WO2017161852A1 - Red fluoride phosphor powder and preparation method therefor and use thereof - Google Patents
Red fluoride phosphor powder and preparation method therefor and use thereof Download PDFInfo
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- WO2017161852A1 WO2017161852A1 PCT/CN2016/100896 CN2016100896W WO2017161852A1 WO 2017161852 A1 WO2017161852 A1 WO 2017161852A1 CN 2016100896 W CN2016100896 W CN 2016100896W WO 2017161852 A1 WO2017161852 A1 WO 2017161852A1
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- XPIIDKFHGDPTIY-UHFFFAOYSA-N F.F.F.P Chemical compound F.F.F.P XPIIDKFHGDPTIY-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 title abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- ZDLRUHBQIZPTMS-UHFFFAOYSA-M [Mn](=O)(=O)([O-])F.[K+] Chemical compound [Mn](=O)(=O)([O-])F.[K+] ZDLRUHBQIZPTMS-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
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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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/644—Halogenides
- C09K11/645—Halogenides with alkali or alkaline earth metals
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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
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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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- 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
Definitions
- the invention relates to the technical field of luminescent materials, and more particularly to a red fluoride phosphor powder and a preparation method and application thereof.
- White LEDs have the advantages of energy saving, long life and environmental friendliness, which will become a new generation of lighting sources.
- the mainstream commercial white LEDs are now realized by coating a yellow Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) phosphor with a blue chip (light-emitting wavelength of 440-480 nm).
- this method usually has a high color temperature (CCT>4500K) and a low color rendering index (Ra ⁇ 80) due to the lack of red light components.
- an appropriate amount of red phosphor is usually incorporated to enhance the emission of the white LED in the red region.
- the emission peak is too wide, the red light after 650 nm is not sensitive to the human eye, the absorption spectrum is too wide, and the reabsorption phenomenon occurs when it is mixed with other yellow phosphors, and the preparation conditions are severe. Not economic enough. Therefore, the use is limited.
- the present invention provides a red fluoride phosphor according to the deficiencies of the prior art white LED materials.
- Another object of the present invention is to provide a method and an application for the preparation of the above phosphor.
- the present invention successfully incorporates Mn 4+ into the K 2 NaAlF 6 and K 2 LiAlF 6 phosphor powder matrix, and synthesizes a phosphor which can be excited by violet light and blue light and emits a strong red light at 635 nm. Since it can be excited by ultraviolet and blue light, and the red light emission is a series of peaks that hardly reabsorb with YAG, the phosphor is expected to be used to package white LEDs.
- the invention provides a red fluoride phosphor with a chemical composition of: A 2 A'M 1-x F 6 :xMn 4+ , 0 ⁇ x ⁇ 0.3, and x is the doping of Mn 4+ ions with respect to M Molar percentage factor;
- A is one or more of K, Rb, and Cs;
- A' is one or more of Li, Na, K, Rb;
- M is one or more of Al, Sc, V, Ga, Y, In, Gd, Lu, and Bi.
- A' is Li or Na.
- M is Al or Ga.
- the chemical composition of the phosphor is K 2 LiAlF 6 :Mn 4+ , K 2 LiGaF 6 :Mn 4+ , K 2 NaAlF 6 :Mn 4+ , K 2 NaGaF 6 :Mn 4+ , Cs 2 NaScF 6 : Mn 4+ , Rb 2 KScF 6 : Mn 4+ or K 2 NaScF 6 : Mn 4+ .
- the phosphor chemical composition is K 2 LiAlF 6 :Mn 4+ or K 2 NaAlF 6 :Mn 4+ .
- the invention provides a method for preparing the above red fluoride phosphor, the method comprising the following steps:
- a 2 A'MF 6 and potassium fluoromanganate prepared in S1 are added to hydrofluoric acid for reaction, and the red fluoride phosphor is obtained by stirring and centrifuging.
- the reaction temperature in the S2 is room temperature.
- the reaction time is 0.5 to 3 h, and the S2 is centrifuged and washed with acetone.
- the present invention has the following beneficial effects:
- the invention discloses a novel red fluoride phosphor powder, which is simple in synthesis, easy to obtain raw materials, and can generate strong red light narrow band emission under the excitation of violet light and blue light, and has a pole on the package white LED material. Great application prospects.
