WO2020098148A1 - 一种高性能窄带荧光粉及其制备方法 - Google Patents

一种高性能窄带荧光粉及其制备方法 Download PDF

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WO2020098148A1
WO2020098148A1 PCT/CN2019/071839 CN2019071839W WO2020098148A1 WO 2020098148 A1 WO2020098148 A1 WO 2020098148A1 CN 2019071839 W CN2019071839 W CN 2019071839W WO 2020098148 A1 WO2020098148 A1 WO 2020098148A1
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cesium
acid
preparation
phosphor
sif
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王静
刘永
黄霖
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中山大学
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    • 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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    • 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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  • the invention belongs to the technical field of luminescent materials, and particularly relates to a high-performance narrow-band phosphor and a preparation method thereof.
  • White LED has many advantages such as long service life, low power consumption, fast response speed, small size, energy saving and environmental protection, and can be widely used in the fields of lighting and display backlight.
  • mainstream white LEDs are all realized by mixing blue light and yellow light. Due to insufficient red light components, their color rendering is very low, which seriously affects the quality of lighting light.
  • the color gamut of the display backlight obtained in this way is narrow, and the image color cannot be truly reproduced. In order to obtain high color rendering white light and a wide color gamut backlight device, it is necessary to add an appropriate red phosphor.
  • Mn 4 + -doped fluoride red phosphors have received widespread attention because they can be excited by ultraviolet light or blue light to produce bright red light emission.
  • Mn 4+ doped fluoride red phosphor is mainly synthesized by wet method, and its mainstream synthesis methods include etching method, hydrothermal method, co-precipitation method and ion exchange method.
  • the purpose of the present invention is to overcome the defects or shortcomings of low external quantum efficiency and instability in high-temperature and high-humidity environment of the red phosphor in the prior art, and to provide a preparation method of high-performance narrow-band phosphor.
  • the phosphor prepared by the low-temperature co-precipitation method has high external quantum efficiency and narrow-band emission peak; in addition, through passivation treatment, its moisture resistance is greatly improved.
  • the passivated phosphor is at high temperature and high humidity (temperature Under the environment of 85 ° C and relative humidity of 85%), the luminous intensity remains 75-80% after 168 hours, and it has great application prospect in the field of high-efficiency white light illumination and wide color gamut display.
  • the preparation method provided by the invention is low in cost, simple, easy to implement, excellent in performance, and suitable for large-scale industrial production.
  • Another object of the present invention is to provide a high-performance narrow-band phosphor.
  • Another object of the present invention is to provide the application of the above-mentioned high-performance narrow-band phosphor in the field of lighting and display.
  • a high-performance narrow-band phosphor preparation method includes the following steps:
  • the present invention uses a low-temperature co-precipitation method to prepare high-performance narrow-band phosphors, which lowers the solubility of Cs 2 SiF 6 : Mn 4+ in HF under lower temperature conditions, is beneficial to increase the yield of the product, and the prepared Cs 2 SiF 6 : Mn 4+ phosphor has high external quantum efficiency and narrow band emission peak, and its external quantum efficiency can reach 83%; in addition, passivation treatment with reducing solution can make Cs 2 SiF 6 : The MnF 6 2- on the surface of the Mn 4+ phosphor reacts with the reducing solution to form a passivation layer of Cs 2 SiF 6 on the surface of the phosphor, which greatly improves the humidity resistance.
  • the passivated phosphor at high temperature and high humidity (temperature 85 °C) Relative humidity is 85%). After 168 hours, the luminous intensity remains 75-80%, and it has great application prospects in the field of high-efficiency white light illumination and wide color gamut display.
  • the preparation method provided by the invention is low in cost, simple, easy to implement, excellent in performance, and suitable for large-scale industrial production.
  • the molar fraction of Mn in the Cs 2 SiF 6 : Mn 4+ phosphor initial product is 5-12%.
  • the Cs 2 SiF 6 : Mn 4+ phosphor at this molar fraction has more excellent luminous intensity and external quantum effect.
  • the hexafluoromanganate in S1 is one or more of potassium hexafluoromanganate or cesium hexafluoromanganate.
