0.0% of hydrofluoric acid.
The wavelength of the blue light is 440-490 nm.
The preparation method of the red luminescent material adopts a liquid phase method, and various raw materials are in the stoichiometric ratio. The method specifically comprises the following steps: firstly, adding ferric oxide and potassium hexafluoromanganate into a hydrofluoric acid solution, stirring for 30-60 minutes until the ferric oxide and the potassium hexafluoromanganate are completely dissolved, then adding potassium fluoride and cesium fluoride, and continuously stirring for 2-6 hours. Washing the obtained precipitate with anhydrous ethanol and glacial acetic acid for 3 times, and drying in vacuum drying oven for 24 hr to obtain orange red powder as final product.
The red luminescent material of the invention shows strong red light emission (the emission peak is about 633 nm) under the excitation of blue light, and the luminous efficiency is high. The CIE value of the emission spectrum of the sample is close to the standard value (national television Standard Committee) of red NTSC (national television Standard)x= 0.67,y= 0.33)。
Drawings
FIG. 1 shows Cs in example 12KFeF6: Mn4+XRD diffractogram of (a);
FIG. 2 shows Cs in example 12KFeF6: Mn4+Scanning electron microscope pictures;
FIG. 3 shows Cs in example 12KFeF6:Mn4+Room temperature excitation spectrum (monitoring wavelength of 633 nm) and emission spectrum (excitation wavelength of 453 nm);
FIG. 4 shows Cs in example 12KFeF6:Mn4+And commercial YAG Ce3+An electroluminescence spectrogram of a warm white LED device manufactured by the yellow fluorescent powder and the blue LED chip under the excitation of 20 mA current.
Detailed Description
Example 1:
0.76 g of iron trioxide and 0.12 g of potassium hexafluoromanganate were dissolved in 50ml of hydrofluoric acid (40 wt%), stirred at room temperature for 60 minutes until the dissolution was completed, and 0.58 g of potassium fluoride and 3.04 g of cesium fluoride were further added to this solution to react for 3 hours. Washing the precipitate with anhydrous ethanol and glacial acetic acid for 3 times, and drying in vacuum drying oven for 24 hr to obtain orange red powder as final product Cs2KFeF6:Mn4+。
The XRD diffraction pattern of the phosphor is shown in figure 1, and the diffraction peak and matrix Cs of the sample2KFeF6The JCPDS82-2216 card is completely consistent, and no diffraction peak of any hetero-phase is observed, which indicates that the synthesized sample has high purity and is in a three-dimensional crystal structure.
FIG. 2 shows Cs2KFeF6: Mn4+The particle size of the sample is 1-3 μm.
FIG. 3 shows the room temperature excitation spectrum (monitored wavelength at 633 nm) and the emission spectrum (excitation wavelength at 453 nm) of a sample, which shows strong broadband excitation in both the UV (320 nm ~ 390 nm) and blue (400 nm ~ 500 nm), with the strongest excitation peak at about 453 nm, the emission of the sample under 453 nm blue excitation is a series of peaks, with the strongest emission peak at about 633 nm, the spectral CIE coordinate values are:x=0.695,y= 0.305. Our sample CIE values are close to the Standard values of red NTSC (national Television Standard Committee) ((R))x=0.67,y=0.33)
FIG. 4 shows Cs2KFeF6:Mn4+And commercial YAG Ce3+An electroluminescence spectrogram of a warm white LED device manufactured by yellow fluorescent powder and a blue LED chip under the excitation of 20 mA current, wherein the emission peak of ~ 460nm blue light is originated from the emission of a GaN chip, and the emission peak in the range of 500nm to 600nm is originated from YAG (yttrium aluminum garnet): Ce3+Yellow light emission. The emission of our samples is in the red region, with the strongest emission at 633 nm. The warm white LED has low color temperature and high color rendering index.