- Example 1 is an X-ray diffraction chart of a K 2 LiAlF 6 :Mn 4+ phosphor in Example 2.
- Example 2 is a scanning electron micrograph of K 2 LiAlF 6 :Mn 4+ phosphor in Example 2.
- Example 3 is a graph showing an excitation spectrum and an emission spectrum of a K 2 LiAlF 6 :Mn 4+ phosphor in Example 2.
- Example 4 is an X-ray diffraction chart of the K 2 LiAlF 6 :Mn 4+ phosphor in Example 7.
- Figure 5 is a scanning electron micrograph of K 2 LiAlF 6 :Mn 4+ phosphor in Example 7.
- Fig. 6 is a graph showing an excitation spectrum and an emission spectrum of a K 2 LiAlF 6 :Mn 4+ phosphor in Example 7.
- Fig. 7 is an X-ray diffraction chart of the K 2 NaAlF 6 :Mn 4+ phosphor in Example 13.
- Figure 8 is a scanning electron micrograph of K 2 NaAlF 6 :Mn 4+ phosphor in Example 13.
- Figure 9 is a graph showing an excitation spectrum and an emission spectrum of a K 2 NaAlF 6 :Mn 4+ phosphor in Example 13.
- K 2 MnF 6 crystals were prepared according to the method described in the document Angew. Chem-Ger. Edit. 65, 304-304 (1953).
- Figure 1 is an X-ray powder diffraction showing that the product is a K 2 LiAlF 6 structure having a cubic phase. Scanning electron micrographs show that the synthesized powder has a particle size of about 300 nm, as shown in Figure 2.
- the excitation and emission spectra of the phosphors were measured by an FSP920 (Edinburgh Instrument) fluorescence spectrometer, see Figure 3.
- Table 1 shows the important physicochemical and optical performance parameters of the prepared phosphor, including the doping concentration of Mn, the ratio of the raw materials prepared, and the luminescence intensity of the sample, which is 100% of the strongest luminescence sample, and the rest are expressed as Relative luminous intensity.
- the absolute quantum yield of the sample synthesized in Example 4 was 54.11%, and the fluorescence lifetime was 8.9 ms.
- the heat quenching performance is good.
- the luminous intensity is 75.5% at room temperature.
- Table 1 Raw material ratio and relative luminous intensity of K 2 LiAlF 6 :Mn 4+ red phosphor preparation
- Figure 4 is an X-ray powder diffraction showing that the product is a K 2 LiAlF 6 structure having a cubic phase.
- a scanning electron micrograph shows that the synthesized powder has a particle size of about 600 nm, as shown in FIG.
- the excitation and emission spectra of the phosphors were measured by an FSP920 (Edinburgh Instrument) fluorescence spectrometer, see Figure 6.
- Table 2 shows the important physicochemical and optical performance parameters of the prepared phosphor, including the doping concentration of Mn, the ratio of the raw materials prepared, and the luminescence intensity of the sample, which is 100% of the strongest luminescence sample, and the rest are expressed as Relative luminous intensity.
- Example 7 The sample synthesized in Example 7 had an absolute quantum yield of 10.80% and a fluorescence lifetime of 7.9 ms.
- samples with different Mn doping concentrations can be prepared under the same conditions of other synthesis (see Examples 8-11), the specific raw material ratio and the prepared fluorescence. Powder information is also given in Table 2.
- Figure 7 is an X-ray powder diffraction showing that the product is a K 2 NaAlF 6 structure having a cubic phase. Scanning electron micrographs show that the synthesized powder has a particle size of about 200-500 nm, as shown in FIG.
- the excitation and emission spectra of the phosphors were measured by an FSP920 (Edinburgh Instrument) fluorescence spectrometer, see Figure 9.
- Table 3 shows the important physicochemical and optical performance parameters of the prepared phosphor, including the doping concentration of Mn, the ratio of the raw materials prepared, and the luminescence intensity of the sample, which is 100% of the strongest luminescence sample, and the rest are expressed as Relative luminous intensity.
- the sample synthesized in Example 14 has good heat quenching performance. After the optimization of the synthesis conditions, when the temperature is heated to 425 K, the luminescence intensity is 87.7% at room temperature. By changing the mass of K 2 MnF 6 in the raw material, samples with different Mn doping concentrations can be prepared under the same conditions of other synthesis (see Examples 13-17), the specific raw material ratio and the prepared fluorescence. Powder information is also given in Table 3.