  • the silicon-containing compound in S1 is one or more of silicon dioxide, ethyl orthosilicate, fluorosilicic acid, silicon dioxide powder, silicon powder or quartz.
  • the compound containing cesium in S1 is cesium carbonate, cesium fluoride, cesium stearate, cesium hydroxide, cesium formate, cesium acrylate, cesium propionate, cesium sulfate, cesium hydrogen carbonate, cesium oxide, cesium nitrate Or one or more of cesium acetate.
  • the time of the co-precipitation reaction in S2 is 1 to 150 min.
  • the time of the co-precipitation reaction in S2 is 5-50 min.
  • the temperature of the co-precipitation reaction in S2 is -40 to -20 ° C.
  • the acid solution can provide an acid environment to ensure that MnF 6 2- reacts with the reducing solution.
  • the acid solution in S3 is one or more of glacial acetic acid, propionic acid, butyric acid, hydrofluoric acid, oleic acid, hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.
  • the concentration of the acid solution in S3 is 1-15 mol / L.
  • the reducing solution in S3 is one or more of ascorbic acid, phosphorous acid or formic acid.
  • a high-performance narrow-band phosphor is prepared by the above preparation method.
  • the high-performance narrow-band phosphor is used in the fields of white light illumination and wide color gamut display.
  • the present invention has the following beneficial effects:
  • the high-performance narrow-band phosphor prepared by the low-temperature co-precipitation method has high external quantum efficiency and narrow-band emission peak; in addition, through passivation treatment, its moisture resistance is greatly improved, and the passivated phosphor is high in high temperature In a humid environment (temperature 85 ° C, relative humidity 85%), the luminous intensity remains 75 to 80% after 168 hours, and it has great application prospects in the field of high-efficiency white light illumination and wide color gamut display.
  • the preparation method provided by the invention is low in cost, simple, easy to implement, excellent in performance, and suitable for large-scale industrial production.
  • Example 1 is an X-ray diffraction pattern of unpassivated Cs 2 SiF 6 : Mn 4+ phosphor in Example 3;
  • Example 3 is the excitation and emission spectra of the unpassivated Cs 2 SiF 6 : Mn 4+ phosphor in Example 3;
  • Figure 3 shows the unpassivated Cs 2 SiF 6 : Mn 4+ phosphor and the passivated Cs 2 SiF 6 : Mn 4+ phosphor in Example 3 after aging for 168h at a temperature of 85 ° C and a relative humidity of 85% Physical map;
  • FIG. 5 is an electroluminescence spectrum diagram of a white LED device obtained by combining the passivated Cs 2 SiF 6 : Mn 4+ phosphor with ⁇ -SiAlON: Eu 2+ green powder and blue chip in Example 3.
  • FIG. 5 is an electroluminescence spectrum diagram of a white LED device obtained by combining the passivated Cs 2 SiF 6 : Mn 4+ phosphor with ⁇ -SiAlON: Eu 2+ green powder and blue chip in Example 3.
  • This embodiment provides Cs 2 SiF 6 : Mn 4+ phosphor powder, which is prepared by the following preparation method.
  • K 2 MnF 6 crystals were prepared according to the method described in the document Angew. Chem-Ger. Edit. 65, 304-304 (1953).
  • K 2 MnF 6 is used as the manganese source, and other manganese sources, such as cesium hexafluoromanganate, have the same effect.
  • Example 5 is the same as Example 3 except that the silicon-containing compound selected is ethyl orthosilicate (0.5208 g).
  • the performance of the prepared Cs 2 SiF 6 : Mn 4+ phosphor is similar to that in Example 3.
  • Example 6 is the same as Example 3 except that the selected cesium-containing compound is cesium hydroxide (0.3748 g).
  • the performance of the prepared Cs 2 SiF 6 : Mn 4+ phosphor is similar to that in Example 3.
  • the reaction temperature (-40 to 0 ° C) in step (2) is adjusted to obtain Cs 2 SiF 6 : Mn 4+ phosphor before and after passivation.
