WO2017161852A1 - 一种红色氟化物荧光粉及其制备方法和应用 - Google Patents

一种红色氟化物荧光粉及其制备方法和应用 Download PDF

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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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phosphor
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preparation
fluoride phosphor
red fluoride
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王静
朱怡雯
黄霖
龚书铭
苏锵
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Sun Yat Sen University
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    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/64—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing aluminium
    • C09K11/644—Halogenides
    • C09K11/645—Halogenides with alkali or alkaline earth metals
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/64—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing aluminium
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    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
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  • 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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  • Engineering & Computer Science (AREA)
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  • Luminescent Compositions (AREA)

Abstract

本发明提供一种红色氟化物荧光粉，化学组成通式为：A2A'M1-xF6:xMn4+，x为掺杂Mn4+离子相对M占的摩尔百分比系数，且0<x≤0.3。本发明另外提供上述荧光粉的制备方法。本发明红色氟化物荧光粉原料易得，制备方法简单，且该荧光粉可被紫光和蓝光激发，产生较强的主峰位于635nm的红色荧光，是一种优异的可应用于封装白光LED的材料，在照明和显示领域中具备极大的应用前景。

Description

一种红色氟化物荧光粉及其制备方法和应用 技术领域
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。
背景技术
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。
发明内容
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。
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。
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。
本发明通过以下技术方案达到上述技术目的：
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；
其中A为K、Rb、Cs中的一种或几种；
A’为Li、Na、K、Rb中的一种或几种；
M为Al、Sc、V、Ga、Y、In、Gd、Lu、Bi中的一种或几种。
优选地，其中A为K。
优选地，其中A’为Li或Na。
优选地，其中M为Al或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+。
更优选地，所述荧光粉化学组成为K2LiAlF6:Mn4+或K2NaAlF6:Mn4+。
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：
S1.制备A2A’MF6；
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。
优选地，所述S2中反应温度为室温。
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。
与现有技术相比，本发明具有如下有益效果：
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。
附图说明
图1为实施例2中K2LiAlF6:Mn4+荧光粉的X射线衍射图。
图2为实施例2中K2LiAlF6:Mn4+荧光粉的扫描电镜照片。
图3为实施例2中K2LiAlF6:Mn4+荧光粉的激发光谱和发射光谱图。
图4为实施例7中K2LiAlF6:Mn4+荧光粉的X射线衍射图。
图5为实施例7中K2LiAlF6:Mn4+荧光粉的扫描电镜照片。
图6为实施例7中K2LiAlF6:Mn4+荧光粉的激发光谱和发射光谱图。
图7为实施例13中K2NaAlF6:Mn4+荧光粉的X射线衍射图。
图8为实施例13中K2NaAlF6:Mn4+荧光粉的扫描电镜照片。
图9为实施例13中K2NaAlF6:Mn4+荧光粉的激发光谱和发射光谱图。
具体实施方式
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。
下面以说明而不是限制的方式给出制备例。
实施例1：K2MnF6的制备
根据文献Angew.Chem-Ger.Edit.65,304-304(1953)中所述的方法制备K2MnF6晶体。
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。
实施例2-6：K2LiAlF6:Mn4+荧光粉的制备
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。
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。
表1：K2LiAlF6:Mn4+红色荧光粉制备的原料配比以及相对发光强度
Figure PCTCN2016100896-appb-000001
实施例7-11：K2LiAlF6:Mn4+荧光粉的制备
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。
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。
表2：K2LiAlF6:Mn4+红色荧光粉制备的原料配比以及相对发光强度
Figure PCTCN2016100896-appb-000002
实施例12-17：K2NaAlF6:Mn4+荧光粉的制备
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。
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。
表3：K2NaAlF6:Mn4+红色荧光粉制备的原料配比以及相对发光强度
Figure PCTCN2016100896-appb-000003

Claims (10)

  1. 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；
    其中A为K、Rb、Cs中的一种或几种；
    A’为Li、Na、K、Rb中的一种或几种；
    M为Al、Sc、V、Ga、Y、In、Gd、Lu、Bi中的一种或几种。
  2. 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。
  3. 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。
  4. 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。
  5. 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+。
  6. 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+。
  7. 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：
    S1.制备A2A’MF6；
    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。
  8. 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。
  9. 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。
  10. 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。
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CN115197702A (zh) * 2021-04-08 2022-10-18 中国科学院宁波材料技术与工程研究所 一种氟化物盐近红外荧光粉及其制备方法和应用
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