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Abstract
The present invention provides a red fluoride phosphor powder having a chemical formula of: A2A'M1-xF6:xMn4+, x is the mole percent coefficient of the doped Mn4+ ions relative to M, and 0 <x≤0.3. The present invention further provides a method for preparing the above-mentioned phosphor powder. The raw material of the red fluoride phosphor powder of the invention is easy avaiable, and the preparation method is simple. The phosphor powder can be excited by violet and blue light to produce a strong red fluorescence with a main peak at 635nm, which is an excellent material suitable for encapsulating white LED, with great application prospects in the fields of lighting and display.
Description
本发明涉及发光材料技术领域，更具体地，涉及一种红色氟化物荧光粉及其制备方法和应用。The invention relates to the technical field of luminescent materials, and more particularly to a red fluoride phosphor powder and a preparation method and application thereof.
白光LED具有节能，寿命长，环境友好等优点将成为新一代的照明光源。现在主流的商用白光LED是通过蓝光芯片(发光波长440-480nm)涂覆黄色Y3Al5O12:Ce3+(YAG:Ce3+)荧光粉一起发光实现的。但是这种方法通常因为缺少红光成分，所以色温较高(CCT>4500K)，显色指数低(Ra<80)。为了解决这一问题，通常会掺入适量的红色荧光粉来增强白光LED在红光区域的发射。而传统的氮化物商业红色荧光粉，发射峰太宽，650nm以后的红光对人眼不敏感，吸收光谱太宽又使得其和其他黄色荧光粉混合时发生重吸收现象，而且制备条件严苛，不够经济。因而使用上受到限制。White LEDs have the advantages of energy saving, long life and environmental friendliness, which will become a new generation of lighting sources. The mainstream commercial white LEDs are now realized by coating a yellow Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) phosphor with a blue chip (light-emitting wavelength of 440-480 nm). However, this method usually has a high color temperature (CCT>4500K) and a low color rendering index (Ra<80) due to the lack of red light components. In order to solve this problem, an appropriate amount of red phosphor is usually incorporated to enhance the emission of the white LED in the red region. In the traditional nitride commercial red phosphor, the emission peak is too wide, the red light after 650 nm is not sensitive to the human eye, the absorption spectrum is too wide, and the reabsorption phenomenon occurs when it is mixed with other yellow phosphors, and the preparation conditions are severe. Not economic enough. Therefore, the use is limited.
发明内容Summary of the invention
本发明根据现有技术中白光LED材料的不足，提供了一种红色氟化物荧光粉。The present invention provides a red fluoride phosphor according to the deficiencies of the prior art white LED materials.
本发明的另一目的在于提供上述荧光粉的制备方法和应用。Another object of the present invention is to provide a method and an application for the preparation of the above phosphor.
本发明首次成功在K2NaAlF6和K2LiAlF6荧光粉基质中掺入Mn4+，合成了能被紫光和蓝光激发的，能发射出较强的位于635nm红光的荧光粉。由于它能被紫外和蓝光激发，而且红光发射是一系列尖峰，几乎不会和YAG发生重吸收现象，所以，该荧光粉有望被用于封装白光LED。For the first time, the present invention successfully incorporates Mn 4+ into the K 2 NaAlF 6 and K 2 LiAlF 6 phosphor powder matrix, and synthesizes a phosphor which can be excited by violet light and blue light and emits a strong red light at 635 nm. Since it can be excited by ultraviolet and blue light, and the red light emission is a series of peaks that hardly reabsorb with YAG, the phosphor is expected to be used to package white LEDs.
本发明通过以下技术方案达到上述技术目的：The present invention achieves the above technical objectives by the following technical solutions:
本发明提供了一种红色氟化物荧光粉，化学组成为：A2A’M1-xF6:xMn4+,0<x≤0.3，x为掺杂Mn4+离子相对M所占的摩尔百分比系数；The invention provides a red fluoride phosphor with a chemical composition of: A 2 A'M 1-x F 6 :xMn 4+ , 0<x≤0.3, and x is the doping of Mn 4+ ions with respect to M Molar percentage factor;
其中A为K、Rb、Cs中的一种或几种；Where A is one or more of K, Rb, and Cs;
A’为Li、Na、K、Rb中的一种或几种；A' is one or more of Li, Na, K, Rb;
M为Al、Sc、V、Ga、Y、In、Gd、Lu、Bi中的一种或几种。M is one or more of Al, Sc, V, Ga, Y, In, Gd, Lu, and Bi.