  • Example 3 XRD test was performed on the Cs 2 SiF 6 : Mn 4+ phosphor prepared before passivation prepared in Example 3, as shown in FIG. 1. It can be seen from FIG. 1 that the obtained phosphor has a cubic phase Cs 2 SiF 6 structure. As shown in FIG. 2, it is a scanning electron micrograph of the phosphor, and the particle size of the phosphor is about 5-20 ⁇ m. The excitation and emission spectra of the phosphor are measured by FSP920 (Edinburgh Instrument) fluorescence spectrometer, as shown in Figure 3. It can be seen from FIG. 3 that the phosphor has strong absorption in the blue region and narrow-band red light emission with the strongest emission peak at 631 nm.
  • Examples 1 to 4 by changing the mass of K 2 MnF 6 in the raw materials, samples with different Mn doping concentrations can be prepared under the condition that other synthesis conditions remain unchanged.
  • the phosphors of Examples 1 to 4 without passivation treatment were subjected to luminous intensity measurement, and the results are shown in Table 2.
  • the external quantum effects of the Cs 2 SiF 6 : Mn 4+ phosphors provided in Examples 1 to 4 are all greater than 75%, and the external quantum efficiency of the Cs 2 SiF 6 : Mn 4+ samples obtained in Example 3 is 83%.
  • the external quantum efficiencies of Cs 2 SiF 6 : Mn 4+ before passivation prepared in Example 7 under different temperature conditions were all determined to be higher than 78%.
  • a white LED device with different light colors is prepared by combining the passivated phosphor of Example 3 with ⁇ -SiAlON: Eu 2+ green powder and a blue chip.
  • One of the white light LED device electroluminescence spectrum is shown in FIG. 5. It can be seen from the figure that a white LED device with high lumen and wide color gamut can be obtained by combining the passivated phosphor with ⁇ -SiAlON: Eu 2+ green powder.
  • the pre-passivated Cs 2 SiF 6 : Mn 4+ and the passivated Cs 2 SiF 6 : Mn 4+ prepared in Example 3 were placed in a constant temperature and humidity box at 85 ° C. and 85% relative humidity for aging experiments. After a period of time, the spectral data of the sample is tested, and the spectral data before and after aging are compared as a measure of the moisture resistance of the sample.