Example 2:
0.72 g of iron sesquioxide and 0.25 g of potassium hexafluoromanganate solution are weighed outAfter stirring for 50 minutes at normal temperature in 40ml of hydrofluoric acid (40 wt%) until the dissolution was completed, 0.57 g of potassium fluoride and 3.04 g of cesium fluoride were further added to the solution to react for 4 hours. Washing the precipitate with anhydrous ethanol and glacial acetic acid for 3 times, and drying in vacuum drying oven for 24 hr to obtain orange red powder as final product Cs2KFeF6:Mn4+。
Example 3:
0.76 g of iron trioxide and 0.12 g of potassium hexafluoromanganate were dissolved in 40ml of hydrofluoric acid (40 wt%), stirred at room temperature for 60 minutes until the dissolution was completed, and 0.57 g of potassium fluoride and 3.04 g of cesium fluoride were further added to the solution to react for 6 hours. Washing the precipitate with anhydrous ethanol and glacial acetic acid for 3 times, and drying in vacuum drying oven for 24 hr to obtain orange red powder as final product Cs2KFeF6:Mn4+。
Claims (4)
1. Mn-doped blue light excitation4+The hexafluoroferrite red luminescent material comprises the following chemical components: cs2KFe1-xF6:xMn4 +(ii) a x is the corresponding doping Mn4+Ion relative to Fe3+Molar percentage coefficient of ion, 0<x ≤ 0.10。
2. Blue light excited Mn-doped according to claim 14+The hexafluoroferrite red luminescent material is characterized in that the blue light refers to light with the wavelength of 420-480 nm.
3. Blue light excited Mn-doped according to claim 14+The preparation method of the hexafluoroferrite red luminescent material is characterized in that the preparation method is a liquid phase method and comprises the following steps: firstly, adding ferric oxide and potassium hexafluoromanganate into a hydrofluoric acid solution, stirring for 30-60 minutes until the ferric oxide and the potassium hexafluoromanganate are completely dissolved, then adding potassium fluoride and cesium fluoride, and continuously stirring for 2-6 hours; washing the obtained precipitate with anhydrous ethanol and glacial acetic acid for 3 times, and drying in vacuum drying oven for 24 hr to obtain orange red powder as final product.
4. Blue light excited Mn-doped according to claim 34+The preparation method of the hexafluoroferrite red luminescent material is characterized in that the types of the used raw materials and the mass percentage of the raw materials are respectively 58.0 ~ 63.0.0 percent of cesium fluoride, 8.0 ~ 11.0.0 percent of potassium fluoride, 0.2 ~ 10.0.0 percent of potassium hexafluoromanganate, 14.0 ~ 20 percent of ferric oxide and 8.0 ~ 15.0.0 percent of hydrofluoric acid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5549844A (en) * | 1995-03-24 | 1996-08-27 | Eastman Kodak Company | Radiographic phosphor panel, phosphor and phosphor modification method |
| CN105733572A (en) * | 2016-03-24 | 2016-07-06 | 中山大学 | Red fluoride fluorescent powder as well as preparation method and application thereof |
| CN106753360A (en) * | 2016-11-10 | 2017-05-31 | 云南民族大学 | The hexafluoride red illuminating material and preparation method of a kind of Mn (IV) activation |
| CN107592880A (en) * | 2015-05-18 | 2018-01-16 | 通用电气公司 | For the method for the fluoride phosphor for preparing MN doping |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5549844A (en) * | 1995-03-24 | 1996-08-27 | Eastman Kodak Company | Radiographic phosphor panel, phosphor and phosphor modification method |
| CN107592880A (en) * | 2015-05-18 | 2018-01-16 | 通用电气公司 | For the method for the fluoride phosphor for preparing MN doping |
| CN105733572A (en) * | 2016-03-24 | 2016-07-06 | 中山大学 | Red fluoride fluorescent powder as well as preparation method and application thereof |
| CN106753360A (en) * | 2016-11-10 | 2017-05-31 | 云南民族大学 | The hexafluoride red illuminating material and preparation method of a kind of Mn (IV) activation |
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