优选地，其中A为K。Preferably, wherein A is K.
优选地，其中A’为Li或Na。
Preferably, wherein A' is Li or Na.
优选地，其中M为Al或Ga。Preferably, wherein M is Al or Ga.
优选地，所述荧光粉化学组成为K2LiAlF6:Mn4+、K2LiGaF6:Mn4+、K2NaAlF6:Mn4+、K2NaGaF6:Mn4+、Cs2NaScF6:Mn4+、Rb2KScF6:Mn4+或K2NaScF6:Mn4+。Preferably, the chemical composition of the phosphor is K 2 LiAlF 6 :Mn 4+ , K 2 LiGaF 6 :Mn 4+ , K 2 NaAlF 6 :Mn 4+ , K 2 NaGaF 6 :Mn 4+ , Cs 2 NaScF 6 : Mn 4+ , Rb 2 KScF 6 : Mn 4+ or K 2 NaScF 6 : Mn 4+ .
更优选地，所述荧光粉化学组成为K2LiAlF6:Mn4+或K2NaAlF6:Mn4+。More preferably, the phosphor chemical composition is K 2 LiAlF 6 :Mn 4+ or K 2 NaAlF 6 :Mn 4+ .
本发明提供上述红色氟化物荧光粉的制备方法，所述方法包括以下步骤：The invention provides a method for preparing the above red fluoride phosphor, the method comprising the following steps:
S1.制备A2A’MF6；S1. Preparation of A 2 A'MF 6 ;
S2.将S1中制备得到的A2A’MF6和氟锰酸钾加入到氢氟酸中反应，搅拌离心后获得所述红色氟化物荧光粉。S2. A 2 A'MF 6 and potassium fluoromanganate prepared in S1 are added to hydrofluoric acid for reaction, and the red fluoride phosphor is obtained by stirring and centrifuging.
优选地，所述S2中反应温度为室温。Preferably, the reaction temperature in the S2 is room temperature.
优选地，所述反应时间为0.5～3h，所述S2中离心后采用丙酮洗涤。Preferably, the reaction time is 0.5 to 3 h, and the S2 is centrifuged and washed with acetone.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明公开了一种新型红色氟化物荧光粉,所述荧光粉合成简便,原料易得,且能在紫光和蓝光激发下，产生较强的红光窄带发射,在封装白光LED材料上具备极大的应用前景。The invention discloses a novel red fluoride phosphor powder, which is simple in synthesis, easy to obtain raw materials, and can generate strong red light narrow band emission under the excitation of violet light and blue light, and has a pole on the package white LED material. Great application prospects.
图1为实施例2中K2LiAlF6:Mn4+荧光粉的X射线衍射图。1 is an X-ray diffraction chart of a K 2 LiAlF 6 :Mn 4+ phosphor in Example 2.
图2为实施例2中K2LiAlF6:Mn4+荧光粉的扫描电镜照片。2 is a scanning electron micrograph of K 2 LiAlF 6 :Mn 4+ phosphor in Example 2.
图3为实施例2中K2LiAlF6:Mn4+荧光粉的激发光谱和发射光谱图。3 is a graph showing an excitation spectrum and an emission spectrum of a K 2 LiAlF 6 :Mn 4+ phosphor in Example 2.
图4为实施例7中K2LiAlF6:Mn4+荧光粉的X射线衍射图。4 is an X-ray diffraction chart of the K 2 LiAlF 6 :Mn 4+ phosphor in Example 7.
图5为实施例7中K2LiAlF6:Mn4+荧光粉的扫描电镜照片。Figure 5 is a scanning electron micrograph of K 2 LiAlF 6 :Mn 4+ phosphor in Example 7.
图6为实施例7中K2LiAlF6:Mn4+荧光粉的激发光谱和发射光谱图。Fig. 6 is a graph showing an excitation spectrum and an emission spectrum of a K 2 LiAlF 6 :Mn 4+ phosphor in Example 7.
图7为实施例13中K2NaAlF6:Mn4+荧光粉的X射线衍射图。Fig. 7 is an X-ray diffraction chart of the K 2 NaAlF 6 :Mn 4+ phosphor in Example 13.