  • Example 4 is the change of the spectral data before the passivation of Cs 2 SiF 6 : Mn 4+ and the passivated Cs 2 SiF 6 : Mn 4+ prepared in Example 3 under the conditions of temperature 85 °C and relative humidity 85% Figure. It can be seen from FIG. 4 that the sample before passivation of Example 3 turned brown after aging for 168 hours (shown in FIG. 4a), the luminous intensity of the sample remained 13.6% of the initial intensity; while the passivated sample remained Orange (shown in Figure 4b), the luminous intensity of the sample remains 75.0% of the initial intensity, indicating that the moisture resistance of the phosphor after passivation has been greatly improved.

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Abstract

本发明涉及一种高性能窄带荧光粉及其制备方法。所述制备方法包括如下步骤：S1：将六氟锰酸盐溶解于HF溶液，搅拌下加入含硅的化合物和含铯的化合物得混合溶液；S2：于-40～-10℃下进行共沉淀反应，得沉淀物，离心，清洗，干燥后得Cs 2SiF 6:Mn 4+荧光粉初产物；S3：将Cs 2SiF 6:Mn 4+荧光粉初产物加入酸溶液中，搅拌条件下加入还原性溶液，搅拌，离心，洗涤，干燥即得到高性能窄带荧光粉。本发明提供的制备方法成本低、简单、易行、性能优异、适合于规模化工业生产；制备得到的高性能窄带荧光粉外量子效率高，耐湿性能好。

Description

一种高性能窄带荧光粉及其制备方法 技术领域
本发明属于发光材料技术领域，具体涉及一种高性能窄带荧光粉及其的制备方法。
背景技术
白光LED具有使用寿命长、低功耗、响应速度快、体积小、节能环保等诸多优点，可以广泛应用于照明和显示背光源等领域。目前主流的白光LED均使用蓝光和黄光混合而实现，由于红光成分不足，其显色性很低，使得照明光线的质量受到了严重影响。同时采用这种方式得到的显示背光源的色域较窄，不能真实地还原图像色彩。为了得到高显色性的白光和宽色域的背光源器件，均需添加适当的红色荧光粉。
近年来，Mn 4+掺杂的氟化物红色荧光粉由于能够被紫外光或蓝光激发，产生明亮的红光发射，受到了人们的广泛关注。目前，Mn 4+掺杂的氟化物红色荧光粉主要采用湿法合成，其主流合成方法包括刻蚀法、水热法、共沉淀法以及离子交换法。例如，日本研究者采用蚀刻法合成了的A 2BF 6:Mn 4+(A:K,Na,Cs；B:Si,Ge,Sn,Ti等)红色荧光粉(Journal of Applied Physics 2008,104(2):317)，此方法存在所需反应时间长、量子效率低以及使用硅片、钛片、锗粒等价格较贵的初始原料，不适用于大规模生产；水热法通常可以得到形貌均一的荧光粉颗粒，然而在高温下MnF 6 2-不稳定使得合成的红色荧光粉的量子效率也很低；2014年，研究人员采用离子交换法合成了内量子效率达到98％的K 2TiF 6:Mn 4+红光荧光粉，然而该荧光粉的外量子效率还不够高(小于60％)(Nature Communications 2014，5,4312)；随后，人们采用共沉淀法合成了Cs 2SiF 6:Mn 4+(ACS Photonics 2017,4,2556-2565)和KNaSiF 6:Mn 4+(ACS Applied Materials&Interfaces 2016,8,11194-11203)红色荧光粉，它们的外量子效率分别为71％和41％(均低于75％)，还有很大的提升空间。此外，这些红色荧光粉还存在高温高湿环境下不稳定的问题，严重影响了的器件的使用寿命。
