CN110684527B - 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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- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title description 2
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 14
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- OJOWXSLGSMTXEO-UHFFFAOYSA-H [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] Chemical compound [Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[Mn](=O)(=O)([O-])F.[K+].[K+].[K+].[K+].[K+].[K+] OJOWXSLGSMTXEO-UHFFFAOYSA-H 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims description 7
- 239000011698 potassium fluoride Substances 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- -1 hexafluoro compound Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 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
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
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- 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
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- 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
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Abstract
The invention relates to an inorganic materialThe field of functional materials and discloses Mn-doped material excited by blue light4+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 with the wavelength 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+Activated fluoride red phosphors, due to their strongest excitation band in the blue region, can be combined with GaNThe blue light emission of the chip is perfectly matched, so that the red emission efficiency of the luminescent material is high, and the color purity is high. 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+Molar percentage coefficient of ion, 0<x is less than or equal to 0.10. The raw materials used by the invention are respectively in the following types by mass percent: cesium fluoride: 58.0-63.0%; potassium fluoride: 8.0-11.0%; potassium hexafluoromanganate: 0.2-10.0%; iron oxide: 14.0-20%; hydrofluoric acid: 8.0 to 15.0 percent.
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 complete dissolution, then adding potassium fluoride and cesium fluoride, and continuing 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 of red NTSC (national Television Standard Committee) ((R))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 JCPDS 82-2216 standard 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 (monitoring wavelength of 633 nm) and the emission spectrum (excitation wavelength of 453 nm) of the sample. The sample shows strong broadband excitation in an ultraviolet region (320 nm-390 nm) and a blue region (400 nm-500 nm), and the strongest excitation peak is about 453 nm. Under 453 nm blue light excitation, the emission of the sample is a series of peaks, and the strongest emission peak is about 633 nm. The spectrum 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 the yellow fluorescent powder and the blue LED chip under the excitation of 20 mA current. In the figure, the blue light emission peak at 460nm originates from the emission of a GaN chip, and the emission peak in the range of 500nm to 600nm originates from YAG 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 trioxide and 0.25 g of potassium hexafluoromanganate were dissolved in 40ml of hydrofluoric acid (40 wt%), stirred at room temperature for 50 minutes until the dissolution was completed, and 0.57 g of potassium fluoride and 3.04 g of cesium fluoride were further added to this 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 (3)
1. Mn-doped blue light excitation4+The hexafluoroferrite red luminescent material is characterized by comprising 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 a vacuum drying oven for 24 hr to obtain orange red powder as final product;
the raw materials used in the method comprise the following components in percentage by mass: cesium fluoride: 58.0-63.0%; potassium fluoride: 8.0-11.0%; potassium hexafluoromanganate: 0.2-10.0%; iron sesquioxide: 14.0-20%; hydrofluoric acid: 8.0 to 15.0 percent.
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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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- 2019-07-24 CN CN201910670906.7A patent/CN110684527B/en active Active
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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