图8为实施例13中K2NaAlF6:Mn4+荧光粉的扫描电镜照片。Figure 8 is a scanning electron micrograph of K 2 NaAlF 6 :Mn 4+ phosphor in Example 13.
图9为实施例13中K2NaAlF6:Mn4+荧光粉的激发光谱和发射光谱图。Figure 9 is a graph showing an excitation spectrum and an emission spectrum of a K 2 NaAlF 6 :Mn 4+ phosphor in Example 13.
下面结合实施例对本发明进行进一步的说明。但本领域技术人员了解，下述实施例不是对本发明保护范围的限制，任何在本发明基础上做出的改进和变化，都在本发明的保护范围之内。The invention will now be further described in conjunction with the examples. However, those skilled in the art understand that the following embodiments are not intended to limit the scope of the present invention, and any modifications and variations made on the basis of the present invention are within the scope of the present invention.
下面以说明而不是限制的方式给出制备例。The preparation examples are given below by way of illustration and not limitation.
实施例1：K2MnF6的制备
Example 1: Preparation of K 2 MnF 6
根据文献Angew.Chem-Ger.Edit.65,304-304(1953)中所述的方法制备K2MnF6晶体。K 2 MnF 6 crystals were prepared according to the method described in the document Angew. Chem-Ger. Edit. 65, 304-304 (1953).
将0.45g KMnO4和9g KHF2溶于30ml氢氟酸(49％)中，搅拌20分钟，然后逐步滴入约1.2ml双氧水(30wt.％)，溶液中逐步生成黄色的沉淀，将溶液过滤后得到沉淀物，用丙酮清洗后在60℃烘2小时即得到K2MnF6。0.45 g of KMnO 4 and 9 g of KHF 2 were dissolved in 30 ml of hydrofluoric acid (49%), stirred for 20 minutes, and then gradually dropped into about 1.2 ml of hydrogen peroxide (30 wt.%), a yellow precipitate was gradually formed in the solution, and the solution was filtered. Thereafter, a precipitate was obtained, which was washed with acetone and then baked at 60 ° C for 2 hours to obtain K 2 MnF 6 .
实施例2-6：K2LiAlF6:Mn4+荧光粉的制备Example 2-6: Preparation of K 2 LiAlF 6 :Mn 4+ Phosphor
称取氯化锂(LiCl)0.4239g，氯化铝(AlCl3·6H2O)2.4143g，氟氢化钾(KHF2)2.3431g，加入20ml水中，得到白色沉淀。将沉淀洗涤，70℃干燥24小时，得到K2LiAlF6。称取氟铝酸锂钾(K2LiAlF6)0.2261g，氟锰酸钾(K2MnF6)0.0025g，加入氢氟酸2ml，室温搅拌反应2小时，用丙酮洗涤所得固体，然后于真空干燥箱中干燥24小时，最后所得到粉末为最终K2LiAlF6:Mn4+荧光粉。0.4239 g of lithium chloride (LiCl), 2.4143 g of aluminum chloride (AlCl 3 ·6H 2 O), and 2.3431 g of potassium hydrogen fluoride (KHF 2 ) were weighed and added to 20 ml of water to obtain a white precipitate. The precipitate was washed and dried at 70 ° C for 24 hours to obtain K 2 LiAlF 6 . Weigh out 0.2261 g of potassium fluoroaluminate (K 2 LiAlF 6 ), 0.0025 g of potassium fluoromanganate (K 2 MnF 6 ), add 2 ml of hydrofluoric acid, stir the reaction at room temperature for 2 hours, wash the solid with acetone, and then vacuum. Drying in a dry box for 24 hours, the final powder obtained was the final K 2 LiAlF 6 :Mn 4+ phosphor.