因此，开发一种高外量子效率同时兼具优异耐湿性能的红色荧光粉是很有必要的。
发明内容
本发明的目的在于克服现有技术中红色荧光粉的外量子效率低，高温高湿环境下不稳定的缺陷或不足，提供一种高性能窄带荧光粉的制备方法。本发明利用低温共沉淀法制备得到的荧光粉具有较高的外量子效率和窄带发射峰；另外，通过钝化处理，大大提高了其耐湿性能，钝化后的荧光粉在高温高湿(温度85℃相对湿度85％)的环境下168小时后发光强度保持了75～80％，在高效白光照明和宽色域显示领域具有极大的应用前景。本发明提供的制备方法成本低、简单、易行、性能优异、适合于规模化工业生产。
本发明的另一目的在于提供一种高性能窄带荧光粉。
本发明的另一目的在于提供上述高性能窄带荧光粉在照明和显示领域中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种高性能窄带荧光粉的制备方法，包括如下步骤：
S1：将六氟锰酸盐溶解于HF溶液，搅拌下加入含硅化合物和含铯的化合物得混合溶液；
S2：于-40～-20℃下进行共沉淀反应，得沉淀物，离心，清洗，干燥后得Cs 2SiF 6:Mn 4+荧光粉初产物；所述Cs 2SiF 6:Mn 4+荧光粉初产物中Mn的摩尔分数为4～20％；
S3：将Cs 2SiF 6:Mn 4+荧光粉初产物加入酸溶液中，搅拌条件下加入还原性溶液，搅拌，离心，洗涤，干燥即得到高性能窄带荧光粉。
本发明利用低温共沉淀法来制备高性能窄带荧光粉，在较低的温度条件下，降低Cs 2SiF 6:Mn 4+在HF中的溶解度，有利于提高产物的产率，制备得到的Cs 2SiF 6:Mn 4+荧光粉具有较高的外量子效率和窄带发射峰，其外量子效率可达83％；另外，利用还原性溶液对其进行钝化处理，可使得Cs 2SiF 6:Mn 4+荧光粉表层的MnF 6 2-与还原性溶液反应在荧光粉表层形成Cs 2SiF 6的钝化层，从而大大提高耐湿性能，钝化后的荧光粉在高温高湿(温度85℃相对湿度85％)的环境下168小时后发光强度保持了75～80％，在高效白光照明和宽色域显示领域具有极大的应用前景。
本发明提供的制备方法成本低、简单、易行、性能优异、适合于规模化工业 生产。
优选地，所述Cs 2SiF 6:Mn 4+荧光粉初产物中Mn的摩尔分数为5～12％。
该摩尔分数下的Cs 2SiF 6:Mn 4+荧光粉具有更为优异的发光强度和外量子效应。
本领域中常规的六氟锰酸盐、含硅的化合物和含铯的化合物均可用于本发明中。
优选地，S1中六氟锰酸盐为六氟锰酸钾或六氟锰酸铯中一种或几种。
优选地，S1中含硅的化合物为二氧化硅、正硅酸乙酯、氟硅酸、二氧化硅粉末、硅粉或石英中一种或几种。
优选地，S1中所述含铯的化合物为碳酸铯、氟化铯、硬脂酸铯、氢氧化铯、甲酸铯、丙烯酸铯、丙酸铯、硫酸铯、碳酸氢铯、氧化铯、硝酸铯或乙酸铯中一种或几种。
优选地，S2中共沉淀反应的时间为1～150min。
更为优选地，S2中共沉淀反应的时间为5～50min。
优选地，S2中共沉淀反应的温度为-40～-20℃。
酸溶液可提供一个酸性环境，保证MnF 6 2-与还原性溶液发生反应。
优选地，S3中酸溶液为冰醋酸、丙酸、丁酸、氢氟酸、油酸、盐酸、硫酸、磷酸或硝酸中一种或几种。
优选地，S3中酸溶液的浓度为1～15mol/L。
优选地，S3中还原性溶液为为抗坏血酸、亚磷酸或甲酸中的一种或几种。
上述几种还原性溶液可达到较好的钝化效果。
一种高性能窄带荧光粉，通过上述制备方法制备得到。
上述高性能窄带荧光粉在照明和显示领域中的应用也在本发明的保护范围内。
优选地，所述高性能窄带荧光粉在白光照明和宽色域显示领域中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明利用低温共沉淀法制备得到的高性能窄带荧光粉具有较高的外量子效率和窄带发射峰；另外，通过钝化处理，大大提高了其耐湿性能，钝化后的荧光粉在高温高湿(温度85℃相对湿度85％)的环境下168小时后发光强度保持 了75～80％，在高效白光照明和宽色域显示领域具有极大的应用前景。本发明提供的制备方法成本低、简单、易行、性能优异、适合于规模化工业生产。
附图说明
图1为实施例3中未钝化的Cs 2SiF 6:Mn 4+荧光粉的X射线衍射图；
图2为实施例3中未钝化的Cs 2SiF 6:Mn 4+荧光粉的扫描电镜照片；
图3为实施例3中未钝化的Cs 2SiF 6:Mn 4+荧光粉的激发光谱和发射光谱图；
图3为实施例3中未钝化的Cs 2SiF 6:Mn 4+荧光粉与钝化的Cs 2SiF 6:Mn 4+荧光粉在温度85℃、相对湿度85％条件下老化168h后的实物图；
图5为实施例3中钝化的Cs 2SiF 6:Mn 4+荧光粉与β-SiAlON:Eu 2+绿粉和蓝光芯片结合得到的白光LED器件电致发光光谱图。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
实施例1～4
本实施例提供Cs 2SiF 6:Mn 4+荧光粉，通过如下制备方法制备得到。
(1)K 2MnF 6的制备
根据文献Angew.Chem-Ger.Edit.65,304-304(1953)中所述的方法制备K 2MnF 6晶体。
将0.45g KMnO 4和9g KHF 2溶于30ml氢氟酸(49％)中，搅拌30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80℃烘2小时即得到K 2MnF 6。
各实施例以K 2MnF 6作为锰源，选用其它的锰源，如六氟锰酸铯也具有一样的效果。
(2)钝化前的Cs 2SiF 6:Mn 4+荧光粉的制备
将一定量的六氟锰酸钾(K 2MnF 6)溶解于6.5ml HF(40wt.％)溶液中；随后，在搅拌条件下依次加入0.93ml氟硅酸(H 2SiF 6 32wt.％)和0.8146g碳 酸铯(Cs 2CO 3)；转入低温恒温水浴锅中，于-40℃温条件下充分搅拌30min，得到沉淀物；最后将所得沉淀物离心，用甲醇清洗，50℃干燥2h得到橙色的荧光粉。
(3)钝化后的Cs 2SiF 6:Mn 4+荧光粉的制备
取Cs 2SiF 6:Mn 4+荧光粉加入1mL的酸性溶液中；在搅拌条件下加入一定量的还原性溶液中，随后搅拌30min；最后，将固液体系经过离心，用甲醇清洗，50℃干燥2h得到钝化的荧光粉。
实施例1～4中各条件控制如表1：
表1 Cs 2SiF 6:Mn 4+荧光粉制备条件控制
Figure PCTCN2019071839-appb-000001
实施例5～6
实施例5除选用的含硅化合物为正硅酸乙酯(0.5208g)外，其余均与实施例3一致。制备得到的Cs 2SiF 6:Mn 4+荧光粉的性能与实施例3类似。
实施例6除选用的含铯的化合物为氢氧化铯(0.3748g)外，其余均与实施例3一致。制备得到的Cs 2SiF 6:Mn 4+荧光粉的性能与实施例3类似。
实施例7
按照实施例3提供的制备方法，对步骤(2)中的反应温度(-40～0℃)进行调控，得到钝化前后的Cs 2SiF 6:Mn 4+荧光粉。
对实施例3制备得到的钝化前的Cs 2SiF 6:Mn 4+荧光粉进行XRD测试，如图1。从图1可知，得到的荧光粉为立方相的Cs 2SiF 6结构。如图2所示，为该荧光粉的扫描电镜图，该荧光粉的粒径大约为5～20μm。通过FSP920型(Edinburgh Instrument)荧光光谱仪测量该荧光粉的激发和发射光谱，如图3。从图3可知，该荧光粉在蓝光区有很强的吸收和最强发射峰在631nm的窄带红光发射。
实施例1～4中，通过改变原料中的K 2MnF 6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。对实施例1～4中未钝化处理的荧光粉进行发光强度测定，其结果如表2所示。实施例1～4提供的Cs 2SiF 6:Mn 4+荧光粉 的外量子效应均大于75％，其中，实施例3得到的Cs 2SiF 6:Mn 4+样品的外量子效率为83％。此外，对实施例7在不同温度条件下制备得到的钝化前的Cs 2SiF 6:Mn 4+的外量子效率进行测定，均高于78％。
表2实施例1～4中未钝化处理的荧光粉的相对发光强度
  相对发光强度
对照组 65％
实施例1 83％
实施例2 100％
实施例3 92％
实施例4 74％
将实施例3钝化的荧光粉与β-SiAlON:Eu 2+绿粉和蓝光芯片结合制备出不同光色的白光LED器件，其中之一白光LED器件电致发光光谱图如图5所示。由图可知，将钝化的荧光粉与β-SiAlON:Eu 2+绿粉结合可得到高流明和宽色域的白光LED器件。
将实施例3制备的钝化前的Cs 2SiF 6:Mn 4+和钝化的Cs 2SiF 6:Mn 4+测置于85℃、85％相对湿度的恒温恒湿箱中进行老化实验。经过一段时间后测试样品的光谱数据，并比较老化前后的光谱数据，作为样品耐湿性能的度量。
图4为实施例3中制备的钝化前的Cs 2SiF 6:Mn 4+和钝化的Cs 2SiF 6:Mn 4+在温度85℃、相对湿度85％条件下老化后光谱数据的变化图。由图4可以看出，实施例3钝化前的样品在老化168小时后发生了变为棕色(图4a所示)，样品发光强度保持了初始强度的13.6％；而钝化的样品仍然保持橙色(图4b所示)，样品发光强度保持了初始强度的75.0％，表明钝化后的荧光粉的耐湿性能得到了很大的提高。
对不同温度条件下制备得到的钝化前的Cs 2SiF 6:Mn 4+的发光强度进行测定，结果如表3。
表3不同温度条件下的钝化前的Cs 2SiF 6:Mn 4+的相对发光强度
不同温度/℃ 相对发光强度
10 83％
0 93％
-10 95％
-20 97％
-40(实施例3) 100％
由上述结果可知，反应温度为-40～-10℃时，相对发光强度较强，反应温度 为-40℃时，荧光强度最强，是10℃下的相对发光强度的1.20倍。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种高性能窄带荧光粉的制备方法，其特征在于，包括如下步骤：