图1为X射线粉末衍射表明产物是具有立方相的K2LiAlF6结构。扫面电镜照片表明合成的粉末粒径大约为300nm，如图2所示。通过FSP920型(Edinburgh Instrument)荧光光谱仪测量了荧光粉的激发和发射光谱，见图3。表1给出了所制备的荧光粉的重要物化和光学性能参数，包括Mn的掺杂浓度，制备原料配比以及样品的发光强度，以发光最强样品为100％，其余皆表示为对其的相对发光强度。其中实施例4所合成的样品绝对量子产率为54.11％，荧光寿命8.9ms。热淬灭性能较好，经过合成条件优化后，当温度加热至425K时，发光强度为室温时的75.5％。通过改变原料中的K2MnF6的质量，在其他合成条件不变的情况下，可以制备出不同Mn掺杂浓度的样品(见实施例3-6)，其具体原料配比和所制备荧光粉信息同样在表1中给出。Figure 1 is an X-ray powder diffraction showing that the product is a K 2 LiAlF 6 structure having a cubic phase. Scanning electron micrographs show that the synthesized powder has a particle size of about 300 nm, as shown in Figure 2. The excitation and emission spectra of the phosphors were measured by an FSP920 (Edinburgh Instrument) fluorescence spectrometer, see Figure 3. Table 1 shows the important physicochemical and optical performance parameters of the prepared phosphor, including the doping concentration of Mn, the ratio of the raw materials prepared, and the luminescence intensity of the sample, which is 100% of the strongest luminescence sample, and the rest are expressed as Relative luminous intensity. The absolute quantum yield of the sample synthesized in Example 4 was 54.11%, and the fluorescence lifetime was 8.9 ms. The heat quenching performance is good. After the optimization of the synthesis conditions, when the temperature is heated to 425K, the luminous intensity is 75.5% at room temperature. By changing the mass of K 2 MnF 6 in the raw material, samples with different Mn doping concentrations can be prepared under the same conditions of other synthesis (see Examples 3-6), the specific raw material ratio and the prepared fluorescence. Powder information is also given in Table 1.
表1：K2LiAlF6:Mn4+红色荧光粉制备的原料配比以及相对发光强度Table 1: Raw material ratio and relative luminous intensity of K 2 LiAlF 6 :Mn 4+ red phosphor preparation
实施例7-11：K2LiAlF6:Mn4+荧光粉的制备Example 7-11: Preparation of K 2 LiAlF 6 :Mn 4+ Phosphor
称取氯化锂(LiCl)0.8479g，氯化铝(AlCl3·6H2O)2.4143g，氟氢化钾(KHF2)2.3431g，加入20ml水中，得到白色沉淀。将沉淀洗涤，70℃干燥24小时，得到K2LiAlF6。称取氟铝酸锂钾(K2LiAlF6)0.2261g，氟锰酸钾(K2MnF6)0.0025g，加入氢氟酸2ml，室温搅拌反应30分钟，用丙酮洗涤所得固体，然后于真空干燥箱中干燥24小时，最后所得到粉末为最终K2LiAlF6:Mn4+荧光粉。0.8479 g of lithium chloride (LiCl), 2.4143 g of aluminum chloride (AlCl 3 ·6H 2 O), and 2.3431 g of potassium hydrogen fluoride (KHF 2 ) were weighed and added to 20 ml of water to obtain a white precipitate. The precipitate was washed and dried at 70 ° C for 24 hours to obtain K 2 LiAlF 6 . Weigh out 0.2261 g of potassium fluoroaluminate (K 2 LiAlF 6 ), 0.0025 g of potassium fluoromanganate (K 2 MnF 6 ), add 2 ml of hydrofluoric acid, stir the reaction at room temperature for 30 minutes, wash the obtained solid with acetone, and then vacuum. Drying in a dry box for 24 hours, the final powder obtained was the final K 2 LiAlF 6 :Mn 4+ phosphor.
图4为X射线粉末衍射表明产物是具有立方相的K2LiAlF6结构。扫面电镜照片表明合成的粉末粒径大约为600nm，如图5所示。通过FSP920型(Edinburgh Instrument)荧光光谱仪测量了荧光粉的激发和发射光谱，见图6。表2给出了所制备的荧光粉的重要物化和光学性能参数，包括Mn的掺杂浓度，制备原料配比以及样品的发光强度，以发光最强样品为100％，其余皆表示为对其的相对发光强度。其中实施例7所合成的样品绝对量子产率为10.80％，荧光寿命7.9ms。通过改变原料中的K2MnF6的质量，在其他合成条件不变的情况下，可以制备出不同Mn掺杂浓度的样品(见实施例8-11)，其具体原料配比和所制备荧光粉信息同样在表2中给出。Figure 4 is an X-ray powder diffraction showing that the product is a K 2 LiAlF 6 structure having a cubic phase. A scanning electron micrograph shows that the synthesized powder has a particle size of about 600 nm, as shown in FIG. The excitation and emission spectra of the phosphors were measured by an FSP920 (Edinburgh Instrument) fluorescence spectrometer, see Figure 6. Table 2 shows the important physicochemical and optical performance parameters of the prepared phosphor, including the doping concentration of Mn, the ratio of the raw materials prepared, and the luminescence intensity of the sample, which is 100% of the strongest luminescence sample, and the rest are expressed as Relative luminous intensity. The sample synthesized in Example 7 had an absolute quantum yield of 10.80% and a fluorescence lifetime of 7.9 ms. By changing the mass of K 2 MnF 6 in the raw material, samples with different Mn doping concentrations can be prepared under the same conditions of other synthesis (see Examples 8-11), the specific raw material ratio and the prepared fluorescence. Powder information is also given in Table 2.
表2：K2LiAlF6:Mn4+红色荧光粉制备的原料配比以及相对发光强度Table 2: Raw material ratio and relative luminescence intensity of K 2 LiAlF 6 :Mn 4+ red phosphor preparation
实施例12-17：K2NaAlF6:Mn4+荧光粉的制备Example 12-17: Preparation of K 2 NaAlF 6 :Mn 4+ Phosphor
称取氯化钠(NaCl)0.5844g，氯化铝(AlCl3·6H2O)2.4143g，氟氢化钾(KHF2)2.3431g，加入20ml水中，得到白色沉淀。将沉淀洗涤，70℃干燥24小时，得到K2NaAlF6。称取氟铝酸钠钾(K2NaAlF6)0.4843g，氟锰酸钾(K2MnF6)0.0015g，加入氢氟酸2ml，室温搅拌反应30分钟，用丙酮洗涤所得固体，然后于真空干燥箱中干燥24小时，最后所得到粉末为最终K2NaAlF6:Mn4+荧光粉。
0.5844 g of sodium chloride (NaCl), 2.4143 g of aluminum chloride (AlCl 3 ·6H 2 O), and 2.3431 g of potassium hydrogen fluoride (KHF 2 ) were weighed and added to 20 ml of water to obtain a white precipitate. The precipitate was washed and dried at 70 ° C for 24 hours to obtain K 2 NaAlF 6 . Weigh 0.4843 g of potassium fluoroaluminate (K 2 NaAlF 6 ), 0.0015 g of potassium fluoromanganate (K 2 MnF 6 ), add 2 ml of hydrofluoric acid, stir the reaction at room temperature for 30 minutes, wash the obtained solid with acetone, and then vacuum. Drying in a dry box for 24 hours, the final powder obtained was the final K 2 NaAlF 6 :Mn 4+ phosphor.
图7为X射线粉末衍射表明产物是具有立方相的K2NaAlF6结构。扫面电镜照片表明合成的粉末粒径大约为200-500nm，如图8所示。通过FSP920型(Edinburgh Instrument)荧光光谱仪测量了荧光粉的激发和发射光谱，见图9。表3给出了所制备的荧光粉的重要物化和光学性能参数，包括Mn的掺杂浓度，制备原料配比以及样品的发光强度，以发光最强样品为100％，其余皆表示为对其的相对发光强度。其中实施例14所合成的样品热淬灭性能较好，经过合成条件优化后，当温度加热至425K时，发光强度为室温时的87.7％。通过改变原料中的K2MnF6的质量，在其他合成条件不变的情况下，可以制备出不同Mn掺杂浓度的样品(见实施例13-17)，其具体原料配比和所制备荧光粉信息同样在表3中给出。Figure 7 is an X-ray powder diffraction showing that the product is a K 2 NaAlF 6 structure having a cubic phase. Scanning electron micrographs show that the synthesized powder has a particle size of about 200-500 nm, as shown in FIG. The excitation and emission spectra of the phosphors were measured by an FSP920 (Edinburgh Instrument) fluorescence spectrometer, see Figure 9. Table 3 shows the important physicochemical and optical performance parameters of the prepared phosphor, including the doping concentration of Mn, the ratio of the raw materials prepared, and the luminescence intensity of the sample, which is 100% of the strongest luminescence sample, and the rest are expressed as Relative luminous intensity. The sample synthesized in Example 14 has good heat quenching performance. After the optimization of the synthesis conditions, when the temperature is heated to 425 K, the luminescence intensity is 87.7% at room temperature. By changing the mass of K 2 MnF 6 in the raw material, samples with different Mn doping concentrations can be prepared under the same conditions of other synthesis (see Examples 13-17), the specific raw material ratio and the prepared fluorescence. Powder information is also given in Table 3.