    S1：将六氟锰酸盐溶解于HF溶液，搅拌下加入含硅的化合物和含铯的化合物得混合溶液；
    S2：于-40～-10℃下进行共沉淀反应，得沉淀物，离心，清洗，干燥后得Cs 2SiF 6:Mn 4+荧光粉初产物；所述Cs 2SiF 6:Mn 4+荧光粉初产物中Mn的摩尔分数为4～20％；
    S3：将Cs 2SiF 6:Mn 4+荧光粉初产物加入酸溶液中，搅拌条件下加入还原性溶液，搅拌，离心，洗涤，干燥即得到高性能窄带荧光粉。
  2. 根据权利要求1所述制备方法，其特征在于，S1中六氟锰酸盐为六氟锰酸钾或六氟锰酸铯中一种或几种。
  3. 根据权利要求1所述制备方法，其特征在于，S1中含硅的化合物为二氧化硅、正硅酸乙酯、氟硅酸、二氧化硅粉末、硅粉或石英中一种或几种。
  4. 根据权利要求1所述制备方法，其特征在于，S1中所述含铯的化合物为碳酸铯、氟化铯、硬脂酸铯、氢氧化铯、甲酸铯、丙烯酸铯、丙酸铯、硫酸铯、碳酸氢铯、氧化铯、硝酸铯或乙酸铯中一种或几种。
  5. 根据权利要求1所述制备方法，其特征在于，S2中共沉淀反应的时间为1～150min。
  6. 根据权利要求5所述制备方法，其特征在于，S2中共沉淀反应的温度为-40～-20℃。
  7. 根据权利要求1所述制备方法，其特征在于，S3中酸溶液为冰醋酸、丙酸、丁酸、氢氟酸、油酸、盐酸、硫酸、磷酸或硝酸中一种或几种。
  8. 根据权利要求1所述制备方法，其特征在于，S3中还原性溶液为为抗坏血酸、亚磷酸或甲酸中的一种或几种。
  9. 一种高性能窄带荧光粉，其特征在于，通过权利要求1～8任一所述制备方法制备得到。
  10. 权利要求9所述高性能窄带荧光粉在照明和显示领域中的应用。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114956003A (zh) * 2022-06-14 2022-08-30 郑州大学 一种四价锰掺杂氟氧钨酸钠红光荧光粉体的反滴共沉淀制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111778020A (zh) * 2020-07-07 2020-10-16 温州大学 一种用于提高锡酸盐红光材料的发光效率与抗湿性的加工方法
CN113337273A (zh) * 2021-04-30 2021-09-03 湖南师范大学 一种氟化物荧光粉的处理方法
CN114736681B (zh) * 2022-04-29 2023-08-01 江西离子型稀土工程技术研究有限公司 一种四价锰离子掺杂的氟化物红色荧光材料的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038774A (zh) * 2014-05-01 2015-11-11 通用电气公司 制备发红光磷光体的方法
CN105038776A (zh) * 2015-06-18 2015-11-11 北京宇极科技发展有限公司 锰(Mn4+)掺杂的氟化物荧光粉体材料的制备及表面改性的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038774A (zh) * 2014-05-01 2015-11-11 通用电气公司 制备发红光磷光体的方法
CN105038776A (zh) * 2015-06-18 2015-11-11 北京宇极科技发展有限公司 锰(Mn4+)掺杂的氟化物荧光粉体材料的制备及表面改性的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SONG ET AL.: "Highly Efficient and Stable Narrow-Band Red Phosphor Cs2SiF6:Mn4+ for High- Power Warm White LED Applications", ACS PHOTONICS, 15 September 2017 (2017-09-15), pages 2556 - 2565, XP055707691, ISSN: 2330-4022 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114956003A (zh) * 2022-06-14 2022-08-30 郑州大学 一种四价锰掺杂氟氧钨酸钠红光荧光粉体的反滴共沉淀制备方法
CN114956003B (zh) * 2022-06-14 2023-09-15 郑州大学 一种四价锰掺杂氟氧钨酸钠红光荧光粉体的反滴共沉淀制备方法

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