表3：K2NaAlF6:Mn4+红色荧光粉制备的原料配比以及相对发光强度Table 3: Raw material ratio and relative luminous intensity of K 2 NaAlF 6 :Mn 4+ red phosphor preparation
Claims (10)
- 一种红色氟化物荧光粉，其特征在于，化学组成为：A2A’M1-xF6:xMn4+,0<x≤0.3，x为掺杂Mn4+离子相对M所占的摩尔百分比系数；A red fluoride phosphor characterized by a chemical composition of: A 2 A'M 1-x F 6 :xMn 4+ , 0<x≤0.3, and x is a doped Mn 4+ ion with respect to M Molar percentage factor;其中A为K、Rb、Cs中的一种或几种；Where A is one or more of K, Rb, and Cs;A’为Li、Na、K、Rb中的一种或几种；A' is one or more of Li, Na, K, Rb;M为Al、Sc、V、Ga、Y、In、Gd、Lu、Bi中的一种或几种。M is one or more of Al, Sc, V, Ga, Y, In, Gd, Lu, and Bi.
- 根据权利要求1所述的红色氟化物荧光粉，其特征在于，其中A为K。The red fluoride phosphor according to claim 1, wherein A is K.
- 根据权利要求1所述的红色氟化物荧光粉，，其特征在于，其中A’为Li或Na。The red fluoride phosphor according to claim 1, wherein A' is Li or Na.
- 根据权利要求1所述的红色氟化物荧光粉，，其特征在于，其中M为Al或Ga。The red fluoride phosphor according to claim 1, wherein M is Al or Ga.
- 根据权利要求1所述的红色氟化物荧光粉，，其特征在于，所述荧光粉化学组成为K2LiAlF6:Mn4+、K2LiGaF6:Mn4+、K2NaAlF6:Mn4+、K2NaGaF6:Mn4+、Cs2NaScF6:Mn4+、Rb2KScF6:Mn4+或K2NaScF6:Mn4+。The red fluoride phosphor according to claim 1, wherein the phosphor chemical composition is K 2 LiAlF 6 :Mn 4+ , K 2 LiGaF 6 :Mn 4+ , K 2 NaAlF 6 :Mn 4 + , K 2 NaGaF 6 : Mn 4+ , Cs 2 NaScF 6 : Mn 4+ , Rb 2 KScF 6 : Mn 4+ or K 2 NaScF 6 : Mn 4+ .
- 根据权利要求1所述的红色氟化物荧光粉，其特征在于，所述荧光粉化学组成为K2LiAlF6:Mn4+或K2NaAlF6:Mn4+。The red fluoride phosphor according to claim 1, wherein the phosphor chemical composition is K 2 LiAlF 6 :Mn 4+ or K 2 NaAlF 6 :Mn 4+ .
- 一种权利要求1所述的红色氟化物荧光粉的制备方法，其特征在于，所述方法包括以下步骤：A method of preparing a red fluoride phosphor according to claim 1, wherein the method comprises the steps of:S1.制备A2A’MF6；S1. Preparation of A 2 A'MF 6 ;S2.将S1中制备得到的A2A’MF6和氟锰酸钾加入到氢氟酸中反应，搅拌离心后获得所述红色氟化物荧光粉。S2. A 2 A'MF 6 and potassium fluoromanganate prepared in S1 are added to hydrofluoric acid for reaction, and the red fluoride phosphor is obtained by stirring and centrifuging.
- 根据权利要求7所述的制备方法，其特征在于，所述S2中反应温度为室温。The preparation method according to claim 7, wherein the reaction temperature in the S2 is room temperature.
- 根据权利要求7所述的制备方法，其特征在于，所述反应时间为0.5～3h，所述S2中离心后采用丙酮洗涤。The preparation method according to claim 7, wherein the reaction time is 0.5 to 3 hours, and the S2 is centrifuged and then washed with acetone.
- 权利要求1至6任一所述的荧光粉在照明和显示领域中的应用。 Use of the phosphor of any one of claims 1 to 6 in the field of illumination and display.
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